JPH03772A - Unsymmetrical dioxazine compound and method for dyeing or printing fiber material using the same - Google Patents

Abstract

NEW MATERIAL:An unsymmetrical dioxazine compound, in the form of the free acid, of formula I wherein R is alkyl, phenyl, etc.; R1, R2 and R3 are each H or alkyl; W is carbonyl or sulfonyl; Y is alkylene, phenylene, etc.: Z is -SO2 CH=CH2, etc.; X1 and X2 are each H, halogen, etc.; and Q is amino, etc. USE:A dioxazine dye which can dye or print a material containing hydroxyl groups and/or amide groups, especially a cellulose fiber, a natural or synthetic polyamide fiber, a polyurethane fiber, leather, etc., with a color tone excellent in light-fastness, moisture-fastness, chlorine-fastness, etc. PREPARATION:A dioxazine compound of formula II is acylated to produce a compound of formula III. The resulting compound and amines of formulae IV and V are condensed with a 2,4,6-trihalogeno-s-triazine in an arbitrary order, thereby producing a compounded of formula I.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is applicable to materials containing hydroxyl groups and/or amide groups, particularly cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc. The present invention relates to improved new dioxazine compounds suitable for dyeing and printing blended fibers and allowing light-fast, wet-fast and chlorine-fast dyeing, and their applications.

<Prior art> Reactive dyes having a dioxazine skeleton in the molecular structure of the dye are known, but they are insufficient in terms of dyeing performance, such as level dyeing, build-up property, dyeing speed, or fastness, especially chlorine fastness. Therefore, further improvement is desired.

<Problems to be solved by the invention> The fastness of dyed or printed products of materials containing hydroxyl groups and/or amide groups, especially the fastness to chlorine, is not at a satisfactory level in the case of fibers containing droxyl groups. However, the present inventors have earnestly endeavored to improve this level and have discovered a dioxazine compound that can solve the above problem.

[Means for Solving the Problems] The present invention provides a free acid form of the following general formula (1) [wherein R is an optionally substituted alkyl or phenyl group, R1
, R and R3 are each independently hydrogen or an alkyl group which may have a substituent, W is a carbonyl group or a sulfonyl group, and Y is an alkylene, phenylene or naphthylene group which may have a substituent. Wow, Z bar 5O2CH
-CH.

or -5o, CH, CH, Z'(Z' represents a group that is eliminated by the action of an alkali) %X1 and X: have hydrogen, halogen, lower alkyl group, lower alkoxychlorine or a substituent Yl is an alkylene, phenylene or naphthylene group which may have a substituent, zl is -8o, CH-CHl or -5o, C
H, CH, Z''(Z'' represents a group that is eliminated by the action of an alkali). ) represents a group represented by ] The present invention provides an asymmetric dioxazine compound represented by the following, and a method for dyeing or printing an a-fiber material using the asymmetric dioxazine compound.

In the general formula (1), R-W- (RlW has the above-mentioned meaning) represents an acyl group, and examples of such an acyl group include alkyl or arylcarbonyl groups such as an acetyl group, a propionyl group, and a benzoyl group. Examples include alkyl or arylsulfonyl groups such as a methanesulfonyl group, a p-toluenesulfonyl group, and a p-toluenesulfonyl group. Among these acyl groups, substituted acyl groups include maleinyl group, succinyl group, o-lm- and p-carboxylphenylcarbonyl group, o-lm- and p-sulfophenylcarbonyl group, o-m- and p- -sulfophenylsulfonyl group is exemplified.

Examples of the amino group represented by Q which may have a substituent include alkylamino, N,N-dialkyl 1), cycloalkylamino, aralkylamino, arylamino, mixed substituted amino, for example, N-alkyl -N-
cyclohexylamino and N-alkyl-N-arylamino, as well as amino containing heterocyclic groups (which cyclic groups may further have addition-fused carbocyclic rings), and their amino nitrogen atoms. Examples include amino in which is an N-heterocyclic ring member (this N-heterocycle may further contain another heteroatom depending on the case). The alkyl mentioned above may be linear or branched, and may be of low molecular weight or high molecular weight, but C1-C4 alkyl is preferred. As cycloalkyl, aralkyl and aryl, groups such as cyclohexyl, benzyl, phenethyl, phenyl and naphthyl are particularly preferred. Examples of heterocyclic groups are furan,
These include thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzoxazole, benzthiazole and benzoxazole. Preferred as amino in which the amino nitrogen atom is a ring member of an N-heterocyclic ring are 6-membered N-heterocyclic ring compounds, which may further contain nitrogen, oxygen and sulfur as heteroatoms. good. The above alkyl, cycloalkyl, aralkyl, aryl,
Heterocyclic rings and N-heterocyclic rings further include halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4-alkyl, C1-C4-alkoxy, acylamino, ureido, and droxy, carboxy, sulfomethyl. and sulfo. Examples of amino represented by Q include -NH,,
Methylamino, ethylamino, propylamino, butylamino, hexylamino, β-methoxyethylamino,
β-ethoxyethylamine, r-methoxypropylamine, N.

N-dimethylamino, N,N-diethylamino, β-chloroethylamino, β-cyanoethylamino, N,N-
Di-β-hydroxyethylamino, β-hydroxyethylamino, T-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, anisidine, phenetidine, 2+, 8- and 4-sulfoanilino, 2.4
- and 2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 8- 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-cissulfonaphthyl(υ
-amino,8.6.8-trisulfonaphthyl-(1)-
Amino, 4.6.8-trisulfonaphthyl-(1)-amino, 6-sulfonaphthyl-(2)-amino, 4.8-
Disulfonaphthyl-(2)-amino, 8.6.8-)disulfonaphthyl-(2)-amino, 4.6.8-trisulfonaphthyl-(2)-amino, pyridyl-(2)-amino , morpholino, piperidino, pipedino, ethanolamino, methanolamino, N,N-jetanol-amino, N,N-dimetatouramino, N-ethanol-
Naphthylene optionally substituted with N-methylamino and N-ethyl-N-methanolamino, β-carboxyethylamino, β-sulfoethylamino, N-(/-sulfoethyl)-, for example, as an alkylene group. is -(CHs) 1 (C
HI) 5-(CHI)! Examples include O(CHz)x-.

The phenylene group or naphthylene group which may have a substituent is preferably one or two substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chlorine, bromine, and sulfo. means a bond leading to phenylene or sulfo 1 which may be present. ), etc.

Examples of the group that is eliminated by the action of an alkali represented by Z%Z# include sulfuric acid ester, thiosulfuric acid ester, phosphoric acid ester, acetic ester, and nogen.

As the alkyl which may have a substituent for R1, R,, R, and R4, C1 to C, alkyl is preferable,
Examples of optionally substituted groups include hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy,
Alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl are preferred.

Particularly preferable R,, R,, R, and R4 are, for example, hydrogen, methyl, ethyl, n-propyl, iS〇-propyl, n-butyl, 1so-butyl, sec-butyl, 2-hydroxyethyl, 2-hydroxyethyl, -hydroxypropyl,
8-hydroxypropyl, 2-hydroxybutyl, 8-
Hydroxybutyl, 4-hydroxybutyl, 2.8-dihydropropyl, 3.4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 8-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2
-ethoxyethyl, 8-methoxypropyl, 8-ethoxypropyl, 2-hydroxy-3-methoxypropyl,
Chloromethyl, bromomethyl, 2-chloroethyl, 2-
Bromoethyl, 8-chloropropyl, 8-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl, 8-carboxypropyl, 4-carboxybutyl, 1.2-dicarboxyethyl, carbamoylmethyl, 2 -carbamoylethyl, 8
-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl,
2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 8-methoxycarbonylpropyl, 8-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyl Oxyethyl, 2-ethylcarbonyloxyethyl, 8-methylcarbonyloxypropyl, 8
-Ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 8- Sulfamoylpropyl, 4
- Sulfamoylbutyl can be mentioned.

As X, , X, , halogen is particularly preferred, and chlorine and bromine are particularly preferred.

The compounds of the invention are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the soda, potassium and lithium salts.

The compound of the present invention can be produced, for example, in the following manner. The following general formula (formula) obtained by acylating a known dioxazine compound represented by the following - Sappaku (in the formula, R1, R3, Xl and x2 have the above-mentioned meanings) by a conventional method (wherein, R%R,, R3, W%X, and X2 have the above-mentioned meanings. and Z has the meaning given above.
(V) (In the formula, Q has the above-mentioned meaning.) It can be produced by condensing each of them with 2.4.6-dolyhalogeno8-)riazine in any order. .

Alternatively, a well-known dioxazine compound represented by -Sakura (nl) and an amine represented by -Sakura (5), and further the general formula (V
) to 2.4.6-trihalogeno S-) riazine in any order to condense them to each other in any order. X Haha0 'F'N'e, X+, Xs
, R1, R1, Rs, Q%Y and Z have the meanings given above. ) The dioxazine intermediates represented by (9) to (b) are acylated by a conventional method, and the dioxazine intermediates represented by (9) to (b) are then condensed with the remaining amines in any order. I can do it.

In the condensation reaction with 2.4.6-trihalogeno-s-)riazine, the order is not particularly limited,
Also, the reaction conditions are not particularly limited, but - secondly, temperature -
The pH is adjusted to 2 to 9 at 10 to 40 degrees Celsius, the pH is 2 to 9 at 0 to 70 degrees Celsius in the second stage, and the pH is adjusted to 2 to 7 at 10 to 100 degrees Celsius in the case of tertiary condensation to form the general formula. (A dioxazine compound represented by Il or a salt thereof can be obtained.

The compound of the present invention has pongee reactivity and can be used for dyeing or printing hydroxy group-containing or carbonamide group-containing materials. Preferably, the material is used in the form of a pongee material or in the form of a blend thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol.

Cellulose fiber material is cotton, and other plants am,
For example, linen, hemp, jute and ramie wA fibers are preferred. Regenerated cellulose fibers are, for example, viscose, stable and filament viscose.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, 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 materials, especially on the above-mentioned fiber materials, by a method depending on the physical and chemical properties.

For example, cellulosic fiber materials may be used in the presence of an acid concentration agent such as soda carbonate, tertiary phosphorus soda, caustic soda, etc., optionally with the addition of a neutral salt, such as mirabilite or common salt, and, if desired, a solubilizing agent, a penetrant or a leveling agent. Dyeing agents are also used and the process is carried out at relatively low temperatures. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after the actual dyeing temperature has been reached, or even before then, optionally in portions.

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

When printing is carried out on cellulose fibers, either in one phase, e.g. by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-1600 C, or in two phases, e.g. Alternatively, it can be carried out by printing with a weakly acidic printing paste, passing it through a hot alkaline bath containing an electrolyte, or overpadding with a padding liquid containing an alkaline electrolyte, followed by steaming or dry heat treatment.

Thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used in the printing pastes, if desired in combination with customary printing auxiliaries and/or dispersants, such as, for example, urea.

Suitable acid binders for fixing the compounds of the invention with 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 heated conditions. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Examples of such acid binders include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, secondary potassium, primary, secondary, or tertiary sodium phosphate, silicate soda, and sodium trichloroacetate.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out first by exhaustion under pH control from an acidic or slightly acidic dye bath, and then by changing to a neutral or even alkaline pH value for fixation. I can do it. Dyeing can usually be carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as a condensation product of cyanuric chloride and 8 times the mole of aminobenzenesulfonic acid or aminobenzenesulfonic acid or For example, addition products of stearylamine and ethylene oxide can also be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials.

Particularly suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, sweat resistance, acid hydrolysis resistance and alkali resistance, Furthermore, it has good chlorine resistance, abrasion resistance and ironing resistance.

In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility, exhaustion, and fixation properties, and is a dyed product with stable quality that is not easily affected by changes in dyeing temperature and dye bath ratio. It is characterized by the points that can be obtained and achieved.

Another characteristic of the dyed product is that there is little discoloration during fix treatment or resin processing, and there is little change due to contact with basic substances during storage.

Hereinafter, the present invention will be explained in detail with reference to Examples.

In the examples, parts and % represent parts by weight and % by weight, respectively.

Example 1 59 parts of the dioxazine intermediate 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 a pH of 5 to 8.0 to 80°C until the reaction was completed. To this, 17 parts of sulfinyl acid was added, and the mixture was stirred at pH 5-8 and at 10-50° C. until the reaction was completed. Furthermore, 28 parts of 1-aminobenzene-8-β-sulfatoethyl sulfone was added to pH 8-6.80-8.
By stirring at 0°C until the reaction was completed, an asymmetric dioxazine compound represented by the following structural formula was obtained as a free acid.

Example 2 λmax 5851m (in an aqueous medium) The dioxazine intermediate used here was synthesized as follows.

In place of the dioxazine intermediate of the following structural formula Example 1 as the free acid, the same mole of the dioxazine intermediate represented by the above structural formula as the free acid was used in the same manner as in Example 1 to obtain, as the free acid,
An asymmetric dioxazine compound represented by the following structural formula was obtained.

Dissolve 55 parts of the dioxazine compound shown in 600 parts of water, add 10 parts of acetic anhydride, and adjust the pH to 2-7.10-50.
The asymmetric dioxazine intermediate was obtained by stirring at °C until the reaction was completed.

(Space below) λmax 585 nm (However, in an aqueous medium) The dioxazine intermediate used here was prepared in the same manner as in Example 1 using the following structural formula as an equimolar free acid instead of the dioxazine compound used in Example 1. The corresponding asymmetric dioxazine compounds were obtained.

(Hereinafter referred to as blank space) It was obtained in the same manner as in Example 1 using the dioxazine compound shown below.

Example 8 0.1, 0.8 and 0.6 parts of each of the asymmetric dioxazine compounds described in Example 1.2 were each dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, and the mixture was heated to 60°C. The temperature was raised, 4 parts of sodium carbonate was added, and dyeing was carried out for 1 hour. After washing with water, soaping, rinsing with water and drying, a dyed reddish blue color having excellent fastness properties, especially chlorine fastness, and good build-up properties was obtained.

Examples 4 to 115 Equimolar amounts of dioxazine intermediate obtained by the same method as in Example 1) and 1-aminobenzene-8 of Example 1
- In place of β-sulfatoethyl sulfone, equimolar amounts of the amine (5) in the table are used (wherein X indicates a degree of sulfonation of about 1.2) to prepare the dioxazine intermediate of Example 1. Instead, 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 an equimolar amount of the dioxazine intermediate represented by the above structural formula as the free acid.

λmax 585 nm (in aqueous medium) (in the formula
shows a degree of sulfonation of about 1.2. ) The dioxazine intermediate used here was synthesized as follows.

65 parts of the dioxazine intermediate used in Examples 86-51 was added to 500 parts of 5-80X fuming sulfuric acid, and 20-70X
After stirring until the reaction is complete at °C, the reaction mass is
A dioxazine intermediate was obtained by charging in ice water and salting out.

Examples 117-188 Equimolar amounts of dioxazine intermediate (4) obtained in Example 116 and 1-aminobenzene-3-β- of Example 116
In the table, equivalent moles of sulfate ethyl sulfone (
The corresponding asymmetric dioxazine compounds were obtained in the same manner as in Example 11 (using the amines in Example 5).

(The following is a blank space) Example 188 A corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 1, using an equimolar amount of the following amine in place of the sulfanilic acid in Example 1.

(1) Ortanilic acid (2) Methanic acid (8) 1-aminonaphthalene-8,6-disulfonic acid (4) 1-aminonaphthalene-4,6,8-trisulfonic acid (5) 2-aminonaphthalene-4 , 8-disulfonic acid (6) 2-aminonaphthalene-8,6,8-1 lysulfonic acid (7) Aniline-2,5-disulfonic acid (8)
Aniline (9) ffl-Toluidine QI O-anisidine I Ammonia fi3 Ethylamino αj Ethanol-Anene I β-Alanine (15 Taurine-based IN-Methyl taurine Example 184 Implemented in place of sulfanilic acid in Examples 4 to 182) Even when the amines (1) to (16) used in Example 188 were used, corresponding asymmetric dioxazine compounds were similarly obtained.

Example 186 0.1, 0.8 and 0.6 parts of each of the asymmetric dioxazine compounds described in Examples 4 to 182 were dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, and the mixture was treated for 60 times. A reddish blue dyed product was obtained which was excellent in various fastnesses, particularly chlorine fastness, and had good build-up properties.

Example 186 In the actual tfa example 1, 1-7 further nobenzene-8-β-
The same compound as in Example 1 was also obtained by reversing the order of reaction of sulfatoethyl sulfone and sulfanilic acid.

Example 187 55 parts of a dioxazine compound represented by the following structural formula as a free acid and 1 cyanuric chloride
Add 8 parts to 1500 parts of water and adjust to pH 5-8 with soda carbonate.
．． The mixture was stirred at 0 to 80°C until the reaction was completed. Add 17 parts of sulfuric acid to this and adjust the pH to 5-8.10-60.
The mixture was stirred at ℃ until the reaction was completed. Next, 10 parts of acetic anhydride was added to this, and the mixture was stirred at pH 2 to 7.10 to 50° C. until the reaction was completed. Furthermore, 1-aminobenzene-8-β-sulfur 1-toethylsulfone 2s part G, t,
The asymmetric dioxazine compound obtained by stirring at pH 8-6.80-80°C until the reaction is completed is
It was the same as the asymmetric dioxazine compound obtained in Example 1.

Example 188 In Example 187, 1-aminobenzene-8-7-
The same compound as Example 187 was also obtained by switching the order of reaction of sulf-1-toethyl sulfone and sulfanilic acid.

Example 189 56 parts of a dioxazine compound represented by the following structural formula as a free acid and 1 cyanuric chloride
Add 8 parts to 1,500 parts of water and adjust to pH 5 with soda.
The mixture was stirred at 8.0 to 80°C until the reaction was completed. Add 17 parts of sulfuric acid to this and adjust the pH to 5-8.10-5.
The mixture was stirred at 0°C until the reaction was completed. Next, in this
28 parts of 1-aminobenzene-8-β-sulfatoethylsulfone was added, and the mixture was stirred at pH 8-6.80-80° C. until the reaction was completed. Furthermore, the asymmetric dioxazine compound obtained by adding 10 parts of acetic anhydride and stirring until the reaction was completed at pH 2-7.10-60°C is the same as the asymmetric dioxazine compound obtained in Example 1. there were.

Example 140 In Example 189, 1-aminobenzene-8-β-
The same compound as Example 189 was also obtained by switching the order of sulfatoethyl sulfone and sulfanilic acid.

Example 141 Aniline-2,5-disulfone l? 25.111 water 15
00 parts with sodium carbonate while neutralizing it and dissolving it. To this, 18 parts of cyanuric chloride was added at 5 to 80°C, and the mixture was stirred until the reaction was completed. 59 parts of the dioxazine intermediate obtained in Example 1 was added to the reaction solution, and the reaction was completed while neutralizing the liberated hydrochloric acid with sodium carbonate. Furthermore, 1-aminobenzene-8-β-sulfatoethyl sulfone 28
The reaction was completed by raising the temperature to 50 to 70°C while maintaining the pH at 2 to 5. The obtained asymmetric dioxazine compound was the same as the compound obtained in Example 188 (7).

Example 142 59 parts of the dioxazine intermediate obtained in Example 1 was added to 15 parts of water.
cyanuric chloride 1 at a temperature of 6 to 80°C.
8 parts of the mixture was added, and the mixture was stirred while maintaining the pH at 2 to 7 with sodium carbonate until the reaction was completed. Then 1-aminobenzene-8-
Add 28 parts of β-sulfatoethyl sulfone to pH2
The mixture was stirred at 10 to 50° C. while maintaining the temperature at 10 to 50° C. until the reaction was completed.

Next, in this, 1-N-ethylaminobenzene-8-
Add 81 parts of β-sulfatoethyl sulfone and adjust the pH to 2.
By stirring at 40 to 90° C. until the reaction was completed while maintaining the temperature at 40 to 60° C., an asymmetric dioxazine compound represented by the following structural formula was obtained as a free acid.

(Hereafter the margins H, N (N So, C, H, O5O, H)
Corresponding asymmetric dioxazine compounds were obtained in the same manner as in Example 142 using lζ in place of β-sulfatoethyl sulfone and an equimolar amount of the amine shown by the following structure.

bu, ki, (JSO,H (7) H,N-(CH,), QC,H45o,
C,H,CI(s) H,N-(C)i city QC,H,
30,Cl-C)1゜Example 144 Instead of the dioxazine intermediate used in Example 142,
Corresponding asymmetric dioxazine compounds were obtained in the same manner as in Example 142 using equimolar amounts of the dioxazine intermediates used in Examples 9 to 182.

Example 145 In Example 144, even if the amines (1) to (8) used in Example 148 were used instead of 1-N-ethylaminobenzene-8-β-sulfatoethyl sulfone, the same result could be obtained. An asymmetric dioxazine compound corresponding to was obtained.

Example 146 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds described in Examples 142, 148, 144 and 145 were each 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 soda carbonate was added, and dyeing was carried out for 1 hour. After washing with water, soaping, rinsing with water and drying, a dyed reddish blue color was obtained which showed poor fastness, especially fastness to chlorine, and good build-up properties.

Example 147 Each of the same asymmetric dioxazine compounds used in Examples 8, 185, and 146 were used to make colored pastes with the following compositions.

Asymmetric dioxazine compound 5 parts urine
5 parts Sodium alginate (5%
) Motonori 50 parts Boiling water 2
5 parts baking soda 2 parts balance 13 parts This color paste was printed on mercerized cotton broadcloth, and after intermediate drying, it was heated at 100℃.
Steamed for 5 minutes, washed with hot water, soaped, washed with hot water, and dried. The obtained dyed product was excellent in various fastnesses, particularly in chlorine fastness, and had good build-up properties.

(Margin below)

Claims (4)

[Claims] (1) In the form of free acid, there are the following general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [In the formula, R is an optionally substituted alkyl or phenyl group, and R_1, R_2 and R_3 are each independently hydrogen or an alkyl group which may have a substituent, W is a carbonyl group or a sulfonyl group, Y is an alkylene, phenylene or naphthylene group which may have a substituent,
Z is -SO_2CH=CH_2 or -SO_2CH_2
CH_2Z'(Z' represents a group that is eliminated by the action of an alkali), X_1 and X_2 are hydrogen, halogen, lower alkyl group, lower alkoxy group, or phenoxy group,
Q is an amino group that may have a substituent or ▲A mathematical formula, a chemical formula, a table, etc.▼{In the formula, R_4 is hydrogen or an alkyl group that may have a substituent, and Y_1 is a substituent. Z_1 is -SO_2CH=CH_2 or -SO
_2CH_2CH_2Z''(Z'' represents a group that is eliminated by the action of an alkali). } represents a group represented by. ] An asymmetric dioxazine compound represented by (2) The compound according to claim 1, wherein X_1 and X_2 are chlorine or bromine. (3) The compound according to claim 1 or 2, wherein R_1 and R_3 are hydrogen. (4) A method for dyeing or printing a fiber material, which comprises using the asymmetric dioxazine compound according to claim 1.