JP2754656B2 - 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> Although reactive dyes having a dioxazine skeleton in the molecular structure of the dye are known, dye performance aspects, such as leveling properties, build-up properties, dyeing speed, or fastness, especially chlorine fastness, are known. Is insufficient, and further improvement is desired.

<Problems to be Solved by the Invention> The durability of dyes or prints of materials containing a hydroxyl group and / or an amide group, especially chlorine durability, is a satisfactory level especially in the case of hydroxyl group-containing fibers. Instead, the present inventors worked diligently to this level up,
A dioxazine compound that can solve the above problem has been found.

<Means for Solving the Problems> The present invention provides the following general formula (I) in the form of a free acid. [Wherein, R represents a sulfo group, a halogen, an alkoxy group,
R ₁ , R ₂ and R ₃ are each independently hydrogen or a lower alkyl group which may have a substituent, R ₄ is hydrogen, a lower alkyl group which may have a substituent or an acyl group. , X ₁ , X ₂
Is hydrogen, a halogen, a lower alkyl group, a lower alkoxy group or a phenoxy group, Y is an alkylene, phenylene or naphthylene group which may have a substituent, and Z is -SO ₂ C
H = CH ₂ or —SO ₂ CH ₂ CH ₂ Z ′ (Z ′ is a group capable of leaving by the action of an alkali), Q is a halogen, a lower alkoxy group, an amino group which may be substituted, Wherein R ₅ is hydrogen or a lower alkyl group which may have a substituent, Y ₁ is an alkylene which may have a substituent, a phenylene or a 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). And a method for dyeing or printing a fiber material characterized by using the asymmetric dioxazine compound.

Here, R is exemplified by a sulfo group, a halogen such as chlorine and bromine, and an alkoxy group such as a methoxy group and an ethoxy group. Among them, a sulfo group is particularly preferable.

Examples of the halogen represented by Q include fluorine, chlorine and bromine, and fluorine and chlorine are particularly preferred.

Examples of the lower alkoxy group represented by Q include a methoxy group and an ethoxy group.

Examples of the optionally substituted amino group represented by Q include alkylamino, N, N-dialkylamino, cycloalkylamino, aralkylamino, arylamino, and mixed-substituted amino groups such as N- Alkyl-
N-cyclohexylamino and N-alkyl-N-arylamino, and also an amino group containing a heterocyclic group (this cyclic group can have a further addition-fused carbocyclic ring) and its amino And an amino group in which the nitrogen atom is an N-heterocyclic ring member (this N-heterocycle may optionally contain another heteroatom). 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 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 can be mentioned.

Examples of the alkylene group which may have a substituent represented by Y and 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 1 or 2 selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo.
Phenylene group which may be substituted by one substituent or naphthylene group which may be substituted by 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, for example, sulfate, thiosulfate,
Phosphoric esters, acetic esters, halogens and the like correspond to this.

R ₁ , R ₂ , R ₃ , R ₄ and the lower alkyl which may have a substituent of R ₅ are preferably C _{1 to} C ₄ alkyl, and the optionally substituted group may be hydroxy. , Cyano,
Alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl are preferred.

Particularly preferred R ₁ , R ₂ , R ₃ , R ₄ and R ₅ include, for example, hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxy Ethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl,
-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, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-
Examples include sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, and 4-sulfamoylbutyl.

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

The acyl group represented by R _4, an acetyl group, a propionyl group, Mareiniru group, such as benzoyl group, an alkyl, alkenyl or aryl group, a methanesulfonyl group, an alkyl or arylsulfonyl group such as p- toluenesulfonyl group is exemplified Is done.

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. In the form of the free acid, the following general formula (II) (Wherein R, R ₁ , R ₃ , R ₄ , X ₁ and X ₂ have the above-mentioned meanings) and dioxazines represented by the following general formula (III) (Wherein R ₂ , Y and Z have the same meaning as described above), and in the form of a free acid, except for the case where Q represents halogen, the following general formula (IV) HQ ( IV) (in the formula, Q has the meaning described above except for halogen) by condensing each compound with 2,4,6-trihalogeno-s-triazine 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 asymmetric dioxazine compound represented by the general formula (I) or a salt thereof can be obtained by condensation while adjusting to H2 to H7.

The dioxazine represented by the formula (II) can be synthesized by a method known per se, for example, as follows.

The following general formula (V) (Wherein X ₁ and X ₂ have the meaning described above, and X ₃ and X ₄
Represents halogen. 1,4-benzoquinone represented by the following general formula (VI): (Wherein R ₁ has the above-mentioned meaning.) In the form of diaminobenzene and a free acid represented by the following general formula (VII): Wherein R, R ₃ and R ₄ have the meanings given above, provided that
The substitution position of R is the o-position of NR ₃ R ₄ or the p-position of the sulfo group. ) And condensed with diaminobenzene represented by the following formula (VIII) (Wherein, R, R ₁ , R ₃ , R ₄ , X ₁ and X ₂ have the above-mentioned meanings, provided that the substitution position of R is the o-position of NR ₃ R ₄ or the p-position of the sulfo group. The dianilide compound represented by the general formula (II) is produced and optionally cyclized in the presence of an oxidizing agent to obtain a dioxazine of the general formula (II).

When R is a sulfo group, a dioxazine compound represented by the general formula (II) in which R is a sulfo group is obtained by sulfonating a dioxazine compound in which R is hydrogen in the general formula (II). I can do it.

Further, if R ₃ and / or R ₄ is a lower alkyl group which may have a substituent, the corresponding R ₃ and /
Alternatively, it can also be obtained by alkylating a dianilide compound of the general formula (VIII) wherein R ₄ is hydrogen, a dioxazine of the general formula (II) or an asymmetric dioxazine of the general formula (I).

When R ₄ is an acyl group, the corresponding dianilide compound of the general formula (VIII) wherein R ₄ is hydrogen;
It can also be obtained by acylating a dioxazine of I) or an asymmetric dioxazine compound of the general formula (I).

The compound of the present invention has fiber reactivity and can be used for dyeing or printing a material containing a hydroxy group or a carbonamide group. 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 drying.

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 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 during fixation or resin processing of the obtained dyed product 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 26.8 parts of 1,4-phenylenediamine-2,6-disulfonic acid and 18.8 parts of 1,4-phenylenediamine-2-sulfonic acid were dissolved in 500 parts of water. Next, 24.6 parts of chloranil was added, the pH was adjusted to 4 to 8 at room temperature, and the mixture was stirred until the reaction was completed. Thereafter, salting out was performed, and the crystals were isolated and dried. The resulting dianilide compound is represented by the following structure as a free acid.

62.9 parts of the obtained dianilide compound was added with 10 to 30% fuming sulfuric acid.
The mixture was added to 1500 parts at 0 to 15 ° C and stirred at 15 to 40 ° C until the reaction was completed. The reaction mixture was poured into ice water, the precipitated crystals were separated, water was added to the obtained cake, and the pH was adjusted to 3 to 6 with a sodium hydroxide solution. Next, salting out was performed using sodium chloride, and the precipitated crystals were isolated. The obtained oxazines are represented by the following structure as a free acid.

62.5 parts of the obtained dioxazines were dissolved in 1500 parts of water, 18.5 parts of cyanuric chloride was added at a temperature of 5 to 30 ° C., and the mixture was stirred until the reaction was completed while maintaining the pH at 2 to 7 with a sodium carbonate solution. Next, 17.3 parts of sulfanilic acid were added, and the same pH was added.
At 30 to 50 ° C. The reaction solution was salted out with sodium chloride, and the precipitated crystals were separated. This compound is a dioxazine intermediate compound having the following structure as a free acid.

90.8 parts of the obtained dioxazine intermediate compound is dissolved in water, 28.1 parts of 1-aminobenzene-3-β-sulfateethylsulfone is added, and while maintaining the pH at 2 to 5, 50 to 70 ° C.
The mixture was stirred under the same conditions until the reaction was completed.
Add potassium chloride to the reaction mixture that has dropped to room temperature,
The precipitated crystals were isolated. This compound is an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 2 A dianilide compound represented by the following structure as a free acid was obtained in the same manner as in Example 1 except that equimolar bromanil was used instead of chloranil of Example 1.

The dianilide compound was reacted in the same manner as in Example 1 to obtain a dioxazine represented by the following structure as a free acid.

Using this dioxazine, a reaction was carried out in the same manner as in Example 1 to obtain a dioxazine intermediate compound represented by the following structure as a free acid.

Using this dioxazine intermediate compound, a reaction was carried out in the same manner as in Example 1. The obtained compound is an asymmetric dioxazine compound represented by the following structure as a free acid.

Dyeing Example 1 0.1, 0.3 and 0.6 parts of the asymmetric dioxazine compounds obtained in Examples 1 and 2 were each dissolved in 200 parts of water, and 10 parts of sodium sulfate and 10 parts of cotton were added. And stained for 1 hour. Washing, soaping, washing and drying were carried out to obtain a blue dyed product having excellent pitting strength and, in particular, chlorinating potency and having a good build-up property.

Examples 3 to 50 In the same manner as in Example 1 except that 1,4-phenylenediamine-2,6-disulfonic acid of Example 1 was replaced with an equimolar compound of the formula (VII) in the table, respectively. The dioxazines (II) corresponding to were obtained. The obtained dioxazines were obtained in the same manner as in Example 1 to obtain the corresponding dioxazine intermediate compounds.
The corresponding asymmetric dioxazine compounds were obtained in the same manner as in Example 1, except that equimolar amine of the formula (III) in the table was used in place of aminobenzene-3-β-sulfatoethylsulfone.

Example 51 The corresponding dioxazine intermediate compound was obtained by substituting the equimolar amine below for the sulfanilic acid of Example 1.

(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 For each of the obtained dioxazine intermediate compounds, 1-
Aminobenzene-3-β-sulfatoethylsulfone was reacted in the same manner as in Example 1 to obtain a corresponding asymmetric dioxazine compound.

Example 52 In Examples 3 to 50, the corresponding asymmetric dioxazine compounds were similarly obtained by using the amines (1) to (16) used in Example 51 instead of the sulfanilic acid.

Dyeing Example 2 0.1, 0.3, and 0.6 parts of each of the asymmetric dioxazine compounds described in Examples 3 to 52 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 blue dyed product having excellent durability, especially chlorine durability, and good build-up properties.

Example 53 The same compound as in Example 1 was obtained by changing the reaction order of sulfanilic acid and 1-aminobenzene-3-β-sulfatoethylsulfone in Example 1.

Example 54 25.3 parts of aniline-2,5-disulfonic acid were added to and dissolved in 250 parts of water while neutralizing with sodium carbonate. 5-30 ° C here
Then, 18.5 parts of cyanuric chloride was added thereto, and the mixture was stirred until the reaction was completed. To the reaction mixture, 62.5 parts of the dioxazine obtained by the method described in Example 1 was added. The reaction was terminated while neutralizing the liberated hydrochloric acid with sodium carbonate. The obtained dioxazine intermediate compound was the same as the compound obtained in Example 51 (7).

To this dioxazine intermediate compound, 28.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added,
While maintaining the pH at 2 to 5, the temperature was raised to 50 to 70 ° C, and the mixture was stirred until the reaction was completed. Potassium chloride was added to this mixture, and the precipitated crystals were isolated. This compound is an asymmetric dioxazine compound having the following structure as a free acid.

This compound was the same as the asymmetric dioxazine compound obtained in Example 51 (7).

Examples 55 to 69 In the same manner as in Example 1 except that 1,4-phenylenediamine-2,6-disulfonic acid in Example 1 was replaced with an equimolar compound of the formula (VII) in the table, The corresponding dioxazines (II) were obtained. Using the obtained dioxazines, an equimolar compound of the formula (IV) in the table was used in place of the sulfanilic acid of Example 1, and 1-aminobenzene-3-β-sulfatoethylsulfone of Example 1 was used instead of Equivalent to the procedure of Example 1 or Example 53 using an equimolar amine of the formula (III) in the table, or in place of the aniline-2,5-disulfonic acid of Example 54 Compound of general formula (IV) in the table, 1-aminobenzene-3
The corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 54, or using any method, except that equimolar amine of the general formula (III) in the table was used instead of -β-sulfatoethylsulfone. .

Dyeing Example 3 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds described in Examples 54 to 69 were each dissolved in 200 parts of water, and 10 parts of sodium sulfate and 10 parts of cotton were added. 4 parts were added and stained for 1 hour. Washing, soaping, washing and drying were carried out to obtain a blue dyed product having excellent durability, especially chlorine durability, and good build-up properties.

Example 70 Using 18 parts of 2-methoxy-4,6-dichloro-s-triazine and 62.5 parts of the dioxazine described in Example 1, the pH was measured.
The reaction was carried out at 2 to 7, 30 to 50 ° C, and further reacted with 28.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone. Salting out gave an asymmetric dioxazine compound represented by the following structure as a free acid.

Examples 71 to 97 In place of the dioxazines of Example 70, the dioxazines in the following table were used, and in place of 2-methoxy-4,6-dichloro-s-triazine, the compounds described in the third column of the following table were replaced with 1 Example 70 using an amine of the following general formula (III) in place of -aminobenzene-3-β-sulfatoethylsulfone
The corresponding asymmetric dioxazine compounds were obtained in the same manner as in the above.

Dyeing Example 4 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds described in Examples 70 to 97 were dissolved in 200 parts of water, and 10 parts of sodium sulfate and 10 parts of cotton were added. 4 parts were added and stained for 1 hour. Washing, soaping, washing and drying were carried out to obtain a blue dyed product having excellent durability, especially chlorine durability, and good build-up properties.

Example 98 The dioxazine intermediate compound obtained in Example 1 was dissolved in water, excess diethyl sulfate was added, and the pH was 6 to 9, 50 to 90.
The reaction was carried out at ℃ to obtain a dioxazine intermediate compound represented by the following structure as a free acid.

The above dioxazine intermediate compound is added with an equimolar amount of 1
-Aminobenzene-3-β-sulfatoethylsulfone was added to water and stirred at pH 2-5, 50-70 ° C until the reaction was completed. Salt was added to the reaction mixture, and the precipitated crystals were isolated. This compound is an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 99 Using each of the dioxazine intermediate compounds obtained in Example 51, a corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 98.

Staining Example 5 Each of the dioxazine compounds described in Examples 98 and 99.
Dissolve 1, 0.3 and 0.6 parts in 200 parts of water, add 10 parts of sodium sulfate and 10 parts of cotton, raise the temperature to 60 ° C, add 4 parts of sodium carbonate, and add 1 part.
Time stained. Washing, soaping, washing and drying were carried out to obtain a blue dyed product having excellent durability, especially chlorine durability, and good build-up properties.

Example 100 The dioxazine intermediate compound obtained in Example 1 was dissolved in water, excess acetic anhydride was added, and the reaction was carried out at 30 to 70 ° C to obtain a dioxazine intermediate compound represented by the following structure as a free acid. .

To this dioxazine intermediate compound was added an equimolar amount of 1-aminobenzene-3-β-sulfatoethylsulfone to water, and the mixture was stirred at pH 2 to 5 and 50 to 70 ° C. until the reaction was completed. Salt was added to the reaction mixture, and the precipitated crystals were isolated. This compound is an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 101 Using each of the dioxazine intermediate compounds obtained in Example 51, a corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 100.

Dyeing Example 6 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound described in Examples 100 and 101 were dissolved in 200 parts of water, respectively.
10 parts 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 blue dyed product having excellent durability, particularly chlorine durability, and good build-up properties.

Example 102 62.5 parts of the dioxazine obtained in Example 1 was dissolved in 1500 parts of water, 18.5 parts of cyanuric chloride was added at a temperature of 5 to 30 ° C, and the reaction was completed while maintaining the pH at 2 to 7 with sodium carbonate. Stirred until done. Next, 28.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the mixture was reacted at 10 to 50 ° C. while maintaining the pH at 2 to 6, to obtain an asymmetric dioxazine compound represented by the following structure as a free acid. .

Examples 103 to 150 In the same manner as in Example 1, except that 1,4-phenylenediamine-2,6-disulfonic acid of Example 1 was replaced with an equimolar compound of the formula (VII) in the following table, The corresponding dioxazines (II) were obtained. The obtained dioxazines were reacted with 18.5 parts of cyanuric chloride to obtain the corresponding dioxazine intermediate compounds.
The corresponding asymmetric dioxazine compounds were obtained in the same manner as in Example 102, except that in place of 1-aminobenzene-3-β-sulfatoethylsulfone of the above, an equimolar amount of the amine of the general formula (III) in the table was used. Was.

Dyeing Example 7 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound described in Examples 102 to 150 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 blue dyed product having excellent durability, especially chlorine durability, and good build-up properties.

Example 151 To a final reaction solution obtained in the same manner as in Example 102, 17.3 parts of sulfanilic acid was added, and the mixture was kept at pH 5 to 5 while maintaining pH 2 to 5.
The mixture was stirred at 0 ° C. until the reaction was completed to obtain the same asymmetric dioxazine compound as that obtained in Example 1.

In addition, the same asymmetric dioxazine compounds as those obtained in Examples 3 to 50 were obtained by treating the asymmetric dioxazine compounds described in Examples 103 to 150 in the same manner.

Example 152 Asymmetric dioxazine compound 101.8 obtained in Example 102
Was dissolved in 1500 parts of water, and 1-aminobenzene-3-β
28.1 parts of sulfate ethyl sulfone was added, and the mixture was reacted at 40 to 90 ° C. while maintaining the pH at 2 to 6 with a sodium carbonate solution to obtain an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 153 Instead of 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 152, each of the asymmetric dioxazine compounds obtained in Examples 103 to 150 was replaced with an equimolar amine represented by the following structure. Was used to obtain the corresponding asymmetric dioxazine compounds in the same manner as in Example 152.

_{(6) H 2 N- (CH} 2) 2 OC 2 H 4 SO 2 C 2 H 4 Cl (7) H 2 N- (CH 2) 2 OC 2 H 4 SO 2 CH = CH 2 staining Example 8 Dissolve 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound described in Examples 152 and 153 in 200 parts of water, respectively,
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 blue dyed product having excellent durability, especially chlorine durability, and good build-up properties.

Example 154 Dioxazines represented by the above structure as a free acid 54.6
Was added to 1000 parts of 5-28% fuming sulfuric acid, and the reaction was carried out at 80 to 100 ° C. The reaction mixture was poured into ice water, the precipitated crystals were separated, water was added to the obtained cake, and the pH was adjusted to 2 to 7 with a sodium hydroxide solution. Next, 18.5 parts of cyanuric chloride is added at a temperature of 5 to 30 ° C., and sodium carbonate solution is used.
While maintaining the pH 2 to 7, the mixture was stirred until the reaction was completed. Thereafter, 17.3 parts of sulfanilic acid were added, and at the same pH, 30 to 50.
The reaction was carried out at ℃. Then, 18.1 aminobenzene-4-β-sulfatoethylsulfone 28.1 was added to the reaction mixture.
The temperature is raised to 50-70 ° C while maintaining the pH at 2-5,
The mixture was stirred under the same conditions until the reaction was completed. Potassium chloride was added to the reaction mixture cooled to room temperature, and the precipitated crystals were isolated. The compounds obtained were obtained in Examples 3 and 19
And the respective asymmetric dioxazine compounds obtained in the above.

Printing Examples Using the same asymmetric dioxazine compounds used in Dyeing Examples 1 to 8, color pastes having the following compositions were prepared.

5 parts of asymmetric dioxazine compound 5 parts of urine 5 parts of 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 and dried at 100 ° C after intermediate drying. Steamed for 5 minutes, rinsed, soaped, rinsed and dried. The obtained dyed product was excellent in various fastnesses, particularly excellent in fastness in chlorine, and had good build-up properties.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahide Ikeo 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Sumitomo Chemical Co., Ltd. (72) Inventor Takashi Omura Konohana-ku, Osaka-shi, Osaka No. 3-98, Kasuganaka, Sumitomo Chemical Co., Ltd. (56) References JP-A-61-14265 (JP, A) JP-A-63-211378 (JP, A) JP-A-63-243387 (JP) JP-A-58-65759 (JP, A) JP-A-58-71957 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 62/503 D06P 1/38 CA (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. The following general formula in the form of a free acid: [Wherein, R represents a sulfo group, a halogen atom or an alkoxy group, and R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or
Hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, represents a lower alkyl group optionally substituted with a substituent selected from the group consisting of sulfo and sulfamoyl, R ₄ is hydroxy, cyano , Alkoxy,
An alkyl group optionally substituted with a substituent selected from the group consisting of halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl, a hydrogen atom, an alkylcarbonyl group, and an alkenyl optionally substituted with carboxyl A carbonyl group, an arylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group which may be substituted with methyl, X ₁ and X ₂ are a hydrogen atom, a halogen atom,
Represents a lower alkyl group, a lower alkoxy group or a phenoxy group, and Y represents a — (CH ₂ ) ₂ — group, a — (CH ₂ ) ₃ — group,
An alkylene group selected from a (CH ₂ ) ₃ O (CH ₂ ) ₂ — group and a — (CH ₂ ) ₂ O (CH ₂ ) ₂ — group, methyl, ethyl, methoxy, ethoxy, nitro, carboxy, chlorine, bromine and a substituted phenylene group which may be substituted by a group, or an optionally naphthylene group optionally substituted by a sulfo selected from the group consisting of sulfo, Z is, -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH
₂ Z ′ (Z ′ represents a sulfate, thiosulfate, phosphate, acetate or halogen), and Q represents alkyl, cycloalkyl, aralkyl,
An amino group which may be substituted by a substituent selected from the group consisting of aryl and heterocyclic groups, and an amino group wherein the amino nitrogen atom is a ring member of an N-heterocyclic ring (wherein the above substituent and N- heterocyclic ring, further, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acetylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo And may be substituted by
The N-heterocyclic ring may further contain another hetero atom in the ring. ), A halogen atom, an alkoxy group, or a formula -N (R ₅ ) -Y ₁ -Z ₁ wherein R ₅ is a hydrogen atom or a hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, Alkylcarbonyloxy, represents an alkyl group which may be substituted with a substituent selected from the group consisting of sulfo and sulfamoyl, and Y ₁ represents-(C
H _{2) 2} - group, - (CH _{2) 3} - _{group, - (CH 2) 3 O} (CH 2) 2
An alkylene group selected from a — group and — (CH ₂ ) ₂ O (CH ₂ ) ₂ — group, methyl, ethyl, methoxy, ethoxy, chlorine,
Represents a phenylene group which may be substituted by a substituent selected from the group consisting of bromine and sulfo, or a naphthylene group which may be substituted by sulfo, and Z ₁ represents -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Z ″ (Z ″ represents a sulfate, thiosulfate, phosphate, acetate or halogen). ] 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 is a sulfo group. 4. The compound according to claim 1, wherein R ₁ is hydrogen. 5. Y is a methyl group, an ethyl group, a methoxy group,
An ethoxy group, a chlorine, bromine, nitro group, a sulfo group, and a phenylene group which may be substituted with one or two substituents selected from the group of a carboxy group, or which may be substituted with a sulfo group. The compound according to any one of claims 1 to 4, which is a good naphthylene group. 6. A compound represented by the following general formula in the form of a free acid: Wherein R, R ₁ , R ₃ , R ₄ , X ₁ and X ₂ have the same meaning as in claim 1. ] The dioxazine shown by these. 7. A compound of the following formula in the form of a free acid: Dioxazines represented by the formula: 8. A method for dyeing or printing a fiber material, comprising using the asymmetric dioxazine compound according to claim 1.