JP2794844B2 - 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, enables light fastness and wet fastness, and its application.

<Related Art> A reactive dye having a dioxazine skeleton in the molecular structure of the dye is known, but is insufficient in dyeing performance, for example, leveling property, build-up property, dyeing speed, or fastness. Level up 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 is not at a satisfactory level, especially in the case of a hydroxyl group-containing fiber. Have diligently improved this level, and have found a dioxazine compound that can solve the above problem.

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

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-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-hydroxymethyl Amino, 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 and Y ₁ include-(CH ₂ ) ₂ -,-(CH ₂ ) _3- and-.
_{(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 in which one sulfo may be substituted, 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 lower alkyl which may have a substituent represented by R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , C _{1 to} C ₄ alkyl is preferable, and as the optionally substituted group, , Hydroxy,
Preference is given to cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl.

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-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl , 4-hydroxybutyl, 2,3-dihydropropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxy Propyl, 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 exists in the form of a free acid or a salt thereof, and particularly, an alkali metal salt and an alkaline earth metal salt, particularly, a soda salt, a potassium salt, and a lithium salt are preferable.

The compound of the present invention can be produced, for example, as follows. The following general formula (II) (Wherein, R, R ₁ , R ₃ , R ₄ , X ₁ and X ₂ have the above-mentioned meanings) and a dioxazine compound represented by the following general formula (II)
I) (Wherein R ₂ , Y and Z have the same meaning as described above), and except for the case where Q represents chlorine, the following general formula (IV) HQ ′ (IV) (wherein , Q ′ has the meaning of the above-mentioned Q excluding chlorine)) and 2,4,6-trihalogeno-s-triazine are condensed in any order.

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 dioxazine compound 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 above-mentioned meanings, and X ₃ and X ₄ represent a halogen.) A 1,4-benzoquinone represented by the following general formula (VI) (Wherein, R ₁ has the above-mentioned meaning.) And a diaminobenzene represented by the following general formula (VII): (Wherein R ₃ and R ₄ have the above-mentioned meanings), and condensed with a diaminobenzene represented by the following general formula (VIII) (Wherein R ₁ , R ₃ , R ₄ , X ₁ and X ₂ have the above-mentioned meanings), and optionally cyclization in the presence of an oxidizing agent to give a compound A dioxazine compound of the formula (II) is obtained.

The dioxazine compound represented by the general formula (II) can also be synthesized by the following method. 1,4-benzoquinone represented by the general formula (V), diaminobenzene represented by the general formula (VII) and the following general formula (IX) (Wherein, R ₆ represents an alkyl group, and R ₁ has the above-mentioned meaning), and condensed to give the following general formula (X) (Wherein X ₁ , X ₂ , R ₁ , R ₃ , R ₄ and R ₆ have the above-mentioned meanings), and optionally cyclization in the presence of an oxidizing agent. At the same time, dealkylation is performed to obtain a dioxazine compound of the general formula (II).

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

In addition, it can be synthesized by the following method. The following general formula (XI) (Wherein X ₁ , X ₂ and R ₁ have the above-mentioned meanings) and a compound represented by the general formula (IV) by 2,4,6-trihalogen-s-triazine To the following general formula (XII) (Wherein X ₁ , X ₂ , R ₁ and Q have the above-mentioned meanings, and X represents a halogen). Thereafter, the dioxazine intermediate of the general formula (XII) is alkylated by a usual method, and the amine represented by the general formula (III) is condensed to obtain the compound (I) of the present invention.

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 drying and padding at room temperature or at elevated temperature, it can be fixed by steaming or dry heat.

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

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

Acid binders suitable for immobilizing the compounds of the invention on cellulose fibers are, for example, alkali metals or alkaline earth metals and inorganic or organic acids or compounds which liberate alkali under heating and water-soluble basic salts. 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 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 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 the influence of fluctuations in the dyeing temperature and the dyeing bath ratio is not easily lifted 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 In the form of the free acid, 54.5 parts of the dioxazine compound represented by the above structural formula was dissolved in 1500 parts of water, 18.5 parts of cyanuric chloride was added, and the pH was adjusted to 8 to 7 using a sodium carbonate solution at 5 to 30 ° C. Was stirred until the reaction was completed. Thereafter, sodium chloride was added to separate the crystals. Water the cake obtained
Dissolve in 1500 parts, add 17.3 parts of sulfanilic acid, adjust to pH 6-9 with sodium carbonate solution, and maintain the same pH.
The reaction was performed at 0-50 ° C. Sodium chloride was added to the reaction mixture to obtain a dioxazine intermediate having the following structure as a free acid.

83 parts of the obtained dioxazine intermediate was dissolved in 1000 parts of water, 28.1 parts of 1-aminobenzene-3-β-sulfateethylsulfone was added, and while maintaining the pH at 2 to 5, 50 to 80 ° C.
And stirred until the reaction was completed. Potassium chloride was added thereto, and the mixture was filtered. An asymmetric dioxazine compound represented by the following structural formula was obtained as a free acid.

Example 2 The same operation as in Example 1 was carried out, except that the following amine was used in an equimolar manner in place of the sulfanilic acid used in Example 1, to obtain a corresponding asymmetric dioxazine compound.

(1) Alternyl acid (2) Metanylic 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 3 1-aminobenzene-3-β-sulfateethyl used in Example 1 A corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 1 except that an equimolar amount of an amine represented by the following structural formula was used instead of the sulfone.

Example 4 In place of the dioxazine compound used in Example 1, an equimolar amount of the dioxazine compound represented by the following structural formula was used as the free acid, and the same operation as in Example 1 was performed to obtain a corresponding asymmetric dioxazine compound. .

Example 5 Using 18 parts of 2-methoxy-4,6-dichloro-s-triazine and 54.5 parts of the dioxazine compound used in Example 1, the mixture was reacted at 30 to 50 ° C. and pH 2 to 7, and further reacted with 1-amino acid. Benzen-3-β-sulfate ethyl sulfone 28.1
Reacted with parts. Salting out gave an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 6 2-methoxy-4,6-dichloro-s used in Example 5
-Instead of triazine, an equimolar amount of 2-ethoxy-4,6-
The corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 5 using dichloro-s-triazine.

Example 7 In place of 1-aminobenzene-8-β-sulfatoethylsulfone used in Example 5, an equimolar amine represented by the following structural formula was used, and the corresponding method was performed in the same manner as in Example 5. An asymmetric dioxazine compound was obtained.

Example 8 54.5 parts of the dioxazine compound used in Example 1 was mixed with 1500 parts of water.
18.5 parts of cyanuric chloride, and 5 to 30 ° C.
Then, the pH was adjusted to 3 to 7 using a sodium carbonate solution, and the mixture was stirred until the reaction was completed. Thereafter, sodium chloride was added to separate the crystals. Next, the obtained cake was dissolved in 1500 parts of water, 28.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and while maintaining the pH at 2 to 6, 1
The reaction was carried out at 0 to 50 ° C to obtain an asymmetric dioxazine compound represented by the following structural formula as a free acid.

Example 9 Instead of 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 8, the same operation as in Example 8 was performed using an equimolar amine represented by the following structural formula. The corresponding asymmetric dioxazine compound was obtained.

Example 10 93.8 parts of the asymmetric dioxazine compound obtained in Example 8 was dissolved in 1500 parts of water, and 1-aminobenzene-3-β-
28.1 parts of sulfate ethyl sulfone were 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 structural formula as a free acid.

Example 11 Instead of 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 10, an equimolar amount of an amine represented by the following structural formula was used, and the corresponding method was performed in the same manner as in Example 10. An asymmetric dioxazine compound was obtained.

Example 12 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound described in Examples 1 to 11 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 sodium carbonate was added. 4 parts were added and stained for 1 hour. Washing, soaping, washing and drying were performed to obtain a blue dyed product having excellent fastness properties and good build-up properties.

Example 13 83 parts of the dioxazine intermediate obtained in Example 1 was added to 1000 parts of water.
And dissolved in 41 parts of ethylene chlorohydrin. After adjusting the pH to 6 to 9 with a sodium hydroxide solution, the mixture was stirred at the same pH at 60 to 90 ° C. until the reaction was completed, potassium chloride was added, and the mixture was passed. The obtained product was a dioxazine intermediate having the following structure as a free acid.

Dissolve 87.4 parts of this dioxazine intermediate in 1000 parts of water,
28.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the mixture was stirred at 50 to 80 ° C. while maintaining the pH at 2 to 5 until the reaction was completed. To this was added potassium chloride and passed. An asymmetric dioxazine compound having the following structure as a free acid was obtained.

Example 14 18.8 parts of 1,4-phenylenediamine-2-sulfonic acid and 21.6 parts of 2-aminoethyl-5-aminobenzenesulfonic acid
Parts are dissolved in 1000 parts of water and adjusted to pH 5-7. afterwards,
24.6 parts of chloranil are added, and the pH is adjusted to 5 to 8 with sodium carbonate solution.
And stirred at 15-30 ° C. until the reaction was completed. Sodium chloride was added to the reaction mixture, followed by filtration.
Drying at 80 ° C. gave a dianilide compound having the following structure as a free acid.

57.7 parts of the resulting dianilide compound was added to 900 parts of 5-30% fuming sulfuric acid containing 1.7 parts of potassium iodide, and 5
The reaction was carried out at 2525 ° C. Thereafter, the reaction mixture was discharged into ice water to remove the precipitated crystals. The obtained cake was dissolved in 1500 parts of water, adjusted to pH 5 to 7 with a sodium hydroxide solution, and then salted out with sodium chloride. After that, a dioxazine compound represented by the following structural formula was obtained as a free acid.

25.3 parts of aniline-2,5-disulfonic acid were added to 100 parts of water, adjusted to pH 7, and 18.5 parts of cyanuric chloride were added. Thereafter, the pH was adjusted to 5 to 7 with sodium carbonate solution,
The mixture was stirred at 0 ° C. until the reaction was completed. This reaction mixture was added to a solution in which 57.3 parts of the above dioxazine compound was dissolved in 1500 parts of water, and the mixture was stirred at 20 to 50 ° C. while adjusting the pH to 5 to 7 with a sodium carbonate solution until the reaction was completed. Thereafter, sodium chloride was added to obtain a dioxazine intermediate having the following structure as a free acid.

Dissolve 93.8 parts of this dioxazine intermediate in 1500 parts of water,
28.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the mixture was stirred at 50 to 80 ° C. while maintaining the pH at 2 to 5 until the reaction was completed. Potassium chloride was added thereto, and the mixture was filtered. An asymmetric dioxazine compound having the following structure as a free acid was obtained.

Example 15 2-aminoethyl-5-aminobenzenesulfonic acid 4
3.2 parts were dissolved in 1000 parts of water and adjusted to pH 5-7. Thereafter, 24.6 parts of chloranil was added, and the pH was adjusted to 5 with sodium carbonate solution.
The mixture was stirred at 15 ° C to 40 ° C until the reaction was completed. Sodium chloride was added to the reaction mixture, and the precipitated crystals were separated and dried at 80 ° C. This was a dianilide compound having the following structure as a free acid.

60.5 parts of the resulting dianilide compound is added to 1800 parts of 5-30% fuming sulfuric acid containing 1.7 parts of potassium iodide,
The reaction was carried out at 2525 ° C. Then, the reaction mixture was discharged into ice water, and the precipitated crystals were removed. The obtained cake was dissolved in 1500 parts of water, adjusted to pH 5 to 7 with a sodium hydroxide solution, and then salted out with sodium chloride. The cake obtained after passing through this was the same compound as the dioxazine compound (λmax = 615 nm) obtained in Example 14. Using this compound, the same asymmetric dioxazine compound as the compound obtained in Example 14 was obtained in the same manner as in Example 14.

Example 16 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound described in Example 13 and Example 14 were dissolved in 200 parts of water, respectively.
10 parts of sodium sulfate and 10 parts of cotton were added, the temperature was raised to 60 ° C., and 4 parts of sodium carbonate was added, followed by dyeing for 1 hour. Washing, soaping, washing and drying were performed to obtain a blue dyed product having excellent fastness properties and good build-up properties.

Example 17 In place of the sulfanilic acid used in Example 1, an equimolar amine was used, and the same operation as in Example 13 was performed to obtain a corresponding asymmetric dioxazine compound.

(1) Alternyl acid (2) Metanylic 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 18 1-aminobenzene-3-β-sulfateethyl used in Example 13 The same operation as in Example 13 was carried out using an equimolar amine having the following structure in place of the sulfone,
The corresponding asymmetric dioxazine compounds were obtained.

Example 19 The same operation as in Example 14 was carried out using the following amine in an equimolar amount instead of the aniline-2,5-disulfonic acid used in Example 14, to obtain a corresponding asymmetric dioxazine compound.

(1) Alternyl acid (2) Metanylic 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) sulfanilic acid (8) aniline (9) m-toluidine (10) o-anisidine (11) ammonia (12) Ethylamine (13) Ethanolamine (14) β-alanine (15) Taurine (16) N-methyltaurine Example 20 Instead of 1-aminobenzene-3-β-sulfate ethylsulfone used in Example 14, etc. The same operation as in Example 14 was performed using mol of the amine represented by the following structure,
The corresponding asymmetric dioxazine compounds were obtained.

Example 21 Instead of the dioxazine compound used in Example 1, an equimolar amount of the dioxazine compound represented by the following structure was used.
The same operation as in Example 1 and Example 13 was performed to obtain a corresponding asymmetric dioxazine compound.

Example 22 The same procedure as in Example 14 was carried out, except that chloranil used in Example 14 was replaced with an equimolar bromanil to obtain a corresponding asymmetric dioxazine compound.

Example 23 The same procedure as in Example 15 was carried out, except that chloranil used in Example 15 was replaced with an equimolar bromanil, to obtain a corresponding asymmetric dioxazine compound.

Example 24 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds obtained in Examples 17 to 23 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 performed to obtain a blue dyed product having excellent fastness properties and good build-up properties.

Example 25 Using 18 parts of 2-methoxy-4,6-dichloro-s-triazine and 57.3 parts of the dioxazine compound obtained in Example 14, reacted at 30 to 50 ° C. and pH 2 to 7, and further reacted with 1- Aminobenzene-3-β-sulfateethylsulfone 28.1
Reacted with parts. Salting out gave an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 26 2-methoxy-4,6-dichloro-s used in Example 25
-Instead of triazine, an equimolar amount of 2-ethoxy-4,6-
The corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 25 using dichloro-s-triazine.

Example 27 In place of 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 25, and using an equimolar amine having the following structure, in the same manner as in Example 25,
The corresponding asymmetric dioxazine compounds were obtained.

Example 28 57.3 parts of the dioxazine compound obtained in Example 14 was added to water 15
Then, 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 8 to 7 with a sodium carbonate solution. Next, 1-aminobenzene-3
-Β-sulfate ethyl sulfone (28.1 parts) was added, pH2
The reaction was carried out at 10 to 50 ° C. while maintaining the temperature at 〜6 to give an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 29 In place of 1-aminobenzene-3-β-sulfateethylsulfone used in Example 28, and using an equimolar amine having the following structure, in the same manner as in Example 28,
The corresponding asymmetric dioxazine compounds were obtained.

Example 30 96.6 parts of the asymmetric dioxazine compound obtained in Example 28 was dissolved in 1500 parts of water, and 1-aminobenzene-3-β-
28.1 parts of sulfate ethyl sulfone were 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 31 In place of 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 30 and using an equimolar amine represented by the following structure, by the same operation as in Example 30,
The corresponding asymmetric dioxazine compounds were obtained.

Example 32 0.1 to 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds obtained in Examples 25 to 31 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 performed to obtain a blue dyed product having excellent fastness properties and good build-up properties.

Example 33 Using each of the same asymmetric dioxazine compounds used in Examples 12, 16, 24 and 32, a color paste having the following composition was made.

Dioxazine compound 5 parts Urine 5 parts Sodium alginate (5%) original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad, dried at 100 ° C after intermediate drying. Steamed for a minute, rinsed, soaped, rinsed, and dried. The resulting dyed product was excellent in various fastnesses and had good build-up properties.

Examples 34 to 45 In place of the 2-aminoethyl-5-aminobenzenesulfonic acid used in Example 14, the same procedure as in Example 14 was carried out, except that an equimolar amine having the following structure was used. An asymmetric dioxazine compound was obtained.

Example 46 Using an equimolar amount of aniline-2,5-disulfonic acid instead of the sulfanilic acid used in Example 1, the asymmetric dioxazine compound obtained by the same operation as in Example 1 is sulfomethylated by a usual method. The resulting asymmetric dioxazine compound was the same as the asymmetric dioxazine compound obtained in Example 34.

Example 47 A dioxazine intermediate obtained by the same procedure as in Example 1 using an equimolar amount of aniline-2,5-disulfonic acid instead of the sulfanilic acid used in Example 1 was subjected to hydroxyethylation using ethylene oxide. And then subjected to sulfuric acid esterification by a conventional method to obtain an asymmetric dioxazine compound identical to the asymmetric dioxazine compound obtained in Example 35.

Example 48 Using an equimolar amount of aniline-2,5-disulfonic acid instead of the sulfanilic acid used in Example 1, the asymmetric dioxazine compound obtained by the same operation as in Example 1 was converted into a methylol by a usual method. The asymmetric dioxazine compound obtained by the subsequent sulfuric esterification was prepared in Example
The same compound as the asymmetric dioxazine compound obtained in 37.

Example 49 In place of aniline-2,5-disulfonic acid used in Examples 34 to 45, the following amines were used in equimolar amounts.
By performing the same operation as described above, corresponding asymmetric dioxazine compounds were obtained.

(1) Alternyl acid (2) Metanylic 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) sulfanilic acid (8) aniline (9) m-toluidine (10) o-anisidine (11) ammonia (12) Ethylamine (13) Ethanolamine (14) β-alanine (15) Taurine (16) N-methyltaurine Example 50 1-aminobenzene-3-β- used in Examples 34 to 45
The same operation as in Examples 34 to 45 was performed using an equimolar amine having the following structure in place of sulfate ethyl sulfone to obtain a corresponding asymmetric dioxazine compound.

Example 51 The same operation as in Examples 34 to 45 was performed, except that chloranil used in Examples 34 to 45 was replaced with an equimolar amount of bromanil, to obtain a corresponding asymmetric dioxazine compound.

Example 52 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds obtained in Examples 34 to 45 and Examples 49 to 51 were dissolved in 200 parts of water, and 10 parts of sodium sulfate and 10 parts of cotton were added. Temperature rises,
4 parts of sodium carbonate was added and dyed for 1 hour. Washing, soaping, washing and drying were performed to obtain a blue dyed product having excellent fastness properties, particularly excellent chlorine fastness property, and good build-up properties.

Example 53 The asymmetric dioxazine compound represented by the following structure was obtained as a free acid by subjecting the asymmetric dioxazine compound obtained in Example 5 to sulfomethylation by a conventional method.

Example 54 2-methoxy-4,6-dichloro-s used in Example 5
-Instead of triazine, an equimolar amount of 2-ethoxy-4,6
Using -dichloro-s-triazine, a corresponding asymmetric dioxazine compound which was sulfomethylated was obtained in the same manner as in Example 5 and Example 53.

Example 55 In the same manner as in Example 5 and Example 53, except that 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 5 was replaced with an equimolar amine having the following structure, The corresponding asymmetric dioxazine compounds, each of which was sulfomethylated, were obtained.

Example 56 The asymmetric dioxazine compound obtained in Example 8 was subjected to sulfomethylation by a conventional method to obtain an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 57 In the same manner as in Example 8 and Example 56, except that 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 8 was replaced with an equimolar amine having the following structure, The corresponding asymmetric dioxazine compounds, each of which was sulfomethylated, were obtained.

Example 58 103.2 parts of the asymmetric dioxazine compound obtained in Example 56 was dissolved in 1500 parts of water, 28.1 parts of 1-aminobenzene-3-β-sulfateethylsulfone was added, and the mixture was maintained at pH 2 to 6 with a sodium carbonate solution. At 40 to 90 ° C. to obtain an asymmetric dioxazine compound represented by the following structure as a free acid.

Example 59 In the same manner as in Example 58, except that 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 58 was replaced with an equimolar amine having the following structure,
The corresponding asymmetric dioxazine compounds were obtained.

Example 60 The asymmetric dioxazine compound obtained by subjecting the asymmetric dioxazine compound obtained in Example 10 to sulfomethylation by a conventional method was the same compound as the asymmetric dioxazine compound obtained in Example 58.

Example 61 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds obtained in Examples 53 to 59 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 fastness properties, especially chlorine fastness property, and good build-up properties.

Example 62 A color paste having the following composition was prepared using each of the same asymmetric dioxazine compounds used in Examples 52 and 61.

Dioxazine compound 5 parts Urine 5 parts Sodium alginate (5%) original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad, dried at 100 ° C after intermediate drying. Steamed for a minute, rinsed, soaped, rinsed and dried. The obtained 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 Naka 3-chome No. 1 98 Sumitomo Chemical Co., Ltd. (56) Reference European publication 170838 (EP, A2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 62/503 CA (STN)

Claims (5)

(57) [Claims] 1. The following general formula in the form of a free acid: (In the formula, R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen or a lower alkyl group which may have a substituent, and X ₁ and X ₂ represent a hydrogen, a halogen, a lower alkyl group, a lower alkyl group. an alkoxy group or a phenoxy group, Y may have a substituent group alkylene, phenylene or naphthylene group, Z is -SO ₂ CH = C
Q represents chlorine, a lower alkoxy group, an optionally substituted amino group or H ₂ or —SO ₂ CH ₂ CH ₂ Z ′ (Z ′ represents a group capable of leaving under the action of an alkali); 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 removable by the action of an alkali) represent. Represents a group represented by｝. ] The non-target dioxazine compound shown by these. 2. A method according to claim 1 X ₁ and X ₂ is chlorine or bromine
The compound according to the above. 3. The compound according to claim ₁ , wherein R ₁ is hydrogen. 4. 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 by one or two substituents selected from the group of a carboxy group, or which may be substituted by a sulfo group The compound according to any one of claims 1 to 3, which is a good naphthylene group. 5. A method for dyeing or printing a fiber material, comprising using the asymmetric dioxazine compound according to claim 1.