JP2767866B2 - Dioxazine ether 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 ether compound which is suitable for dyeing and printing fibers and which enables light-fast and wet-fast dyeing, and its application.

<Prior art> Reactive dyes having a dioxazine skeleton in the molecular structure of the dye are known, but the dyeing performance is inadequate in terms of dyeing performance, for example, leveling properties, build-up properties, 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. Worked diligently to find a dioxazine ether compound that could 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: Wherein X is a halogen, A is an optionally substituted alkyl, alkoxy or phenoxy group, or a compound of the formula Wherein W ₁ and W ₂ each independently represent an optionally substituted aliphatic or aromatic cross-linking group, Q ₁ and
Q ₂ is each independently an optionally substituted amino group or formula R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or a lower alkyl group which may be substituted,
Y _1, Y ₂ and Y ₃ which may have a separate substituent together alkylene, phenylene or naphthylene group, Z _1,
Z ₂ and Z ₃ are each independently —SO ₂ CH = CH ₂ or —SO ₂ CH ₂
CH ₂ Z ′ (Z ′ represents a group capable of leaving by the action of an alkali.) ] And a method for dyeing or printing a fiber material characterized by using the compound.

Here, the halogen represented by X is preferably chlorine or bromine.

Examples of the amino group optionally having a substituent represented by Q ₁ and Q ₂ include alkylamino, N, N-dialkylamino, cycloalkylamino, aralkylamino, arylamino, a mixed-substituted amino group, For example, N-alkyl-N-cyclohexylamino and N-alkyl-
N-arylamino, an amino group further containing a heterocyclic group (this cyclic group may further have an addition-fused carbocyclic ring), and the amino nitrogen atom is an N-heterocyclic And an amino group which is a ring member (this N-heterocyclic ring may optionally contain another hetero atom). The alkyl in the above may be straight-chain or branched, and may be low-molecular or high-molecular, but is preferably C ₁ -C ₄ alkyl.
Particularly preferred as cycloalkyl, aralkyl and aryl are groups such as cyclohexyl, benzyl, phenethyl, phenyl and naphthyl. Examples of heterocyclic groups include furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole. Preferred as the amino group in which the amino nitrogen atom is a ring member of an N-heterocyclic ring is a 6-membered N-heterocyclic ring compound, which further contains nitrogen, oxygen and sulfur as heteroatoms. Is also good. The above alkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclic ring further include
Halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ - alkyl, C ₁ -C ₄
-Alkoxy, acylamino, ureido, hydroxy,
It may be substituted by carboxy, sulfomethyl and sulfo. Examples of the amino group represented by Q ₁ and Q ₂ include -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-8-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, 2-, 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, 8,6,8-trisulfonaphthyl- (2) -amino, 4,6,8-trisulfonaphthyl- (2) -amino, pyridyl- (2) -amino ,
Morpholino, piperidino, piperazino, N-β-hydroxyethyl-N-methylamino and N-ethyl-N-
Examples include hydroxymethylamino, β-carboxyethylamino, β-sulfoethylamino, N- (β-sulfoethyl) -N-methylamino and the like.

Examples of the optionally substituted alkylene group represented by Y ₁ , Y ₂ and Y ₃ include-(CH ₂ ) ₂ -,-(CH ₂ ) _3- and-
(CH ₂ ) ₂ O (CH ₂ ) ₂ — and the like. Further, as the phenylene group or naphthylene group which may have a substituent, preferably methyl, ethyl, methoxy, ethoxy,
Phenylene which may be substituted by one or two substituents selected from the group consisting of chlorine, bromine and sulfo or naphthylene which may be substituted by one sulfo, (In the formula, the bond indicated by an asterisk is Means a bond that leads to ) Etc. can be given.

Examples of the group which is eliminated by the action of an alkali represented by Z 'include sulfate, thiosulfate, phosphate, acetate, and halogen.

As the optionally substituted lower alkyl represented by R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , C ₁ -C ₄ alkyl is preferable, and the optionally substituted group is , Hydroxy,
Preferred are cyano, alkoxy, halogen, carbomoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl.

Particularly preferred R ₁ , R ₃ 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,
-Hydroxybutyl, 2,3-dihydroxypropyl, 3,4
-Dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl, chloro Methyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl,
-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-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-
Sulfamoylpropyl and 4-sulfamoylbutyl can be mentioned.

Substituted represented by W ₁ and W ₂ are alkylene groups C ₂ -C ₄ be mentioned as those aliphatic bridging group, ethylene, propylene is particularly preferred.

Examples of the optionally substituted aromatic crosslinking group represented by W ₁ and W ₂ include a phenylene group or a naphthylene group substituted by 0, 1, 2, or 3 sulfo groups.

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 X, A, W ₁ and R ₂ have the above-mentioned meanings) and a dioxazine intermediate represented by the following general formula (III) (Wherein R ₁ , Y ₁ and Z ₁ have the above-mentioned meanings) and the following general formula (IV) H-Q ₁ (IV) (wherein Q ₁ has the above-mentioned meanings) Or an amine represented by the following general formula (V): (Wherein, R ₅ , Y ₃ and Z ₃ have the above-mentioned meanings) 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 ether compound represented by the general formula (I) or a salt thereof can be obtained by condensation while adjusting to H2 to H7.

The dioxazine intermediate represented by the formula (II) is known per se, and is synthesized by a known method.

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 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 a neutral or weakly acidic printing paste and passing this through a hot electrolyte-containing alkaline bath, or by overpadding with an alkaline electrolyte-containing padding solution, and 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 friction resistance and iron resistance.

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

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

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

Example 1 19 parts of the dioxazine intermediate represented by the above structural formula in the form of the free acid is placed in 200 parts of water, 11 parts of cyanuric chloride and aniline
200 parts of an aqueous solution containing a condensate obtained by reacting 15.2 parts of 2,5-disulfonic acid was added, and the mixture was stirred at pH 7 to 9 and 10 to 30 ° C. until the reaction was completed. Furthermore, aniline-3-β-
16.9 parts of sulfate ethyl sulfone were added, and pH 2 to 6, 3
By stirring at 0-70 ° C. until the reaction is completed,
Dioxazine represented by the following structural formula in the form of free acid
An ether compound was obtained.

Example 2 In place of the dioxazine intermediate of Example 1, in the form of the free acid, the following structural formula By using an equimolar amount of a dioxazine intermediate represented by the following method and in the same manner as in Example 1, in the form of a free acid,
A dioxazine ether compound represented by the following structural formula was obtained.

Example 3 The corresponding dioxazine ether compound was obtained by performing the same operation as in Example 1 using the following amine in an equimolar amount instead of the aniline-2,5-disulfonic acid of Example 1.

(1) Orthanilic acid (2) Metanylic acid (3) Sulfanilic acid (4) 1-Aminonaphthalene-3,6-disulfonic acid (5) 1-Aminonaphthalene-4,6,8-trisulfonic acid (6) 2 -Aminonaphthalene-1,5-disulfonic acid (7) 2-aminonaphthalene-4,8-disulfonic acid (8) 2-aminonaphthalene-3,6,8-trisulfonic acid (9) 2-aminonaphthalene-4 , 6,8-Trisulfonic acid (10) aniline-2,4-disulfonic acid (11) aniline (12) N-methylaniline (13) N-ethylaniline (14) m-toluidine (15) p-toluidine ( 16) m-chloroaniline (17) p-anisidine (18) p-aminobenzoic acid (19) ammonia (20) ethylamine (21) β-hydroxyethylamine (22) β-alanine (23) taurine (24) N- Methyl taurine (25) o- Minobenzoic acid Example 4 The corresponding dioxazine ether compound was obtained in the same manner as in Example 1 except that the following amines were used in equimolar amounts instead of aniline-3-β-sulfatoethylsulfone used in Example 1. Was.

_{(14) H 2 N- (CH} 2) 2 OC 2 H 4 SO 2 C 2 H 4 Cl (15) H 2 N- (CH 2) 2 OC 2 H 4 SO 2 CH = CH 2 (16) H 2 _{N- (CH 2) 3 OC 2} H 4 SO 2 CH = dioxazine that CH ₂ example 5 example instead dioxazine intermediate used in 1-4, expressed in the form of an equimolar of the free acid by the following structural formula By using the intermediate, the corresponding dioxazine ether compound was obtained.

Example 6 26.7 parts of the dioxazine intermediate of Example 10 (10) was
Add 0 part, add 11 parts of cyanuric chloride, stir at pH 6-9, 0-30 ° C until the reaction is completed, add 10.4 parts of metanilic acid, stir at pH 6-9, 10-40 ° C until the reaction is completed. did. To this reaction solution, 16.9 parts of aniline-3-β-sulfatoethylsulfone was added, and the mixture was stirred at pH 2 to 6 and 30 to 70 ° C. until the reaction was completed. A dioxazine ether compound was obtained.

Example 7 Instead of metanilic acid of Example 6, equimolar aniline-3
-Β-Sulfate Ethyl Sulfone Reaction
By the same operation as in Example 6 except that the pH is adjusted to 5 to 7,
Dioxazine represented by the following structural formula in the form of free acid
An ether compound was obtained.

Example 8 0.1, 0.3 and 0.6 parts of each of the dioxazine ether compounds described in Examples 1 to 7 were dissolved in 200 parts of water, respectively.
0 parts and 10 parts of cotton were added, the temperature was raised to 60 ° C., 4 parts of sodium carbonate was added, and dyed for 1 hour. Washing, soaping, washing and drying were performed to obtain a bluish-red dyed product having excellent fastness properties and good build-up properties.

Example 9 A color paste having the following composition was prepared using each of the dioxazine ether compounds described in Examples 1 to 7.

Dioxazine ether compound 5 parts Urea 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad, dried at 100 ° C for 5 minutes after intermediate drying. After steaming, washing with water, soaping, washing with water and drying, a bluish-red print having excellent fastness was obtained.

Example 10 18 parts of the dioxazine intermediate represented by the above structural formula in the form of the free acid is placed in 200 parts of water, and 5.5 parts of cyanuric chloride and aniline are added.
200 parts of an aqueous solution containing a condensate obtained by reacting 7.6 parts of 2,5-disulfonic acid was added, and the mixture was stirred at pH 7 to 9 and 10 to 30 ° C. until the reaction was completed. Further, 8.4 parts of aniline-3-β-sulfate ethyl sulfone was added, and pH 2 to 6, 30 to
By stirring at 70 ° C. until the reaction was completed, a dioxazine ether compound represented by the following structural formula was obtained in the form of a free acid.

Example 11 The same operation as in Example 10 is carried out using the equimolar amines (1) to (25) described in Example 3 in place of the aniline 2,5-disulfonic acid of Example 10. Gave the corresponding dioxazine ether compound.

Example 12 Same as Example 10 except that the aniline-3-β-sulfatoethylsulfone used in Example 10 was replaced with an equimolar amine of (1) to (16) described in Example 4 By performing the above operation, the corresponding dioxazine ether compound was obtained.

Example 13 The corresponding dioxazine ether compound was obtained by using a dioxazine intermediate represented by the following structural formula in the form of an equimolar free acid instead of the dioxazine intermediate used in Examples 10 to 12.

Example 14 0.1, 0.3 and 0.6 parts of each of the dioxazine ether compounds described in Examples 10 to 13 were each dissolved in 200 parts of water, and sodium sulfate was added.
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 bluish red dyeing product having excellent fastness properties and good build-up properties.

Example 15 A color paste having the following composition was made using each of the same dioxazine ether compounds used in Examples 10 to 13.

Dioxazine ether compound 5 parts Urine 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad, dried at 100 ℃ After steaming for 5 minutes, washing with hot water, soaping, washing with hot water and drying, a bluish-red print having excellent fastness properties was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naoki Harada 3-1-198, Kasuga, Konohana-ku, Osaka-shi, Osaka Inside Sumitomo Chemical Co., Ltd. (72) Inventor Takashi Omura Kasuga-hi, Konohana-ku, Osaka, Osaka No. 3-98 No. 98 in Sumitomo Chemical Co., Ltd. (56) References JP-A-63-170463 (JP, A) JP-A-63-207859 (JP, A) (58) Fields investigated (Int. . ^6, DB name) C09B 62/503 D06P 1/38 CA (STN ), REGISTRY (S TN)

Claims (4)

(57) [Claims] 1. The following general formula in the form of a free acid: [Wherein, X represents a halogen, and A represents a formula Wherein W ₁ and W ₂ each independently represent a C _{2 to} C ₅ alkylene group whose carbon chain may be interrupted by an oxygen atom or a phenylene group which may be substituted by sulfo. And Q ₁ and Q ₂ are each independently an amino group substituted with an aryl (wherein the substituent is
Further, it may be substituted by halogen, nitro, cyano, trifluoromethyl, lower alkyl, lower alkoxy, carboxy, sulfomethyl or sulfo. )
Or a group represented by the formula —N (R ₅ ) —Y ₃ —Z ₃ , wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ independently of one another are hydrogen or lower alkyl Represents a group, Y ₁ , Y ₂ and Y ₃
, Independently of one another, - (CH _{2) 2} - group, - (CH _{2) 3} - alkylene group selected from the group methyl, ethyl, methoxy, ethoxy, chlorine, with a substituent selected from the group of bromine and sulfo Represents a phenylene group which may be substituted, and Z ₁ , Z ₂ and Z ₃ each independently represent -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH
₂ Z '(Z' represents a sulfate, thiosulfate, phosphate, acetate or halogen). ] The dioxazine ether compound shown by these. 2. The compound according to claim _1, wherein W ₁ and W ₂ are each independently a C ₂ -C ₄ alkylene group. 3. The method according to claim 1, wherein X is chlorine or bromine.
The compound according to the above. 4. A method for dyeing or printing a fiber material, comprising using the dioxazine ether compound according to claim 1.