JP2953000B2 - 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 and improved asymmetric dioxazine compound suitable for dyeing and printing fibers, which enables light-fast, wet-fast and chlorine-fast dyeing, and its application.

<Related Art> Reactive dyes having a dioxazine skeleton in the molecular structure of the dyes are known, but are inferior in dyeing performance, such as leveling properties, build-up properties, dyeing speed, or fastness, particularly chlorine fastness. It is sufficient, and further improvement is desired.

<Problems to be Solved by the Invention> The fastness of dyeing or printing a material containing a hydroxyl group and / or an amide group, especially the fastness of chlorine, especially in the case of a hydroxyl group-containing fiber, is not at a satisfactory level. The present inventors have worked diligently to improve this level,
An asymmetric dioxazine compound that can solve the above problem has been found.

<Means for Solving the Problems> The present invention provides a compound represented by the following general formula (I) in the form of a free acid: [In the formula, x ₁ and x ₂ are each independently hydrogen, halogen, a lower alkyl group, a lower alkoxy group, or a phenoxy group;
Is an aliphatic or aromatic cross-linking group which may have a substituent, Q ₁ and Q ₂ are independently a lower alkoxy group, an amino group which may have a substituent or Wherein R ₅ is hydrogen or a lower alkyl group which may have a substituent, Y ₃ is an alkylene which may have a substituent, a phenylene or a naphthylene group, and Z ₃ is -SO ₂ CH = CH ₂
Or _{-SO 2 CH 2 CH 2 Z '} ( wherein, Z' represents. A group removable by the action of an alkali) represent. ｝, Y ₁ and Y ₂
Is an alkylene which may have a substituent independently of each other,
A phenylene or naphthylene group, R ₁ , R ₂ , R ₃ and R ₄ are
Z ₁ and Z ₂ independently of each other independently represent a hydrogen or a lower alkyl group which may have a substituent, and Z ₁ and Z ₂ independently represent —SO ₂ CH 2CH ₂ or —SO ₂ CH ₂ CH ₂ Z ″ (wherein 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 compound.

Here, examples of the lower alkoxy group represented by Q ₁ and Q ₂ include a methoxy group and an ethoxy group.

Examples of the amino group optionally having a substituent represented by Q ₁ and Q ₂ include alkylamino, N, N-dialkylamino, cycloalkylamino, aralkylamino, arylamino, and a mixed-substituted amino group such as N-alkyl-N-cyclohexylamino and N-alkyl-N-
Arylamino, further an amino group containing a heterocyclic group (this cyclic group can further have an addition-fused carbocyclic ring), and the amino nitrogen atom is an N-heterocyclic ring member And the like (an N-heterocyclic ring may optionally contain another hetero atom), and the like. The alkyl in the above may be straight-chain or branched, and may be low-molecular or high-molecular, 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, more heterocyclic rings and N- heterocyclic ring, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, acylamino, ureido, It may be substituted by hydroxy, carboxy, sulfomethyl and sulfo. Examples of the amino group represented by Q ₁ and Q ₂ include:
-NH _2, methylamino, hydroxymethylamino, ethylamino, propylamino, butylamino, N, N-dihydroxy-methylamino, hexylamino, beta-methoxy-ethylamino, beta-ethoxyethyl amino, .gamma.-methoxypropylamino, N , N-dimethylamino, 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-sulfophenyl Amino, 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.

Q ₁ and Q ₂ may independently represent different groups, but are preferably the same groups from a synthetic viewpoint.

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

Examples of the alkylene group which may have a substituent represented by Y ₁ , Y ₂ and Y ₃ include-(CH ₂ ) ₃ -,-(CH ₂ )
₂ -,-(CH ₂ ) ₂ O (CH ₂ ) _2- and the like. 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. A phenylene group which may be substituted or a naphthylene group which may be substituted with one sulfo; (In the formula, the bond indicated by the star 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.

As the lower alkyl group which may have a substituent of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , alkyl of C _{1 to} C ₄ is preferable, and as the group which may be substituted, Hydroxy, cyano,
Alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl are preferred. R ₂ and R ₃ are particularly preferably hydrogen. Preferred R ₁ , R ₄ and R ₅ include, for example, hydrogen, methyl, ethyl, n-propyl, is
o-propyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl,
3-hydroxypropyl, 2-hydroxybutyl, 3-
Hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2
-Ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl,
Chloromethyl, bromomethyl, 2-chloroethyl, 2-
Bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, Carbamoylethyl, 3
-Carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl,
2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyl Oxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3
-Ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-
Sulfamoylethyl, 3-sulfamoylpropyl,
Examples include 4-sulfamoylbutyl, with hydrogen, methyl and ethyl being particularly preferred.

Examples of the aliphatic crosslinking group which may have a substituent represented by W include a C _{2 to} C ₄ alkylene group, and among them, ethylene and propylene are particularly preferred.

Examples of the aromatic crosslinking group which may have a substituent represented by W include a phenylene group or a naphthylene group substituted with 0, 1, 2 or 3 sulfo groups,
Among them, a phenylene group substituted by one or two sulfo groups is particularly preferred.

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 ₂ , R ₃ , x ₁ , x ₂ and W have the above-mentioned meanings) and a dioxazine intermediate represented by the following general formula (II)
I)-(VI) (Wherein, R ₁ , R ₄ , Y ₁ , Y ₂ , Z ₁ , Z ₂ , Q ₁ and Q ₂ have the above-mentioned meanings), and 2,4,6-trihalogeno- It is obtained by condensing each of the s-triazines 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 ~ 9, and more tertiary at pH 10 ~ 100 ° C, pH 2 ~ 7
To obtain an asymmetric dioxazine compound represented by the general formula (I) or a salt thereof.

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

The following general formula (VII) obtained by condensing the corresponding aniline compound with chloranil (Wherein R ₂ , R ₃ and W have the above-mentioned meanings). The dioxazine intermediate of the general formula (II) is cyclized in some cases in the presence of an oxidizing agent to give a dioxazine intermediate. can get.

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. The cellulosic fiber material is preferably cotton or other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose staples and filament viscose.

Carbonamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
4.

The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material, by a method depending on physical and chemical properties.

For example, when exhaustion dyeing is performed on cellulose fibers, an acid binder such as sodium carbonate, sodium tertiary phosphate, sodium hydroxide, sodium bicarbonate or the like is added in the presence of a neutral salt such as sodium sulfate or sodium chloride, and if necessary, a dissolution aid is added. An agent, a penetrant or a leveling agent is used in combination at a temperature of 100 ° C. or less. The neutral salt which promotes the exhaustion of the dye can be added in portions depending on the case.

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 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. Such acid binders include, for example, 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 cellulose fiber materials, good light fastness and sweat fastness, excellent wet fastness, such as washing fastness,
It has peroxide washing fastness, sweat fastness, acid hydrolysis fastness and alkali fastness, as well as good chlorine fastness, rub fastness and iron fastness.

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 17.7 parts of the asymmetric dioxazine intermediate represented by the above structural formula in the form of the free acid are suspended in 200 parts of water, and 11 parts of cyanuric chloride and 15.2 parts of 1-aminobenzene-2,5-disulfonic acid are added to the suspension. Is added. pH 8-10,
Secondary condensation is performed at a temperature of 30 to 50 ° C., and after completion of the reaction, 1-aminobenzene-3-β-sulfatoethylsulfone 1
By adding 6.8 parts and further performing tertiary condensation, an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid was obtained.

Example 2 In the same manner as in Example 1 except that the dioxazine intermediate and 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 1 were replaced with the compounds in columns 2 and 3 in the following table, Synthesis was performed to obtain the corresponding asymmetric dioxazine compound. These compounds were dyed to give dyeings of the shades shown in column 4 of the table below.

Example 3 1-aminobenzene used in Examples 1 and 2
The same operations as in Examples 1 and 2 were respectively performed using the following amines instead of 2,5-disulfonic acid to obtain the corresponding asymmetric dioxazine compounds.

(1) Methanylic acid (2) Sulfanilic acid (3) Altanilic acid (4) Aniline (5) 1-Aminobenzene-2,4-disulfonic acid (6) Ethylamine (7) Ammonia (8) O-aminobenzoic acid ( 9) β-hydroxyethylamine (10) β-alanine (11) taurine (12) N-methyltaurine (13) 1-aminonaphthalene-4,6,8-trisulfonic acid (14) 2-aminonaphthalene-1, 5-disulfonic acid (15) 2-aminonaphthalene-3,6,8-trisulfonic acid (16) N-methylaniline (17) N-ethylaniline (18) p-aminobenzoic acid (19) 1-aminonaphthalene -3,6-disulfonic acid (20) 2-aminonaphthalene-4,8-disulfonic acid (21) 2-aminonaphthalene-4,6,8-trisulfonic acid (22) m-chloroaniline (23) m- Toluidine 24) p-Toluidine (25) p-anisidine Example 4 In the form of the free acid, 21.5 parts of the asymmetric dioxazine intermediate represented by the above structural formula was converted to 2-methoxy-4,6-dichloro-s
-In addition to an aqueous dispersion of 10.8 parts of triazine, a condensation reaction is carried out at pH 6 to 8 and at a temperature of 40 to 60 ° C. After the reaction is complete,
A third condensation reaction was carried out by adding 16.8 parts of -aminobenzene-3-β-sulfatoethylsulfone to obtain an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

Example 5 Cyanuric chloride used in Examples 1 and 2 and 1
In the same manner as in Examples 1 and 2, using an equimolar amount of 2-methoxy-4,6-dichloro-s-triazine instead of the condensate with -aminobenzene-2,5-disulfonic acid, The corresponding asymmetric dioxazine compounds were obtained.

Example 6 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound obtained in Examples 1 to 5 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. Performs washing, soaping, washing and drying, and has excellent fastness properties, especially chlorine fastness.
A blue dyed product having good build-up properties was obtained.

Example 7 Using each of the asymmetric dioxazine compounds obtained in Examples 1 to 5, a color paste having the following composition was produced.

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, dried at 100 ℃ Steamed for 5 minutes, rinsed, soaped, rinsed and dried. The resulting dyed product was excellent in various fastnesses, particularly fastness to chlorine, and had good build-up properties.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Yutaka Kayane 3-1-198, Kasuga, Konohana-ku, Osaka-shi, Osaka Inside Sumitomo Chemical Co., Ltd. (72) Inventor Shigeru Kawabata, Kasuga, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (1) 98, Sumitomo Chemical Co., Ltd. (72) Inventor Naoki Harada 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (56) References 1-28967 (JP, A) JP-A-1-185370 (JP, A) JP-A-2-209969 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 62/503 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. The following general formula in the form of a free acid: [In the formula, x ₁ and x ₂ are each independently a hydrogen, a halogen, a lower alkyl group, a lower alkoxy group or a phenoxy group, W is an aliphatic or aromatic crosslinking group which may have a substituent, Q ₁ and Q ₂ are independently a lower alkoxy group, an optionally substituted amino group or Wherein R ₅ is hydrogen or a lower alkyl group which may have a substituent, Y ₃ is an alkylene which may have a substituent, a phenylene or a naphthylene group, and Z ₃ is -SO ₂ CH = CH ₂
Or _{-SO 2 CH 2 CH 2 Z '} ( wherein, Z' represents. A group removable by the action of an alkali) represent. Wherein Y ₁ and Y ₂ each independently represent an alkylene, phenylene or naphthylene group which may have a substituent, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen or a substituent. Z ₁ and Z ₂ may be independently —SO ₂ CH ＝ CH ₂ or —SO ₂ CH ₂ CH ₂ Z ″ (where Z ″ is eliminated by the action of an alkali) Represents a group represented by :). ] The asymmetric dioxazine compound represented by these. 2. The method according to claim 1, wherein x ₁ and x ₂ are chlorine or bromine.
The compound according to the above. 3. The method of claim 1, wherein R ₂ and R ₃ are hydrogen.
The compound according to the above. 4. The compound according to claim 1, wherein W is ethylene, propylene, phenylene or phenylene having one or two sulfo groups. 5. A method for dyeing or printing a fiber material, comprising using the asymmetric dioxazine compound according to claim 1.