JPH0753833B2 - Monoazo compound and method for dyeing or printing fiber material using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a monoazo compound and a method for dyeing or printing a fiber material using the same.

2. Description of the Related Art Conventionally, various reactive dyes have been widely used for dyeing and printing fiber materials. For example, Japanese Examined Patent Publication No. 39-18184 discloses a red reactive dye (monoazo compound) composed of vinyl sulfone-based and monochlorotriazine-based reactive groups.

Problems to be Solved by the Invention However, known red reactive dyes have dyeing performance surfaces (for example, solubility, build-up property, wash-off property, discharge property) and various fastness surfaces (for example, acid hydrolysis fastness, In view of the high market demand for chlorine fastness), there is a strong demand for further improved dyes.

The inventors of the present invention have made intensive studies in order to improve the drawbacks of the above-mentioned known dyes by satisfying such a demand, and further to find a novel compound which can widely satisfy the requirements required for dyes. Completed the invention.

Means for Solving the Problems The present invention provides the following general formula (I) in the form of a free acid. (In the formula, R ₁ is C ₁ -C ₄ alkyl, β-carboxyethyl, β-carboxyvinyl or C ₁ -C ₄ alkyl, phenyl optionally substituted with nitro, sulfo or halogeno, and ₂ is hydrogen, methyl or sulfo, R ₃ and
R ₄ is independently of each other hydrogen or optionally substituted alkyl, A ₁ and A ₂ are independently of each other a group (Wherein B ₁ and B ₂ independently of each other represent hydrogen, methyl, ethyl, methoxy, ethoxy, halogeno or sulfo) or a naphthylene group optionally substituted with one sulfo, and Z ₁ And Z ₂ independently of each other, —SO ₂ CH═CH ₂
Or —SO ₂ CH ₂ CH ₂ Y (Y is a group capable of leaving by the action of an alkali). ] The monoazo compound shown by these, and the method of dyeing or printing a fiber material using the same are provided.

In formula (I), the optionally substituted alkyl represented by R ₃ and R ₄ includes the groups described in JP-A-59-122549, preferably methyl or ethyl. . Suitably at least one of R ₃ and R ₄ is hydrogen.

Examples of A ₁ and A ₂ correspond to the groups described in the same publication. Preferably, A ₁ and A ₂ are independently of each other (In the formula, R ₁ and R ₂ have the above-mentioned meanings), and it is preferable that B ₁ and B ₂ are hydrogen, methyl or methoxy, and it is particularly preferable that both are hydrogen. .

When Z ₁ and Z ₂ are —SO ₂ CH ₂ CH ₂ Y, those known as a group capable of leaving by the action of an alkali correspond to this, and examples thereof include sulfate, thiosulfate, Examples include acetoxy and chloro. Preferred Z ₁ and Z ₂ are
Both are cases of β-sulfatoethyl sulfone, and vinyl sulfone may be partially mixed therein.

R ₁ is preferably, for example, methyl, ethyl, n- or
iso-propyl, β-carboxyethyl, β-carboxyvinyl, phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-nitrophenyl, 2-, 3- or 4
-Sulfophenyl and 2-, 3- or 4-chlorophenyl and the like can be mentioned.

In the monoazo compound of the present invention represented by the general formula (I), the following general formula (II) in the form of free acid is used. [In the formula, R ₅ represents hydrogen or sulfo, R ₆ represents hydrogen, methyl or ethyl, and R ₁ has the above meaning. ] The monoazo compound represented by

The compound of the present invention may be present in the form of a free acid, but is preferably an alkali metal salt or an alkaline earth metal salt,
For example, sodium salt and potassium salt may be mentioned.

The monoazo compound represented by the general formula (I) of the present invention can be produced, for example, as follows.

The following general formulas (III), (IV), (V) and (VI) [In the formula, R _{1 to} R ₄ , A ₁ , A ₂ , Z ₁ and Z ₂ have the above meanings. ] It can synthesize | combine by the usual diazotization, coupling, and condensation reaction using the compound shown by these and cyanuric chloride.

Examples of the compound represented by the general formula (IV) include 2,4-
Diaminobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 2,4-diaminobenzene-1,5-disulfonic acid, 2,5-diaminobenzene-1,4-disulfonic acid, 2,4
-Diamino-5-methylbenzenesulfonic acid and the like can be mentioned.

Of these, 2,4-diaminobenzenesulfonic acid and 2,4-diaminobenzene-1,5-disulfonic acid are preferable.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing a hydroxy group-containing or carbonamide group-containing material. The material is preferably used in the form of a fibrous material or of a blended material thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulosic fiber materials or regenerated products thereof and polyvinyl alcohol. Cellulosic fiber materials are cotton, as well as other vegetable fibers such as linen,
Hemp, jute and ramie fibers are preferred. Regenerated cellulosic fibers are, for example, viscose, staple and filament viscose.

Carbonamide group-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, such as wool and other animal hair, silk, leather, polyamide-6,6,
Polyamide-6, polyamide-11 and polyamide4-.

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 exhaustion dyeing on cellulose fibers, sodium carbonate, sodium phosphate tribasic, in the presence of an acid binder such as caustic soda, optionally a neutral salt, such as sodium sulfate or salt,
If desired, a solubilizing agent, a penetrating agent, or a leveling agent is used in combination, and the reaction is performed at a relatively low temperature. The neutral salt, which accelerates the exhaustion of the dyestuff, can be added only after the original dyeing temperature has been reached or before, optionally in divided portions.

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

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

For printing pastes, pastes or emulsifiers, such as sodium alginate or starch ether, are used, if desired in combination with customary printing aids and / or dispersants, such as urea.

Suitable acid binders for fixing 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 when heated. In particular, alkali metal hydroxides and alkali metal salts of weak or medium-strength inorganic or organic acids are mentioned, of which soda salts and potassium salts are particularly preferable. Examples of such an acid binder include caustic soda, caustic potash, baking soda, sodium carbonate, sodium formate, potassium carbonate, sodium primary, secondary or tertiary phosphate, sodium silicate, sodium trichloroacetate and the like.

Dyeing of synthetic and natural polyamide and polyurethane fibers should be carried out by first exhausting from an acidic or weakly acidic dyeing bath under the control of a pH value, and then changing it to a neutral, and possibly alkaline, pH value for fixing. Can be done by Dyeing is usually carried out at a temperature of 60 to 120 ° C., but in order to achieve level dyeing, a common leveling agent such as a condensation product of cyanuric chloride and 3 times moles 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, excellent fastness to sunlight, fastness to sweat and formalin, excellent fastness to wetness, for example, fastness to washing, fastness to peroxidative washing, fastness to chlorine, fastness to bleaching chlorine. , Fastness to sweat, fastness to acid hydrolysis and alkali resistance, and good fastness to rubbing and iron. In addition, it has extremely excellent build-up properties, level dyeing properties and wash-off properties, as well as good solubility and high exhaustion, fixing properties, discharge properties, dyeing temperature, alkali agent, inorganic salt addition amount, and dyeing bath ratio. It is characterized in that it is hardly affected by fluctuations and a dyed product of stable quality is obtained.

Further, the compound of the present invention shows excellent build-up property and excellent alkali stability in cold batch up dyeing, and almost no difference in concentration and hue difference between fixation at low temperature and fixation at 25 ° C. It has the property of being less susceptible to hydrolysis by agents.

The present invention is described in detail below with reference to examples. In the examples, part means part by weight.

Example 1 To 400 parts of water, 18.8 parts of 2,4-diaminobenzenesulfonic acid and 18.5 parts of cyanuric chloride are added, and the first condensation is completed at pH 2-3.

Then, after adding 28.1 parts of 1-aminobenzene-4-β-sulfatoethyl sulfone to complete the second condensation at pH 4 to 5, diazotization is carried out by a conventional method.

To this solution, 37.5 parts of 1-propionylamino-8-hydroxynaphthalene-3,6-disulfonic acid was added, and 0 to 5
The coupling is terminated at ℃, pH 5 ~ 7.

Next, 28.1 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone was added, and the mixture was added at 60-70 ° C and pH 4-5 to give a third solution.
After completing the condensation, salting out, filtering, washing, and drying are performed, and the following formula in the form of free acid is used. A monoazo compound represented by

Examples 2 to 25 1-propionylamino-8-used in Example 1
Hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, 1-aminobenzene-4-β
Instead of -sulfatoethyl sulfone and 1-aminobenzene-3-β-sulfatoethyl sulfone, column A (compound of formula (III)) and column B (formula (I
V)), column C (compound of formula (V)) and column D (compound of formula (VI)) were synthesized in the same manner as in Example 1 to obtain the corresponding monoazo compounds. Get
It was dyed to obtain a dyed product having a color tone shown in the column E.

Dyeing Example 1 0.3 part of each of the monoazo compounds obtained in Examples 1 to 2
Dissolve in 00 parts of water, add 10 parts of Glauber's salt, add 10 parts of cotton and 60
Raise the temperature to ℃. Then, after 20 minutes, 4 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After completion of dyeing, washing with water and soaping were carried out to obtain dyed products excellent in dyeing performance and various fastnesses. Even when the dyeing temperature, the bath ratio and the addition amount of the inorganic salt were slightly changed, a dyed product with good reproducibility and stable quality was obtained.

Dyeing example 2 Color paste composition Each of the monoazo compounds obtained in Examples 1 to 5 5 parts Urea 5 parts Sodium alginate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Color paste having the above composition Is printed on mercerized cotton broad cloth, and after intermediate drying, steaming is performed at 100 ° C for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish.

In this way, a printed article having excellent dyeing performance and various fastnesses was obtained.

Dyeing Example 3 25 parts of each of the monoazo compounds obtained in Examples 1 to 25 are dissolved in hot water and cooled to 25 ° C. Immediately after adding 5.5 parts of 32.5% caustic soda aqueous solution and 150 parts of water glass of 50 degree Baume to make the total amount to 1,000 parts at 25 ° C, use this solution as a padding solution to wind up a cotton fabric. Seal with polyethylene film and store in a room at 20 ℃.

The cotton fabric padded in the same manner and rolled up and sealed with a polyethylene film is stored in a room at 5 ° C. After leaving each padding cloth for 20 hours, the dyed product is washed with cold water and then with hot water, soaped in boiling detergent, further washed with cold water and dried to finish.

When the hue difference and the density difference between the dyed product left at 20 ° C. for 20 hours and the dyed product left at 5 ° C. for 20 hours were examined, almost no difference was observed. In addition, a dyed product having good build-up properties was obtained by cold batch-up dyeing.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Omura 3-98 Kasugadenaka, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. (56) Reference JP-A-58-71957 (JP, A) ) JP-A-60-215068 (JP, A) JP-B 39-18184 (JP, B1) Science and Industry 42 (11) P. 583-594 (1968)

Claims (7)

[Claims] 1. The following general formula (I) in the form of a free acid. (In the formula, R ₁ is C ₁ -C ₄ alkyl, β-carboxyethyl, β-carboxyvinyl, or C ₁ -C ₄ alkyl,
Nitro, sulfo or halogeno optionally substituted phenyl, R ₂ is hydrogen, methyl or sulfo, R ₃ and
R ₄ is independently of each other hydrogen or optionally substituted alkyl, A ₁ and A ₄ are independently of each other a group (In the formula, B ₁ and B ₂ each independently represent hydrogen, methyl, ethyl, methoxy, ethoxy, halogeno or sulfo) or naphthylene optionally substituted with one sulfo, and Z ₁ and Z _2, independently of one another, (the Y is a group removable by the action of an alkali.) -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Y represent. ] The monoazo compound shown by these. 2. R ₁ is methyl, ethyl, n- or iso-
Propyl, β-carboxyethyl, β-carboxyvinyl, phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-nitrophenyl, 2-3
The monoazo compound according to claim 1, which is -or 4-sulfophenyl, or 2-, 3- or 4-chlorophenyl. 3. The monoazo compound according to claim 1 or 2, wherein R ₃ and R ₄ are each independently hydrogen, methyl or ethyl. 4. A ₁ and A ₂ are independently of each other. (In the formula, B ₁ and B ₂ have the meanings defined in claim 1.) The monoazo compound according to any one of claims 1 to 3. 5. The monoazo compound according to any one of claims 1 to 4, wherein Z ₁ and Z ₂ are simultaneously β-sulfatoethyl sulfone. 6. The following general formula (II) in the form of a free acid. [In the formula, R ₅ represents hydrogen or sulfo, R ₆ represents hydrogen, methyl or ethyl, and R ₁ has the meaning described in claim 1. ] The monoazo compound of Claim 1 shown by these. 7. The following general formula (I) in the form of a free acid. (In the formula, R ₁ is C ₁ -C ₄ alkyl, β-carboxyethyl, β-carboxyvinyl, or C ₁ -C ₄ alkyl,
Phenyl which may be substituted with nitro, sulfo or halogeno, R ₂ is hydrogen, methyl or sulfo, R ₃ and R ₄ are each independently hydrogen or optionally substituted alkyl, A ₁ and A ₂ are Independent of each other (Wherein B ₁ and B ₂ independently of each other represent hydrogen, methyl, ethyl, methoxy, ethoxy, halogeno or sulfo) or a naphthylene group optionally substituted with one sulfo, and Z ₁ And Z ₂ independently of each other, —SO ₂ CH═CH ₂
Or —SO ₂ CH ₂ CH ₂ Y (Y is a group capable of leaving by the action of an alkali). ] The method of dyeing or printing the fiber material characterized by using the monoazo compound shown by these.