JP2000273341A - Monoazo compounds or their salts and their application to fiber materials - Google Patents

Abstract

(57) [Problem] To provide a cellulose fiber reactive monoazo compound useful as an orange to scarlet reactive dye. SOLUTION: General formula (I) (I) wherein n is 0, ¹ , R ¹ is hydrogen or methyl, R ² is hydrogen, a displaceable alkyl, Y is —SO ₂ CH ＝ CH ₂ or the like, and X is a displaceable pyridinio. Represent. Or a salt thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reactive monoazo compound or a salt thereof useful as, for example, an orange-scarlet reactive dye, and to its application to a fiber material.

[0002]

2. Description of the Related Art Various orange to scarlet reactive dyes have been known. For example, monoazo dyes having a vinylsulfonylbenzene-based fiber reactive group and a pyridiniotriazine-based fiber reactive group in a molecule are known. As shown by the following structural formula, a compound in which a β-sulfatoethylsulfonyl group is substituted at the m-position of an —NH— group substituted on a benzene ring is known (JP-A-60-173060). See).

[0003]

Embedded image

[0004]

However, even if the fiber material is dyed using the above-mentioned known dyes, the dyeing performance (exhaustion characteristics, fixation rate, build-up property, color value, and unfixed dye fiber material) Easy to remove), storage stability in dry, wet and solution state, dye reproducibility, solubility in dye bath, etc., compatibility with other reactive dyes, dyeing condition in compound dyeing, Suitability for more economical dyeing formulas, and various fastnesses (chlorine resistance, light resistance, sweat resistance, sweat and sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance, washing resistance to peroxide washing) Etc.) are not sufficiently satisfactory, and development of a fiber-reactive monoazo compound excellent in the above-mentioned various properties, particularly excellent in dyeing performance, is desired.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that, compared to known reactive dyes, the dyeing reproducibility, leveling properties, and wash-off properties are good, the dyeing performance is more excellent, and a low salt concentration is obtained. As a result of extensive research to develop compounds that can be dyed and give various orange-scarlet dyeings and prints that are excellent in fastness, as a result of the pyridiniotriazine-based fiber reactive group, On the opposite side to -NH- or -N (substituted C
₁ -C ₄ alkyl) - via a group, p- vinylsulfonyl group or the position monoazo compound having a specific structure groups comprising a vinylsulfonyl group is bonded fiber reactive group of the benzene series which is substituted by the action of an alkali Have achieved the above object, and have completed the present invention.

That is, the present invention provides a compound represented by the following general formula (I):

[0007]

Embedded image (I)

[Wherein, n represents 0 or 1;¹Is
Represents a hydrogen atom or a methyl group;^TwoIs a hydrogen atom,
Or a hydroxyl group, a cyano group, an alkoxy group,
Boxy group, carbamoyl group, alkoxycarbonyl group,
Alkylcarbonyloxy group, sulfo group, sulfamoi
C which may be substituted with ₁
~ C_FourY represents a group -SO_TwoCH = CH
_TwoOr -SO_TwoCH_TwoCH_TwoZ (Z is desorbed by the action of alkali
X is a carboxy group or carbamoyl
Pyri optionally substituted by one or two substituents of the group
Represents a zinio group. Or a monoazo compound thereof
Salt, and dye or print textile materials with it
It provides a method. Hereinafter, the present invention is described in detail.
Will be described.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a monoazo compound represented by the aforementioned general formula (I) or a salt thereof, wherein R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a hydrogen atom.

In the monoazo compound (I) or a salt thereof, R ² is a hydrogen atom, a hydroxyl group, a cyano group, an alkoxy group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group,
Represents a C ₁ -C ₄ alkyl group which may be substituted with a sulfo group, a sulfamoyl group or a halogen atom. Specific examples of the substituted C ₁ optionally -C ₄ alkyl groups include 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-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl,
4-cyanobutyl, methoxymethyl, ethoxymethyl,
2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-
3-methoxypropyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxy Carbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyl Oxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, - methylcarbonyloxy butyl,
4-ethylcarbonyloxybutyl, sulfomethyl, 2
-Sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl , 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl and the like.

R ² is preferably a hydrogen atom, methyl or ethyl, and particularly preferably a hydrogen atom.

In the present invention, the monoazo compound (I) or
In that salt, Y is a group -SO_TwoCH = CH_TwoOr -S
O_TwoCH_TwoCH_TwoRepresents Z, where Z is the action of alkali
Represents a leaving group. As Z, for example, a sulfate ester
Group, thiosulfate group, phosphate group, acetate ester
Group, halogeno, or carboxy group or carbamoy
A pyridinio group which may be substituted with 1 to 2 of
And so on. Z is a sulfate ester
And one or two carboxy or carbamoyl groups
Preferred is a pyridinio group which may be substituted with Y's
Preferred specific examples include -SO_TwoCH = CH_Two, -SO
_TwoCH_TwoCH_TwoOSO_ThreeH, -SO_TwoCH_TwoCH_Two-X₀(X₀
Is a group which may be substituted with 1 to 2 carboxy groups.
Represents a liginio group. ), Etc .;
_TwoCH_TwoCH _TwoOSO_ThreeH is particularly preferred.

In the monoazo compound (I) or a salt thereof according to the present invention, X is a pyridinio group which may be substituted by one or two substituents of a carboxy group or a carbamoyl group. As a raw material compound for introducing such a pyridinio group into a triazine ring, for example, pyridine, picolinic acid, nicotinic acid, isonicotinic acid, quinolinic acid, 2,4-pyridinedicarboxylic acid, isosincomeronic acid, dipicolinic acid, cinchomerone Acid, dinicotinic acid,
Examples thereof include nicotinamide, isonicotinamide, and cinchomeronamide. Among them, pyridine, nicotinic acid, isonicotinic acid, nicotinamide and isonicotinamide are preferable, and nicotinic acid and isonicotinic acid are particularly preferable.

In the monoazo compound (I) or a salt thereof according to the present invention, n is 0 or 1, preferably 0.

The monoazo compound (I) or a salt thereof in the present invention may be, for example, a mixture of a free acid form and a salt thereof, but is preferably an alkali metal salt, an alkaline earth metal salt, And a mixture containing them, and among them, a soda salt, a potassium salt, a lithium salt and a mixture containing them are particularly preferable.

The method for producing the monoazo compound (I) in the present invention is not particularly limited, but for example, it can be produced as follows. The following general formula (II)

[0017]

Embedded image (II)

Wherein n and R ¹ have the same meanings as described above. A compound represented by the following general formula (III):

[0019]

Embedded image (III)

Wherein R ² and Y have the same meaning as described above. And a raw material compound for introducing the pyridinio group represented by X into the triazine ring, with 2,4,6-trichloro-s-triazine or 2,4,6-trifluoro-s -Can be produced by condensing triazine with an arbitrary sequence.

In the condensation reaction with 2,4,6-trichloro-s-triazine or 2,4,6-trifluoro-s-triazine, the order and conditions of each condensation reaction are not particularly limited. Temporarily -10 ° C
PH 1 to 9 at ４０40 ° C., and secondarily at temperature 0 to 70 ° C.
H4-10, tertiary temperature 10-100 ° C and pH1
It is preferable to condense while adjusting to 8.

The method for producing the compound represented by the general formula (II) is not particularly limited.

[0023]

Embedded image (V)

Wherein n represents the same meaning as described above. The compound represented by the following general formula (VI)

[0025]

Embedded image (VI)

Wherein R ¹ has the same meaning as described above. ]
A compound of the general formula (II) can be obtained by a diazo coupling reaction with the compound represented by the formula:

The monoazo compound of the present invention or a salt thereof has a vinylsulfonylbenzene-based fiber reactive group and a pyridiniotriazine-based fiber reactive group in the molecule, and can be used as a dye for dyeing and printing a fiber material. it can. The fiber material is not particularly limited as long as it contains a hydroxy group and / or an amide group. For example, natural or regenerated cellulose fiber, natural or synthetic polyamide fiber, polyurethane fiber, leather, and a blend containing these are used. Materials and the like can be mentioned.

As the natural cellulose fiber, specifically,
Cotton, linen, hemp, jute, ramie fibers and the like can be mentioned. Preferably, it is cotton.

As the regenerated cellulose fiber, specifically,
Rayon, polynosic, cupra fiber, and trade names “Tencel”, “Toughcell”, “Modal”, “Certima” and the like can be mentioned.

As natural or synthetic polyamide fibers, specifically, wool, silk, polyamide-6,6, polyamide-
6, polyamide-11, polyamide-4 and the like.

Examples of the blended material containing these include a blended material of these fiber materials, and a blended material of these fiber materials and synthetic fibers such as polyester, nylon, and acrylic.

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

Specifically, there may be mentioned, for example, a method of dyeing or printing on the above-mentioned fiber by an exhaust dyeing method, a cold batch-up method, a continuous dyeing method, a printing method or the like. For example, in the case of dyeing cellulose fibers by the exhaust dyeing method, sodium carbonate, sodium bicarbonate, sodium tertiary phosphate, in the presence of an acid binder such as caustic soda, if necessary, a salt salt such as sodium sulfate, sodium chloride. In addition, if necessary, a solubilizing agent, a penetrating agent or a leveling agent is used in combination, and 30 to 1
A method of dyeing at a temperature of about 00 ° C. is exemplified. Here, the addition of the acid binder, neutral salt, etc. may be performed at once,
Further, the division may be performed by a conventional method.

When the cellulose fiber is dyed by the cold batch-up method, neutral salts such as sodium sulfate and sodium chloride,
Further, a method of padding with an acid binder such as caustic soda or sodium silicate, followed by treatment in a hermetically sealed packaging material at a constant temperature and the like is exemplified.

In the case where cellulose fibers are dyed by a continuous dyeing method, padding is carried out at room temperature or at an elevated temperature by a known method in the presence of an acid binder such as sodium carbonate or sodium bicarbonate, and then steaming or drying heat. After the fiber is immersed in a padding solution in which the compound of the present invention is dissolved, a neutral salt such as sodium sulfate or sodium chloride, and an acid binder such as caustic soda or sodium silicate are padded. And a two-phase padding method for treating by steaming or drying.

In the case of printing on cellulose fiber, printing is carried out in one phase with a printing paste containing an acid binder such as baking soda, and then steaming at a high temperature of 80 ° C. or higher. Printing with a neutral or weakly acidic printing paste and passing it through an electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and then treating by steaming or dry heat treatment. Is exemplified. Here, the printing paste may contain a sizing agent such as sodium alginate and starch ether and / or an emulsifier, and if necessary, a printing aid and / or a dispersant such as urea. May be.

When the compound of the present invention is dyed or printed on cellulose fibers, the acid binder used is not particularly limited, and examples thereof include an alkali metal hydroxide, an alkali metal or an alkaline earth metal and an inorganic or organic acid. And a compound that releases an alkali under heating. In particular, mention may be made of alkali metal hydroxides and alkali metal salts of inorganic acids or organic acids of weak to moderate strength, of which sodium or potassium hydroxides, sodium salts and potassium salts are preferred.
Specific examples of such an acid binder include the above-mentioned sodium carbonate, sodium bicarbonate, sodium tertiary phosphate, sodium hydroxide, sodium silicate, potassium hydroxide, sodium formate, potassium carbonate, primary or secondary sodium phosphate, trichloroacetic acid. Soda or the like can also be used.

In the case of exhaustion dyeing on synthetic or natural polyamide fiber or polyurethane fiber, acidic to
A method in which the compound of the present invention is exhausted in a weakly acidic dyeing bath while controlling the pH, and then the pH is changed to neutral to alkaline at a temperature of about 60 to 120 ° C. is exemplified. Here, if necessary, a leveling agent or the like, for example, a condensation product of cyanuric chloride and aminobenzenesulfonic acid, a condensation product of cyanuric chloride and aminonaphthalenesulfonic acid, an addition product of stearylamine and ethylene oxide, etc. A leveling agent may be used.

The compound of the present invention can be used by mixing with other dyes, if necessary, in order to obtain a desired hue, as long as the characteristics of the present invention are not impaired. The dye used in combination is not particularly limited as long as it is a reactive dye.For example, as a reactive group, a sulfatoethyl sulfone group, a vinyl sulfone group, a monochlorotriazine group, a monofluorotriazine group, a mononicotinic acid triazine group,
At least one of a dichlorotriazine group, a difluoromonochloropyrimidine group, and a trichloropyrimidine group
Dyes having at least one species, or Sumifix, S
umifix Supra, Sumifix HF, Remazol, Levafix
, Procion, Cibacron, Basilen, Drimarene, K
ayacion, dyes commercially available under the titles such as Kayacelon React, and further, JP-A-50-178, JP-A-56-948
3, JP-A-56-15481, JP-A-56-118976, JP-A
56-128380, JP-A-57-2365, JP-A-57-89679
JP-A-57-143360, JP-A-59-15451, JP-A-5
8-191755, JP-A-59-96174, JP-A-59-161463
No., JP-A-60-6754, JP-A-60-123559, JP-A-60-123559
No. 60-229957, JP-A-60-260654, JP-A-61-126
No. 175, JP-A-61-155469, JP-A-61-225256,
JP-A-63-77974, JP-A-63-225664, JP-A-1-185
No. 370, JP-A-3-770, JP-A-5-32907, JP-A-5
-117538, JP-A-5-247366, dyes described in JP-A-6-287463, and CIReactiveBlue 1
9, dyes represented by CIReactive Black 5, and the like.

[0040]

The monoazo compound (I) of the present invention or a salt thereof is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. It is particularly suitable for dyeing and printing of cellulose fiber materials, and dyeings and prints obtained from this compound have good light fastness, sweat and sun light fastness, chlorine fastness, and wet fastness (for example, washing fastness, excessive fastness). (Oxidative washing resistance, sweat resistance, acid hydrolysis resistance and alkali resistance), and also has good friction resistance and iron resistance.

The monoazo compound (I) of the present invention or a salt thereof has good solubility and excellent dyeing power (build-up property, level dyeing property, wash-off property, exhaustion / fixing property), In particular, it has excellent dyeing power in dark colors and low salt concentration. And it is less affected by fluctuations in the dyeing temperature, the amount of dyeing assistants such as salts and alkaline agents and bath ratio,
A dyestuff of stable quality can be obtained.

Further, the obtained dyed product is excellent in that the discoloration during fix processing or resin processing is small, and the change due to contact with a basic substance during storage is small.

[0043]

The present invention will be described in more detail with reference to the following examples. In the examples, "parts" represents parts by weight.

Example 1 The free acid synthesized by a conventional method has the formula (1)

[0045]

Embedded image (1)

45.34 parts of a monoazo intermediate represented by the following formula and 18.44 of 2,4,6-trichloro-s-triazine
Was condensed at a pH of 3 to 8 and a temperature of 10 to 40 ° C. to obtain a compound having a free acid form represented by the formula (2).

[0047]

Embedded image (2)

In addition, pH 3-8, temperature 10-60 ° C,
In an aqueous medium, 28.13 parts of aniline-4-β-sulfatoethylsulfone were condensed to obtain a compound having a free acid form represented by the formula (3).

[0049]

Embedded image (3)

In addition, pH 1 to 6, temperature 30 to 100
C., 12.31 parts of nicotinic acid are condensed in an aqueous medium,
A compound having a free acid form represented by the following formula (4) (λmax in aqueous solution: 512 nm) was obtained.

[0051]

Embedded image (4)

Example 2 Except that 2,4,6-fluoro-s-triazine was used in place of 2,4,6-trichloro-s-triazine, the free acid was synthesized by the same method as in Example 1 above. Is a compound represented by the formula (4).

Example 3 In Example 1 above, the order of the condensation reaction of the monoazo intermediate (1), aniline-4-β-sulfatoethylsulfone and nicotinic acid with 2,4,6-trichloro-s-triazine was changed. Even when synthesized, a monoazo compound having a free acid form represented by the formula (4) is obtained.

Example 4 In place of the monoazo intermediate (1), aniline-4-β-sulfatoethylsulfone and nicotinic acid used in Examples 1 and 2, the compounds in the second column of the table below, Except for using the compound in column and the compound in column 4,
By synthesizing according to Examples 1 and 2, the corresponding monoazo compounds are obtained.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

Example 5 0.3 part of the monoazo compound of the formula (4) obtained in Example 1 was
Dissolve in 0 parts of water, add 20 parts of Glauber's salt, and further add 10% of cotton
And heated to 60 ° C. After reaching 60 ° C, 3
After a lapse of 0 minutes, 4 parts of sodium carbonate was added, and dyed at the same temperature for 1 hour. Next, washing and soaping were performed. The wash-off property at the time of washing and soaping was good, and the coloring amount of the dyeing wastewater was slight. The resulting dyed product was uniform and dark in color. During dyeing, the solubility was good, the exhaustion properties were excellent, the fixation rate was high, and a high color value was exhibited. Light resistance of the obtained dyed product,
All the fastnesses of sweat resistance, sweat-sun resistance, chlorine resistance, hydrolysis resistance, alkali hydrolysis resistance, washing resistance, and peroxide washing resistance were all good.

Example 6 The monoazo compound to be used was changed from those of the formula (4) to Examples 2 to 4
Dyeing is carried out in accordance with Example 5, except that the compound obtained in the above is changed. The dyeings obtained have the same quality as the dyeings obtained in Example 5.

Example 7 Example 5 except that the amount of sodium sulfate was changed from 20 parts to 10 parts.
Dyeing is carried out in accordance with & 6. The dyed product obtained is Example 5
And have the same quality as the dyeings obtained in 6.

Example 8 Dyeing is carried out according to Examples 5 and 6, except that the amount of sodium sulfate used is changed from 20 parts to 4 parts. The dyed product obtained is Example 5
And the same quality as the dyed product obtained in Example 6.

Example 9 Except that the temperature of the dyeing was changed from 60 ° C. to 70 ° C.
Staining is performed according to 8. The dyeings obtained have excellent fastnesses.

Example 10 Except that the temperature of the dyeing was changed from 60 ° C. to 80 ° C.
Staining is performed according to 8. The dyeings obtained have excellent fastnesses.

Example 11 Instead of using 0.3 part of each monoazo compound, 0.3 part of each monoazo compound and a sodium salt of a condensate of methylnaphthalenesulfonic acid and formaldehyde (degree of sulfonation 110%, average degree of polymerization 1. 8) Dye according to each of Examples 5 to 10, except that 0.06 parts of the mixture is used. The dyeings obtained have the same quality as the dyeings obtained in Examples 5 to 10.

Example 12 Monoazo compound 0.1 instead of 0.3 part monoazo compound
Dyeing is carried out according to each of Examples 5 to 11, except that parts or 0.6 parts are used. The dyed product obtained using 0.6 part of the monoazo compound is sufficiently thicker than that using 0.3 part of the monoazo compound, and the build-up properties of the monoazo compound used are all good.

Example 13 Using each of the monoazo compounds obtained in Examples 1 to 4, a color paste having the following composition is prepared.

[0067] color paste composition monoazo compound 5 parts Urea 5 parts Sodium alginate (5%) stock paste 50 parts Hot water 25 parts sodium bicarbonate 2 parts Balance (water) 13 parts Total 100 parts

This color paste is printed on mercerized cotton broad, and after intermediate drying, steaming is performed at 100 ° C. for 5 minutes, and washed with hot water, soaping, hot water, and dried.
Finish. The dyeings obtained are all uniform and dark. All the fastnesses of the resulting prints are good.

Example 14 30 parts of the monoazo compound obtained in Examples 1 to 4 were each dissolved in hot water and then cooled to 25 ° C. In this dye solution,
Immediately after adding 15 parts of a 32.5% aqueous solution of caustic soda and 150 parts of water glass of 50 degrees Baume and adding water at 25 ° C. to make the total amount 1000 parts, the cotton cloth is padded with this liquid as a padding liquid. Roll up the padded cotton fabric, seal with polyethylene film,
After leaving it at room temperature for 20 hours, it is washed and dried in a conventional manner. The dyeings obtained are all uniform and dark. All the fastnesses of the dyed product obtained are good.

Example 15 20 parts of the monoazo compound obtained in Examples 1 to 4 were each dissolved in hot water and then cooled to 25 ° C. In this dye solution,
Immediately after adding 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate and further adding water at 25 ° C. to make the total amount 1000 parts, the cotton cloth is padded with this liquid as a padding liquid. The padded cotton fabric is dried at 120 ° C. for 2 minutes and then
The dye is fixed by steaming at 00 ° C. for 5 minutes.
The dyeings obtained are all uniform and dark. All the fastnesses of the dyed product obtained are good.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Noriyuki Katsuta 3-1-198 Kasuganaka, Konohana-ku, Osaka City, Osaka Sumitomo Chemical Co., Ltd. F-term (reference) 4H056 JA02 JB02 JB03 JD08 4H057 AA02 BA07 BA24 DA01 DA24 DA34 EA01 GA04 GA07

Claims (6)

[Claims] 1. A compound of the general formula (I)(I) wherein n represents 0 or 1;¹Is a hydrogen atom
Represents a methyl group;^TwoIs a hydrogen atom or hydro
Xyl group, cyano group, alkoxy group, carboxy group,
Rubamoyl group, alkoxycarbonyl group, alkyl carb
Bonyloxy group, sulfo group, sulfamoyl group or
C optionally substituted with a halogen atom ₁~ C_FourArchi
Y represents a group -SO_TwoCH = CH_TwoOr -SO_Two
CH_TwoCH_TwoZ (Z is a group which leaves by the action of an alkali)
X represents one or two carboxy or carbamoyl groups
Represents a pyridinio group which may be substituted by
You. Or a salt thereof. 2. The monoazo compound or a salt thereof according to claim 1, wherein n is 0. 3. The monoazo compound or a salt thereof according to claim 1, wherein R ¹ is a hydrogen atom. 4. The monoazo compound or a salt thereof according to claim 1, wherein R ² is a hydrogen atom. 5. The monoazo compound or a salt thereof according to claim 1, wherein X is a pyridinio group substituted with a carboxy group. 6. A method for dyeing or printing a fiber material, comprising using the monoazo compound according to claim 1 or a salt thereof.