JPH10183000A - Monoazo compound and dyeing or printing of textile material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a monoazo compound which is an aliphatic vinyl sulfone- based reactive dye, good in exhaustion characteristics and fixing ratio, having excellent buildup properties and a high color value and capable of providing a yellow dyed and printed materials good in bonding stability of fiber-dye. SOLUTION: This monoazo compound is represented by formula I [X is Cl, F, etc.; Z<1> is vinyl, CH2 CH2 OSO3 H, etc.; (n) is 2 or 3; (m) is an integer of 2-6], e.g. a monoazo compound represented by formula II. The compound represented by formula I is obtained by condensing a monoazo intermediate compound represented by formula III and a compound represented by the formula H2 N(CH2 )m SO2 Z<1> with 2,4,6-trichloro-s-triazine, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aliphatic vinyl sulfone monoazo compound and a method for dyeing or printing a fiber material using the same.

[0002]

2. Description of the Related Art Various reactive dyes have been known, and are widely used in the field of dyeing or printing fiber materials. For example, as an aliphatic vinyl sulfone-based reactive dye,

[0003]

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Wherein A is an aliphatic group having 2 to 6 carbon atoms,
X is a halogen atom, SO ₃ H group, OH group, OR ₁ group, S
Represents an H group or an SR ₁ group, and D represents a monoazo-based organic dye residue. Monoazo compounds represented by｝ (JP-A-58-1983)
No. 65759) is known.

[0005]

However, even if the fiber material is dyed or printed by using these monoazo compounds as reactive dyes, the exhaustion properties and the exhaustion properties are higher than the current required level.
Fixing rate, build-up property, color value, easy removal of unfixed dye from fiber material, storage stability in dry, wet and solution state, reproducibility, solubility, compatibility with other reactive dyes Compatibility, dyeing finish in compound dyeing, suitability for more economical dyeing formulation, etc., and overall fastness, such as light fastness, sweat fastness, sweat sunlight fastness, chlorine fastness , Acid-fast hydrolysis fastness, alkali fastness, washing fastness, peroxide washing fastness, thermal discoloration, phototropy, fiber-dye bond stability, etc. The development of a satisfactory yellow reactive dye is desired.

[0006]

Under these circumstances, the present inventors have shown that in dyeing or printing processing, they have excellent exhaustion properties, a high fixation rate, excellent build-up properties, and high color value. Easy to wash and remove unfixed dye from fiber material, good storage stability in dry state, wet state and solution state, reproducibility, solubility, compatibility with other reactive dyes, in compound dyeing Good degree of dyeing, suitability for economical dyeing formulation, etc., and overall fastness, for example, light fastness, sweat fastness, sweat and sun fastness, chlorine fastness, acid hydrolysis fastness To develop a reactive dye which gives yellow dyeings and prints with good alkali fastness, washing fastness, peroxide washing fastness, heat discoloration, phototropy, and fiber-dye bond stability. As a result of intensive research, it has a specific structure Monoazo compound of the aliphatic vinyl sulfone system, found to exhibit the desired performance characteristics, and have completed the present invention. That is, in the present invention, the form of the free acid is represented by the following general formula (I)

[0007]

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Wherein X represents chloro, fluoro or optionally substituted pyridinio; Z ¹ represents vinyl or the group —CH ₂ CH ₂ Z, where Z is —OSO ₃
H, -SSO ₃ H, -OCOCH ₃ or -OPO ₃ H ₂
And n represents 2 or 3, and m represents an integer of 2 to 6.モ ノ represented by a monoazo compound and a salt thereof,
And a method for dyeing or printing a fiber material using the same. Hereinafter, the present invention will be described in detail.

[0009]

Monoazo compound in the present invention DETAILED DESCRIPTION OF THE INVENTION, but is represented by the general formula (I), wherein, Z ¹
Represents a vinyl or a radical -CH ₂ CH ₂ Z, wherein the Z is _{-OSO 3 H, -SSO 3 H,} -OCOCH 3 or -O
Represents PO ₃ H ₂ . Z ¹ is preferably a group —CH ₂ CH ₂ Z, in which Z is preferably —OSO ₃ H or —SSO ₃ H, and particularly preferably —OSO ₃ H.

The monoazo compound (I) of the present invention
In the formula, the substitution positions of the two or three sulfo groups substituted with the 2-naphthylazo group are arbitrary, and specific examples of the 2-naphthylamine corresponding to the 2-naphthylazo group include the following. Is exemplified.

[0011]

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As the 2-naphthylazo group, a group substituted with two sulfo groups is particularly preferable.
A 2-naphthylazo group corresponding to naphthylamine-4,8-disulfonic acid and 2-naphthylamine-3,6-disulfonic acid is particularly preferred. Among those substituted with three sulfo groups, 2-naphthylamine-3 is preferred. 2-Naphthylazo groups corresponding to 2,6,8-trisulfonic acid and 2-naphthylamine-4,6,8-trisulfonic acid are preferred.

In the monoazo compound (I) of the present invention,
m represents an integer of 2 to 6, and m is preferably 2 or 3.
Particularly, 2 is preferable.

X represents chloro, fluoro or optionally substituted pyridinio, which may be pyridinio, 2-, 3- or 4-carboxypyridinio, 2-, 3- or 4- Examples include carbamoylpyridinio and the like. X is preferably chloro, fluoro,
3-carboxypyridinio (nicotinic acid group), 3-carbamoylpyridinio (nicotinamide), 4-carboxypyridinio (isonicotinic acid group), 4-carbamoylpyridinio (isonicotinamide), Among them, chloro or fluoro is particularly preferred.

The monoazo compound (I) in the present invention is
It may be in the form of a free acid, a salt thereof, or a mixture thereof. Preferred are alkali metal salts, alkaline earth metal salts, and mixtures containing them. Of these, soda salts, potassium salts, lithium salts, and mixtures containing them are preferred.

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 free acid has the following general formula (II)

[0017]

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[Wherein, n represents the same meaning as described above. A monoazo intermediate compound represented by the following general formula (III):

[0019]

Embedded image H ₂ N— (CH ₂ ) _m —SO ₂ Z ¹ (III)

Wherein m and Z ¹ have the same meanings as described above. A compound represented by the formula: 2,4,6-trichloro-s-triazine or 2,4,6-trifluoro-
It can be produced by condensing s-triazine in any order. When X in the monoazo compound (I) is an optionally substituted pyridinio, the compound can be produced by condensing a pyridine corresponding to the optionally substituted pyridinio with the compound obtained here. .

In the condensation reaction with 2,4,6-trichloro-s-triazine or 2,4,6-trifluoro-s-triazine, the order is not particularly limited, and the reaction conditions are not limited. Although it is not particularly limited, firstly, at a temperature of −10 ° C. to 40 ° C., pH 4 to 9, at a second temperature of 0 to 70 ° C., pH 4 to 9, and at a third temperature of 30 to 100 ° C., if necessary. Condensate while adjusting to pH 1-7.

As the compound represented by the general formula (III),
For example,

[0023]

Embedded image H ₂ NCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OSO ₃ HH ₂ NCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ SSO ₃ H H ₂ NCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ H ₂ NCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OCOCH ₃ H ₂ NCH ₂ CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OSO ₃
H H ₂ NCH ₂ CH ₂ CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ O
SO ₃ H H ₂ NCH ₂ CH ₂ SO ₂ CH = CH ₂

And the like.

The compound of the present invention has an aliphatic vinyl sulfone-based fiber reactive group and can be used as a dye for dyeing and printing a fiber material. 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, Nerin, hemp, jute, ramie fiber 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.

Further, as a blended material containing these,
Other than blended materials of these fiber materials, these fiber materials,
Blend materials with synthetic fibers such as polyester, nylon and acrylic can also be exemplified.

The compounds according to the invention can be applied to the abovementioned materials, in particular to the abovementioned fibrous materials, in a manner depending on the physical and chemical properties,
It can be dyed or printed.

Specifically, there may be mentioned, for example, a method of dyeing or printing 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, when dyeing cellulose fibers by the exhaust dyeing method, sodium carbonate, sodium bicarbonate,
In the presence of an acid binder such as sodium tertiary phosphate or caustic soda, neutral salts such as sodium sulfate and sodium chloride are added as necessary, and if necessary, a dissolution aid, a penetrant or a leveling agent is used in combination. , 30-
A method of dyeing at a temperature of about 100 ° C. is exemplified. Here, the addition of the acid binder, the neutral salt, and the like may be performed at once, or may be performed in a divided manner by a conventional method.

In the case of dyeing cellulose fibers 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 salt, 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. , Sodium formate, potassium carbonate, primary or secondary sodium phosphate, sodium trichloroacetate and 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 triazine mononicotinate group,
At least one of a dichlorotriazine group, a difluoromonochloropyrimidine group, and a trichloropyrimidine group
Dyes having at least one species, or Sumifix, Su
mifix Supra, Remazol, Levafix, Procion, Cibacr
on, Basilen, Drimarene, Kayacion, Kayaceleon Reac
dyes commercially available under the titles such as
50-178, JP-A-56-9483, 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-58-191755, JP-A-59-96174, JP-A-59-161463, JP-A-60-6754, JP-A-60-1235
No. 59, JP-A-60-229957, JP-A-60-260654, JP-A-61-126175, JP-A-61-155469, JP-A-61-2252
No. 56, JP-A-63-77974, JP-A-63-225664, JP-A-Hei.
No. 1-185370, JP-A-3-770, JP-A-5-32907, JP-A-5-117538, JP-A-5-247366, dyes described in JP-A-6-287463, and CIReactive Blue
19. Dyes represented by CIReactive Black 5 are exemplified.

[0039]

EFFECTS OF THE INVENTION The monoazo compound of the present invention has excellent exhaustion properties, high fixation rate, excellent build-up properties and high color value in dyeing and printing treatment of fiber material, and is a fiber material of unfixed dye. Easy to remove from washing, good storage stability in dry state, wet state and solution state, reproducibility, solubility, compatibility with other reactive dyes, dyeing condition in compound dyeing, economical The suitability for the dyeing formulation is good, and by using this, overall fastness, for example, light fastness, sweat fastness, sweat and sun fastness, chlorine fastness, acid hydrolysis fastness, A yellow dyed product and a printed product having excellent alkali fastness, washing fastness, and peroxide washing fastness, and having good thermal discoloration property, phototropic property, and fiber-dye bond stability can be obtained. In addition, the dyed product and the printed product obtained using the monoazo compound of the present invention have a small discoloration at the time of fix processing, resin processing, mercerize processing, and the like, and have little discoloration due to contact with a basic substance during storage.

[0040]

The present invention will be described below in detail with reference to examples. In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 20.3 parts of 2-naphthylamine-4,8-disulfonic acid were diazotized in a conventional manner, and 13.7 parts of 2-methoxy-5-methylaniline was subjected to a coupling reaction in an aqueous medium in a conventional manner. This gave a monoazo intermediate compound. On the other hand, in an aqueous medium, 2- (β-sulfatoethylsulfonyl)
23.3 parts of ethylamine and 18.4 parts of cyanuric chloride are condensed according to a conventional method, and the obtained monoazo intermediate compound is condensed under conditions of pH 3 to 9, 10 to 60 ° C, A monoazo compound having a free acid form represented by the following formula was obtained. This compound showed λmax = 412 nm in an aqueous medium. It also showed a yellow color on cotton.

[0042]

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Example 2 A monoazo compound having the following structure was synthesized in the same manner as in Example 1 except that 13.5 parts of cyanuric fluoride was used instead of cyanuric chloride used in Example 1. Obtained. This compound showed λ max = 412 nm in aqueous medium. It also showed a yellow color on cotton.

[0044]

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Example 3 In Example 1 and Example 2, instead of using 2-naphthylamine-4,8-disulfonic acid and 2- (β-sulfatoethylsulfonyl) ethylamine, respectively, the following table was used. The corresponding monoazo compounds were obtained by condensing the starting materials described in the first and second columns according to Examples 1 and 2. Each of these compounds exhibited the color tone shown on the hue column in the following table on cotton.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

Example 4 The following pyridines were condensed to each of the monoazo compounds obtained in Examples 1 to 3 according to a conventional method, and X in the monoazo compound (I) was substituted. A monoazo compound which was a good pyridinio was obtained. Pyridines: pyridine, 2-carboxypyridine, 3-
Carboxypyridine, 4-carboxypyridine, 2-cabamoylpyridine, 3-cabamoylpyridine, 4-cabamoylpyridine, 3-cyanopyridine, 3-chloropyridine. Each of the obtained compounds showed the same color tone as the monoazo compounds obtained in Examples 1 to 3 before condensing pyridines on cotton.

Example 5 0.3 part of each of the monoazo compounds obtained in Examples 1 to 4 was dissolved in 200 parts of water, 20 parts of Glauber's salt was added, 10 parts of cotton was further added, and the temperature was raised to 60 ° C. Warmed. After the temperature reached 60 ° C., 30 minutes later, 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 when any of the compounds was used, and the coloring amount of the dyeing wastewater was slight. The resulting stain is
All were uniform and deep yellow. 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, sweat resistance, sweat sunlight resistance, chlorine resistance, hydrolysis resistance of the obtained dyed product,
All of the fastnesses to alkali resistance, washing resistance, and peroxide washing resistance were good. The thermochromic properties and phototropic properties were also good.

Example 6 Dyeing was carried out in the same manner as in Example 5 except that the amount of sodium sulfate used was changed from 20 parts to 10 parts. All of the obtained dyed products had the same quality as the dyed product obtained in Example 5.

Example 7 Dyeing was carried out in the same manner as in Example 5 except that the amount of sodium sulfate used was changed from 20 parts to 4 parts. All of the obtained dyed products had the same quality as the dyed product obtained in Example 5.

Example 8 In each of Examples 5 to 7, dyeing was carried out in the same manner as in Examples 5 to 7, except that the dyeing temperature was changed from 60 ° C. to 70 ° C. Each of the obtained dyed products had the same quality as the dyed products obtained in Examples 5 to 7.

Example 9 In each of Examples 5 to 8, each bisazo compound 0.3
Instead of using 0.3 part of each bisazo compound and 0.06 part of a sodium salt of a condensate of methylnaphthalenesulfonic acid and formaldehyde having a degree of sulfonation of 110% and an average degree of polymerization of 1.8. Examples 5-8
Staining was performed according to each of the above. Each of the obtained dyed products had the same quality as the dyed products obtained in Examples 5 to 8.

Example 10 Instead of using 0.3 part of the monoazo compound in each of Examples 5 to 9, 0.1 part of the monoazo compound or
Dyeing was performed according to each of Examples 5 to 9, except that 0.6 part was used. The obtained dyed product shows a sufficiently deep yellow color tone when 0.6 part of the monoazo compound is used as compared with the case where 0.3 part is used, and in each of Examples 1 to 4, It was found that the build-up properties of the obtained monoazo compounds were all good. The other qualities were equivalent to those of the dyed products obtained in Examples 5 to 9, respectively.

Example 11 Using each monoazo compound obtained in each of Examples 1 to 4, a color paste having the following composition was prepared.

[0057] 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, followed by washing with water, soaping, washing with hot water, and drying.
Finished. The resulting dyed products were all uniform and deep yellow. Light fastness, sweat resistance, sweat and sunlight resistance, chlorine resistance, hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance of the obtained printed matter were all good. Was. The thermochromic properties and phototropic properties were also good.

Example 12 30 parts of the monoazo compound obtained in each of Examples 1 to 4 was dissolved in hot water and then cooled to 25 ° C. To this dye solution was added 15 parts of a 32.5% aqueous solution of caustic soda and 150 parts of 50 ° water glass, and water was added at 25 ° C. to make the total amount 1000 parts. The cotton fabric was padded. Roll up the padded cotton fabric, seal with polyethylene film and
After leaving at room temperature of 5 ° C. for 20 hours, it was washed by a conventional method and dried to finish. The resulting dyed products were all uniform and deep yellow. Light fastness, sweat resistance, sweat and sunlight resistance, chlorine resistance, hydrolysis resistance, alkali resistance, washing resistance and peroxide washing resistance of the obtained dyed product were all good. Was. The thermochromic properties and phototropic properties were also good.

Example 13 20 parts of the monoazo compound obtained in each of Examples 1 to 4 was dissolved in hot water and then cooled to 25 ° C. To this dye solution, 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate were added, and water was added at 25 ° C. to make the total amount 1000 parts. The cotton fabric was padded. The padded cotton fabric was dried at 120 ° C. for 2 minutes and then steamed at 100 ° C. for 5 minutes to fix the dye. The resulting dyed products were all uniform and deep yellow. Light fastness, sweat resistance, sweat sunlight resistance, chlorine resistance, hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance of the obtained dyed product were all good. Was. The thermochromic properties and phototropic properties were also good.

Claims (7)

[Claims] (1) The free acid is represented by the following general formula (I): Wherein X represents chloro, fluoro or optionally substituted pyridinio; Z ¹ is vinyl or a group —CH
₂ CH ₂ Z, where Z is —OSO ₃ H, —SSO
₃ H, —OCOCH ₃ or —OPO ₃ H ₂ ; n
Represents 2 or 3, and m represents an integer of 2 to 6. A monoazo compound represented by the formula or a salt thereof. 2. The compound according to claim 1, wherein Z ¹ is a group —CH ₂ CH ₂ OSO ₃ H or —CH ₂ CH ₂ SSO ₃ H, or a salt thereof. 3. The compound according to claim 1, wherein Z ¹ is a group —CH ₂ CH ₂ OSO ₃ H, or a salt thereof. 4. The compound according to claim 1, wherein n is 2, or a salt thereof. 5. The compound according to claim 1, wherein m is 2 or 3, or a salt thereof. 6. The method according to claim 1, wherein X is chloro or fluoro.
Or a salt thereof. 7. A method for dyeing or printing a fiber material, comprising using the compound according to claim 1 or a salt thereof.