JPH06220352A - Reactive dyestuff composition and method for dyeing or printing the same - Google Patents

Abstract

PURPOSE:To obtain the subject composition comprising two kinds of specific anthraquinone reactive dyestuffs, excellent in solubility in water and alkali solutions, good in the stability of dyestuff solutions, and giving uniformly deep dyed or printed articles. CONSTITUTION:The objective composition comprises an anthraquinone dyestuff of formula I in the form of a free acid and an anthraquinone dyestuff of formula II in the form of a free acid preferably so that the weight ratio of the dyestuff of formula I to the dyestuff of formula II is 90:10 to 10:90. The composition is usually prepared by compounding the dyestuffs of formulas I and II and, if necessary, an inorganic salt such as sodium chloride, a dispersing agent such as naphthalene sulfonic acid formaldehyde condensate, a solubility-improving agent such as epsilon-caprolactam, etc. The dyestuffs of formulas I and II are preferably used in the form of Na salt, K salt or Li salt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a reactive dye composition having excellent solubility and stability in water and an aqueous alkaline solution, and a fiber material, particularly a cellulosic fiber material or a cellulosic fiber, using the reactive dye composition. The present invention relates to a method for uniformly dyeing or printing a contained fiber material.

[0002]

2. Description of the Related Art Conventionally, reactive dyes have been widely used for dyeing and printing cellulosic fibers. As a method for dyeing or printing those fiber materials, various methods such as an exhaust dyeing method, a one-bath padding method, a cold batch-up method and a one-phase printing method are used. In order to achieve uniform dyeing and printing without spots by these methods, it has sufficient solubility in the preparation of dye solutions, padding solutions and printing dyes, and there is no precipitation or gelation of dyes. There is a need for reactive dyes with good stability. For example, cold patch-up staining
An aqueous solution containing an alkali such as caustic soda, sodium carbonate, sodium triphosphate, sodium silicate, etc. is used to adjust the padding solution, but the properties such as the precipitation or gelation of the dye in the dyeing bath during padding are used. It is preferable that the dyeing can be completed without any change. With the automation of dyeing factories in recent years, dyes are stored in the form of an aqueous solution that is easy to measure. In this case, in order to dye or print cellulosic fibers in a dark color using reactive dyes, ,
It is desirable that the dye aqueous solution that is stored has a dye concentration as high as possible, which requires high solubility of the reactive dye. Furthermore, the dye precipitates or gels even during long-term storage at any concentration from a relatively dilute dye concentration of 0.1 wt% or less to a high dye concentration of 50 wt% or more, especially in cold conditions. It is desirable that it is stable without changing the properties. From the above, in the case of anthraquinone dyes, Japanese Patent Application Laid-Open No.
A method for improving the solubility has been proposed in JP-A 5-107582, JP-A-60-108472 and the like.

[0003]

However, when dyeing or printing using a specific commercially available anthraquinone-based reactive dye, the solubility of the reactive dye in water or an aqueous alkaline liquid is still insufficient. And
In addition, there is a problem that the stability of the solution is not sufficient, and there is a strong demand for a technique for developing a dye having good solubility and good solution stability.

[0004]

The inventors of the present invention have excellent solubility in water and an aqueous alkaline solution, and when the dye is stored in an aqueous solution or during dyeing or printing, A stable dye solution without precipitation or the like can be obtained, and as a result of extensive studies for the purpose of obtaining a specific anthraquinone-based reactive dye composition capable of obtaining a uniform and deep dyeing or printing in dyeing or printing, the present invention can be completed. I arrived.

Thus, the present invention relates to the formula (I) in the form of the free acid.

[0006]

[Chemical 3]

Anthraquinone-based reactive dye of formula (II) in the form of free acid

[0008]

[Chemical 4]

A reactive dye composition comprising an anthraquinone-based reactive dye represented by the above in an amount of 99 to 1% by weight based on the dye composition and a cellulose-based fiber material or a cellulose-based fiber material using the same. Provided is a method for dyeing or printing a contained fiber material.

The anthraquinone-based reactive dyes represented by the formulas (I) and (II) have already been disclosed in Japanese Examined Patent Publication 35-10632.
It is known in Japanese Patent Publication.

Formulas (I) and (II) in the present invention
The anthraquinone-based reactive dye represented by is present in the form of a free acid or in the form of a salt thereof, and particularly, an alkali metal salt and an alkaline earth metal salt, and further, a sodium salt, a potassium salt and a lithium salt are preferable.

In the present invention, the mixing weight ratio of the anthraquinone-based reactive dye represented by the formula (I) and the anthraquinone-based reactive dye represented by the formula (II) is 99: 1 to 1:99.
Is preferable, and more preferably 90:10 to 10:90.

The reactive dye composition of the present invention may be an alkylated dye represented by the formula (I) and a dye represented by the formula (II) and, if necessary, an inorganic salt such as sodium chloride and anhydrous sodium sulfate. Dispersants such as formaldehyde condensates of naphthalene sulfonic acid, ε-caprolactam, polyoxyethylene derivatives, naphthalene derivatives, anthraquinone derivatives and other dissolution enhancers, dust scattering inhibitors, phosphates, acetates and other pH stabilizers, polyphosphoric acid It can be obtained by mixing a water softening agent such as salt, an antifoaming agent, water and other known dyeing aids by a known method. The mixing is not particularly limited, and it may be carried out in advance before it is used for dyeing, it may be mixed at the time of dyeing, or further at the time of producing the reactive dye. When a dissolution enhancer such as ε-caprolactam is used, its amount is preferably 30% by weight or less, more preferably 20% by weight or less, based on the dye mixture.

The reactive dye composition of the present invention can be used in combination with other dyes, if necessary, in order to obtain a desired hue. The dye used as a mixture is not particularly limited, and a known reactive dye can be used, but preferably a sulfatoethylsulfone group, a vinylsulfone group, a monochlorotriazine group as a reactive group,
A dye having at least one or more of at least one of a monofluorotriazine group, a dichlorotriazine group, a monopyridinio (including hydroxycarbonyl or aminocarbonyl substitution) triazine group, a difluoromonochloropyrimidine group, or a trichloropyrimidine group, or Sumifix, Sumifix Supra, Remazol, Levafix
, Procion, Cibacron, Basilen, Drimarene, Kayac
Dyes marketed under the generic names such as ion and Kayacelon React are preferred.

The reactive dye composition of the present invention is not particularly limited in its form and may be a known form, and may be in the form of powder, granules, or liquid. Absent. When the reactive dye composition of the present invention is an aqueous liquid composition, the content of the dye mixture is usually 5 to 50% by weight based on the aqueous liquid composition. In this case, the content of the inorganic salt is preferably 30% by weight or less, more preferably 20% by weight or less, still more preferably 10% by weight or less with respect to the aqueous liquid composition.

The cellulosic fiber material in the method of the present invention is not particularly limited, but natural or regenerated cellulosic fibers such as cotton, linen, hemp, jute, ramie fiber, viscose human silk and bemberg are exemplified. It Examples of fiber materials containing cellulosic fibers include cotton / polyester blended products, cotton / nylon blended products, and cotton / wool blended products.

As the dyeing and printing methods in the method of the present invention, known methods may be used. In the exhaust dyeing method, known inorganic neutral salts such as anhydrous Glauber's salt and salt, and sodium carbonate, sodium bicarbonate, caustic soda, caustic potash, Examples of the method include dyeing with a known acid binder such as sodium triphosphate or a commercially available synthetic alkali agent alone or in combination, but the dyeing aid is not limited thereto. The amount of the inorganic neutral salt or acid binder used at this time is not limited, but at least 1 g / L or more is preferable, and 200 g / L or more may be used. Further, the inorganic neutral salt and the acid binder may be added to the dyeing bath all at once, or may be divided and added by a conventional method. In addition, dyeing assistants such as leveling agents, slow-dyeing agents, and bath softeners may be used in combination by known methods, but the dyeing assistants are not particularly limited to these. The dyeing temperature is usually 30 to 95 ° C., and particularly preferably 60 to
95 ° C. In the cold batch-up dyeing method, a known inorganic neutral salt such as anhydrous Glauber's salt and salt, and a known acid binder such as caustic soda and sodium silicate are used for padding, and then allowed to stand in a closed packaging material at a constant temperature. A method of dyeing is exemplified. In the continuous dyeing method, a known acid binder such as sodium carbonate or sodium bicarbonate is mixed with the dye padding solution,
After padding by a known method, a one-bath padding method of dyeing by dry heat or steam, and, after padding with a dye, a known inorganic neutral salt such as anhydrous sodium sulfate and sodium chloride, and a known acid bond such as caustic soda and sodium silicate. An example is a two-bath padding method in which the agent is padded and dyed by dry heat or steam heat by a known method. In the printing method, after printing a printing paste containing a known acid binder such as sodium bicarbonate, a one-phase printing method in which printing is performed by dry heat or steaming, and after printing the printing paste, salt is printed. Inorganic neutral salts such as caustic soda and sodium silicate
An example is a two-phase printing method in which a known acid binder such as Da is added to a high temperature solution of 80 ° C. or higher for printing. The dyeing and printing methods employed in the present invention include, in addition to these, methods using an inkjet method and the like, and are not limited in any way.

According to the method of the present invention, in practice, it has excellent solubility in water and an aqueous alkaline solution, and further has a dilute dye concentration of 5% by weight or less, for example 0.1% by weight or less. To 50% by weight or more, it is possible to obtain a reactive dye composition having good stability for a long period of time even in the state of an aqueous solution having a high dye concentration, and to obtain a uniform and deep dyeing or printing in dyeing or printing.

[0019]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 Formula (1) in the form of the free acid

[0021]

[Chemical 5]

50 parts of the dye represented by the formula (2) in the form of free acid

[0023]

[Chemical 6]

50 parts of the dye of formula (1) were thoroughly mixed. (A) 250 g of the dye composition obtained above was dissolved in hot water, cooled to 25 ° C., and water was added to bring the total amount to 2
It was adjusted to 1 L at 5 ° C. The obtained dye solution was a clear solution without crystal precipitation. (B) Furthermore, this dye solution was stable without precipitation and gelation of the dye even after storage at -5 ° C for 3 months. (C) 100 g of the dye composition obtained above was dissolved in hot water and then cooled to 25 ° C. Add 1 g of sodium alginate and 1 part of sodium metanitrobenzene sulfonate to this dye solution.
Immediately after adding 0 g and 10 g of sodium carbonate and further adding water to make the total amount to 1 L at 25 ° C., a cotton fabric was padded using this liquid as a padding liquid. Dry the padded cotton fabric at 120 ° C for 2 minutes, then at 100 ° C for 1
The dye was fixed by steaming for 0 minutes. The obtained dyed product was washed by a conventional method to remove unfixed dye, and then dried to finish. The resulting dyed product was a uniform and clear deep blue color without spots. (D) When the dye solution obtained in the item (c) was allowed to stand at 25 ° C., no dye deposition was observed in the dye solution even after 8 hours and it was stable.

Example 2 90 parts of the dye of the formula (1) in the form of the free acid, 10 parts of the dye of the formula (2) in the form of the free acid and 5 parts of ε-caprolactam, 2 parts of disodium phosphate and 3 parts of anhydrous sodium sulfate was thoroughly mixed. (A) 250 g of the dye composition obtained above was dissolved in hot water, cooled to 25 ° C., and water was added to bring the total amount to 2
It was adjusted to 1 L at 5 ° C. The obtained dye solution was a clear solution without crystal precipitation. (B) Furthermore, this dye solution was stable without precipitation and gelation of the dye even after storage at -5 ° C for 3 months. (C) 100 g of the dye composition obtained above was dissolved in hot water and then cooled to 25 ° C., and 150 g of sodium silicate of 50 ° Baume and 32.5% aqueous solution of caustic soda 2
Add 5 mL and immediately add water to bring the total volume to 25 ° C.
Was adjusted to 1L. Immediately thereafter, a cotton fabric is padded with this dye solution by a known method, immediately rolled up, sealed with a polyethylene film, and placed in a room at 20 ° C.
After standing for 0 hour, the dyed product was washed by a conventional method to remove unfixed dye, and then dried to finish. The resulting dyed product was a uniform and clear deep blue color without spots. (D) The dye solution obtained in the item (c) was allowed to stand at 25 ° C., but after 120 minutes, precipitation of the dye was not observed in the dye solution and it was stable.

Example 3 55 parts of the dye of the formula (1) in the form of the free acid, 45 parts of the dye of the formula (2) in the form of the free acid and naphthalenesulfonic acid and formaldehyde condensate (sodium salt) 2
0 parts were mixed well. (A) 200 g of the dye composition obtained above was dissolved in boiling water, cooled to 25 ° C., and water was added to bring the total amount to 2
It was adjusted to 1 L at 5 ° C. The obtained dye solution was a clear solution without crystal precipitation. (B) Furthermore, this dye solution was stable without precipitation and gelation of the dye even after storage at -5 ° C for 3 months. (C) 50 g of the dye composition obtained above was dissolved in hot water and then cooled to 25 ° C. Sodium alginate (1 g) was added to the dye solution, and water was further added to bring the total amount to 1 L at 25 ° C. Immediately thereafter, this solution was used as a padding solution to pad a cotton fabric. Padded cotton fabric at 120 ℃
And dried for 2 minutes. Then, the cotton fabric stuffed with the above dye was padded using an aqueous solution having a total amount of 1 L to which 250 g of sodium chloride, 30 mL of a 32.5% sodium hydroxide aqueous solution and 10 g of sodium metanitrobenzenesulfonate were added, and this cotton fabric was further padded. 1 at 100 ° C
The dye was fixed by steaming for a minute. The obtained dyed product was washed by a conventional method to remove unfixed dye, and then dried to finish. The resulting dyed product was a uniform and clear deep blue color without spots.

EXAMPLE 4 20 parts of the dye of the formula (1) in the form of the free acid, 80 parts of the dye of the formula (2) in the form of the free acid and sodium dihydrogen phosphate / sodium tripolyphosphate buffer 3 The parts were mixed well. (A) After dissolving 300 g of the dye composition obtained above in hot water, it was cooled to 25 ° C. and water was added to bring the total amount to 2
It was adjusted to 1 L at 5 ° C. The obtained dye solution was a clear solution without crystal precipitation. (B) Furthermore, this dye solution was stable without precipitation and gelation of the dye even after storage at -5 ° C for 3 months. (C) 100 g of the dye composition obtained above was dissolved in hot water and then cooled to 25 ° C. Add 1 g of sodium alginate and 1 part of sodium metanitrobenzene sulfonate to this dye solution.
Immediately after adding 0 g and 10 g of sodium carbonate and further adding water to make the total amount to 1 L at 25 ° C., a cotton fabric was padded using this liquid as a padding liquid. Dry the padded cotton fabric at 120 ° C for 2 minutes, then at 100 ° C for 1
The dye was fixed by steaming for 0 minutes. The obtained dyed product was washed by a conventional method to remove unfixed dye, and then dried to finish. The resulting dyed product was a uniform and clear deep blue color without spots. (D) The dye solution obtained in (c) was allowed to stand at 25 ° C., but no dye deposition was observed in the dye solution even after 8 hours, and the dye solution was stable.

Example 5 65 parts of the dye of the formula (1) in the form of the free acid, 35 parts of the dye of the formula (2) in the form of the free acid, 15 parts of ε-caprolactam, sodium dihydrogen phosphate (dihydrate) 0.68 parts of water salt) and 6 parts of sodium tripolyphosphate were thoroughly mixed. (A) After dissolving 150 g of the dye composition obtained above in hot water, it was cooled to 25 ° C. and water was added to bring the total amount to 2
It was adjusted to 1 L at 5 ° C. The obtained dye solution was a clear solution without crystal precipitation. (B) Furthermore, this dye solution was stable without precipitation and gelation of the dye even after storage at -5 ° C for 3 months. (C) 100 g of the dye composition obtained above was dissolved in hot water and then cooled to 25 ° C. Add 1 g of sodium alginate and 1 part of sodium metanitrobenzene sulfonate to this dye solution.
Immediately after adding 0 g and 20 g of sodium bicarbonate and further adding water to make the total amount 1 L at 25 ° C., a cotton fabric was padded using this liquid as a padding liquid. The padded cotton fabric was dried at 120 ° C for 2 minutes and then steamed at 100 ° C for 10 minutes to fix the dye. The obtained dyed product was washed and finished by a conventional method. The resulting dyed product was a uniform and clear deep blue color.

Example 6 55 parts of the dye represented by the formula (1) in the form of a free acid, 45 parts of the dye represented by the formula (2) in the form of a free acid and anhydrous sodium sulfate.
2 parts and 0.5 part of common salt were mixed well. (A) 250 g of the dye composition obtained above was dissolved in hot water, cooled to 25 ° C., and water was added to bring the total amount to 2
It was adjusted to 1 L at 5 ° C. The obtained dye solution was a clear solution without crystal precipitation. (B) Furthermore, this dye solution was stable without precipitation and gelation of the dye even after storage at -5 ° C for 3 months. (C) 80 g of the dye composition obtained above, 100 urea
A printing paste consisting of 550 g of 4% sodium alginate, 250 g of hot water and 20 g of sodium bicarbonate was obtained. The obtained printing paste is printed on a 40th mercerized cotton broad cloth by a usual method and then dried, and then at 100 ° C. for 10 minutes.
The ming process was performed. Then wash with water, wash with hot water, soaping,
It was washed with hot water, washed with water, and dried. The cotton broad cloth obtained was a uniform deep blue color.

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[Procedure amendment]

[Submission date] March 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009] dyeing fiber materials containing a cellulose fiber material or cellulosic fiber materials using the same reactive dye composition and the anthraquinone reactive dye characterized by comprising Nde containing <br/> represented by or printing Provide a way to do.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025] 10 parts of the dye and ε- caprolactam 5 parts represented by the formula (2) in the form of 90 parts of a dye represented by the formula (1) in the form of Example 2 free acid free acid, disodium phosphate 2 parts, and 3 parts of anhydrous sodium sulfate was thoroughly mixed. (A) 250 g of the dye composition obtained above was dissolved in hot water, cooled to 25 ° C., and water was added to bring the total amount to 2
It was adjusted to 1 L at 5 ° C. The obtained dye solution was a clear solution without crystal precipitation. (B) Furthermore, this dye solution was stable without precipitation and gelation of the dye even after storage at -5 ° C for 3 months. (C) 100 g of the dye composition obtained above was dissolved in hot water and then cooled to 25 ° C., and 150 g of sodium silicate of 50 ° Baume and 32.5% aqueous solution of caustic soda 2
Add 5 mL and immediately add water to bring the total volume to 25 ° C.
Was adjusted to 1L. Immediately thereafter, a cotton fabric is padded with this dye solution by a known method, immediately rolled up, sealed with a polyethylene film, and placed in a room at 20 ° C.
After standing for 0 hour, the dyed product was washed by a conventional method to remove unfixed dye, and then dried to finish. The resulting dyed product was a uniform and clear deep blue color without spots. (D) The dye solution obtained in the item (c) was allowed to stand at 25 ° C., but after 120 minutes, precipitation of the dye was not observed in the dye solution and it was stable.

Front page continued (72) Inventor Akihiro Takuma 3-1,98 Kasugade, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd. (72) Inventor Sho Takahashi 3--1, Kasugade, Konohana-ku, Osaka No. 98 Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. The formula (I) in the form of the free acid: An anthraquinone-based reactive dye of formula (II) in the form of a free acid A reactive dye composition comprising a dye mixture comprising an anthraquinone-based reactive dye represented by: 2. The reaction according to claim 1, wherein the mixing weight ratio of the anthraquinone-based reactive dye represented by the formula (I) and the anthraquinone-based reactive dye represented by the formula (II) is 99: 1 to 1:99. Dye composition. 3. A method for dyeing or printing a cellulosic fiber material or a fiber material containing cellulosic fibers using the reactive dye composition according to claim 1.