JPH025780B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to compositions of reactive dyes which are highly soluble in water or aqueous lye. More specifically, the present invention uses CI Reactive Blue 19 from 1 to
99 parts by weight and the formula in free acid form (In the formula, R is -CH ₂ CH ₂ OSO ₃ M or -CH=CH ₂
(where M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary amine) containing 99 to 1 part by weight of a dye (assuming 100% dyeing intensity for CI Reactive Blue 19). The present invention relates to a reactive dye composition comprising: The present invention also relates to a dyeing method using this reactive dye composition. An object of the present invention is to provide a composition of a blue reactive dye which has extremely high solubility in water or an aqueous alkaline solution and which can obtain a uniform and high color yield when dyeing cellulose fibers. . Reactive dyes are often used as energy-saving dyes, for example, in cold patch batch dyeing methods, and in this case, an alkali is usually added in advance to the dye solution prepared for padding. The dye is stored at room temperature until it is packed into the fiber.
It is necessary that the dye be maintained in a stable state in the prepared dyeing bath without causing property changes such as precipitation aggregation or gelation. Among these types of reactive dyes, CI Reactive Blue 19 in particular is an extremely useful blue dye with excellent fastness and beautiful hue, but it is also selected when used in the cold patch batch dyeing method. Depending on the conditions, such as the type and amount of alkali added, or the length of time used for dyeing, uneven dyeing, irritation, or a decrease in color yield may sometimes occur.The solution to these problems is dyeing. In many cases, this was left to technical management. Regarding CI Reactive Blue 19, many improvement methods have been proposed by adding anti-gelling agents, hydrotrobes, or certain surfactants such as formalin condensates of naphthalene sulfonic acid. In some cases, these additives are extremely expensive, and in many cases, effectiveness can only be expected by using large amounts of such additives. Therefore, solving the above-mentioned drawbacks of CI Reactive Blue 19 has been a long-standing challenge in the industry. As a result of various studies, the present inventors found that
It has now been found that a reactive dye composition comprising CI Reactive Blue 19 plus the compound represented by the formula surprisingly remains stable for long periods of time in an aqueous alkaline dye bath, giving uniform dyeing and high color yield. This effect appears to be due to the fact that the addition of the compound of formula prevents Reactive Blue 19 from associating in the aqueous alkaline dyebath. Such effects are specific phenomena observed only with specific dye combinations. The compound represented by the formula used in the present invention itself has the performance as a reactive dye and contributes to dyeing, but when used alone, it has insufficient solubility in an aqueous alkaline solution and is not practical. I can't offer it. However, it was found that a composition prepared by adding Reactive Blue 19 to the reactive dye of the formula was stable when dissolved in an aqueous alkaline solution and gave a good blue dye, and it became possible to put the reactive dye of the formula into practical use. Ta. In the reactive dye composition for blue dyeing according to the invention, the relative amounts of reactive dye of the formula Reactive Blue 19 can therefore be varied within a wide range, as mentioned above. The present invention will be explained in detail below. The compound represented by the formula used in the present invention can be obtained by condensing 1-amino-4-bromanthraquinone-2-sulfonic acid and 4-aminophenyl-β-oxyethylsulfone, and then esterifying it with sulfuric acid. After that, if necessary, it can be easily obtained by further converting it into an alkali metal, alkaline earth metal, or quaternary ammonium salt. In addition, compounds in which R is -CH=CH ₂ are produced as by-products in the above reaction process, but
It can also be obtained by treating the sulfatoethyl compound in the presence of hydroxide ions. The shape of the composition of the present invention is not particularly limited,
It may be a solid such as powder, granules, or granules, or a liquid such as a solution, slurry, or paste containing water or a suitable solvent as a medium. The composition of the present invention can be prepared by mixing the compound represented by the formula with CI Reactive Blue 19 in a specified proportion by conventional means, or by mixing CI Reactive Blue 19 with CI Reactive Blue 19
It can also be produced as a mixture by mixing 3-aminophenyl-β-oxyethylsulfone and 4-aminophenyl-β-oxyethylsulfone in the process of producing. The composition of the present invention contains 1 to 99 parts by weight, preferably 5 to 95 parts by weight, of CI Reactive Blue 19 and a dye represented by the formula (staining intensity 100% for CI Reactive Blue 19).
%), preferably 95 to 5 parts by weight. In the composition of the present invention, various conventional auxiliary agents such as diluents, dust scattering preventive agents, etc. are usually added and mixed in arbitrary proportions. Known auxiliary agents may be added and mixed in any proportion. The composition of the present invention can be used under normal conditions in various methods conventionally applied to reactive dyes, such as cold patch batch method, exhaust dyeing method, and textile printing method, to dye cellulose fibers. . The present invention will be explained below with reference to examples, but the present invention is not limited to these examples. Moreover, parts in the examples represent parts by weight. Examples 1 to 8 and Comparative Examples 1 to 2 While stirring 305 parts of water using a thermometer, a condenser, and a four-neck flask with a stirrer, 1-amino-4-
Sodium promuanthraquinone-2-sulfonate
100 parts (100%), 15 parts (100%) of 4-aminophenyl-β-oxyethylsulfone, 48 parts of bicarbonate of soda
1 part, 2.4 parts of cuprous chloride, and 1.6 parts of steel powder were added, and the mixture was stirred for 16 hours while maintaining the liquid temperature at 68 to 70°C. Next, 37 parts of 35% hydrochloric acid was added, the liquid volume was adjusted to 1000 parts with water, the temperature was raised to 80°C, the mixture was stirred for 2 hours, and the liquid volume was further adjusted to 1500 parts with water, and 105 parts of sodium chloride was added. Then, 30 parts of potassium chloride was added, and the mixture was gradually cooled to 40°C and filtered. This was washed with 670 parts of 7% sodium chloride solution,
After sufficiently removing the liquid, it was dried at 100°C to obtain 103 parts of sodium 1-amino-4-(4'-β-oxyethylsulfonylphenylamino)anthraquinone-2-sulfonate. Next, 100 parts of sodium 1-amino-4-(4'-β-oxyethylsulfonylphenylamino)anthraquinone-2-sulfonate obtained by the above method was added to concentrated sulfuric acid whose temperature was controlled at 15 to 20°C. After esterification by stirring at the same temperature for 16 hours, post-treatment was performed to obtain the formula below. [1-Amino-4-(4'-β-sulfatoethylsulfonylphenylamino)anthraquinone-
2-sodium sulfonate] dye (staining strength 112%, dye content 89% by weight)
Obtained 168 copies. A small amount of anti-dusting oil and a wetting improver were added to this dye, and 10 parts by weight of sodium anthraquinone-2-sulfonate, known as a hydrotrope, and Demol RN (a formalin condensate of naphthalene sulfonic acid, manufactured by Kao Atlas Co., Ltd.) were added. By mixing, a dye component (a) with a dyeing intensity of 100% was prepared. On the other hand, CI Reactive Blue 19, a well-known dye, has the following formula: [1-Amino-4-(3'-β-sulfatoethylsulfonylphenylamino)anthraquinone-
2-sodium sulfonate], but using a dye containing this as the main component, the dye component (a)
A dye component (b) with a dyeing strength of 100% was prepared by mixing auxiliary agents in the same manner as above. The above two dye components (a) and dye component (b) were mixed in various proportions and a dye bath stability test in alkaline conditions was conducted. The results are as follows, showing extremely high stability compared to the comparative example. Dye bath stability test in alkaline 50g of dye composition with dyeing concentration of 100% at 70~80℃
Pour about 300g of warm water and dissolve completely. about 40
At ℃, add 100 g of urea and 2 ml of Leonil KS (migration inhibitor, manufactured by Hoechst), add water to make 800 ml, and use it as a dye solution. On the other hand, add 200 g of water glass of 45 to 48° B′e to make 200 ml, mix it with the above dye solution, immediately pour it into the tray of a small pad roll printing machine, and pad it onto the endlessly sewn cotton fabric. . 50 minutes after the start of padding, cut out a small piece of the dyed cloth.
Place between polyethylene sheets and leave at 20±1℃ for 16 hours. In order to evaluate the stability of the dyeing bath and the bluishness of the dyed cloth dyed with it, a dyed specimen for evaluation is prepared in advance, and each dye composition is evaluated based on this. Grade 5 is if it is dyed in a stable bath and has no red tinge at all and is uniformly dyed blue. If the dye becomes insolubilized in the bath, and therefore has almost no blue tinge and a marked red tinge (reddish-brown), it is graded 0. It is visually divided into five levels between grades 5 and 0. However, all of the dyeing baths of grades 5 to 1 are stable, and the dyed fabrics dyed with these have only a slight difference in blue tint, so all of them can be put to practical use. On the other hand, grade 0 cannot be put to practical use at all.

[Table] Examples 9 to 10 and Comparative Example 3 A dye mainly composed of the dye represented by the formula (a) was mixed with a small amount of dust prevention oil, a wetting improver, and the above-mentioned Demol RN, and a dyeing strength of 100 was obtained. % dye composition (a') was prepared. Furthermore, using a dye whose main component is the dye represented by the formula (), the dyeing intensity was determined in the same manner as in the case of (a′).
A 100% dye composition (b') was prepared. The above two dye compositions (a') and (b') were mixed in the proportions shown in the table below, and the dye bath stability test in alkaline conditions described above was conducted. The results are as follows, showing extremely high stability compared to the comparative example.

[Table] Example 11 Using a thermometer, a condenser, and a four-necked flask with a stirrer, 1-amino-4-
Sodium bromoanthraquinone-2-sulfonate
100 parts (100%), 45 parts (100%) of 3-aminophenyl-β-oxyethylsulfone, 32 parts (100%) of 4-aminophenyl-β-oxyethylsulfone,
42 parts of sodium bicarbonate, 1.9 parts of cuprous chloride, and 0.9 parts of copper powder were charged, and the mixture was stirred for 16 hours while maintaining the liquid temperature at 68 to 70°C. Next, 37 parts of 35% hydrochloric acid was added, the liquid volume was adjusted to 1000 parts with water, the temperature was raised to 80°C, the mixture was stirred for 2 hours, and the liquid volume was further adjusted to 1500 parts with water. part, add 30 parts of potassium chloride, 40%
It was gradually cooled down to This was washed with 670 parts of 7% sodium chloride solution,
After thoroughly removing the liquid, dry at 100℃ to obtain 1-amino-
Sodium 4-(3'-β-oxyethylsulfonylphenylamino)anthraquinone-2-sulfonate and 1-amino-4-(4'-β-oxyethylsulfonylphenylamino)anthraquinone-2-
104 parts of a mixture of sodium sulfonate were obtained. Next, 100 parts of the above mixture was charged into concentrated sulfuric acid whose temperature was controlled at 25 to 30°C, and the mixture was stirred for 16 hours at the same temperature for esterification. ) A dye mixture consisting of dyes whose main components are dyes shown by the formula (dyeing strength
133%, dye content 75% by weight) 155 parts were obtained. A small amount of anti-dusting oil, wetting improver and Demol RN were added to this dye mixture to prepare a dye composition (c) consisting of a dye mixture. The above dye composition was subjected to the above-mentioned alkaline dye bath stability test, and the results were as follows, showing extremely high stability.

【table】

Claims (1)

[Claims] 1. Reactive Blue 19 as a dye component.
99 parts by weight and formula as free acid form (In the formula, R is -CH ₂ CH ₂ OSO ₃ M or -CH=CH ₂
and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary amine) containing 99 to 1 part by weight of a dye (assuming 100% staining intensity for CI Reactive Blue 19). A reactive dye composition characterized by: 2 Reactive Blue 19 as a dye component from 1 to 1
99 parts by weight and formula as free acid form (In the formula, R is -CH ₂ CH ₂ OSO ₃ M or -CH=CH ₂
and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary amine) containing 99 to 1 part by weight of a dye (assuming 100% staining intensity for CI Reactive Blue 19). A method for dyeing cellulose fibers, characterized by using a reactive dye composition.