JPH0316392B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention relates to a blended dye for polyester fibers which dyes polyester fibers in a rubine color excellent in various fastnesses, particularly wet fastnesses, and has good dyeability. (Prior Art) Recently, polyester cloth has been subjected to various post-processing such as water-repellent finishing, hand-improving finishing, antistatic finishing, sanitary finishing, etc. Since the above-mentioned post-processing involves high-temperature treatment, dyes bleed from already dyed fibers, etc., resulting in a problem that various fastnesses, especially wet fastnesses, of the fibers, etc. are reduced. On the other hand, with the recent rationalization of dyeing methods, particularly from the viewpoint of saving capital and energy, lowering the dye bath ratio (for example, lowering the ratio of dyeing material to dyeing solution from 1:30 to 1:10), Reducing the proportion of dispersant used (e.g., reducing the dye cake to dispersant ratio from 1:3 to 1:1) and further increasing the dyeing conditions to higher temperatures for a short time (e.g., from 130°C for 1 hour to 135°C)
x 0.5 hours), etc.
Dyeing conditions are becoming increasingly harsh. Moreover, all of these harsher dyeing conditions have a disadvantageous effect on the dispersion stability of the dye, so even if the disperse dye has relatively good dispersion stability using conventional dyeing methods, However, the recent streamlined dyeing methods often result in poor dispersion stability. As a result, the dye that has deteriorated in dispersion and aggregated adheres to the surface of the dyed object in the form of an excessive residue, reducing the abrasion fastness of the dyed object.In addition, in the case of a dyed object that has many layers, the outer layer and inner layer The dyeing density varies in different parts, making it impossible to obtain a dyed product with uniform density. (Problems to be Solved by the Invention) As a red dye to overcome these problems, the present applicant has proposed the following structural formula [] having a specific crystal modification. We proposed a monoazo dye shown by (Special request 1986
(Refer to No. 298484) This monoazo dye can be dyed well even under harsh dyeing conditions, has excellent abrasion fastness and light fastness, and the dyed material can be subjected to post-processing such as polyurethane processing and silicone processing. It is a red dye with excellent wet fastness after being applied. However, dyes are generally not only used singly but also in various combinations for color matching.
When this red dye is combined with other dyes,
The excellent effects of the above dyes may not be exhibited. In other words, even if the above dyes are excellent,
Depending on the dye that is blended, its superiority cannot be utilized. This tendency is particularly strong when blending with orange dyes. (Means for Solving the Problems) In view of the above circumstances, the present inventors have developed a polyester fiber that can exhibit high wet fastness, abrasion fastness, and light fastness even when blended with the above monoazo dye. As a result of various studies on compounded dyes for similar use,
Only when mixed with certain monoazo dyes,
The present invention was completed after discovering that the object of the present invention can be achieved. That is, the present invention provides the following general formula [] and one very strong peak at a diffraction angle (2θ) of about 14.2°, one strong peak at about 24.5°,
Furthermore, a monoazo dye having a crystal modification characterized by an X-ray diffraction pattern (CuKα) showing four weak peaks at approximately 16.9°, 23.6°, 25.3° and 26.8° was added at 10 to 90°.
Weight% and general formula below [] (In the formula, X and Y each independently represent a hydrogen atom or a chlorine atom.)
The gist is a blended dye for polyester fibers containing ~10% by weight. The present invention will be explained in detail below. In the present invention, it is essential to blend the monoazo dye of the above structural formula [] with the monoazo dye of the above general formula [], and the blending ratio of both is 10:90 to 90: 10 (weight ratio), preferably
The ratio is 50:50 to 90:10 (weight ratio). The monoazo dye of the above structural formula [] used in the present invention has one very strong peak at a diffraction angle (2θ) of about 14.2°, one strong peak at about 24.5°, and
It has a crystal modification (hereinafter referred to as "α-type crystal") characterized by an X-ray diffraction pattern (CuKα) showing four weak peaks at approximately 16.9°, 23.6°, 25.3°, and 26.8°. In cases other than this crystal type,
Unable to exhibit good dyeing properties under severe dyeing conditions. The monoazo dye of the α-type crystal is, for example,
Structural formula below [] The compound represented by is diazotized by a conventional method, and then the following formula [] A monoazo compound of the above structural formula [] is synthesized by coupling with the compound shown in an aqueous medium at a temperature of 0 to 10°C. The cake of the monoazo compound obtained by this synthesis is a crystal modification that is almost amorphous (hereinafter referred to as "β-type crystal"). In contrast, in the present invention, this cake is further treated under specific conditions to form α-type crystals. In this case, a treatment method under specific conditions includes dispersing a cake of β-type crystals in, for example, an aqueous medium, and optionally dispersing sulfite parfum whose main component is a formaldehyde condensate of naphthalene sulfonic acid and sodium lignin sulfonate. In the presence of a dispersant such as a waste liquid concentrate, 60 to 130℃, preferably 80 to
A method of stirring at a temperature of 100°C for 0.5 to 30 hours, preferably 1 to 10 hours, or alcohols such as methanol, ethanol or butanol, ethers such as dioxane, ethylene glycol,
Dispersed in an organic solvent such as glycol ether, 15
A method of stirring at a temperature of ~100°C, preferably 20~80°C for about 0.5 to 10 hours is adopted. Alternatively, it is also possible to directly obtain a monoazo compound in the form of α-type crystal by dissolving the compound of the formula [] in an organic solvent such as methanol and coupling the compound with the compound of the formula [] in the organic solvent. can. The α-type crystal and β-type crystal in the monoazo compound represented by the above structural formula [] will be explained with reference to the drawings. Figures 1 and 2 are X-ray diffraction diagrams recorded using a proportionate counter to record the diffraction state of CuKα rays in powder X-ray diffraction method, where the horizontal axis is the diffraction angle (2θ) and the vertical axis is the diffraction angle. Indicates the strength of each. Figure 1 shows the new crystal form α of the present invention.
type crystal, especially the diffraction angle (2θ) of approx.
It has one very strong peak at 14.2°, one strong peak at about 24.5°, and four weak peaks at about 16.9°, 23.6°, 25.8°, and 26.8°. FIG. 2 shows a conventional β-type crystal, which is clearly different from the α-type crystal shown in FIG. The diffraction angles determined by X-ray diffraction always match with an error of about ±0.1° if they are of the same crystal type, and these drawings clearly show the difference in crystal modification. Due to this difference in crystal type, the behavior of the monoazo compound during dyeing differs, and in the case of the present invention, good dyeing can be achieved even if dyeing methods are employed at high temperatures and under harsh conditions. . On the other hand, although there are several types of crystal forms of the monoazo dye of the general formula [], good results can be obtained with any of the crystal forms of this dye. Therefore, the crystal type of this dye is not particularly limited. For example, the compound represented by the general formula [] is the following structural formula [] (In the formula, X and Y are the same as defined above.) A compound represented by the following formula is diazotized by a conventional method, and then the following formula [] It can be easily produced by coupling it with the compound shown below. Fibers that can be dyed with the azo dye mixture of the present invention include polyester fibers made of polyethylene terephthalate, polycondensates of terephthalic acid and 1,4-bis-(hydroxymethyl)cyclohexane, or fibers such as cotton, silk, and wool. Examples include blended products and blended woven products of natural fibers and the above-mentioned polyester fibers. In order to dye polyester fibers using the dye of the present invention, since the dyes represented by the general formulas [] and [] are insoluble or sparingly soluble in water, naphthalenesulfonic acid is used as a dispersant in a conventional manner. Dyeing or printing may be carried out by preparing a dye bath or printing paste in which a condensate with formaldehyde, a higher alcohol sulfate, a higher alkylbenzene sulfonate, etc. are dispersed in an aqueous medium. For example, in the case of dip dyeing, polyester fibers or their blends can be dyed with excellent fastness by applying ordinary dyeing methods such as high temperature dyeing, carrier dyeing, and thermosol dyeing. In this case, even better results can be obtained if an acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath. Furthermore, in the case of the blended dye of the present invention, it is possible to exhibit excellent effects even under severe dyeing conditions. The effect can be particularly fully exhibited when applied to dyeing conditions where the amount of dyeing solution is 15 times or less (the amount of dyeing liquid relative to the object to be dyed), and furthermore, the dispersant ratio (the amount of dispersant relative to the dye cake) is 1 times or less. (Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples. [Example of production of dye crystals of general formula []] 5.4 g of N-ethyl-N-benzoyloxyethylaniline was dispersed in 300 ml of 2% sulfuric acid at 0 to 3°C to prepare a coupling component solution. 6-Nitro-2-aminobenzothiazole 5.1
Dissolve g in 60 ml of phosphoric acid/acetic acid = 1/1 solution,
% nitrosyl sulfuric acid at 0° C. for 2 hours to prepare a diazo solution. This diazo solution was dropped into the coupling component solution for 3 hours, and then
After the reaction at °C, the precipitated crystals were filtered off, washed with water and dried to obtain 9.6 g of brown crystals. When the monoazo dye powder obtained in this reaction was analyzed by X-ray diffraction, it was found that
It is a β-type crystal, and its X-ray diffraction pattern is shown in Figure 2. Next, the obtained β-type crystals were dispersed in 20 times the amount of water and stirred at 90 to 95° C. for 3 hours to effect crystal transition. After completion of the crystal transition, the crystals were filtered and dried, and the resulting crystals were analyzed by X-ray diffraction, and were found to be α-type crystals as shown in the X-ray diffraction pattern shown in FIG. [Example of production of dye crystals of general formula []] 5.8 g of N-cyanoethyl-N-benzoyloxyethylaniline was dispersed in 300 ml of 2% sulfuric acid at 0 to 3°C to prepare a coupling component solution. 2.8 g of p-nitroaniline was diazotized using nitrosyl sulfuric acid in 10 ml of sulfuric acid in a conventional manner, and the diazotization was carried out at 0° C. for 2 hours to prepare a diazo solution.
This diazo solution was dropped into the coupling component solution, and after reacting at 0°C for 3 hours, the precipitated crystals were filtered off.
After washing with water and drying, 8.4 g of orange crystals represented by the following structural formula were obtained. The λmax (in acetone) of this product is 455n
It was m. Example 1 0.25% of each of the monoazo compounds obtained in the above production examples
A dyeing bath was prepared by dispersing a total of 0.5 g in water 1 containing 0.25 g of naphthalene sulfonic acid-formaldehyde condensate and 0.25 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
When 100 g of the dye was immersed and dyed at 135° C. for 30 minutes, soaping, washing with water, and drying were performed, the dispersibility of the dye was good, and the dyed fabric was uniformly dyed. The dyed fabric obtained also had good bluish-red color fastness to light, grade 6, and color fastness to abrasion, grade 5. Further, the wet fastness after polyurethane processing is shown in Table 1. In addition, when a similar dyeing test was carried out using the β-type crystal monoazo compound in the process of production in the above production example, partial aggregation of the dye occurred in the dye bath, resulting in an unevenly dyed fabric and poor abrasion resistance and fastness. The degree was significantly inferior to grade 1. Example 2 In Example 1, the naphthalene sulfonic acid-formaldehyde condensate and higher alcohol sulfuric ester were each tripled to 0.75 g, the water was tripled to 3, and the dyeing temperature was changed to 130°C for 60 minutes to produce a slightly milder dye. As a result of the dyeing method, the α-type crystal of the present invention [] can be dyed as well as in Example 1, and the obtained dyed fabric has a light fastness of class 6 and a rub fastness of class 5. It was good and warm. On the contrary,
When the β-type crystal of [ ] was used, a slight improvement was observed compared to Example 1, but unevenly dyed fabric was still obtained, and the abrasion fastness was grade 3. Example 3 A mixture of 0.35 g of α-type crystal dye of general formula [] obtained in the above production example and 0.15 g of dye of general formula [] was mixed with 0.5 g of naphthalene sulfonic acid-formaldehyde condensate, and a paint shaker was added. The dye was pulverized to obtain a finely divided dye. The mixture was thoroughly mixed with the base paste having the composition shown below to obtain 100 g of colored paste. Composition of base glue Carboxymethyl cellulose glue 30g Tartaric acid 0.2g Aromatic carrier (Sunfloren SN, manufactured by NICCA CHEMICAL CO., LTD., trade name) 0.3g Water 68.5g Total 99.0g This colored paste was printed on the polyester fiber. Stamped, 100
After intermediate drying at 170°C, the color was developed by holding in superheated steam at 170°C for 7 minutes, followed by soaping, washing with water, and drying. A polyester cloth printed in a good red color was obtained. Comparative Examples 1 to 7 In the method of Example 1, the type of dye to be blended was changed to CI-Disperse R-, which is a typical commercially available dye.
145 or the same O-31 and dyed in the same manner, and the wet fastness after polyurethane processing was measured, and the results shown in Table 1 were obtained.

【table】

[Fastness evaluation method after polyurethane processing]

(1) Polyurethane processing method After soaking in a 1% solution of Hydran F-24K,
Cure for 2 minutes at 160℃. (2) Washing fastness A multi-fiber was attached to a dyed cloth treated with polyurethane, and a washing test was conducted according to AATCC washing method A, and the contamination of the nylon fibers of the multi-fiber was determined on a gray scale. (3) Alkaline sweat fastness JIS L-
Tests were conducted in accordance with the 0848A method, except that nylon cloth and silk cloth were used as the attached cloths, and the degree of contamination of the silk cloth was determined on a gray scale. (4) Water fastness JIS L-
The test was conducted according to the 0846A method except that a silk cloth was attached instead of the nylon cloth, and the degree of contamination of the silk cloth was determined on a gray scale. Example 4 α of the general formula [ ] according to the method of Example 1
Polyester fabrics were dyed using various blended dyes of monoazo dyes consisting of type crystals and monoazo dyes of the general formula [] shown in Table 2 to obtain dyed fabrics with the colors shown in Table 2. We measured the wet fastness (alkali sweat fastness) of the obtained dyed fabric after polyurethane processing.
The results shown in Table 2 were obtained.

【table】

[Table] (Effects of the invention) As described above, the combination of dyes specified in the present invention produces orange to bluish reds, especially orange colors, with extremely good wet fastness after post-processing, which is particularly in demand in the market. A dyed fabric with a rubine tone is obtained. These primarily meet the need for dyes with good wet fastness for use in the sports clothing sector. On the other hand, none of the combinations of typical commercially available dyes or combinations of dyes in which typical commercially available dyes are one of the blending components have satisfactory post-processing resistance, making it impossible to meet market demands. In addition, as mentioned in Comparative Example 7, when the β-type crystal of the monoazo compound of the general formula () is used, even in combination with the monoazo compound (), dispersion of the dye solution deteriorates, resulting in failure. Only level dyed fabrics could be obtained, and the resistance to subsequent processing was poor.As described above, dye mixtures that are fully suitable for the rational dyeing method of the present invention and have good resistance to post-processing are extremely effective. It is useful.

[Brief explanation of the drawing]

Figure 1 is an X-ray diffraction diagram of an α-type crystal of a monoazo compound of the general formula [] obtained in a production example of the present invention, and Figure 2 is an X-ray diffraction diagram of a β-type crystal. The axis represents the diffraction angle (2θ), and the vertical axis represents the diffraction intensity.

Claims (1)

[Claims] 1. The following general formula [] and one very strong peak at a diffraction angle (2θ) of about 14.2°, one strong peak at about 24.5°,
Furthermore, a monoazo dye having a crystal modification characterized by an X-ray diffraction pattern (CuKα) showing four weak peaks at approximately 16.9°, 23.6°, 25.3° and 26.8° was added at 10 to 90°.
Weight% and general formula below [] (In the formula, X and Y each independently represent a hydrogen atom or a chlorine atom.)
A blended dye for polyester fibers containing ~10% by weight.