JPS642632B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to disperse dye compositions.
More specifically, the present invention aims to commercialize disperse dyes by atomizing a dye cake in an aqueous medium containing a specific surfactant to form a uniform dispersion liquid, which exhibits an excellent atomization promoting effect. It is a composition.
Furthermore, the present invention relates to a disperse dye composition containing an anionic surfactant that exhibits excellent dispersibility in a dye bath during high-temperature, high-pressure dyeing, and does not cause specks due to poor dispersion during continuous dyeing or printing. Normally, the commercialization of disperse dyes involves converting the dye cake into β-
A commonly used method is to micronize the dye to a particle size of approximately 1μ in an aqueous medium containing a surfactant such as sodium salt of a formaldehyde condensate of naphthalene sulfonic acid (hereinafter abbreviated as SNF), and then form a uniformly dispersed liquid. It is. However, this method requires a large amount of surfactant to promote atomization or compensate for insufficient dispersion effects, and has the disadvantage that it takes a long time to form particles. Furthermore, when dyeing using the disperse dye obtained in this way, this SNF
Although it exhibits good dispersibility at relatively low water temperatures of 60°C or lower, it still has the disadvantage that its dispersibility decreases at relatively high temperatures of 60°C or higher. As one method to overcome this drawback, in addition to the above-mentioned SNF, it is usually obtained by condensing 2-naphthol-6-sulfonic acid with cresolsulfonic acid and formaldehyde, which has excellent atomization promotion ability and high-temperature dispersion ability. The combined use of surfactants (hereinafter abbreviated as SNF) has been carried out. However, this SNCF has a high foaming property, which impairs workability during dye production and causes trouble during dyeing.Also, when the pH decreases, dye products may gel, and dyeing In addition, the solubilizing power of water-insoluble dyes is large,
There are drawbacks such as a reduction in the dye adhesion rate to the fibers, and even such a technique that uses SNF and SNCF in combination still cannot achieve a sufficiently satisfactory effect. Recently, in the dye industry, there has been a strong demand for surfactants that exhibit excellent atomization promotion ability during dye production and surfactants that exhibit excellent high-temperature dispersion ability during dyeing, especially high-temperature and high-pressure dyeing. The reasons for this are improved productivity by reducing the amount of surfactant used during atomization or shortening the atomization time, resource conservation,
This is because they expect energy savings. Furthermore,
With the development of dyeing methods using disperse dyes, there has been a shift from large bath ratio/long-time dyeing to small bath ratio/short time dyeing. Small bath ratio - for short-time dyeing, increase in dye concentration of the dye solution;
Dispersion failure is becoming more likely to occur in dye baths due to high-speed liquid flow and rapid temperature rise due to the liquid circulation method instead of the cloth circulation method, and the situation is such that dyeing troubles are likely to occur due to this. If a surfactant with high-temperature dispersion ability appears, it will be possible for the dye manufacturing industry to increase the concentration of dye products and reduce transportation and storage costs. It is expected that dyes will be used more effectively by reducing load and improving dyeing efficiency. As a result of intensive research in order to obtain a dye composition as described above, the present inventors found that the dye composition is an aliphatic aldehyde condensate salt of partially sulfonated creosote oil, and the number of sulfone groups is 2.7 to 3.4 mmol/g. A disperse dye composition in which anionic surfactants are well suited for the above purpose, and when used in the production of disperse dyes, exhibit extremely excellent ability to promote atomization, and furthermore, when incorporated into disperse dyes, exhibit extremely high temperature dispersion ability. The inventors have discovered that a product can be obtained, and have arrived at the present invention. The anionic surfactant, which is the active ingredient of the present invention, can be obtained by condensing a partially sulfonated product of creosote oil with an aliphatic aldehyde.
It can be easily produced by adding creosote oil to a product and then condensing it with an aliphatic aldehyde. Furthermore, it can also be produced by condensing creosote oil with an aliphatic aldehyde under acidic sulfuric acid, followed by partial sulfonation. The creosote oil used here is specified in the Japanese Industrial Standard JIS K-2439 (1978), and is a mixture of various compounds obtained from coal carbonization tar, and is a mixture of various compounds obtained from coal carbonized tar. It is classified into three types depending on the amount: No. 1, No. 2, and No. 3, and all of them can be used. The main components of creosote oil are naphthalene, methylnaphthalene, dimethylnaphthalene, diphenyl, acenaphthene, fluorene, anthracene, triphenyl, carbazole, pyrene, chrysene, and pitches. In carrying out the present invention, the above creosote oil may be used as it is, or its fractionated components may be used. Therefore, the concept of creosote oil includes creosote oil and fractionated fractions of creosote oil. Therefore, as shown in the examples, naphthalene can also be blended with creosote oil. However, in the present invention, it is important that among the various components that make up creosote oil, it contains an aromatic hydrocarbon compound having three or more membered rings such as anthracene.
Since the dye composition characterized by the product of the present invention cannot be obtained using only an aromatic hydrocarbon compound having two or fewer members such as benzene or naphthalene, the proportion of creosote oil is 50% by weight or more, preferably 70% by weight. It is important to do the above. Further, specific examples of the aliphatic aldehyde include lower aliphatic aldehydes such as formaldehyde and acetaldehyde, and among them, it is preferable to use formaldehyde. An example of the production of the anionic surfactant according to the present invention is as follows. Creosote oil or a fractionated fraction of creosote oil is first sulfonated with sulfuric acid to obtain a sulfonated product or a partially sulfonated product of the raw material. Next, after adding a certain amount of creosote oil or a fractionated fraction of creosote oil, 0.5 to 1.0 times the mole of aliphatic aldehyde based on the total amount of charge was added, and the mixture was heated under acidic sulfuric acid.
The condensation reaction is carried out at a temperature of around 100℃. The resulting condensation reaction product is neutralized with calcium carbonate or calcium hydroxide, and after separating the precipitated calcium sulfate, sodium carbonate or ammonium carbonate is added to the liquid to make the sodium salt or ammonium salt (liming soda). Alternatively, the condensation reaction product is directly neutralized with sodium carbonate, sodium hydroxide, or ammonium carbonate to form the condensate into a sodium salt or ammonium salt, and the product is then concentrated or concentrated to dryness. It is important that the anionic surfactant according to the present invention has a number of sulfone groups, which is a barometer of the number of sulfone groups contained therein, in the range of 2.7 to 3.4 mmol/g. If the number of sulfone groups is larger than the above range, the ability to promote atomization and the ability to disperse at high temperatures will be unfavorable. On the other hand, if the number of sulfone groups is smaller than the above range, the solubility in water will be low, which is not preferred in practice. The number of sulfone groups means the number of moles of bonded sulfone groups contained per unit weight of a sample, and is expressed by the following formula. Number of sulfone groups (mmol/gram) = Number of moles of bonded sulfone groups/molecular weight of reaction product x 1000 The amount of bonded sulfone groups is the value obtained by subtracting the sulfone groups of sodium sulfate from the amount of all sulfone groups. . The anionic surfactant according to the present invention exhibits an excellent ability to promote atomization of a dye cake during the production of disperse dyes, and the resulting dispersion exhibits extremely good dispersion stability. Furthermore, it exhibits excellent dispersion ability even at relatively high temperatures such as in high-temperature and high-pressure dyeing. Furthermore, because the pH dependence is small, gelation of disperse dye products does not occur even if the pH decreases, and the decrease in dispersion in the dye bath is extremely small. In addition, since the foaming property is low, there is little effect on workability during dye production, and troubles caused by bubbles during dyeing are extremely small. With the advent of such excellent surfactants, it has been possible to reduce the amount of surfactants used in dye production, improve productivity by shortening atomization time, save resources and energy, and reduce the amount of surfactants in dye products. It is possible to obtain a disperse dye composition with high industrial value, such as miniaturization of dye products, reduction in transportation and storage costs, reduction in dyeing waste load, and effective use of dyes by improving dyeing rate. In the present invention, the anionic surfactant used in the disperse dye composition is limited to aliphatic aldehyde condensate salts of partially sulfonated creosote oil, which have a sulfone group number of 2.7 to 3.4 mmol/g. It is distinctive in its use. By limiting the number of sulfone groups in this way, it has become possible to significantly improve the high-temperature dispersibility of the dye, which was previously impossible, and it has become possible to significantly increase the ability to promote atomization. It is. As shown in the Examples, this effect cannot be achieved by known dispersants for dyes. For example, in Example 2, in addition to the anionic surfactant according to the present invention, a known formaldehyde condensate of naphthalene sulfonic acid (SNF),
Regarding the known formaldehyde condensate of creosote oil sulfonic acid (SCF) and the known condensate of 2-naphthol-6-sulfonic acid, cresol sulfonic acid, and formaldehyde (SNCF),
The results of high-temperature dispersibility evaluation are shown, and as can be seen in Table 4, at the high temperatures shown in Example 2, conventionally known dye dispersants gel or even when they do not gel. Its dispersibility is extremely low. This shows that only the anionic surfactant according to the present invention can exhibit high-temperature dispersibility and can be applied to high-temperature and high-pressure dyeing techniques. Furthermore, in addition to the effect that the anionic surfactant according to the present invention exhibits a remarkable effect on high-temperature dispersion performance, it also exhibits another effect that it has a large ability to promote atomization. In Example 1, the ability of the anionic surfactant according to the present invention to promote atomization was evaluated together with known dispersants for dyeing, but the anionic surfactant according to the present invention was more effective than any of the known dispersants for dyes. The agent has a large ability to promote fine particles, and is superior to known agents in terms of the performance required of general dye dispersants. Although the amount of the anionic surfactant used in the present invention is not particularly limited, it is appropriate that the weight ratio of the anionic surfactant to the dye is 1:0.5 to 5. Further, the disperse dye composition of the present invention has the above-mentioned SNF,
A surfactant such as SNCF or lignin sulfonate may also be used in combination. The present invention will be explained in more detail below with reference to production examples and examples of anionic surfactants to be included in the dye composition of the present invention, but the present invention is not limited by the following unless it exceeds the gist thereof. do not have.
In addition, all "parts" in the examples indicate parts by weight. Production example 1 164 parts of creosote oil was heated to 80°C, 157 parts of concentrated sulfuric acid was added with stirring at 80 to 100°C for 1 hour, and then heated to 110 to 100°C while being dehydrated under reduced pressure of 100 to 200 mmHg.
The creosote oil was sulfonated by reaction at 120°C for 5 hours. Next, add 100 parts of water to this, raise the temperature to 90℃, and add 43 parts of 37% formalin to 90~
Addition takes 3 hours while maintaining the temperature at 100°C.
The condensation reaction was carried out at 105°C for 12 hours. Next, add 200 parts of water to this, and add 44 parts of calcium hydroxide at room temperature.
After adding 25 parts of calcium carbonate and stirring for about 30 minutes, the produced calcium sulfate was separated. Add 64 parts of sodium carbonate to this solution to adjust the pH to 8 to 10, stir for about 30 minutes, separate the produced calcium carbonate (hereinafter the process after formalin condensation is referred to as liming sodation), and then concentrate the solution. The mixture was dried to obtain 261 parts of a product having 3.34 sulfonic groups. Production example 2 164 parts of creosote oil was heated to 80℃, and concentrated sulfuric acid was added.
After adding 127 parts at 80~100℃ for 1 hour, 100~
5 at 110-120℃ while dehydrating under 200mmHg vacuum.
Creosote oil was sulfonated by a time reaction. Next, 25 parts of creosote oil and 100 parts of water were added to this, the temperature was raised to 90°C, and 37% formalin 49
100-105 parts was added over 2 hours at 90-100°C.
The condensation reaction was carried out at ℃ for 15 hours. Then add water to this
Add 250 parts, perform liming sodation in the same manner as in Production Example 1, concentrate the liquid to dryness,
275 parts of a product having 3.21 sulfone groups was obtained. Production example 3 164 parts of creosote oil was heated to 80℃, and concentrated sulfuric acid was added.
After adding 127 parts at 80~100℃ for 1 hour, 100~
7 at 120-130℃ while dehydrating under 200mmHg vacuum.
Sulfonation of creosote oil was carried out by a time reaction. Then add 38 parts of naphthalene and water to this.
Add 150 parts and raise the temperature to 90℃, add 80 parts of 37% formalin at 90 to 100℃ for 4 hours, and raise the temperature to 100 to 105℃.
The condensation reaction was carried out for 20 hours. Then add water to this
Add 300 parts, perform liming sodation in the same manner as in Production Example 1, concentrate the liquid to dryness,
284 parts of a product having 3.13 sulfone groups was obtained. Production example 4 Distillate up to 250℃ obtained by fractional distillation of creosote oil
Heat 143 parts to 80℃ and 108 parts of concentrated sulfuric acid to 100-120℃.
After the addition, which took 1 hour, the reaction was carried out at 120 to 130°C for 7 hours while dehydrating under reduced pressure of 100 to 200 mmHg to sulfonate the fraction up to 250°C. Next, add 26 parts of naphthalene and 150 parts of water to 90
The temperature was raised to .degree. C., 40 parts of 37% formalin was added at 90 to 100.degree. C. over 2 hours, and a condensation reaction was carried out at 100 to 105.degree. C. for 12 hours. Next, 200 parts of water was added thereto, liming sodation was carried out in the same manner as in Production Example 1, and the liquid was concentrated to dryness to obtain 261 parts of a product having 3.38 sulfone groups. Production Example 5 Contrary to Production Example 4, 182 parts of the distillate at 250°C or higher was mixed with 80
After adding 108 parts of concentrated sulfuric acid at 90-110°C for 1 hour, the reaction was carried out at 110-120°C for 5 hours while dehydrating under a reduced pressure of 100-200 mmHg. sulfonation was carried out. Next, 26 parts of naphthalene and 150 parts of water were added to this, and the temperature was raised to 90°C.
40 parts of 37% formalin was added over 2 hours at 90-100°C, and a condensation reaction was carried out at 100-105°C for 12 hours. Next, 200 parts of water was added thereto, liming was carried out in the same manner as in Production Example 1, and the liquid was concentrated to dryness to obtain 297 parts of a product having 2.90 sulfone groups. Production example 6 (comparative product) 164 parts of creosote oil was heated to 80℃, and concentrated sulfuric acid
After adding 98 parts at 80-90℃ for 1 hour, 100-200 parts
The creosote oil was sulfonated by carrying out a reaction at 120 to 130° C. for 7 hours while dehydrating under a reduced pressure of mmHg. Next, 66 parts of creosote oil and 100 parts of water were added to this, the temperature was raised to 90°C, and 37% formalin 49
100-105 parts was added over 2 hours at 90-100°C.
The condensation reaction was carried out at ℃ for 15 hours. Since this product had poor solubility in water, liming sodation was not performed, but it was directly neutralized with a 20% aqueous sodium hydroxide solution, and then concentrated to dryness to obtain 307 g of a product. The number of sulfone groups in this product was 2.51. Note that this product had poor solubility in water and was unsuitable as a dye composition. Example 1 A disperse dye cake was atomized using the surfactant produced in the above production example in the required amount below, and the atomization state of the resulting dispersion was examined to determine the ability to promote atomization. Mixing conditions

[Table] Atomization conditions Sand grinder manufactured by Gokarashi Seisakusho 1500 rpm x 5 to 10 hours After atomization as described above, the Otsutawa sand was separated to obtain a dye dispersion. Next, the ability to promote atomization was determined using the dye dispersion liquid by the following method. 1-1 Centrifugation method Take 20 g of the above dye dispersion, centrifuge at 3000 rpm for 10 minutes, then gently remove the supernatant, bone dry the sediment, weigh it, and calculate the sedimentation rate using the following formula. The ability to promote atomization was determined. Sedimentation rate = Sedimentation amount/solid content of dye dispersion x 100 For comparison, results when other surfactants were used alone are also shown. The results were as shown in Table 1.

[Table] 1-2 Paper spreading method Pour a specified amount of 0.5% dye solution prepared using the dye dispersion into the center of the paper sandwiched between specified glass plates, check the degree of spreading and residual amount, and atomize. The promoting ability was determined. (a) For Toyo Paper No. 5A, 2 sheets of paper, 2 glass plates (15 x 15 x 0.5 cm)
0.8ml of 0.5% dye solution (b) For Toyo Paper No. 5C, 1 sheet of paper, 2 glass plates (20 x 20 x 1 cm),
0.5ml of 0.5% dye solution The degree of spreading is determined by the following formula, and the larger the value, the better the ability to promote atomization. Spreading degree (%) = Spreading distance of dye / Spreading distance of water and dye × 100 In addition, the residual degree indicates the remaining percentage of coarse dye particles at the injection point of the dye solution, and the higher the value is on a 5-level evaluation, the better. be. The results of atomization performed in the above manner are shown in Tables 2 and 3. In addition, Table 2 shows CI.
DisperseBlue202: Surfactant = 100:100, atomization time 10 hours, results are shown in Table 3 CI.
The results show that DisperseRed60:surfactant=100:100 and atomization time was 7 hours.

【table】

[Table] As is clear from Tables 1, 2, and 3 above, in the atomization of disperse dye cake, the dye crude product of the present invention produces a small amount of particles compared to the case of using SNF or similar products of the present invention. Shows excellent ability to promote atomization with a small amount of surfactant and in a short period of time. Example 2 The atomized dye dispersion obtained in Example 1 was adjusted to pH 7 to 8 with a dilute solution of sulfuric acid or sodium hydroxide, and then heat treated at 70°C for 4 hours to disperse the dye in a relatively concentrated system. The thermal stability of the liquid was investigated. The evaluation was made by determining the state change due to heat or PH change and the agglomeration state of dye particles using the paper development method used in Example 1. The results were as shown in Table 4.
In addition, Table 4 shows CI.DisperseBlue202: Surfactant =
This shows the results of the dye dispersion obtained by atomization for 10 hours at a mixing ratio of 100:100, and the paper in Table 2
Changes in stability can be seen by comparing with the results of No. 5A.

[Table] As is clear from Table 4 above, the dye composition of the present invention, in a relatively concentrated dye dispersion,
Shows superior dispersion stability compared to when SNF or other surfactants are used. Example 3 Based on Example 1, various dye dispersions were prepared by atomization at the following blending ratios.

[Table] Next, the above dye dispersion liquid was dyed in the following manner, and the dispersion ability under high temperature and high pressure was examined. 3-1 High-temperature dispersibility by casing spot method Using the above dye dispersion, high-temperature dispersibility was investigated under the following dyeing conditions. Equipment High-temperature and high-pressure dyeing machine (Chuo Rikaki Seisakusho) Dyeing conditions Dye 1.5 (dye purity) 0wf Fabric to be dyed Polyester processed yarn fabric Bath ratio 1:10 PH 4.5 Temperature 110, 120, 130℃ Judgment was made on the surface of the dyed fabric The test is conducted with or without spots, and the higher the value, the better the dispersibility. The results are shown in Table 5.

[Table] 3-2 High-temperature dispersibility determined by diometer method The high-temperature dispersibility was investigated using the above dye dispersion under the following dyeing conditions. Equipment, high temperature and high pressure dyeing side coloring device (Suga Test Instruments Manufacturing Co., Ltd.) Dyeing conditions Dye 1.5% (dye purity) 0wf Object to be dyed Polyester spun yarn Packing density 0.3 g/cm ³ PH 4.5 Bath ratio 1:20 Judgment is made on the surface of the dyed object The evaluation was conducted based on the presence or absence of generated tar-like dye, and the higher the value, the better the dispersibility in a 5-level evaluation. The results are shown in Table 6.

[Table] As is clear from Tables 5 and 6 above, the dye composition of the present invention can be used under relatively severe dispersion conditions such as high-temperature and high-pressure dyeing using a surfactant such as SNF or SCF. It shows superior dispersion stability compared to the case of

Claims (1)

[Claims] 1 An aliphatic aldehyde condensate salt of partially sulfonated creosote oil, the number of sulfone groups being
A disperse dye composition characterized in that it contains 2.7 to 3.4 mmol/gram of anionic surfactant.