JPH0478667B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an antistatic agent for vinylon comprising a polyoxyalkylene carbazole adduct. (However, R is at least one selected from the group consisting of H and CH ₃ ; R' is at least one selected from the group consisting of H and CH ₃ ; however, R
When is H, R' is CH ₃ , and when R' is H, R is CH ₃ . n is 0 to 500, and
m is 0 to 500, provided that n+m=2 to 1000. The present invention relates to a vinylon antistatic agent characterized by being composed of a polyoxyalkylene carbazole adduct having the structure represented by: (Prior art and its problems) Various antistatic agents for vinylon have been reported, but generally, cationic, amphoteric, and some nonionic (polyoxyalkylene such as amines and alcohols) ethers, etc.), and some anionic (phosphate-based) surfactants. However, such surfactant-based antistatic agents for vinylon (1) are generally less effective at low humidity, and (2) are effective both in water and in oil (including plastics). (3) Target objects are limited. (4) There are few products with long-lasting antistatic properties. (5) Poor heat resistance. (6) Cationic surfactants are irritating, sensitizing, and It has drawbacks such as toxicity. (Means for Solving the Problems) The present inventors have conducted various studies to overcome the drawbacks of conventional antistatic agents for vinylon surfactants. By adding alkylene oxides to this, it is formally known as a nonionic surfactant.
It was discovered that by using it, it not only has practical advantages such as low irritation, low toxicity, and stability, but also has an excellent antistatic effect on vinylon.
The present invention was achieved based on this knowledge. The present invention is based on the general formula (1) (However, R is at least one selected from the group consisting of H and CH ₃ ; R' is at least one selected from the group consisting of H and CH ₃ ; however, R
When is H, R' is CH ₃ , and when R' is H, R is CH ₃ . n is 0 to 500, and m
The present invention relates to an antistatic agent for vinylon characterized by comprising a polyoxyalkylenecarbazole adduct having a structure represented by: 0 to 500, provided that n+m=2 to 1000. The polyoxyalkylene carbazole adduct of the present invention is produced by dissolving carbazole in an organic solvent and adding a catalytic amount of at least one catalyst selected from the group consisting of hydroxides and oxides of alkali metals or alkaline earth metals. is added and dehydrated in an inert gas atmosphere that does not substantially contain molecular oxygen by heating, reduced pressure, blowing inert gas, etc. at a temperature of 50 to 250°C under normal pressure or It is obtained by carrying out an addition reaction with alkylene oxides under pressure, neutralizing the catalyst with an acid after the reaction, removing it if necessary, and then recovering the organic solvent by means of distillation. The number of moles of alkylene oxide added in the present invention is 2 to 1000 moles on average, and the alkylene oxide is mainly ethylene oxide and/or propylene oxide. The polyoxyalkylene carbazole adduct of the present invention is a carbazole with ethylene oxide and/or
Or propylene oxide is added in blocks. The antistatic agent for vinylon of the present invention can be used for vinylon fibers and the like. The antistatic agent for vinylon of the present invention is used by coating or impregnating the surface of vinylon in the form of an aqueous solution. When making an aqueous solution, the concentration used is usually 0.1 to 3.0.
% by weight, preferably in the range 0.3-1.5% by weight. (Effects of the Invention) The characteristics of the antistatic agent for vinylon of the present invention are as follows. (1) The antistatic effect remains unchanged even at low humidity. (2) Since it has low foaming properties, there is no need to worry about problems caused by foam. (3) It is extremely convenient to use due to its excellent heat resistance and hard water resistance. (4) Excellent temporary antistatic effect. (5) Good long-lasting effects. (6) It has good compatibility with water, oil, and plastics, so it can be used in a wide range of applications. (7) Economical as it is effective at low concentrations. (8) It can be used either by external application or by spraying. (9) Validly applied to vinylon. (10) It has low toxicity and can be used safely over a wide range of areas. It is believed that the excellent antistatic effect described above can be achieved because the carbazole group is introduced into the molecular structure. Carbazole groups are electrically conductive and are used in photoreceptors, conductive polymers, etc., and because they exhibit unique electronic, charge, and optical behavior, they are thought to greatly contribute to antistatic performance. . (Examples) Next, the present invention will be explained by examples, but the present invention is not limited to the scope of the examples. The raw materials used in the examples have the following general formula (1) It is a polyoxyalkylene carbazole adduct having the structure represented by the formula, where n, m, R, and R' are respectively shown in the description of the examples. Example 1 83.6 g (0.5 mol) of carbazole with a purity of 99%, 0.95 g of potassium hydroxide, and 334.4 g of xylene were placed in a stainless steel autoclave, the atmosphere was replaced with nitrogen gas, the initial pressure was 1 Kg/cm ² , and the temperature was 147°C. 66.1g (1.5mol) of ethylene oxide in 2.5 hours
Added. During this time, the reaction temperature was maintained at 145-150°C. Lower the temperature after 1 hour of aging and adjust the pH to 6.5 with acetic acid.
After neutralization, heat at 120℃20mmHg while breathing nitrogen.
xylene was recovered. (Theoretical value of 3 moles, OH value = 187.7) The liquid carbazole ethylene oxide adduct thus obtained had a hydroxyl value of 190, and the number of moles of ethylene oxide added was 2.9 moles on average. Using the obtained raw material 1 (n=3, m=0, R=H), the surface resistivity (Ω) was measured at relative humidity of 27% and 60%. The results were as shown in Table 1. Test method: A 10 x 10 cm piece of vinylon cloth for dyeing (manufactured by Shirozome Co., Ltd.) was desized and deoiled with carbon tetrachloride, then immersed for 3 minutes in 100ml of a 1% aqueous solution of the above raw materials, and then thoroughly After being left at ℃ for 5 hours, it was dried overnight in a desiccator at room temperature under reduced pressure, and then measured using a super insulation resistance tester (manufactured by Yokogawa Huretspat Card Co., Ltd.) to measure the surface resistivity (Ω) at 23℃. was measured. Example 2 83.6 g (0.5 mol) of carbazole with a purity of 99%, 0.95 g of potassium hydroxide, and 334.4 g of xylene were placed in a stainless steel autoclave, the atmosphere was replaced with nitrogen gas, the initial pressure was 1 Kg/cm ² , and the temperature was 147°C. Then, 154.2 g (3.5 mol) of ethylene oxide was added over 2.5 hours. During this time, the reaction temperature was maintained at 145-150°C. After 1 hour of aging, lower the temperature and adjust the pH with acetic acid.
After neutralizing to 6.5, incubate at 120℃ for 20 minutes while breathing nitrogen.
Xylene was collected at mmHg. (7 mole theoretical value OH value = 118.1) The liquid carbazole ethylene oxide adduct thus obtained had a hydroxyl value of 119, and the number of moles of ethylene oxide added was 6.9 moles on average. Using the obtained raw material 2 (n=7, m=0, R=H), the relative humidity was adjusted to 27% and the relative humidity was adjusted in the same manner as in Example 1.
The surface resistivity (Ω) was measured at 60%. The results were as shown in Table 1. Comparative Example 1 Surface resistivity (Ω) was measured at relative humidity of 27% and 60% using water in the same manner as in Example 1. The results were as shown in Table 1. Comparative Example 2 Commercially available nonionic surfactant [Sanyo Chemical Industries, Ltd.]
Example 1 using product name: Sunstat 2012-A]
Similarly, surface resistivity (Ω) was measured at relative humidity of 27% and 60%. The results were as shown in Table 1.

[Table] Example 3 A 0.1% by weight aqueous solution of the raw material 2 obtained in Example 2 was prepared, and the superfoam strength was measured by the JISK-3362 (1978) Ross Miles method. The results were as shown in Table 2. Comparative Example 3 JISK-3362 using 7 mole ethylene oxide adduct of linear secondary alcohol having 12 to 14 carbon atoms
(1978) measured the superfoam force using the Ross Miles method. The results were as shown in Table 2.

[Table] Example 4 Using the raw material 1 obtained in Example 1, the thermal decomposition loss rate in air was measured by thermobalance gravimetry. The results were as shown in Table 4. Analysis conditions Sample 17 mg Heating rate 10°C/min Air flow rate 30 ml/min Comparative example 4 Using a 3 mole ethylene oxide adduct of a linear secondary alcohol with 12 to 14 carbon atoms, it was measured in air by thermobalance gravimetry. The pyrolysis loss rate was measured. The results were as shown in Table 4. Analysis conditions Sample 17mg Heating rate 10℃/min Air flow rate 30ml/min

【table】 [Brief explanation of drawings]

FIG. 1 is a diagram showing changes in antistatic ability of an antistatic agent with respect to changes in humidity.

Claims (1)

[Claims] 1 General formula (1) (However, R is at least one selected from the group consisting of H and CH ₃ ; R' is at least one selected from the group consisting of H and CH ₃ ; however, R
When is H, R' is CH ₃ , and when R' is H, R is CH ₃ . n is 0 to 500, and m
is 0 to 500, provided that n+m is 2 to 1000.