JPH0478665B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an antistatic agent for nylon 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 an antistatic agent for nylon, characterized by comprising a polyoxyalkylene carbazole adduct having the structure represented by: (Prior art and its problems) Various antistatic agents for nylon have been reported, but generally they are cationic, amphoteric, and some nonionic (polyoxyalkylene such as amines and alcohols). (ethers, etc.) and some anionic (phosphate-based) surfactants are used. However, such surfactant-based antistatic agents for nylon (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 inventors have conducted various studies to overcome the drawbacks of conventional surfactant antistatic agents for nylon. By adding alkylene oxides to this and using it formally as a nonionic surfactant, it not only has practical advantages such as low irritation, low toxicity, and stability, but also has excellent properties for nylon. It was discovered that it has an antistatic effect, and based on this knowledge, the present invention was achieved. 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 nylon, characterized in that it consists of a polyoxyalkylene carbazole 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, and after the reaction, neutralizing the catalyst with an acid, removing this 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 has carbazole with ethylene oxide and/or
Or propylene oxide is added in blocks. The antistatic agent for nylon of the present invention can be used for nylon fibers, nylon resin products, nylon films, and the like. The antistatic agent for nylon of the present invention can be applied to or impregnated on the surface of nylon in the form of an aqueous solution, or
It is elaborated and used. When making an aqueous solution, the concentration used is usually 0.1 to 3.0.
Weight % is preferably 0.3 to 1.5 weight %, and when kneaded into an object, it is 0.2 to 3.0 weight %, preferably 0.3 to 2.0 weight %. (Effects of the Invention) The characteristics of the antistatic agent for nylon 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) Can be used by external application, spraying, or internal kneading. (9) Validly applicable to nylon. (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. After immersing a 10 x 5 cm piece of nylon cloth (degreased with carbon tetrachloride and deoiled) for 3 minutes in 60 ml of a 1% by weight aqueous solution of the obtained raw material 1 (n = 3, m = 0, R = H), Use a sufficiently dry test cloth, rub it with a plastic rod, and apply a static electricity checker [Nippon Kapowder Co., Ltd.].
The charging voltage was measured using a 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, heat at 120℃ 20mm while inhaling nitrogen.
Xylene was recovered with Hg. (7 mole theoretical value OH value = 118.1) The liquid carbazole ethylene oxide adduct obtained in this way has a hydroxyl value of 119,
The average number of moles of ethylene oxide added was 6.9 moles. The charging voltage was measured using a 1% by weight aqueous solution of the obtained raw material 2 (n=7, m=0, R=H) according to Example 1.
It was measured in the same way. Example 3 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, 220.3 g (5.0 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, heat at 120℃ 20mm while inhaling nitrogen.
Xylene was recovered with Hg. (Theoretical value of 10 moles, OH value = 92.4) The liquid carbazole ethylene oxide adduct thus obtained had a hydroxyl value of 93.1, and the number of moles of ethylene oxide added was 9.9 moles on average. The withstand voltage measurement method using a 1% by weight aqueous solution of the obtained raw material 3 (n=10, m=0, R=H) was carried out in Example 1.
It was measured in the same way. Example 4 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. 440.5 g (10 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, heat at 120℃ 20mm while inhaling nitrogen.
Xylene was recovered with Hg. (Theoretical value of 20 moles, OH value = 53.6) The liquid carbazole ethylene oxide adduct thus obtained had a hydroxyl value of 54, and the number of moles of ethylene oxide added was 19.8 moles on average. The charging voltage measurement method using a 1% by weight aqueous solution of the obtained raw material 4 (n=20, m=0, R=H) was carried out in Example 1.
It was measured in the same way. Example 5 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, 1101 g (25.0 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, heat at 120℃ 20mm while inhaling nitrogen.
Xylene was recovered with Hg. (Theoretical value of 50 moles, OH value = 23.7) The liquid carbazole ethylene oxide adduct thus obtained had a hydroxyl value of 24.2, and the number of moles of ethylene oxide added was 49 moles on average. The charging voltage measurement method using a 1% by weight aqueous solution of the obtained raw material 5 (n=50, m=0, R=H) was carried out in Example 1.
It was measured in the same way. Example 6 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, 2203 g (50.0 mol) of ethylene oxide was added over 5.0 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, heat at 120℃ 20mm while inhaling nitrogen.
Xylene was recovered with Hg. (Theoretical value of 100 moles, OH value = 12.3) The liquid carbazole ethylene oxide adduct thus obtained had a hydroxyl value of 12.5, and the number of moles of ethylene oxide added was 98 moles on average. The charging voltage measurement method using a 1% by weight aqueous solution of the obtained raw material 6 (n=100, m=0, R=H) was carried out in Example 1.
It was measured in the same way. Example 7 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. 6608 g (150 mol) of ethylene oxide was added over 5.0 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, heat at 120℃ 20mm while inhaling nitrogen.
Xylene was recovered with Hg. (Theoretical value of 300 moles, OH value = 4.2) The liquid carbazole ethylene oxide adduct thus obtained had a hydroxyl value of 4.3, and the number of moles of ethylene oxide added was 295 moles on average. The charging voltage measurement method using a 1% by weight aqueous solution of the obtained raw material 7 (n=300, m=0, R=H) was carried out in Example 1.
It was measured in the same way. Example 8 83.6 g (0.5 mol) of carbazole with a purity of 99%, 500 g of xylene, and 0.95 g of potassium hydroxide were placed in a stainless steel autoclave, the atmosphere was purged with nitrogen gas, the initial pressure was 1 Kg/cm ² , and the temperature was 147°C. 154.2 g (3.5 mol) of ethylene oxide was added over 5 hours. During this time, the reaction temperature was maintained at 145-150°C. After 1 hour of aging, 87.0g (1.5 mol) of propylene oxide was added for 2 hours.
Added. 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 phosphoric acid.
After neutralizing to 6.0, heat at 120℃ 20mm while breathing nitrogen.
Xylene was recovered with Hg. The carbazole ethylene oxide/propylene oxide adduct thus obtained had a hydroxyl value of 87.8, and an average of 6.9 mol of ethylene oxide and 2.9 mol of propylene oxide were added. Obtained raw material 8 (n=7, m=3, R=H, R
The charging voltage was measured in the same manner as in Example 1 using a 1% by weight aqueous solution of =CH ₃ ). Example 9 83.6 g (0.5 mol) of carbazole with a purity of 99%, 500 g of xylene, and 0.95 g of potassium hydroxide 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. 220.3 g (5.0 mol) of ethylene oxide was added over 5 hours. During this time, the reaction temperature was maintained at 145-150°C. After 1 hour of aging, 87.0g (1.5 mol) of propylene oxide was added for 2 hours.
Added. 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 phosphoric acid.
After neutralizing to 6.0, heat at 120℃ 20mm while breathing nitrogen.
Xylene was recovered with Hg. The carbazole ethylene oxide/propylene oxide adduct thus obtained had a hydroxyl value of 72.8, and an average of 9.9 mol of ethylene oxide and 2.9 mol of propylene oxide were added. Obtained raw material 9 (n=10, m=3, R=H,
The charging voltage was measured in the same manner as in Example 1 using a 1% by weight aqueous solution of R'=CH ₃ ). Example 10 83.6 g (0.5 mol) of carbazole with a purity of 99%, 500 g of xylene, and 0.95 g of potassium hydroxide 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. 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, 290.0 g (5.0 mol) of propylene oxide was added over 2 hours. During this time, the reaction temperature was maintained at 145-150°C. After 1 hour of aging time, lower the temperature and add phosphoric acid.
After neutralizing to PH6.0, heat at 120℃20 while breathing in nitrogen.
Xylene was collected at mmHg. The carbazole ethylene oxide/propylene oxide adduct thus obtained had a hydroxyl value of 53.7, and an average of 6.9 mol of ethylene oxide and 9.9 mol of propylene oxide were added. Obtained raw material 10 (n = 7, m = 10, R = H,
The charging voltage was measured in the same manner as in Example 1 using a 1% by weight aqueous solution of R'=CH ₃ ). Comparative Example 1 The charging voltage was measured in the same manner as in Example 1 using water. The results of Examples 1 to 10 and Comparative Example 1 are shown in Table 1.

[Table] Example 11 A 0.1% by weight aqueous solution of raw materials 2 to 10 obtained in Examples 2 to 10 was prepared, and foaming power was measured by the JISK-3362 (19678) Ross Miles method. The results were as shown in Table 2. Comparative Example 2 JISK-3362 using 7 mole ethylene oxide adduct of linear secondary alcohol having 12 to 14 carbon atoms
(19678) measured foaming power using the Ross Miles method. The results were as shown in Table 2.

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

【table】

[Table] Example 13 Using raw material 2 obtained in Example 2, relative humidity 27%
The surface resistivity (Ω) was measured at a relative humidity of 60%. The results were as shown in Table 4. Example 14 Using raw material 8 obtained in Example 8, relative humidity was 27%.
The surface resistivity (Ω) was measured at a relative humidity of 60%. The results were as shown in Table 4. Test method A 10 x 10 cm piece of nylon cloth for dyeing (manufactured by Shikisensha) was desized and deoiled with carbon tetrachloride, dried, and immersed in 100 ml of a 1% aqueous solution of the above raw materials for 3 minutes, and then thoroughly soaked in 60 cm. 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. Comparative Example 4 Surface resistivity (Ω) was measured using water in the same manner as in Example 13 at relative humidity of 27% and 60%. The results were as shown in Table 4. Comparative Example 5 Commercially available betaine surfactant [Sanyo Chemical Industries, Ltd.
The surface resistivity (Ω) was measured at relative humidity of 27% and 60% in the same manner as in Example 13 using Sunstat 1007 (trade name). The results were as shown in Table 4. Comparative Example 6 Commercially available nonionic surfactant [Sanyo Chemical Industries, Ltd.]
Example 13 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 4. Comparative Example 7 Commercially available cationic surfactant [Marubishi Yuka Kogyo Co., Ltd.]
The surface resistivity (Ω) was measured at relative humidity of 27% and 60% in the same manner as in Example 13 using Bevinar KR (trade name). The results were as shown in Table 4. Comparative Example 8 Commercially available cationic surfactant [Marubishi Yuka Kogyo Co., Ltd.]
Similar to Example 13, surface resistivity (Ω) was measured at a relative humidity of 27% and a relative humidity of 60% using Beviner CS (trade name: Beviner CS). The results were as shown in Table 4.

[Table] Example 15 Using raw material 2 obtained in Example 2, relative humidity 27%
The surface resistivity (Ω) was measured at a relative humidity of 60%. The results were as shown in Table 5. Test method A 10 x 10 cm nylon resin plate was washed with carbon tetrachloride, then a toluene solution of the above raw material was applied to the nylon resin plate, which had been deoiled and dried using a bar ^coater.
g/ ^cm2 , and then thoroughly heated at 60°C for 50 minutes.
After being left for a long time, the material was dried in a desiccator at room temperature and under reduced pressure overnight, and the surface resistivity (Ω) at 23°C was measured using a super insulation resistance tester (manufactured by Yokogawa Hiretsupat Card Co., Ltd.). . Comparative Example 9 Surface resistivity (Ω) was measured using water in the same manner as in Example 15 at relative humidity of 27% and 60%. The results were as shown in Table 5. Comparative Example 10 Surface resistivity (Ω) was measured at relative humidity of 27% and 60% in the same manner as in Example 15 using a commercially available nonionic surfactant [Toho Chemical Co., Ltd., trade name: Antex SA-300B]. Measurements were made. The results were as shown in Table 5.

【table】 [Brief explanation of the drawing]

FIG. 1 is a diagram showing changes in antistatic ability of an antistatic agent with respect to changes in humidity. FIG. 2 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.