JPH0478668B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an antistatic agent for acrylic 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 acrylic, characterized by comprising a polyoxyalkylenecarbazole adduct having the structure represented by: (Prior art and its problems) Various antistatic agents for acrylic have been reported, but generally, cations, amphoteric ions, and some non-ions (polyoxygens such as amines and alcohols) alkylene ethers, etc.), and some anionic (phosphate-based) surfactants. However, such surfactant-based antistatic agents for acrylics (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 surfactant acrylics, and as a result, the carbazole group has been replaced with a lipophilic group. 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 acrylic.
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 acrylic, characterized in that it is composed 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 is a carbazole with ethylene oxide and/or
Or propylene oxide is added in blocks. The antistatic agent for acrylic of the present invention can be used for acrylic fibers, acrylic resin products, etc. The antistatic agent for acrylic of the present invention is used by coating or impregnating the surface of acrylic 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 acrylic 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) Effectively applied to acrylic. (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 period, 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 a relative humidity of 27% and a relative humidity of 60%. The results were as shown in Table 1. Test method: A 10 x 10 cm piece of acrylic cloth for dyeing (manufactured by Shirozome Co., Ltd.) 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. After leaving it at ℃ for 5 hours, it was dried in a desiccator at room temperature and under reduced pressure overnight, and the surface resistivity (Ω) at 23℃ was measured using a super insulation resistance tester (manufactured by Yokogawa Hyulettsu Card Co., Ltd.). was measured. Comparative Example 1 Surface resistivity (Ω) was measured using water in the same manner as in Example 1 at relative humidity of 27% and 60%. The results were as shown in Table 1. Comparative Example 2 Surface resistivity (Ω) was measured at relative humidity of 27% and 60% in the same manner as in Example 1 using a commercially available betaine surfactant [Sanyo Chemical Industries, Ltd., product name: Sunstat 1007]. I did it. The results were as shown in Table 1.

[Table] Example 2 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 adjusted. 87.0g (1.5g) of propylene oxide in 2 hours.
mol) added. During this time, the reaction temperature was maintained at 145-150°C. After 1 hour of aging, 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 6.0, incubate at 120℃ for 20 minutes while breathing in nitrogen.
Xylene was collected at mmHg. The carbazole propylene oxide and ethylene oxide adduct thus obtained had a hydroxyl value of 87.8, 2.9 mol of propylene oxide,
An average of 6.9 moles of ethylene oxide was added to each. Obtained raw material 2 (n=3, m=7, R=CH ₃ ,
The surface resistivity (Ω) was measured at relative humidity of 27% and 60% using R′=H). The results were as shown in Table 2. [Test method] An acrylic resin plate of 100 x 100 x 3 mm was washed with carbon tetrachloride, and a toluene solution of the above raw material was applied to the acrylic resin plate which had been deoiled and dried using a bar coater.
After applying it to a concentration of 3×10 ^-5 g/cm ² , apply it thoroughly.
After leaving at 60℃ for 5 hours, overnight at room temperature under reduced pressure.
After drying in a desiccator, the surface resistivity (Ω) at 23° C. was measured using a super insulation resistance meter (manufactured by Yokogawa Hyulettsu Card Co., Ltd.). Comparative Example 3 Surface resistivity (Ω) was measured at relative humidity of 27% and 60% using water in the same manner as in Example 2. The results were as shown in Table 2. Comparative Example 4 Surface resistivity (Ω) was measured at relative humidity of 27% and 60% in the same manner as in Example 2 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 2.

[Table] Example 3 A 0.1% by weight aqueous solution of the raw material 2 obtained in Example 2 was prepared, and the foaming power was measured by the Ross Miles method according to JISK-3362 (1978). The results were as shown in Table 3. Comparative Example 5 JISK-3362 using 7 mole ethylene oxide adduct of linear secondary alcohol having 12 to 14 carbon atoms
(1978) measured foaming power using the Ross Miles method. The results were as shown in Table 3.

[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 6 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】

【table】 [Brief explanation of drawings]

FIGS. 1 and 2 are diagrams 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.