JP2527697B2 - Antistatic agent for synthetic polymer materials - Google Patents

Description

The present invention relates to an antistatic agent for synthetic polymer materials.

Synthetic polymeric materials are usually highly hydrophobic and consequently have the property of being easily charged, which is a major obstacle to the manufacturing process of these materials and their use.

The present invention relates to an antistatic agent for synthetic polymer materials for eliminating the above obstacles.

<Prior art and its problems> Conventionally, as an antistatic agent for synthetic polymer materials, a conductive agent such as carbon or conductive metal powder or a surfactant has been used. These are kneaded into a synthetic polymer material or coated on the surface thereof. However, the conductive agent is used in a large amount necessary to obtain a corresponding effect, and the addition method thereof is difficult, and it is difficult to obtain a more transparent material, and the conductive agent itself is expensive, so Has a problem that the usable range is considerably limited.

On the other hand, the surfactant is properly selected from many types and is applied in many cases. Among these, many proposals have been made regarding the internally added type which is used by kneading into a synthetic polymer material. However, when a surfactant is used as an internal addition type antistatic agent, the compatibility with the anionic surfactant is poor, and it is difficult to use it because uniform dispersion is difficult or decomposition degradation occurs when heated. There is a point. In addition, cations having a quaternary nitrogen in the molecule and amphoteric surfactants have a good antistatic property but have a very poor heat resistance, and in fact, can be used only in a very limited range. There is. Furthermore, nonionic surfactants have better compatibility with synthetic polymer materials than the above-mentioned ionic surfactants, but their antistatic properties are weak, and their effects disappear over time at room temperature or high temperature. There is a problem that it is easy. As internal addition type antistatic agents for polycarbonate and polyester resins that are molded at high temperature, various metal salts of organic sulfonic acids have been reported (West German Patent No. 3004017), but these are resins. There is a problem that the compatibility with and heat resistance is insufficient, and there is also a report that a phosphonium salt of an organic sulfonic acid having a substituted hagerone group is used as a flame retardant for polycarbonate (US Pat. No. 4093589). However, this product has a problem that the effect as an antistatic agent cannot be expected at all.

On the other hand, the coating type which is applied to the surface of a synthetic polymer material is used as a surfactant alone or together with a polymer, a lubricant and other substances, but conventional antistatic agents of this kind have many disadvantages. However, there is a problem in that, for example, the effect is not sufficiently obtained under low humidity, or the effect disappears when heated to a high temperature in the steps such as a drying step, stretching, heat setting, and heat molding after coating.

<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a new antistatic agent for synthetic polymer materials (hereinafter, simply referred to as antistatic agent) that solves the above conventional problems. It is a thing.

However, the inventors of the present invention have earnestly studied to obtain an antistatic agent that has good antistatic properties, heat resistance, and can impart antistatic properties with little humidity dependence to synthetic polymer materials. Have found that certain phosphonium sulfonate compounds are correct and suitable.

That is, the present invention relates to an antistatic agent comprising a phosphonium sulfonate represented by the following general formula (I).

[However, A is an alkyl group having 1 to 3 carbon atoms. R ^{1 to} R ⁴ are
Simultaneously the same or different, an aliphatic or aromatic hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms having a hydroxyl group or a cyano group as a substituent. The phosphonium sulfonate represented by the general formula (I) is composed of an organic sulfonate anion and an organic phosphonium cation. Specific examples of the organic sulfonate anion include methyl sulfonate, ethyl sulfonate,
Propyl sulfonate, and mixtures thereof. Further, specific examples of the phosphonium cation include
Tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmertylphosphonium, tributylethylphosphonium, trioctylmethylphosphonium, trimethylbutylphosphonium, trimethyloctylphosphonium, trimethyllaurylphosphonium, trimethylstearylphosphonium, triethyloctylphosphonium, tributyl Aliphatic phosphoniums such as octylphosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylethylphosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium and the like are mentioned. Furthermore, tetramethylolphosphonium, tri (2-cyanoethyl) methylphosphonium, tri (2-
Cyanoethyl) ethylphosphonium, tri (2-cyanoethyl) benzylphosphonium, tri (3-hydroxypropyl) methylphosphonium, tri (3-hydroxypropyl) benzylphosphonium, trimethyl (2-hydroxyethyl) phosphonium, tributyl (2-hydroxyethyl) Phosphonium having a hydroxyl group or a cyano group as a substituent such as phosphonium can also be used.

The phosphonium sulfonate of the present invention is composed of any combination of these organic sulfonate anions and organic phosphonium cations, but the present invention is not limited to these specific examples. Such phosphonium sulfonate is obtained by mixing a metal salt or ammonium salt of a corresponding organic sulfonate and a quaternary phosphonium salt in a solvent and washing and separating an inorganic salt produced as a by-product, or an organic salt such as methanol, isopropanol or acetone. It can be produced by extracting phosphonium sulfonate with a solvent.

The antistatic agent of the present invention composed of the phosphonium sulfonate represented by the general formula (I) is used, and various properties can be imparted to the synthetic polymer material by using its antistatic property and heat resistance. There is a method.

One of them is a method of internally adding to a synthetic polymer material. In this method, the antistatic agent is usually added or mixed at the time of polymer production or processing, directly or in the form of a master chip containing a high concentration of the antistatic agent in advance. Also in the case of the present invention, these conventional methods can be used. For example polyethylene,
Polypropylene, polystyrene and other polyolefins, polymethylmethacrylate, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polycaprolactam and other thermoplastic resins can be added and mixed directly during processing or by master chips, and during polymethylmethacrylate cast molding. Alternatively, polyethylene terephthalate or the like may be added and mixed before or during the polymerization step. In order to obtain preferable results by these internal addition methods, it is usually preferable to use the antistatic agent of the present invention in the range of 0.1 to 10% by weight, and the range of 0.3 to 5% by weight based on the synthetic polymer material. Is even better. The antistatic agent of the present invention is superior to conventional ionic surfactants such as anion, cation, and amphoteric surfactant, or nonionic surfactants,
It has more excellent heat resistance, and in particular, phosphonium, which has the same hydrocarbon group and does not have a substituent, is particularly excellent in heat resistance. Therefore, it is more suitable for polymer materials with higher processing temperatures such as polycarbonate and polyethylene terephthalate. The desirable characteristics are exhibited.

Another method of applying the antistatic agent to the synthetic polymer material is a method of applying the antistatic agent of the present invention alone or together with other substances to the surface thereof. The antistatic agent of the present invention is particularly effective when this method is applied. In this method, due to the dispersibility of the antistatic agent into the resin and the surface transferability and compatibility of the antistatic agent, which is a problem in the above-mentioned method of adding to the inside, the processing amount is limited and the compounding amount from the viewpoint of processability and physical properties. There is an advantage that there are few restrictions. As a means for specifically applying to the surface of the synthetic polymer material, various means such as a dipping method, a spray method, a roller coating method and a gravure coating method of a solvent, a dispersion or an emulsion containing the antistatic agent of the present invention. In addition, the surface to be treated may be subjected to a physical treatment such as corona treatment or plasma treatment, or a chemical treatment such as application of an anchor coating agent before application. In addition, it is of course possible to apply a liquid containing only an antistatic agent as a main purpose of imparting antistatic properties, but by adding it to a processing liquid used for other purposes and treating together, antistatic properties can be simultaneously obtained. It is also effective to give. For example, in the technical field in which the polymer is mainly used to improve the surface properties, that is, when a coat for imparting adhesiveness, printability, gas barrier property, water vapor permeation resistance, hardness, etc. to the surface is used, A good antistatic property can be imparted by applying together with the agent. These mainly contain an acrylic polymer, a vinyl polymer, a vinylidene chloride polymer, a polymer such as polyester, and a film-forming inorganic substance such as silica sol or alumina sol, and a film is formed on the surface after coating. However, even if the antistatic agent of the present invention is used in this coating film, good results can be obtained. As examples of similar uses, examples of inks, paints, magnetic paints, examples of fiber treatments such as soft finish and antifouling finish, and many applications thereof are possible. As another example of applying to the surface, it is possible to use in combination with a low molecular weight organic substance such as a lubricating component. For example, it is effective as a component of a fiber treatment oil agent that can be used in a fiber manufacturing process by using a synthetic ester as a lubricant, a mineral oil, a polyether or the like, or an alkyl phosphate salt as a lubricant. This makes it possible to prevent electrostatic damage during the process. By applying the antistatic agent of the present invention to the surface of these synthetic polymer materials by various means, due to its good heat resistance property, for example, in the process of film, fiber, etc. which is heated in the stretching process after coating. Also in the case of (1), a good result can be obtained without losing the effect, and in addition, a more stable and good result having less humidity dependency than the conventional one can be obtained. In order to obtain a desired effect by adding it to a treatment agent to be used in combination with others, it varies depending on the type and purpose of the treatment agent to be used in combination, but usually in the range of 0.1 to 20% by weight with respect to the treatment agent to be used in combination, More preferably, the antistatic agent of the present invention is added within the range of 1 to 10% by weight.

Examples will be given below to make the constitution and results of the present invention more specific, but the present invention is not limited to these examples.

<Examples, etc.> Test Category 1-1 (Examples) The antistatic agents a to e of the present invention described in Table-1 were treated with Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) to obtain polymethylmethacrylate, A predetermined amount was mixed with each of polycarbonate and polyethylene. The obtained resin composition was molded at a predetermined temperature with a hot press (manufactured by Toyo Seiki Co., Ltd.) to prepare a sheet having a thickness of 2 mm. After checking the appearance of each sheet and comparing it with Planck, leave it in a constant temperature and humidity room at 20 ° C x 65% RH overnight and then in the same atmosphere, use a super insulation resistance tester (SM
The surface resistance was measured by -5E type, manufactured by Toa Denpa Kogyo KK. The results are shown in Table-1.

-Test Category 1-2 (Comparative Example) Using the conventional antistatic agents described in Table-2, an experiment was conducted in the same manner as in Test Category 1-1, and the same comparison and measurement were performed. The results are shown in Table-2.

Note) * 1 is 1 ogΩ, φ is PMMA is polymethylmethacrylate, PC is polycartonate, PE is polyethylene.

The kneading conditions are 130 ° C x 5 minutes for PMMA and 2 for PC.
60 ° C x 5 minutes, 150 ° C x 5 minutes for PE.

A and R ^{1 to} R ⁴ correspond to the respective symbols in the general formula (I).

Regarding the appearance, each sheet was visually observed for hue and transparency, and a sheet having the same hue and transparency as a blank prepared in the same manner except that no antistatic agent was used was good.

 These are the same below.

The surface resistance of each PMMA, PC and PE blank was 13 <.

-Test Category 2 (Examples and Comparative Examples) A 0.5% aqueous solution of the antistatic agent described in Table 3 was prepared, and a polyethylene sheet or a polyester sheet was dipped therein. Then, after drying at 80 ℃ × 5 minutes
The surface resistance was measured by controlling the humidity overnight at 20 ° C x 30% RH (Table-
3、20 ℃ × 30% RH). Then, heat treatment was further performed at 150 ° C. for 10 minutes, humidity was controlled at 20 ° C. × 65% RH overnight, and then the surface resistance was measured again (after heat treatment in Table 3) to see the heat resistance of the effect. . The results are shown in Table-3.

-Test Category 3 (Examples, Comparative Examples) Vinylidene chloride latex or polyester aqueous dispersion (terephthalic acid / isophthalic acid / ethylene glycol /
Neopentyl glycol / 5-sulfoisophthalic acid copolymer) was added to the polymer in the amount shown in Table 4 and diluted to 5%. It was applied using a coater. 80 ° C
After drying for 5 minutes, the humidity was controlled overnight at 20 ° C. and 30% RH, and the coated surface was observed to measure the surface resistance. The results are shown in Table-4.

-Test Category 4 (Examples and Comparative Examples) The oil agents of each example shown in Table 5 were prepared by mixing. Using a 15% by weight emulsion of each of these oil agents, commercially available polyester filaments (76 denier × 36 filaments) that had been degreased with cyclohexane and dried were oiled with an oiling roller to attach 0.6% by weight of the oil agent.
Using a μ-meter (manufactured by Eiko Sokki Co., Ltd.) in an atmosphere of 25 ° C. × 65% RH for each sample, two contact type heaters having an initial tension of 20 g and a length of 220 ° C. × 50 cm, and then a chromium-plated satin friction body The contact angle was 90 °) and the running speed was 300 m / min, and the filamentous electrification voltage (generated electricity in Table 5) immediately after passing through the friction body was measured to confirm the antistatic effect. The results are shown in Table-5.

<Effects of the Invention> As is clear from the results in each table, the present invention described above has excellent heat resistance and little humidity dependence, and thus is excellent in charging a synthetic polymer material. There is an effect that the preventive property can be imparted.

Claims (2)

(57) [Claims] 1. An antistatic agent for a synthetic polymer material, which comprises a phosphonium sulfonate represented by the following general formula (I). [However, A is an alkyl group having 1 to 3 carbon atoms. R ^{1 to} R ⁴ are
Simultaneously the same or different, an aliphatic or aromatic hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms having a hydroxyl group or a cyano group as a substituent. ] 2. The formula (I), wherein R ¹ , R ² and R ³ are the same and are an aliphatic or aromatic monovalent hydrocarbon group having 1 to 8 carbon atoms. Antistatic agent for synthetic polymer materials.