JPH0129500B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to an antistatic agent for synthetic polymer materials. Synthetic polymeric materials are usually highly hydrophobic and, as a result, have the property of being easily charged, and this property poses a major obstacle in the manufacturing process of these materials and in the use of their products. The present invention relates to an antistatic agent for synthetic polymer materials that eliminates these obstacles. <Conventional technology and its problems> Conventionally, in order to prevent charging of synthetic polymer materials,
Attempts have been made to prevent various troubles by using conductive agents such as carbon or conductive metal powder, or surfactants, and kneading them into synthetic polymer materials or coating them on their surfaces. However, according to the conductive agent,
It is not common because it requires a large amount to be used, the method of addition is difficult, it is difficult to obtain a transparent material, and the conductive agent is expensive, so the range in which it can actually be used is quite limited. . On the other hand, antistatic agents mainly composed of surfactants are appropriately selected from among many types and are applied in many situations. Among these, many proposals have been made for the internal addition type, which is kneaded into synthetic polymer materials, because it has advantages in terms of processing steps compared to the coating type, which requires a separate coating process. However, when used as an internally added antistatic agent, anionic surfactants are difficult to use because they have poor compatibility and are difficult to disperse uniformly, and decompose and deteriorate when heated. Although cationic and amphoteric surfactants contained in the molecule have good antistatic properties, they have very poor heat resistance and can only be used within a very limited range. Furthermore, nonionic surfactants have better compatibility with synthetic polymer materials than the ionic surfactants mentioned above, but their antistatic properties tend to be weaker, and their effectiveness deteriorates over time at room or high temperatures. There are drawbacks that can easily disappear. On the other hand, the coating type used on the surface of synthetic polymeric materials uses surfactants alone or together with polymers, lubricants, and other substances, but this type of conventional antistatic agent has many disadvantages. For example, the effect may not be sufficiently obtained in low humidity conditions, or the drying process or stretching process after application may not be sufficient.
If heated to high temperatures during processes such as heat setting and heat forming, the effect may disappear. <Problems to be Solved by the Invention and Means for Solving the Problems> In view of the above-mentioned circumstances, the present inventors have developed an antistatic property that has good antistatic properties, heat resistance, and is less dependent on humidity. As a result of intensive research in order to obtain an antistatic agent for synthetic polymer materials that can be applied, it was discovered that a specific phosphonium sulfonate compound is properly suitable, and the present invention was achieved. That is, the present invention relates to an antistatic agent for synthetic polymer materials characterized by containing a phosphonium sulfonate represented by the following general formula () as an important component. [However, A is an alkyl group or alkenyl group having 4 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, a naphthyl group, or a naphthyl group substituted with an alkyl group having 1 to 18 carbon atoms. Base. ^R1 to ^R4 are the same or different hydrocarbon groups having 1 to 18 carbon atoms, or hydrocarbon groups having 1 to 18 carbon atoms having a substituent. ] The phosphonium sulfonate represented by the general formula () consists of an organic sulfonate anion and an organic phosphonium cation. Specific examples of the organic sulfonate anion include butyl sulfonate,
Octyl sulfonate, lauryl sulfonate,
Aliphatic sulfonates such as myristyl sulfonate, hexadecyl sulfonate, 2-ethylhexyl sulfonate, and mixtures thereof; substituted phenyls such as p-tosylate, butylphenyl sulfonate, dodecylphenyl sulfonate, octadecyl phenyl sulfonate, dibutylphenyl sulfonate; Examples include sulfonates, substituted or unsubstituted naphthylsulfonates such as naphthylsulfonate, diisopropylnaphthylsulfonate, and dibutylnaphthylsulfonate. Specific examples of the organic phosphonium cations include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, tributylethylphosphonium, trioctylmethylphosphonium, trimethylbutylphosphonium, trimethyloctylphosphonium, trimethyllaurylphosphonium. , aliphatic phosphoniums such as trimethylstearylphosphonium, triethyloctylphosphonium, tributyloctylphosphonium, triphenylmethylphosphonium, triphenylethylphosphonium,
Examples include aromatic phosphoniums such as triethylbenzylphosphonium and tributylbenzylphosphonium. Furthermore, tetramethylolphosphonium, tri(2-cyanoethyl)methylphosphonium, tri(2-cyanoethyl)ethylphosphonium, tri(2-cyanoethyl)benzylphosphonium, tri(3-hydroxypropyl)methylphosphonium, tri(3-hydroxypropyl)
Phosphoniums having substituents such as benzylphosphonium, trimethyl(2-hydroxyethyl)phosphonium, and tributyl(2-hydroxyethyl)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. A method for imparting preferable antistatic properties to synthetic polymer materials by using the antistatic agent of the present invention containing phosphonium sulfonate represented by the general formula () as an important component and utilizing its good antistatic properties and heat resistance. Various means are possible. One method is to add it internally to a synthetic polymer material to impart desirable antistatic properties. In this method, additives are usually added and mixed during polymer production or processing, either directly or in the form of master chips containing a high concentration of additives. It can be carried out using these conventional methods. For example, polyethylene
Thermoplastic resins such as polyolefins such as polypropylene and polystyrene, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polycaprolactam can be added and mixed directly during processing or with a master chip, and during cast molding of polymethyl methacrylate or It can also be advantageously added before or during the polymerization process of polyethylene terephthalate and the like. To obtain preferable results using these internal addition methods, the antistatic agent of the present invention is usually added in an amount of 0.1 to 10% by weight based on the molded product.
It is best to use it within the range of , more preferably 0.3 to
It is 5% by weight. The antistatic agent of the present invention has better heat resistance than conventional anionic, cationic, amphoteric, etc. ionic surfactants or nonionic surfactants, and in particular, the antistatic agent has superior heat resistance when compared to conventional anionic, cationic, amphoteric, etc. ionic surfactants or nonionic surfactants. Phosphonium, which does not contain phosphonium, has particularly excellent heat resistance, so its favorable characteristics are exhibited even more when applied to polymeric materials that require higher processing temperatures, such as polycarbonate and polyethylene terephthalate. Another method for imparting antistatic properties to synthetic polymeric materials is to apply the antistatic agent of the present invention alone or together with other substances to the surface thereof. The application can be carried out by various methods such as dipping, spraying, roller coating, gravure coating, etc. using a solution, dispersion, or emulsion containing the antistatic agent of the present invention. If necessary, the surface to be treated may be subjected to physical treatment such as corona treatment or plasma treatment, or chemical treatment such as application of an anchor coating agent before coating. It is of course possible to apply with a solution containing only an antistatic agent for the main purpose of imparting antistatic properties, but by adding it to a processing solution used for other purposes and processing it together, antistatic properties can be achieved at the same time. It is also useful to give For example, in the field of technology that attempts to improve the surface properties of polymers, in other words, when applying coating agents to impart adhesion, printability, gas barrier properties, water vapor permeability resistance, hardness, etc. to the surface, these It can be applied in combination with the above agent to impart good antistatic properties. These materials generally contain organic polymers such as acrylic polymers, vinyl polymers, vinylidene chloride polymers, and polyesters, and film-forming inorganic substances such as silica sol and alumina sol, and after being applied, they form a film on the surface. When the antistatic agent of the present invention is used in this coating film, good effects can be obtained. Similar usage examples include inks, paints, magnetic paints, fiber treatments such as flexible finishes and antifouling finishes, and many other applications. As another example of applying it to the surface, it is also possible to use it in combination with a low-molecular organic substance such as a lubricating component. For example, synthetic esters as lubricants,
It is also useful as a component of a fiber processing oil that can be used in the fiber manufacturing process by using it with mineral oil, polyether, etc., or with an alkyl phosphate salt as a lubricant, thereby reducing static electricity during the process. It is possible to prevent failure. By applying the antistatic agent of the present invention to the surface of these synthetic polymer materials by various means, its good heat-resistant properties can be used in the process of producing films, fibers, etc. that are heated in the stretching process after application. It is possible to obtain good effects without losing the effect even within the temperature range, and at the same time, it is possible to obtain a more stable and good effect with less temperature dependence than the conventional ones. Examples will be given below to make the structure and effects of the present invention more concrete, but the present invention is not limited to these Examples. <Examples, etc.> ● Test Category 1-1 (Example) Antistatic agents a to f of the present invention listed in Table-1
A predetermined amount of the mixture was kneaded into polymethyl methacrylate, polycarbonate, and polyethylene using a Laboplast Mill (manufactured by Toyo Seiki Co., Ltd.). The resulting resin compositions were each molded at a predetermined temperature using a hot press manufactured by Toyo Seiki Co., Ltd. to produce sheets with a thickness of 2 mm. After checking the appearance of each sheet and comparing it with a blank, it was left in a constant temperature and humidity room at 20°C x 65% RH overnight, and then tested using a super insulation resistance tester (SM) under the same atmosphere.
-5E type, manufactured by Toa Denpa Kogyo Co., Ltd.) to measure the surface resistance. The results are shown in Table-1. ● Test category 1-2 (comparative example) Using the conventional antistatic agent listed in Table 2,
The same experiment as in Test Category 1-1 was conducted, and the same comparisons and measurements were made. The results are shown in Table-2.

【table】

[Table] ● Test Category 2 (Example, Comparative Example) A 0.5% aqueous solution of the antistatic agent listed in Table 3 was prepared, and a polyethylene sheet or a polyester sheet was immersed in it. Then, 80℃×
After drying for 5 minutes, adjust the humidity overnight at 20℃ x 30%RH.
Surface resistance was measured in the same manner as in Example 1. Furthermore, the heat treatment was performed at 150°C for 10 minutes, and the humidity was conditioned at 20°C and 65% overnight, and then the heat resistance of the effect was examined. Display the results.
Shown in 3.

【table】

[Table] ● Test Category 3 (Example, Comparative Example) Polymer After adding the antistatic agent in the amount shown in Table 4, the solution was diluted to 5% and coated on the surface of the polyester film using a bar coater. After drying at 80° C. for 5 minutes, the humidity was controlled overnight at 20° C. and 30% RH, and the coated surface was observed and the surface resistance was measured in the same manner as in Example 1. The results are shown in Table-4.

[Table] ●Test Category 4 (Example, Comparative Example) The formulations of the oils listed in Table 5 were adjusted. Using a 15% by weight emulsion of each of these oils, a commercially available polyester filament (76 denier x 36 filaments), which had been previously degreased with cyclohexane and dried, was oiled with an oiling roller to deposit 0.6% by weight of the oil. each sample
Using a μ-meter (manufactured by Eiko Sokki Co., Ltd.) in an atmosphere of 25℃ x 65%RH, the initial tension was 20g, and the temperature was 220℃
Two 50cm long contact heaters were run at a speed of 300m/min, followed by a chrome-plated matte friction body (contact angle of 90 degrees), and the charged voltage of the yarn immediately after passing through the friction body was measured to see the antistatic effect. . The results are shown in Table-5.

[Table] <Effects of the Invention> As is clear from the results in each table, the present invention described above has the characteristics of having good heat resistance and low humidity dependence, and can be applied to synthetic polymer materials. It has the effect of imparting excellent antistatic properties.

Claims (1)

[Scope of Claims] 1. An antistatic agent for synthetic polymer materials, characterized in that it contains a phosphonium sulfonate represented by the following general formula () as an important component. [However, A is an alkyl group or alkenyl group having 4 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, a naphthyl group, or a naphthyl group substituted with an alkyl group having 1 to 18 carbon atoms. Base. ^R1 to ^R4 are the same or different hydrocarbon groups having 1 to 18 carbon atoms, or hydrocarbon groups having 1 to 18 carbon atoms having a substituent. [2] The synthetic polymer material according to claim 1, wherein R ¹ , R ² , and R ³ in the general formula () are the same and are aliphatic or aromatic monovalent hydrocarbon groups having 1 to 8 carbon atoms. Antistatic agent.