JPS62230835A - Antistatic agent for synthetic polymer - Google Patents

Abstract

PURPOSE:To provide an antistatic agent for synthetic polymeric material, composed of a specific phosphonium sulfonate compound, having excellent antistaticity and heat-resistance and capable of imparting a polymer with antistaticity having low sensitivity to moisture. CONSTITUTION:The objective antistatic agent is composed of a compound of formula I (A is 4-18C alkyl, alkenyl, etc.; R<1>-R<4> are 1-18C hydrocarbon group or substituted 1-18C hydrocarbon group; preferably R<1>, R<2> and R<3> are same 1-8C aliphatic or aromatic univalent hydrocarbon groups) derived from a phosphonium sulfonate anion (e.g. butylsulfonate, octylsulfonate, etc.) and an organic phosphonium cation (e.g. tetramethyl phosphonium). The agent is compounded to a polymeric material or applied to the surface of the material e.g. by spraying at an amount of 0.1-10wt%.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to antistatic agents for synthetic polymeric 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 to eliminate these obstacles. <Prior art and its problems> Conventionally, in order to prevent charging of synthetic polymer materials, carbon or conductive Using a conductive agent such as a conductive metal bed or a surfactant,
Attempts have been made to prevent various problems by kneading them into synthetic polymer materials or coating them on their surfaces. It is not common because it is difficult to obtain a transparent material and the conductive agent is expensive, and 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 have poor compatibility, are difficult to disperse uniformly, and decompose and deteriorate when heated, making them difficult to use.
Cationic and amphoteric surfactants that have quaternary nitrogen in their molecules have good antistatic properties, but have very poor heat resistance.
It can only be used in a very limited range. Furthermore, although nonionic surfactants have better compatibility with synthetic polymer materials than the ionic surfactants mentioned above, they tend to have weaker antistatic properties and may lose their effectiveness over time at room or high temperatures. It has the disadvantage that it easily disappears. 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 under low humidity conditions, and the effect may disappear when heated to high temperatures in a drying process, stretching, heat setting, thermoforming, etc. after coating.

<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 in that it contains a phosphonium sulfonate represented by the following general formula (I) as an important component.

RZ R4 [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 having 1 to 18 carbon atoms
Naphthyl group substituted with an alkyl group. R1-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 general formula (I) consists of an organic sulfonate anion and an organic phosphonium cation. Specific examples of the organic sulfonate anions include aliphatic sulfonates such as butylsulfone-1,1ctylsulfonate, laurylsulfonate, myristylsulfonate, hexadecylsulfonate, 2-ethylhexylsulfonate, and mixtures thereof, p-tosylate, Butylphenyl sulfonate, dodecyl phenyl sulfonate, octadecyl sulfonate,
Substituted phenyl sulfonates such as dibutylphenyl sulfonate, naphthylsulfonate, diisopropylna 7
Examples include substituted or unsubstituted naphthylsulfonates such as tylsulfonate and dibutylnaphthylsulfonate. Specific examples of the organic phosphonium cations include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, tributylethylphosphonium, trioctylmethylphosphonium, trimethylbutylphosphonium, trimethyloctylphosphonium, trimethyllaurylphosphonium. ,
Examples include aliphatic phosphoniums such as trimethylstearylphosphonium, triethyloctylphosphonium, and tributyloctylphosphonium, and aromatic phosphoniums such as triphenylmethylphosphonium, triphenylethylphosphonium, triethylbenzylphosphonium, and tributylbenzylphosphonium. Furthermore, tetramethylolphosphonium, tri(2-cyanoethyl)methylphosphonium, tri(2-cyanoethyl)ethylphosphonium, tri(2-cyanoethyl)benzylphosphonium, tri(3-hydroxypropyl)methylphosphonium, tri(3-cyanoethyl)methylphosphonium, Phosphoniums having substituents such as hydroxypropyl)benzylphosphonium, trimethyl(2-hydroxyethyl)phosphonium, and tributyl(2-hydroxyethyl)phosphonium can also be used.

The phosphonium sulfonate of the present invention is composed of various combinations of these organic sulfonate anions and organic phosphonium cations, but the present invention is not limited to these specific examples.

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, desirable antistatic properties are imparted to synthetic polymer materials. Various methods 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 advance in the form of a master chip containing a high concentration of additives. It can be implemented using the law. For example, thermoplastic resins such as polyolefins such as polyethylene, 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; It can also be advantageously added during molding or before or during the polymerization of polyethylene terephthalate or the like. In order to obtain preferable results using these internal addition methods, it is usually best to use the antistatic agent of the present invention in the molded product in an amount of 0.1 to 10% by weight, preferably 0.3 to 10% by weight. 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, especially when hydrocarbon groups are substituted with other Since phosphonium having no group has particularly excellent heat resistance, its preferable properties are exhibited even more when applied to polymeric materials such as polycarbonate and polyethylene terephthalate, which require high processing temperatures.

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 it is also possible to apply antistatic properties by adding it to a processing solution used for other purposes and processing it together. It is also useful to add them at the same time. For example, technical fields that aim to improve surface properties mainly using polymers,
That is, when applying a coating agent to impart adhesion, printability, gas barrier properties, water vapor permeability resistance, hardness, etc. to the surface, it can be applied in combination with these agents to impart good antistatic properties. . These 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. Although it functions in the form of a film, good effects can be obtained by using the antistatic agent of the present invention in this coating film. Examples of similar uses include ink, paint,
Examples of magnetic paints, examples of fiber treatments such as flexible finishes and antifouling finishes,
Many other applications are possible. 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, it is useful as a component of a fiber processing oil that can be used in the fiber manufacturing process by being used with synthetic esters, mineral oils, polyethers, etc. as lubricants, or with alkyl phosphate salts, etc. as lubricants. It is possible to prevent static electricity damage during the process. By applying the antistatic agent of the present invention to the surface of these synthetic polymeric materials, its good heat-resistant properties make it possible to apply the antistatic agent of the present invention to the surface of these synthetic polymeric materials. It is possible to obtain good results without losing the effect even during the process, and at the same time, it is possible to obtain a more stable and good effect with less temperature dependence than conventional products.

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) Using the antistatic agent a% f of the present invention listed in Table 1, polymethyl methacrylate was , polycarbonate, and polyethylene in a predetermined amount, and the obtained resin composition was molded at a predetermined temperature using a hot press made by Toyo Seiki Co., Ltd. to a thickness of 211 mm.
A sheet II was produced.

After checking the appearance of each sheet and comparing it with the blank, leave it in a constant temperature and humidity room at 20℃ x 65%RH overnight.
The surface resistance was measured under the same atmosphere using a super insulation resistance meter (Model SM-5E, manufactured by Toa Denpa Kogyo Co., Ltd.). The results are shown in Table-1.

- Test Category 1-2 (Comparative Example) Using the conventional antistatic agents 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.

(C3H7)2 φ is 0. PMMA is polymethyl methacrylate, PC is polycarbonate, and PE is polyethylene.

The crosstalk conditions were 130°C x 5 minutes for PMMA, 260°C x 5 minutes for PC, and 150°C x 5 minutes for PE.

A, R' to R4 correspond to each symbol in general formula (I).

These are the same below.

・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, it was heated at 80°C After drying for 5 minutes, the humidity was conditioned overnight at 20°C x 30% RH, and the surface resistance was measured in the same manner as in Example 1.Then, it was further heat treated at 150°C x IO minutes, and the humidity was conditioned overnight at 20°C x 65%. After that, the heat resistance of the effect was examined.The results are shown in Table 3.

・Test Category 3 (Example, Comparative Example) Vinylidene chloride latte Nox or polyester aqueous dispersion (terephthalic acid/isophthalic acid/ethylene glycol/
Neopentyl glycol 15-sulfoisophthalic acid copolymer) was added to the polymer in the amount of antistatic agent listed in Table 4, diluted to 5 ml, and coated on the surface of the polyester film with a bar coater. It was applied using. 8
After drying at 0°C for 5 minutes, the humidity was controlled overnight at 20°C and 30% RH.
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.

・Test Category 4 (Example, Comparative Example) The oils for each side listed in Table 5 were mixed and adjusted.

Using a 15% by weight emulsion of each of these oils, commercially available polyester filaments (76 denier x 36 filaments) were degreased with cyclohexane and dried.
Lubricate with an oiling roller and add 0.6% by weight of oil.
Attached. Using a μm meter (manufactured by Eiko Sokki Co., Ltd.) in an atmosphere of 25°C x 6s% RH, each sample was measured at an initial tension of 20
f, two contact type heaters of 220℃ x 501 length, then chrome-plated satin friction body (contact angle 90 degrees), 30℃
The yarn was run at a speed of 0.0 m/min, and the charged voltage of the yarn immediately after passing through the friction body was measured to examine the antistatic effect. The results are shown in Table-5.

Note) a, b, (!l　g) are the same as Tables 1 to 3.

A-1: Trimethylolpropane (PO/EO=15
/g5) Random adduct, MW = 3000 A-2; Butanol (PO/EO = 60/40) Random adduct, MW = 1700 A-3; 2-ethylhexyl stearate N-1: PO
E(6) Nonylphenyl ether B-1: Fog(4)
Octyl phosphate KB-2; triethanolamine instearate B-3; alkyl sulfonate Na <Effects of the invention> As is clear from the results in each table, the present invention described above has good heat resistance. In addition, it has the property of having little humidity dependence, and has the effect of imparting excellent antistatic properties to synthetic polymer materials.

Claims (1)

[Claims] 1. An antistatic agent for synthetic polymer materials, characterized in that it contains a phosphonium sulfonate represented by the following general formula (I) as an important component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [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, or a naphthyl group. or carbon number 1-18
Naphthyl group substituted with an alkyl group. R^1 to R^4 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 compound according to claim 1, wherein R^1, R^2, and R^3 of the general formula (I) are the same and are aliphatic or aromatic monovalent hydrocarbon groups having 1 to 8 carbon atoms. Antistatic agent for synthetic polymer materials.