JPH0770361A - Antistatic agent - Google Patents

Abstract

(57) [Summary] [Object] To provide an antistatic agent having an excellent antistatic ability. An antistatic agent comprising a bisphosphonium bissulfonate compound represented by Chemical formula 1 as an active ingredient. [Chemical 1]

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic agent, and more particularly to an antistatic agent containing a bisphosphonium bissulfonate compound as an active ingredient.

[0002]

2. Description of the Related Art In recent years, various methods for preventing electrostatic damage have been proposed, but in many cases, the use of an antistatic agent has solved the problem. Antistatic agents are broadly classified into external antistatic agents and internal antistatic agents depending on the method of use. External antistatic agent is sprayed from the outside,
It is used by means such as dipping or coating, and most of them are water-soluble surfactants. For this reason, there is a drawback in that the antistatic effect is easily lost by aging, washing, or the like.

The internal antistatic agent is used by adding an additive to a polymer material. As a material to be added, a method of using a surfactant and a method of adding conductive fine particles are used. There is. Although metal powder, carbon, etc. are used as the conductive fine particles, it is necessary to add a considerable amount in order to uniformly disperse these fine particles in the polymer material and obtain conductivity. However, there are drawbacks such as the possibility of changes in physical properties and difficulty in obtaining a transparent product. On the other hand, surfactants used as antistatic agents include anionic, cationic and nonionic surfactants. Since the hydrophilic part and the lipophilic part coexist in the molecule, there is an advantage that even if it is added to the inside of a certain substance, it leaches out at the interface, and it is appropriately selected from many types. Widely applied.

However, the anionic surfactant is
The compatibility is poor, and it is difficult to disperse uniformly, and decomposition and deterioration occur when heated. Further, the catechin-based surfactant having a quaternary ammonium group is excellent in antistatic property but has very poor heat resistance and can be used only in a very limited range. Further, the nonionic surfactant has excellent antistatic property, but has a problem such as deterioration of compatibility thermal stability with a polymer material.

[0005]

In view of the above facts, the present inventors have conducted earnest studies to obtain an antistatic agent having excellent antistatic property and high heat resistance, and as a result, the bisphosphonium bissulfonate compound was obtained. The fact that an antistatic agent containing as an active ingredient exhibits excellent antistatic properties was found, and the present invention was completed.

[0006]

That is, the antistatic agent to be provided by the present invention is represented by the following general formula (1):

[0007]

[Chemical 4] [Wherein R ^{1 to} R ⁶ represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group, and the alkyl group, the aryl group and the aralkyl group are a hydroxy group or It may be substituted with an alkoxy group. Y represents a linear or branched alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group, and R ⁷ is a linear or branched alkyl group having 1 to 40 carbon atoms or a general Formula (2)

[Chemical 5] (In the formula, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or the general formula (3).

[Chemical 6] (In the formula, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). ] It is a structural feature that the bisphosphonium bissulfonate compound represented by the following is used as an active ingredient.

The present invention will be described in more detail below.
The bis (phosphonium sulfonium) salt compound according to the present invention has two organic phosphonium cations (hereinafter, referred to as “phosphonium cations”) in its main chain in the molecule, and two organic sulfonate anions as its counter ion. Represented by the following general formula (1) having (hereinafter referred to as “sulfonate anion”),

[0009]

[Chemical 7]

In the formula, specific examples of R ^{1 to} R ⁶ are:
Hydrogen atom; C1 to C1 such as methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl, octyl, dodecyl and isopropyl groups
8 a linear or branched alkyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group; an aralkyl group such as a benzyl group, a phenylyl group; the alkyl group, the aryl group and the aralkyl group are a hydroxy group or an alkoxy group. May be substituted with; and the like. Of these, an alkyl group, an aryl group and an aralkyl group are preferable, and an alkyl group and an aryl group are more preferable. Further, R ₁ , R ₂ and R ₃ may be the same group or different groups.

Y is a linear or branched alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, ethylethylene group; phenylene group, 2,3-dimethylphenylene group, 2 Examples thereof include substituted or unsubstituted arylene groups such as a 5,5-dimethylphenylene group, p-xylylene group, and m-xylylene group.

R ⁷ is a hydrogen atom; methyl group, ethyl group, butyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, dodecyl group, isopropyl group, hexadecyl group, octadecyl group, eicosyl group, pentaeico group. A linear or branched alkyl group having 1 to 40 carbon atoms such as a sil group; R in the general formula (2) or the general formula (3)
⁸ is a hydrogen atom; a straight chain having 1 to 20 carbon atoms such as methyl group, ethyl group, butyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, dodecyl group, isopropyl group, hexadecyl group and octadecyl group. Examples thereof include an alkylphenyl group and an alkylnaphthyl group which are chain-like or branched alkyl groups.

Next, in the bisphosphonium bissulfonate represented by the general formula (1), the phosphonium cations will be described more specifically. Ethylenebistriethylphosphonium, ethylenebistrin-butylphosphonium, ethylenebistrin-hexylphosphonium, Ethylenebistrin-octylphosphonium, ethylenebistrin-decylphosphonium, ethylenebistrin-
Dodecylphosphonium, ethylenebistrin-hexadecylphosphonium, ethylenebistrin-octadecylphosphonium, ethylenebisoctadecyldiethylphosphonium, ethylenebistri (2-cyanoethyl) phosphonium, ethylenebistri (3-hydroxypropyl) phosphonium, ethylenebistribenzylphosphonium, ethylenebistriphosphonium Phenylphosphonium, ethylene bistricresyl phosphonium and the like, the ethylene group is also a methylene group, trimethylene group, tetramethylene group, pentamethylene group, ethylethylene group, phenylene group, 2,3-dimethylphenylene group, 2,5 -A bisphosphonium cation substituted with a dimethylphenylene group, a p-xylylene group, an m-xylylene group, or the like.

Examples of the sulfonate anion include alkyl sulfonates such as octyl sulfonate, decyl sulfonate, dodecyl sulfonate, tetradecyl sulfonate, hexadecyl sulfonate, octadecyl sulfonate, eicosyl sulfonate and docosyl sulfonate; benzene sulfonate and methylbenzene sulfonate. , Alkyl benzene sulfonate such as butyl benzene sulfonate, octyl benzene sulfonate, decyl benzene sulfonate, octadecyl benzene sulfonate, dodecyl benzene sulfonate, tetradecyl benzene sulfonate, hexadecyl benzene sulfonate, octadecyl benzene sulfonate, eicosyl benzene phosphonate; methyl naphthyl sulfonate, ethyl na Chill sulfonates, alkyl naphthyl sulfonates such as dimethyl naphthyl sulfonate, and the like.

The bisphosphonium bissulfonate compound which is the antistatic agent of the present invention is composed of a desired combination of the organic phosphonium cation and the organic sulfonate anion, but is not particularly limited.

Further, in the use thereof, if necessary, an antioxidant, an ultraviolet protective agent, a weathering agent, an antiblocking agent, a pigment, a reinforcing agent, a lubricant and other antistatic agents may be added. .

Method for Producing Antistatic Agent The bisphosphonium bissulfonate compound as the antistatic agent of the present invention may be produced by any method, but one example is shown below as an industrial production method.

General formula (4)

[Chemical 8] (Wherein R ^{1 to} R ³ have the same meanings as described above) and / or the general formula (5).

[0019]

[Chemical 9] (In the formula, R ^{4 to} R ⁶ have the same meanings as described above), and a triorganophosphine represented by the general formula (6)

[0020]

[Chemical 10] (In the formula, Y has the same meaning as above, and X represents halogen.)
By reacting with a dihalide represented by
General formula (7)

[0021]

[Chemical 11] (In the formula, R ^{1 to} R ⁶ , Y and X have the same meanings as described above.) To obtain a bisphosphonium dihalogenide.

Then, the general formula (8)

[Chemical 12] The antistatic agent of the present invention can be obtained by reacting with an organic sodium sulfonate represented by the formula (wherein R ⁷ has the same meaning as described above).

In the above reaction, the general formula (4) and /
Alternatively, the reaction between the compound of the general formula (5) and the compound of the general formula (6) can be carried out at room temperature to 150 in the presence of an organic solvent or in the absence of a solvent.
The reaction is preferably performed at 1 ° C for 1 to 10 hours. When an organic solvent is used, n-hexane, n-heptane, n-octane, benzene, toluene, xylene and the like can be mentioned. In addition, triorganophosphine is preferably used in an amount of 2 to 5 times the molar amount of the dihalogenated alkyl.
Further, the reaction of the compounds of the general formulas (7) and (8) is preferably carried out in a water solvent at room temperature to 100 ° C. for 1 to 10 hours. In addition, the organic sulfonic acid sodium is 2 times mol to 5 times the bisphosphonium halogenide.
It is recommended to use double mole.

The method of applying the antistatic agent according to the present invention to a polymer material may be any method, for example, the antistatic agent may be directly applied at the time of polymer production or processing, or in the form of a master chip. It can be added and mixed for use. In order to obtain a preferable antistatic ability by these internal addition methods, 0.1 to 10% by weight, preferably 0.3 to 5% by weight of the antistatic agent of the present invention is suitable for the molded product.

As another method of imparting the antistatic ability, a solution, dispersion or emulsion containing the antistatic agent according to the present invention is dipped in a spray method, a spray method or a roller coating method. ,
It can be carried out by various means such as a gravure coat method. If necessary, the surface to be treated or a chemical treatment such as application of an anchor coating agent may be performed before the application.
The compound according to the present invention also has flame retardancy and antibacterial properties.

[0026]

EXAMPLES The present invention will be further described below with reference to examples.

<Example> The antistatic agents a to g of the present invention shown in Table 1 were added to polycarbonate (PC), polymethylmethacrylate (PMMA) and polyethylene (PE) in predetermined amounts in a Henschel mixer. And mixed at a predetermined temperature with an injection molding machine (3N31A manufactured by Niigata Iron Works) to obtain a sheet of 100 mm × 100 mm × 2 m. After each sheet was compared with a blank and evaluated for appearance, it was left in a constant temperature and humidity room at 20 ° C x 65% RH overnight, and under the same atmosphere, a super insulation resistance meter (SM-5E type, Toa Denpa Kogyo Co., Ltd.) was used. Surface resistance was measured. The results are shown in Table 1.

[0028]

[Table 1]

The molding temperature was 290 ° C. for PC, 180 ° C. for PMMA, and 200 ° C. for PE. Regarding the appearance, each sheet was visually observed for hue and transparency, and those having the same hue and transparency as the blank were regarded as good.

<Comparative example> Using the conventional antistatic agents h to l described in Table 2, the same experiment as in the example was conducted, and the same comparison and measurement were carried out. The results are shown in Table 2.

[0031]

[Table 2]

[0032]

The antistatic agent according to the present invention can reduce the surface resistance and volume resistivity and impart conductivity to various synthetic resins and rubbers, and thus can exhibit good antistatic ability. . Further, since the antistatic agent according to the present invention has good thermal stability, it can maintain its effect with durability without decomposition at the processing temperature of resin or rubber.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Iijima 9-15-1, Kameido, Koto-ku, Tokyo Japan Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. The following general formula (1): [Wherein R ^{1 to} R ⁶ represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group, and the alkyl group, the aryl group and the aralkyl group are a hydroxy group or It may be substituted with an alkoxy group. Y represents a linear or branched alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group, and R ⁷ is a linear or branched alkyl group having 1 to 40 carbon atoms or a general Formula (2) (In the formula, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or the general formula (3): (In the formula, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). ] The antistatic agent characterized by using the bisphosphonium bis sulfonate compound represented by these as an active ingredient.