JP3053666B2 - Polysulfide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a building member, an aircraft,
The present invention relates to an antistatic or conductive polysulfide composition used for a sealing material of a vehicle or the like.

[0002]

2. Description of the Related Art Polysulfide compositions can be easily vulcanized at room temperature, have no vulcanization shrinkage, are excellent in oil resistance, weather resistance, and low-temperature flexibility, and are widely used in building materials, sealing materials for aircraft, vehicles and the like. Have been.

[0003] This kind of polysulfide composition is easily charged because of its high electrical insulation. When charged, dust is likely to be adsorbed, which reduces the value of the product and causes various adverse effects. In order to prevent electrification of the polysulfide composition, generally, carbon black or conductive metal powder is blended.

[0004]

However, when carbon black or conductive metal powder is blended, the product becomes black or an opaque color peculiar to metal powder, and a colorless and transparent product or a product of a desired color can be obtained. I can't.

In addition, carbon black and conductive metal powder cannot achieve a sufficient effect unless they are added in a large amount (about 10% by weight). Workability at the time of construction is poor, and it is disadvantageous in terms of cost.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a polysulfide which can be colored to a desired color, has no deterioration in physical properties, and is excellent in antistatic property or conductivity. It is to provide a composition.

[0007]

In order to achieve the above-mentioned object, the polysulfide composition of the present invention contains a quaternary ammonium salt represented by the following general formula.

[0008]

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Here, R ¹ , R ² and R ³ are each an alkyl group, one of which is an alkyl group having 8 to 18 carbon atoms, and the rest are each independently an alkyl group having 1 to 5 carbon atoms. It is. R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, and n is an integer of 1 to 5. X represents an anion of hydrochloric acid, chloric acid, perchloric acid, sulfonic acid, or nitric acid, that is, an acid radical.

In the present invention, polysulfide is a liquid polymer having mercapto groups at both ends obtained by condensing an alkali polysulfide and an organic compound having chlorine atoms at both ends.

[0011] Such a liquid polymer is commercially available, for example, referred to as Thiokol LP (manufactured by Toray Thiokol) and Permapol P (manufactured by Nippon Shokubai Co., Ltd.). In this liquid polymer, mercapto groups at both ends are oxidized by a curing agent (vulcanizing agent) such as a metal peroxide such as lead peroxide, calcium peroxide or zinc peroxide, ferric dimethylcarbamate, or sulfur. It becomes a rubbery high molecular polymer by the SS bond.

In the present invention, such a polysulfide contains a quaternary ammonium salt represented by the above general formula to form a polysulfide composition.

[0013] Such quaternary ammonium salts are already known. Further, in such a quaternary ammonium salt, that of the part, it is also known that is effective in the antistatic synthetic resin products such as polyvinyl chloride (JP-B 40-7366 Patent Publication reference). But such a second
Against special materials, such as quaternary ammonium salt polysulfide compositions it is not known with antistatic effect.

Quaternary ammonium represented by the above general formula
In the salt , the carbon number and the n number of the alkyl group and the alkylene group are determined in consideration of compatibility with the polysulfide polymer, bleeding, antistatic effect, and the like.

As the number of carbon atoms and the number n of the alkyl group and the alkylene group increase, the compatibility generally decreases. Also,
When two or all of R ¹ , R ² and R ³ have 8 to 18 carbon atoms, the compatibility with the polysulfide polymer is deteriorated.
The anion of X is particularly preferably an anion of perchloric acid in view of characteristics such as an antistatic effect and thermal stability.

[0016] In the present invention, quaternary ammonium salts described above, with respect to 100 parts of polysulfide typically 0.5
It is contained in the range of up to 10 parts by weight. Among them, the preferred range is 1 to 5 parts by weight.

[0017] When the content of the quaternary ammonium salt is less than 0.5 part by weight, the antistatic effect can not be sufficiently manifested. Conversely, if the amount is more than 10 parts by weight, the compatibility with polysulfide deteriorates, leading to leaching to the surface of the product. The adverse effect of doing so appears.

The polysulfide composition of the present invention includes:
Various conventional additives such as a curing agent (vulcanizing agent) and other additives such as a plasticizer, a filler, an ultraviolet absorber, and a coloring agent are contained as necessary. As the curing agent (vulcanizing agent), the above-mentioned metal peroxides such as lead peroxide, calcium peroxide, and zinc peroxide;
Ferric dimethylcarbamate, sulfur and the like are used.

As the plasticizer, for example, diisodecyl phthalate, dibutoxyethyl phthalate, dihexyl glycol adipate, di-2ethylhexyl glycol adipate and the like are used. As the filler, for example, calcium carbonate or the like is used. As the ultraviolet absorber, for example, benzotriazole or the like is used. Also,
Various pigments or dyes are used as the colorant.

[0020]

[Action] polysulfide compositions containing a suitable amount of quaternary ammonium salt represented by the general formula above, the ion conductivity of the quaternary ammonium salt antistatic performance or the conductivity is remarkably improved.

[0021] that of the part in such a quaternary ammonium salt, that is effective in the antistatic synthetic resin products such as polyvinyl chloride, are known as described above. However, for special materials, such as such quaternary ammonium salts are polysulfide compositions, it is not known to express significant antistatic properties.

The antistatic properties or electrical conductivity of polysulfide compositions of the present invention includes a special molecular structure of polysulfide polymers that are not present in the synthetic resin such as polyvinyl chloride, the molecular structure of the quaternary ammonium salt It is presumed that the interaction is conspicuously expressed. In this regard, the present invention is quite novel and has significant differences over the prior art.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. Example 1 100 parts by weight of polysulfide (Permapol P-965: manufactured by Nippon Shokubai Co., Ltd.), 50 parts by weight of diisodecyl phthalate, 60 parts by weight of calcium carbonate , a fourth amp represented by the following general formula
A sealing material was prepared by mixing 5 parts by weight of a monium salt , 1 part by weight of sulfur, and 0.5 part by weight of benzotriazole.

[0024]

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This sealing material was rolled on a polyethylene sheet to a thickness of 2 mm and cured for 48 hours to prepare a sheet. After leaving this sheet at 20 ° C. × 65% RH for 24 hours, the sheet was measured for its surface resistivity and volume resistivity in accordance with JIS K-6911.

As a result, the surface resistivity is 8.0 × 10 ⁸ Ω,
The volume resistivity is 2.5 × 10 ⁸ Ω · cm, which is sufficient performance as an antistatic sealing material. 100 parts by weight Example 2 polysulfide (perm pole P-965), dibutoxyethyl off start 30 parts by weight, 15 parts by weight of dihexyl glycol adipate, 60 parts by weight of calcium carbonate, performed
5 parts by weight of the same quaternary ammonium salt used in Example 1 ,
A sealing material was prepared by mixing 1 part by weight of sulfur and 0.5 part by weight of benzotriazole. Other than that, it carried out similarly to Example 1.

As a result, the surface resistivity is 7.5 × 10 ⁶ Ω,
The volume resistivity is 5.0 × 10 ⁶ Ω · cm, and has sufficient performance as an antistatic sealing material. Example 3 100 parts by weight of polysulfide (Permapol P-965), 45 parts by weight of di-2ethylhexyl glycol adipate, 50 parts by weight of calcium carbonate , and a fourth alcohol represented by the following general formula
A sealing material was prepared by mixing 2 parts by weight of ammonium salt , 0.5 parts by weight of sulfur and 0.5 parts by weight of benzotriazole. Other than that, it carried out similarly to Example 1.

[0028]

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As a result, the surface resistivity is 3.0 × 10 ⁷ Ω,
The volume resistivity is 1.0 × 10 ⁷ Ω · cm, which is sufficient performance as an antistatic sealing material. Comparative Example 1 In Example 1, no quaternary ammonium salt was added. Other than that, it carried out similarly to Example 1.

As a result, the surface resistivity is 2.3 × 10 ¹¹ Ω,
The volume resistivity is 1.0 × 10 ¹¹ Ω · cm and does not have antistatic performance. Comparative Example 2 In Example 1, 100 parts by weight of polyvinyl chloride having an average polymerization degree of 1300 was blended in place of 100 parts by weight of polysulfide. Other than that, it carried out similarly to Example 1.

As a result, the surface resistivity is 5.3 × 10 ¹⁰ Ω,
The volume resistivity is 1.0 × 10 ¹⁰ Ω · cm, and the antistatic performance is poor. Comparative Example 3 In Example 1, 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1300 was added instead of 100 parts by weight of polysulfide, and no quaternary ammonium salt was added. Other than that, it carried out similarly to Example 1.

As a result, the surface resistivity is 5.3 × 10 ¹² Ω,
The volume resistivity is 1.0 × 10 ¹² Ω · cm and does not have antistatic performance.

[0033]

As described above, the polysulfide composition of the present invention contains an appropriate amount of a specific quaternary ammonium salt , thereby exhibiting excellent antistatic properties or conductivity.

[0034] The polysulfide composition is colorless and transparent, and can be colored freely. Therefore, when this is used as a sealing material, for example, compared with a conventional polysulfide composition containing carbon black or conductive metal powder, a beautiful construction according to the surrounding color tone can be performed, and discomfort with the surroundings can be eliminated. be able to.

Further, compared to the conventional polysulfide composition containing carbon black or conductive metal powder, sufficient antistatic properties or conductivity can be exhibited only by adding a relatively small amount of the quaternary ammonium salt. Therefore, there is no decrease in physical properties, the workability is good, and the cost is low.

Furthermore, whereas the antistatic or conductive mechanism by carbon black or conductive metal powder is an electron conductivity, the fourth antistatic or conductive mechanism according ammonium salt because it is ionic conductivity, Ya conventional carbon black The conductivity can be easily adjusted as compared to the polysulfide composition containing the conductive metal powder. Therefore, by finely adjusting the electric conductivity, it is possible to expand applications requiring antistatic properties or conductivity. The polysulfide composition of the present invention has the above advantages.

Claims (1)

(57) [Claims] 1. A fourth ammonium represented by the following general formula:
A polysulfide composition containing a salt . Embedded image Here, R ¹ , R ² , and R ³ are each an alkyl group, one of which is an alkyl group having 8 to 18 carbon atoms, and the rest are each independently an alkyl group having 1 to 5 carbon atoms. . R ⁴ is an alkylene group having 2 to ⁴ carbon atoms;
Is an integer of 1 to 5. X is hydrochloric acid, chloric acid, perchloric acid,
Shows anions of sulfonic acid and nitric acid.