JPH0586217A - Method for modifying conductivity of resin molded product - Google Patents

Abstract

PURPOSE:To highly improve the conductivity of a resin molded product without damaging the physical properties of the resin molded product, by kneading the raw material of the resin molded product with the complex of a specific polyether substance with an electrolyte salt, and subsequently molding the kneaded product. CONSTITUTION:A raw material of a resin molded product, such as a polyolefin resin, is kneaded with the complex of an organic compound having a skeleton of formula I [Z is active hydrogencontaining compound group; Y is active hydrogen, 1-20C alkyl, (alkyl)aryl; (m) is 1-250; (k) is 1-12; A is group of formula II (n) is 0-25; R is 1-20C alkyl, (alkyl)aryl)] with an electrolyte soluble therein, such as lithium stearyl sulfonate, and subsequently molded by an injection- molding method, etc. The surface of the obtained resin molded product is treated with plasma to obtain a molded product highly improved in the conductivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying the electrical conductivity of resin moldings.

[0002]

2. Description of the Related Art As a conventional method for improving the conductivity of a resin molding, there is a method of kneading carbon black, carbon fiber, conductive mica or the like into a resin. However,
In such a conventional method for improving the electrical conductivity of the resin molded body, it is not possible to improve the electrical conductivity unless a large amount of a conductive substance such as carbon black is kneaded, so that physical property deterioration of the resin molded body is avoided. In addition, there is a problem of coloring such as black, and its use is limited.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the conventional method, and does not impair the physical properties of the resin molded body and causes the coloring problem without increasing the conductivity of the resin molded body. It is an object to provide a method that can be significantly improved.

[0004]

In the present invention, the above problems are solved by kneading a complex of a specific polyether substance and an electrolyte salt into a raw material for a resin molded body and molding the mixture. That is,
The method of the present invention uses the following general formula for the raw material of the resin molded body:

[0005]

[Chemical 3]

[Wherein Z is an active hydrogen-containing compound residue, Y
Is an active hydrogen group, or an alkyl group, an aryl group, an alkylaryl group, m is an integer of 1 to 250, k is an integer of 1 to 12,
A is the general formula:

[0007]

[Chemical 4]

(N represents an integer of 0 to 25, R represents an alkyl group, an aryl group, or an alkylaryl group having 1 to 20 carbon atoms) and an organic compound having a skeleton and an electrolyte salt soluble in these compounds. Is kneaded, the kneaded product is molded, and then the surface of the obtained resin molded product is subjected to plasma treatment.

In the present invention, as a raw material for the resin molded body, a polyolefin resin such as polyethylene or polypropylene, A
Any resin having a high surface resistance value such as BS resin, acrylic resin, polyamide resin, polyvinyl chloride resin, polycarbonate resin, polyacetal resin, or phenol resin can be used.

The organic compound having a skeleton of the formula (hereinafter referred to as polyether) used for the complex kneaded into the raw material for the resin molded product is a compound obtained by reacting an active hydrogen-containing compound with glycidyl ethers. Preferably.

Examples of such active hydrogen-containing compounds include monoalcohols such as methanol and ethanol; dialcohols such as ethylene glycol, propylene glycol and 1,4-butanediol; glycerin, trimethylolpropane, sorbitol, sucrose and polyalcohol. Polyhydric alcohols such as glycerin; butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aniline, benzylamine, phenylenediamine, and other amine compounds; monoethanolamine , Compounds having different active hydrogen-containing groups in one molecule, such as diethanolamine, can be used, and polyhydric alcohols are preferably used. Next, as the glycidyl ethers to be reacted with such an active hydrogen-containing compound, for example,
Alkyl- or aryl- or alkylaryl-polyethylene glycol glycidyl ethers represented by the following formula

[0012]

[Chemical 5]

(However, R and n have the same meanings as in the general formula), typical examples of R are linear alkyl groups such as methyl group, ethyl group, propyl group and butyl group, Isopropyl group, sec-butyl group, branched alkyl group such as tert-butyl group, phenyl group, naphthyl group,
Examples thereof include aryl or alkylaryl groups such as nonylphenyl group, tolyl group and benzyl group. Among them, those in which n is 1 to 15 and R has 1 to 12 carbon atoms are particularly preferably used.

As a catalyst used when reacting glycidyl ethers, basic catalysts such as sodium methylate, caustic soda, caustic potash, and lithium carbonate are generally used. However, acidic catalysts such as boron trifluoride and
Amine-based catalysts such as trimethylamine and triethylamine are also useful.

The main chain terminal group Y of the polyether may be an active hydrogen group or the same alkyl group, aryl group or alkylaryl group as the side chain terminal group R (Y
Is an alkyl group, an aryl group, or an alkylaryl group, the same group as the side chain terminal group R can be mentioned).
In order to introduce an alkyl group, an aryl group, or an alkylaryl group at the end of the main chain, a halogen compound may be generally reacted. Examples of such compounds include methyl chloride, methyl bromide, methyl iodide, and chloride. Linear alkyl halides such as ethyl, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, butyl chloride, butyl bromide, butyl iodide, isopropyl chloride, isopropyl bromide, isopropyl aio Branched alkyl halides such as daid, sec-butyl chloride, sec-butyl bromide, sec-butyl iodide, tert-butyl chloride, tert-butyl bromide, tert-butyl iodide, chlorobenzene, bromobenzene, and i. Odobenzene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene,
2-bromonaphthalene, 1-iodonaphthalene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene,
There may be mentioned aryl or alkylaryl type halides such as o-iodotoluene, m-iodotoluene, p-iodotoluene, benzyl chloride, benzyl bromide and the like. These may be used alone or in combination of two or more.

Further, as the soluble electrolyte salt forming a complex with such a polyether, for example, LiI, LiCl, Li
_{ClO 4, LiSCN, LiBF 4,} LiAsF 6, LiCF 3 SO 3, LiC 6 F 13 S
O ₃ , LiCF ₃ CO ₂ , LiHgI ₃ , NaI, NaSCN, NaBr, KI, CsSC
N, AgNO ₃ , CuC ₁₂ Mg (ClO ₄ ) _2, etc., at least Li, Na,
Inorganic ionic salt containing one of K, Cs, Ag, Cu or Mg, lithium stearyl sulfonate, sodium octyl sulfonate, lithium dodecylbenzene sulfonate, sodium naphthalene sulfonate, lithium dibutylnaphthalene sulfonate, octyl naphthalene sulfonate potassium,
Organic ion salts such as potassium dodecylnaphthalene sulfonate may be mentioned.

The amount of such soluble electrolyte salt added is not particularly limited, but is 0.5% with respect to the polyether.
It is preferably about 10 wt%. Further, the amount of the complex of the polyether and the soluble electrolyte salt used is preferably 1 to 30% by weight, and particularly preferably 1 to 10% by weight based on the raw material of the resin molded body.

Next, as a method for forming a complex of polyether and a soluble electrolyte salt, water, methanol, and
Methyl ethyl ketone, tetrahydrofuran, acetone,
A method of obtaining a complex by dissolving a soluble electrolyte salt in a single or mixed solution having high compatibility with polyether such as methylene chloride, uniformly mixing the solution and the polyether, adjusting a complex solution, and then removing the solvent. Is preferred. However, in some cases, the polyether and the soluble electrolyte salt may be kneaded into the resin molded material to form a complex in the resin molded material.

The complex of polyether and soluble electrolyte salt is
As a method of kneading into the resin molded material, any of commonly used methods such as a twin-screw extruder and a heat roll type can be used, and also as a molding method of the resin molded body, injection molding, extrusion molding, calendering. Any of processing, compression molding and SMC method can be used.

The plasma treatment is carried out by exciting a low-pressure oxidizing gas such as oxygen or a gas obtained by mixing nitrogen, argon, or the like with high-frequency discharge, microwave discharge, or the like to generate an active gas, which is then treated. The method of contacting the surface of the product (molded body) is used, but the pressure at that time is usually 0.1 to 5 Torr,
Preferably, it is 0.2 to 1.0 Torr, and the temperature is 40 to 100.
C., and the treatment time may be about 10 seconds to 10 minutes.
The processing gas is preferably 18 to 90% by volume of oxygen.

In the present invention as described above, when the cation of the soluble electrolyte salt of the above complex kneaded in the resin is a usual polyether using an alkylene oxide such as ethylene oxide or propylene oxide, the main chain coplanar line is used. It was able to move only inside the structure (spiral structure), while in addition to the ether bond oxygen in the side chain, it can also move through the side chain and the cation moves between molecules. In order to achieve this, it was usually necessary for the main chains to approach each other (approaching in a segmental motion), but it became possible to move through the side chains, which facilitated cation transfer. It is possible to obtain higher ionic conductivity, reduce the resistance value thereof, and obtain a high-quality resin molded product having excellent conductivity.

[0022]

【Example】

Example 1 Using ethylene glycol (30 g) as a starting material and potassium hydroxide (7 g) as a catalyst, the following formula is used.

[0023]

[Chemical 6]

2390 g of n-butyltriethylene glycol glycidyl ether was reacted for desalting and purification,
1738 g of an organic compound represented by the formula (where the substituents and the like are as follows) having a molecular weight of 4758 (calculated from a hydroxyl value) was obtained.

[0025]

[Chemical 7]

A solution of 25 g of lithium thiocyanate in 100 g of methanol was added to 500 g of the above organic compound, and the mixture was stirred to form a uniform solution. Then, methanol in the solution was topped under reduced pressure to obtain a complex. 30 g of this complex and 1 kg of polypropylene resin were kneaded in a twin-screw extruder at 180 ° C for 10 minutes, and the kneaded material was molded (230 mm × 230 mm × 230 mm × 230 mm × 2) at the same temperature for 2 minutes by hot pressing with a pressure of 50 kg / cm ^2. 3 mm), and the surface of the obtained molded product was supplied with oxygen at a gas flow rate of 6.75 l / min.
A test piece was prepared by performing a plasma treatment for 1 minute at 89% by volume, 11% by volume of nitrogen, a pressure of 0.2 mmHg, a temperature of 40 ° C. and an output of 1200 W.

Example 2 Starting from 20 g of glycerin and using potassium hydroxide as a catalyst
First, the formula below is shown using 6g.

[0028]

[Chemical 8]

2160 g of n-hexyldiethylene glycol glycidyl ether was reacted for desalting and purification,
Molecular weight represented by the formula (however, the substituents are as follows)
1861 g of an organic compound of 9443 (calculated from the hydroxyl value) was obtained.

[0030]

[Chemical 9]

A solution prepared by dissolving 25 g of potassium thiocyanate in 200 g of acetone was added to 500 g of the above organic compound, and the mixture was stirred to form a uniform solution. Then, acetone was decompressed and topped,
A complex was obtained. 50 g of this complex and 1 kg of polypropylene resin were kneaded in a twin-screw extruder at 180 ° C for 10 minutes, and the kneaded material was molded by the hot pressing method at a temperature of 2 minutes and a pressure of 50 kg / cm ^2.
(230 mm x 230 mm x 3 mm), and the surface of the obtained molded body is subjected to a plasma treatment for 1 minute at a gas flow rate of 6.75 l / min, oxygen 89% by volume, nitrogen 11% by volume, pressure 0.2 mmHg, temperature 40 ° C, output 1200 W. Then, the test piece was created.

Example 3 Starting from 20 g of 1,4-butanediol and using 5 g of potassium hydroxide as a catalyst, the following formula is used.

[0033]

[Chemical 10]

1800 g of phenylethylene glycol glycidyl ether was reacted to carry out desalting and purification, and a molecular weight of 71 represented by the formula (provided that the substituents and the like are as described below).
1461 g of 90 (calculated from hydroxyl value) of the organic compound was obtained.

[0035]

[Chemical 11]

A solution prepared by dissolving 25 g of sodium perchlorate in 100 g of methanol was added to 500 g of the above organic compound, and the mixture was stirred to form a uniform solution. Then, methanol was vacuum-topiced to obtain a complex. 50g of this complex and 1kg of polypropylene resin
Was kneaded with a twin-screw extruder at 180 ° C for 10 minutes, and the kneaded material was molded for 2 minutes at the same temperature by a hot press method with a pressure of 50 kg / cm ² (230 mm × 230 mm × 3 mm), and the obtained molding was obtained. A test piece was prepared by subjecting the surface of the body to plasma treatment at a gas flow rate of 6.75 l / min, oxygen 89% by volume, nitrogen 11% by volume, pressure 0.2 mmHg, temperature 40 ° C., output 1200 W for 1 minute.

Example 4 Starting from 15 g of butylamine and using 9 g of potassium hydroxide as a catalyst, the following formula is used.

[0038]

[Chemical formula 12]

After reacting 3100 g of n-hexylhexaethylene glycol glycidyl ether, the reaction was carried out by using 1.2 equivalents of methyl chloride with respect to the hydroxyl group to carry out terminal methylation, followed by desalting and purification. 2501 g of an organic compound having a molecular weight of 14,388 (calculated from a hydroxyl value), represented by the following substituents) was obtained.

[0040]

[Chemical 13]

A solution of 25 g of lithium perchlorate in 100 g of methanol was added to 500 g of the above organic compound, and the mixture was stirred to form a uniform solution. Then, methanol was topped under reduced pressure to obtain a complex. 70g of this complex and 1Kg of polypropylene resin
Was kneaded with a twin-screw extruder at 180 ° C for 10 minutes, and the kneaded material was molded for 2 minutes at the same temperature by a hot press method with a pressure of 50 kg / cm ² (230 mm × 230 mm × 3 mm), and the obtained molding was obtained. A test piece was prepared by subjecting the surface of the body to plasma treatment at a gas flow rate of 6.75 l / min, oxygen 89% by volume, nitrogen 11% by volume, pressure 0.2 mmHg, temperature 40 ° C., output 1200 W for 1 minute.

Comparative Example 1 kg of polypropylene resin was kneaded in a twin-screw extruder at 180 ° C. for 10 minutes, and then molded (230 mm × 230 mm × 3 mm) at the same temperature for 2 minutes by a hot press method by applying a pressure of 50 kg / cm ² to obtain a product. The surface of the formed compact was gas flow rate 6.75 liters / minute, oxygen 89% by volume, nitrogen 11% by volume, pressure 0.2 mmHg, temperature 40 ° C., output 1200 W, 1
Plasma treatment was performed for a minute to prepare a test piece.

Results The test pieces obtained in Examples 1 to 4 and Comparative Example were not significantly different in physical properties and appearance, and the results of measuring the surface resistance value and the tensile yield strength were as follows. Surface resistance (Ω ) Tensile yield strength (Kg / cm ² ) Example 1 4.1 × 10 ¹² 321 Example 2 3.2 × 10 ¹² 325 Example 3 1.9 × 10 ¹² 318 Example 4 2.8 × 10 ¹² 319 Comparative Example 2 × 10 ¹⁶ or more 330 [Measurement method of surface resistance value] Applied voltage 50 using a super insulation resistance meter 4329A type made by YHP (Yokogawa Hewlett Packard)
The surface resistance was measured 30 seconds after the voltage was applied at 0V.

[0044]

EFFECTS OF THE INVENTION In the present invention, a resin which has been conventionally considered to have a problem with conductivity is used, and a molded product having remarkably improved conductivity is obtained without substantially impairing the physical properties and hue of the resin. You can

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Claims (1)

[Claims] 1. A raw material for a resin molded body is represented by the following general formula: [Wherein Z is an active hydrogen-containing compound residue, Y is an active hydrogen group or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkylaryl group, m is an integer of 1 to 250, k is an integer of 1 to 12, A is the following general formula: (N is an integer of 0 to 25, R is an alkyl group having 1 to 20 carbon atoms,
Representing an aryl group or an alkylaryl group)], a complex of an organic compound having a skeleton represented by the formula] and an electrolyte salt soluble in these is kneaded, and the kneaded product is molded, and then the surface of the obtained resin molded product is A method for modifying the electrical conductivity of a resin molding, which comprises performing a plasma treatment.