JPH04202231A - Modification of conductivity of resin molding - Google Patents

Abstract

PURPOSE:To obtain a resin molding of improved electric conductivity without detriment to its properties and without causing its discoloration by molding a mixture obtained by kneading a resin molding material with a specified complex. CONSTITUTION:An organic compound (i) having a skeleton of formula I {wherein Z is a residue of an active hydrogen, compound; Y is an active hydrogen group; 1-20C alkyl or (alkyl)aryl; m is 1-250; k is 1-12; and A is a group of formula II [wherein n is 0-25; R is 1-20C alkyl or (alkyl) aryl]} is mixed with 0.5-10wt.%, based on component (i), component (i)-soluble electrolyte salt (ii) dissolved in a solvent highly compatible with component (i), and the solvent is removed from the mixture to obtain a complex (b). A resin molding material (a) is kneaded with 1-30wt.%, based on component (a), component (b) to obtain a mixture. This mixture is molded to obtain a resin molding.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for modifying the conductivity of a resin molded article.

2. Description of the Related Art Conventional methods for modifying the conductivity of resin molded bodies include methods of kneading carbon black, carbon fiber, conductive mica, etc. into resin.

However, in such conventional methods for improving the conductivity of resin molded bodies, conductivity cannot be improved unless a large amount of conductive material such as carbon blank is kneaded, resulting in a decrease in the physical properties of the resin molded body. This cannot be avoided, and there is also the problem of coloration, such as black, which limits its use.

Problems to be Solved by the Invention The present invention eliminates the drawbacks of such conventional methods and significantly improves the conductivity of resin molded bodies without impairing the physical properties of the resin molded bodies or causing problems with coloring. Our goal is to provide a method that enables this.

Means for Solving the Problems The present invention solves the above problems by kneading a complex of a specific polyether substance and an electrolyte salt into a raw material for a resin molded product and molding the mixture.

That is, in the method of the present invention, the following formula (1); Alkyl group, aryl group, alkylaryl group,
m is an integer from 1 to 250, k is an integer from 1 to 12, and A is a numerical formula.
An integer of ~25, R represents an alkyl group, aryl group, or alkylaryl group having 1 to 20 carbon atoms] and an electrolyte salt soluble therein. Characterized by shaping the mixture.

In the present invention, as raw materials for resin moldings, polyolefin resins such as polyethylene and polypropylene, ABS resins, acrylic resins, polyamide resins, polyvinyl chloride resins, polycarbonate resins, polyacetal resins, phenolic resins, etc. with high surface resistance values are used. Any resin can be used.

In addition, as the organic compound having the 0-type skeleton (hereinafter referred to as polyether) used in the complex to be kneaded into the raw material for the resin molding, a compound prepared by reacting an active hydrogen-containing compound with glycidyl ethers is used. is preferred.

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; and glycerin, trimethylolpropane, sorbitol, sucrose, polyglycerin, and the like. Polyhydric alcohol; amine compounds such as butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aniline, benzylamine, phenylenediamine; monoethanolamine, Any compound having different types of active hydrogen-containing groups in one molecule such as tanolamine can be used, and among them, polyhydric alcohols are preferably used.

Next, the glycidyl ethers to be reacted with such an active hydrogen-containing compound include, for example, alkyl- or aryl- or alkylaryl-polyethylene glycol glycidyl ethers O represented by the following formula (wherein R and n are equal to (similar to formula (2)) can be used, but typically, R is a linear alkyl group such as a methyl group, ethyl group, propyl group, butyl group, isopropyl group, 5ec-butyl group, tert- Examples thereof include branched alkyl groups such as a butyl group, aryl or alkylaryl groups such as a phenyl group, a naphthyl group, a nonylphenyl group, a tolyl group, and a benzyl group. Among them n
is 1-15, and those in which R has 1 to 12 carbon atoms are particularly preferably used.

When reacting glycidyl ethers, basic catalysts such as sodium methylate, caustic soda, caustic potash, and lithium carbonate are generally used, but acidic catalysts such as boron trifluoride, trimethylamine, triethylamine, etc. Also useful are amine-based catalysts such as.

The main chain terminal group Y of the polyether may be an active hydrogen group or an alkyl group, aryl group, or alkylaryl group similar to the side chain terminal group R (if Y is an alkyl group, an aryl group, or If it is an alkylaryl group,
In order to introduce an alkyl group, aryl group, or alkylaryl group to the end of the main chain (for example, a group similar to the side chain terminal group R), it is generally sufficient to react with a halogen compound. are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide,
Linear alkyl type halides such as butyl chloride, butyl bromide, butyl iodide, etc., isopropyl chloride, isobrobyl bromide, isopropyl iodide, 5
ec-butyl chloride s Branched alkyl type halides such as 5ec-butyl bromide, 5ec-butyl iodide, tert-butyl chloride, tert-butyl bromide, tert-butyl iodide, etc., chlorohenzene, promohenzene, iodobenzene , 1-chloronaphthalene, 2-chloronaphthalene, 1
-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 0-chlorotoluene, -chlorotoluene, p-chlorotoluene, 0-bromotoluene, topromotoluene, p-bromotoluene, 0-iodotoluene, - Such compounds as iodotoluene, p-iodotoluene, benzyl chloride, benzyl bromide, etc.
and alkylaryl type halides. These may be used alone or in combination of two or more.

Furthermore, examples of soluble electrolyte salts forming complexes with such polyethers include Lil XLjCI, LiC
lO4, Li5CN, LiBF, , LiAsFi
, LiCFaSOs, LiC6F 1ssJ, LiCF
:+COz, LiHgl3, Nal, Na5CN 5
NaBr, Kl, Cs5CN, AgN0*, C
At least Lis such as uC+tMg(CIOa)z
Na, K% C3% Inorganic ionic salt containing one of Ag, Cu or Mg, lithium stearylsulfonate, sodium octylsulfonate, lithium dodecylhenzenesulfonate, sodium naphthalenesulfonate, lithium dibutylnaphthalenesulfonate, octyl Examples include organic ionic salts such as potassium naphthalene sulfonate and potassium dodecylnaphthalene sulfonate.

The amount of such soluble electrolyte salt added is not particularly limited, but is 0.5 to 10 ei based on polyether.
It is preferable that it is about t%.

The amount of the complex of polyether and soluble electrolyte salt to be used is 1 to 30 wt%, especially 1 to 30 wt%, based on the raw material for the resin molded body.
It is preferably 10@t%.

Next, as a method for forming a complex between a polyether and a soluble electrolyte salt, a soluble electrolyte salt is added in advance to a single or mixed solution that is highly compatible with the polyether, such as water, methanol, methyl ethyl ketone, tetrahydrofuran, acetone, methylene chloride, etc. A preferred method is to melt the polyether, uniformly mix this solution and polyether to prepare a complex solution, and then remove the solvent to obtain the complex. However, in some cases, the polyether and the soluble electrolyte salt may be individually kneaded into the raw material for the resin molded body to form a complex in the raw material for the resin molded body.

The complex of polyether and soluble electrolyte salt can be kneaded into the raw material for the resin molding by any method used for boat fishing, such as a two-wheel extruder or hot roll method. As a method, injection molding, extrusion molding, calendar processing, compression molding, SCM method, etc. can all be used.

Function In the present invention, when the cation of the soluble electrolyte salt of the complex kneaded into the resin is a polyether using an ordinary alkylene oxide such as ethylene oxide or propylene oxide, the main chain has a spiral structure (spiral structure). In contrast, since there is an ether-bonded oxygen in the side chain, it is possible to move only through the side chain, and because the cation can move between molecules. Normally, it was necessary for the main chains to approach each other (approximation by segment motion), but it is now possible to move through the side chains, making cation movement easier, so it is possible to achieve higher ion rates than before. It is possible to obtain a high-quality resin molded body that exhibits conductivity and lowers its resistance value, and has excellent conductivity.

Example 1 Using 30 g of ethylene glycol as a starting material and 7 g of potassium hydroxide as a catalyst, 2390 g of n-butyltriethylene glycol glycidyl ether shown in the following formula was reacted to perform desalting and purification. 1738 g of an organic compound having a molecular weight of 475B (calculated from the hydroxyl value) and having a molecular weight of 475B (calculated from the hydroxyl value) was obtained.

Z: ct+z-o- CH,-0- A: -CH2-CH-0- □ CHz-0-(CHz-CHz-0) 3-CHz-C
Hz-CHz-CLY: H m: 9 to 22 Lithium thiocyanate 2 to 500 g of the above organic compound
A solution of 5 g dissolved in 100 g of methanol was added and stirred to obtain a homogeneous solution, and the methanol in the solution was then topped under reduced pressure to obtain a complex.

This complex 30. and Ikg of polypropylene resin were kneaded in a twin-screw extruder at 180°C for 10 minutes, and this kneaded product was molded (230mm x 230mm x 3mm
) L., a test piece was created.

Example 2 Using 20 g of glycerin as a starting material and using 6 g of potassium hydroxide as a catalyst, 2160 g of n-hexyldiethylene glycol glycidyl ether shown in the following formula was first reacted for desalting and purification. 1,861 g of an organic compound with a molecular weight of 9,443 (calculated from the hydroxyl value) was obtained.

A knee CHz-CH-0- CHzO(CHzCHJ) 2CH2CH,C)1. C
H2CH2CH.

Y:H m:13 to:3 Potassium thiocyanate 25% in 500g of the above organic compound
A solution of 200 g of acetone was added thereto, stirred to obtain a homogeneous solution, and then topped with acetone under reduced pressure to obtain a complex.

50g of this complex and Ikg of polypropylene resin were kneaded in a twin-screw extruder at 180°C for 10 minutes, and the kneaded product was molded at the same temperature for 2 minutes using a hot press method under a pressure of 50kg/cm (230cm x 230m). A test piece was obtained.

Example 3 Using 20 g of 1,4-butanediol as a starting material and using 5 g of potassium hydroxide as a catalyst, υ phenylethylene glycol glycidyl ether 180 as shown in the following formula was prepared.
0g was reacted and desalted and purified to obtain a product with a molecular weight of 7190 (
1461 g of an organic compound (calculated from the hydroxyl value) was obtained.

Y: ■ m: 19 to: 3 above organic compound 500. 25g of sodium perchlorate inside
A solution prepared by dissolving 100 g of methanol was added thereto, stirred to obtain a homogeneous solution, and then methanol was added to the mixture under reduced pressure to obtain a complex.

50g of this complex and Ikg of polypropylene resin were kneaded in a twin-screw extruder at 180°C for 10 minutes, and the kneaded product was molded at the same temperature for 2 minutes using a hot press method under pressure of 50kg/cm2 (230+wm x 230m+a x 3).
mm) A test piece was prepared.

Example 4 Starting with 15 g of butylamine! # quality, using 9 g of potassium hydroxide as a catalyst, then n-hexylhexaethylene glycol glycidyl ether 3100 as shown in the following formula.
g was reacted and desalted and purified to obtain a product with a molecular weight of 14,360, which is represented by formula 0 (however, the substituents etc. are as follows).
2497 g of an organic compound (calculated from hydroxyl value) was obtained.

Z: CHx-CHz-CHx-CHt-! 1-A
Knee CH2-CH-0- CIIzO (CHzCHzO), C) 12cH2cH
2cH2cH2cH3Y:H m: 17:2 In 500g of the above organic compound, 25g of lithium perchlorate
A solution prepared by dissolving 100 g of methanol was added thereto, stirred to obtain a homogeneous solution, and then methanol was added to the mixture under reduced pressure to obtain a complex.

70g of this complex and Ikg of polypropylene resin were kneaded in a twin-screw extruder at 180°C for 10 minutes, and the mixed material was molded at the same temperature for 2 minutes using a hot press method using a pressure of 50kg and 7cm (230cm rigid x 230mm x 31111).
L/, a test piece was obtained.

Example 5 Using 20 g of 1.4-butanediol as a starting material and using 5 g of potassium hydroxide as a catalyst, 1,800 g of phenylethylene glycol glycidyl ether shown in the following formula was reacted, and then methyl chloride was added to the hydroxyl group in an amount of 1. After reacting with 2 equivalents and terminal methylation, desalting and purification are performed to obtain an organic compound 14 with a molecular weight of 7190 (calculated from the hydroxyl value) represented by formula 0 (however, the substituents etc. are as follows).
61g was obtained.

Y: -CI (3 m:19:3 25 g of sodium perchlorate in 500 g of the above organic compound
A solution prepared by dissolving 100 g of methanol was added thereto, stirred to obtain a homogeneous solution, and then the methanol was trapped under reduced pressure to obtain a complex.

50 g of this complex and I kg of polypropylene resin were kneaded at 180°C for 10 minutes using a twin-screw extruder, and the kneaded product was molded (23 (1+s x 230 mm x 3 +
++a) L. A test piece was created.

Comparative Example: Ikg of polypropylene resin was heated to 180°C using a twin-screw extruder.
Knead for 10 minutes, then mold at the same temperature for 2 minutes using a hot press method with a pressure of 50 kg/am2 (230 mm x 230 m
Mark × 311 Im) L, a test piece was created.

Results The test pieces obtained in Examples 1 to 5 and Comparative Example had no significant difference in physical properties and appearance, and the results of measuring their surface resistance and tensile yield strength were as follows.

Tensile yield strength (Ω) -Ja King knee Example 1 1.2X1014313 Example 2 1.5X1014320 Example 3 1.3X10" 323 Example 4
8. I X 10” 310 Example 5
1.5 x 10 eyes 326 comparative example 2
XIO" or more 330 [Method for measuring surface resistance value] Measure the surface resistance 30 seconds after applying a voltage of 500 V using a super insulation resistance meter 4329A manufactured by YHP (Yokogawa Heuret Puff Card). did.

Effects of the Invention According to the present invention, a molded article with significantly improved conductivity can be obtained by using a resin that has been thought to have a problem with IT properties without substantially impairing the physical properties and hue of the resin. .

Claims (1)

[Scope of Claims] The following general formula Z-[(A)_m-Y]_k(1) is used as a raw material for a resin molded body [where Z is an active hydrogen-containing compound residue, and Y is an active hydrogen group or a carbon number of 1] ~20 alkyl, aryl, or alkylaryl groups, m is an integer of 1 to 250, k is 1 to 12
An integer, A is the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (2) (n is an integer of 0 to 25, R is an alkyl group, aryl group, or alkylaryl group having 1 to 20 carbon atoms) ]
1. A method for modifying the conductivity of a resin molded article, which comprises kneading a complex of an organic compound having a skeleton represented by the formula and an electrolyte salt soluble therein, and molding the mixture.