JPS5993740A - Resin composition - Google Patents

Abstract

PURPOSE:A composition, obtained by incorporating a carbonaceous solid-resin composite material prepared by treating the surface of a carbonaceous material with a fluorine-containing high polymer in a thermoplastic resin, and having improved electric conductivity and physical properties, e.g. kneadability and moldability, etc. without losing the characteristics thereof even on molding at high temperatures. CONSTITUTION:A resin composition obtained by incorporating a solid-resin composite material prepared by treating the surface of a carbonaceous material, e.g. graphite, carbon black, activated carbon, carbon fibers or graphite fibers, with a fluorine-containing high polymer in a thermoplastic resin. The solid-resin composite material is prepared by grafting a fluorine-containing monomer onto the surface of the carbonaceous material or adsorbing a metallic salt capable of imparting electric charges to the surface of the carbonaceous material, and bringing the surface of the carbonaceous material into contact with a medium containing the fluorine-containing high polymer having the electric charges opposite to that of the metallic salt. The amount of the resin in the composite material is 0.1-40wt%, preferably 0.1-20wt% based on the carbonaceous material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition, and particularly to a resin composition useful in various applications requiring biconductivity.

Today, cable covering materials such as high voltage cables and communication cables, antistatic materials, shield attachments, resistance and resistance heating elements, electrode materials, electronic materials, packaging materials, plastics such as automobile parts, hoses, belts, safety shoes, etc. 2. Description of the Related Art Conductive resin compositions are widely used in rubber-related products such as flooring materials, switching elements, ignition cables, and static eliminating rolls.

As such resin compositions, those in which conductive carbonaceous materials such as carbon black and graphite are kneaded into a matrix resin are conventionally known.
There is a limit to the amount of filler material that can be blended into this matrix resin.
In the following applications that require electrical conductivity, for example, if carbon black is blended into polyethylene and kneaded, extrusion molding or injection molding is difficult as it is, so rubber-like substances are added to improve the kneading and molding properties. must be improved,
In addition to the unavoidable deterioration of physical properties, there has been a need to develop resin compositions with higher performance in terms of conductivity, kneading properties, and moldability.

From this point of view, the present inventors developed a matrix resin (a conductive carbonaceous material (two) blended together and treated the surface thereof with a resin to improve the adhesion of the carbonaceous material to the matrix resin). Attempts were made to improve the kneading properties and moldability of the resulting resin composition, thereby making it possible to incorporate a large amount of carbonaceous material into the matrix resin.

However, with conventional surface treatments for carbonaceous materials, problems arise with the heat resistance and corrosion resistance of the resin attached to the surface of the carbonaceous material, and when exposed to high temperature and high shear during kneading with matrix resin or molding, the carbonaceous material The resin on the surface of the material will thermally decompose, and the various properties of this carbonaceous material that were surface-treated with resin will be impaired, and as a result, molding may become impossible, or kneadability, moldability, and other physical properties may deteriorate. I ran into a problem where it could drop.

In view of these points of view, the present inventor Tera has developed a product that has excellent electrical conductivity (2) and physical properties such as kneading and moldability, as well as excellent heat resistance, such as during wire cross-circuiting and molding (2) high temperature. As a result of intensive research on two resin compositions whose physical properties do not deteriorate even when exposed to discovered that a resin composition containing
This has led to the present invention.

In the present invention C=, examples of the conductive carbonaceous material that can be blended into the thermoplastic resin serving as the matrix include graphite, carbon black, activated carbon, carbon fiber, graphite fiber, etc.
Particularly preferred are graphite and carbon black.

The graphite may be natural graphite or artificial graphite. Also,
Examples of carbon black include conventionally known Ketjen black, acetylene black, fire black, lamp black, thermal black, channel black, roll black, and disfluorac. The particle size of carbon black is ]5-600
On the other hand, graphite is a particle and has higher conductivity than carbon black.

In addition, the present invention (2), surface treatment I of the carbonaceous material
The fluorine-containing polymer used in X is one containing one or more fluorine atoms in one unit of the polymerized or copolymerized polymer. The fluorine-containing polymers include fluorine-containing polymers obtained by polymerizing fluorine-substituted olefins such as vinyl fluoride, vinylidene fluoride, chlorofluorinated ethylene, tetrafluoroethylene, propylene pentafluoride, and propylene hexafluoride. Substituted polyolefins have the following general formula, and R
2 is a fluorine-substituted alkyl group represented by the general formula -CA Hm F2R3''C, where ! is an integer of 1 to 18, and m is 0
-2 is an integer of 1, R is an integer of 1 to 2, and R3 is a hydrogen atom, a fluorine atom, a phenyl group, or a fluorine-substituted phenyl group. ] Polyfluoroalkyl acrylates obtained by polymerizing fluoroalkyl acrylates shown in ], poly(fluoroalkylethylene glycol) esters obtained by polymerizing (fluoroalkylethylene glycol) esters, and the above-mentioned fluorine-substituted olefins. and other olefins that can be copolymerized with fluoroalkyl acrylates, fluorine-substituted olefins, acrylic acid, methacrylic acid, α-chloroacrylic acid, itaconic acid, maleic anhydride, maleic acid, fumaric acid, etc. Unsaturated carboxylic acids, vinyl halides such as vinyl chloride and vinyl fluoride, styrenes such as sterene and α-methylstyrene, aliphatic vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, and lauryl methacrylate. Fluorine-containing copolymers obtained by copolymerizing unsaturated carboxylic acid esters, fluoroalkyl acrylates, perfluoroalkyl vinyl ethers, etc., or the above-mentioned fluorine-substituted polyolefins, polyfluoroalkyl acrylate a, Fluorine-containing resins such as poly(fluoroalkylethylene glycol) esters and fluorine-containing copolymers can be used as phenol resins, acrylic resins, epoxy resins, polyamideimide resins, urethane resins, propylene-styrene copolymer resins, and ethylene-styrene. Examples include modified fluorine-containing resins obtained by modifying with resins such as copolymer resins and parahydroxybenzoic acid resins, and preferably polyfluoroalkyl acrylates obtained by polymerizing fluoroalkyl acrylates.

Methods for producing a solid-resin composite by surface-treating the carbonaceous material with such a fluorine-containing polymer include conventionally known methods, such as interfacial polymerization, in 5i
tu polymerization method, liquid curing coating method, phase separation method from aqueous solution,
There are phase separation methods from organic solutions, submerged drying methods, melt dispersion cooling methods, inclusion exchange methods, powder bed methods, air suspension coating methods, spray drying methods, vacuum evaporation methods, electrostatic coalescence methods, etc. A preferred method is to graft-polymerize a fluorine-containing vinyl monomer such as fluorine-substituted olefins or fluoroalkyl acrylate a onto the surface of the carbonaceous material, or to impart an electric charge to the surface of the carbonaceous material. After adsorbing the metal salt to be obtained, one of the fluorine-containing polymers having an opposite charge to that of the metal salt is adsorbed.
This method involves contacting a polymer-containing medium containing a species or two or more species. The solid-resin composite obtained by these methods has a strong bond between the carbonaceous material and the fluorine-containing polymer, and the surface of the carbonaceous material (the fluorine-containing polymer adheres uniformly). .

As a method for producing a solid-resin composite by graft polymerization of a fluorine-containing vinyl monomer, various polymerization methods such as bulk polymerization method, solution polymerization method, etc. can be used in the presence of a radical polymerization initiator. However, a method in which a carbonaceous material and a fluorine-containing vinyl monomer are suspended in an aqueous medium (Φ: combined) in the presence of a compound that generates sulfite ions is particularly preferred; The medium is generally water, but is not limited to this, and an aqueous medium such as a mixture of water and methanol can also be used.
As an intermediate initiator, a compound that generates sulfite ions in an aqueous medium, such as blowing sulfur dioxide, an aqueous sulfite solution, or sodium bisulfite,
Sulfites such as ammonium bisulfite, persulfates such as exposed potassium persulfate, sodium persulfate, and ammonium perbitic acid can be used alone or in combination.

The solid-resin composite obtained in this way has a concentration point for free radicals on the surface of the carbonaceous material 4.
One type of fluorine-containing vinyl resin produced by a polymerization reaction is chemically graft-bonded. This solid-resin composite tree]i'i3 is a carbonaceous material (
01 to 4.0 weight ratio, preferably 0 to 20 weight ratio.

In addition, after adsorbing a metal salt that can impart a charge to the surface of the carbonaceous material (2), a fluorine-containing polymer having a charge opposite to that of the metal salt is adsorbed onto the surface of the carbonaceous material. In method C2 for producing a solid-resin composite using a polymer-containing medium (=contact method) containing one or more species, the metal salts that can be used include Ag1.FeCA3, Fe2O3,
Mg C10, fiJ CA3, Fe(OH)3
, FeSO4.

Positively charged substances such as Na25o4 or Ba CA2
Examples of the polymer-containing medium used include emulsions of polyfluoroalkyl acrylates or copolymers thereof, copolymers of fluoroalkyl acrylates and styrene, ethylene, etc. Examples include polymer emulsions, poly(fluoroalkylethylene glycol) ester emulsions, and fluorine-substituted olefin copolymers. The amount of resin in this solid-resin composite is 0.1 to 40 parts by weight, preferably 0.1 to 20 parts by weight, relative to the carbonaceous material (2 parts by weight).

The thermoplastic resin composition that constitutes the resin paste of the present invention and serves as the matrix resin may be any material as long as it can be kneaded and molded with a solid-resin composite, for example, polyethylene, polypropylene, etc. , polyisobutylene, polyene or their copolymers '-J, vinyl halides such as vinyl chloride and vinyl fluoride, styrene compounds such as styrene and α-methylstyrene, and vinyl acetate. Vinyl resins obtained by polymerizing or copolymerizing fatty acid vinyl esters, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, unsaturated carboxylic acid esters such as methyl acrylate and methyl methacrylate, etc. Examples include plastic fluorine-containing resins. These thermoplastic resins may be used alone, or may be used as a blend of two or more resins. Also, these thermoplastic ff&-!
I'lE resin ζ, various additives such as lubricants,
It is also possible to add plasticizers, stabilizers, etc.

The solid compounded in the above heat 1 4' Q-ilj resin-
The proportion of the resin composite may be varied depending on the intended use of the resin composition. (= means that the proportion of carbonaceous material in the resin composition is usually 5 to 70 parts by weight, preferably 15 to 60 parts by weight. If the proportion of carbonaceous material is less than 5% by weight, it is difficult to obtain a substance with satisfactory conductivity. Moreover, if the amount exceeds 700 parts by weight, it will be difficult to obtain satisfactory physical properties in terms of kneading and moldability.

A resin composition containing a solid-resin composite and a thermoplastic resin is prepared by uniformly mixing (mixing and kneading, It is preferable to form pellets, and these pellets can be formed by press molding, extrusion molding,
It can be molded into the desired product by injection molding, sheeting, etc.

In addition, when preparing this resin composition, flame retardants, pigments, plasticizers, stabilizers, antioxidants, ultraviolet absorbers, crosslinking agents, wetting agents, and other solid substances that are usually added to thermoplastic resins are added.
A modifier or the like may be used to improve the density between the resin composite and the thermoplastic resin.

The resin composition of the present invention is not only excellent in physical properties such as conductivity, kneadability, and moldability, but also has excellent properties such as heat control and surface properties. Departure (3
! Even if it is exposed to a height of 4 m during crosstalk or molding, there is little deterioration in physical properties such as conductivity, i, and 1ffj degrees.

Hereinafter, the present invention will be explained in detail based on Examples and Comparative Examples ζ2.

CAI Preparation of solid-resin composites and their adhesion properties (1)
Trial oqN[tl, 3.4. and 9 prepared with an average particle size of 30. 100 g of Ketjen black (by weight) S or 100 g of natural graphite with an average particle size of 6 μ is suspended in 1200 weight portions of water, and 7 parts of oleic acid (pH) and Fe CA3 6 H200 ,3
Add the filtrate and the vinyl monomers shown in Table 1, and add 0.7 parts by weight of persulfuric acid and Na I (SO30,
7 parts by weight were added to the mixture:)'C for 5 hours with stirring, and then filtered, washed with water, and dried to form a solid-resin composite with a vinyl resin on the surface of the solid having a graph I shape. Obtained. The production amount of the obtained solid-resin composite and the amount of resin are shown in Table 1 (Table 2).

(2) Preparation of Samples Nα2 and 10 100 parts by weight of the above natural graphite was suspended in 1200 parts by weight of water, and 07 parts by weight of sodium oleate and the
Add the vinyl monomers shown in the table and add 6 weight coefficient H to ζ et al.
117 parts by weight of 2SO3 aqueous solution was added and reacted with stirring at 60°C for 3 hours, then filtered, washed with water, and dried. The amount of produced solid-resin composite and the amount of resin are shown in Table 1 (2).

(8) Sample N (preparation of L 5 and 6) Parts of Ketjen Black or Graph Eye 00 car] were suspended in 1000 parts by weight of water, and while stirring, this (
200.5 parts by weight of FeC) and .6H as a charge-imparting substance were added, and then the fluorine-substituted polyolefin copolymer solution shown in Table 1 (product name Lumiflon LF 302 D, manufactured by Asahi Glass Co., Ltd.) was added with 100 parts by weight of acetone. Add the diluted material and contact for 1 hour.
l Solid-resin composite of 1 to 12 and polyethylene (product name Showa Denko Co., Ltd., product name: SHOREX ■r6o5oc)
were mixed in the proportions shown in Table 2, and heated and kneaded for 3 minutes using a kneading roll or a Banbury mixer. A resin composition was prepared.

Regarding the resin compositions of each example and comparative example, press temperature 200"C and press pressure 4.0
Form a 1cm thick sheet under the condition of kg/ar+2,
Test specimens were made by punching out dumbbells, and each test specimen (two specimens and their (a) low resistance tensile strength (JIS K
7113) was measured. The results are shown in Table 2.
.

As is clear from Table 2, Comparative Examples 1 and 2 are as follows:
When kneaded with a Banbury mixer, which is thought to generate good shear heat, the tensile strength is significantly lower than when kneaded with a kneading roll. In contrast, in the case of Examples j to 4 in which the surface treatment of the carbonaceous material was carried out with a fluorine-containing polymer, the heat-suppressing inertia Because of this, the resin on the solid surface does not undergo thermal decomposition even when kneaded in a Banbury mixer, and there is no decrease in tensile strength at all.

I
II1 Director-General Kazuo Wakasugi 1'11'] /: Shisho J,,57teI Patent 11 No. 2088672
Name of Zuwaaki Itsuki 1111 Composition 3, Flli
Relationship with 11 (/l) of those who do in
, :l Higashidoor Miyako Chuo-ku Ginrin 6-17-2 t%”
;1 ('<fortune) (664) Nippon Steel Chemical Industry Form Company Representative Daisou Imai 4th Director Rihito 〒104 ' Short story 03 (54
13) 16751I9i 8th floor 7, Ebara Building, 7-14-2 Ginza, Chuo-ku, Tokyo Target of amendment (2) Submit pages 16 and 18 of the specification (no changes to the contents!) as shown in the attached sheet.

Then, after 10 minutes and 30 minutes after heating to 250°C in an electric furnace, the weight loss rate was measured and the heat resistance was investigated. The results are shown in Table 1.

It has been found that a solid-resin composite surface-treated with a fluoropolymer has good heat resistance.

Table 1: The resin on the solid surface does not thermally decompose even when kneaded.
There is no decrease in tensile strength at all.

Table 2

Claims (1)

[Scope of Claims] (1) A resin composition characterized by containing a thermoplastic resin and a solid-resin composite obtained by surface-treating a carbonaceous material with a fluorine-containing polymer. (2) The carbonaceous material is one or more selected from the group consisting of graphite, carbon black, activated carbon, carbon fiber, and graphite fiber.
1. The fat composition according to claim 1, which comprises a combination of: (3) The resin composition according to claim 2, wherein the carbonaceous material is graphite and/or carbon black. (4.) The solid-resin composite is obtained by graft polymerizing the surface of a carbonaceous material (a difluorinated vinyl monomer), according to any one of claims 1 to 3. (5) The solid-resin composite adsorbs a metal salt capable of imparting a charge to the surface of a carbonaceous material, and then adsorbs a fluorine-containing polymer having an opposite charge to that of the metal salt. ] Seed or 2 f!l
The southern resin composition according to any one of claims 1 to 3, which is obtained by contacting with a polymer-containing medium containing i or more.