JPH04103659A - Electrically conductive resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent moldability, heat resistance, mechanical strength, stable electrical conductivity and rapid charging properties by immersing a composition comprising a specific polyamide and an electrically conductive filler in an iodine-containing electrolyte solution, and doping the composition with iodine. CONSTITUTION:A composition comprising (A) 100 pts.wt. polyamide (preferably nylon 22, nylon 4 and nylon 46) having a ratio (CH2/NHCO) of methylene group to amide group in a polymer main chain of 1-4 and (B) 1-200 pts.wt. electrically conductive filler (e.g. carbon powder, carbon fiber or graphite) is immersed in (C) an iodine-containing electrolyte solution (e.g. aqueous solution of potassium iodine or aqueous solution of zinc iodine) dissolving 1-100 pts.wt. iodine and doped with a given amount of iodine under a voltage loaded condition or voltage unloaded condition to give an electrically conductive resin composition having excellent molding properties, heat resistance, mechanical strength and stable electrical conductivity and rapid charging properties.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a conductive resin composition and a method for producing the same.

More specifically, the present invention relates to a conductive resin composition comprising polyamide and a conductive filler and doped with iodine, and a method for producing the same.

The conductive resin composition of the present invention has excellent moldability, heat resistance, and mechanical strength, as well as stable conductivity and quick chargeability, so it is particularly applicable as electrodes, battery display elements, and various sensor materials. Ru.

(Prior Art) It is known that polyamide such as nylon 6 absorbs iodine, which is a positive electrode active material, to form an adduct, and that this adduct exhibits conductivity (7 Jamamoto).

etc,, J, Mater, Sci,, 21.60
4 (1986)), and it is also known that when such an adduct is used as a battery, it has the following characteristics. Namely: ■It has very high current efficiency and energy efficiency.

■Continuous charging and discharging is possible. ■Has an electromotive force of approximately 1.3 $8), which is compatible with nickel-cadmium batteries.

■Can draw large current. ■Features include quick charging.

However, conventional iodine adducts using nylon 6 and nylon 66 have improved moldability and heat resistance due to the addition of iodine.

There was a problem in that the mechanical strength decreased significantly.

Furthermore, although the charging speed is fast, it is not necessarily sufficient, and further improvements are needed.

Thus, although polyamide iodine adducts have excellent conductive properties, they have low moldability, heat resistance, and mechanical strength, and for this reason, they have been used in electrodes and batteries to date.

It was never used as a display element or a sensor material for each god.

(Problem to be Solved by the Invention) In view of the above circumstances, the object of the present invention is to provide a conductive resin composition that has excellent moldability, heat resistance, and mechanical strength, as well as stable conductivity and quick chargeability. The purpose of this invention is to provide a manufacturing method for the same.

(Means for Solving the Problems) As a result of intensive research aimed at solving the problems, the present inventors discovered a conductive resin composition consisting of a specific polyamide, a conductive filler, and iodine as a doping agent. 1 thing
The present invention has been achieved by discovering that all the problems of the present invention can be solved.

That is, the present invention consists of 100 parts by weight of a polyamide whose methylene group to amide group ratio (CHz/NHCO) in the polymer main chain is 1 to 4 and 1 to 200 parts by weight of a conductive filler, and iodine is used as a doping agent. 1 to 1000 parts by weight of a conductive resin composition. Furthermore, in producing the conductive resin sulfate, the present invention involves immersing a resin composition made of polyamide and a conductive filler in an electrolyte solution in which iodine is dissolved, under a voltage load state or under a no voltage load state. The present invention relates to a method for producing a conductive resin composition, which is characterized by doping a predetermined amount of iodine.

The polyamide used in the present invention has a ratio of methylene groups to amide groups in the polymer main chain (CI (t/NHCO
) is 1 to 4.

The polyamide used in the present invention can be obtained by polycondensing a diamine component and a dicarboxylic acid component, or by polycondensing amino acids or lactams. Such diamine components include ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, and the like. Such dicarboxylic acids include oxalic acid, succinic acid, and adipic acid. Such amino acids include 2-aminoethanoic acid, 3-aminopropanoic acid, 4-aminobutanoic acid, and 5-aminopentanoic acid. Such lactams include 2-pyrrolidone.

A part of the polyamide of the present invention may be replaced with other copolymer components. The copolymerization component is not particularly limited, and known amide group-forming components can be used. Typical examples of copolymerized components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, ε-caprolactam, ω-
Lactams such as lauryl lactam. Undecamethylene diamine.

Dodecamethylene diamine, 2,2.4-/2.4.4
-) Limethylhexamethylenediamine, 5-methylnonamethyldiamine, metaxylylenediamine, paraxylylenediamine, ■, 3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino -3-aminomethyl-3,5,5-trimethylcyclohexane, bis(3-methyl-4-aminocyclohexyl)methane, 2°2-bis(4-aminocyclohexyl)propane.

Diamines such as bis(aminopropyl)piperazine and aminoethylpiperazine, and speric acid, azelaic acid,
Sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid.

2-methylterephthalic acid, 5-methylisophthalic acid, 5
-Sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid.

Examples include dicarboxylic acids such as diglycolic acid.

The polyamide preferably used to achieve the objects of the present invention is nylon 22. Nylon 4 and nylon 46
It is.

The method for producing the polyamide used in the present invention is arbitrary. For example, any polymerization method such as an interfacial polymerization method, a melt polymerization method, a solution polymerization method, or a solid phase method can be used.

There is no particular restriction on the relative viscosity of the polyamide used in the present invention, but one in the range of 1.5 to 5.0 is preferably used. If the relative viscosity is less than 1.5, it is not preferable because a resin composition having satisfactory moldability, mechanical strength, and heat resistance cannot be obtained. If the relative viscosity of the polyamide exceeds 5.0, the moldability will be significantly reduced, which is not preferred. In the present invention, relative viscosity uses 96% sulfuric acid,
Depth 1g/d! ! ,.

Measure at 25°C.

Examples of the conductive filler used in the present invention include carbon powder, carbon fiber, graphite, metal powder, and metal fiber. These fillers can be selected depending on the use and purpose.

Representative examples of electrolyte solutions used to dissolve iodine in the present invention include aqueous solutions of potassium iodide, calcium iodide, sodium iodide, barium iodide, magnesium iodide, zinc iodide, nickel iodide, etc. It is.

The amount of the conductive filler used in the present invention is 1 to 200 parts by weight per 100 parts by weight of the polyamide.

The electrical conductivity of the resin composition of the present invention increases as the amount of the conductive filler increases.

Heat resistance and mechanical strength are generally improved. But 20
If it exceeds 0 parts by weight, moldability may deteriorate, which is not preferable. On the other hand, if the amount of the conductive filler is less than 1 part by weight, the heat resistance and mechanical strength will be insufficient. Further, in that case, there is a possibility that iodine cannot be doped quickly, which is not preferable.

In the present invention, the amount of iodine blended as a doping agent is 1 to 1000 parts by weight per 100 parts by weight of polyamide. As the amount of iodine doped increases, a higher current value can be obtained. However, as the amount of iodine doped increases, the heat resistance, mechanical strength, and moldability of the resin composition decrease. On the other hand, if the amount of iodine doped is small, a high current value cannot be obtained. Therefore, the most preferable iodine doping amount is polyamide 100.
The amount is 1 to 1000 parts by weight.

The resin composition of the present invention can be obtained by immersing a resin composition made of polyamide and a conductive filler in an electrolyte solution in which iodine is dissolved, and doping it with a predetermined amount of iodine under a voltage load or no voltage load. It will be done. The resin composition of the present invention can be obtained more quickly by doping under voltage load.

The resin composition of the present invention may contain pigments, heat stabilizers, and antioxidants as long as they do not significantly impair its properties.

It is also possible to add weatherproofing agents, H fuel agents, plasticizers, mold release agents, reinforcing materials, and the like. Such heat stabilizers include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, or mixtures thereof. In particular, copper compounds are the most effective. Reinforcing materials include clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica alumina, magnesium oxide, and calcium silicate.

Asbestos, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, aluminum hydroxide, calcium hydroxide, barium sulfate,
Potassium light bread, sodium light bread, Tetsumen bread, glass balloon, carbon black, zinc oxide, antimony dioxide, oxalic acid.

Granules, zinc oxide, zeolite 5 hydrotalcite, metal fibers, metal whiskers, ceramic whiskers,
Examples include potassium titanate, boron titanate, mica, and glass fiber.

Furthermore, it is also possible to add other polymers to the resin composition of the present invention, if necessary. Rubbery copolymers such as polybutadiene, butylene-styrene copolymer, acrylic rubber, ethylene-propylene copolymer, EPDM, natural rubber, chlorinated butyl rubber, and chlorinated polyethylene can be used as the bending polymer.

Styrene-butadiene block copolymer, butadiene-
Elastomers such as styrene radial teleblock copolymers, nylon 6, nylon 66, nylon 12. Other polyamides such as nylon 610.

Polypropylene, butadiene-acrylonitrile copolymer, polyvinyl chloride, PET, polyacecool 1, polyvinylidene fluoride, polysulfone, PPS, polyethersulfone, phenoxy resin.

Examples include PPO, PMMA, and polyetherketone.

In the present invention, the method for producing the resin composition comprising polyamide and conductive filler is arbitrary. For example, the components of such a resin composition can be mixed using a panburi mixer, tumbler mixer, or other methods, and then molded by methods such as direct injection molding, extrusion molding, and blow molding. After mixing each component using a panburi mixer, tumbler mixer, or other method, the mixture is melt-mixed using an extruder or the like to form pellets, which are then injection molded or extruded.

It can be made into a molded article by a method such as blow molding.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 Nylon 46 resin (manufactured by Unitika ■, F5000)
Mix 100 parts by weight and 20 parts by weight of carbon powder (Ketchen Black) in a tumbler, and heat at 90°C for 16 minutes.
Vacuum dried for hours. This was then melted and kneaded in a twin-screw presser (manufactured by Ikegai Iron Works, PC?+45) at a cylinder temperature of 300°C to obtain pellets. This pellet was molded using an injection molding machine (manufactured by Nippon Steel Corporation, JlooS) at a cylinder temperature of 300° C. to obtain a rectangular test piece with a width of 10 mm and a length of 50 m. The weight of this test piece was 1.24g.

300 cc of water was placed in a beaker, and 100 g of zinc iodide was dissolved therein. Further, 30 g of iodine was dissolved in this solution to prepare an iodine electrolyte solution. A rectangular test piece formed in this zinc iodide solution was immersed at 25° C. for 24 hours to perform doping with 1 iodine.

After taking out the rectangular test piece, it was vacuum dried at 100°C for 24 hours. The weight of the test piece after vacuum drying is 1.72
It was g.

Table 1 lists the physical properties of the test pieces before and after doping.

Table 1 Physical Properties of Resin Composition The resin composition was electrically connected and doped at 25° C. for 24 hours. After taking out the rectangular test piece, it was vacuum dried at 100'C for 24 hours. The weight of the test piece after vacuum drying is 2.
It was 21g.

Table 2 lists the physical properties of the test piece after doping.

Table 2 Physical Properties of Resin Composition Example 2 Using the rectangular test piece molded in Example 1 and the same doping solution as in Example 1, iodine doping was performed under a voltage load of <7.5V as follows. .

i.e. put a zinc plate into one side of the doping solution.

A rectangular test piece was placed in the other. Example 3 Nylon 46 resin (Manufactured by Unitika, F5000)
100 parts by weight of carbon fiber and 20 parts by weight of carbon fiber (manufactured by Toho Racon ■, Besphite f (TA-C3-N) were mixed in a tumbler and vacuum dried at 90°C for 16 hours. Then, this was mixed in a twin-screw presser. (manufactured by Ikegai Iron Works, PCM45) at a cylinder temperature of 300°C to obtain pellets.The pellets were then molded using an injection molding machine (manufactured by Nippon Steel Corporation, JLO) at a cylinder temperature of 300°C.
oS) at a cylinder temperature of 300° C. to obtain a rectangular test piece with a thickness of 2 mm, a width of 10 mm, and a length of 5,011,111 mm.

The weight of this test piece was 1.28 g.

300 cc of water was placed in a beaker, and 100 g of zinc iodide was dissolved therein. Further, 30 g of iodine was dissolved in this solution to prepare an iodine electrolyte solution. A rectangular test piece formed in this zinc iodide solution was immersed at 25°C for 24 hours to perform iodine doping.

After taking out the rectangular test piece, it was vacuum dried at 100°C for 24 hours. The weight of the test piece after vacuum drying is 1.78
It was g.

Table 3 lists the physical properties of the test pieces before and after doping.

(Effects of the Invention) The conductive resin composition of the present invention has excellent moldability, heat resistance, and mechanical strength, as well as stable conductivity and quick chargeability, so it can be used in electrodes, batteries, display elements, etc. Widely used as a sensor material in advanced industrial fields.

Patent applicant: Unitika Co., Ltd.

Claims (2)

[Claims] (1) Ratio of methylene groups to amide groups in the polymer main chain (C
A conductive resin composition comprising 100 parts by weight of a polyamide having a H_2/NHCO) of 1 to 4 and 1 to 200 parts by weight of a conductive filler, and containing 1 to 1000 parts by weight of iodine as a doping agent. (2) Ratio of methylene groups to amide groups in the polymer main chain (C
A conductive resin composition comprising 100 parts by weight of a polyamide with H_2/NHCO) of 1 to 4 and 1 to 200 parts by weight of a conductive filler, and containing 1 to 1000 parts by weight of iodine as a doping agent. During production, a resin composition consisting of an aliphatic polyamide and a conductive filler is immersed in an electrolyte solution in which iodine is dissolved, and a predetermined amount of iodine is doped under a voltage-loaded state or under a no-voltage-loaded state. A method for producing a conductive resin composition.