JPH0649184A - Production of conductive resin composite - Google Patents

Abstract

PURPOSE:To produce a conductive resin composite which comprises a general- purpose resin and a conductive polymer layer formed on the surface of the resin and can have various shapes without detriment to the characteristics of the resin and in which the thickness of the conductive layer is easily controllable and various kinds of general-purpose resin are usable. CONSTITUTION:The composite is produced by dissoving a monomer (A) which forms a conductive polymer by electrolytic polymn. and an electrolyte in a polymerizable monomer (B) other than a polycondensable monomer, pouring the resulting soln. into an electrolytic polymn. cell, applying direct-current voltage to the cell to electrolytically polymerize monomer A, and polymerizing monomer B.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conductive resin composite. [0002] Various proposals have already been made for obtaining a composite of a general-purpose resin and a conductive polymer. For example, JP-A-6
In the 1-157522 publication, first, a method for forming a conductive polymer layer on a general-purpose resin by contacting a general-purpose resin containing an oxidizing agent with a solution or vapor of a monomer that becomes a conductive polymer by oxidative polymerization. It is shown. JP-A-60-105532 discloses that the surface of an anode is coated with a general-purpose resin, and electrolysis is performed by facing the cathode in an electrolytic solution containing a monomer that becomes a conductive polymer by electrolytic polymerization. A method of producing a conductive polymer in a resin to obtain a conductive resin composite is shown. Japanese Unexamined Patent Publication (Kokai) No. 61-3742 discloses a method in which a general-purpose resin sheet is impregnated with an electrolytic polymerization solution, and then electrodes are pressed from both sides of the sheet to carry out electrolytic polymerization to obtain a conductive composite. ing. However, Japanese Patent Laid-Open Publication No.
According to the method of 1-157522, it was difficult to control the content and thickness of the conductive polymer in the conductive composite obtained. According to the method of JP-A-60-105532, only a film-shaped composite can be obtained, and it is difficult to make the surface of a general-purpose resin having a large thickness conductive. In the method of Japanese Patent Laid-Open No. 61-3742, it is necessary to impregnate a general-purpose resin sheet with an electrolytic polymerization solution, so that it is necessary to make the resin porous, etc. The characteristics are lost. The present invention is based on the original characteristics of general-purpose resins such as
It is intended to provide a method for obtaining a composite of a general-purpose resin and a conductive polymer without impairing mechanical strength and the like. Moreover, the present invention provides a method capable of producing a conductive resin composite having various shapes and easily controlling the thickness of the conductive layer. [0007] That is, the present invention is (a)
In a polymerizable monomer other than a condensation system, (b) a monomer that becomes a conductive polymer by electrolytic polymerization and (c) an electrolyte are dissolved, and the solution is injected into an electrolytic polymerization cell, and a DC voltage is applied to the cell. The present invention relates to a method for producing a conductive resin composite, in which a component (b) is subjected to electrolytic polymerization and then a component (a) is polymerized. The conductive resin composite of the present invention has a conductive layer made of a conductive polymer on the surface of a general-purpose resin. That is, a layer made of a conductive polymer formed by electrolytically polymerizing the monomer of the component (b) is formed on the surface of a layer of a general-purpose resin formed by polymerizing a polymerizable monomer other than the condensation type (a). It has been formed. In the conductive resin composite of the present invention, the thickness of the general-purpose resin and the conductive resin layer can be appropriately set, and the ratio thereof is not particularly limited, but the ratio of the conductive polymer layer to the general-purpose resin layer is generally 0. .00000
01 to 1. The polymerizable monomer other than the condensation system which is the component (a) in the present invention is a low molecular weight compound during polymerization such as addition polymerization reaction, polyaddition reaction, cyclopolymerization reaction, isomerization polymerization reaction and ring-opening polymerization reaction. A monomer that forms a polymer without elimination of components. Typical examples of the monomer include addition-polymerizable monomers such as methacrylic acid esters, acrylic acid esters, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, and their derivatives; A mixture of a polyol and a polyisocyanate compound, which are raw materials for the urethane resin, and a glycidyl compound, which is a raw material for the epoxy resin, are also applicable. Above all, addition-polymerizable monomers containing 50% or more of acrylic acid ester and methacrylic acid ester are preferable. The component (a) is used by previously mixing with what is called a catalyst, an initiator or a curing agent suitable for the polymerization of the component. Further, if necessary, it is possible to add a colorant, a light diffusing agent, a reinforcing agent, a filler, a release agent, a stabilizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, etc. is there. The monomer which becomes a conductive polymer by electrolytic polymerization which is the component (b) of the present invention is dissolved in the component (a),
It is a compound that becomes polymerized by oxidation and reduction and becomes conductive. For example, five-membered heterocyclic compounds such as pyrrole, thiophene, furan, selenophene, tellurophen, and isothianaphthene, and their alkyl groups, halogens, hydroxyl groups, carboxyl groups, alkylene oxide groups, oxyalkyl groups, alkylsulfonic acids and salts thereof, etc. Derivatives: aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, azulene, pyrene, carbazole, pyridazine and aniline and their alkyl groups, halogens, hydroxyl groups, carboxyl groups, alkylene oxide groups, oxyalkyl groups, alkyl sulfonic acids and their salts And the like. Of these, a hetero five-membered cyclic compound and its derivative are preferable, and pyrrole and its derivative are particularly preferable. Further, two or more kinds of the above monomers can be used in combination. The amount of the component (b) used may be determined according to the required area and thickness of the conductive film, and is generally 0.0000001 to 1 in weight ratio with respect to the component (a). The electrolyte which is the component (c) of the present invention means (a)
It is an electrolyte that is dissolved in the component, and is for supplying electricity during the electrolytic polymerization of component (b). For example LiCl
O ₄ , LiBF ₄ , LiCF ₃ SO ₃ , LiPF ₆ , L
inorganic ionic salts such as iAsF ₆ , AgClO ₄ and the like;
Or a protonic acid salt such as sodium alkylsulfonate, sodium alkylbenzenesulfonate, and the like;
Examples include organic quaternary ammonium salts such as (C ₂ H ₅ ) ₄ NClO ₄ ; polymeric salts such as sodium polymethacrylate; and other various compounds such as protic acids and esters. Two or more of the above electrolytes can be used in combination. These amounts are generally about 0. 1 kg of component (a).
It is 0001 to 10 mol. More preferably 0.001
~ 1 mol. A solution prepared by mixing the components (a), (b), and (c),
Further, the electrolyte solvent (d) of the component (c) may be added. This solvent (d) is for facilitating the energization of the solution,
There is no particular limitation as long as it dissolves the electrolyte of component (c) and mixes it uniformly in the mixed solution of components (a), (b), and (c). For example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, glymes such as tetraethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, glycols such as polypropylene glycol, propylene carbonate, ethylene carbonate,
Formamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, tetramethylurea,
Dimethyl sulfoxide, acetonitrile, methanol,
Examples include ethanol and water. Also, two or more of the above solvents can be used in combination. The amount of this solvent is 0.001 to 100 parts by weight based on 100 parts by weight of the component (a). When it exceeds 100 parts by weight, the mechanical strength and the like of the obtained conductive resin composite are lowered. (A), (b), (c) components and, if necessary,
(d) The liquid in which the components are mixed and dissolved is injected into the electrolytic polymerization cell. The electrolytic polymerization cell of the present invention is a mold having an internal shape capable of transferring a desired shape to a so-called resin, and a working electrode having a shape for forming a conductive film having a desired shape,
It incorporates a counter electrode and is capable of heating, cooling, or ultraviolet irradiation suitable for polymerizing and curing the component (a). The material of the electrode is not particularly limited as long as it is conductive and corrosion-resistant, for example, stainless steel, copper,
Metals such as aluminum, platinum, gold, and palladium, tin oxide, conductive metal oxides such as indium oxide, and those such as glass, various metal ceramics, various synthetic resins on a suitable substrate such as plating, vapor deposition, sputtering, etc. The thing deposited by the method is mentioned. Next, by applying a DC voltage to the electrolytic polymerization cell,
The component (b) is electrolytically polymerized. If the component (b) becomes a polymer having conductivity by oxidation, the electrode side on which the conductive film is formed serves as an anode, and conversely, if the component (b) becomes a polymer having conductivity by reduction. The electrode side on which the conductive film is formed is the cathode. Applied voltage is about 1mV-100V
Is. Current density and electropolymerization time are (a), (b), (c)
When each component and its ratio are determined, it depends on the desired layer of the conductive polymer layer. Generally, the current density is 0.000
01 to 1000 mA / cm ³ or so, preferably 0.000
It is preferable to carry out electrolytic polymerization at about 1 to 100 mA / cm ³ . Under this condition, the correlation between the amount of energized charge and the thickness of the conductive resin layer formed on the monomer contact surface of the electrode of the specific size to be used can be obtained, and this can be used as a guideline to facilitate the electrolytic polymerization time. You can decide. The thickness of the conductive polymer layer can be selected depending on the intended use of the conductive resin composite, but is generally 0.001 μm to 1 mm.
It is a degree. The component (b) in the solution may be completely consumed in the electrolytic polymerization, or a part of the component (a) or the components (a) and (d) may not be completely consumed in the electrolytic polymerization. It may remain in a mixed state without being dissolved therein. After the completion of electrolytic polymerization, the component (a) is polymerized, but this polymerization method is not special, and it may be carried out by a known polymerization method of the component (a) used in the cell. That is, at the time when the electrolytic polymerization layer of the component (b) is completed,
The component (a) remains unpolymerized. By subjecting the electrolytic polymerization cell containing such a system to the conditions of a commonly used polymerization method, the polymerization reaction of the component (a) is caused. For example, when the addition polymerizable monomer is used as the component (a), depending on the initiator or catalyst used, for example,
The radical polymerization reaction is carried out at a temperature (usually about 0 to 150 ° C.) effective for polymerizing the used component (a). When the polyol and polyisocyanate are used as the component (a), they are used at a temperature (usually about 0 to 100 ° C.) effective for reacting the two components, depending on the catalyst used. The whole amount of the component is subjected to a urethanization reaction. Further, when the glycidyl compound is used as the component (a), it is cured under conditions suitable for the curing agent used.
When irradiating with ultraviolet rays, polymerization is carried out with a sufficient irradiation amount. After the polymerization of the component (a), the cell is disassembled and the conductive resin composite is taken out. According to the present invention, a composite having conductivity can be obtained without impairing the original characteristics of various general-purpose resins. Further, according to the present invention, it is possible to produce various shapes of conductive composites, and it is possible to easily control the thickness of the conductive layer. The conductive resin composite obtained by the present invention,
It can be applied to antistatic materials, electromagnetic wave shielding materials, electrodes and the like. The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The method steps in the embodiments will be described with reference to the drawings. First, the above-mentioned component (a) (catalyst, initiator,
(Including a curing agent), component (b) and component (c), and optionally component (d) and additives to prepare an electrolyte solution. Then, the solution 4 obtained as shown in (1-1) is injected into the electrolytic polymerization cell. After that, a direct current is passed between the working electrodes 3 using the direct current power source 1 to electrolytically polymerize the component (b). Thus, as shown in (1-2), (b)
The conductive polymer layer 6 produced by electrolytic polymerization of the components is uniformly formed on the surface of the working electrode 3. If two or more kinds of monomers are used as the component (b), the respective monomers are polymerized under different electrolytic polymerization conditions to obtain two or more conductive polymer layers. In this state, the electrolytic polymerization cell
By placing under conditions for the polymerization of component (a), (a)
Polymerize the components. As a result, a polymer layer formed by the polymerization of the component (a) is formed in a state of being in close contact with the conductive polymer layer 6 to obtain the conductive resin composite of the present invention. Then, when the electrolytic polymerization cell is disassembled, a conductive resin composite in which a conductive polymer layer is formed on the general-purpose resin layer 7 is obtained as shown in (1-3). The evaluation items in the examples are as follows. -The surface resistivity of the conductive film was measured by a two-terminal method using a custom-made digital multimeter type CDM-200. -Mechanical strength was measured by flexural strength and flexural modulus according to JIS K7203.・ The thickness of the conductive film is made by ERICENSEN GMBH & COKG (Elishen)
PAINT INSPECTION GAGE PIG455 type was used for measurement. Example 1 0.1 liter of methyl methacrylate was added with LiClO ₄ 0.
01 mol, 0.005 mol of pyrrole and 0.5 mmol of azobisisobutyronitrile were dissolved. This solution was poured into an electrolytic polymerization cell consisting of two glass plates (surface resistivity 100 Ω, 12 cm x 12 cm) coated with indium tin oxide (ITO) sandwiching a polyvinyl chloride gasket having a thickness of 3 mm, and the direct current was applied. GOOD WILL INSTRUME as a power supply
NT CO., LTD Goodwill Instrument Model GPR
-1830 was used as an electrode with ITO as an electrode, and a constant voltage of 10 V was applied between both electrodes for 5 minutes to carry out electrolytic polymerization. Current density electrolytic polymerization Initial 0.17 mA / cm ^2, was at the end 0.13 mA / cm ^2. Then, place the electrolytic polymerization cell in a water bath at 75 ° C. for 3 hours,
It was placed in an air bath at 120 ° C. for 1 hour to carry out radical polymerization of methyl methacrylate. Then, the electrolytic polymerization cell was disassembled to obtain a methyl methacrylate polymer-polypyrrole composite having a thickness of 3 mm. The thickness of the polypyrrole layer is 1.5 μm,
Surface resistivity 1.4 × 10 ⁵ Ω, bending strength 1320 kg
f / cm ² , flexural modulus was 34000 kgf / cm ² . Example 2 In Example 1, L was replaced with 0.01 mol of LiClO _4.
iBF ₄ was performed in the same manner except that the amount was 0.01 mol, and the thickness was 3
mm of methyl methacrylate polymer-polypyrrole composite was obtained. The current density is 0.14 mA / cm ^{2 at} the beginning of electrolytic polymerization and 0 at the end.
It was 10 mA / cm ² . The thickness of the polypyrrole layer is 1.3μ
m, surface resistivity of 6.0 × 10 ⁴ Ω, bending strength of 125
0 kgf / cm ^2, a flexural modulus of 33600kgf / cm ^2. Example 3 In Example 1, L was replaced with 0.01 mol of LiClO _4.
The same procedure was carried out except that 0.01 mol of iCF ₃ SO ₃ was used to obtain a methyl methacrylate polymer-polypyrrole composite having a thickness of 3 mm. Current density is 0.14mA / c at the beginning of electrolytic polymerization
m ² and 0.10 mA / cm ² at the end. The thickness of the polypyrrole layer is 1.3 μm, the surface resistivity is 1.0 × 10 ⁵ Ω, the bending strength is 1280 kgf / cm ² , and the bending elastic modulus is 33800.
It was kgf / cm ² . Example 4 A methyl methacrylate polymer-polypyrrole composite having a thickness of 3 mm was obtained in the same manner as in Example 1 except that a stainless steel plate was used instead of the ITO glass. Current density electrolytic polymerization Initial 0.35 mA / cm ^2, was at the end 0.26 mA / cm ^2.
The thickness of the polypyrrole layer is 3 μm and the surface resistivity is 1.4 ×
The flexural strength was 10 ⁵ Ω, the flexural strength was 1320 kgf / cm ² , and the flexural modulus was 33000 kgf / cm ² . Example 5 In Example 1, 0.005 mol of thiophene was used instead of 0.005 mol of pyrrole, and electropolymerization was carried out at 5 V at 20V.
The same procedure was repeated except that the procedure was carried out for 3 minutes to obtain a methyl methacrylate polymer-polythiophene composite having a thickness of 3 mm. Current density electrolytic polymerization Initial 0.31 mA / cm ^2, was at the end 0.24 mA / cm ^2. Surface resistivity is 5 × 10 ⁹ Ω, bending strength is 130
0 kgf / cm ^2, a flexural modulus of 33000kgf / cm ^2. Example 6 In Example 1, N- was used instead of 0.005 mol of pyrrole.
Using 0.005 mol of methylpyrrole, electrolytic polymerization 1
The same procedure was repeated except that the procedure was carried out at 0 V for 5 minutes to obtain a methyl methacrylate polymer-poly N-methylpyrrole composite having a thickness of 3 mm. Current density electrolytic polymerization Initial 0.17 mA / cm ^2, was at the end 0.13 mA / cm ^2. Surface resistivity is 2.5 × 10 ⁹
Ω, flexural strength 1270 kgf / cm ² , flexural modulus 33
It was 200 kgf / cm ² . Example 7 In Example 1, 0.2 liter of methyl methacrylate, 0.02 mol of LiClO ₄ , 0.01 mol of pyrrole and 1 mmol of azobisisobutyronitrile were used, and a polyvinyl chloride gasket was formed to a thickness. 5 mm, and the radical polymerization conditions were 60 ° C. in a water bath for 7 hours and 120 in an air bath.
A methyl methacrylate polymer-polypyrrole composite having a thickness of 5 mm was obtained in the same manner except that the temperature was kept at 1 ° C. for 1 hour. Current density is 0.17mA / cm ^{2 at} the beginning of electrolytic polymerization, and 0.13mA / cm ^{2 at} the end
^{Was 2} . The thickness of the polypyrrole layer is 1.5 μm, the surface resistivity is 5 × 10 ⁵ Ω, and the bending strength is 1250 kgf / cm.
² , the flexural modulus was 34000 kgf / cm ² . Example 8 In Example 1, 0.4 liter of methyl methacrylate, 0.04 mol of LiClO ₄ , 0.02 mol of pyrrole, and 2 mmol of azobisisobutyronitrile were used, and a gasket made of polyvinyl chloride was used. 10 mm in thickness except that the radical polymerization conditions were 10 mm in a water bath, 40 ° C. for 10 hours, 60 ° C. for 5 hours, 80 ° C. for 5 hours, and 120 ° C. for 1 hour in an air bath. To obtain a methyl methacrylate polymer-polypyrrole complex. Current density electrolytic polymerization Initial 0.17 mA / cm ^2, was at the end 0.13 mA / cm ^2.
The thickness of the polypyrrole layer was 1.5 μm. The surface resistivity was 1.2 × 10 ⁶ Ω. Bending strength is 120
0 kgf / cm ^2, a flexural modulus of 34000kgf / cm ^2. Example 9 A methyl methacrylate polymer having a thickness of 3 mm was prepared in the same manner as in Example 1 except that the electrolytic polymerization time was changed to 3 minutes.
A polypyrrole composite was obtained. The current density is 0 at the beginning of electrolytic polymerization.
17mA / cm ^2, it was at the end of 0.14mA / cm ^2. Thickness of polypyrrole layer is 1 μm, surface resistivity is 3 × 10 ⁵ Ω, bending strength is 1300 kgf / cm ² , bending elastic modulus is 34000 kg.
It was f / cm ² . Example 10 A methyl methacrylate polymer-polypyrrole composite having a thickness of 3 mm was obtained in the same manner as in Example 1 except that the electrolytic polymerization time was changed to 10 minutes. Current density is the initial stage of electrolytic polymerization
0.17mA / cm ^2, it was at the end of 0.10mA / cm ^2. The thickness of the polypyrrole layer is 3 μm and the surface resistivity is 2.5 × 10.
^The flexural strength was ⁴ Ω, the flexural strength was 1300 kgf / cm ² , and the flexural modulus was 34000 kgf / cm ² . Example 11 The same procedure as in Example 1 was repeated except that 0.24 ml of water was added to the solution to change the electrolytic polymerization voltage to 8V.
A methyl methacrylate polymer-polypyrrole composite having a thickness of 3 mm was obtained. Current density electrolytic polymerization initial 0.10mA / cm ^2, was at the end 0.08 mA / cm ^2. The thickness of the polypyrrole layer is 1.0 μm, the surface resistivity is 8.5 × 10 ⁴ Ω, the bending strength is 1140 kgf / cm ² , and the bending elastic modulus is 35600 kgf /.
It was cm ² . Example 12 In the same manner as in Example 1 except that 3.6 ml of acetonitrile was added to the solution to change the electrolytic polymerization voltage to 6 V, the same procedure as in Example 1 was carried out to give a methyl methacrylate polymer-polypyrrole composite having a thickness of 3 mm. Obtained. Current density is 0.10 mA at the beginning of electrolytic polymerization
/ Cm ² and 0.08 mA / cm ² at the end. The thickness of the polypyrrole layer is 1.0 μm, the surface resistivity is 2.9 × 10 ⁴ Ω,
Flexural strength 1010 kgf / cm ² , flexural modulus 3000
It was 0 kgf / cm ² . Example 13 A methyl methacrylate polymer having a thickness of 3 mm was prepared in the same manner as in Example 1 except that 2.3 ml of tetraethylene glycol dimethyl ether was added to the solution to change the electrolytic polymerization voltage to 6.5 V. -A polypyrrole complex was obtained. Current density is 0.10mA / cm ^{2 at} the beginning of electrolytic polymerization, 0.08 at the end
It was mA / cm ² . The thickness of the polypyrrole layer is 1.0μ
m, surface resistivity 1.8 × 10 ⁵ Ω, bending strength 12
70 kgf / cm ^2, a flexural modulus of 33100kgf / cm ^2.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic of the method of the present invention. [Explanation of Codes] In the figure, (1-1) shows a state in which the liquid has been injected into the electrolytic polymerization cell. In the figure, (1-2) shows the situation when electrolytic polymerization was completed. In the figure, (1-3) indicates the generated conductive resin composite. In the figure, 1 indicates a DC power supply. 2 shows a gasket. 3 indicates an electrode. 4 is (a), (b),
(c) shows a mixed solution of components. 5 indicates the outer frame of the cell.
Reference numeral 6 represents the generated conductive polymer layer. 7 indicates a general-purpose resin portion.

Claims (1)

Claims: (a) For polymerizable monomers other than the condensation system,
(b) Monomers that become conductive polymers by electrolytic polymerization,
And (c) an electrolyte is dissolved, the solution is injected into an electropolymerization cell, a DC voltage is applied to the cell to electropolymerize the component (b), and then polymerization of the component (a) is conducted. Method for producing resin composite. 2. The method according to claim 1, wherein the solution further contains the solvent (d) as the component (c).