JP3132219B2 - Method for producing conductive resin composite - Google Patents

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] There have already been various proposals as a method for obtaining a composite of a general-purpose resin and a conductive polymer. For example, JP
No. 1-157522 discloses a method of forming a conductive polymer layer on a general-purpose resin by first 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. [0003] Japanese Patent Application Laid-Open No. Sho 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 electrolyte solution containing a monomer that becomes a conductive polymer by electrolytic polymerization. A method is disclosed in which a conductive polymer is formed in a resin to obtain a conductive resin composite. Japanese Patent Application Laid-Open No. 61-3742 discloses a method of impregnating a general-purpose resin sheet with an electrolytic polymerization solution and then pressing electrodes from both sides of the sheet to perform electrolytic polymerization to obtain a conductive composite. ing. [0005] However, Japanese Unexamined Patent Publication No.
According to the method disclosed in JP-A 1-157522, it was difficult to control the content and thickness of the conductive polymer in the obtained conductive composite. In the method disclosed in JP-A-60-105532, only a film-like 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 JP-A-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 and the like. Characteristics are lost. [0006] The present invention relates to the essential properties of general-purpose resins, for example,
An object of the present invention is to provide a method for obtaining a composite of a general-purpose resin and a conductive polymer without impairing mechanical strength or the like. Moreover, the present invention provides a method capable of manufacturing conductive resin composites of various shapes and easily adjusting the thickness of the conductive layer. [0007] The present invention provides (a)
In a polymerizable monomer other than the condensation system, (b) a monomer that becomes a conductive polymer by electrolytic polymerization and (c) an electrolyte are dissolved, 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 the component (b) is subjected to electrolytic polymerization by application, followed by the polymerization of the component (a). 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, on the surface of the general-purpose resin layer formed by polymerizing a polymerizable monomer other than the (a) condensation type, a layer made of a conductive polymer formed by electrolytic polymerization of the monomer of the component (b) is provided. 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 is not particularly limited, but the ratio of the conductive polymer layer to the general-purpose resin layer is generally about 0. 0.0000000
It is 01 to 1. The polymerizable monomer other than the condensation type, which is the component (a) in the present invention, has a low molecular weight during polymerization, such as an addition polymerization reaction, a polyaddition reaction, a cyclization polymerization reaction, an isomerization polymerization reaction, or a ring-opening polymerization reaction. A monomer that forms a polymer without elimination of components. Representative examples of the monomer include addition polymerizable monomers such as methacrylates, acrylates, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, and derivatives thereof; A mixture of a polyol and a polyisocyanate compound as raw materials of a urethane resin, a glycidyl compound as a raw material of an epoxy resin, and the like are also applicable. Above all, addition polymerizable monomers containing 50% or more of acrylic acid esters and methacrylic acid esters are preferable. The component (a) is preliminarily mixed with a so-called catalyst, initiator and curing agent suitable for the polymerization of the component. Furthermore, it is also possible to add a coloring agent, a light diffusing agent, a reinforcing agent, a filler, a mold release agent, a stabilizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, etc., if necessary. is there. The component (b) of the present invention, which is a monomer which becomes a conductive polymer by electrolytic polymerization, is dissolved in the component (a),
It is a compound that becomes polymerized by oxidation and reduction and becomes conductive. For example, pyrrole, thiophene, furan, selenophene, tellurophene, isothianaphthene and other five-membered heterocyclic compounds and their alkyl groups, halogens, hydroxyl groups, carboxyl groups, alkylene oxide groups, oxyalkyl groups, alkylsulfonic acids and salts thereof 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, alkylsulfonic acids, and salts thereof. And the like. Among them, a 5-membered heterocyclic compound and a derivative thereof are preferable, and pyrrole and a derivative thereof are particularly preferable. Further, two or more 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 to the component (a). The electrolyte which is the component (c) of the present invention includes (a)
This is an electrolyte that dissolves in the component, and is used to supply electricity during the electropolymerization of the 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 protic acid salt such as sodium alkyl sulfonate, sodium alkylbenzene sulfonate;
Organic quaternary ammonium salts such as (C ₂ H ₅ ) ₄ NClO ₄ ; polymer salts such as polysodium methacrylate; and other compounds such as protonic acids and esters. Further, two or more of the above electrolytes can be used in combination. These amounts are generally in the range of 0.1 kg / kg of component (a).
0001 to 10 mol. More preferably 0.001
１1 mol. The solution obtained by mixing the components (a), (b) and (c)
Further, a solvent (d) for the electrolyte 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 the electrolyte of the component (c) is dissolved and uniformly mixed with the mixed solution of the 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,
Ethanol, water and the like can be mentioned. Further, two or more of the above solvents can be used in combination. The amount of the solvent is 0.001 to 100 parts by weight based on 100 parts by weight of the component (a). If it exceeds 100 parts by weight, the mechanical strength and the like of the obtained conductive resin composite will decrease. The components (a), (b) and (c) and, if necessary,
(d) The solution in which the components are mixed and dissolved is poured 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 has a built-in counter electrode and can be heated, cooled, or irradiated with ultraviolet light 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, for example, glass, various metal ceramics, and various synthetic resins on a suitable base such as plating, evaporation, and sputtering. And those deposited by the method. Next, a DC voltage is applied to the electrolytic polymerization cell.
(b) The component is subjected to electrolytic polymerization. If the component (b) becomes a polymer having conductivity by oxidation, the electrode side on which the conductive film is formed is used as an anode, and if the component (b) becomes a polymer having conductivity by reduction, The electrode on which the conductive film is formed is used as a cathode. Applied voltage is about 1mV ~ 100V
It is. The current density and electropolymerization time are (a), (b), (c)
Once the components and their ratios are determined, the desired layer of the conductive polymer layer is determined. Generally, the current density is 0.000
About 0.01 to 1000 mA / cm ³ , preferably 0.000
It is preferable to perform electrolytic polymerization at about 1 to 100 mA / cm ³ . Under this condition, if the correlation between the amount of electric charge and the thickness of the conductive resin layer formed on the monomer contact surface of the electrode of a specific size to be used is obtained, the electrolytic polymerization time can be easily determined using this as a guide. Can be determined. The thickness of the conductive polymer layer can be selected depending on the required application of the conductive resin composite, but is generally 0.001 μm to 1 mm.
It is about. The component (b) in the solution may be completely consumed by the electrolytic polymerization, or may be partially consumed in the component (a) or the component (a) and the component (d) without being consumed by the electrolytic polymerization. It may not be dissolved therein, and may remain in a mixed state. After the completion of the electrolytic polymerization, the component (a) is polymerized. This polymerization method is not particularly limited, and may be a known polymerization method of the component (a) used in the cell. That is, at the time when the electropolymerized layer of the component (b) is completed,
(a) The component remains in an unpolymerized state. The polymerization reaction of the component (a) is caused by placing the electrolytic polymerization cell containing such a system under the conditions of a commonly used polymerization method. For example, when the addition polymerizable monomer is used as the component (a), depending on the used initiator or catalyst, for example,
The radical polymerization reaction is carried out at a temperature (usually about 0 to 150 ° C.) effective for polymerizing the component (a) used. When the polyol and the polyisocyanate are used as the component (a), the polyol and the polyisocyanate are used at a temperature (usually about 0 to 100 ° C.) effective for the reaction of the two components depending on the catalyst used. The entire amount of the component is subjected to a urethanization reaction. When the glycidyl compound is used as the component (a), the composition is cured under conditions suitable for the curing agent used.
When irradiating with ultraviolet rays, polymerization is performed with a sufficient irradiation amount. After the completion of the polymerization of the component (a), the cell is disassembled to take out the conductive resin composite. According to the present invention, a composite having conductivity can be obtained without deteriorating the inherent properties of various general-purpose resins. Further, according to the present invention, it is possible to produce conductive composites of various shapes, and the thickness of the conductive layer can be easily controlled. The conductive resin composite obtained by the present invention,
It can be applied to antistatic materials, electromagnetic wave shielding materials, electrodes and the like. Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The steps of the method in the embodiment will be described with reference to the drawings. First, the component (a) (catalyst, initiator,
(Including a curing agent), component (b) and component (c), and if necessary, component (d) and additives to prepare an electrolyte solution. Next, the solution 4 obtained as shown in (1-1) is injected into the electrolytic polymerization cell. Thereafter, a DC current is passed between the working electrodes 3 using the DC power supply 1 to subject the component (b) to electrolytic polymerization. Thus, as shown in (1-2), (b)
The conductive polymer layer 6 generated by the electrolytic polymerization of the components is uniformly formed on the surface of the working electrode 3. If two or more monomers are used as component (b), each monomer is polymerized under different electrolytic polymerization conditions to obtain two or more conductive polymer layers. In this state, the electrolytic polymerization cell is
(a) by subjecting it to conditions for the polymerization of the components,
The components are polymerized. As a result, a layer of a polymer formed by polymerization of the component (a) is formed in a state in which the layer is in close contact with the conductive polymer layer 6, and the conductive resin composite of the present invention is obtained. Thereafter, 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 as shown in (1-3) is obtained. Evaluation items in the embodiment are based on the following method. -The surface resistivity of the conductive film was measured by a two-terminal method using a digital multimeter model CDM-200 manufactured by Custom Co., Ltd.・ Mechanical strength was measured for flexural strength and flexural modulus according to JIS K7203.・ The thickness of the conductive film is ERICHSEN GMBH & COKG (Erichen)
PAINT INSPECTION GAGE (Paint Inspection Gage) It measured using PIG455 type. EXAMPLE 1 LiClO ₄ 0.1 g in 0.1 liter of methyl methacrylate
01 mol, 0.005 mol of pyrrole and 0.5 mmol of azobisisobutyronitrile were dissolved. This solution was injected into an electrolytic polymerization cell consisting of two glass plates (surface resistivity: 100Ω, 12 cm × 12 cm) coated with indium-tin oxide (ITO) sandwiching a 3 mm-thick polyvinyl chloride gasket. GOOD WILL INSTRUME as power supply
Model GPR of NT CO., LTD Goodwill Instrument Company
Using -1830, a constant voltage of 10 V was applied between the electrodes using ITO as an electrode 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. Thereafter, the electrolytic polymerization cell was placed in a water bath at 75 ° C. for 3 hours,
It was put in an air bath at 120 ° C. for 1 hour to perform radical polymerization of methyl methacrylate. Thereafter, 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,
The surface resistivity is 1.4 × 10 ⁵ Ω and the bending strength is 1320 kg
f / cm ² , and the flexural modulus was 34000 kgf / cm ² . Example 2 In Example 1, L was used instead of 0.01 mol of LiClO _4.
The same procedure was repeated except that iBF _{4 was} 0.01 mol.
mm of a methyl methacrylate polymer-polypyrrole complex was obtained. The current density is 0.14 mA / cm ^{2 at} the beginning of electropolymerization and 0.
It was 10 mA / cm ² . The thickness of the polypyrrole layer is 1.3μ
m, surface resistivity 6.0 × 10 ⁴ Ω, bending strength 125
0 kgf / cm ^2, a flexural modulus of 33600kgf / cm ^2. Example 3 In Example 1, L was used instead of 0.01 mol of LiClO _4.
The same operation was performed 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 flexural strength is 1280 kgf / cm ² , and the flexural modulus is 33800.
kgf / cm ² . Example 4 A 3 mm thick methyl methacrylate polymer-polypyrrole composite 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 ×
10 ⁵ Ω, flexural strength was 1320 kgf / cm ² , and 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 20 V for 5 minutes.
The procedure was repeated in the same manner except that the reaction was carried out for 1 minute 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 5 × 10 ⁹ Ω, bending strength 130
0 kgf / cm ^2, a flexural modulus of 33000kgf / cm ^2. Example 6 N-type was prepared in the same manner as in Example 1 except that 0.005 mol of pyrrole was used.
Using 0.005 mol of methylpyrrole, 1
The same operation was performed except that the operation was performed 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. 5 mm, and the radical polymerization conditions were 60 ° C. for 7 hours in a water bath, 120 minutes in an air bath.
The same procedure was repeated except that the temperature was changed to 1 hour at a temperature of 1 ° C. to obtain a methyl methacrylate polymer-polypyrrole composite having a thickness of 5 mm. The current density is 0.17 mA / cm ^{2 at} the beginning of electropolymerization and 0.13 mA / cm 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. 10 mm, and 10 minutes at 40 ° C. in a water bath, 5 hours at 60 ° C., 5 hours at 80 ° C., and 1 hour at 120 ° C. in an air bath. A methyl methacrylate polymer-polypyrrole complex of the formula (1) was obtained. 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. Flexural strength is 120
0 kgf / cm ^2, a flexural modulus of 34000kgf / cm ^2. Example 9 A 3 mm-thick methyl methacrylate polymer was prepared in the same manner as in Example 1 except that the electrolytic polymerization time was changed to 3 minutes.
A polypyrrole complex 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. The thickness of the polypyrrole layer is 1 μm, the surface resistivity is 3 × 10 ⁵ Ω, the flexural strength is 1300 kgf / cm ² , and the flexural modulus is 34000 kg.
f / cm ² . Example 10 A 3 mm-thick methyl methacrylate polymer-polypyrrole composite was obtained in the same manner as in Example 1 except that the electrolytic polymerization time was changed to 10 minutes. Current density is at the beginning 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
⁴ Ω, flexural strength was 1300 kgf / cm ² , and flexural modulus was 34000 kgf / cm ² . Example 11 The procedure of Example 1 was repeated, except that 0.24 ml of water was added to the solution and the electropolymerization voltage was changed to 8 V.
A 3 mm thick methyl methacrylate polymer-polypyrrole composite 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 flexural strength is 1140 kgf / cm ² , and the flexural modulus is 35600 kgf /
It was cm ^2. Example 12 The procedure of Example 1 was repeated, except that 3.6 ml of acetonitrile was added to the solution, and the electrolytic polymerization voltage was changed to 6 V, to obtain a 3 mm-thick methyl methacrylate polymer-polypyrrole composite. 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 is 1010 kgf / cm ² , flexural modulus is 3000
It was 0 kgf / cm ² . Example 13 The procedure of Example 1 was repeated except that 2.3 ml of tetraethylene glycol dimethyl ether was added to the solution, and the electropolymerization voltage was changed to 6.5 V. A methyl methacrylate polymer having a thickness of 3 mm was obtained. -A polypyrrole complex was obtained. The current density is 0.10 mA / cm ^{2 at} the beginning of electrolytic polymerization and 0.08 at the end
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 diagram of the method of the present invention. [Description of Signs] In the figure, (1-1) shows a state in which the injection into the electrolytic polymerization cell has been completed. In the figure, (1-2) shows the situation when the electrolytic polymerization is completed. In the figure, (1-3) shows the generated conductive resin composite. In the figure, reference numeral 1 denotes a DC power supply. 2 shows a gasket. Reference numeral 3 denotes an electrode. 4 is (a), (b),
(c) Shows a mixed solution of the components. Reference numeral 5 denotes an outer frame of the cell.
Reference numeral 6 denotes the formed conductive polymer layer. 7 shows a general-purpose resin part.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 27/00-27/42 C08G 61/12

Claims (1)

(57) [Claims] [Claim 1] (a) The polymerizable monomers other than the condensation system include:
(b) monomers that become a conductive polymer by electrolytic polymerization,
And (c) dissolving the electrolyte, injecting the solution into an electropolymerization cell, applying a DC voltage to the cell to electropolymerize the component (b), and then polymerize the component (a). A method for producing a resin composite. 2. The method according to claim 1, wherein the solution further comprises a solvent (d) as the component (c).