JPS6233259B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a conductive composition containing a conductive particulate phenolic resin, and more specifically, to a conductive composition containing a conductive particulate phenolic resin. The present invention relates to a conductive resin composition or a conductive rubber composition containing a particulate phenolic resin. Conventional technology Conventionally, conductivity-imparting fillers used in electromagnetic shielding materials generally include powders such as carbon black, aluminum powder, copper powder, and nickel powder, brass fibers, nickel fibers, stainless steel fibers, and carbon fibers. Fibers, even glass fibers,
Materials have been developed in which glass beads, mica, carbon fibers, etc. are plated with nickel, silver, or copper. However, even if the above-mentioned carbon black or aluminum powder is used in large amounts in resin or rubber, it is difficult to obtain a highly conductive composition.
In addition, metal powder and metal fibers have poor dispersibility in resins and rubbers, and not only do they damage molds and extrusion ferrules, but also have high specific gravity, making the resulting products heavy. Further, glass fibers, glass beads, mica or carbon fibers plated with metal have problems such as the metal plating film often peeling off or pulverizing when kneaded into resin or rubber, and the specific gravity is large. Problems to be Solved by the Invention The present inventors have previously provided a novel conductive granular phenolic resin that does not have the above-mentioned problems. Therefore, an object of the present invention is to provide a conductive resin composition or a conductive rubber composition containing a novel conductive particulate phenolic resin. Another object of the present invention is to provide a conductive composition containing a granular conductive phenolic resin which is in the form of particles or powder and has good flow properties and has good moldability. Still another object of the present invention is to have an apparent specific gravity of 1.5 to 3.0.
An object of the present invention is to provide a light-weight conductive composition containing a conductive particulate phenolic resin. Still another object of the present invention is to provide a conductive composition in which the surface of the conductive phenolic resin particles is coated with metal, and therefore does not damage the nozzle or mold during molding. be. Still another object of the present invention is to provide a conductive composition containing a conductive particulate phenol resin having an appropriate particle size distribution and therefore having excellent electromagnetic shielding properties. Further objects and advantages of the invention will become apparent from the description below. Means for Solving the Problems These objects and advantages of the present invention are such that, according to the present invention: (C) The surface of granular phenolic resin is metal-coated with a size that allows 50% by weight of the total to pass through a 100-meter mesh sieve, and the free phenol content is 50 ppm or less as measured by liquid chromatography. This is achieved by incorporating a conductive particulate phenolic resin into a resin or rubber. The conductive granular phenolic resin previously proposed by the present inventors and used in the present invention will be explained below. The granular phenolic resin used for metal coating in the present invention is infusible, insoluble, and has excellent heat resistance.
The specific gravity is small at 1.2 to 1.3, and most of the particles (A) have a particle size of 0.1 to 1.3.
150μ, and (B) at least the entire
The size is such that 50% by weight can pass through a 100 ml mesh sieve, and (C) the free phenol content is as measured by liquid chromatography.
Less than 50ppm. Therefore, the conductive granular phenolic resin used in the present invention, which is obtained by chemically plating or vacuum plating the above granular phenolic resin, has excellent heat resistance and a specific gravity of 1.5.
Since it is as small as ~3.0, it has good uniform dispersibility in plastics and rubber, and can also reduce the weight of the target material.
Furthermore, since the conductive particulate phenolic resin used in the present invention has a shape appropriately distributed within the particle size range of 0.1 to 150 μm, it is optimal for applications such as electromagnetic shielding. In this case, if necessary, it can be pulverized or classified before use. Furthermore, the conductive granular phenolic resin used in the present invention has a low specific gravity and exhibits excellent conductivity even when the proportion of metal plated is small, making it extremely economical. The granular phenolic resin used in the present invention can be prepared by known methods such as JP-A-57-17701 and JP-A-58.
- The product manufactured according to No. 17114 can be used, and its outline is shown below. At room temperature, while stirring a mixed aqueous solution consisting of 15 to 22% by weight of hydrochloric acid and 7 to 15% by weight of formaldehyde, phenol or a mixture of phenol and a nitrogen-containing compound such as urea, melamine, or aniline is added to the mixed aqueous solution. Add to the reaction system at a ratio of 1/15 or less, and stop stirring and let stand before cloudiness forms in the reaction system. While the reaction system is left standing, pink granular phenolic resin is generated and precipitated. Next, the entire reaction system was stirred again for 60 to 70 minutes.
After completing the reaction by heating and raising the temperature to a temperature of .degree. C., it is washed with water, and then neutralized with a 0.1 to 1% by weight ammonia aqueous solution, washed with water, dehydrated, and dried. Most of the granular phenolic resins have a particle size of 0.1
Consisting of primary particles of ~150 μm or secondary aggregates thereof, at least 50% by weight, preferably 90% by weight of the total, has a size that allows it to pass through a 100-meter mesh sieve, but the peak size is between 1 and 50 μm. It is distributed so that it has . In the present invention, resins with a particle size of less than 0.1μ are difficult to handle and have no advantage in the purpose or application of the present invention, and resins with a particle size of more than 150μ tend to settle when used in adhesives or paints, resulting in poor dispersibility or conductivity. There's a problem. The granular phenolic resin according to the present invention has a free phenol content of 500 ppm or less, preferably 10 ppm or less, as measured by liquid chromatography, and when heated and refluxed in 500 ml of substantially anhydrous methanol, The following formula S = (W ₀ - W ₁ /W ₀ ) × 100 [In the formula, W ₀ is the weight of the resin used (g) W ₁ is the weight of the resin remaining after heating and refluxing (g) S is the weight of the resin used (g) The methanol solubility (wt%) of the resin is shown. ] Use materials with a methanol solubility of 10% by weight or less; however, materials with a high free phenol content or high methanol solubility may cause welding or peeling of the plating during the metal plating process or when mixed with plastics or paints. do. Chemical plating is usually applied to the metal plating in the present invention. The granular phenolic resin used in the present invention is inexpensive in its own manufacturing method, and can be plated with ordinary chemical plating even if pretreatment is omitted. The metals for metal plating applied to the present invention include:
For example, gold, silver, copper, nickel, chrome, platinum,
Examples include tin, zinc, etc., and these may be appropriately selected and used depending on the purpose and processing method. To explain an example of chemical nickel plating, granular phenolic resin is immersed in a 50% methanol aqueous solution to degrease it, and then stannous chloride is applied.
Sensitization treatment is performed by adding water to 100 g and 50 ml of hydrochloric acid and immersing the whole in a bath adjusted to 1000 c.c. at a temperature of 30°C for 2 minutes. Next, water was added to 0.1 g of palladium chloride and 1 c.c. of hydrochloric acid to make the total volume 400 c.c. In an activation treatment bath, the mixture was treated at a temperature of 40°C for 2 minutes and then washed with water. Add water to 30g, 10g of sodium hypophosphite and 10g of sodium citrate to make 1000c.c.
By processing in a bath at a temperature of 60°C, nickel can be firmly and uniformly adhered to the surface of the granular phenolic resin. in this case,
The amount of metal deposited by plating can be adjusted by the temperature of the plating bath and the plating processing time. Chemical plating of other metals can be performed in the same manner as above by using the desired metal salt. Since the granular phenolic resin used in the present invention has excellent plating properties, it is also possible to directly immerse it in a plating bath for plating without performing the above-mentioned pretreatment. Also, the purpose
Depending on the application, electroplating may be performed after chemical plating. The conductive granular phenolic resin obtained by the above method can be used as it is or after being crushed or classified according to the purpose and mixed with various resins or rubbers to form conductive or semiconductive compositions. The shape of the product can be a molded product, a laminate, a fiber, a sheet, a film, an adhesive, a paint, or the like. The apparent specific gravity of the conductive particulate phenolic resin used in the present invention is 1.5 to 3.0, preferably 1.8 to 2.3. If the above apparent specific gravity is less than 1.5, it is difficult to uniformly coat the surface of the granular phenolic resin with metal, and therefore the conductivity of the conductive phenolic granular resin tends to vary, and the metal peels off when mixed with resin or rubber. Easy to do. On the other hand, if the apparent specific gravity of the conductive particulate phenolic resin exceeds 3.0, the conductive phenolic resin becomes expensive, and furthermore, the conductivity is not further improved because the specific gravity increases. The electrical resistance of the conductive particulate phenolic resin used in the present invention is 1000Ω or less, preferably 10Ω or less in the measurement method of the present invention. If the electrical resistance exceeds 1000Ω, the conductivity of the conductive composition will decrease, which is not preferable. Further, the conductive particulate phenolic resin used in the present invention preferably has a size that allows at least 50% by weight of the resin to pass through a 100-meter mesh sieve in terms of dispersibility and processability in resins and rubbers. Conventional conductive fillers are metal-plated metal powders, metal fibers, or inorganic fillers such as silica, mica, and glass beads.All of them have a large apparent specific gravity and are hard. has the disadvantage of being easily peeled off. The present invention is characterized in that conductive granular phenolic resin having the above characteristics is mixed with various resins or rubbers as a conductive filler.
The granular phenolic resin used in the present invention is an organic filler with a low specific gravity and excellent heat resistance and chemical resistance, and therefore the apparent specific gravity of the conductive composition is reduced. It is extremely important for electromagnetic shielding materials to be lightweight and to be able to be mixed and dispersed homogeneously when mixed with conductive fillers in resins, adhesives, paints, or rubbers. Moreover, since the difference in apparent specific gravity between the conductive particulate phenolic resin and various resins or rubbers is small, a homogeneously mixed composition can be provided. Furthermore, since the conductive phenolic resin particles used in the present invention are made by coating the granular phenolic resin, which is an organic filler, with metal, it has elasticity, and therefore, the plating metal is difficult to peel off even during processing such as kneading. Molded products obtained from the conductive composition of the present invention do not damage extrusion nozzles or molds, and have glossy surfaces with little roughness. Furthermore, most of the primary particles of the conductive granular phenolic resin used in the present invention are distributed in the particle size range of 0.1 to 150 microns, so it is easy to close-pack them into resin or rubber. Even when used in large amounts, the mechanical strength of products obtained from the conductive resin composition is unlikely to be impaired. The conductive composition of the present invention contains, in addition to the conductive particulate phenolic resin described above, a curable resin, a plastic resin, a rubber, or a mixture of two or more thereof. Preferred examples of the curable resin of the present invention include resol resins, novolac resins, epoxy resins, furan resins, melamine resins, urea resins, and unsaturated polyester resins. Among such curable resins, resol resins, novolak resins and epoxy resins are particularly preferably used. The curable resin can be used alone or in combination of two or more. As the plastic resin of the present invention, thermoplastic resins known in the field of polymers are widely used. For example, polyethylene resin, polypropylene resin,
Polystyrene resin, acrylic resin, ABS resin,
General-purpose engineering plastics such as vinyl resin, polyphenylene oxide resin, polyphenylene sulfide resin, fluorine resin, polyacetal resin, polyamide resin, polyester resin, polycarbonate resin, or polyurethane resin are preferably used. Among these, polypropylene resin, ABS resin, acrylic resin, and polyamide resin are particularly preferably used for electromagnetic shielding. Such thermoplastic resins can be used alone or in combination of two or more. The rubber used in the present invention is a substance that exhibits so-called rubber elasticity in a cured (or crosslinked or vulcanized) state or as it is, and is a substance that exhibits so-called rubber elasticity, such as natural rubber, which is well known in the technical field. Or, for example, polybutadiene, polyisoprene, copoly(butadiene-styrene), copoly(butadiene-acrylonitrile), copoly(ethylene-propylene), polyisobutylene, copoly(isobutylene-isoprene), polychloroprene, polyacrylate rubber, polysulfide, silicone rubber, Synthetic rubbers such as chlorinated polyethylene, fluororubber, chlorosulfonated polyethylene or polyurethane are preferably used. These rubbers may be used in combination of two or more. In the present invention, the above-mentioned curable resin, thermoplastic resin, and rubber may be used as a mixture of two or more types depending on the purpose and use. In the conductive composition of the present invention, the conductive particulate phenolic resin is preferably mixed in an amount of 5 to 900 parts by weight, more preferably 30 to 300 parts by weight, based on 100 parts by weight of the above-mentioned curable resin, plastic resin, or rubber. and use it. In this case, the blending ratio of the conductive granular phenolic resin depends on the characteristics of the conductive granular phenolic resin used, such as the type of metal plating, the type and amount of other conductive fillers used together, or the resin or rubber used. It varies depending on the type etc. For example, when the conductive granular phenolic resin of the present invention and short brass fibers are used as the third component in the thermoplastic resin, a conductive composition with even better electromagnetic shielding properties can be provided. For example, rubber is usually blended with carbon black, but in this case, the amount of conductive particulate phenolic resin blended can be reduced due to the synergistic effect with carbon black. In the conductive composition of the present invention, when the conductive granular phenolic resin in the above range is blended, a product that is lightweight and has excellent conductivity and mechanical properties can be obtained. However, when the blending ratio is small, Even if a large amount of other conductive filler is used, it will be difficult to obtain a material that has the objects of the present invention, such as light weight, high conductivity, and excellent workability. On the other hand, the above mixing ratio is
If the amount exceeds 900 parts by weight, even if the resin or rubber is dissolved in a solution or the like and used as a binder for the conductive particulate phenolic resin, the conductive particulate phenolic resin will simply fall off easily, and no more desirable benefits will be seen. do not have. The conductive phenolic resin particles of the present invention are powders or granular fine powders, and have strong peeling strength between the granular phenolic resin and the surface-coated metal, and have a low specific gravity, making it easy to mix and disperse into various resins and rubbers. Even when mixed into a solution, conductive phenolic resin particles rarely settle, and furthermore, when mixed into a resin or rubber, the metal plating may peel off or damage the nozzle or mold of a molding machine. Not often. In the present invention, the conductive particulate phenolic resin can be mixed with various resins or rubbers using a conventionally known method, such as a V-type blender, kneader, mixer, roll, or kneader. Depending on the type of resin or rubber used, the conductive composition of the present invention may have a
Although heat treatment at ~300°C is required, the conductive granular phenolic resin used in the present invention has excellent heat resistance and chemical resistance, so this does not impair the purpose of the present invention in any way. Effects of the Invention Molded products, fibers, sheets, films, paints, and adhesives obtained from the conductive composition of the present invention have excellent conductivity, can be made lightweight, and have excellent surface gloss, so they can be used as electromagnetic shielding materials. It is suitable as Examples Hereinafter, the present invention will be specifically described with reference to Examples. In addition, measurements of particle diameters, etc. in the Examples were performed by the following method. Further, the conductive granular phenolic resin used in the examples was prepared by repeatedly performing trial production of the corresponding Run No. 1. Method for measuring 0.1-150μ particles Sample approximately 0.1g of each sample. Such sampling is performed five times from different locations for one sample. 1 of each approximately 0.1 g sample sampled
Place each section on a glass slide for microscopic observation. To facilitate observation of the sample placed on a slide glass, spread it out so that the particles do not overlap as much as possible. Microscopic observation shows that there are 10 to 50 particles or powdery substances and/or their secondary aggregates in the field of view under an optical microscope.
Try to do this for the locations that exist. It is usually desirable to observe at a magnification of 10 ² to ^{10 3} times. The sizes of all particles present in the field of view under the light microscope are read and recorded by a measurer in the field of view under the light microscope. The content (%) of particles with a size of 0.1 to 150μ is determined by the following formula. Content rate (%) of 0.1 to 150μ particles = N ₁ /N ₀ × 100 N ₀ : Number of particles whose dimensions were read under a microscope N ₁ : Number of particles with dimensions of 0.1 to 150 μ out of N ₀ The results of 5 samples per sample represent the content of particles from 0.1 to 150 microns as an average value. 2. Amount passing through a 100 Tyler mesh sieve After massaging the dry sample thoroughly by hand if necessary, accurately weigh out approximately 10 g of it, and shake it through a 100 Tyler mesh sieve (the size of the sieve) in small portions over 5 minutes. : 200mmφ, shaking condition: 200RPM), and shake for another 10 minutes after adding the sample. The amount of passage through a 100 tiler mesh is calculated using the following formula. 100 Tyler mesh passing surface (weight %) = W ₀ - _{W 1} /W ₀ × 100 W ₀ : Input amount (g) W ₁ : Amount remaining on the sieve without passing through the 100 Tyler mesh sieve (g ) 3 Determination of free phenol content Approximately 10 g of a sample passed through a 100-meter mesh is accurately weighed and heated under reflux for 30 minutes in 190 g of 100% methanol. The liquid passed through a glass filter (No. 3) was subjected to high performance liquid chromatography (6000A manufactured by Waters, USA) to quantify the phenol content in the liquid, and the free phenol content in the sample was determined from a separately prepared calibration curve. I asked for it. The operating conditions for high performance liquid chromatography are as follows. Equipment: 6000A manufactured by Waters Co., USA Column carrier: μ-Bondapak C ₁₃ Column: 1/4 inch diameter x 1 foot length Column temperature: Room temperature Eluent: Methanol/water (3/7, volume ratio) Flow Speed: 0.5ml/min Detector: UV (254nm), Range0.01
(1 mV) The phenol content in the liquid was determined from a previously prepared calibration curve (relationship between phenol content and peak height based on phenol). 4. Heat fusion properties at 100°C Approximately 5 g of a sample passed through a 100-meter mesh was inserted between two 0.2 mm thick stainless steel plates, and this was prepared using a heat press machine (manufactured by Co., Ltd.) preheated to 100°C. It was pressed with an initial pressure of 50 kg for 5 minutes using a single-acting compression molding machine (manufactured by Shindo Metal Industry Co., Ltd.). After releasing the press, the hot-pressed sample was taken out from between the two stainless steel plates. If the sample taken out is clearly fixed to form a flat plate due to melting or fusion, it is determined that the sample has fusible properties, and if there is almost no difference between before and after hot pressing, the sample is judged to be It was judged to be infusible. 5. Alcohol Resistance Test Approximately 10 g of the sample is accurately weighed (the accurately weighed weight is defined as W ₀ ), and heated under reflux for 30 minutes in approximately 500 ml of 100% methanol. Pass through a glass filter (No. 3), and then remove the remaining sample on the filter.
After washing with 100 ml of methanol, the filter residue sample was then dried at a temperature of 70° C. for 2 hours (the exact weighed weight is W ₁ ). Methanol solubility was determined using the following formula. The lower the methanol solubility, the better the alcohol resistance. Methanol solubility (wt%) = W ₀ - W ₁ /W ₀ ×10
0 6 Bulk density 100 that is cut off at the 100ml mark
Pour the 100ml graduated sample into a 100ml graduated cylinder from 2cm above the rim of the cylinder. The bulk density is determined by the following formula. Bulk density (g/ml) = W (g)/100 (ml) W: Weight per 100 ml (g) 7 Apparent specific gravity Measured by the flotation method. 8 Electrical resistance 10mm of plastic with a 10mm square steel plate bottom
After filling a square container with powder for measurement to a thickness of 10 mm while applying a pressure of 10 kg/cm ² , cover it with a 10 mm square steel plate and measure the electrical resistance between the bottom of the steel plate and the copper plate lid. did. 9 Volume resistivity value Measured according to ASTM D25710 Surface electrical resistance value The electrical resistance value was measured between 1 cm on the surface of the test piece using a tester. 11 Electromagnetic wave transmission loss Measured according to the in-pipe method using a frequency of 3 GHz. 12 Bending strength Measured according to JIS-K-6911-1979. [Manufacture of granular phenolic resin] 15 kg of a mixed aqueous solution consisting of 18% by weight hydrochloric acid and 10% by weight formaldehyde was added to each of the 4 reaction solutions of 20. In each flask, 22℃
Run No. 1 to Run No. 4 below while stirring at a temperature of
A predetermined amount of a mixed aqueous solution having the composition shown in was added.

[Table] In either case, when the mixed aqueous solution was continued to be stirred after being added, it rapidly became cloudy in 15 to 60 seconds.
As soon as the mixture became cloudy, stirring was stopped and the mixture was allowed to stand still.
The internal temperature gradually rose and 30 minutes after the water became cloudy, a pink (Run No. 1 to Run No. 3) or white (Run No. 4) slurry or resinous material was observed in each case. . The contents of each were then heated to 70°C for 60 minutes while stirring, and then heated to 70-71°C.
The mixture was heated and stirred for 10 minutes at a temperature of . After washing each of the above contents with water, they were treated in a 0.2% by weight ammonia aqueous solution at a temperature of 60°C for 60 minutes.
It was dried at a temperature of 2 hours. Table 1 shows the yield of the reaction product obtained by the above method,
The content of 0.1 to 150μ particles, the amount passing through a 100-meter mesh sieve, the free phenol content, the thermal adhesiveness at 100°C, the methanol solubility, and the bulk density were shown.

[Production of conductive granular phenolic resin 1]

After washing 10 g of each of the granular phenolic resins obtained in Run No. 1 to Run No. 4 with a 50% methanol mixed aqueous solution, water was added to 100 g of stannous chloride and 50 ml of hydrochloric acid to adjust the total amount to 1000 c.c. The specimens were immersed in a heated bath for 2 minutes at a temperature of 30°C. Next, 0.2 g of palladium chloride and 2 c.c. of hydrochloric acid were added to water to make a total volume of 800 c.c., and immersed for 2 minutes at a temperature of 40°C and then washed with water. 60 g of nickel chloride, It was immersed for 60 minutes at 60°C in a bath made by adding water to 20g of sodium hypophosphite and 20g of sodium citrate to make the total volume 2000cc, then washed with water and dried. Table 2 shows the specific gravity and electrical resistance values of the plated granular phenolic resins obtained in Run No. 1 to Run No. 4 and the nickel powder as Run No. 5 to Run No. 8.

[Production of conductive granular phenolic resin 2]

The granular phenolic resin obtained in Run No. 1 to Run No. 4 was heated to 200°C in air after passing through a 100-meter mesh.
Heat treatment was performed at a temperature of 5 hours. Then 100g of each
, nickel chloride 600g, sodium hypophosphite 200g
Add water to 200g of sodium citric acid to bring the total amount to 20g.
[Manufacture of conductive granular phenolic resin-1]
The plating process was carried out according to the following. Table 3 shows the apparent specific gravity, bulk density, amount of passage through 100 tile mesh, and electrical resistance values of the nickel-plated products using the granular phenolic resin obtained in Run No. 1 to Run No. 4 as raw materials for Run No. 9 to Run No. Shown as .12.

[Production of conductive granular phenolic resin 3]

Add water to 300g of nickel chloride, 100g of sodium hypophosphite, and 100g of sodium citrate to make 1000c.c.
The mixed aqueous solution prepared above was divided into 5 equal parts, and 10 g of the resin obtained in Run No. 1 was added to each part. Then heat these to 70℃
At the temperature of 10 minutes (Run No. 13), 30 minutes (Run No.
14), 1 hour (Run No. 15), 2 hours (Run No. 16) and 5 hours (Run No. 17). Each was washed with boiling water and then dried. Table 4 shows the specific gravity and electrical resistance of the samples obtained in Run No. 13 to Run No. 17.

[Manufacture of conductive granular phenolic resin 4]

Silver nitrate in 1500ml of 0.5% by weight ammonia aqueous solution
Dissolve 30g of Run No. 1 granular phenolic resin 30
g was stirred and dispersed. Next, while continuing to slowly stir, 2% by weight formaldehyde aqueous solution was added.
500 ml of the resin was dropped, and the surface of the granular phenol resin was plated with silver, followed by washing with water and drying. The specific gravity of the obtained sample was 1.9, and the electrical resistance was 0.1Ω.
(Run No. 18). [Manufacture of conductive granular phenolic resin 5] Water was added to 25 g of copper sulfate, 100 g of Rothsiel, and 25 g of sodium hydroxide to prepare a solution with a total volume of 1000 ml, and 10 g of the resin obtained in Run No. 3 was sufficiently dispersed. Then 5% by weight formaldehyde aqueous solution
After dropping 200 ml of the resin and applying copper plating to the surface of the granular phenolic resin, it was washed with water and dried. The specific gravity of the obtained sample was 1.8, and the electrical resistance was 0.5Ω.
It was (Run No.19). Example 1 Into the separable flask of 1, 282 g of distilled phenol, 369 g of 37% by weight formalin, and 26
Add 150g of aqueous ammonia (by weight%), raise the temperature from room temperature to 70°C in 60 minutes while stirring, and then heat to 70°C.
Stir and heat for 90 minutes at a temperature of ~72°C. Next, let it cool and add 300g of methanol little by little.
Dehydration was carried out by azeotropic distillation under reduced pressure of 40 mmHg, 700 g of methanol was added as a solvent, and a transparent yellow-brown resol resin solution was taken out. The resol resin solution thus obtained had a solid content of 33% by weight when a portion of it was removed from methanol. The above resol resin solution is 40g each in terms of solid content.
RunNo.13, RunNo.14, RunNo.9, RunNo.15, Run
After solution-mixing 60 g each of the conductive granular phenolic resins obtained in Run No. 16 and Run No. 17, the mixture was air-dried at room temperature for 24 hours, and then heat-treated in a dryer at 60° C. for 30 minutes. Using a press, a portion of each of the mixtures thus prepared was placed in a mold preheated to 150°C, and heat treated for 30 minutes under a pressure of 200 kg/cm ² to form a mold with dimensions of 40 mm in width and 40 mm in length. Three molded specimens of 80 mm and 2.0 to 2.3 mm thickness were obtained for each mixture. Table 5 shows the apparent specific gravity and electrical resistance of the conductive granular phenolic resin described above, as well as the apparent specific gravity, volume resistivity, and bending strength measured using three molded test pieces each for Run No. 20 to Run No. 25. It was shown to.

[Table] As is clear from Table 5, molded test pieces with excellent conductivity cannot be obtained from conductive granular phenolic resin with an apparent specific gravity of 1.4 and an electrical resistance of 1200Ω.
If the apparent specific gravity is high, the volume of the conductive granular phenolic resin in the test molded product becomes small, no improvement in volume resistivity is observed, and the apparent specific gravity also increases, which is undesirable. Example 2 0.58 parts by weight of conductive granular phenolic resin of Run No. 9 per 1 part by weight of 6 nylon (manufactured by Kanebo Gosen Co., Ltd.)
Using a kneader (PEX-30, manufactured by NSK Ltd.), a composition prepared by mixing part by weight with 0.08 parts by weight of short brass fibers (manufactured by Kobe Cast Iron Works) with a diameter of 30 microns and a length of 1.5 mm was mixed to give a composition of 250 to 270. Pellets were obtained by kneading at a temperature of °C. Next, the obtained pellets are molded at a temperature of 240 to 260°C.
Injection molded at an injection pressure of 100-150Kg/ ^cm2 , 100mm
Six molded plates with a square shape and a thickness of 3 mm were obtained. As a comparative example, commercially available glass beads with an average density of 2.5 g/cc and an average particle size of 16 microns were plated according to Run No. 15 to obtain nickel plated glass beads with an apparent specific gravity of 3.4 and an electrical resistance of 0.1 Ω. . Six molded plates were obtained in the same manner as described above, except that the nickel-coated glass beads were used instead of the conductive particulate phenolic resin.
Three of the six test pieces were heat treated in a dryer at 180°C for 8 hours. Table 6 shows the specific gravity, volume resistivity, electromagnetic wave transmission loss, and bending strength of the test pieces obtained by the above method.
Shown as No. 26 to Run No. 29.

[Table] In Table 6, when the cross sections of the test pieces of Run No. 28 and Run No. 29 were observed under a microscope, a large amount of metal plating had peeled off from the glass beads. Example 3 Nitrile rubber (Hiker OR25: Nippon Zeon)
100 parts by weight, 5 parts by weight of zinc white, 1.5 parts by weight of stearic acid, 1.5 parts by weight of Aritax, 3 parts by weight of pine tar
While kneading 1 part by weight of accelerator DM, 2 parts by weight of sulfur, and 40 parts by weight of carbon black on an open roll at 95°C, 1, 7, and 40 parts of the conductive granular phenol resin obtained in Run No. 11 were added to the mixture, respectively. ，
After mixing 100, 200 parts by weight and 300 parts by weight, a sheet with a thickness of 2.0 mm was extruded. Each rubber sheet was then heat treated at a temperature of 140°C for 2 hours. Table 7 shows the
The amount of conductive granular phenolic resin in Run No. 11,
The extrudability, apparent specific gravity, and volume resistivity of each rubber sheet are shown as Run No. 30 to Run No. 35.

[Table] The sheet of Run No. 35 in Table 7 had a somewhat lacking surface smoothness. Example 4 Epoxy resin solution diluted to 50% by weight with 75 g each of conductive granular phenol resins of Run No. 6, Run No. 18, and Run No. 19 (Epomiku manufactured by Mitsui Petrochemical Co., Ltd.)
R301G-10) Three types of test plates were prepared by repeatedly applying 50 g of the paste-like material mixed with stirring to a 15 cm square x 3 mm thick polypropylene plate with a brush until the film thickness was approximately 1 mm. After air-drying each of the obtained boards for a day and night, they were heated to 165 cm under a pressure of 10 kg/ ^cm2.
The surface electrical resistance values of those heat-treated at a temperature of ℃ for 30 minutes were 0.05 to 0.15Ω. Example 5 An equal weight part of the conductive granular phenolic resin of Run No. 8 that passed through the 300 tyler mesh was blended with polypropylene resin (J-600 manufactured by Mitsui Petrochemicals Co., Ltd.) in accordance with Example 2. Pellets were obtained by kneading at a temperature of ~280°C. The pellets thus obtained were melt-spun at a temperature of 220 to 240°C using a spinneret with a hole diameter of 0.3 mmφ, resulting in fibers with an average fiber diameter of 60 microns, which had a volume resistivity of 5.4 Ω when measured by bundling the fibers. It was cm.

Claims (1)

[Scope of Claims] 1 (A) Contains granular primary particles or secondary aggregates thereof with a particle size of 0.1 to 150μ, and (B) At least 50% by weight of the total can pass through a 100-meter mesh sieve. (C) Granular or powdered phenol/aldehyde resin with a free phenol content of 50 ppm or less as measured by liquid chromatography, or granular or powdered nitrogen-containing phenol/aldehyde resin (hereinafter referred to as granular phenol). Apparent specific gravity of metal-coated surface of resin (abbreviated as “resin”)
A conductive composition made of a resin or rubber containing a conductive granular phenolic resin having an electrical resistance of 1.5 to 3.0 and an electrical resistance of 1000Ω or less. 2. The composition according to claim 1, wherein the resin is a curable resin or a thermoplastic resin. 3. The composition according to claim 1 or 2, wherein the curable resin is a phenolic resin, an epoxy resin, a furan resin, or an unsaturated polyester resin. 4 The thermoplastic resin is polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, ABS resin, polyphenylene oxide resin,
Polyphenylene sulfide resin, vinyl resin,
Claim 1 which is a fluororesin, polyacetal resin, polyamide resin, polyester resin, polycarbonate resin or polyurethane resin
The composition according to item 1 or 2. 5 Rubber is natural rubber, polybutadiene, polyisoprene, copoly(butadiene-styrene),
Copoly(butadiene-acrylonitrile), copoly(ethylene-propylene), polyisobutylene, copoly(isobutylene-isoprene), polychloroprene, polyacrylate rubber, polysulfide, silicone rubber, chlorinated polyethylene,
The composition according to claim 1, which is fluororubber, chlorosulfonated polyethylene or polyurethane. 6 The particulate phenolic resin accounts for at least 90% of the total
2. The composition according to claim 1, wherein the weight percent of the composition is such that it can pass through a 100-meter mesh sieve. 7 The granular phenolic resin has a free phenol content measured by liquid chromatography.
The composition according to claim 1 or 6, which has a content of 10 ppm or less. 8 When 10 g of granular phenolic resin is heated under reflux in 500 ml of substantially anhydrous methanol, the following formula S = (W ₀ - _{W 1} /W ₀ ) x 100 [where W ₀ is used] The weight of the resin (g),
W ₁ is the weight (g) of the resin remaining after heating and refluxing,
S represents methanol solubility (wt%) of the resin.] The composition according to any one of claims 1 or 6 to 7, wherein the methanol solubility represented by the following is 10 wt% or less. 9. The composition according to claim 1 or any one of claims 6 to 8, wherein the metal coating is chemical plating. 10. The composition according to claim 1 or any one of claims 6 to 9, wherein the metal is nickel, silver, or copper. 11 Conductive granular phenolic resin has an apparent specific gravity of 1.8
2.3. A composition according to claim 1 or any one of claims 6 to 10, wherein the composition is of .about.2.3. 12 Conductive granular phenolic resin has electrical resistance of 10Ω
Claims 1 or 6 which are:
The composition according to any one of items 1 to 11. 13. Claim 1, wherein the conductive granular phenolic resin has a size such that at least 50% by weight of the entire conductive phenolic resin can pass through a sieve of 100 Tyler mesh.
The composition according to item 1 or any one of items 6 to 12. 14. The composition according to any one of claims 1 to 13, wherein the conductive particulate phenolic resin is present in an amount of 5 to 900 parts by weight based on 100 parts by weight of the resin or rubber. 15. The composition according to any one of claims 1 to 14, wherein the conductive particulate phenolic resin is present in an amount of 30 to 3,300 parts by weight based on 100 parts by weight of the resin or rubber. 16. The composition according to any one of claims 1 to 15, wherein the conductive composition is a molded article, sheet, film, or fiber. 17. The composition according to any one of claims 1 to 16, wherein the conductive composition is heat-treated at a temperature of 50 to 300°C.