JPS59152936A - Hybrid resin composition with excellent electromagnetic resistance and rigidity - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent electromagnetic shielding effect, rigidity, formability and heat resistance, useful as the housing of electronic appliances, etc., and composed of specific amounts of specific scaly non-metallic inorganic particles, specific electrically conductive fibrous material, electrically conductive fine particles, and a resin. CONSTITUTION:The objective composition is prepared by mixing (A) 10- 50pts.wt. of scaly non-metallic inorganic particles 1 coated with an electrically conductive substance having a volume resistivity of <=1OMEGA.cm (preferably silver, graphite, etc.) (preferably a mica-group mineral etc. having an average aspect ratio of >=10 and coated with 1/5-1 times weight of an electrically conductive substance), (B) 1-20pts.wt. of electrically conductive fibrous material 2 (preferably metallic fibers, or organic fibers coated with metal or mixed with fine metal powder) and/or electrically conductive fine particles 3 (preferably silver, graphite, etc.) having volume resistivity of <=1OMEGA.cm, and (C) 30-80pts.wt. of a resin 4 (e.g. polyvinyl chloride, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hybrid resin composition having excellent electromagnetic resistance and rigidity. More specifically, the conductive inorganic powder 10 is a scale-like nonmetallic inorganic powder whose surface is coated with a conductive substance having a volume resistivity of 1 Ω·m or less.
50! (1) 1 to 20 parts by weight of conductive fibrous material and/or conductive fine particles having a volume resistivity of 10 m or less, and 30 to 80 parts by weight of zero resin. Excellent electromagnetic resistance and rigidity. The present invention relates to a hybrid resin composition.

In recent years, with the development of electronic devices, a new social problem called electromagnetic interference has arisen. This is caused by problems such as computers malfunctioning due to various noises in various environments.9 Recently, various devices are controlled by computers, which can lead to major accidents. In particular, due to demands for lighter and more compact equipment, one of the problems is that most of the housings are made of plastic, and in the United States, regulatory values such as the FCC have been established. As a countermeasure, currently 1) metal spraying, 2)
Three methods or materials are used: 1) conductive paint, and 3) plastics mixed with conductive filler.
Method 3) is expensive and has a short lifespan, and recently the technical field 3) has been attracting attention. However, such a conductive filler~
Metal fibers, metal flakes, and metal or graphite fine particles are being considered for this purpose, but it is not easy to mix large amounts of metal fibers or metal flakes into resin to obtain molded products, and it is difficult to obtain molded products during injection molding or extrusion molding. Because these fillers are soft, their shape changes during melt-kneading.
Moreover, it is unevenly distributed in the molded product, making it difficult to obtain the expected performance.

On the other hand, the electromagnetic blocking effect cannot be observed unless the amount of the metal fibers or the metal fly flakes added is small. Furthermore, making the housing of an electronic device electrically conductive is extremely dangerous in the event of a leakage, and insulation is also required. In this way, seemingly contradictory properties are required: conductivity on the one hand and insulation on the other. Furthermore, rigidity and heat resistance are also required for the housings of electronic and communication equipment9, and a material that satisfies all of these requirements has not yet been developed, and electromagnetic interference has not yet been fully investigated. The current situation is that this has not been done.

In view of the above-mentioned current situation, the present inventors have conducted intensive research to develop a material that satisfies the above conditions. As a result, the optical surface of the scale-like nonmetallic inorganic powder is replaced with a conductive material as a conductive filler. It was discovered that a resin composition prepared by mixing a resin and a conductive inorganic powder coated with a resin in a certain proportion has excellent electromagnetic resistance and rigidity, and the patent application No. 57-1972 was previously filed.
A patent application was filed as No. 29. Compared to metal fibers and metal flakes, the conductive inorganic powder exhibits an excellent electromagnetic barrier effect even when added in small amounts, is less likely to break when mixed with resin, and has the characteristics of improving rigidity. are doing. However, such conductive treatment increases costs, and when performing secondary processing such as vacuum forming after kneading, extrusion molding, and subsequent secondary processing such as vacuum forming, moldability decreases due to improved rigidity. There remains a problem. As a result of further research, the present inventors found that by using a small amount of conductive fibrous material and/or conductive fine particles in addition to the above two components, the amount of the conductive inorganic powder (p1) added could be reduced. The inventors have discovered that, despite the decrease, electromagnetic resistance can be improved and moldability can also be improved, leading to the present invention. That is, the present invention provides: (1) scaly nonmetal a
10 to 50 parts by weight of a conductive inorganic powder or granule whose surface is coated with a conductive substance having a volume resistivity of 1 Ω·m or less; 1 to 20 parts by weight of sexual characteristic particles and/or particles, and 3 parts of resin.
This is a hybrid resin composition with excellent electromagnetic resistance, rigidity, and moldability, comprising 0 to 8 parts of ON.

The hybrid resin composition of the present invention is a material suitable for housing materials for computer electronic equipment and communication equipment, and has a resistance of 20 to 60% against electromagnetic waves in the frequency range of 10 kilohertz to 1 gigahertz. It has an electromagnetic barrier effect with a decibel delay, and has excellent rigidity and heat resistance, with a bending modulus of elasticity 3 to 8 times higher than that of resin alone, and a heat distortion temperature of 30 to 150 degrees Celsius. ing.

The scaly nonmetallic inorganic powder used in the present invention includes:
Examples include mourning, merc, sericite, glass flakes, layered graphite, vermiculite, bentonite, attapulgite, etc.

The scale-like nonmetallic inorganic powder preferably has an average diameter of 5 to 3,000 μm and an average aspect ratio of 10 or more from the viewpoint of moldability and various physical properties of the molded product. In particular, the mica family,
Natural or artificial minerals belonging to the brittle mineral group or the chlorite group are the most preferably used scaly inorganic compounds, specifically natural muscovite (muscovite), gold porphyry (muscovite), etc.
Mica (biotite), vermiculite (vermiculite), synthetic backstones containing fluorine, etc. can be mentioned.

Can any conductive substance with a volume resistivity of 1 Ω·cnl or less be used as the conductive substance covering the surface of the scaly nonmetallic inorganic powder?
1. Silver, copper, iron, nickel, aluminum, tin, chromium, titanium, zinc, gold, platinum or an alloy thereof, or graphite is suitable from the viewpoint of concave paths, etc.; Although it depends on the mixing ratio with the resin, it is preferable that the surface of the scaly inorganic powder is covered with 115 to 1*X times as much of the above-mentioned conductive material as the scale-like inorganic powder.
If the amount of the i2I coating lid is less than the amount of 115N of the scale-like inorganic powder, the electromagnetic shielding effect will be small;
If the amount of N is more than double the amount, it is not preferable because it may have the effect of decomposing and deteriorating the resin mixed at high temperatures. Any method may be used to cover the surface with the conductive substance, but for example, the scale-like inorganic powder is dispersed in a metal salt compound solution of an appropriate 71:1 # degree, and then the scaly inorganic powder is soaked in a bath solution. Electroless plating methods, vacuum evaporation methods, sputtering methods, ion blating methods, etc. can be used, such as a method in which metal particles are precipitated on the surface of a scale-like inorganic powder by reducing. It is also possible to use a method in which the surface of the scaly inorganic powder is coated with a suitable binder and then fine particles of a conductive substance are attached thereto. The thickness of the covered conductive material is 0.01 μm to 1 m×, preferably 0.01 μm to 1 m×
．． A thickness of 0.05 to 100 μm is desirable in terms of performance.

The conductive fibrous material used in the present invention has a volume resistivity of 1 Ωm or less and any conductive fibrous material can be used, but usually has an average aspect ratio of 10 or more and an average diameter of 0.1 μm. ~3, average fiber length 10μm ~ 50m
Those with a value of 1+ are preferably used.

In terms of conductivity, formability, price, etc., metal fibers, metal-coated organic or inorganic fibers, carbon fibers, graphite fibers,
Either organic fibers mixed with metal fine particles or carbon fine particles, or a mixture of 21 or more thereof are suitable. More specifically, metal fibers include iron, stainless steel, aluminum, nickel, copper, brass, bronze, lead, etc. obtained by drawing methods, melt spinning methods, cutting methods, shearing methods, crystallization methods, etc.
Tan 9- Short fibers and whiskers such as gesten and molybdenum can be used, and examples of metal-coated organic or inorganic fibers include glass fibers whose surfaces are plated, coated, or burnished with aluminum or nickel, and general antistatic materials. Organic fibers, etc. can be used, and as carbon fibers or graphite fibers, any fibers made from acrylic fibers, rayon, petroleum pitch, coal pitch, etc. as starting materials can be used, and as organic fibers mixed with metal fine particles or carbon fine particles, ID silver can be used. Conductive fibers can be used in which fine metal particles such as copper, brass, nickel, aluminum, and iron, and conductive graphite fine particles such as acetylene black and Ketjen blank are dispersed in organic fibers with a relatively high melting point such as polyester. . Further, the conductive fine particles used in the present invention usually have an average diameter of 10
Silver, copper, brass, nickel, aluminum, 0 μm or less,
Examples include metal fine particles such as iron, and conductive graphite fine particles such as acetylene black and touch en black.

The role of the conductive fibrous material and the conductive fine particles in the present invention is that the conductive fine particles are formed by connecting the scaly 10-conductor inorganic powder, which is the main conductor and sister filler. When dispersed in the medium, it forms a chain-like aggregate structure, and in effect functions in the same way as a conductive fibrous material.

The resin used in the present invention may be any moldable polymeric material, such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, hS@resin, ABS resin, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyurethane. Resin, polyacetal resin, polyimide resin, thermoplastic resin before nylon resin and its copolymer, polyvinyl acetate, vinyl acetate-ethylene copolymer,
Emulsion-like resins such as polyvinyl chloride and polyacrylic acid esters, latex-like resins or lump rubbers of SBR and various loincloth natural and synthetic rubbers, unsaturated polyesters (
Standing (moon effect, epoxy resin, phenolic resin, urea resin,
Thermoplastic resins such as melamine resins can be melted.

In addition, in the present invention, fillers such as calcium carbonate, barium sulfate, and clay, pigments such as carbon black and titanium oxide, anti-aging agents, ultraviolet absorbers,
A silane coupling agent, an internal mold release agent, etc. can be added as appropriate.

In order to fully exhibit the effects of the present invention, resin 30 to 80%
10 to 50% of the conductive inorganic powder for the heavy part] [The placed part and the conductive fibrous material and/or the conductive fine particles'
Is it necessary to strictly mix 5r, 1 to 20M parts? 1C If the conductive inorganic powder is less than 100 parts, or if the conductive fibrous material and/or the conductive fine particles are 1 part by volume. If the amount is less than 50 parts by weight, the conductivity will be low and the electromagnetic shielding effect will be poor. If the amount of fine particles is more than 20 parts by weight, it becomes difficult to mold and it is difficult to obtain a molded product with a beautiful appearance. Any method can be used to obtain the desired molded product by mixing conductive particles (hereinafter referred to as conductive fillers) with a resin, but for example, if the resin is the aforementioned thermoplastic resin, In this case, it is preferable to mix the conductive fillers and the resin in the desired ratio in advance, knead them in an extruder, mold them into a pellet shape, and then obtain a molded product in the desired shape with an injection molding machine. . It is also possible to extrude it into a sheet using a kneading extrusion plate and then mold it into a desired shape by vacuum forming or pressure forming. If the plastic has the shape of an emulsion or latex as described above, there is a method in which it is mixed in the same way, made into a sheet, and further dried and shaped into the desired shape by heat pressing, etc. It is also possible to adopt a method of spraying a slurry directly onto the surface of a frame or the like, forming the slurry, and then drying it. When the resin is thermosetting E41J resin, a very commonly adopted method is used, but SMC-? It is also possible to further enhance the effect by using hybrid reinforcement of the conductive filler and glass fiber as a compound such as BMC.

The thus obtained molded product according to the present invention has excellent properties such as 13-electromagnetic resistance and rigidity, and its performance is evaluated as follows. !
The method for measuring the magnetic shielding effect is based on the US FCC (Feclera).
lCommunicationComm1ssio
Although it is preferable to follow the method specified in item (n), it is also possible to carry out the evaluation simply by the method described, for example, on page 31 or page 38 of "Kogyo Zazai" Vol. 29, December issue. In this method, a motor or spark is used as the noise source, and the signal is received by an antenna and detected by a spectrum analyzer or field strength meter, but a quasi-peak detection method is used for detection. Should. On the other hand, the flexural modulus, tensile strength,
Measuring and evaluation methods for heat distortion temperature, etc., are determined by JIS standards or ASTM standards corresponding to individual plastics.

As described above, the resin composition according to the present invention is excellent in 'fM, magnetic shielding property, rigidity, heat resistance, etc., so it can be used in video games, electronic plate making machines, electronic typewriters, electronic time recorders, electronic desk calculators, electronic 14- Sewing machine, electronic register, microwave oven, burner computer, facsimile, copying machine, printer, VT
R, plotter, word processor, nice play,
Ultrasonic diagnostic equipment! ! : It can be widely applied as a housing material for electronic equipment, communication equipment, medical equipment, and measurement equipment. Although the present invention will be specifically explained, the present invention is not limited to these Examples. In the examples, unless otherwise specified, all p "parts" mean "N parts".

Example 1 and Comparative Example 1.2.3 Nickel was deposited on the surface of phlogopite powder (Suzolite Mica manufactured by Kuraray, Canada) with an average diameter of 90 μm and an average aspect ratio of 50 by electroless plating. The nickel content determined from the amount of weight loss after washing the metal coating and mica with nitric acid was about 30%. 0.5 of the amount of mica while stirring a pellet of commercially available polypropylene resin used as IJ Lux fat in a Henschel mixer. l) Ethoxysilane and a predetermined amount of the metal-coated mica powder and metal fibers were mixed together. The metal fibers used here were short brass fibers with an average diameter of 60 μm and an average fiber length of 3 mm (average aspect ratio of 50), and the mixing ratio was resin 7 mm.
0 parts by weight of the metal coating to mica powder 25] [Okibe,
The amount of the metal fiber is 5 parts by weight.

Subsequently, the mixture was fed to a single-screw extruder and melt mixed at 250°C to obtain pellets. Furthermore, a test piece was obtained from the obtained pellet by injection molding, and a sheet-like product having a thickness of 3 mm was obtained by extrusion molding. The method of preparing the resin composition according to ASTM 0648 (loading, &18.
The heat deformation temperature measured at 6 to 9/d) was 124° C., and the flexural modulus was 4.8×10′ kp/ca measured by a method based on ASTM D 790.

Furthermore, the obtained sheet-like material was
We created an electromagnetic interference effect measuring device similar to the method described on page 38 of the issue, used the motor as the noise source, and analyzed it with a spectrum analyzer.The results were 30 dB for a frequency of 10 MHz and 34 dB for a frequency of 100 MHz. It had a shielding effect of 39 decibels in decibels, 1 gigahertz.

Using the same metal-coated mica powder, brass fibers and polygron resin as in Example 1, a resin composition alone (Comparative Example 1), a resin composition in which only the metal-coated mica was added in an amount of 25% by weight (Comparative Example 2), and A molded article of a resin composition (Comparative Example 3) containing only the brass fibers in an amount of 5% by weight was similarly obtained and its physical properties were measured. As a result, only the resin, only the metal-coated mica powder 2
5! The heat deformation temperatures of the composition containing 5 weight i% of brass fibers and the composition containing only 5% of brass fibers were 58°C, 119°C and 65°C, respectively.
℃ and the bending modulus of elasticity is 1.2 x 10”f.
/tri %4.0xlO'ly/- and 4.8
X 10'kf/c! It was I.

In addition, in the case of Comparative Example 2, the 41L magnetic shielding effect was 18 dB, 22 dB, and 28 dB at frequencies of 10 MHz, 100 MHz, and 1 GHz, respectively, but in the case of Comparative Examples 1 and 3, it was at all frequencies. All of them had an output of 2 to 3 decibels (17-), but had little effect. From the above results, it is clear that the hybrid resin composition according to the present invention has superior rigidity, heat resistance, and electromagnetic resistance compared to the resin alone and a small amount of gold T714 fiber added.

Further, it is clear that the hybrid resin composition of the present invention can significantly improve electromagnetic resistance compared to a single additive of metallized cumulus mica.

Example 2 and Comparative Example 4.5.6 Copper was deposited on the surface of Indian white mother powder granules (average diameter: 60 μm, average aspect ratio: 32) by electroless plating. In this case, no 1! By varying the concentration of the metallizing ion solution and the precipitation time, copper-coated mica powder particles having a metal content of 353 i% and an amount of 13M were obtained. Also conductive a
m fibrous material: average diameter 20 μm 1 average fiber length 2.5
1111 (average aspect ratio 125) aluminum-deposited glass fiber was used.

Next, using a commercially available polybutylene terephthalate resin as a matrix resin, 2
By molding and heating at 40°C, 40% of the copper-containing i3518-wt% and 13% of copper-containing mother powder particles were each added.
Hybrid resin composition containing M amount%, 7 μm%, and 31 amounts of the aluminum-deposited glass fiber (Example 2 and Comparative Example 4), conductive mica powder with a copper content of 35% Attempts were made to obtain test pieces and sheet-like products consisting of a hybrid resin composition (Comparative Example 5) containing granular 401 cap and 25% by weight of the aluminum-deposited glass fiber (Comparative Example 5) and a resin alone (Comparative Example 6). However, in the case of Comparative Example 5, the crosstalk was so severe that it was impossible to obtain a test piece! ! There wasn't. The physical properties of these molded products were measured in the same manner as in Example 1. As a result, the heat distortion temperatures of Example 2 and Comparative Examples 4 and 6 were 173°C, 69°C, and 60°C, respectively. In addition, the bending elastic modulus is 9.5X10kf/d, 3.2X1
0'Plum/I-#! , 2', 5X10' plum/-.

Furthermore, the electromagnetic interference effect of Example 2 was 31 decibels at 10 MHz, 42 decibels at 100 MHz, and 46 denbels at 1 kilohertz. On the other hand, the electromagnetic shielding effect of Comparative Example 4 was 2 to 5 denbels in all frequency ranges.
Comparative Example 6 failed at 2 to 3 decibels. According to the above results, when the content of 24-electrode scale-like inorganic powder is small,
The conductivity is poor and the electromagnetic shielding effect is poor, so it is a reed.
However, when a fibrous material is added to a material with a composition ratio of the present invention, molding becomes difficult. It is clear that it has a shielding effect.

Example 3 The aluminum composite powder granules with an average particle size of 250 μm and an average aspect ratio of 65 were damaged by Lf) containing 40 layers of aluminum by vacuum evaporation on the surface of the aluminum composite powder granules 45]jol
t part and average i11 [0.1 μm Ketjen blank (
A paste was prepared by mixing and stirring 15M parts of graphite particles) and 4ON parts of a commercially available unsaturated polyester resin, and adding a curing agent consisting of a combination of methyl ethyl ketone peroxide and cobalt naphthenate to the mixture. Next, the paste was impregnated into a glass mat, successively laminated and cured at room temperature, and further post-cured at 100° C. to produce a 5 mm thick 1fXfi FRP board. The electromagnetic shielding effect of the FRP board was 45 dB at 100 MHz. From the examples, it is clear that the resin composition of the present invention has an excellent electromagnetic shielding effect.

% Applicant: RiRa Co., Ltd. Representative Patent Attorney Ken Honda = 21- Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office Excellent Hybrid Resin Composition 3, Relationship with the Amendment Person Case Patent Applicant: 1621 Sakazu, Kurashiki City (108) Rira Co., Ltd. Representative Director Ueno et al.-4, Agent Telephone: Tokyo 03 (277) 3182 5, "Detailed Description of the Invention" column and "Brief Description of Drawings" column of the specification to be amended, and Drawing 6, Contents of the amendment (1) Lines 3 to 3 from the bottom of page 5 of the specification On page 6, line 12, “
The conductive inorganic powder material has led to the present invention. ” and insert the following text.

[In other words, it is difficult to deform plastically and has a bending elastic modulus of 2×
Mica-based inorganic powder or 7 x 10
When conductive inorganic powder particles made of 5kQ/d glass flakes whose surfaces are coated with a predetermined conductive substance are used as a component of the resin composition, there will be almost no deformation or damage during resin composition, and the rigidity will increase. They have found that they can improve the electromagnetic barrier effect, do not cause uneven distribution in the molded product, and exhibit excellent electromagnetic barrier effects even when added in small amounts compared to metal fibers or metal flakes. The excellent effect is thought to be due to the high rigidity of the scaly nonmetallic inorganic powder serving as the base material.

However, such conductive treatment increases costs, and after cross-wiring, extrusion molding to form a sheet, and further secondary processing such as vacuum forming, the rigidity is improved but formability is reduced. There remains the problem of doing so.

BACKGROUND ART Hybrid resin compositions have been known that exhibit excellent properties due to the synergistic effect of using different types of additives together.

The field of electromagnetic barrier materials is no exception; for example, in JP-A-54-56200, 10 to 25 conductive short fibers are
Electromagnetic shielding materials containing 2 to 40 volume percent conductive particulate matter are shown. Furthermore, JP-A-57-65754 discloses a conductive plastic composition for shielding electromagnetic waves containing 0.2 to 5 volume percent of metal fibers and 1 to 10 volume percent of metal powder.

However, all such hybrid compositions are made of metal, and by mixing and adding two types of metals with different shapes, the number of contact points between them is increased and the conductivity is increased. Although they are effective, metal fibers and metal flakes are easily deformed and shredded when kneaded with resin and molded, causing nozzle clogging and reducing moldability. Furthermore, if the mixing time is relatively long or the deformation speed during kneading is high, it may be easily damaged or cut, and the desired electromagnetic shielding effect may not be obtained.

The flexural modulus of such metal materials is, for example, 2.6xto'kg/cI for aluminum alloys and 3.6xto'kg/cI for copper alloys. IX1
o5kg/ai is relatively low and is therefore considered to be easily deformed, but such properties are not improved in any way by the above-mentioned hybrid composition.

For the above reasons, metallic conductive filler-based hybrid compositions have a relatively low deformation rate when, for example, injection molding, and can only be applied to large, simple-shaped molded products with large gates. . In general, when two types of fillers with different rigidities and shapes are mixed, it is said that the filler with low rigidity or the fibrous filler with a high anubect ratio will be easily damaged or deformed. In the case of a hybrid system of conductive inorganic powder whose surface is coated with a conductive substance (hereinafter sometimes referred to as scaly inorganic powder) and metal fibers, the metal fibers may be deformed or damaged. It is expected that it will become more intense. However, when the present inventors molded a hybrid resin composition in which the scaly nonmetallic inorganic powder and granules and metal fibers were blended into a resin,
Surprisingly, it was discovered that almost no deformation or damage to the metal fibers was observed, and the present invention was achieved based on the discovery that the resin was significantly improved compared to a resin containing metal fibers alone. (2) "...No. 1" in the second line from the bottom of page 6 of the specification
It is an ibrit-based resin composition. '', add the following sentence.

[Although it is difficult to clearly explain the mechanism by which the excellent effects of the present invention are expressed, the present inventors interpret it as follows.

One of the features of the present invention is the rigidity, elastic deformability, and shape (scaly) of the scale-like inorganic powder. Therefore, when a resin composition containing such a filler is molded by injection molding or the like, Powder is easily oriented. The oriented scale-like inorganic powder reduces the contact resistance and reduces the volume resistivity of the molded product, which not only increases the electromagnetic shielding effect, but also reduces rigidity in the case of hybrid resin compositions. In addition, it has the effect of protecting the metal fibers that are easily plastically deformed, and in the process of kneading the composition, the metal fibers are sandwiched between the scaly inorganic powder particles and flow, thereby preventing deformation and damage. Fig. 1 is a cross-sectional view of a resin molded product showing this as a model. In Fig. 1, 1 is a scale-like conductive nonmetallic inorganic powder, and 2 is a conductive fibrous material. , 4 is a resin.However, when conductive particles are used instead of metal fibers, the chain-like agglomerated state formed in the resin is protected from crosstalk and flow process, which prevents deformation and damage. It is thought that this material peels off and exhibits an excellent electromagnetic barrier effect. Figure 2 is a cross-sectional view of a resin molded product that shows this as a model. 3 is a conductive fine particle. is a cross-sectional model of a conventional hybrid molded product made from a composition containing resin mixed with metal flakes and metal fibers.
It is damaged and unevenly distributed, does not exhibit a satisfactory electromagnetic shielding effect, and has poor rigidity and formability.

5 is a metal flake. ” (3) Add the following sentence after “Act as a servant.” on page 11, line 4 of the specification.

[The volume resistivity value is often used as a physical property value to specify the material used in the present invention, so this will be explained below. First, the volume resistivity, which is used as a characteristic value of the conductive material to be coated on the surface of the scale-like nonmetallic inorganic powder, is a property specific to the material. It can be expressed as a characteristic value. As the measurement method, a conventional method for evaluating the conductivity of metal plates or metal rods can be adopted. On the other hand, the volume resistivity used to specify the properties of conductive fibrous materials and conductive fine particles must be the value of those in the form of fibers or fine particles, rather than the properties inherent to the materials. For example, in the case of metal fibers, even though the basic volume resistivity of the material is about 10 to 10 Ω・α, the value when processed into a fiber shape using the measurement method described below is 10 to 1.
It is approximately 0 Ω·α, and may even exceed 1 Ω·α due to oxidized and degraded tubes on the surface. On the other hand, glass fiber has 10
Although it is an insulating material with a volume resistivity of Ω·α or more, the fiber whose surface is coated with aluminum shows a value of about 10Ω·α, which is within the range that can be used in the present invention. Regarding the method for measuring the volume resistivity of fibrous materials or fine particles, it is possible to measure by the four-probe method, which does not seem to have any particular regulations. However, in this case, the contact resistance between the conductive fibrous materials or conductive fine particles is not measured, and the value varies depending on the packing pressure. Strictly speaking, the measured values should be compared when the volume fraction of the sample in the container is the same, but in general, in the case of conductivity with a volume resistivity of 1Ω・1 or less, there is only slight variation due to the packing method. Usually 50g/
Conductivity can be evaluated by measuring under a charge of about Cl. (4) Delete "," in line 10 from the bottom of page 20 of the specification.

Enter.

``Example V Mochi Ministry 3 Examples 7 and 8 Nickel was deposited on the surface of phlogopite powder (produced in Canada, ■Kuraray Susolite Mica) with an average diameter of 220 μm and an average aspect ratio of 60 by an electroless plating method. The nickel content of this metal-coated mica is about 20% by weight, and the volume resistivity measured by the four-probe method under a load of 5 Ωg/rrt when filled in an insulating cylindrical container is 5.6 × 1.
It was 0Ω.-. Similarly measured average diameter 60 μm,
The volume resistivity of a brass fiber with a length of 3 mm is 2.5 x 10Ω・
It was G. Next, using ABS resin as a matrix resin, 60 parts by weight of AB8 resin was added with 3 parts of the nickel-coated mica.
After melt-mixing 0 parts by weight of brass fibers and 10 parts by weight of brass fibers at 2408C in a single-screw extruder, the mixture was cut into strands by WY to obtain pellets. Subsequently, a test piece was obtained from the obtained pellet by injection molding, and a sheet-like product having a thickness of 3 mm was obtained by extrusion molding (Example 4).

In place of this nickel-coated mica, the average diameter I
A composition containing 30 parts by weight of aluminum flakes (volume resistivity 7.4 x 10 Ω cm) with an average diameter of 3 μm (comparative example 7) and nickel powder with an average diameter of 3 μm (volume resistivity 7 x 10 Ω cm) ) (Comparative Example 8) was tried to be molded in the same manner as in Example 4, but the aluminum flake-added composition (Comparative Example 7) caused nozzle clogging during extrusion molding and could not be molded. There wasn't. Therefore, in Comparative Example 7, a test piece was obtained by cross-wiring using a Pufst Mill manufactured by Toyo Seiki ■ and then molding into a predetermined shape using a hot press. The heat distortion temperatures of molded products obtained from these compositions were as shown in Example 4. 115°C19 in the order of Comparative Example 7.8
The temperature was 3°C and 194°C, and the flexural modulus was 9.8
10 ky/d, 3.3 x 10'kg/aN,
3. OX was 10 kg/ctl. Also thickness 3
The blocking effect of my plate against electromagnetic waves with a frequency of 100 MHz is 40 decibels, 135 decibels, and 1, respectively.
It was 0 decibep. From the above results, it is clear that the hybrid resin composition according to the present invention has excellent rigidity, heat resistance, and electromagnetic resistance. In Comparative Example 7, in which a scale-like conductive metal piece was used as a substitute for the body, the formability was extremely deteriorated, and as a result, the metal pieces and metal fibers were deformed and unevenly distributed in the molded product, resulting in poor electromagnetic performance. It was not possible to obtain any positive effect.

Further, in the case of Comparative Example 8 in which non-scaly metal particles were used, the metal fibers were slightly deformed, and an excellent electromagnetic shielding effect could not be obtained.

The differences in the state of the conductive powder and metal fibers in the molded products obtained in Example 4, Comparative Example 7, and Comparative Example 8 are shown in the optical micrographs shown in Figures 3, 4, and 5. This is clear by comparing the magnification of 14 times, respectively.

To 60 parts by weight of ABS resin, 38 parts by weight of nickel-coated mica obtained in Example 4 and 2 parts by weight of Ketjen Black (volume resistivity lXl01 Ω cm ) having an average diameter of 0.1 μm, which is a conductive car pump hook, were blended. Then, a test piece was obtained by molding in the same manner as in Example 4 (Example 5). A
A composition containing only 97 parts by weight of BS resin and 3 parts by weight of Ketjen Black (Comparative Example 9) and ABS resin 60
Example 5 was also applied to a composition (Comparative Example 10) containing 38 parts by weight of the same aluminum flakes and 2 parts by weight of Ketjen Black as used in Comparative Example 7.
However, it was difficult to extrude the aluminum flake-added composition (Comparative Example 10), so a molded product was obtained using the same hot bleine method as in Comparative Example 7. The heat distortion temperatures of molded products obtained from these compositions were 1139C, 193°C, and 95°C in the order of Example 5, Comparative Example 9, and Comparative Example 10.
and the bending elastic modulus is 12.5×1okg/d, respectively.
2.8 ×1 o'ky/al, 3.4 xtok
g/cJ. In addition, the blocking effect of a plate with a thickness of 3 mm against electromagnetic waves at a frequency of 100 MHz is 4 mm, respectively.
They were 5 decibels, 2-3 decibels, and 36 decibels.

From the above results, it is clear that the hybrid resin composition according to the present invention has excellent rigidity, heat resistance, and electromagnetic resistance. Comparative Example 90 composition was one in which Ketjen Black was blended in almost the same proportion as in Example 5, but the molded product had almost no electromagnetic interference effect and did not contain the conductive inorganic material, which is one of the constituent elements of the present invention. It can be seen that an excellent electromagnetic barrier effect can only be achieved when it is blended with powder and granules and molded.

The composition of Comparative Example 10 had worse moldability than the composition of Comparative Example 7, and was extremely brittle with severe uneven distribution of metal pieces. ” (6) Next to the column “1. Detailed explanation of the invention in the specification”, write “4.
Provide a column for ``Brief explanation of the drawing'' and enter the following text in this column.

"FIG. 1 is a schematic diagram of a cross section of a molded product obtained from a hybrid resin composition comprising a conductive inorganic powder, a conductive fibrous material, and a resin according to the present invention.

FIG. 2 is a schematic diagram of a cross section of a molded product obtained from a hybrid resin composition comprising conductive inorganic powder, conductive fine particles, and resin of the present invention.

FIG. 3 is a schematic diagram of a cross section of a molded product obtained from a conventional hybrid resin composition consisting of conductive fibrous material, metal flakes, and resin.

(14x magnification) Figures 5 and 6 are mirror photographs (
(14x magnification).

1... Conductive inorganic powder 2... Conductive fibrous material 3... Conductive fine particles 4...Resin 5...Metal flakes" (7) Revise the drawings on separate sheets.

Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6

Claims (1)

[Scope of Claims] (1) (5) 10 to 50 parts by weight of a conductive inorganic powder or granule obtained by coating the surface of a scaly nonmetallic inorganic powder with a conductive substance having a volume resistivity of 1 Ω·m or less and (c) electromagnetic, fragility, and rigidity consisting of 1 to 20 parts by weight of conductive fibrous material and/or conductive fine particles having a volume resistivity of 1 Ω m or less, and 30 to 80 parts by weight of zero resin. and a hybrid resin composition with excellent moldability. (2) The scale-like non-metallic inorganic powder is a powder whose surface is coated with a conductive material in an amount of 115 to IJk times that of the scale-like non-metallic powder. The resin composition according to scope item (1). (8) The scale-like nonmetallic inorganic powder has an average aspect ratio (
The resin composition according to claim 1 or 2, which is a granular material having a diameter to thickness ratio of 10 or more. (4) The scale-like nonmetallic inorganic powder is a natural or artificial mineral belonging to the mica group, brittle mica group, or chlorite group. The resin composition according to item (8). (6) The conductive substance is silver, aluminum, copper, nickel, chromium, titanium, tin, antimony, zinc, gold,
Claim No. 1, which is at least one metal selected from platinum and iron alone or an alloy containing the same, or graphite
), (2), (8), or (4). (6) Claims (1), (2), (8), (4), or the like, wherein the cough conductive fibrous material is a fibrous material with an average aspect ratio of 10 or more. The resin composition according to item (6). (7) The conductive fibrous material is any of metal fibers, organic or inorganic fibers coated with metal, carbon fibers, graphite fibers, organic fibers mixed with metal fine particles or carbon fine particles,
or a mixture of two or more thereof, Claims (1), (2), (8), (4)2-, (5), or (6). The resin composition described in . (8) The conductive fine particles include silver, aluminum, copper, nickel, chromium, titanium, tin, antimony, zinc, gold,
Claims (1), (2), (8), and (4) are fine particles of at least one metal selected from platinum and iron, an alloy containing the same, or graphite. section,
The resin composition according to item (5), item (6) or item (7).