JP2003261688A - Semi-conductive resin molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semi-conductive resin molded article having a uniform resistance value in the semi-conductive region. <P>SOLUTION: The semi-conductive molded article is comprised by molding a conductive thermal plastic resin composition composed by mixing (C) the thermal plastic resin and/or a thermal plastic elastomer of 0.1-80 pts.wt. except the component (C) to a conductive resin component comprising (A) a matrix thermal plastic resin and (B) a fine carbon fiber having an average fiber diameter of 200 nm or less of 0.1-20 wt.%. The component 3 (C) is not completely dissolved with the component 1 (A) and is dispersed in a sea-island form, the component 3 (C) forms a dispersion phase in an island form and an average value of the short diameter Rmin of the dispersion phase of the component 3 (C) is 10 μm or less. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductive resin molded article, and for example, in the fields of electric and electronic and automobiles, more specifically, semiconductive rollers and belts for copying machines and printers, and various types of products. The present invention relates to an antistatic material, particularly to a semiconductive resin molded product having a uniform resistance value in a semiconductive region, which is suitable for antistatic parts such as trays, cases, jigs and tools in manufacturing and conveying electronic devices.

[0002]

2. Description of the Related Art In recent years, as electronic devices such as magnetic heads for hard disk drives have been remarkably densified, destruction of the devices by ESD (electrostatic discharge) has become serious. As a result, anti-static components such as device carrier trays and jigs are required to not only quickly dissipate the electrostatic charge, but also to generate a small contact current when the device contacts the anti-static components. It's starting to happen. That is, these antistatic components are required to have semi-conductivity controlled in an appropriate range without the electric resistance value of the surface being too high or too low.

Conventionally, the semiconductive component, carbon black and carbon fibers in a thermoplastic resin, but that by molding a resin composition of the conductive component was added such hydrophilic polymers have been used, 10 ⁴ ~ The semiconducting region of 10 ¹⁰ Ω largely depends on the amount of the conductive component added and the molding conditions, and it is difficult to precisely control the semiconducting property.

On the other hand, such an antistatic component for electronic devices has not only semiconductivity whose electric resistance value is controlled within an appropriate range, but also dust generation due to dropping of the conductive filler from the surface of the molded product. It is required that the amount is small, and it is said that a thermoplastic resin to which fine carbon fibers are added is suitable for this requirement (Japanese Patent Laid-Open No. 8-508534).
Issue Bulletin). However, even in this case, since the resistance value greatly depends on the molding conditions and the like, it is difficult to control the resistance to a sufficiently narrow semiconductive region.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned conventional problems and to provide a semiconductive resin molded product having a uniform resistance value in a semiconductive region.

[0006]

The semiconductive resin molded article of the present invention comprises (A) a matrix thermoplastic resin and (B) 0.1 to 20% by weight of fine carbon fibers having an average fiber diameter of 200 nm or less. To 100 parts by weight of the conductive resin component
A semiconductive resin molded article obtained by molding a conductive thermoplastic resin composition comprising 0.1 to 80 parts by weight of a thermoplastic resin other than the component (A) and / or a thermoplastic elastomer, The component (C) is not completely compatible with the component (A) and is dispersed in a sea-island shape to form the island-shaped dispersed phase. The average value of the minor axis is 10 μm or less.

Fine carbon fibers having an average fiber diameter of 200 nm or less can exhibit conductivity with a small addition amount as compared with conventional carbon fibers and carbon black, and therefore have low dust generation, appearance of molded products, and molded products. It is known as an excellent conductive filler because of its excellent properties.

However, the thermoplastic resin molded product containing such fine carbon fibers is apt to greatly change its conductivity depending on molding conditions, and it is difficult to uniformly control the resistance value of the semiconductive region. Met. As a result of examining the reason, the present inventor has come to the following conclusion.

That is, in a thermoplastic resin molded article containing fine carbon fibers, the fine carbon fibers are dispersed in the thermoplastic matrix resin in a state of being entangled with each other. Conductivity is developed by forming a conductive network.

This thermoplastic resin molded article is molded through a process of melting, flowing, and cooling and solidifying by a molding process such as injection molding of a thermoplastic resin composition containing fine carbon fibers. Due to the shearing forces generated, FIG.
As shown in (a), as a result of the orientation of the fine carbon fibers 2 in the matrix resin 1, the entanglement and contact between the fine carbon fibers 2 become insufficient and the conductivity becomes low.

Next, the fine carbon fibers 2 oriented in the matrix resin 1 are dispersed while the temperature of the matrix resin 1 is high (the viscosity is low) in the initial stage of the cooling and solidification process.
As shown in (b) and FIG. 2 (c), the orientation is relaxed and a conductive network is formed, and as a result, the conductivity is improved. This phenomenon is verified by reheating the molded product having low conductivity (high resistance value) molded under the condition that the fine carbon fibers 2 are extremely oriented, whereby the conductivity of the heated part is improved. To be done. This phenomenon occurs not only in a molding process in which a resin is completely melted and fluidized like injection molding and extrusion molding, but also in a molding method in which a semi-molten sheet is stretched and molded like a vacuum molding. The same occurs, and the conductivity (resistance value) changes due to the orientation of the fine carbon fibers in the drawing process and the relaxation of the orientation in the cooling process.

Based on the above-mentioned mechanism of developing conductivity,
In order to control the conductivity of the molded product in the semi-conductive region, it is necessary to form an appropriate contact state without excessive orientation or relaxation of the fine carbon fibers. That is, for example, in FIG.
In the state where the fine carbon fibers 2 are sufficiently oriented as shown in (a), the conductivity is generally 10 ¹² Ω or more, which is shown in FIG.
In the state where the orientation of the fine carbon fibers 2 is sufficiently relaxed as shown in (c), the conductivity is generally 10 ⁴ Ω or less.
In order to obtain semiconductivity in the range of 0 ⁴ to 10 ¹⁰ Ω, it is desired that the orientation of the fine carbon fibers 2 be moderately relaxed in the state as shown in FIG. However, 1
In order to obtain the conductivity of the semiconductive region of 0 ⁴ to 10 ¹⁰ Ω,
Moderately relaxing the orientation of the fine carbon fibers is difficult to realize with good reproducibility, because the orientation of the fine carbon fibers and the state of the relaxation change particularly sensitively to the molding conditions. For molded products with complicated shapes,
Even within the same molded product, the resistance value varies depending on the part, and it is extremely difficult to uniformly control the resistance value of each part.

For example, in an injection-molded product, in the vicinity of a gate, which is a resin injection port, or in a thin wall portion, a large shearing force is applied, so that fine carbon fibers are oriented and conductivity is easily lowered (resistance value is high). On the other hand, at the flow end, since the shearing force is low, the orientation of the fine carbon fibers is low and the conductivity is likely to be high (the resistance value is low). If the cooling rate is decreased or the amount of fine carbon fiber is increased in order to improve the conductivity near the gate (reduce the resistance value), the resistance value at the flow end becomes low, resulting in a uniform resistance value. Sex cannot be secured. Further, generally, the shear rate and the cooling rate increase near the surface of the molded product, and are easily affected by the molding conditions. Therefore, in many semiconductive resin molded products such as antistatic parts, the fluctuation of the surface resistance value is likely to be large.

The present inventor conducted a study to stably obtain a semiconductive molded product based on the mechanism of the conductivity development due to the orientation and the relaxation of the orientation of the fine carbon fibers in the molding process. It was found that good semiconductivity can be realized by forming the island-like dispersed phase of the component (C) in the matrix resin of the component (A).

That is, in the present invention, in order to prevent an excessive increase in conductivity caused by the excessive relaxation of the orientation of the fine carbon fibers in the matrix resin during the cooling process, FIG. As described above, the non-conductive or low-conductive second resin and / or the component (C) 2 of the elastomer, which is different from the matrix resin 1 of the component (A), is compatible with the component (A) 1 of the matrix resin. The fine carbon fibers 2 are dispersed in a sea-island shape, and the dispersed phase of the component (C) 3 is used.
Semi-conductivity is realized by electrically dividing the conductive network of. Thus, in order to divide the conductive network of the fine carbon fibers 2 in the dispersed phase of the component (C) 3, in the present invention, most of the fine carbon fibers 2 are (A) as shown in FIG. ) It is desirable that the fine carbon fibers 2 are dispersed in the component 1 and the fine carbon fibers 2 are substantially absent in the component 3 (C).

As a method for confirming that the fine carbon fibers 2 do not substantially exist in the component (C) 3, for example, the cross section of the molded product is etched to remove the component (C), and then observed with a microscope. Then, it may be confirmed that the fine carbon fibers are not present (the network is not formed) in the portion after the component (C) is removed.

The dispersed phase of the component (C) exerts an effect of partially dividing the conductive network formed by the fine carbon fibers and an effect of inhibiting relaxation of the orientation of the fine carbon fibers in the cooling process, This can prevent the conductivity from becoming excessively high (the resistance value becoming excessively low).

As a result, for example, in order to improve the conductivity (reduce the resistance value) in the vicinity of the gate of the injection-molded product or in the thin-walled part, the cooling rate is decreased or the amount of fine carbon fibers added is increased. However, an excessive increase in conductivity (reduction in resistance value) does not occur at the flow end or the like, and a semiconductive resin molded product having a uniform resistance value can be obtained.

FIG. 1 (b) shows the dispersed phase of the component (C) 3 dispersed in the component (A). The size and shape of the dispersed phase differ depending on the viscosity of the component (C), the viscosity ratio of the component (C) and the component (A), the compatibility, the kneading conditions during production, and the like.
In addition, the dispersed phase of the component (C) may be stretched in the flow direction during the flow of the molding process to form a dispersed phase oriented in a fibrous or layered form.

The size of the dispersed phase of the component (C) in the present invention is 10 μm or less in the minor axis of the dispersed phase (that is, the value measured at the point where the diameter is the minimum. R _{min in} FIG. 1B). .
When the minor axis R _min of the dispersed phase of the component (C) is larger than 10 μm, the effect of the present invention cannot be obtained, and the conductivity is excessively increased (the resistance value is excessively lowered).

The reason will be described below.

That is, if the disperse phase of the component (C) has a large minor axis and the dispersed state is rough at the same blending ratio of the component (C), the distance between the disperse phases becomes large as a result.
In the interval between the dispersed phases, that is, in the portion where the component (C) does not exist, there is no effect of inhibiting the relaxation of the fine carbon fibers or an effect of dividing the conductive network, and therefore it is not possible to prevent an excessive increase in conductivity. . Therefore, in order to obtain the effect of the present invention, it is necessary to add a large amount of the component (C), but addition of a large amount of the component (C) not only lowers the strength of the obtained molded product, but also ( The sea-island phase of the components (A) and (C) is inverted, the component (C) becomes the sea phase, the component (A) containing the fine carbon fibers becomes the dispersed phase (island), and the conductive network of the fine carbon fibers becomes Not formed, causing an extreme decrease in conductivity.

From the above, the dispersed phase of the component (C) inhibits the relaxation of the orientation of the fine carbon fibers, and
In order to appropriately divide the conductive network of the fine carbon fibers, it is important that the minor axis R _min of this dispersed phase is as small as 10 μm or less. However, the component (C) becomes (A)
When the components are molecularly compatible with each other and are completely uniformly dispersed, the effect of inhibiting the relaxation of the fine carbon fibers and the effect of dividing the conductive network of the fine carbon fibers become small, and the effect of the present invention cannot be obtained. .

In the present invention, the minor axis R _min of the dispersed phase of the component (C) is 2 times or more and 200 times or less, and particularly 2 times or more and 50 times or less, the average fiber diameter of the fine carbon fibers. It is desirable in terms of exhibiting excellent semiconductivity.

When the dispersed phase of the component (C) is in a fibrous or layered shape, the minor axis R _min and major axis (values measured at the point where the diameter becomes maximum. FIG. 1B) R _max ), that is, the aspect ratio (major axis / minor axis) is preferably 50 or less, and more preferably 30 or less. If the aspect ratio is larger than this, the effect of dividing the conductive network of the fine carbon fibers becomes too large, and the conductivity is extremely lowered, which is not desirable.

In the present invention, the minor axis and the aspect ratio of the dispersed phase of the component (C) are the average of the values measured at 30 points using a microscope.

Further, the average distance between the dispersed phases of the component (C) is 10 times or more the average diameter of the fine carbon fibers and is 10,0.
It is preferably 00 times or less in terms of uniform semiconductivity.

Further, by using, as a part or all of the component (C), those whose viscosity increase and solidification rate in the cooling process are much slower than those of the component (A), an excessive increase in conductivity is caused. Not only can it be prevented, but also an excessive decrease in conductivity (increase in resistance value) can be improved.

That is, for example, in the low conductivity portion (high resistance portion) such as the vicinity of the gate of the injection molded product, the extreme orientation of the fine carbon fibers is relaxed within the time until the resin is solidified in the cooling process. It will happen without fail. On the other hand, by delaying the solidification rate of the whole amount or a part of the component (C), the relaxation of the orientation of the fine carbon fibers around the component (C) can be promoted and the resistance value can be stabilized.

In order to bring out the above effects, a thermoplastic resin and / or a thermoplastic elastomer in which all or part of the component (C) has a glass transition temperature (Tg) as shown in the following (i) or (ii): (Hereinafter, it may be referred to as a “low Tg component”.) (i) When the component (A) is an amorphous resin, a thermoplastic resin and / or a thermoplastic resin having a glass transition temperature (Tg) lower than the glass transition temperature (Tg) of the component (A) by 120 ° C. or more. Elastomer (ii) When the component (A) is a crystalline resin, a thermoplastic resin and / or a thermoplastic elastomer having a glass transition temperature (Tg) lower than the crystalline melting point (Tm) of the component (A) by 200 ° C. or more.

In the present invention, as the thermoplastic resin,
It is preferable to use a polycarbonate resin having a good balance of dimensional accuracy, heat resistance, mechanical properties, and the like.

The effect of the dispersed phase of the component (C) according to the present invention is that the average fiber diameter of the conductive filler is 20.
This is achieved when used in combination with a fine carbon fiber having a diameter of 0 nm or less.
In a molded article of a resin composition containing a conductive filler such as carbon fiber or metal exceeding 1, since the conductive fillers are less entangled with each other, the relaxation of orientation in the cooling process and the effect of forming a conductive network are extremely high. Therefore, the effect of the addition of the component (C) is low.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the semiconductive resin molded product of the present invention will be described in detail below.

First, the constituent components of the conductive thermoplastic resin composition which is a molding material for the semiconductive resin molded article of the present invention will be described.

(A) Thermoplastic resin As the thermoplastic resin of the component (A), for example, polycarbonate, polyarylate, polyphenyl sulfone, polyether sulfone, polyetherimide, polyoxymethylene, polystyrene, alicyclic polyolefin. , Polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyamide, polyether ether ketone, and other thermoplastic resins.
One or two or more of these may be appropriately selected and used according to properties such as mechanical strength and moldability depending on the use of the semiconductive resin molded product.

Among the above-mentioned thermoplastic resins, examples of the amorphous thermoplastic resin include polycarbonate, polyarylate, polyphenyl sulfone, polyether sulfone,
Polyetherimide, modified polyoxymethylene, polystyrene, alicyclic polyolefin and the like, on the other hand,
Examples of the crystalline thermoplastic resin include polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide and polyamide.

Among these thermoplastic resins, polycarbonate resin is preferable in terms of good balance of dimensional accuracy, heat resistance, mechanical properties and the like. As the polycarbonate resin, for example, a general one produced by reacting a raw material containing a dihydric phenol compound as a main component with phosgene by a solution method such as an interfacial polymerization method, a pyridine method, and a chloroformate method is used. can do.

When a polycarbonate resin is used as the thermoplastic resin, the melt flow rate (MFR) of the polycarbonate resin is 2 g / 10 minutes or more and 30 g / 10 minutes or less, especially 4 g / 10 in the measurement of 280 ° C. and 2.16 Kg load. It is desirable that the time is not less than 15 minutes and not more than 15 minutes.

(B) Fine carbon fiber The fine carbon fiber of the component (B) used in the present invention has an average fiber diameter of 200 nm or less, and is generally produced by a vapor phase growth method. As the fine carbon fibers, for example, carbon fibrils described in JP-A-8-508534 can be used.

That is, carbon fibrils have a graphite outer layer deposited substantially concentrically along the columnar axis of the fibrils, the fiber center axis of which is not straight, but undulating and tubular. Has a morphology.

The average fiber diameter of carbon fibrils is 200 nm.
Or less, preferably 100 nm or less, more preferably 50 nm or less.
nm or less. The fiber diameter of carbon fibrils depends on the production method of carbon fibrils and has a slight distribution, but the average fiber diameter referred to here is an average value measured at five points under microscope observation.

The average fiber diameter of carbon fibrils is 200 nm
If it is larger, the contact between fibrils in the matrix resin will be insufficient, a large amount of addition will be required to develop conductivity, and stable conductivity will be difficult to obtain.

The average fiber diameter of carbon fibrils is 0.1 n
m, especially 0.5 nm or more is desirable. If the average fiber diameter is smaller than this, the production is extremely difficult.

Carbon fibrils have a ratio of length to diameter (length / length).
A diameter ratio, that is, an aspect ratio) of 5 or more is preferable,
In particular, those having a length / diameter ratio of 100 or more are preferable because a conductive network can be easily formed, and excellent conductivity can be obtained with a small amount of addition. A more preferable carbon fibril length / diameter ratio is 1000 or more. The fiber diameter and fiber length (and aspect ratio) of this carbon fibril
Is an average value of 10 measured values in observation with a transmission electron microscope.

The wall thickness of the carbon fibrils having a fine tubular form (wall thickness of tubular body) is usually 3.5 to 75 nm.
It is a degree. This is usually about 0.1 of the outer diameter of the fibril.
Corresponds to 0.4 times.

When at least a part of carbon fibrils is in the form of aggregates, carbon fibrils are added to the resin composition as a raw material,
The fact that it does not contain fibril aggregates having a diameter of greater than about 50 μm, especially 10 μm, measured on the basis of area, makes it possible to add a small amount to obtain a predetermined conductivity, and to obtain mechanical properties of the obtained molded product. Is desirable in that it does not decrease

Further, in the present invention, since the fine carbon fibers such as carbon fibrils have a meandering fiber shape, the entanglement of the fibers is increased, and conductivity is obtained with a small amount of addition. Is desirable because of its great effect.

In order to obtain such entanglement, the fine carbon fiber used in the present invention preferably has a bending degree of 5 ° or more, preferably 20 ° or more, more preferably 40 ° or more.

The degree of bending of the fine carbon fiber is determined by, for example, removing the resin component of the semiconductive resin molded article of the present invention by a solvent or ion sputtering to expose the fine carbon fiber, or
Alternatively, it can be measured by observing an ultrathin section cut out from the molded product with an electron microscope. In this case, the fine carbon fibers in the surface layer within 50 μm from the surface of the molded product are measured.

As shown in FIG. 3, the degree of bending was obtained by observing the fine carbon fibers 2 such as carbon fibrils with a microscope and measuring 5 times the fiber diameter (fiber diameter (portion d in FIG. 2) on the same fiber. , A distance between two arbitrary points A, B is selected by a method such as measuring along the fiber with a divider, etc., and tangent lines L _A , L _B are drawn at the respective points to intersect the tangent lines L _A , L _B. The outside angle of Q (angle indicated by α in FIG. 2) is measured. The average value of 10 points is taken and this is taken as the degree of bending.

This angle is 0 ° if the fiber is straight, 180 ° if it is a semicircle, and 36 if it is a circle.
It becomes 0 °.

The degree of bending α obtained by performing such measurement
However, if it is 5 ° or more, preferably 20 ° or more, more preferably 40 ° or more, a fine carbon fiber is easily entangled with each other to form a network, and the non-conductive fiber is prevented from falling off and the antistatic property is prevented. It is preferable in terms of application.

Normal carbon fiber (pitch type, PAN
The system) is a rigid and linear fiber having a fiber diameter of about 7 to 13 μm, and the bending degree is less than 5 °. Such straight fibers do not entangle with each other,
It is difficult to form a network structure.

In the present invention, as the fine carbon fiber,
Commercially available products such as "BN" manufactured by Hyperion Catalysis International, Inc. can be used.

The fine carbon fibers used in the present invention include
A thermoplastic resin as the component (A), or various surface treatments or treatments with a dispersant may be applied. As the treating agent in this case, for example, a coupling agent such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or a block or graft copolymer of a non-polar segment and a polar segment can be used. .

In the present invention, the content of the fine carbon fiber is 0.1 to 20% by weight in the total amount of the conductive resin component of the thermoplastic resin of the component (A) and the fine carbon fiber of the component (B), It is preferably 0.5 to 8% by weight. If the content of the fine carbon fiber is less than this range, it is not possible to obtain sufficient antistatic performance in the obtained molded product, and if the content of the fine carbon fiber is more than this range, the moldability is lowered, and There is a possibility that the physical properties such as the strength of the molded product may be deteriorated.

As the thermoplastic resin (C) and / or the thermoplastic elastomer (C) component, in addition to the above-mentioned thermoplastic resins mentioned as the thermoplastic resin which can be used as the component (A), various thermoplastic elastomers, for example, Olefin-based elastomers, styrene-based elastomers, ester-based elastomers, amide-based elastomers, urethane-based elastomers and the like can be used.

The component (C) may be any one of those thermoplastic resins and / or thermoplastic elastomers that is different from the thermoplastic resin selected as the component (A).
The seeds may be used or two or more kinds may be used in combination.

In order to disperse the component (C) in the component (A) so that the minor axis of the dispersed phase of the component (C) is 10 μm or less, the component (C) is relatively different from the component (A). It is desirable to use those having good compatibility.

For example, when a polycarbonate resin is used as the component (A), it is desirable to use a component having a polar group as the component (C). Specifically, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polysulfone, polyether sulfone, polyetherimide, polyamide, ester elastomer, amide elastomer, urethane elastomer, glycidyl group, carboxylic acid, silanol group, etc. Examples thereof include polar group-modified polyolefin modified with a polar group and polar group-modified polystyrene. When a non-polar component such as polyolefin, polystyrene, olefin elastomer or styrene elastomer is used, it is desirable to use a compatibilizing component such as the above polar group modified product or silane coupling agent.

Among the above polar group-modified products, examples of the glycidyl-modified product include ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-graft-polymethyl methacrylate, ethylene-glycidyl methacrylate-graft-polystyrene and the like. To be

Examples of the acid-modified product include non-polar resins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene butene copolymer, polystyrene and styrene elastomer, and maleic anhydride and fumaric acid. , Acrylic acid, methacrylic acid, and the like, which are obtained by melt-mixing and grafting an unsaturated carboxylic acid such as acrylic acid and methacrylic acid in the presence of a radical generator such as an organic peroxide.

The silanol-modified product may be, for example, a compound of the general formula: RSiR ' _n Y _3-n (wherein R is an ethylenically unsaturated hydrocarbon or oxyhydrocarbon group, R'is an aliphatic saturated hydrocarbon group). , Y is a hydrolyzable organic group, and n is 0, 1 or 2) and the ethylenically unsaturated silane compound is melt-mixed in the presence of a radical generator such as an organic peroxide. It can be obtained by.

The Tg of the polycarbonate resin (14
Examples of the low Tg component having a Tg lower than that of 0 to 150 ° C. by 120 ° C. include various elastomers such as polyethylene, polypropylene, olefin elastomers, styrene elastomers, ester elastomers, amide elastomers and urethane elastomers. .

In a fixing jig used for assembling and protecting an antistatic component for an electronic device, particularly a magnetic head for a hard disk drive, to fix the head for carrying and carrying, not only semiconductivity but also dust generation property. That there are few
Excellent slidability with the head is required. When using the semiconductive resin molded article of the present invention for such applications,
When a polar group-modified polyolefin such as a glycidyl group is used in whole or in part as the component (C), not only stable semiconductivity but also less dust generation due to falling of the dispersed phase and excellent slidability Therefore, it is preferable.

Various elastomers as the component (C) will be described below.

(1) Olefin-based Elastomer (Olefin-based TPE) Examples of the olefin-based TPE include olefin-based copolymer rubber, specifically ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene. An elastic body of an amorphous random copolymer containing olefin as a main component, such as a copolymer rubber (EPDM), or an elastic body obtained by heat-treating them in the presence of an organic peroxide and mainly crosslinking by radicals as a basic component. The thing contained is mentioned.

As such an olefin copolymer rubber, the above-mentioned ethylene / propylene copolymer rubber (EP
M), ethylene / 1-butene copolymer rubber (EPM),
As non-conjugated dienes, aliphatic dienes such as butene-1,1,4-hexadiene, 5-ethylidene norbornene, 5
Examples thereof include ethylene / propylene / non-conjugated diene copolymer rubbers using methylnorbornene, 5-vinylnorbornene, dicyclopentadiene, dicyclooctadiene and the like.

The production method and shape of these ethylene / propylene copolymer rubbers are not particularly limited.

(2) Styrene-based plastic elastomer (styrene-based TPE) Examples of the styrene-based TPE include hydrogenated products of styrene / butadiene block copolymers, hydrogenated products of styrene / isoprene block copolymers, or a mixture thereof. Examples thereof include those containing a hydrogenated product of the selected styrene / conjugated diene block copolymer as a basic component.

The hydrogenated product of the styrene / conjugated diene block copolymer is a hydrogenated product of a styrene / butadiene block copolymer, a hydrogenated product of a styrene / isoprene block copolymer, or a mixture thereof.
Specific examples thereof include a styrene / ethylene / butylene / styrene copolymer, or a styrene / ethylene / propylene / styrene copolymer which is a hydrogenated product of a styrene / isoprene block copolymer, or a mixture thereof. .

(3) Additional compounding material (arbitrary component) The above-mentioned olefin-based and styrene-based elastomer components are added to the above-mentioned olefin-based and styrene-based elastomer components within a range not significantly impairing the effects of the present invention. , 000), various thermoplastic resins, various elastomers, talc, calcium carbonate, glass fibers, various fillers such as glass balloons, and the like.

The hydrocarbon type rubber softening agent can play an important role in controlling the flexibility of the olefin type and styrene type elastomer compositions.

Such a hydrocarbon type rubber softening agent (average molecular weight is generally 300 to 2,000, preferably 500)
Of 1,500 to 1,500), based on 100 parts by weight of hydrogenated olefin copolymer rubber or styrene / conjugated diene block copolymer, 0 to 250 parts by weight, particularly 20 to
It is preferable to add 200 parts by weight. Such a hydrocarbon-based softening agent for rubber is a mixture in which an aromatic ring, a naphthene ring and a paraffin ring are combined, and a paraffin chain carbon number of which is 50% or more of the total carbon is a paraffin type. It is called oil and has 30 carbon atoms in the naphthene ring.
Those having 45% to 45% are called naphthenic oils, and those having more than 30% of aromatic carbons are called aromatic oils. Of these, paraffinic oil is preferably used.

As the thermoplastic resin in the above-mentioned additional compounding material component, polypropylene, ethylene resin, polyolefin resin such as polybutene-1 resin, polystyrene, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer are used. Polystyrene resin such as coalescing, polyphenylene ether resin, polyamide resin such as nylon 6 and nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyoxymethylene homopolymer,
A polyoxymethylene-based resin such as a polyoxymethylene copolymer, a polymethylmethacrylate-based resin, or the like can be used.

As the ethylene resin, polyethylene,
Examples thereof include ethylene / α-olefin copolymers, ethylene / vinyl acetate copolymers, ethylene / (meth) acrylic acid copolymers and ethylene / (meth) acrylic acid ester copolymers.

Examples of the polyethylene include low density polyethylene (branched ethylene polymer), medium density and high density polyethylene (linear ethylene copolymer).

Examples of the above-mentioned ethylene / α-olefin copolymer include ethylene / butene-1 copolymer and ethylene / α-olefin copolymer.
Representative examples thereof include a hexene copolymer, an ethylene / heptene copolymer, an ethylene / octene copolymer, an ethylene-4-methylpentene-1 copolymer and the like.

One kind of thermoplastic resin may be used,
A plurality of kinds may be used, and the addition amount thereof is generally 1 to 300 parts by weight, preferably 20 to 250 parts by weight, based on 100 parts by weight of the hydrogenated product of the olefin copolymer rubber or the styrene / conjugated diene block copolymer. It is preferable to mix them.

(4) Ester-based elastomer As the ester-based elastomer, an aromatic polyester is used as a hard component, a polyester polyether block copolymer using an aliphatic polyether as a soft component, an aromatic polyester as a hard component, and a soft component as a soft component. Examples thereof include polyester polyester block copolymers using an aliphatic polyester.

The polyester polyether block copolymer is an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, an aromatic dicarboxylic acid or its alkyl ester, and a polyalkylene ether having a weight average molecular weight of 400 to 6000. It is obtained by polycondensing an oligomer obtained by an esterification reaction or a transesterification reaction using glycol as a raw material.

Here, as the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those known as a raw material for polyester, particularly a raw material for polyester elastomer can be used. Examples thereof include ethylene glycol and propylene glycol. , Trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol and the like are preferable, and 1,4-butanediol, ethylene glycol, and the like are preferable.
Particularly preferably, the main component is 1,4-butanediol, and one kind or two or more kinds can be used.

As the aromatic dicarboxylic acid, those known as raw materials for polyesters, particularly polyester elastomers can be used, and terephthalic acid, isophthalic acid,
Examples thereof include phthalic acid and 2,6-naphthalenedicarboxylic acid, preferably terephthalic acid and 2,6-naphthalenedicarboxylic acid, and particularly preferably terephthalic acid as a main component. You may use together the above. Examples of the alkyl ester of aromatic dicarboxylic acid include dimethyl esters such as dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate and 2,6-dimethyl naphthalate, and dimethyl terephthalate and 2,6-dimethyl naphthalate are preferable. However, dimethyl terephthalate is particularly preferable, and two or more of these can be used in combination. In addition to the above, small amounts of trifunctional diols, other diols and other dicarboxylic acids and their esters may be copolymerized, and further, aliphatic dicarboxylic acids such as adipic acid or alicyclic dicarboxylic acids, or An alkyl ester or the like may also be used as a copolymerization component.

As the polyalkylene ether glycol, those having a weight average molecular weight of 400 to 6000 are used, preferably 500 to 4,000, particularly preferably 600 to 3,000. When the molecular weight is less than 400, the block property of the copolymer is insufficient, and when the weight average molecular weight exceeds 6000, the physical properties of the polymer deteriorate due to phase separation in the system. Here, as the polyalkylene ether glycol, polyethylene glycol, poly (1,2 and 1,3-propylene ether) glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, a block or random copolymerization of ethylene oxide and propylene oxide. Examples thereof include a combination, a block or random copolymer of ethylene oxide and tetrahydrofuran. Particularly preferred is polytetramethylene ether glycol.

The content of the polyalkylene ether glycol is preferably 5 to 95% by weight, more preferably 10 to 85% by weight, and particularly preferably 20 to 80% by weight, based on the resulting block copolymer. . If this content is more than 95% by weight, it is difficult to obtain a polymer by polycondensation.

On the other hand, the polyester polyester block copolymer has a weight average molecular weight of 400 to 6000.
In place of the polyalkylene ether glycol of, a polyester oligomer condensed from an aliphatic or alicyclic dicarboxylic acid and an aliphatic diol, a polyester oligomer synthesized from an aliphatic lactone or an aliphatic monoolcarboxylic acid, and 2 to 2 carbon atoms It is obtained by polycondensing an oligomer obtained by an esterification reaction or a transesterification reaction using 12 aliphatic and / or alicyclic diols and an aromatic dicarboxylic acid or an alkyl ester thereof as raw materials.

Examples of the polyester oligomer of 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,
Aliphatic dicarboxylic acid such as 4'-dicarboxylic acid or one or more of aliphatic dicarboxylic acid such as succinic acid, oxalic acid, adipic acid, sebacic acid and ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, etc. Polyester oligomer having a structure condensed with one or more of the diols of
Examples of polycaprolactone-based polyester oligomers synthesized from ε-caprolactone, ω-oxycaproic acid, and the like.

Examples of such polyester polyether block copolymers include commercially available polymers such as "Perprene P" (trade name of Toyobo Co., Ltd.), "Hytrel" (trade name of DuPont Toray Co., Ltd.), and "Low Mod". (Nippon Gee Plastic Co., Ltd. product name), "Nichigo Polyester" (Nippon Synthetic Chemical Industry Co., Ltd. product name), "Teijin Polyester Elastomer" (Teijin Co., Ltd. product name), etc. There is a commercially available polymer "Perprene S" (trade name of Toyobo Co., Ltd.).

(5) Polyamide Elastomer A polyamide elastomer has polyamide (nylon 6,66,11,12, etc.) as the hard segment and polyether or polyester as the soft segment. For example, the polyether block amide is represented by the following general formula [I].

[0090]

[Chemical 1]

The polyether block amide represented by the above general formula [I] used in the present invention is a substance known per se as disclosed in US Pat. No. 3,044,978 and the like. is there.

Examples thereof include (a) salts of diamine and dicarboxylic acid, lactams or aminodicarboxylic acids (PA constituents), (b) polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol ( It is produced by polycondensing PG constituents) and (c) dicarboxylic acid.

Commercially available products of polyether block amide include "Pebax" (trade name of Toray Industries, Inc.), "Daiamide-PAE" (trade name of Daicel-Huls),
"UBE Polyamide Elastomer" (trade name of Ube Industries, Ltd.), "Novamit PAE" (trade name of Mitsubishi Chemical Co., Ltd.), "Grelax A" (trade name of Dainippon Ink and Chemicals Co., Ltd.), Examples include "Grillon ELX, ELY" (trade name, manufactured by MUS Japan Co., Ltd.).

(6) Urethane Elastomer A polyurethane elastomer is a diisocyanate and a short chain glycol (ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A, etc.).
And a soft segment composed of diisocyanate and a long-chain polyol. Here, the long-chain polyol has a molecular weight of 4
100-6,000 poly (alkylene oxide) glycols, such as polyethylene glycol, poly (1,2 and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, etc. Such polyether-based ones or polyester-based ones such as polyalkylene adipates, polycaprolactones and polycarbonates are used. This type of thermoplastic polyurethane elastomer is a compound having a structure represented by the following general formula [II].

[0095]

[Chemical 2]

As this type of diisocyanate compound, known and conventional compounds such as phenylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate and hexamethylene diisocyanate can be used.

Commercially available products of the above-mentioned polyurethane elastomers include "Elastolan" (trade name of Takeda Birdish Urethane Co., Ltd.), "Miractran" (trade name of Nippon Miractolane Co., Ltd.), "Resamine P" (Dainichi Seika) Industrial Co., Ltd. product name), "U-FINE P" (Asahi Glass Co., Ltd.)
Product name) etc.

The flexural modulus (ASTMD790) of the thermoplastic elastomer used as the component (C) is 50.
Addition of an elastomer is preferable to be 0 or less, and to have a bending elastic modulus of 1/5 or less, more preferably 1/8 or less, of the bending elastic modulus (ASTM D790) of the thermoplastic resin as the component (A) to be used. This is preferable in that the effect of improving conductivity is large.

In the present invention, the blending amount of the component (C) is 0.1 to 80 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). . If the blending amount of the component (C) is less than this, (C)
If the effects of the invention cannot be sufficiently obtained by mixing the components, and if there are too many, the dispersed phases of the (A) component and the (C) component are reversed, and the (C) component becomes the sea phase, as described above. , The conductivity is impaired.

Particularly, the blending amount of the component (C) is 0.1 to 10, preferably 0.3 to 10 in terms of the weight ratio with respect to the component (B).
It is preferably 5.

When a low Tg component such as the above (i) or (ii) is used as a part or the whole of the component (C), this low Tg component is the sum of the components (A) and (B). 50 parts by weight or less, preferably 1 to 20 parts by weight with respect to 100 parts by weight. If the compounding amount of the low Tg component is less than this range, the effect of its addition cannot be obtained sufficiently, and if it is more than this range, the mechanical strength and heat resistance of the resulting molded article are impaired, which is not desirable.

Further, the content of the low Tg component in the component (C) is preferably 0.5 to 80 parts by weight in 100 parts by weight of the component (C), because the conductivity is uniform.

(D) Additive Component In the conductive thermoplastic resin composition of the present invention, in addition to the above components (A) to (C), if necessary, additional components may be added within a range that does not impair the above performance. It can be blended.

Examples of such additional components include glass fiber, silica fiber, silica-alumina fiber, potassium titanate fiber, aluminum borate fiber, and other inorganic fibrous reinforcing materials, aramid fiber, polyimide fiber, fluororesin fiber. Organic fibrous reinforcements such as, talc, calcium carbonate,
Inorganic fillers such as mica, glass beads, glass powder, glass balloons, fluororesin powders, solid lubricants such as molybdenum disulfide, plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, and UV absorption. Agents, neutralizing agents, lubricants, compatibilizers, antifog agents, antiblocking agents,
Various additives such as slip agents, dispersants, colorants, antibacterial agents, optical brighteners and the like can be mentioned.

Further, a conductive filler other than the fine carbon fibers used in the present invention may be added to the conductive thermoplastic resin composition according to the present invention as an additional component. Examples of such conductive fillers include metal-based fillers such as aluminum, silver, copper, zinc, nickel, stainless steel, brass and titanium, graphite (artificial graphite, natural graphite), glassy carbon particles, pitch-based carbon fibers, Examples include conductive fillers such as PAN-based carbon fibers, metal oxide-based fillers such as titanium oxide, zinc oxide, tin oxide, and indium oxide.

[0106] Among the metal oxide fillers, in the case where excess electrons are generated due to the presence of lattice defects to exhibit conductivity, a dopant added to increase conductivity may be used. . For example, aluminum is used as a dopant for zinc oxide, antimony is used for tin oxide, and tin is used for indium oxide. Further, a carbon fiber or the like may be coated with a metal, or a composite conductive filler in which conductive tin oxide or conductive carbon is formed on the surface of potassium titanate whiskers or aluminum borate whiskers may be used.

(E) Manufacturing Method The conductive thermoplastic resin composition according to the present invention can be manufactured by a usual thermoplastic resin processing method. For example, after the components (A), (B) and (C) and all the additional components to be blended as required are pre-mixed, a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder,
It can be produced by melt-kneading with a biaxial kneading extruder, a kneader or the like.

The semiconductive resin molded article of the present invention can be manufactured by molding such a conductive thermoplastic resin composition by various melt molding methods. Specific examples of the molding method include compression molding, extrusion molding, vacuum molding, blow molding, and injection molding. Among these molding methods, a remarkable effect can be obtained especially in the injection molding method and the vacuum molding method.

When the conductive thermoplastic resin composition according to the present invention is manufactured, a masterbatch in which a high concentration of the component (B) is added to a part of the component (A) in advance is prepared. When the masterbatch is produced by diluting the component (A) and the component (C), the fine carbon fibers of the component (B) are not excessively mixed in the dispersed phase of the component (C), so that the effect of the present invention becomes large. . Alternatively, the total amount of the component (A) may be mixed in advance with the total amount of the component (B), and then the component (C) may be added and mixed.

When the semiconductive resin molded article of the present invention is used as an antistatic component for electronic devices, the surface resistance value is 10 ⁴ to 10 ¹⁰ Ω, preferably 10 ⁵ to 10 ⁹
It is preferable to control in the range of Ω because charging is less likely to occur and the contact current is small.

Such control of the surface resistance value is performed by the viscosity of the component (B), the viscosity ratio of the component (A) and the component (B), and (B).
The blending ratio of the component and the component (C) and the molding conditions (resin temperature, mold temperature, molding pressure, etc.) are adjusted appropriately, and the orientation of the fine carbon fiber of the component (B) and its degree of relaxation, the component (C) It suffices to control the degree of disruption of the conductive network of the fine carbon fibers and the inhibition of the relaxation of the orientation of the fine carbon fibers by the dispersed phase.

Incidentally, the surface resistance value is generally obtained in the unit of (Ω / □) by converting the resistance value into a shape factor in consideration of the thickness of the measurement sample and the sneak of the current in the width direction. In the case of a molded product having a complicated shape, this conversion is extremely difficult. On the other hand, in practical use, the apparent resistance value including the shape is important, and it is not always necessary to use the unit (Ω / □) converted by the shape. Therefore,
In the present invention, the surface resistance value (Ω) is used for evaluation.

[0113]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below.

The blended raw materials used in the examples and comparative examples are as follows. Polycarbonate resin: "Upilon S3000" (trade name) manufactured by Mitsubishi Engineering Plastics (Tg =
146 ° C.) Fine carbon fiber: Hyperion Catalysis International's type “BN” (trade name) (average fiber diameter = 1)
0 nm, average fiber length = 0.5 μm or more, length / diameter ratio = 5
0 or more, bending degree = 122 °) EPR (ethylene propylene copolymer): “EP912P” (trade name) manufactured by Japan Synthetic Rubber Co., Ltd. (Tg <−50 ° C.) GMA-PE (ethylene glycidyl methacrylate copolymer): Sumitomo Chemical company "Bond First E" (trade name) (Tg = -23 ° C) PP (polypropylene): Nippon Polychem Co., Ltd. "Novatech MA4U" (trade name) (Tg = 8 ° C) PET (polyethylene terephthalate): Nihon Uni Unipet "RT553C" (trade name) manufactured by PET (Tg
= 80 ° C.) PEI (polyether imide): GE Plastics “Ultem 1000” (Tg = 218 ° C.) PAR (polyarylate resin): Unitika Ltd. “U polymer U100” (trade name) (Tg = 182)
℃)

Examples 1 to 5 and Comparative Examples 1 to 4 Each material was mixed in the composition shown in Table 1, and a twin-screw extruder (“PCM45” manufactured by Ikegai Iron & Steel Co., L / D = 32 (L; screw length) , D; screw diameter)) and barrel temperature 3
00 ° C (however, 350 ° C in Example 5 and Comparative Example 4),
Melt kneading was performed at a screw rotation speed of 160 rpm to obtain pellets of the conductive polycarbonate resin composition.

In the mixing and kneading, a masterbatch was prepared by adding 15% by weight of fine carbon fiber to a polycarbonate resin in advance, and the masterbatch was diluted with the remaining components to give a predetermined mixing amount.

With respect to the conductive thermoplastic resin composition thus obtained, the surface resistance of the molded product, the minor axis of the dispersed phase and the aspect ratio were measured by the following methods, and the results are shown in Table 1.

Surface Resistance Value Using each conductive thermoplastic resin composition, shown in FIG. 4 with a 75 ton injection molding machine at a cylinder temperature of 310 ° C., a mold temperature of 90 ° C. and an injection speed of 15 to 17 cc / sec. A resistance-measurement sheet sample 10 was molded. Regarding this resistance value measurement sheet sample 10, the surface resistance values of the gate portion (film gate side) 10A and the end portion 10B were measured using DIA Instrument Co., Ltd. Hiresta UP.
Probe (2 probe probe, distance between probes 20mm,
It was measured using a probe diameter of 2 mm). The applied voltage is 10 V if the resistance value is less than 1 × 10 ⁶ Ω, and the resistance value is 1 ×
When it was 10 ⁶ Ω or more, the measurement was performed with 100V.

The minor axis and aspect ratio of the dispersed phase of the component (C) were measured for the surface resistance measuring parts 10A and 10B of the sheet sample 10 for measuring the minor axis and aspect ratio of the dispersed phase.

The injection-molded article containing the fine carbon fibers has the largest shearing force in the vicinity of the surface thereof and has a high cooling rate, resulting in low conductivity. Therefore, the surface resistance value and practical charging characteristics of the molded product are governed by the dispersed state near the surface. Therefore, in the measurement of the minor axis and the aspect ratio of this dispersed phase, the dispersed phase was observed within a depth range of 50 μm from the surface.

Further, it was confirmed that the shape of the dispersed phase of the component (C) was elongated along the flow direction of the resin, and therefore the diameter was the largest in the flow direction and the smallest in the depth direction. It was confirmed that Therefore, the value obtained by measuring the diameter of the dispersed phase in the flow direction was taken as the major axis and the value obtained as measured in the depth direction was taken as the minor axis.

From the above, a thin section of a cross section along the flow direction of the resin was cut out from the sample, stained with this, and then the dispersed phase was observed with a transmission electron microscope.
0 pieces were randomly selected, the minor axis and the major axis were measured, and the average value thereof was calculated.

In this microscopic observation, it was confirmed that fine carbon fibers were scarcely present in the dispersed phase of the component (C).

With respect to the conductive polycarbonate resin compositions used in Example 1 and Comparative Examples 1 and 2, the molding temperature dependency of conductivity was examined by the following method, and the results are shown in Table 2. The relationship between the surface resistance value and the molding temperature is shown in FIG.

Dependence of Conductivity on Molding Temperature Changing the molding temperature at the time of injection molding the resistance sample sheet 10 using the compositions used in Example 1, Comparative Example 1 and Comparative Example 2. Then, molding was performed while changing the cooling rate (mold temperature 90 ° C. injection speed 15 to 17 c
c / sec). Next, in the central portion 10C of the obtained sheet sample 10, the surface resistance value and the minor axis of the dispersed phase of the component (C) (only for Example 1) were measured in the same manner as above.

[0126]

[Table 1]

[0127]

[Table 2]

From Tables 1 and 2 and FIG. 5, the following is clear.

That is, in the case of the semiconductive resin molded products of the present invention of Examples 1 to 5, extremely uniform conductivity distribution can be obtained in the semiconductive region having a resistance value of 10 ⁴ to 10 ¹⁰ Ω. Moreover, the dependency of the conductivity on the injection molding temperature is small, and stable semiconductivity can be obtained under any conditions.

On the other hand, in Comparative Examples 1 to 3, uniform semiconductivity cannot be obtained.

In particular, as can be seen from the comparison between Example 5 and Comparative Example 3, if the minor axis of the dispersed phase of the component (C) is outside the range of the present invention even with the same composition formulation, The effect of the invention cannot be obtained.

Further, when the component (C) is compatible with the component (A) and the component (C) does not form a dispersed phase of 10 μm or more as in Comparative Example 4, there is a large variation in conductivity. The effect of the present invention cannot be obtained.

[0133]

As described above in detail, according to the present invention, there is provided a semiconductive resin molded product having uniform conductivity in a semiconductive region having a resistance value of 10 ⁴ to 10 ¹⁰ Ω.

[Brief description of drawings]

1A is a schematic cross-sectional view showing a sea-island structure of a semiconductive resin molded product according to an embodiment, and FIG. 1B is a schematic cross-sectional view showing a dispersed phase of a component (C). FIG.

FIG. 2 is a schematic diagram illustrating a conductive network made of fine carbon fibers.

FIG. 3 is an explanatory diagram of a method for measuring the degree of bending of fine carbon fibers according to the present invention.

FIG. 4 is a plan view showing a resistance value measurement sheet sample molded in Examples and Comparative Examples.

FIG. 5 is a graph showing the molding temperature dependence of conductivity in Example 1 and Comparative Examples 1 and 2.

[Explanation of symbols]

1 (A) component (matrix resin) 2 Fine carbon fiber ((B) component) 3 (C) component 10 Resistance value measurement sheet sample

Continued front page    F-term (reference) 4F072 AA02 AA08 AB10 AB14 AB15                       AB18 AD04 AD05 AD37 AD41                       AD42 AD43 AD44 AD46 AD52                       AK15 AL11 AL16 AL19                 4J002 BB152 BC031 BK001 BP012                       CB001 CE001 CF061 CF071                       CF102 CF161 CG001 CH091                       CK022 CL001 CL072 CL082                       CM041 CN011 CN031 DA016                       FA046 FD016 FD116 GM00                       GM01 GQ00 GQ02                 5G301 DA20 DA42 DD05

Claims (5)

[Claims] 1. (A) a matrix thermoplastic resin;
(B) Fine carbon fiber 0.1 having an average fiber diameter of 200 nm or less
To 20% by weight, 100 parts by weight of a conductive resin component, and 0.1 to 80 parts by weight of a thermoplastic resin other than the components (C) and (A) and / or a thermoplastic elastomer. A semiconductive resin molded article obtained by molding a resin composition, wherein the component (C) is not completely compatible with the component (A),
Semi-conductive material characterized in that the component (C) is dispersed in a sea-island shape to form an island-shaped dispersed phase, and the average value of the minor axis of the dispersed phase of the (C) component is 10 μm or less. Resin molded product. 2. The mean value of the short diameters of the dispersed phase of the component (C) according to claim 1, which is not less than 2 times and not more than 200 times the average fiber diameter of the fine carbon fibers of the component (B). Semi-conductive resin molded product. 3. The thermoplastic resin as the component (A) according to claim 1, wherein the thermoplastic resin as the component (A) is an amorphous resin, and at least a part of the component (C) is the thermoplastic resin as the component (A). A semiconductive resin molded article, which is a thermoplastic resin and / or a thermoplastic elastomer having a glass transition temperature (Tg) lower by 120 ° C. or more than the glass transition temperature (Tg) of 1. 4. The thermoplastic resin as the component (A) according to claim 1 or 2, wherein the thermoplastic resin is a crystalline resin, and
At least a part of the component is a thermoplastic resin and / or a thermoplastic elastomer having a glass transition temperature (Tg) lower by 200 ° C. or more than the crystal melting point (Tm) of the thermoplastic resin of the component (A). Semi-conductive resin molded product. 5. The semiconductive resin molded article according to claim 1, wherein the component (A) is a polycarbonate resin.