JP2007297501A - Conductive molded product and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive molded product having a satisfactory surface resistivity even if molding a thermoplastic resin composition containing very fine conductive fibers by usual molding method and molding conditions, and a method of manufacturing the same. <P>SOLUTION: A conductive layer 1 containing the very fine conductive fibers formed on the molded product is formed by heating the molded product to expose the very fine conductive fibers 2 to the surface, to project the fibers from the surface or to contain the fibers in the molded product in a depth less than 100 nm from the surface. This heating is implemented by making the temperature of the molded product raised from the glass transition temperature of the thermoplastic resin composition containing very fine conductive fibers to be in the temperature range 30°C higher than the melting temperature of the composition, or heating at a temperature within the range where the viscosity is 5.0×10<SP>3</SP>to lower than 1.0×10<SP>7</SP>Pa s. All of the molded products obtained by publicly known methods, such as injection molding, extrusion molding, press molding, transfer molding and laminate molding, can be used. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive molded body in which a conductive layer containing ultrafine conductive fibers such as carbon nanotubes is formed on a molded body, and a method for manufacturing the same.

2. Description of the Related Art Conventionally, electronic components such as IC chips and hard disks, trays that transport silicon wafers and semiconductors, IC sockets, connectors, wafer tweezers, and the like have a problem of causing electrical breakdown when charged with static electricity. In order to prevent electric breakdown due to static electricity, an antistatic molded body using a resin composition to which carbon black, ketjen black, acetylene black or the like is added is used.
Recently, a molded product imparted with antistatic or conductive properties using carbon nanotubes has been developed. A mixture composition of carbon nanotubes and a thermoplastic resin is injection molded to produce 10 ¹ to 10 ⁹ Ω / □. There is also known a conductive material having a surface resistance value (Patent Document 1).
JP 2003-100147 A

However, the molded body containing carbon black or the like needs to contain a large amount of carbon black or the like in order to obtain conductivity, and its dispersibility is poor, so that a uniform conductive function cannot be exhibited. It was. In addition, there is a risk that carbon black or the like may drop off, and the dropped carbon black or the like adheres to damage electronic components.
On the other hand, the conductive material of Patent Document 1 can obtain conductivity by heating the mixed composition before molding at 20 to 100 ° C. higher than the normal heating temperature and injecting at a low speed. However, there is a problem that the conductivity cannot be sufficiently exhibited, and the resin is deteriorated and decomposed by overheating.

  The present invention has been made in order to address the above-described problems, and the object of the present invention is to use a thermoplastic resin composition containing ultrafine conductive fibers, and to provide a conductive molded article that exhibits sufficient conductivity, And a manufacturing method thereof.

  In order to achieve the above object, a first conductive molded body according to the present invention is a molded body in which a conductive layer containing at least an ultrafine conductive fiber is formed on the surface of the molded body, and the conductive layer comprises: It is formed by heating to expose the ultrafine conductive fiber on the surface or projecting from the surface to reduce the surface resistivity.

  The second conductive molded article of the present invention is a molded article in which a conductive layer containing at least ultrafine conductive fibers is formed on the surface of the molded article, and the conductive layer is heated to be less than 100 nm from the surface. It is characterized in that it is formed by containing ultrafine conductive fibers in the interior thereof and reducing the surface resistivity.

In each of the above conductive molded bodies, it is preferable that the molded body is composed of a base material layer not containing ultrafine conductive fibers and a conductive layer containing ultrafine conductive fibers. Furthermore, the conductive layer preferably has a surface resistivity of 10 ¹² Ω / □ or more before heating, and has a surface resistivity of less than 10 ¹² Ω / □ after heating. Further, the ultrafine conductive fiber is a carbon nanotube, and the carbon nanotube is contained in the conductive layer in an amount of 0.01 to 12.0% by mass, and the surface resistivity of the molded body is 10 ¹ Ω / □ or more and less than 10 ¹² Ω / □. It is also preferable.

  In the first method for producing a conductive molded body according to the present invention, a thermoplastic resin composition containing ultrafine conductive fibers is melt molded to produce a melt molded body, and at least the surface of the melt molded body is heated. The ultrafine conductive fiber is exposed on the surface of the melt-molded product, or protrudes from the surface, or is contained within less than 100 nm from the surface to form a conductive layer having a reduced surface resistivity. It is what.

  In the second method for producing a conductive molded body of the present invention, a thermoplastic resin composition containing ultrafine conductive fibers is melt-molded to produce a melt-molded body, and the melt-molded body is subjected to secondary processing such as cutting. And forming a secondary processed molded body, heating at least the surface of the secondary processed molded body, and exposing or projecting the ultrafine conductive fibers on the surface of the secondary processed molded body, or the surface thereof. The conductive layer having a reduced surface resistivity is formed by being contained within a thickness of less than 100 nm.

  In these production methods, the melt molding is preferably performed by any one of extrusion molding, injection molding, and press molding.

  In the third method for producing a conductive molded body of the present invention, a thermoplastic resin composition containing ultrafine conductive fibers and a thermoplastic resin are co-extruded to form one or both sides of a base material layer made of a thermoplastic resin. Alternatively, a melt-molded body in which a surface layer made of a thermoplastic resin composition containing ultrafine conductive fibers is laminated on the entire surface is prepared, and at least the surface of the melt-molded body is heated to expose the ultrafine conductive fibers on the surface of the melt-molded body. Alternatively, the conductive layer having a reduced surface resistivity is formed by projecting from the surface thereof, or by being contained in the interior of less than 100 nm from the surface.

  According to the fourth method for producing a conductive molded article of the present invention, after injecting a thermoplastic resin composition containing ultrafine conductive fibers into an injection mold, a synthetic resin is further injected into the mold to synthesize A melt-molded product in which a surface layer made of thermoplastic resin containing ultrafine conductive fibers is laminated on the surface of a base material layer made of resin or a melt-molded product in which the periphery of the base material layer is covered with the surface layer is produced, and the melt-molded product The surface resistivity was lowered by heating at least the surface of the body and exposing the ultrafine conductive fibers to the surface of the melt-molded body, or projecting from the surface, or containing the ultrafine conductive fiber in the interior of less than 100 nm from the surface. A conductive layer is formed.

  A fifth method for producing a conductive molded article of the present invention is to produce a surface sheet made of a thermoplastic resin composition containing ultrafine conductive fibers and a base sheet made of a thermoplastic synthetic resin composition, Melt molding in which a surface layer made of a thermoplastic resin composition containing ultrafine conductive fibers is laminated on the surface of a base material layer made of a thermoplastic synthetic resin composition by hot pressing after the surface sheet is laminated on one or both sides of the base material sheet Body is heated, at least the surface of the melt-formed body is heated, and the ultrafine conductive fiber is exposed on the surface of the melt-formed body, or protrudes from the surface, or is contained within less than 100 nm from the surface. Thus, a conductive layer having a reduced surface resistivity is formed.

  According to the sixth method for producing a conductive molded body of the present invention, a transfer film on which a surface layer containing ultrafine conductive fibers is formed in advance, the transfer film is placed in an injection mold, and the mold After injecting the synthetic resin into the base material layer made of synthetic resin and producing the melt-molded body with the surface layer containing the ultra-fine conductive fibers transferred, at least the surface of the melt-molded body is heated to form the ultra-fine conductive material. The fiber is exposed on the surface of the melt-molded body, protrudes from the surface, or is contained within less than 100 nm from the surface to form a conductive layer having a reduced surface resistivity. To do.

  According to the seventh method for producing a conductive molded body of the present invention, a film for laminating containing ultrafine conductive fibers or a film for laminating in which a surface layer containing ultrafine conductive fibers is formed on a film substrate is prepared in advance. After placing the laminating film in the injection mold, after injecting a synthetic resin into the mold to produce a melt molded body in which the laminating film is laminated on the surface of the base material layer made of synthetic resin, Heating at least the surface of the molten molded body to expose the ultrafine conductive fibers on the surface of the molded body, or to protrude from the surface, or to be contained within less than 100 nm from the surface, the surface resistivity is A reduced conductive layer is formed.

  The eighth method for producing an electroconductive molded body of the present invention is to apply and solidify a thermoplastic resin coating solution containing ultrafine conductive fibers on the surface of a molded body obtained by melt molding a synthetic resin, After producing a melt-molded body having a resin coating film containing ultrafine conductive fibers on the surface, at least the surface of the melt-molded body is heated to expose the ultrafine conductive fibers on the surface of the melt-molded body or project from the surface. Or a conductive layer having a reduced surface resistivity is formed by incorporating the composition into the interior less than 100 nm from the surface thereof.

In each of the above production methods, it is preferable that the molten molded body is heated in a temperature range from the glass transition temperature of the ultrafine conductive fiber-containing thermoplastic resin composition to a temperature 30 ° C. higher than the melting point temperature. Moreover, it is also preferable that heating of the melt-molded body is performed in a range where the viscosity of the ultrafine conductive fiber-containing thermoplastic resin composition is 5.0 × 10 ³ Pa · s or more and less than 1.0 × 10 ⁷ Pa · s. Moreover, it is also preferable that heating of the melt-molded body is performed in a heating chamber heated to a temperature range of 30 ° C. higher than the melting point temperature from the glass transition temperature of the thermoplastic resin composition containing ultrafine conductive fibers. Furthermore, it is also preferable that the molten molded body is heated using a hot air, a flame, a heated nichrome wire, a heat medium, a heat press, an infrared heat source, or a microwave.

In the present invention, the term “conductive layer with reduced surface resistivity” or “conductive layer with reduced surface resistivity” means that if the surface resistivity of the melt-formed product is 10 ¹² Ω / □ or more, 10 ^This means that the surface resistivity is reduced to less than ¹² Ω / □, and if the surface resistivity of the melt-formed product is less than 10 ¹² Ω / □, this means that the surface resistivity is further reduced. .
In addition to the case where the ultrafine conductive fiber is exposed on the entire surface of the melt-molded body, protruded from the surface, or contained in the interior of less than 100 nm from the surface, the melt-molded body The case where the above-mentioned state differs depending on the surface portion of the surface and the two or three states are mixed is also included.
Furthermore, when the thermoplastic resin composition containing ultrafine conductive fibers is heated to a temperature range of 30 ° C. higher than the melting point temperature from the glass transition temperature, the viscosity often falls within the above range. In some cases, both ranges coincide with each other, but if different, heating may be performed so that either range is obtained.

The glass transition temperature and melting point of the above-mentioned thermoplastic resin composition containing ultrafine conductive fibers can be determined by measuring the differential scanning calorific value of the composition, and the glass transition temperature is calculated from the linear portion of the base line before the transition. The temperature of the intersection obtained by extrapolating the tangent of the inflection point of the transition region is shown, and the melting point shows the temperature of the intersection of the tangent drawn at the maximum slope points on both sides of the melting peak.
Moreover, the said viscosity shows the viscosity obtained with the shear rate of 1 sec < ^-1 > shear rate with the dynamic-viscoelasticity measuring apparatus.
The melting point can be determined by measuring the differential scanning calorific value if the resin used for the ultrafine conductive fiber-containing thermoplastic resin composition is crystalline, but if the resin is amorphous, the differential scanning calorific value is used. Since it cannot measure, what is necessary is just to heat so that it may become the said viscosity.

In the first conductive molded body of the present invention, the conductive path is satisfactorily formed by the ultrafine conductive fibers exposed on the surface of the conductive layer or protruding from the surface, and the surface resistivity is reduced, and the antistatic or conductive function Can be demonstrated. The reason why this ultrafine conductive fiber is exposed on the surface or protrudes from the surface by heating is not clear at this time, but is a composition that forms the molded body by heating the surface of the molten molded body containing the ultrafine conductive fiber. At least the surface is softened and the viscosity is reduced, and the ultrafine conductive fibers contained in the vicinity of the surface and having strain do not move in a random three-dimensional direction against the softened resin composition in order to eliminate the strain. It seems that the fine conductive fibers contained in close proximity are in an oriented state and the opportunity to contact each other increases, and the softening resin composition that suppresses movement in particular moves to the surface side where it appears to be exposed or protruding. .
Further, as is known in Japanese Patent Application Laid-Open No. 2004-339484, etc., the ultrafine conductive fiber can also be a crystal accelerator for an amorphous resin. These crystals are known to be generated from the vicinity of the ultrafine conductive fiber, and it is considered that the ultrafine conductive fiber moves and improves conductivity with the growth of the microcrystal.

In this way, a conductive layer having a reduced surface resistivity is formed by exposing or projecting the ultrafine conductive fiber, and the ultrafine conductive fiber is also in contact with the ultrafine conductive fiber existing inside the conductive layer to conduct the conductive property. The road can be formed well. Therefore, even if the surface resistivity is 10 ¹² Ω / □ or more before heating, a conductive molded body in which a conductive layer having a surface resistivity reduced to less than 10 ¹² Ω / □ is formed by heating. can do. Moreover, what shows the surface resistivity of less than 10 < ¹² > ohm / square before a heating can be made into the electroconductive molded object in which the conductive layer which further reduced the surface resistivity was formed by heating. . Such a decrease in surface resistivity varies depending on the surface resistivity before heating, but the surface resistivity decreases in the range of 1 to 12 digits. If carbon nanotubes, which are ultrafine conductive fibers, are contained in the conductive layer in an amount of 0.01 to 12.0% by mass, the carbon nanotubes are long and thin. The surface resistivity can be made 10 ¹ Ω / □ or more and less than 10 ¹² Ω / □.

  When static electricity is generated on the surface of the molded body or when it is applied by energization, the second conductive molded body of the present invention can reach the ultrafine conductive fibers contained within 100 nm from the surface by the tunnel effect. The same effect as when the ultrafine conductive fibers are exposed or protruded due to the arrival of static electricity or an applied charge, and the effect of reducing the surface resistivity as in the case of the conductive layer is exhibited. However, if the ultrafine conductive fiber is not contained in the interior of less than 100 nm from the surface, the tunnel effect cannot be exhibited satisfactorily, and no antistatic or conductive function is provided. The reason why the surface of the molded body containing the ultrafine conductive fiber is heated to form a conductive layer having a surface resistivity reduced by containing the ultrafine conductive fiber in the interior of less than 100 nm from the surface is as described above. The fine conductive fibers move randomly in the composition, but do not move until the strain is small and exposed to the surface or protrudes from the surface, stays where the strain disappears, and moves from the surface to the inside of less than 100 nm. It seems to be fixed and formed.

When the entire conductive molded body is made of a thermoplastic resin composition containing ultrafine conductive fibers, the ultrafine conductive fibers inside the molded body randomly move in the three-dimensional direction due to heating, as well as the surface. Thus, the volume resistivity can be improved together with the surface resistivity.
Even if the conductive molded body is subjected to cutting or the like to remove the surface portion, the ultrafine conductive fibers are exposed or protruded on the cutting surface, so that the surface resistivity is 10 ¹ Ω / □ or more and less than 10 ¹² Ω / □. It can be.

  Further, when the conductive molded body is composed of a base material layer not containing ultrafine conductive fibers and a conductive layer containing ultrafine conductive fibers and having a reduced surface resistivity, it is not necessary to heat up to the inside of the molded body, at least By simply heating the surface portion, a conductive layer having a reduced surface resistivity is formed as described above, and an antistatic or conductive function can be exhibited. And various functions, such as mechanical strength required for a molded object, can be provided to a base material layer, and since content of an ultrafine conductive fiber can be decreased, an inexpensive electroconductive molded object can also be provided.

  In the first method for producing a conductive molded body according to the present invention, at least the surface of a melt-molded body containing ultrafine conductive fibers is heated to expose the ultrafine conductive fibers on the surface, protrude from the surface, Therefore, a conductive layer with a reduced surface resistivity can be formed on the surface portion. As described above, the reason why the ultrafine conductive fiber is brought into the above-described state by heating the surface is not clear at present, but the applicant presumes as follows.

The ultrafine conductive fibers contained at least near the surface of the melt-formed product are contained in a state in which they are subjected to shearing force from a mold or the like at the time of melt-molding and are forcedly oriented along the molding flow to have a strain. ing. For this reason, if the content of the ultrafine conductive fiber is small or / and the dispersion is poor, contact between the fibers is not obtained so much and a surface resistivity of 10 ¹² Ω / □ or more is exhibited. However, if the content of the ultrafine conductive fiber is large or / and the dispersion is good, contact between the fibers can be obtained to some extent even if the fibers are arranged and oriented in a strained state, and less than 10 ¹² Ω / □ The surface resistivity is shown. And this ultra fine conductive fiber was moved in a three-dimensional direction at random inside the composition softened by the surface being heated and lowered in viscosity to become a non-oriented state and contained in close proximity. Opportunities for mutual contact with each other are significantly increased, and the amount of the softening resin composition is small and the movement is hardly suppressed, so that it moves to the surface direction and is exposed to the surface, further moved to protrude from the surface, or exposed. It is presumed that a conductive layer having a reduced surface resistivity is formed with no distortion until protruding to a state where it moves from the surface to below 100 nm and is fixed.

In this way, if the molten molded body has a surface resistivity of 10 ¹² Ω / □ or more before heating on the surface and / or surface portion, the surface resistivity of less than 10 ¹² Ω / □ is 10 before heating. If the surface resistivity is less than ¹² Ω / □, a conductive layer having a further reduced surface resistivity is formed, and a conductive molded body exhibiting antistatic or conductive functions can be obtained.

The second method for producing a conductive molded body of the present invention comprises heating at least the surface of a secondary processed molded body obtained by cutting a molten molded body obtained by melt molding an ultrafine conductive fiber-containing thermoplastic resin composition. In the same manner as described above, the conductive layer having a reduced surface resistivity is formed on the portion by exposing the ultrafine conductive fiber to the cutting surface or projecting from the cutting surface or by incorporating the fine conductive fiber into the inside of the cutting surface less than 100 nm. Can be formed.
The melt-formed body also has distortion in the molding flow direction at the time of molding inside, and the ultrafine conductive fibers on the surface of the secondary processed molded body obtained by cutting are also oriented. By heating the formed surface, a conductive layer having a reduced surface resistivity is formed on the surface and / or the surface portion for the same reason as described above, and a conductive molded body that exhibits antistatic or conductive functions. Can be obtained.

In the above manufacturing method, when melt molding is performed by injection molding, it passes through a narrow nozzle, sprue channel, runner, gate, etc. of the injection molding device at high speed, and also compares a relatively narrow molding passage in the injection mold. Therefore, the ultrafine conductive fibers contained in the thermoplastic resin composition containing ultrafine conductive fibers are subjected to a strong shearing force from the nozzle surface, sprue flow path surface, runner surface, gate surface and molding passage surface. Forcibly align and align in the molding flow direction.
Therefore, as described above, when the content of the ultrafine conductive fiber is small or / and the dispersion is poor, the surface resistivity is 10 ¹² Ω / □ or more, and the content of the ultrafine conductive fiber is large or / and the dispersion is low. When it is good, it becomes a melt-molded product showing a surface resistivity of less than 10 ¹² Ω / □. Then, by heating this melt-molded body, at least the ultrafine conductive fibers that existed in the vicinity of the surface randomly move in the three-dimensional direction to become non-oriented and contact each other, as described above. A conductive layer having a reduced rate is formed and exhibits antistatic or conductive functions. Further, when heated to the inside, the ultrafine conductive fibers inside move in the same manner and come into contact with each other, so that the volume resistivity can be improved.

  In addition, when melt molding is performed by extrusion molding, it flows faster in the extrusion mold, although at a slower speed than injection molding, so that the ultrafine conductive fibers receive shearing force from the surface of the extrusion mold and flow in the molding flow direction. Thus, a molten molded body that is forcibly arranged and oriented and exhibits the above-described surface resistivity is obtained. Then, by heating this melt-molded body, as described above, the ultrafine conductive fibers randomly move in the three-dimensional direction to become non-oriented and contact each other, and the surface resistivity as described above. As a result, a conductive layer with reduced resistance is formed, and an antistatic or conductive function is exhibited. Further, when the inside is heated, the volume resistivity can also be improved.

  In addition, when melt molding is performed by press molding, pressure is applied to the sheet softened from the top and bottom during press molding, so that the sheet moves around and extends, and the fine conductive fibers are forcibly arranged and oriented in the four-circumference direction. As a result, a melt-formed product having a strain exhibiting the above surface resistivity is obtained. Therefore, by heating this melt-molded body, as described above, the ultrafine conductive fibers randomly move in the three-dimensional direction to be in a non-oriented state and contact each other, and as described above, the surface resistivity A conductive layer having a reduced resistance can be formed, and when heated to the inside, the volume resistivity can be improved.

According to the third method for producing a conductive molded article of the present invention, a melt molded article in which a surface layer made of a thermoplastic resin containing ultrafine conductive fibers is laminated on one surface, both surfaces, or the entire surface of a base material layer made of a thermoplastic resin. Can be easily produced by coextrusion molding. In this melt-molded body, the ultrafine conductive fiber-containing thermoplastic resin composition forming the surface layer is subjected to shearing force from the coextrusion mold and aligned and oriented in the extrusion direction, and the content of ultrafine conductive fibers is small. When the dispersion is poor, the surface resistivity is 10 ¹² Ω / □ or more, and when the content of the ultrafine conductive fiber is large or / and the dispersion is good, the surface resistivity is less than 10 ¹² Ω / □. It becomes the melt-molded body shown. And by heating this melt-molded body, as described above, the ultrafine conductive fibers contained in the surface layer randomly move in the three-dimensional direction to become non-oriented and contact each other, A conductive layer having a reduced resistivity is formed, and a conductive molded body that exhibits antistatic or conductive functions can be obtained.

Further, according to the fourth method for producing a conductive molded body of the present invention, a melt molded body in which a surface layer of a thermoplastic resin containing ultrafine conductive fibers is laminated on the surface of a base material layer made of a synthetic resin is produced by injection molding. In addition, a melt-molded product in which the periphery of the base material layer is covered with the surface layer can be produced by injection molding. In these melt-molded bodies, the thermoplastic resin composition containing ultrafine conductive fibers forming the surface layer is injected and filled at a high speed, so that it is forced in the direction of molding flow by receiving the same strong shearing force as described above. When the content of the fine conductive fibers is small or / and the dispersion is poor, the surface resistivity is 10 ¹² Ω / □ or more, and the content of the fine conductive fibers is large or / and the dispersion is good. If it exists, it will become a melt-formed body which shows a surface resistivity of less than 10 ¹² Ω / □. And by heating this melt-molded body, as described above, the ultrafine conductive fibers contained in the surface layer randomly move in the three-dimensional direction to become non-oriented and contact each other, A conductive layer having a reduced resistivity is formed, and a conductive molded body that exhibits antistatic or conductive functions can be obtained.

  According to the fifth method for producing a conductive molded article of the present invention, a melt molded article in which a surface layer of a thermoplastic resin composition containing ultrafine conductive fibers is laminated on the surface of a base material layer made of a thermoplastic synthetic resin composition. It can be easily produced by press molding. The surface sheet forming the surface layer of the melt-molded body is softened during press molding and pressure is applied from above and below, so that the surface sheet moves and extends around the four sides, and the ultrafine conductive fibers are also forced in the four directions. A melt-molded body that is aligned and oriented and has a strain exhibiting the above surface resistivity is obtained. Therefore, by heating the surface layer of the melt-molded body, as described above, the ultrafine conductive fibers randomly move in the three-dimensional direction to become non-oriented and contact each other, as described above. A conductive layer having a reduced surface resistivity is formed, and a conductive molded body that exhibits antistatic or conductive functions can be obtained.

According to the sixth method for producing a conductive molded article of the present invention, a melt molded article in which a surface layer containing ultrafine conductive fibers is transferred to the surface of a base material layer made of an injection molded article is produced by injection molding. It is possible to cope with various injection-molded bodies simply by preparing one transfer film. And, the ultrafine conductive fibers on the surface layer of this transfer film are contained in a state of being strained by receiving a force in the coating direction when being applied and arranged and oriented in that direction. When the amount is small or / and the dispersion is poor, the surface resistivity is 10 ¹² Ω / □ or more, and when the content of the ultrafine conductive fiber is large or / and the dispersion is good, the surface is less than 10 ¹² Ω / □. It becomes a melt-molded product showing resistivity. Then, by heating this melt-molded body, as described above, the ultrafine conductive fibers contained in the surface layer randomly move in the three-dimensional direction to be in a non-oriented state, and contact each other, resulting in surface resistance. A conductive layer having a reduced rate is formed, and a conductive molded body that exhibits antistatic or conductive functions can be obtained.

  In the seventh method for producing a conductive molded article of the present invention, a laminate film having a surface layer containing ultrafine conductive fibers or a laminate containing ultrafine conductive fibers is provided on the surface of a base material layer made of an injection molded article. A melt-molded product with a film laminated thereon can be produced by injection molding, and it is possible to easily cope with various injection-molded products by producing only one laminating film. And, the superfine conductive fibers of the surface layer of this laminating film are contained in a state of being strained by receiving a force in the application direction when applied in the same manner as the transfer film and arranging and orienting in the direction. The ultrafine conductive fibers contained in the laminating film are contained in a state of being strained by being aligned and oriented by receiving a force in the extrusion direction during production such as extrusion molding and blow molding. A laminating film having the same surface resistivity is obtained. Then, by heating this melt-molded body, as described above, the ultrafine conductive fibers contained in the surface layer randomly move in the three-dimensional direction to be in a non-oriented state, and contact each other, resulting in surface resistance. A conductive layer having a reduced rate is formed, and a conductive molded body that exhibits antistatic or conductive functions can be obtained.

According to the eighth method for producing a conductive molded article of the present invention, a melt-molded article with a coating film is produced simply by coating and forming an ultrafine conductive fiber-containing resin coating film on the surface of an injection-molded molded article. It can be obtained by a simple method of applying a coating liquid, can be applied to an injection-molded body having a complicated shape, and can be applied to even a small amount of various products. Then, the coating film of the melt-formed body is subjected to a force such as an application direction or a coating liquid injection pressure when applied, and is contained in a state of being aligned and oriented in the direction and having a strain, When the content is low or / and the dispersion is poor, a surface resistivity of 10 ¹² Ω / □ or more is exhibited, and when the content of the ultrafine conductive fiber is high or / and the dispersion is good, the surface resistivity is less than 10 ¹² Ω / □. It becomes a melt-molded product showing surface resistivity. And by heating this melt-molded body, as described above, the ultrafine conductive fibers contained in the coating film randomly move in the three-dimensional direction to become non-oriented and contact each other. A conductive layer having a reduced surface resistivity is formed, and a conductive molded body that exhibits antistatic or conductive functions can be obtained.

In each of the above production methods, when heating of each melt-molded body is performed in a temperature range of 30 ° C. higher than the melting point temperature from the glass transition temperature of the thermoplastic resin composition containing ultrafine conductive fibers, It can be heated to at least a temperature that softens the surface, and the resin composition can be sufficiently softened to enable movement of the fine conductive fibers. Even if the heating is performed in a temperature range in which the viscosity of the thermoplastic resin composition containing ultrafine conductive fibers is in the range of 5.0 × 10 ³ Pa · s or more and less than 1.0 × 10 ⁷ Pa · s, Conductive fibers can move through the low viscosity composition. In particular, a temperature range from a temperature 30 ° C. lower than the melting point to a temperature 30 ° C. higher than the melting point temperature, or a range where the viscosity of the composition is 1.0 × 10 ⁴ Pa · s or more and less than 5.0 × 10 ⁶ Pa · s. When the temperature is within the range, the fine conductive fibers can be moved more satisfactorily, so that the fine conductive fibers are exposed on the surface, protrude from the surface, or are easily contained in the interior of less than 100 nm from the surface. A conductive layer having a reduced surface resistivity can be formed, and the surface resistivity can be reliably reduced to provide a conductive molded body that exhibits an antistatic function or a conductive function.

  Further, when each molten molded body is heated in a heating chamber heated to a temperature range of 30 ° C. higher than the melting point temperature from the glass transition temperature of the thermoplastic resin composition containing ultrafine conductive fibers, The molten molded body can be heated uniformly, the surface of the molten molded body can be heated, or the entire molten molded body can be heated. Moreover, since it can heat continuously, production efficiency can also be improved.

Furthermore, when heating of each melt-formed product is performed by any one of hot air, flame, heated nichrome wire, heat medium, heat press, and infrared heat source, the heating conditions are changed for each melt-formed product. Heating can be performed, and antistatic or conductive properties with stable quality can be imparted. Furthermore, since the surface can be heated rapidly, it is possible to suppress the inside from rising to a temperature equal to or higher than the glass transition temperature, and deformation of each melt-molded product can be prevented.
In addition, when microwaves are used, the ultra-fine conductive fibers are heated by the microwaves, and even the surrounding composition is heated and softened, so that the state of the fine conductive fibers can be sufficiently moved. Can do.

  Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to these.

  FIG. 1 is a cross-sectional view showing an embodiment of the conductive molded body of the present invention, and FIG. 2 is an enlarged cross-sectional view thereof.

  A conductive molded body A shown in FIG. 1 is a conductive tray that conveys electronic components and the like molded by a melt molding method, and the conductive molded body A is a single layer of a resin composition containing ultrafine conductive fibers. It has a substantially rectangular shape, and its central portion is recessed to form a storage portion A1 for storing electronic components and the like, and its periphery is a bag A2. The thickness of the conductive tray molded body A is 0.3 to 3.0 mm, and the size is 500 × 500 mm.

In addition, although A3 is a cover body which consists of a resin film, this cover body A3 can also be produced with the electroconductive molded object of this invention.
Moreover, it cannot be overemphasized that the shape and thickness of the electroconductive molded object A are not limited, However, Thickness is normally made into about 0.1-30.0 mm and used.

  This conductive molded body A is obtained by injection molding or extrusion using a thermoplastic resin composition containing ultrafine conductive fibers in which a known additive necessary for melt molding is added to a thermoplastic synthetic resin and ultrafine conductive fibers 2 are added. The conductive layer 1 is formed by a melt molding method such as molding or press molding.

  Examples of the thermoplastic synthetic resin include olefin resins such as polyethylene and polypropylene, vinyl resins such as polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, and polystyrene, polycarbonate, crystalline / amorphous polyethylene terephthalate, polyarylate, Ester resins such as polybutylene terephthalate and aromatic polyester, ABS resin, polyether ether ketone, polyether sulfone, polyimide, polyacetal, polyether imide, polyamide imide, polystyrene, polyamide, liquid crystal polymer, triacetyl cellulose, these A thermoplastic resin such as a resin copolymer resin, a mixed resin in which these resins are mixed, or the like is used. Additives added to these resins include those generally used for resins such as antioxidants, anti-blocking agents, UV absorbers, stabilizers, antibacterial agents, flame retardants, pigments, and dyes. The

  Examples of the ultrafine conductive fiber 2 include ultrafine carbon fibers such as carbon nanotubes, carbon nanohorns, carbon nanowires, carbon nanofibers, and graphite fibrils, metal nanotubes such as platinum, gold, silver, nickel, and silicon, and metal nanowires. Extra-long metal fibers, ultra-long metal oxide fibers such as metal oxide nanotubes such as zinc oxide, metal oxides such as metal oxide nanowires, etc., have a diameter of 0.3 to 100 nm and a length of 0.1 Each fiber having a length of ˜20 μm, preferably 0.1 to 10 μm is used. These ultrafine conductive fibers are preferably dispersed without uniformly agglomerating and are contained in the conductive layer 1 in contact with each other.

  Among these ultrafine conductive fibers 2, ultrafine carbon fibers are preferable, and carbon nanotubes are most preferably used. The carbon nanotubes are desirable because they have a thin fiber diameter of 0.3 to 80 nm and can be dispersed and brought into contact with each other without agglomeration. These carbon nanotubes include multi-walled carbon nanotubes concentrically provided with a plurality of closed carbon walls with different diameters around the central axis, and single-walled cylindrical carbon walls around the central axis. There is a single-walled carbon nanotube provided, and any carbon nanotube is preferably used. Multi-walled carbon nanotubes can be dispersed one by one, but single-walled carbon nanotubes can be dispersed as a bundle of a plurality of bundles, and it is most preferable to disperse in this way. . It is not excluded that single-walled carbon nanotubes are separated and dispersed one by one.

  These ultrafine conductive fibers 2 are contained in the conductive layer 1 in an amount of 0.01 to 20% by mass, preferably 0.01 to 12.0% by mass, more preferably 0.1 to 5.0% by mass, Evenly distributed. When the content of the ultrafine conductive fiber 2 is increased, the moldability and mechanical strength are deteriorated, and the cost is increased. Therefore, it is preferable to improve the dispersion as much as possible to improve the surface resistivity with a small content. If the ultrafine conductive fiber 2 is a carbon nanotube, it is desirable to contain 0.01 to 12.0% by mass. In particular, it is desirable to contain 0.01 to 8.0% by mass for the single-walled carbon nanotube and 0.01 to 12.0% by mass for the multi-walled carbon nanotube.

  As shown in the enlarged cross-sectional views of FIGS. 2 (1), (2), and (3), one dispersion state of the ultrafine conductive fibers 2 is randomly and uniformly dispersed inside the conductive layer 1, and each other is three-dimensional. In the vicinity of the surface of the conductive layer 1, as shown in FIG. 2 (1), it is randomly exposed on the surface of the conductive layer 1 and has an ultrafine conductivity inside. It is in contact with the fibers 2, is randomly projected from the surface of the conductive layer 1 as shown in FIG. 2 (2), and is in contact with the ultrafine conductive fibers 2 in the interior, as shown in FIG. 2 (3). Although it is not exposed or protruded on the surface of the layer 1, it is contained in the interior of less than 100 nm from the surface, in other words, at a depth t of less than 100 nm from the surface, the ultrafine conductive fiber 2 is not contained and becomes a resin layer and Whether it is in contact with the ultrafine conductive fiber 2 inside A conductive layer 1 having a reduced surface resistivity is formed in the entire thickness direction. That is, the end portion or the middle portion of the ultrafine conductive fiber 2 is randomly curved without being arranged or oriented, and a part thereof is exposed on the surface, protrudes from the surface, or is contained within less than 100 nm from the surface, and other portions Are buried and fixed inside the conductive layer 1 and are in contact with the ultrafine conductive fibers 2 inside. In this dispersed state, the conductive layer 1 having a reduced surface resistivity is formed to the full thickness.

Another dispersion state of the ultra fine conductive fibers 2, FIG. 2 (4) (5) As shown in the enlarged cross sectional view of (6), less contact arranged and oriented in the interior of the conductive layer 1, 10 ¹² Although it has only a surface resistivity of Ω / □ or more, in the vicinity of the surface of the conductive layer 1, as shown in FIG. 2 (4), are randomly exposed on the surface of the conductive layer 1 and are in contact with each other, As shown in FIG. 2 (5), the surface protrudes randomly from the surface of the conductive layer 1 and is in contact with each other, or the surface of the conductive layer 1 is not exposed or protruded as shown in FIG. 2 (6). To less than 100 nm and are dispersed in any state of being in contact with each other. In this dispersed state, the conductive layer 1 having a reduced surface resistivity is formed on or near the surface.

Furthermore, as shown in the enlarged cross-sectional views of FIGS. 2 (7), (8), and (9), still another dispersed state of the ultrafine conductive fibers 2 is to some extent even if they are arranged and oriented inside the conductive layer 1. The contact is obtained and has a surface resistivity of less than 10 ¹² Ω / □, but in the vicinity of the surface of the conductive layer 1, it is randomly exposed on the surface of the conductive layer 1 as shown in FIG. 2 are in contact with each other, are randomly projected from the surface of the conductive layer 1 as shown in FIG. 2 (8) and are in contact with each other, or are exposed on the surface of the conductive layer 1 as shown in FIG. 2 (9). Although not protruding, the conductive layer 1 having a surface resistivity lower than that of the inside is formed by being dispersed in any state of being contained within 100 nm from the surface and in contact with each other. . In this dispersed state, the conductive layer 1 having a reduced surface resistivity is formed on the surface, and the inside has the resistivity of the melt-formed product.

  And in order to disperse | distribute the ultrafine conductive fiber 2 in this way and to form a favorable conductive path, it is preferable to raise the dispersion degree and to raise a contact frequency. Therefore, it is desirable to disperse in the conductive layer 1 in a state where each ultrafine conductive fiber 2 is separated one by one without being entangled, or a bundle of a plurality of bundles is separated one by one. When dispersed in such a manner, even if the content is small, the fine conductive fibers 2 are dispersed and present in a wide range, and are easily brought into contact with each other. Therefore, by setting the content of the ultrafine conductive fiber 2 to 0.01 to 20.0% by mass, preferably 0.1 to 12.0% by mass, a sufficient conductive path is formed in contact with each other. The conductive layer 1 can be formed.

Like this electroconductive molded object A, the ultrafine conductive fiber 2 is exposed in a random state on the surface of the conductive layer 1, or protrudes in a random state, or is contained in a random state inside the surface less than 100 nm. If so, the conductive layer 1 having a surface resistivity reduced to 10 ¹ Ω / □ or more and less than 10 ¹² Ω / □ can be formed. When the surface resistivity is 10 ⁵ Ω / □ or more and less than 10 ¹² Ω / □, the antistatic function is exerted, and static electricity charged on the surface comes into contact with the exposed or protruding ultra-fine conductive fibers 2 and the surface and the inside are extremely fine. It can flow through the conductive path formed by contact between the conductive fibers and reach the end of the conductive layer 1, and can be discharged by discharging at the end. Further, when the surface resistivity is 10 ¹ Ω / □ or more and less than 10 ⁵ Ω / □, it acts as a conductor, exhibits a conductive function, and allows electricity to flow. On the other hand, if the ultrafine conductive fiber 2 is contained within 100 nm from the surface, static electricity charged on the surface due to the tunnel effect reaches the ultrafine conductive fiber 2 inside the surface and exhibits an antistatic function. Is energized to the inside of the ultrafine conductive fiber 2 by the tunnel effect and flows through the conductive layer 1 to act as a conductor and exert a conductive function.

Such an electroconductive molded object A can be manufactured by the method shown with explanatory drawing of the manufacturing method of FIG. 3, for example.
First, the above-mentioned thermoplastic resin, the ultrafine conductive fiber 2 and, if necessary, the above-mentioned additive necessary for melt molding are uniformly mixed to prepare a thermoplastic resin composition containing the ultrafine conductive fiber.

  Then, as shown in FIG. 3, the thermoplastic resin composition containing ultrafine conductive fibers is injected by a known injection molding method to produce a melt molded body 4. That is, as shown in FIG. 3A, the injection molding machine 41 is supplied with the thermoplastic resin composition containing ultrafine conductive fibers, plasticized and melted with a screw 42, and passed through a nozzle 431, a sprue channel 432, and a gate 433. After injection into the molding space 45 of the injection mold 44 and filling the space 45, the mold is cooled and taken out from the mold 44 to produce the injection melt molded body 4 shown in FIG.

As described above, when the melt-molded body 4 is produced by injection molding, the thermoplastic resin composition containing the ultrafine conductive fibers is converted into the narrow nozzle 431 of the injection molding machine 41, the narrow sprue channel 432 of the injection mold 44, the gate. Since it passes through 433 at a high speed and flows through a relatively narrow molding space 45 of the injection mold 44, the molding flow receives a strong shearing force from the nozzle surface, sprue channel surface, gate surface and molding space surface. Due to the force in the direction, the fine conductive fibers 2 are also forcedly arranged and oriented in the molding flow direction and have a large strain. Therefore, if the content of the ultrafine conductive fiber 2 is small or / and the dispersion is poor, as shown in an enlarged view in FIG. 3 (2), contact between the ultrafine conductive fibers 2 cannot be obtained, and the ultrafine conductive fiber 2 is Even if contained, the surface resistivity shows a high value of 10 ¹² Ω / □ or more. However, if the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good, even if the ultrafine conductive fiber 2 is forcibly arranged and oriented in the molding flow direction, contact between the fibers 2 is obtained to some extent. Thus, the surface resistivity is less than 10 ¹² Ω / □ (refer to the internal fiber state in FIG. 2 (7)).

Subsequently, the injection melt molded body 4 is conveyed to the heating chamber 46 as shown in FIG. This heating chamber 46 is heated and kept in a temperature range of 30 ° C. higher than the melting point temperature from the glass transition temperature of the thermoplastic resin composition containing ultrafine conductive fibers, or the viscosity of the composition is 5. It is heated and kept in a temperature range such that it is in the range of 0 × 10 ³ Pa · s or more and less than 1.0 × 10 ⁷ Pa · s. Therefore, while being carried into the heating chamber 46 and being conveyed by the belt conveyor 47, at least the surface of the injection melt molded body 4 is heated, and the temperature is 30 ° C. higher than the melting point temperature from the glass transition temperature. Or / and the composition is in the above viscosity range, and the ultrafine conductive fiber 2 is exposed on the surface for the reasons described above, or protrudes from the surface as shown in FIG. It comes to be contained in the inside of less than 100 nm.
Reference numeral 48 denotes a heat source such as a nichrome wire or a lamp.

When the ultrafine conductive fibers 2 are in such a state, the ultrafine conductive fibers 2 come into contact with each other, so that a conductive path 1 is formed and a conductive layer 1 having a reduced surface resistivity is formed. Therefore, the injection-melt molded article 4 showing a surface resistivity of 10 ¹² Ω / □ or more before heating can be made to have a surface resistivity of less than 10 ¹² Ω / □ by heating. ^The injection melt molded body 4 showing a surface resistivity of less than ¹² Ω / □ can be reduced in surface resistivity by heating. This reduction in surface resistivity due to heating can be a surface resistivity that is one to twelve orders of magnitude lower than the surface resistivity before heating. Specifically, for example, if the surface resistivity is 10 ¹³ Ω / □ before heating, it decreases to be in the range of 10 ¹² Ω / □ to 10 ¹ Ω / □ after heating.

In this way, the heating is performed from a temperature 30 ° C. lower than the melting point temperature of the composition in order to allow the ultrafine conductive fibers 2 to move as much as possible without causing resistance on the surface of the injection melt molded body 4. Heat to a temperature range of 30 ° C. or higher and / or the composition has a viscosity of 1.0 × 10 ⁴ Pa · s or more and less than 5.0 × 10 ⁶ Pa · s. It is preferable to heat to such a temperature.

Subsequently, when the injection melt molded body 4 carried out from the heating chamber 46 is cooled and the ultrafine conductive fiber 2 is fixed in the above state, the surface resistivity is in the range of 10 ¹ Ω / □ or more and less than 10 ¹² Ω / □. The formed conductive layer 1 is formed, and a conductive molded body A containing the ultrafine conductive fiber of the present invention can be obtained.

  Although said heating changes with the magnitude | sizes, shapes, type of resin, conveyance speed, heating temperature, etc. of the injection-melt molded object 4, it is preferable to expose to the said temperature range or the said viscosity range for about 1 to 20 minutes. For example, when the thickness of the injection melt molded body 4 is about 5 mm and the heating temperature is in the temperature range from 30 ° C. lower than the melting point temperature to 30 ° C. higher than the melting point temperature, preferably 1 to 20 minutes in the temperature range. Is preferably heated in the heating chamber 46 for 5 to 20 minutes. In addition, it is preferable that the said heating time is the time after the surface temperature of the injection-melt molded object 4 became in the said temperature range or / and the said viscosity range.

  In addition, it is preferable that only the surface portion of the injection melt molded body 4 is in the above temperature range, and the shape of the melt molded body 4 is not maintained when the injection melt molded body 4 is heated. Because there is a fear. 2 (4) (5) (6) (7) (8) (9) is the dispersion state of the ultrafine conductive fibers 2 in this case, and the conductive layer 1 having a reduced surface resistivity is formed only on the surface. It is done. However, when heated to the inside of the injection melt molded body 4, as described above, the inner ultrafine conductive fibers 2 similarly move in random three-dimensional directions and come into contact with each other. As a result, the conductive layer 1 having a reduced resistance is formed, and the volume resistivity can be improved. In this case, the dispersion state of the ultrafine conductive fibers 2 is as shown in FIGS. 2 (1), (2), and (3).

  Further, the heating is not limited to heating by the heating chamber 46, and any known method may be used. For example, it is also preferable to use a heat source such as hot air, flame, heated nichrome wire, infrared ray, silicon oil, or a heat source, and heat the surface rapidly. Furthermore, it can also heat using a microwave, The method in which a microwave acts on the ultrafine conductive fiber 2 and is heated, and this extends to surrounding resin can also be used.

FIG. 4 is an explanatory view showing another method for producing the conductive molded body A of the present invention.
In this production method, the melt-molded product 5 is produced by extruding the thermoplastic resin composition containing ultrafine conductive fibers by a known extrusion molding method. That is, as shown in FIG. 4 (1), the ultrafine conductive fiber-containing thermoplastic resin composition is subjected to a known extruder 51, plasticized and melted by a screw 52, and has a certain thickness by an extrusion mold 53. Extruded into a plate-like body, the thickness is finely adjusted by polishing rolls 54, 54, and then cooled while being drawn on the conveying roll 55, cut to a certain length, and extruded as shown in FIG. A melt-formed body 5 is produced.

When extrusion molding is performed in this manner, even if the extrusion speed is slower than that of injection molding, the micro conductive fibers 2 are also arranged and oriented in the extrusion direction under the shearing force from the inner surface of the molding flow path of the extrusion mold 53. Therefore, when the content of the ultrafine conductive fiber 2 is small or / and the dispersion is poor, as shown in an enlarged view in FIG. 4 (2), contact between the ultrafine conductive fibers 2 cannot be obtained, and the ultrafine conductive fiber 2 is Even if contained, the surface resistivity shows a high value of 10 ¹² Ω / □ or more. However, if the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good, even if the ultrafine conductive fiber 2 is forcibly arranged and oriented in the molding flow direction, contact between the fibers 2 is obtained to some extent. Thus, the surface resistivity is less than 10 ¹² Ω / □. Further, the ultrafine conductive fibers 2 are forcibly arranged and oriented in the extrusion direction at the time of extrusion molding, and this tendency is greatly oriented toward the surface of the extrusion melt molded body 5 that is closer to the inner surface of the molding flow path of the extrusion mold 53. And has a large distortion.

Subsequently, when this extruded melt-formed body 5 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 are exposed on the surface, or shown in FIG. 4 (3). Thus, the conductive layer 1 that protrudes from the surface or is contained in the interior of less than 100 nm from the surface is formed. Subsequently, when the extruded melt molded body 5 carried out from the heating chamber 46 is cooled to form the conductive layer 1 in which the ultrafine conductive fibers 2 are fixed in the above state, the surface resistivity is 10 ¹ Ω / □ or more and 10 ¹² Ω / □. The electroconductive molded object A of this invention made into the range of less than can be obtained.

FIG. 5 is an explanatory view showing still another manufacturing method of the conductive molded body A of the present invention.
In the production method, first, a press-melt molded body 6 of the thermoplastic resin composition containing ultrafine conductive fibers is produced by a known calender press molding method. That is, using the thermoplastic resin composition containing ultrafine conductive fibers, a thin calender sheet 61 is produced by a calender roll. Subsequently, as shown in FIG. The heated press gloss plates 62 and 62 are heated and pressed to produce a press melt molded body 6 having a constant thickness shown in FIG.

When the calender sheet 61 is heated and pressurized in this way, when the calender sheet 61 is melted and laminated and integrated, the calender sheet 61 flows and extends around the circumference, and the content of the ultrafine conductive fiber 2 is small or / and dispersed. If the condition is poor, as shown in the enlarged view of FIG. 5 (2), the ultrafine conductive fibers 2 are also forced to be arranged and oriented in the four-circumferential direction and have a strain showing a surface resistivity of 10 ¹² Ω / □ or more. It becomes a press-melt molded body 6. In addition, if the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good, this extension is not performed at such a distance, so that it does not receive a large shearing force, and the contact between the fibers 2 is not achieved. It is obtained to some extent and exhibits a surface resistivity of less than 10 ¹² Ω / □.

Subsequently, when this press-melt molded body 6 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 are exposed on the surface or shown in FIG. 4 (3). Thus, the conductive layer 1 that protrudes from the surface or is contained in the interior of less than 100 nm from the surface is formed. Subsequently, when the press melt molded body 6 carried out from the heating chamber 46 is cooled to form the conductive layer 1 in which the ultrafine conductive fibers 2 are fixed in the above state, the surface resistivity is 10 ¹ Ω / □ or more and 10 ¹² Ω / □. The electroconductive molded object A of this invention made into the range of less than can be obtained.

FIG. 6 is an explanatory view showing a method for producing the cut ultrafine conductive fiber molded body A. FIG.
In the production method, the thermoplastic resin composition containing ultrafine conductive fibers is subjected to the injection molding method of FIG. 3, the extrusion molding method of FIG. 4, the press molding method of FIG. 5, or other known melt molding methods. Thus, a melt-formed body 71 having a constant thickness that can be cut as shown in FIG. As described above, the ultrafine conductive fiber 2 contained in the melt-formed body 71 is subjected to shearing force from an injection mold, an extrusion mold, a press gloss plate, or the like, and the injection molding direction, the extrusion molding direction, Arranged and oriented in the pressing direction, and has strain.

The melt-molded body 71 having a certain thickness is made into a secondary-processed molded body 7 that has been subjected to secondary processing using a known method such as cutting and polishing to remove the surface portion. In FIG. 6, the washer 7 (secondary processed molded body 7) is manufactured by cutting into a thin disk shape and further drilling the center. Also in this washer 7, as shown in the enlarged view of FIG. 6 (2), if the ultrafine conductive fibers 2 are arranged and oriented with distortion, the fiber content is low or / and the dispersion is poor A surface resistivity of 10 ¹² Ω / □ or more is exhibited, and when the content of the fiber 2 is large or / and the dispersion is good, a surface resistivity of less than 10 ¹² Ω / □ is exhibited.

Subsequently, when the washer 7 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fiber 2 is exposed on the surface, or the surface as shown in FIG. 6 (3). The conductive layer 1 is formed in such a manner that it protrudes from the surface or is contained in the interior of less than 100 nm from the surface, and the surface resistivity is lowered. Subsequently, when the washer 7 (secondary processed molded body 7) carried out of the heating chamber 46 is cooled to form the conductive layer 1 in which the ultrafine conductive fibers 2 are fixed in the above state, the surface resistivity is 10 ¹ Ω / □ or more. It is possible to obtain a cut conductive molded body A (washer) according to the present invention having a range of less than 10 ¹² Ω / □.

In FIG. 6, the disk-shaped washer 7 is cut, but other known secondary processes such as threading are performed to obtain a required shape, such as a screw, nut, port, gear, or the like. even processed compact, show 10 ¹² Omega / □ or more, or 10 ¹² Omega / □ under the surface resistivity of, by lowering the surface resistivity was similarly heated so, the surface resistivity of 10 A conductive molded body A having a range of ¹ Ω / □ or more and less than 10 ¹² Ω / □ can be obtained.
The cutting process can also be performed after heating the melt molded body 4 to form a conductive molded body in which the conductive layer 1 is formed. In this case, the ultrafine conductive fibers 2 are fixed in a state of being exposed on the surface. Conductive layer 1 is formed.

  FIG. 7 is an enlarged cross-sectional view showing an embodiment of another conductive molded body of the present invention.

  A conductive molded body B shown in FIG. 7 is made of a thermoplastic synthetic resin or a curable synthetic resin that is cured by heat, ultraviolet rays, electron beams, or the like, and is laminated on both surfaces thereof and does not contain ultrafine conductive fibers. In addition, the conductive molded body has a three-layer structure including conductive layers 1 and 1 having a reduced surface resistivity, which is made of a thermoplastic resin containing ultrafine conductive fibers 2. The conductive layer 1 may be formed only on one side of the base material layer 3. The conductive layer 1 may be formed on the entire surface around the base material layer 3.

The base material layer 3 is a layer obtained by molding a thermoplastic synthetic resin or a curable synthetic resin, and if necessary, a composition to which an additive necessary for molding the synthetic resin is added. Is not contained.
As the thermoplastic resin used for the base material layer 3, the resin used for the conductive molded body A is used. In addition, as the curable resin, epoxy resin, unsaturated polyester resin, curable acrylic resin, phenol resin, melamine resin, etc. are used, and by a known molding method such as injection molding, compression molding, casting molding, transfer molding, etc. Molded. However, since it is necessary to laminate and integrate with the conductive layer 1, a thermoplastic resin that is the same as or compatible with the thermoplastic resin used for the conductive layer 1 is preferable in terms of enhancing mutual adhesive bonding. These resins are molded by appropriately adding additives generally used for each resin, such as antioxidants, anti-blocking agents, ultraviolet absorbers, stabilizers, antibacterial agents, flame retardants, pigments, and dyes. Yes. The thickness of the base material layer 3 is preferably about 0.1 to 30.0 mm.

  The conductive layers 1 and 1 are the same as the conductive layer 1 of the conductive molded body A, and the ultrafine conductive fibers 2 contained therein, their dispersed state, exposure to the surface, protrusion from the surface, Since it is the same that it contained in the inside less than 100 nm from the surface and reduced the surface resistivity, the same code | symbol is attached | subjected and detailed description is abbreviate | omitted. However, the thickness of the conductive layer 1 is preferably about 0.01 to 5.0 mm because it is laminated on the surface to exhibit an antistatic or conductive function.

The conductive layer 1, like the conductive molded body A, is a surface layer or coating film on at least the surface of a melt-formed body having a three-layer structure obtained by a known production method such as injection molding, extrusion molding or press molding. Etc. are heated to expose the ultrafine conductive fiber 2 on the surface such as the surface layer, to protrude from the surface, or to be contained within less than 100 nm from the surface to form the conductive layer 1 with reduced surface resistivity. Therefore, it can exhibit antistatic or conductive functions. Therefore, the conductive layer 1 is formed by changing the dispersion state of the ultrafine conductive fibers with the total thickness of the surface layer, the coating film, and the like. However, it does not exclude that the conductive layer 1 is formed only by a surface portion such as a surface layer or a coating film.
The detailed reason why the ultrafine conductive fiber 2 is brought into the above-described state by heating is the same as that of the conductive layer 1 of the conductive molded body A, and the description thereof is omitted.

  In such a conductive molded body B, the base material layer 3 may be formed of a thermoplastic resin or a curable resin, may have insulating properties or may have conductivity, It may be formed of a composition having increased mechanical strength, may be formed using a resin recycled product, or may be formed of a composition to which a glass reinforcing material is added, or a substrate. Since the layer may be multi-layered or any other configuration, the base material layer 3 can impart performance other than the conductivity necessary for the conductive molded body B. In addition, since the conductive layer 1 is for imparting antistatic or conductive function to the conductive molded body B, it is not necessary to make it thicker than necessary, and the amount of the ultrafine conductive fiber 2 can be reduced by the thinning, An inexpensive conductive molded body B can be obtained.

This electroconductive molded object B is manufactured by the method shown in explanatory drawing of the manufacturing method of FIG. 8, for example.
First, a thermoplastic resin, ultrafine conductive fibers 2 and, if necessary, the above-described additives necessary for melt molding of the resin are uniformly mixed to prepare a thermoplastic synthetic resin composition containing ultrafine conductive fibers. On the other hand, a thermoplastic resin composition is prepared by uniformly mixing the above additives with the thermoplastic resin if necessary.

  Then, as shown in FIG. 8 (1), the thermoplastic resin composition is supplied to one extruder 82 and the thermoplastic resin composition containing ultrafine conductive fibers is supplied to the other extruder 83, and this is subjected to three-layer coextrusion. Co-extrusion molding from the mold 84, surface layers 81, 81 made of ultrafine conductive fiber-containing resin composition were laminated on the upper and lower surfaces of the base material layer 3 made of thermoplastic resin as shown in FIG. A three-layered coextrusion melt-formed product 8 is produced. Reference numeral 85 denotes a polishing roll, and 86 denotes a transport roll.

When co-extrusion molding is performed in this manner, shear force from the inner surface of the molding flow path of the co-extrusion die 84 is received, and the ultrafine conductive fibers 2 contained in the surface layers 81 and 81 are also subjected to force in the extrusion direction, Since the surface layers 81 and 81 that are close to the surface are coextruded while being in contact with the molding flow path of the coextrusion die 84, the arrangement and orientation of the ultrafine conductive fibers 2 are more forced. It is made and has a large distortion. Therefore, when the content of the ultrafine conductive fiber 2 contained in the surface layer 81 is small or / and the dispersion is poor, contact between the ultrafine conductive fibers 2 is obtained as shown in an enlarged view in FIG. Furthermore, even if the ultrafine conductive fiber 2 is contained, the surface resistivity shows a high value of 10 ¹² Ω / □ or more. However, if the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good, even if the ultrafine conductive fiber 2 is forcibly arranged and oriented in the molding flow direction, contact between the fibers 2 is obtained to some extent. Thus, the surface resistivity is less than 10 ¹² Ω / □.

Subsequently, when the coextrusion melt-molded body 8 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 are exposed on the surface of the surface layer 81, and FIG. As shown in FIG. 8 (3), the conductive layers 1 and 1 having a reduced surface resistivity are formed by projecting from the surface or being contained within less than 100 nm from the surface. Therefore, the co-extrusion melt-formed product 8 that exhibited a surface resistivity of 10 ¹² Ω / □ or more before heating can be made to have a surface resistivity of less than 10 ¹² Ω / □ by heating. The coextruded melt-molded product 8 having a surface resistivity of less than 10 ¹² Ω / □ can be reduced in surface resistivity by heating. This reduction in surface resistivity due to heating can be a surface resistivity that is one to twelve orders of magnitude lower than the surface resistivity before heating. Specifically, for example, if the surface resistivity is 10 ¹³ Ω / □ before heating, it decreases to be in the range of 10 ¹² Ω / □ to 10 ¹ Ω / □ after heating.

Subsequently, when the coextruded melt-formed body 8 is carried out of the heating chamber 46 and cooled to form the conductive layer 1 in which the above-described state of the ultrafine conductive fiber 2 is fixed, the surface resistivity is 10 ¹ Ω / □ or more and 10 ¹² Ω. A conductive molded body B having a three-layer structure according to the present invention that is less than / □ can be produced.
The coextruded melt-formed body 8 may have the surface layer 81 formed on one surface of the base material layer 3 or the surface layer 81 may be formed on the entire surface of the base material layer 3, in this case, It becomes the electroconductive molded object B of this invention by which only one side or the whole surface was made into the conductive layer 1. FIG.

FIG. 9 is an explanatory view showing another manufacturing method of the conductive molded body B of the present invention.
First, the above-described ultrafine conductive fiber-containing thermoplastic synthetic resin composition is prepared in advance, and a synthetic resin composition in which the above additives are uniformly mixed with a thermoplastic or curable resin, if necessary, is prepared.

  Next, as shown in FIG. 9 (1), the resin composition containing the ultrafine conductive fibers is first injected from one injection molding machine 94 into the injection mold 92, and then the ultrafine conductive fibers are contained. By injecting the synthetic resin composition from another injection molding machine 93 when the resin composition is in a molten state, the center of the ultrafine conductive fiber-containing resin composition is filled with the synthetic resin composition, and FIG. As shown in FIG. 2, a melt-molded body 9 is produced in which the entire surface around the base material layer 3 made of the synthetic resin composition is coated with the surface layer 91 made of the ultrafine conductive fiber-containing resin composition.

The ultrafine conductive fibers 2 contained in the surface layer 91 of the coated melt-molded body 9 thus injection-molded are arranged and oriented in the molding direction. In particular, the surface layer 91 close to the surface is formed on the injection mold 92. Since they are molded while being in contact with each other, the arrangement and orientation of the ultrafine conductive fibers 2 are made more compulsory and have a large strain. Therefore, if the content of the ultrafine conductive fiber 2 is small or / and the dispersion is poor, the surface resistivity is 10 ¹² Ω / □ or more, and the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good. And a coated melt-molded product 9 having a surface resistivity of less than 10 ¹² Ω / □.

Subsequently, when the coated molten molded body 9 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 of the surface layer 91 are exposed on the surface, or FIG. As shown in (3), the conductive layer 1 protrudes from the surface or is contained in the interior of less than 100 nm from the surface, and the conductive layer 1 having a reduced surface resistivity is formed. Subsequently, when the coated melt-molded body 9 is taken out of the heating chamber 46 and cooled to form the conductive layer 1 in which the above-described state of the ultrafine conductive fiber 2 is fixed, the surface resistivity of the entire surface is 10 ¹ Ω / □ or more 10 ^The electroconductive molded object B of this invention made into the range below ¹² ohm / square can be manufactured.

FIG. 10 is an explanatory view showing another manufacturing method of the conductive molded body B of the present invention. This manufacturing method is a method of the conductive molded body B having a two-layer structure in which the conductive layer 1 is laminated only on one side of the molded body.
As shown in FIG. 10 (1), an injection mold 102 used in this manufacturing method has a primary mold 105 and a secondary mold 106 fixed to a fixed mold 103 and a movable mold 104. Yes.

  In order to perform injection molding using such an injection mold 102, first, the thermoplastic resin composition containing ultrafine conductive fibers is injection molded into the primary mold 105. Subsequently, the movable mold 104 is moved to open the mold, but the movable mold 104 is rotated and moved to the secondary mold 106 side while holding the molded product without taking out the molded product, and then the mold is clamped. As shown in FIG. 10 (2), a molding space is formed between the molded product and the female die of the secondary side mold 106, and the synthetic resin composition is injection-molded in the molding space. Then, a two-layer injection melt molded body 10 is produced in which the surface layer 101 made of the thermoplastic synthetic composition containing ultrafine conductive fibers is laminated on the inner surface of the base material layer 3 made of the synthetic resin composition.

The ultrafine conductive fiber 2 contained in the surface layer 101 of the two-layer injection melt molded body 10 thus injection-molded is subjected to a shearing force in the molding direction when being injected into the primary side mold 105, and is forced Have a large strain. Therefore, if the content of the ultrafine conductive fiber 2 is small or / and the dispersion is poor, the surface resistivity is 10 ¹² Ω / □ or more, and the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good. And a two-layer injection melt molded product 10 having a surface resistivity of less than 10 ¹² Ω / □.

Subsequently, when the two-layer injection melt-molded body 10 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 of the surface layer 101 are exposed on the surface. As shown in 10 (3), the conductive layer 1 is formed so as to protrude from the surface or to be contained in the interior of less than 100 nm from the surface, and the surface resistivity is lowered. Subsequently, when the two-layer injection melt-molded body 10 is taken out of the heating chamber 46 and cooled to form the conductive layer 1 in which the above-described state of the ultrafine conductive fiber 2 is fixed, the surface resistivity is 10 ¹ Ω / □ or more and 10 ^12. The electroconductive molded object B of this invention made into the range below (omega | ohm) / square can be manufactured.
It should be noted that which side of the conductive molded body B is used as the conductive layer 1 depends on the required application, and in order to form the conductive layer 1 on the outer surface of the base material layer 3, a synthetic resin is first used. What is necessary is just to injection-mold the thermoplastic resin composition containing ultrafine conductive fibers after injection-molding the composition.

FIG. 11 is an explanatory view showing still another manufacturing method of the conductive molded body B of the present invention.
In the production method, first, the surface sheet 111 is produced by converting the ultrafine conductive fiber-containing thermoplastic resin composition into a thin calender sheet using a known calender roll. On the other hand, the thermoplastic synthetic resin composition is similarly made into a thin calendar sheet to produce the base sheet 112. Subsequently, as shown in FIG. 11 (1), the surface sheets 111 and 111 are stacked on the upper and lower surfaces of the plurality of stacked base material sheets 112, and heated and pressed by heated press gloss plates 113 and 113, respectively. 11 (2), a multilayer press melt molded article 11 in which a surface layer 114 made of a thermoplastic resin composition containing ultrafine conductive fibers is laminated on both upper and lower surfaces of a base material layer 3 made of a thermoplastic synthetic resin composition. Is made.

When the topsheet 111 is heated and pressed together with the base sheet 112 in this way, when the topsheet 111 is melted and laminated, the topsheet 111 flows and spreads around the circumference, and the content of the ultrafine conductive fiber 2 is small or / And if the dispersion is poor, as shown in the enlarged view of FIG. 11 (2), the ultrafine conductive fibers 2 are also forcibly arranged and oriented in the four-circumferential direction, and the strain exhibits a surface resistivity of 10 ¹² Ω / □ or more. The multilayer press melt-formed body 11 having In addition, if the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good, this extension is not performed at such a distance, so that it does not receive a large shearing force, and the contact between the fibers 2 is not achieved. Obtained to some extent, it will exhibit a surface resistivity of less than 10 ¹² Ω / □.

Subsequently, when the multilayer press melt-formed body 11 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 are exposed on the surface, or FIG. 11 (3). As shown, the conductive layer 1 protrudes from the surface or is contained in the interior of less than 100 nm from the surface to form the conductive layer 1 having a reduced surface resistivity. Subsequently, when the multilayer press melt molded body 11 carried out from the heating chamber 46 is cooled to form the conductive layer 1 in which the ultrafine conductive fibers 2 are fixed in the above state, the surface resistivity is 10 ¹ Ω / □ or more and 10 ¹² Ω / The electroconductive molded object B of this invention made into the range below (square) can be obtained.

FIG. 12 is an explanatory view showing another method for producing a conductive molded body B having a two-layer structure according to the present invention.
First, the surface layer 121 containing the ultrafine conductive fibers 2 is formed on a release film 122 such as polyethylene terephthalate by applying and solidifying a coating liquid obtained by dissolving the thermoplastic resin composition containing the ultrafine conductive fibers in a solvent. Thus, a transfer film 123 is prepared as shown in FIG. If necessary, an adhesive coating liquid obtained by dissolving an adhesive resin in a solvent is prepared, and a transfer film having an adhesive layer formed by applying and solidifying the surface of the surface layer is prepared.

When the ultrafine conductive fiber 2 contained in the surface layer 121 of the transfer film 123 is applied, it receives a force in the application direction in a roll coater, a gravure roll, etc., and in the pressure direction of the application pressure in a spray or the like. , And contained in a state of being distorted by alignment and orientation in the direction. Therefore, if the content of the ultrafine conductive fiber 2 is small or / and the dispersion is poor, as shown in an enlarged view in FIG. 12 (2), the ultrafine conductive fiber 2 is also arranged and oriented in the coating / pressure direction. 10 ¹² Ω / □ or more, and if the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good, the contact between the fibers 2 is obtained to some extent, coupled with the small shearing force in the coating / pressure direction. Thus, the surface resistivity is less than 10 ¹² Ω / □.

  Then, as shown in FIG. 12 (1), the transfer film 123 is arranged inside the injection mold 124 so that the release film 122 is on the male mold side. Subsequently, as shown in FIG. 12 (2), the synthetic resin composition is injected into the mold 124 to obtain a molded body in which the transfer film 123 is integrated on the surface, and then the release film 122 is peeled off. By doing so, the transfer melt molded body 12 is produced in which the surface layer 121 made of the ultrafine conductive fiber-containing resin composition is transferred to the surface of the base material layer 3 made of the synthetic resin composition shown in FIG. The surface layer 121 transferred to the transfer melt molded body 12 is also dispersed in the same state as that of the transfer film 123 when the ultrafine conductive fiber 2 is dispersed, and has the same surface resistivity.

Subsequently, when the transfer melt molded body 12 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 contained in the surface layer 121 are exposed on the surface. As shown in FIG. 12 (4), the conductive layer 1 is formed such that it protrudes from the surface or is contained within less than 100 nm from the surface, and the surface resistivity of the surface layer 121 is reduced. Subsequently, when the transfer melt molded body 12 is carried out of the heating chamber 46 and cooled to form the conductive layer 1 in which the above-described state of the ultrafine conductive fiber 2 is fixed, the surface resistivity is 10 ¹ Ω / □ or more and 10 ¹² Ω / □. The electroconductive molded object B of this invention made into the range of less than can be manufactured.

FIG. 13 is an explanatory view showing another method for producing a conductive molded body B having a two-layer structure according to the present invention.
First, the surface layer 131 containing the ultrafine conductive fiber 2 by applying and solidifying a coating liquid obtained by dissolving the above-mentioned ultrafine conductive fiber-containing thermoplastic resin composition in a solvent to the adhesive film substrate 132 made of an acrylic film or the like. As shown in FIG. 13 (1) in an enlarged manner, a laminating film 133 is produced.

Like the transfer film 123, the ultrafine conductive fibers 2 contained in the surface layer 131 of the laminating film 133 receive a force in the direction of application when applying the coating liquid, and are aligned and oriented in that direction. Thus, it is contained in a strained state. The laminating film 133 is also 10 ¹² Ω / □ or more when the content of the ultrafine conductive fiber 2 is small or / and poorly dispersed, and 10 when the content of the ultrafine conductive fiber 2 is large or / and the dispersion is good. The surface resistivity is less than ¹² Ω / □.

  Then, as shown in FIG. 13 (1), after the laminating film 133 is arranged inside the injection mold 134 so that the surface layer 131 is on the male mold side, as shown in FIG. Then, by injecting the synthetic resin composition into the mold 134, as shown in FIG. 13 (3), the laminating film 133 is laminated and integrated on the surface of the base material layer 3 made of the synthetic resin composition. The molded body 13 is produced.

Subsequently, when the laminate melt-formed body 13 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 contained in the surface layer 131 are exposed on the surface. As shown in FIG. 13 (4), it protrudes from the surface or is contained within less than 100 nm from the surface, so that the surface resistivity of the surface layer 131 is lowered and the conductive layer 1 is formed. Subsequently, when the laminate melt molded body 13 is carried out of the heating chamber 46 and cooled to form the conductive layer 1 in which the above-described state of the ultrafine conductive fiber 2 is fixed, the surface resistivity is 10 ¹ Ω / □ or more and 10 ¹² Ω / □. The electroconductive molded object B of this invention made into the range of less than can be manufactured.

  The laminating film 133 is formed by forming the surface layer 131 containing ultrafine conductive fibers on the adhesive film substrate 132, but instead of the ultrafine conductive fiber-containing thermoplastic resin composition. A conductive layer in which the surface resistivity is lowered by heating even when the film for laminating is prepared in advance by a melt molding method such as extrusion molding or blow molding, and laminating using this film in the same manner. 1 can be produced. In this case, it is preferable to select a resin having the same compatibility as the resin of the ultrafine conductive fiber-containing thermoplastic resin composition and the resin of the base material layer.

In FIG. 14, the other manufacturing method of the electroconductive molded object B of the two-layer structure of this invention is shown.
First, as shown in FIG. 14 (1), the synthetic resin composition is injection-molded into an injection mold 142 using a known method to produce a molded body 143 (base material layer 3). Then, as shown in FIG. 14 (2), a coating liquid obtained by dissolving the thermoplastic resin composition containing ultrafine conductive fibers in a solvent is applied to one side of the molded body 143 by a brush or spray, and solidified. Then, as shown in FIG. 14 (3), a melt-molded body 14 is produced in which an ultrafine conductive fiber-containing thermoplastic resin coating 141 is formed on the surface of the base material layer 3 composed of the molded body 143.

Like the transfer film 123, the ultrafine conductive fibers 2 contained in the coating film 141 of the coating film melt-formed body 14 are subjected to a force such as an application direction when applying the coating liquid, and are arranged in that direction. -It is contained in a state of being oriented and distorted. Since this coating film 141 is formed by being applied in the same manner as the transfer film or the laminate film described above, if the content of the ultrafine conductive fiber 2 is small or / and the dispersion is poor, it is 10 ¹² Ω / □ or more. When the content of the conductive fiber 2 is large or / and the dispersion is good, the surface resistivity is less than 10 ¹² Ω / □.

Subsequently, when the coating film melt-formed body 14 is carried into the heating chamber 46 shown in FIG. 3 (3) and heated in the same manner, the ultrafine conductive fibers 2 contained in the coating film 141 are exposed on the surface. As shown in FIG. 14 (4), the conductive layer 1 is formed such that it protrudes from the surface or is contained within 100 nm from the surface to reduce the surface resistivity of the coating film 141. Subsequently, when the coating layer melt-formed body 14 is carried out of the heating chamber 46 and cooled to form the conductive layer 1 in which the above-described state of the ultrafine conductive fiber 2 is fixed, the surface resistivity is 10 ¹ Ω / □ or more and 10 ¹² Ω / The electroconductive molded object B of this invention made into the range less than (square) can be manufactured.
In addition, if a coating liquid is apply | coated to both surfaces or the whole surface of the molded object 143, the electroconductive molded object B which formed the conductive layer 1 on both surfaces or the whole surface by heating this can be manufactured.

In addition, various methods for producing a conductive molded body can be employed without departing from the present invention.
For example, in each of the above production methods, after injection molding the thermoplastic resin composition containing ultrafine conductive fibers into an injection mold, the mold is removed from the molding machine without taking out the melt-molded product, and then the molding is performed. When the product holding mold is heated in the same manner as described above, the ultrafine conductive fibers on at least the surface of the melt-molded product move for the same reason as described above, and the ultrafine conductive fibers are exposed on the surface or exist within less than 100 nm from the surface. Thus, a conductive layer having a reduced surface resistivity is formed. Thereafter, by removing the molded body from the injection mold, a conductive molded body having a surface resistivity of 10 ¹ Ω / □ or more and less than 10 ¹² Ω / □ can be produced.

Furthermore, the transfer film on which the surface layer containing the ultrafine conductive fiber used for the conductive molding B is formed, the laminating film containing the ultrafine conductive fiber, or the surface containing the ultrafine conductive fiber in the adhesive film substrate The laminated film having the layer formed thereon is transferred or laminated to a molded body during extrusion molding using a known transfer technique or laminating technique to form a laminated molten molded body, and then the laminated molten molded body is When heated in the same manner as above, the ultrafine conductive fibers on at least the surface of the laminated melt-molded body move for the same reason as described above, and the ultrafine conductive fibers are exposed on the surface, protrude from the surface, or exist within less than 100 nm from the surface to as becomes, by forming a conductive layer surface resistivity is decreased, producing a conductive molded article B surface resistivity is 10 ¹ Ω / □ or more 10 ¹² Ω / □ under child Can.

  Next, more specific examples of the present invention will be described.

[Example 1]
Multi-walled carbon nanotube-containing polycarbonate resin composition containing 2.5% by mass of multi-walled carbon nanotubes by mixing commercially available polycarbonate resin and multi-walled carbon nanotubes having a diameter of 10 to 20 nm (manufactured by Shenzhen Nanotechport Co., Ltd.) A product was made. This polycarbonate resin was amorphous and had no melting point, but the resin temperature showing a viscosity of 5.0 × 10 ⁴ Pa · s was 220 ° C.
A plate-like injection melt molded product having a size of 30 × 500 mm and a thickness of 2 mm was obtained from this composition using an injection molding machine.
Subsequently, the injection melt molded body was left to heat in a gear oven heated to 230 ° C. for 15 minutes, and then taken out and cooled to obtain a conductive molded body of Example 1.

The surface resistivity was measured for the injection melt molded product and the conductive molded product before and after heating. As a result, the injection-melt molded product showed only a surface resistivity of 9.5 × 10 ¹³ Ω / □ and neither an antistatic function nor a conductive function, but the conductive molded product was 4.5 × 10 ³ Ω / □. The surface resistivity of □ was shown and the conductive function was demonstrated. From this result, it was found that the surface resistivity was lowered only by heating the polycarbonate resin injection melt-molded body having no electrical conductivity.

The surface resistivity is a value measured with a low resistance measuring instrument, Loresta GP, and a high resistance measuring instrument Hiresta UP manufactured by Mitsubishi Chemical Corporation. The Loresta GP is a measuring instrument used for measuring the surface resistivity in the range of 10 ⁻² to 10 ⁷ Ω / □, and the Hiresta UP is in the range of 10 ⁶ to 10 ¹⁴ , and was used properly according to each surface resistivity.
The viscosity at 230 ° C. of the polycarbonate resin composition containing multi-walled carbon nanotubes was measured with a dynamic viscoelasticity measuring device (Modal Compact Rheometer MCR300 manufactured by Pear). The viscosity at a shear rate of 1 sec ⁻¹ was 3. It was 0 × 10 ⁴ Pa · s.

[Example 2]
A commercially available amorphous polyethylene terephthalate resin and a multilayer carbon nanotube-containing polyethylene terephthalate resin composition in which 4% by mass of the multilayer carbon nanotubes used in Example 1 were added and mixed uniformly were prepared. Although this amorphous polyethylene terephthalate resin has no melting point, the resin temperature showing a viscosity of 1.0 × 10 ⁴ Pa · s was 190 ° C.
This composition was injection molded in the same manner as in Example 1 to obtain an injection melt molded body having the same shape. Subsequently, the injection-melt molded article was heated by being left in a gear oven heated to 200 ° C. for 15 minutes, and then taken out and cooled to obtain a conductive molded article of Example 2.

The surface resistivity was measured in the same manner as in Example 1 for the injection melt molded product and the conductive molded product before and after heating. As a result, the injection-melt molded product showed only a surface resistivity of 9.0 × 10 ¹³ Ω / □, while the conductive molded product showed a surface resistivity of 8.5 × 10 ² Ω / □ and showed a conductive function. showed that. From this result, it was found that the surface resistivity is lowered only by heating the polyethylene terephthalate resin injection-melt molded body having no electrical conductivity.
The viscosity of the multi-walled carbon nanotube-containing polyethylene terephthalate resin composition at 200 ° C. was measured in the same manner as in Example 1. As a result, it was 9.7 × 10 ³ Pa · s.

[Example 3]
A commercially available polypropylene resin and a multi-walled carbon nanotube having a diameter of 10 to 20 nm (manufactured by CNT) are uniformly mixed to obtain a multi-walled carbon nanotube-containing polypropylene resin composition containing 3.5% by mass of the multi-walled carbon nanotube. Produced. The melting point temperature of this polypropylene resin was 172 ° C.
This composition was injection molded in the same manner as in Example 1 to obtain an injection melt molded body having the same shape. Subsequently, the injection melt molded article was heated in a gear oven heated to 200 ° C., which was 28 ° C. higher than the melting point temperature, for 15 minutes, and then taken out and cooled to obtain the conductive molding of Example 3. Got the body.
When the viscosity at 200 ° C. of this multi-walled carbon nanotube-containing polypropylene resin composition was measured in the same manner as in Example 1, it was 5.5 × 10 ³ Pa · s.

The surface resistivity was measured in the same manner as in Example 1 for the injection melt molded product and the conductive molded product before and after heating. As a result, the injection-melt molded product showed only a surface resistivity of 1.1 × 10 ¹² Ω / □, while the conductive molded product showed a surface resistivity of 7.8 × 10 ² Ω / □, indicating a conductive function. showed that. From this result, it was found that the surface resistivity was lowered only by heating the polyfluoropyrene resin injection-melt molded article having no electrical conductivity.

[Example 4]
The polycarbonate resin used in Example 1 and a single-walled carbon nanotube [synthesized based on the literature Chemical Physics Letters, 323 (2000), P580-585, diameter 1.3 to 1.8 nm] were uniformly mixed. Thus, a single-walled carbon nanotube-containing polycarbonate resin composition containing 1% by mass of single-walled carbon nanotubes was prepared.
This composition was injection molded in the same manner as in Example 1 to obtain an injection melt molded body having the same shape. Subsequently, the injection melt molded body was left to heat in a gear oven heated to 230 ° C. for 15 minutes, and then taken out and cooled to obtain a conductive molded body of Example 4. When the viscosity at 230 ° C. of this single-walled carbon nanotube-containing polycarbonate resin composition was measured in the same manner as in Example 1, it was 3.5 × 10 ⁴ Pa · s.

The surface resistivity was measured for the injection melt molded product and the conductive molded product before and after heating. As a result, the injection melt molded product showed a surface resistivity of 1.0 × 10 ⁹ Ω / □, while the conductive molded product showed a surface resistivity of 6.5 × 10 ⁴ Ω / □. From this result, it was found that whether the carbon nanotubes are multi-layered or single-walled, the surface resistivity is lowered simply by heating the polycarbonate resin injection melt-molded body.

It is sectional drawing which shows one Embodiment of the electroconductive molded object which concerns on this invention. It is an expanded sectional view of a conductive fabrication object. It is explanatory drawing which shows the manufacturing method of the electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the other electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is an expanded sectional view showing an embodiment of other electroconductive fabrication objects concerning the present invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention. It is explanatory drawing which shows the manufacturing method of the further another electroconductive molded object which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive layer 2 Extra fine conductive fiber 3 Base material layer 4 Injection melt molded body 46 Heating chamber 5 Extrusion melt molded body 6 Press melt molded body 7 Cutting molded body 8 Coextrusion melt molded body 9 Coated melt molded body 10 Two-layer injection melt Molded body 11 Multi-layer press melt molded body 12 Transfer melt molded body 13 Laminated melt molded body 14 Coating film melt molded body

Claims (18)

  A molded body in which a conductive layer containing at least ultrafine conductive fibers is formed on the surface of the molded body, and the conductive layer is heated to expose the ultrafine conductive fibers on the surface or to protrude from the surface. A conductive molded body formed by reducing the surface resistivity.   A molded body in which a conductive layer containing at least ultrafine conductive fibers is formed on the surface of the molded body, and the conductive layer is heated to contain ultrafine conductive fibers in the interior of less than 100 nm from the surface, and the surface resistance A conductive molded body formed by reducing the rate.   The conductive molded body according to claim 1 or 2, wherein the molded body is composed of a base material layer not containing ultrafine conductive fibers and a conductive layer containing ultrafine conductive fibers. The conductive layer has a surface resistivity of 10 ¹² Ω / □ or more before heating and a surface resistivity of less than 10 ¹² Ω / □ after heating. A conductive molded article according to any one of the above. The ultrafine conductive fiber is a carbon nanotube, the carbon nanotube is contained in the conductive layer in an amount of 0.01 to 12.0% by mass, and the surface resistivity of the molded body is 10 ¹ Ω / □ or more and less than 10 ¹² Ω / □. The electroconductive molded object in any one of Claim 1 thru | or 4 characterized by the above-mentioned.   A thermoplastic resin composition containing ultrafine conductive fibers is melt-molded to produce a melt-molded body, and at least the surface of the melt-molded body is heated to expose the ultrafine conductive fibers on the surface of the melt-molded body, or A method for producing a conductive molded article, characterized by forming a conductive layer having a reduced surface resistivity by projecting from the surface or being contained within less than 100 nm from the surface.   A thermoplastic resin composition containing ultrafine conductive fibers is melt-molded to produce a melt-molded body, and the melt-molded body is subjected to secondary processing such as cutting to form a secondary-processed molded body. At least the surface of the body is heated to expose the ultrafine conductive fibers to the surface of the secondary processed molded body, or to protrude from the surface, or to be contained within less than 100 nm from the surface to reduce the surface resistivity. A method for producing a conductive molded body, comprising forming a conductive layer.   The method for producing a conductive molded article according to claim 6 or 7, wherein the melt molding is performed by any one of extrusion molding, injection molding, and press molding.   Thermoplastic resin composition containing ultrafine conductive fibers on one side, both sides, or the entire surface of a base material layer made of a thermoplastic resin by coextrusion molding a thermoplastic resin composition containing ultrafine conductive fibers and a thermoplastic resin A melt-molded body in which a surface layer is laminated, and at least the surface of the melt-molded body is heated to expose the ultrafine conductive fiber on the surface of the melt-molded body, or to protrude from the surface, or A method for producing a conductive molded body comprising forming a conductive layer having a reduced surface resistivity by being contained within 100 nm from the surface.   After injecting a thermoplastic resin composition containing ultrafine conductive fibers into an injection mold, a synthetic resin is further injected into the mold, and a thermoplastic resin containing ultrafine conductive fibers is formed on the surface of the base material layer made of synthetic resin. A melt-molded body in which a surface layer made of resin is laminated or a melt-molded body in which the periphery of the base material layer is covered with the surface layer is manufactured, and at least the surface of the melt-molded body is heated to form the ultrafine conductive fiber into the melt A conductive molded body characterized in that a conductive layer having a reduced surface resistivity is formed by being exposed on the surface of the body, protruding from the surface, or contained in the interior of less than 100 nm from the surface. Manufacturing method.   A surface sheet made of a thermoplastic resin composition containing ultrafine conductive fibers and a base sheet made of a thermoplastic synthetic resin composition were prepared, and heat was applied after the surface sheet was stacked on one or both sides of the base sheet. To produce a melt-molded product in which a surface layer made of a thermoplastic resin composition containing ultrafine conductive fibers is laminated on the surface of a base material layer made of a thermoplastic synthetic resin composition, and at least the surface of the melt-formed product is heated. , Exposing the ultrafine conductive fiber to the surface of the melt-molded product, or projecting it from the surface, or containing the ultrafine conductive fiber in the interior of less than 100 nm from the surface to form a conductive layer with reduced surface resistivity. The manufacturing method of the electroconductive molded object characterized by these.   A transfer film on which a surface layer containing ultrafine conductive fibers is formed in advance, the transfer film is placed in an injection mold, a synthetic resin is injected into the mold, and a substrate made of synthetic resin After producing a melt-molded body in which the surface layer containing the ultrafine conductive fiber is transferred to the surface of the layer, at least the surface of the melt-molded body is heated to expose the ultrafine conductive fiber on the surface of the melt-molded body, or A method for producing a conductive molded article, characterized by forming a conductive layer having a reduced surface resistivity by projecting from the surface or being contained within less than 100 nm from the surface.   A laminate film containing ultrafine conductive fibers or a laminate film in which a surface layer containing ultrafine conductive fibers is formed on a film substrate is prepared in advance, and the laminate film is placed in an injection mold. After a synthetic resin is injected into the mold and a melt-molded body is produced by laminating a laminate film on the surface of a base layer made of synthetic resin, at least the surface of the melt-molded body is heated to produce ultrafine conductive fibers. Is exposed to the surface of the melt-molded body, protrudes from the surface, or is contained in the interior of less than 100 nm from the surface to form a conductive layer having a reduced surface resistivity. A method for producing a conductive molded body.   Applying and solidifying a thermoplastic resin coating liquid containing ultrafine conductive fibers on the surface of a molded body obtained by melt molding a synthetic resin, and forming a molten molded body having a resin coating film containing ultrafine conductive fibers on the surface of the molded body After the production, at least the surface of the melt-formed product is heated to expose the ultrafine conductive fibers on the surface of the melt-formed product, or to protrude from the surface, or to be contained within less than 100 nm from the surface. And forming a conductive layer with a reduced surface resistivity.   The molten molded body is heated in a temperature range of 30 ° C. higher than the melting point temperature from the glass transition temperature of the thermoplastic resin composition containing ultrafine conductive fibers. The manufacturing method of the electroconductive molded object in any one of. The melt-molded body is heated in a range where the viscosity of the ultrafine conductive fiber-containing thermoplastic resin composition is 5.0 × 10 ³ Pa · s or more and less than 1.0 × 10 ⁷ Pa · s. The manufacturing method of the electroconductive molded object in any one of Claim 6 thru | or 14.   The molten molded body is heated in a heating chamber heated to a temperature range of 30 ° C. higher than the melting point temperature from the glass transition temperature of the thermoplastic resin composition containing ultrafine conductive fibers. The manufacturing method of the electroconductive molded object in any one of Claim 6 thru | or 16. The heating of the molten molded body is performed using hot air, a flame, a heated nichrome wire, a heat medium, a heat press, a heat source of infrared rays, or a microwave. The manufacturing method of the electroconductive molded object in any one.

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