JP5660700B2 - Inorganic nanocomposite production equipment - Google Patents

Description

The present invention relates to manufacturing equipment of inorganic nanocomposite.

  The polymer material can be improved or improved in physical properties by mixing and kneading the polymer material with another substance to form a composite material. The case where the other substance is an inorganic material is called a compound. And it can approach the physical property of the more advanced target state by disperse | distributing a finer inorganic material more uniformly in a polymeric material.

  Conventionally, a method for dispersing an inorganic material in a polymer material has been carried out by directly feeding dry powder of an inorganic material having primary particles of micron size or more directly into the polymer material in an extruder equipped with a screw mechanism. However, the agglomeration phenomenon proceeds in the presence of dry powder in the air, so the primary particles of inorganic materials aggregate into particles that are much larger than micron-sized primary particles, and can be dispersed by a machine that applies shear force. Since this agglomeration cannot be completely solved, particles aggregated to a size much larger than the primary particles of the inorganic material remain in the polymer material. Furthermore, for the purpose of dispersing primary particles of inorganic material smaller than micron size in a polymer material, an inorganic material having primary particles of submicron size was developed and used. Due to the progress of the agglomeration of the dry powder, there was a problem that it was impossible to disperse the sub-micron primary particles as the particle size of all the particles in the polymer material.

  Therefore, as a solution to the problem of obtaining a compound in which all inorganic material particles are submicron-sized and dispersed in the polymer material, a slurry in which the primary particles of the inorganic material are dispersed in the polymer material in the submicron-size state. A dispersion method was put into practical use. In this method, the polymer material is melted by a twin screw extruder equipped with a screw, and the pressure in the slurry in which the primary particles of the inorganic material are dispersed in the liquid in a sub-micron size state does not evaporate. The polymer material and the primary particles of the inorganic material are kneaded with a screw under a state in which the pressure is maintained and the slurry is injected into the polymer material placed in this state so that the liquid content in the slurry is not evaporated. Then, the liquid component is then evaporated to disperse the primary particles of the inorganic material in the polymer material. In this slurry dispersion method, a slurry that keeps primary particles of inorganic material in a submicron size state can be easily created by simply dissolving dry powder of inorganic material having primary particles of submicron size in a solution such as water or alcohol. It paid attention to the point which can be used for this application.

  Furthermore, the technology has advanced to the stage of creating inorganic nanocomposites in which the diameter of all inorganic particles dispersed in the polymer material is 100 nm or less (called nanoparticles), and several methods have been developed so far. However, they have various technical and other problems in production.

  As those prior arts, firstly called the in-situ method, a method is known in which a nanoparticle of an inorganic material is synthesized and deposited in a solvent by a chemical process in a solvent to form a dispersed state that is formed as an inorganic particle. Yes. Secondly, a method called an interlayer insertion method is known. This method is a method in which a monomer is inserted and polymerized between layers of a particulate inorganic particle (filler) having a thin layer composition such as a cation, or a polymer is inserted and peeled and dispersed as a nano-order thin film. is there. Thirdly, a method for directly kneading and dispersing fine particles is known. This method is a method in which, in a polymer material, inorganic particles are aggregated and broken by stress, and are crushed and dispersed into primary particles of nano-order (see Patent Document 1).

JP 2006-249276 A

  However, the in-situ method is a method of synthesizing inorganic materials using ionized metals as raw materials in molten polymer materials that are limited by temperature or other state conditions. Even if possible, there are restrictions such as the restriction of substances. Furthermore, since the cost required for the apparatus and operation which synthesize | combine is large, it cannot be said that it is an advantageous method for large-scale production. In addition, as another method, there is a large restriction that a low-viscosity polymer liquid dissolved in a solvent must be prepared. On the other hand, the intercalation method is effective only for a limited inorganic material called a layered composition material having a nano-order layer thickness, and cannot be applied to other materials. In the direct kneading dispersion method, if a large stress is applied to the cohesive failure of particles, the amount of heat generated in the material becomes very large, and on the contrary, the shear stress is lowered and the dispersion does not proceed. Furthermore, there is a problem that the polymer material deteriorates at high temperatures. Further, as shown in FIG. 5 showing the relationship between the primary particle diameter and the apparent aggregation degree, as the primary particle diameter decreases, the primary particle aggregation degree increases dramatically, so that the nanocomposite particle diameter is 100 nm. In the case of the following primary particles, the particles to be dispersed are difficult to be crushed and dispersed into primary particles by the direct kneading dispersion method. In addition, when inorganic material nanoparticles are dispersed in a polymer material, since the applied shear stress is non-uniform, all of the highly aggregated inorganic material nanoparticles are dispersed in the polymer material as particles of 100 nm or less. It was difficult to make. Thus, the direct kneading dispersion method is not an advantageous method for large-scale production.

  In particular, in the case of the intercalation method and the direct kneading and dispersion method, since submicron or nanoparticles of dry powder are handled, human suction of dry submicron or nanoparticles of dry powder causes health damage such as silicosis (mesothelioma) become.

The present invention has been made in view of the above circumstances, and an object of the present invention is an inorganic nanocomposite in which inorganic material nanoparticles are dispersed in a polymer material, and the inorganic material nanoparticles can be easily removed. it is possible to remain uniformly dispersed in primary particles in the polymeric material, and an object thereof is to provide a manufacturing apparatus of an inorganic nanocomposite with industrial value.

The present invention is a sub-micron-sized material in which primary particles of an inorganic material are dispersed in a submicron size in a liquid, which is used to create a compound in which particles of all the inorganic materials are submicron-sized and dispersed in a polymer material. where corresponding to micron slurry, providing a manufacturing apparatus of an inorganic nanocomposites industrially valuable for producing inorganic nanocomposites using nanoslurry dispersed leave nanosized primary particles of the inorganic material in a liquid To do. Nano-slurry in which primary particles of inorganic materials are dispersed in a liquid in a liquid form is extremely difficult to create compared to sub-micron slurries due to the unusually large cohesiveness of the particles. Thus, a nanoparticle slurry having no aggregation phenomenon was achieved by means such as ultrasonic dispersion. The present invention relates to the application of the already developed nano-slurry, and is technically different from the sub-micron slurry.

The inorganic nanocomposite production apparatus according to the present invention has the following features in order to solve the above-described problems.

  A first feature of an inorganic nanocomposite manufacturing apparatus according to the present invention for solving the above problems is an inorganic nanocomposite manufacturing apparatus in which nanoparticles of an inorganic material are dispersed in a polymer material, Polymer material supply means for supplying only the polymer material out of a raw material comprising a polymer material and a slurry in which nanoparticles of the inorganic material are dispersed in a liquid, and heating for applying a temperature at which the polymer material melts Means, a screw means for transporting a molten polymer material heated by the heating means, a front material seal and a rear material seal are provided in the screw means, and the pressure between the material seals of the polymer material is melted. A pressurizing and holding means for holding the pressure after reaching a pressure higher than the pressure value at which the liquid in the slurry does not evaporate due to the temperature of the material to be held The slurry supply means for supplying the slurry into the polymer material melted between the material seals, and the pressure-holding means for preventing the liquid in the slurry from evaporating between the material seals where the raw materials coexist. In a state where the pressure is maintained at a value or higher, the polymer material and the slurry are kneaded in a state where a liquid is interposed around the nanoparticles, and the nanoparticles are dispersed in the polymer material, Kneading and dispersing means for maintaining the nanoparticles in a polymer material in a separated and independent state in the state of primary particles, and evaporating the liquid in the polymer material including the liquid interposed around the nanoparticles, A degassing means for degassing the generated gas by allowing the single particles to remain alone in the polymer material.

  According to this configuration, when the slurry is supplied into the molten polymer material, the pressure is maintained at a pressure higher than the pressure value at which the liquid in the slurry does not evaporate due to the material temperature held by the molten polymer material. Is done. Therefore, the kneading and dispersing means disperses the polymer in the polymer material with the entire outer peripheral surface of the primary particles of the inorganic material being covered with the liquid film. That is, the nanoparticles are dispersed in the polymer material with the liquid interposed between the nanoparticles. Since a liquid is present between each nanoparticle in the dispersion process, even if the nanoparticles of inorganic materials approach each other, the nanoparticles do not aggregate, and the spacing between the nanoparticles increases thereafter, and the polymer material Nanoparticles can be dispersed therein. As a result, the nanoparticles of the inorganic material can be uniformly dispersed in the polymer material in the state of the particle size of the primary particles while each nanoparticle is kept at a certain distance. In addition, after dispersing the nanoparticles in the polymer material as primary particles, the polymer material containing a liquid interposed between the nanoparticles by exposing the polymer material to normal temperature or reduced pressure by a deaeration means The liquid inside is evaporated and the generated gas is deaerated. At this stage, since the primary particles of the nanoparticles are trapped in the polymer material, the aggregation of the nanoparticles does not occur. As a result, it is possible to maintain a state in which the nanoparticles remain at the positions of the nanoparticles dispersed in the polymer material. With the above apparatus configuration, it is possible to produce an inorganic nanocomposite in which the inorganic material nanoparticles are uniformly dispersed in the polymer material while maintaining the primary particles in a continuous manner.

The concentration of the slurry may be 0.1 to 50 W%, preferably 0.1 to 15 W%. According to this configuration, when the concentration of the slurry is 0.1 to 50 W%, preferably 0.1 to 15 W%, a slurry in which the inorganic material nanoparticles are not aggregated can be obtained. As a result, an easy-to-handle slurry can be obtained.

Moreover, the liquid which comprises the said slurry should just be a liquid which can form a slurry, However, You may use water or alcohol especially. According to this configuration, particularly when water or alcohol is used, a slurry having a low cost can be obtained. Further, in the deaeration, in addition to being easy to process the excluded liquid and not harmful to the human body, it is good for the environment.

Above as described in the description manufacturing apparatus inorganic nanocomposite according to the present invention, when supplying the polymeric material to the molten slurry, the liquid in the slurry material temperature polymeric material holds Is maintained at a pressure higher than the pressure value at which it does not evaporate. For this reason, the entire outer peripheral surface of the primary particles of the nanoparticles is dispersed in the polymer material while being covered with the liquid film. That is, the nanoparticles are dispersed in the polymer material with the liquid interposed between the nanoparticles. Since the liquid is interposed between the nanoparticles in the dispersion process, even if the nanoparticles of the inorganic material approach each other, the nanoparticles are not aggregated by the liquid covering the primary particles, and the intervals between the nanoparticles are thereafter increased. It becomes large and the nanoparticles can be dispersed in the polymer material. As a result, the nanoparticles of the inorganic material can be uniformly dispersed in the polymer material in the state of the particle size of the primary particles while each nanoparticle is kept at a certain distance. In addition, after the nanoparticles are dispersed as primary particles in the polymer material, the liquid in the polymer material including the liquid interposed between the nanoparticles is evaporated and the generated gas is deaerated. In the stage, each primary particle of the nanoparticle is trapped in the polymer material, so that no nanoparticle aggregation occurs. As a result, the position of the single primary particle nanoparticles dispersed in the polymer material can be maintained in a remaining state.

It is the figure which showed the manufacturing process of the inorganic nanocomposite concerning a continuous manufacturing method. It is the figure which showed the manufacturing process of the inorganic nanocomposite concerning a batch type manufacturing method. The schematic of the twin-screw extruder concerning this embodiment is shown. The enlarged view of A site | part shown in FIG. 3 is shown. It is the figure which showed the relationship between a primary particle diameter and aggregation degree. The schematic diagram of resin pressure distribution is shown. The slurry supply circuit is shown. The pressure control system of the set pressure of a relief valve is shown. The state conceptual diagram of a slurry is shown. The state conceptual diagram of the nanoparticle disperse | distributed in the polymeric material is shown. The state conceptual diagram of the nanoparticle of the inorganic material disperse | distributed in the polymeric material after deaeration is shown. This shows a poorly dispersed state in which the pressure between the two material seals is insufficient and the moisture evaporation phenomenon occurs simultaneously. The state diagram of water is shown. It is the schematic of the batch type manufacturing apparatus of the inorganic nanocomposite concerning this embodiment.

[First Embodiment]
Hereinafter, a first embodiment for carrying out the present invention will be described with reference to the drawings. 1st Embodiment demonstrates the manufacturing method and manufacturing apparatus which manufacture an inorganic nanocomposite by a continuous type.

(Inorganic nanocomposite)
The inorganic nanocomposite in this embodiment is obtained by dispersing nanoparticles of inorganic material including carbon nanotubes (CNT) in a polymer material.

(Nanoparticles)
The inorganic material nanoparticles in the present embodiment refer to those having a particle size of 100 nm or less.

(slurry)
The slurry in this embodiment means a suspension in which fine solid particles are suspended in a liquid. As shown in FIG. 9, in this embodiment, nanoparticles of inorganic material are primary particles in the liquid. It means something that is dispersed.

(Inorganic nanocomposite production method)
A production method for producing an inorganic nanocomposite in a continuous manner will be described.

  First, as a raw material, a slurry in which nanoparticles of inorganic material are dispersed as primary particles in a liquid and a solid polymer material are prepared. A commercially available slurry can be used. For example, nano particle slurry manufactured by C.I. Kasei Co., Ltd., carbon nanotube (CNT) dispersion manufactured by Meijo Nano Carbon Co., Ltd., etc. are commercially available. Since the slurry concentration of the commercially available nanoparticle slurry is dispersed in a wet state of 0.1 to 15 W%, aggregation does not occur.

  The slurry liquid can be applied in various ways, but an organic solvent and water can be used. Preferably, alcohol or water can be used as an inexpensive one. Also, a mixture of alcohol and water may be used. Examples of the alcohol include methanol, ethanol, isopropyl alcohol and the like. The use of water is advantageous in that it does not have problems such as treatment of steam collected from the vent port 105, especially fire and contamination, and is inexpensive.

  Examples of the inorganic material nanoparticles include carbon nanotubes, metals, metal oxides, metal nitrides, metal nitrogen oxides, metal borides, metal silicides, thermoplastic resins, thermosetting resins, and photocurable resins. At least one selected. More preferred are metal oxides such as silicon oxide, zirconium oxide, titanium oxide, aluminum oxide, iron oxide, yttrium oxide, zinc oxide, silver oxide, barium titanate, calcium carbonate, and magnesium oxide. Only one type of particle may be used, or two or more types may be used in combination.

  As the polymer material, polyolefin, polyamide, polystyrene, polycarbonate, polyethylene terephthalate (PET), or the like can be used.

  FIG. 1 is a diagram showing a process of continuously producing inorganic nanocomposites using a twin screw extruder. As shown in FIG. 1, the process of manufacturing an inorganic nanocomposite includes a polymer material supply process for supplying a polymer material, a melting process for melting the polymer material, and the polymer material held after the melting process. And a pressurizing step of applying a pressure higher than a pressure value at which the liquid in the slurry does not evaporate at the material temperature. Furthermore, after reaching a pressure higher than the pressure value at which the liquid in the slurry does not evaporate in the pressurizing step, the slurry is supplied into the molten polymer material in the pressure holding step for holding the pressure and in the pressure holding step The slurry supplying step and the pressure holding step include a kneading and dispersing step for dispersing the inorganic material nanoparticles in the polymer material after the slurry supplying step. Further, after the kneading and dispersing step, a deaeration step is provided for evaporating the liquid in the polymer material including the liquid around the nanoparticles and degassing the generated gas. The pressure holding process is performed after the pressurizing process and continuously performed until the kneading and dispersing process is completed. The slurry supply step is performed after the pressure of the polymer material melted in the melting step is maintained at a pressure equal to or higher than a pressure value at which the slurry liquid does not evaporate. Each step will be specifically described below.

(Polymer material supply process)
The polymer material supply step is a step of continuously supplying the solid unmelted polymer material from the inlet into the cylinder of the twin-screw extruder by the polymer material supply means. In the polymer material supply step, the molten polymer material may be supplied from the inlet into the cylinder of the twin screw extruder.

(Melting process)
The melting step is a step of heating the polymer material supplied into the cylinder from the charging port by a heating means provided in the cylinder so that the polymer material is melted inside the cylinder. The polymer material is conveyed to the downstream side by rotation of the screw means while being in a molten state inside the cylinder.

(Pressure increase process)
By providing a front seal ring on the screw shaft, a gap is formed between the outer diameter of the front seal single and the inner diameter of the cylinder. This gap becomes a flow path for the molten polymer material, and the flow is hindered by setting this flow path smaller than the flow path in the upstream screw portion, and the previous material seal is placed in the gap by the molten polymer material. Form. Further, by providing the rear seal ring downstream from the front seal ring, a gap is formed between the outer diameter of the rear seal ring and the inner diameter of the cylinder. The gap serves as a flow path for the raw material containing the molten polymer material or slurry, and a subsequent material seal is formed in the gap by the molten polymer material or the raw material containing the slurry. By continuously supplying the polymer material from the inlet and transporting the molten polymer material from the upstream side to the downstream side, the flow is hindered at the upstream material seal portion, and the resin pressure rises. The generated material pressure is prevented from escaping by the subsequent material seal. As a result, the pressure between the material seals is gradually increased. The pressurizing step is a step of increasing the pressure between the material seals by the flow resistance of the raw material and the subsequent material seal in the former material seal part. When the slurry is supplied between the material seals in the later-described slurry supply step, the pressure between the material seals is increased so that the pressure is higher than the pressure value at which the slurry liquid does not evaporate.

(Pressure holding process)
The pressure holding step is a step of holding the pressure between the two material seals after the pressure between the two material seals is increased to a pressure equal to or higher than the pressure value at which the slurry liquid does not evaporate. In the pressurizing step, the pressure between the material seals rises to a pressure equal to or higher than the pressure value at which the slurry liquid does not evaporate. While the polymer material is continuously supplied from the inlet and the specified amount of raw material is flowing between the material seals, the pressure between the material seals is maintained at a pressure value that is equal to or higher than the pressure at which the slurry liquid does not evaporate. It will be in the state.

  As shown in FIG. 4, a non-evaporation dispersion region is formed between the material seals by the pressure raising step and the pressure holding step. The non-evaporation dispersion region is a state in which the polymer material and the slurry melted in the kneading dispersion process described below are in a state where the liquid in the slurry does not evaporate when the slurry is injected between both material seals in the slurry supply process described later. It is an area to be kneaded.

  Here, FIG. 6 is a diagram showing the resin pressure at a predetermined position of the screw. The non-evaporation dispersion region shown in FIG. 6 corresponds to the non-evaporation dispersion region shown in FIG. As shown in FIG. 4 and FIG. 6, the resin pressure increases at the front material seal portion. The generated material pressure is prevented from escaping by the subsequent material seal. Thereby, after the resin pressure between both material seals rises to a pressure equal to or higher than the pressure value at which the liquid in the slurry does not evaporate, the resin pressure is held at that pressure. On the downstream side of the rear material seal portion, the resin pressure is lowered by being depressurized by the vent port. The resin pressure in the non-evaporation dispersion region is maintained at a pressure equal to or higher than the pressure value (moisture evaporation pressure limit value) at which the liquid in the slurry does not evaporate when the slurry is supplied between both material seals in the slurry supply process described later. .

(Slurry supply process)
The slurry supply step is a step of injecting the slurry into the molten polymer material between both material seals by the slurry supply means. When supplying the slurry, in the above pressure holding step, since the pressure between the material seals is maintained at a pressure higher than the pressure value at which the liquid of the slurry does not evaporate, the slurry is injected into the molten polymer material between the material seals. Even so, the liquid in the slurry does not evaporate.

  FIG. 12 shows a poorly dispersed state in which the pressure between the two material seals is insufficient and the moisture evaporation phenomenon occurs simultaneously. This is caused by injecting the slurry into the molten polymer material between the material seals in a state where the pressure between the material seals does not reach the pressure value that does not evaporate the slurry liquid. In other words, when the slurry is injected between both material seals, before the nanoparticles of the inorganic material are dispersed, the liquid interposed between the nanoparticles evaporates, so that the liquid is interposed between the nanoparticles. It will not exist. For this reason, the nanoparticles approach and the aggregation phenomenon starts to occur.

The pressure condition equal to or higher than the pressure value at which the slurry liquid does not evaporate is determined using, for example, the water state diagram shown in FIG. 13 when the slurry liquid is water. That is, the boundary line between the gas phase and the liquid phase, in which water evaporates to become a vapor, passes through a point of 100 ° C. and 1 kg / cm ² and becomes a curve shown in FIG. Even when the water is in a high temperature state, it becomes superheated water that does not evaporate if a pressure higher than this boundary is applied. Using this principle, the pressure between the two material seals is increased so that the material temperature held by the polymer material melted in the melting step is equal to or higher than the pressure value at which the liquid constituting the slurry does not evaporate. Shown as usage conditions in the figure.

(Kneading dispersion process)
The kneading and dispersing step is a step of kneading the molten polymer material and the slurry injected in the slurry supplying step by a kneading and dispersing unit such as a kneading disk. In the kneading and dispersing step, since the pressure between the material seals is maintained at a pressure equal to or higher than the pressure value at which the liquid in the slurry does not evaporate, the polymer material melted in a state where the liquid in the slurry does not evaporate and The slurry is kneaded. Thereby, the nanoparticles of inorganic material are dispersed in the polymer material. FIG. 10 shows a conceptual diagram of the state of nanoparticles dispersed in the polymer material in the kneading and dispersing step. In the kneading and dispersing step, since the liquid in the slurry does not evaporate, as shown in FIG. 10, the nanoparticles are in the polymer material while the entire outer peripheral surface of the primary particles of the nanoparticles are covered with the liquid film. Distributed. Since a liquid exists between each of the nanoparticles, even if the nanoparticles approach each other, the nanoparticles can be dispersed in the polymer material without aggregation. As a result, the nanoparticles of the primary particles are left alone in the polymer material, and the nanoparticles can be dispersed in the polymer material as the primary particles.

(Deaeration process)
In the kneading and dispersing step, the nano-particles of the inorganic material are dispersed in the molten polymer material as primary particles. After the kneading and dispersing step, the raw material conveyed downstream by the rotation of the screw means is eventually conveyed to the place where the deaeration means is provided. The polymer material transported to the place where the deaeration means is provided is in a state where the inorganic material nanoparticles are uniformly dispersed in the polymer material as primary particles. The degassing step is a step of degassing the generated gas by evaporating the liquid in the polymer material including the liquid around the nanoparticles in the atmospheric pressure state or the reduced pressure state by the degassing means. In the degassing step, the liquid in the polymer material is removed by evaporation. Specifically, as shown in FIG. 10, the water around the nanoparticles has been removed as shown in FIG. 11 from the state in which the entire outer peripheral surface of the primary particles of the nanoparticles is covered with a liquid film. It becomes. At this stage, since the primary particles of the nanoparticles are trapped in the polymer material, no aggregation of the nanoparticles occurs. Therefore, the position of the single primary particle nanoparticles dispersed in the polymer material can be maintained in a remaining state. And the inorganic nanocomposite is carried out from the discharge port by transporting the uniformly dispersed inorganic nanocomposite to the discharge port by rotation of the screw means while the inorganic material nanoparticle remains as the primary particle in the polymer material.

(Configuration of continuous production equipment for inorganic nanocomposites)
[Continuous]
A twin-screw extruder 100 capable of continuously producing inorganic nanocomposites will be described as an inorganic nanocomposite production apparatus. FIG. 3 is a schematic view of the twin screw extruder 100. FIG. 4 is an enlarged view of a portion A in FIG. As shown in FIGS. 3 and 4, the twin-screw extruder 100 includes a cylinder 101, a screw 102 (screw means) rotatably disposed in the cylinder 101, and a rotation drive mechanism (not shown) that rotates the screw 102. And a heater (heating means) (not shown) provided on the outer periphery of the cylinder. From the upstream side of the cylinder 101, the inlet 103 for supplying the polymer material, the supply port 104 for supplying the slurry, and the vent port 105 for removing the liquid in the polymer material including the liquid around the nanoparticles (deaeration means) A discharge port 106 through which the manufactured inorganic nanocomposite is carried out is provided. The inlet 103 is provided with a hopper 109 (polymer material supply means) for supplying a polymer material.

  As shown in FIG. 4, the screw 102 has a disk shape that closes the axial cross section in the cylinder 101 and the forward feed screw 102 a such as two forward screws or forward rotor in order from the upstream side. The front seal ring 108a installed so that the plane of the disk is perpendicular to the shaft, the dispersing screw 102b (kneading and dispersing means) having no feeding effect in the axial direction, such as a kneading disk, and the shaft cross section in the cylinder are closed And a post-stage seal ring 108b installed so that the plane of the disk is perpendicular to the axis of the screw 102.

The vent port 105 is for completely removing the liquid in the polymer material including the liquid around the nanoparticles. The raw material is decompressed by the vent port 105, and the generated vapor and a small amount of TiO ₂ particles are removed. Although the number of the vent holes 105 is not particularly limited, in this embodiment, an open vent 105a that is connected to a duct from the upstream and discharges steam to the outside, and a decompression vent 105b (50 to 100 torr) connected to a vacuum pump. A three-stage vent with a vacuum vent 105c (10 torr) connected to a vacuum pump. The screw 102 between the vents is configured to be capable of material sealing. Note that the vacuum vent 105b cannot maintain a high degree of vacuum because the exhaust amount is large, but the vacuum vent 105c can achieve a high vacuum and reduce the moisture value in the polymer material.

  With this configuration, a solid polymer material is supplied from the inlet 103 into the cylinder 101 of the twin-screw extruder 100, and the supplied polymer material is melted inside the cylinder 101 by the heater, It is conveyed downstream by rotation.

  The polymer material melted by the heater is transported to the position where the front seal ring 108a is provided by the progressive screw 102a. As shown in FIG. 4, a gap is formed between the outer diameter of the pre-stage sealing single 108 a and the inner diameter of the cylinder 101. The gap becomes a flow path for the molten polymer material, and the flow is hindered by setting the flow path to be smaller than the flow path at the upstream feed screw 102a portion. Therefore, the pre-stage material seal 107a (pressure increasing pressure holding means) which is a portion having a high solid filling density is formed by the polymer material melted in the gap. In addition, a gap is formed between the outer diameter of the rear seal ring 108 b provided on the downstream side of the front seal ring 108 a and the inner diameter of the cylinder 101. This gap becomes a flow path for the raw material containing the molten polymer material or slurry. Since the flow of the raw material containing the molten polymer material or slurry is hindered by this gap, the latter-stage material seal 107b (pressure boosting pressure means) which is a portion where the solid filling density is high by the raw material containing the molten polymer material or slurry. It is formed.

  By continuously conveying the polymer material melted from the upstream side to the downstream side, the flow is hindered at the front material seal 107a portion, and the resin pressure rises. The generated material pressure is prevented from escaping by the rear material seal 107b. Thereby, the pressure between the material seals 107a and 107b is gradually increased.

  Between the two material seals 107a and 107b, the pressure rises to a predetermined pressure that is equal to or higher than the pressure value at which the slurry liquid does not evaporate. While a polymer material is continuously supplied from the inlet 103 and a predetermined amount of material flows between the material seals 107a and 107b, the pressure between the material seals 107a and 107b is a predetermined value at which the liquid of the slurry does not evaporate. Held in pressure.

  The feed capacity of the raw material is controlled by the screw pitch and the screw depth, but the feed of the raw material can be carried out by installing a reverse feed screw having a feed capacity set smaller than the forward feed screw 102a on the downstream side of the rear seal ring. Can be inhibited and can function as a boosting mechanism. In this case, when the slurry is injected between the material seals 107a and 107b, the reverse feed screw is changed so that the pressure between the material seals 107a and 107b can be maintained at a pressure higher than the pressure value at which the liquid in the slurry does not evaporate. And adjust the return resistance of the reverse feed screw in advance.

  FIG. 7 shows the slurry supply circuit 200. By using this slurry supply circuit 200, it is possible to easily guide the slurry to the supply port 104 of the twin-screw extruder 100 and to stop and restart slurry injection between the material seals 107a and 107b. As shown in FIG. 7, the slurry supply circuit 200 includes a slurry pump 201, a slurry tank 202 that stores the slurry, and a slurry nozzle 203 (slurry supply unit) that injects slurry from a supply port 104 provided in the cylinder 101. A relief valve 204 that regulates the maximum value of the pressure in the circuit between the slurry pump 201 and the slurry nozzle 203 is provided. Note that when using a high concentration slurry, there is a problem that the slurry nozzle 203 is clogged if time is taken to start, and therefore, the slurry tank 202 is provided with a stirrer 206 for stirring the slurry. .

Relief valve 204 can change the relief pressure, the high relief pressure value Ps, the low value as P _0. The slurry nozzle 203 includes a spring 205 that urges the valve in the valve closing direction. When the slurry pressure is applied, the slurry nozzle 203 overcomes the urging force of the spring 205 and opens the slurry nozzle 203. The slurry pressure for opening this nozzle is defined as Pn. The resin pressure at the point where the slurry is injected is Presin. The slurry pressure Pn is set to a value exceeding the resin pressure Presin. With this configuration, when the slurry nozzle 203 is opened, the injection passage is opened, and the slurry starts to be injected between the material seals 107a and 107b.

FIG. 8 shows a pressure control system for the set pressure of the relief valve 204. As shown in FIG. 8, the relief pressure of the relief valve 204 is set to P ₀ when the slurry is not injected between the material seals 107 a and 107 b. Since the pressure of the slurry supply circuit 200 does not exceed the slurry pressure Pn, the slurry nozzle 203 does not open and no slurry is poured between the material seals 107a and 107b. In this case, using the slurry pump 201 as a pressure source, the slurry pump 201 sucks up the slurry from the slurry tank 202 and returns to the slurry tank 202 again to circulate the slurry. That is, this is a case where the relationship of Presin> P ₀ and Pn> P ₀ is established. On the other hand, when the pressure between the material seals 107a and 107b is maintained at a pressure not lower than the pressure value at which the liquid in the slurry does not evaporate, the slurry is injected between the material seals 107a and 107b. At this stage, the relief pressure of the relief valve 204 is set to Ps, and as shown in FIG. 8, when the pressure of the slurry supply circuit 200 gradually increases and exceeds the slurry pressure Pn, the biasing force of the spring 205 of the slurry nozzle 203 is increased. By overcoming the slurry nozzle 203, the slurry is poured between the material seals 107a and 107b. That is, this is a case where the relationship of Presin ≦ Ps and Pn ≦ Ps is established. Thus, switching to Ps the relief pressure of the relief valve 204 from P _0, increasing the pressure of the slurry supply circuit 200 gradually, the injection of the slurry is started and switches the relief pressure from Ps to P _0, the slurry supply When the pressure in the circuit 200 gradually decreases and becomes equal to or lower than Presin, the slurry injection stops.

  With this configuration, the slurry is injected between the material seals 107a in a state where the pressure between the material seals 107a and 107b is maintained at a pressure higher than the pressure value at which the slurry liquid does not evaporate. When the slurry is injected, the molten polymer material and the slurry are kneaded by the dispersion screw 102b. In this kneading and dispersing process, since the space between the material seals 107a is maintained at a pressure equal to or higher than the pressure value at which the slurry liquid does not evaporate, the polymer material and inorganic material nanoparticles melted without the liquid in the slurry evaporating. And are kneaded. That is, the nanoparticles are dispersed in the polymer material while the entire outer peripheral surface of the primary particles of the nanoparticles is covered with the liquid film. Therefore, since the liquid exists between each nanoparticle, even if nanoparticles approach, nanoparticle can be disperse | distributed in a polymeric material, without aggregating. As a result, the nanoparticles of the primary particles are left alone in the polymer material, and the nanoparticles can be dispersed in the polymer material as the primary particles.

  In the kneading and dispersing process, the raw material in which the nanoparticles are uniformly dispersed in the polymer material as primary particles is conveyed in the order of the open vent 105a, the decompression vent 105b, and the vacuum vent 105c by the rotation of the screw 102. Then, each vent port 105 evaporates the liquid in the polymer material including the liquid around the nanoparticles in an atmospheric pressure state or a reduced pressure state, and degass the generated gas. Thereby, the liquid in the polymer material is removed by evaporation. At this stage, since the primary particles of the nanoparticles are trapped in the polymer material, no aggregation of the nanoparticles occurs. Therefore, the position of the single primary particle nanoparticles dispersed in the polymer material can be left and maintained. By transporting the inorganic nanocomposite in which all the inorganic particles are uniformly dispersed in the polymer material to the discharge port 106 by the rotation of the screw 102 while maintaining the particle size of the primary particles, the inorganic nanocomposite is discharged from the discharge port 106. Is carried out.

[Second Embodiment]
Hereinafter, a second embodiment for carrying out the present invention will be described with reference to the drawings. 2nd Embodiment demonstrates the manufacturing method and manufacturing apparatus which manufacture an inorganic nanocomposite by a batch type.

(Inorganic nanocomposite production method)
The manufacturing method which manufactures an inorganic nanocomposite by a batch type is demonstrated.

  FIG. 2 is a diagram illustrating a process of manufacturing an inorganic nanocomposite in a batch manner. As shown in FIG. 2, the process of manufacturing an inorganic nanocomposite in a batch type includes a material supply process for supplying a raw material comprising an unmelted polymer material and a slurry in which nanoparticles of inorganic material are dispersed in a liquid; A sealing step for keeping the raw material composed of the polymer material and the slurry in an airtight state, and a pressure increase to the raw material at a temperature at which the liquid in the slurry does not evaporate at a temperature at which the unmelted polymer material melts A process. Furthermore, after reaching a pressure higher than the pressure value at which the liquid in the slurry does not evaporate in the pressurization step, a pressure holding step for holding the pressure, a melting step for adding a temperature at which the polymer material melts from the outside, and a pressure holding step Thus, in a state where the liquid in the slurry is maintained at a pressure higher than the pressure value at which the liquid does not evaporate, the polymer material melted with the liquid interposed around the nanoparticles and the slurry are kneaded by an external action. And kneading and dispersing step of dispersing the nanoparticles in the polymer material and holding the nanoparticles of the primary particles in the polymer material in a separated and independent state. Furthermore, after the kneading and dispersing step, the pressure in the polymer material including the liquid around the nanoparticles is removed by pressure removal, and the gas generated to leave the nanoparticles alone in the polymer material is removed. It is equipped with a degassing step to worry about. The pressure holding process is performed after the pressurizing process and continuously performed until the kneading and dispersing process is completed. The melting step is performed after the pressure reaches a pressure value or higher at which the slurry liquid does not evaporate, and then the kneading and dispersing step is performed after the slurry supplying step. Each step will be specifically described below.

(Material supply process)
The material supply step is a step of supplying the polymer material and the slurry into the space where the polymer material and the slurry are kneaded by the supply means.

(Sealing process)
A sealing process is a process of isolating the space to which the polymer material and the slurry are supplied from the outside in an airtight state by the sealing means after the material supplying process, thereby making the space a sealed space.

(Pressure increase process)
The pressurizing step is a step of increasing the pressure in the sealed space by the pressurizing means after the sealing step so that the pressure in the sealed space is higher than the pressure value at which the liquid in the slurry does not evaporate at the temperature at which the polymer material melts. . The pressure in the sealed space is adjusted while measuring the pressure in the space with a hydraulic pressure gauge or the like.

(Pressure holding process)
The pressure holding step is a step of holding the pressure in the sealed space by the pressure holding means after the pressure in the sealed space rises to a pressure equal to or higher than the pressure value at which the liquid in the slurry does not evaporate.

(Melting process)
In the melting step, the pressure in the sealed space is maintained from the outside by the heating means in a state where the pressure in the sealed space is maintained at a pressure higher than the pressure value at which the liquid in the slurry does not evaporate at the temperature at which the polymer material melts. In this step, the temperature in the space is raised to a temperature at which the polymer material melts to melt the polymer material. The melting process is performed after the pressure in the sealed space is maintained at a pressure equal to or higher than the pressure value at which the liquid in the slurry does not evaporate at the temperature at which the polymer material melts, and thus the liquid in the slurry does not evaporate.

(Kneading dispersion process)
In the kneading and dispersing step, the pressure in the sealed space is maintained so that the liquid in the slurry is not evaporated, and the polymer material is melted in a state where the polymer material is melted, and the polymer material and the slurry are kneaded by the kneading and dispersing means. This is a step of dispersing inorganic material nanoparticles in a polymer material. In the kneading and dispersing step, since the liquid in the slurry does not evaporate, as shown in FIG. 10, the nanoparticles of the inorganic material are high in the state where the entire outer peripheral surface of the primary particles of the nanoparticles is covered with the liquid film. Dispersed in the molecular material. Since the liquid exists between the nanoparticles, even if the nanoparticles of the inorganic material approach each other, the nanoparticles can be dispersed in the polymer material without aggregation of the nanoparticles. As a result, the nanoparticles of the primary particles are left alone in the polymer material, and the nanoparticles can be dispersed in the polymer material as the primary particles.

(Deaeration process)
In the deaeration step, after the kneading and dispersing step, the liquid in the polymer material including the liquid interposed between the nanoparticles is evaporated by depressurizing the inside of the sealed space by the deaeration means, and the generated gas is This is a deaeration process. That is, as shown in FIG. 10, from the state in which the entire outer peripheral surface of the primary particles of the nanoparticle is covered with the liquid film, the water around the nanoparticle is removed as shown in FIG. At this stage, since the primary particles of the nanoparticles are trapped in the polymer material, no aggregation of the nanoparticles occurs. As a result, it is possible to maintain a state in which the nanoparticles remain at the positions of the nanoparticles dispersed in the polymer material. Thereby, the inorganic nanocomposite in which the nanoparticles of the inorganic material are uniformly dispersed in the polymer material while maintaining the particle diameter of the primary particles can be obtained.

(Configuration of inorganic nanocomposite batch production equipment)
[Batch type]
A batch type manufacturing apparatus 1 as an apparatus for manufacturing inorganic nanocomposites in a batch manner will be described. FIG. 14 is a schematic view of the batch type manufacturing apparatus 1. As shown in FIG. 14, the batch type manufacturing apparatus 1 is positioned by a frame 2, a convex base 3 provided inside the frame 2, and the base 3, and is fixed inside the frame 2. It has a cylinder member 4, an upper member 5 provided on the upper part of the frame 2, and a rotating member 6 (pressure raising means) that is rotatably supported by the frame 2.

  A concave portion 21 for fixing the base 3 is formed on the bottom surface inside the frame 2, and the base 3 is fitted into the concave portion 21 with the convex portion 22 facing upward. The cylinder member 4 is positioned inside the frame 2 by fitting the convex portion 22 of the base 3 from one of the hole portions 23 formed in the cylinder member 4. The positioned cylinder member 4 is fixed by a bolt. One end of the rotating member 6 is fitted from the other side of the hole 23 formed in the cylinder member 4. Thereby, a space is formed in the hole 23 of the cylinder member 4. A sealing member such as an O-ring 7 (sealing means) is provided on the sliding surface between the rotating member 6 and the hole 23 so as to isolate the inside of the space formed in the hole 23 from the outside in an airtight state. . Further, a sealing member (not shown) is provided on the fitting surface between the base 3 and the hole 23. Thereby, a sealed space 8 is formed in the hole 23 of the cylinder member 4.

  In the vicinity of the middle portion of the rotating member 6, a protruding portion 24 protruding in the diameter increasing direction is formed. A tapered roller bearing 9 is provided on the upper portion of the protrusion 24, and the rotating member 6 is rotatably supported by the frame 2 via the tapered roller bearing 9. A pressing member 10 that presses the rotating member 6 is provided on the upper portion of the tapered roller bearing 9, and the pressing member 10 has a configuration in which a tip of a screw portion of a bolt 19 screwed into the upper member 5 abuts. It has become. The pressing member 10 is pressed downward by screwing the bolt 19 screwed into the upper member 5. Accordingly, the pressing member 10 presses the rotating member 6 downward, and the rotating member 6 moves downward. Thereby, the pressure in the sealed space 8 is increased in proportion to the screwing amount of the bolt 19 screwed into the upper member 5.

  A helical stirring blade 11 (kneading / dispersing means) for kneading the polymer material and the slurry supplied in the sealed space 8 is fixed to the lower end of the rotating member 6. A handle 12 is connected to the upper end of the rotating member 6, and the rotating member 6 is rotated in a predetermined direction by rotating the handle 12. With this rotation operation, the stirring blade 11 provided at the lower end of the rotating member 6 rotates to knead the raw materials.

  Two rod-like members 13 are erected on the upper end of the convex portion 22 of the base 3 and function as a baffle plate in the rotation direction of the raw material pushed out along the spiral shape of the stirring blade 11. That is, the rod-shaped member plays a role of preventing or suppressing the accompanying movement of the stirring blade 11 and the raw material during stirring.

  An exhaust passage 25 a is formed in the rotating member 6, and the exhaust passage 25 a is connected to a pipe 28 via a pipe member 27. Note that an exhaust passage 25 b is formed in the piping member 27. Slurry is put into the exhaust passage 25a and the exhaust passage 25b in the material supply step. In addition, a hydraulic pressure gauge 14 that measures the pressure in the sealed space 8 is connected to the exhaust passage 25 a via a piping member 27. The pipe 28 is provided with a relief valve 15 (pressure holding means) that sets the pressure in the sealed space 8 to a predetermined pressure, and an exhaust valve 18 (deaeration means) that opens and closes the pipe 28. When the pressure in the sealed space 8 becomes equal to or higher than a predetermined pressure, the relief valve 15 is opened, so that the inside of the sealed space 8 can be maintained at the predetermined pressure. Further, by opening the exhaust valve 18, the inside of the sealed space 8 can be brought into an atmospheric pressure state.

  A heater 16 (heating means) is provided on the outer peripheral surface of the cylinder member 4, and the temperature in the sealed space 8 can be increased by heating the cylinder member 4. A temperature controller 29 is connected to the heater 16, and the temperature controller 29 controls the heater 16 so that the temperature in the sealed space 8 can be adjusted. The polymer material supplied into the sealed space 8 can be melted by raising the temperature in the sealed space 8 to a temperature at which the polymer material melts. A water flow path 26 is formed in the upper part of the cylinder member 4, and the upper part of the cylinder member 4 heated by the heater 16 can be cooled. Thereby, when the cylinder member 4 is heated by the heater 16, the lowering of the adhesion between the O-ring 7 and the inner wall surface of the cylinder member 4 due to the expansion of the inner peripheral diameter of the cylinder member 4 due to thermal expansion is prevented. can do. Furthermore, it is possible to prevent the O-ring 7 from being shortened due to thermal deterioration.

  The contact surface between the base 3 and the cylinder member 4 is provided with a sealing material such as an aluminum plate 17 so that the polymer material or slurry melted in the sealed space 8 does not leak from the sealed space 8. Yes. The aluminum plate 17 may be anything as long as it can withstand high temperatures.

  In this configuration, in a state where one end of the rotating member 6 is not fitted from the other of the hole portions 23 formed in the cylinder member 4, the space formed by the base 3 and the hole portion 23 of the cylinder member 4 A raw material comprising a polymer material and a slurry is supplied. Thereafter, one end of the rotary member 6 is fitted from the other side of the hole 23 formed in the cylinder member 4, and the sealed space 8 is formed by the base 3, the hole 23 of the cylinder member 4, and the rotary member 6. .

  Thereafter, the bolt 19 screwed into the upper member 5 is screwed to press the rotating member 6 downward, and the pressure in the sealed space 8 is increased. The pressure in the sealed space 8 is maintained at a predetermined pressure equal to or higher than the pressure value at which the liquid in the slurry does not evaporate by the relief valve 15. In a state where the inside of the sealed space 8 is maintained at a predetermined pressure, the temperature in the sealed space 8 is raised by the heater. Thereby, the polymer material in the sealed space 8 is in a molten state. Since the sealed space 8 is maintained at a predetermined pressure, the slurry liquid does not evaporate. Thereafter, in a state where the sealed space 8 is maintained at a predetermined pressure, the stirring blade 11 is rotated by manually rotating the handle, and the molten polymer material and the slurry are kneaded. Thereby, the nanoparticles of inorganic material are dispersed in the polymer material. FIG. 10 shows a conceptual diagram of the state of nanoparticles dispersed in the polymer material in the kneading and dispersing step. In the kneading and dispersing step, since the liquid in the slurry does not evaporate, as shown in FIG. 10, the nanoparticles are in the polymer material while the entire outer peripheral surface of the primary particles of the nanoparticles are covered with the liquid film. Distributed. Since a liquid exists between each of the nanoparticles, even if the nanoparticles approach each other, the nanoparticles can be dispersed in the polymer material without aggregation. As a result, the nanoparticles of the primary particles are left alone in the polymer material, and the nanoparticles can be dispersed in the polymer material as the primary particles.

  After the kneading and dispersing process, the exhaust valve 18 is opened to bring the sealed space 8 into an atmospheric pressure state. The liquid in the polymer material including the liquid around the nanoparticles is evaporated, and the generated gas is deaerated through the exhaust path 25a, the exhaust path 25b, and the pipe 28. Specifically, as shown in FIG. 10, the water around the nanoparticles has been removed as shown in FIG. 11 from the state in which the entire outer peripheral surface of the primary particles of the nanoparticles is covered with a liquid film. It becomes. At this stage, since the primary particles of the nanoparticles are trapped in the polymer material, no aggregation of the nanoparticles occurs. Therefore, the position of the single primary particle nanoparticles dispersed in the polymer material can be maintained in a remaining state. As described above, an inorganic nanocomposite in which nanoparticles of an inorganic material remain primary particles in a polymer material and is uniformly dispersed is produced. Thereafter, the rotating member 6 is extracted from the hole 23 of the cylinder member 4, and the manufactured inorganic nanocomposite is extracted.

[Example]
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. An inorganic nanocomposite was produced under the following use conditions.

(terms of use)
(1) Examples As the polymer material, PET having an IV value (Intringic Viscosity) of 0.64 is used, and anatase-based TiO ₂ nanoparticles are dispersed in the polymer material using the twin-screw extruder 100. The slurry used was TiO ₂ of 15 w% and water of 85 w%. The slurry concentration of this slurry is 15 W%. Although the melting point of PET is around 240 ° C., it immediately solidifies when the slurry is injected. Therefore, the temperature of the PET employed in the dispersion operation is set to 290 ° C., and the PET is melted. PET is supplied from the inlet 103 at 100 kg / hr to start normal operation, and both material seals 107a and 107b are formed. When the slurry is injected into the molten PET between the material seals with the above-described screw configuration and a predetermined extrusion amount, the pressure between the material seals 107a and 107b is a pressure value at which the water constituting the slurry does not evaporate. Confirm in advance. That is, a pressure condition of 70 kg / cm ² or higher is applied to maintain the pressure even when the water constituting the slurry does not evaporate even at 290 ° C. Thereafter, slurry is injected between the material seals 107a and 107b at 200 kg / hr. The effective length (L / D) of the screw 102 is 44.

(Experimental result)
Regarding the dispersibility of TiO ₂ in the obtained master batch, all TiO ₂ nanoparticles were dispersed with a nanoparticle diameter of 100 nm or less, and there were no aggregated particles. The particles of the primary particle size of TiO ₂ prepared in advance were dispersed in the PET. When all the particle raw materials are nano-order, inorganic nano-compound can be easily manufactured. The particle diameter of the dispersed phase after dispersion is the same as the primary particles prepared as an inorganic material, and the particle size distribution is also the same. Accordingly, since the particle distribution itself of the prepared material is in a dispersed state, any small particle dispersed state can be realized by adjusting the material in advance.

  Since the PET melt is a material that deteriorates due to moisture, there is a concern of resin deterioration, but the IV value of the PET obtained in this experiment was 0.51 to 0.55. This is probably because the time during which PET, which is a hydrolyzable resin, was in contact with water was several tens of seconds, so that it did not deteriorate so much. Thus, although the IV value is somewhat reduced in PET, since it is a high-concentration masterbatch, when it is diluted for actual use, the decrease in the IV value can be almost ignored.

  As described above, according to the manufacturing method of the inorganic nanocomposite and the twin screw extruder 100 according to the first embodiment, the raw material comprising the slurry in which the polymer material and the nanoparticles of the inorganic material are dispersed in the liquid. Of these, only the polymer material is supplied into the cylinder 101, and then the polymer material is melted by a heater provided on the outer periphery of the cylinder 101. The polymer material is conveyed to the downstream side while being melted inside the cylinder and being kneaded by the rotation of the forward feed screw 102a. Thereafter, the molten polymer material reaches a position where the pre-stage seal ring 108a is provided. The pre-stage material seal 107a is formed by the molten polymer material flowing into the flow path between the outer diameter of the front-stage seal ring 108a provided on the screw 102 axis and the inner diameter of the cylinder 101, and is provided on the screw 102 axis. A rear material seal 107 b is formed in the gap between the outer diameter of the rear seal ring 108 b and the inner diameter of the cylinder 101. By continuously conveying the polymer material melted from the upstream side to the downstream side, the flow is hindered at the front material seal 107a portion, and the resin pressure rises. The subsequent material seal 107b prevents the generated resin pressure from escaping. As a result, the pressure between the material seals 107a and 107b is gradually increased, and the pressure between the material seals 107a and 107b is increased to a pressure at which the liquid in the slurry does not evaporate due to the material temperature held by the molten polymer material. After that, it is held at that pressure. Thereafter, slurry is injected into the molten polymer material between the material seals 107a and 107b by the slurry nozzle 203. For this reason, even if the slurry is injected between both the material seals 107a and 107b, the liquid of the slurry does not evaporate, and the polymer material and the slurry melted by the dispersion screw 102b provided between the both seal rings 108a and 108b. Kneaded. Since the liquid in the slurry does not evaporate, the entire outer peripheral surface of the primary particles of the nanoparticles is dispersed in the polymer material while being covered with the liquid film. That is, the nanoparticles are dispersed in the polymer material in a state where the liquid is interposed between the nanoparticles of the inorganic material. Since the liquid is interposed between the nanoparticles in the dispersion process, even if the nanoparticles of the inorganic material approach each other, the nanoparticles are not aggregated by the liquid covering the primary particles, and the intervals between the nanoparticles are thereafter increased. It becomes large and the nanoparticles can be dispersed in the polymer material. In addition, the raw material conveyed to the vent port 105 evaporates the liquid in the polymer material including the liquid interposed between the nanoparticles, and degass the generated gas. Since each particle is trapped in the polymer material, no aggregation of the nanoparticles occurs. As a result, the position of the single primary particle nanoparticles dispersed in the polymer material can be maintained in a remaining state. Moreover, since the slurry is used as the raw material, the nanoparticles are not scattered in the air. As a result, humans will not cause health damage such as silicosis due to suction of nanoparticles. Moreover, the inorganic nanocomposite in which the nanoparticles of the inorganic material are uniformly dispersed as the primary particles in the polymer material can be continuously produced by the above method.

  In addition, according to the inorganic nanocomposite manufacturing method and the batch manufacturing apparatus 1 according to the second embodiment, a raw material comprising an unmelted polymer material and a slurry in which nanoparticles of inorganic material are dispersed in a liquid is supplied. After that, the space to which the raw material is supplied is kept in an airtight state to form a sealed space 8. Thereafter, the pressure in the sealed space 8 is increased to a pressure higher than the pressure value at which the liquid in the slurry does not evaporate at a temperature at which the unmelted polymer material melts, and then the pressure is held by the relief valve 15. Then, in a state where the pressure in the sealed space 8 is maintained, the polymer material is melted by adding a temperature at which the unmelted polymer material is melted by the heater 16 to the raw material. Thereafter, in the sealed space 8, the melted polymer material and the slurry are kneaded by the stirring blade 11, and the nanoparticles of the inorganic material are dispersed in the polymer material. The pressure in the sealed space 8 is continuously maintained at a pressure not lower than the pressure value at which the liquid in the slurry does not evaporate until the kneading and dispersing process is completed. Thereby, in the kneading dispersion process, the entire outer peripheral surface of the primary particles of the nanoparticles is dispersed in the polymer material while being covered with the liquid film. That is, the nanoparticles are dispersed in the polymer material with the liquid interposed between the nanoparticles. Therefore, even if the nanoparticles of inorganic materials approach each other, the nanoparticles are not aggregated by the liquid covering the primary particles, and then the intervals between the nanoparticles become large and the nanoparticles are dispersed in the polymer material. Can do. As a result, the nanoparticles of the inorganic material can be uniformly dispersed in the polymer material in the state of primary particles while each nanoparticle is kept at a certain distance. Further, after the kneading and dispersing process, the pressure in the sealed space 8 is removed by the exhaust valve 18 to evaporate the liquid in the polymer material including the liquid interposed between the nanoparticles, and the generated gas is removed. However, at this stage, since the primary particles of the nanoparticles are trapped in the polymer material, aggregation of the nanoparticles does not occur. As a result, the position of the single primary particle nanoparticles dispersed in the polymer material can be maintained in a remaining state. Moreover, since slurry is used as a raw material, nanoparticles do not scatter in the air. As a result, humans will not cause health damage such as silicosis due to suction of nanoparticles. In addition, since the raw material consisting of a slurry in which nanoparticles of inorganic polymer material and inorganic material are dispersed in a liquid is supplied, the nanoparticles of inorganic material are uniformly dispersed in the polymer material as primary particles. Inorganic nanocomposites can be produced in a batch mode.

  Moreover, when the density | concentration of a slurry is 0.1-15 W%, the slurry by which the nanoparticle of an inorganic material does not aggregate can be obtained. As a result, an easy-to-handle slurry can be obtained.

  In addition, when water or alcohol is used as the liquid constituting the slurry, a slurry with few impurities and low cost can be obtained, so that the manufacturing cost of the inorganic nanocomposite can be reduced.

  The inorganic nanocomposite obtained by the production method of the present invention can be used, for example, as a component for photovoltaic power generation. Dispersing the substance to be added in a nano-sized size makes it possible to realize good physical properties, such as a transparent plastic material that is below the wavelength of light and is present despite the presence of the additive substance.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made as long as they are described in the claims. . For example, the following modifications may be made.

  (1) In the second embodiment, a manual handle is used as a mechanism for rotating the rotating member 6, but an electric motor is used instead of the handle, and the output shaft and the rotating member 6 are connected by a belt. The structure which rotates the rotation member 6 may be sufficient.

DESCRIPTION OF SYMBOLS 1 Batch type manufacturing apparatus 2 Frame 3 Base 4 Cylinder member 5 Upper member 6 Rotating member 7 O-ring 8 Sealed space 9 Tapered roller bearing 10 Press member 11 Stirring blade 12 Handle 13 Bar-shaped member 14 Hydraulic pressure gauge 15 Relief valve 16 Heater 18 Exhaust valve 19 Bolt 100 Twin Screw Extruder 101 Cylinder 102 Screw 102a Progressive Screw, 102b Dispersion Screw 103 Input Port 104 Supply Port 105 Vent Port 106 Discharge Port 107a Pre-stage Material Seal, 107b Post-stage Material Seal 108a Pre-stage Seal Ring, 108b Post-stage Seal Ring 200 Slurry Supply circuit 203 Slurry nozzle

Claims (2)

An apparatus for producing an inorganic nanocomposite in which nanoparticles of an inorganic material are dispersed in a polymer material,
A polymer material supply means for supplying only the polymer material among the raw materials consisting of the slurry in which the nanoparticles of the inorganic material are dispersed in a liquid and the polymer material;
Heating means for applying a temperature at which the polymer material melts;
Screw means for transporting the molten polymer material heated by the heating means;
The screw means is provided with a pre-stage material seal and a post-stage material seal, and the pressure between the material seals reaches a pressure higher than the pressure value at which the liquid in the slurry does not evaporate due to the material temperature held by the polymer material. After that, the pressure holding means for holding the pressure,
Slurry supply means for supplying the slurry into the molten polymer material between the material seals;
A state in which a liquid is interposed around the nanoparticles in the state where the pressure between the material seals where the raw materials coexist is maintained at a pressure equal to or higher than a pressure value at which the liquid in the slurry does not evaporate. The polymer material and the slurry are kneaded in kneading, the nanoparticles are dispersed in the polymer material, and the nanoparticles are held in the polymer material in a separated and independent state in a primary particle state. A dispersion means;
A degassing means for evaporating a liquid in a polymer material containing a liquid interposed around the nanoparticles, leaving the nanoparticles alone in the polymer material, and degassing the generated gas;
An inorganic nanocomposite manufacturing apparatus comprising: The inorganic material nanoparticles include carbon nanotubes, metals, metal oxides, metal nitrides, metal nitrogen oxides, metal borides, metal silicides, thermoplastic resins, thermosetting resins, and photocurable resins. The inorganic nanocomposite production apparatus according to claim 1, which is at least one of the following.

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