Method and apparatus for impregnating plastic materials with inorganic substances

Abstract

To provide an inorganic substance infiltration apparatus that infiltrates a metal into a plastic material.SOLUTION: An inorganic substance infiltration apparatus (100) comprises: a chamber part (20) in which a plastic material is put; rotation means (MT) for rotating the chamber part (20) to rock the plastic material; a chamber heater (29) for heating the chamber part to heat the plastic material; a vacuum pump (VP) for bringing the inside of the chamber part into a vacuum state of 10 Pa or less; and a first precursor providing part (11) for providing a gaseous inorganic substance into the chamber part. Then, the inorganic substance infiltration apparatus brings the plastic material in the chamber part into a vacuum state, thereafter, provides the gaseous inorganic substance into the chamber part, and heats and rocks the plastic material, to manufacture an organic and inorganic hybrid material.SELECTED DRAWING: Figure 1

Description

【Technical Field】 【0001】 The present invention relates to an inorganic substance penetration device and method for penetrating an inorganic substance such as a metal into a non-degradable plastic material or a biodegradable plastic material. 【Background Art】 【0002】 Plastic materials such as PP (polypropylene), polyamide, etc. (including injection molding materials and fiber materials) are widely used. Generally, plastic materials have problems such as low heat resistance and low strength. Although plastic materials with improved heat resistance or strength have been proposed, there is a demand for materials with even higher heat resistance or excellent strength. For example, Patent Document 1 discloses a manufacturing method and manufacturing apparatus for supplying a metal to polylactic acid (PLA) having an L-lactide structure as a battery material for a secondary battery. 【0003】 However, Patent Document 1 supplies a metal compound to the L-lactide structure of PLA, obtains modified polylactic acid (PLA), and then polymerizes it. Also, there is a drawback that modified polylactic acid is manufactured using a manufacturing apparatus using a catalyst or the like. 【Prior Art Documents】 【Patent Documents】 【0004】 【Patent Document 1】 International Publication No. 2019 / 009286 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0005】 The problems to be solved are that a metal cannot penetrate into a non-degradable plastic material and that a metal cannot penetrate into a plastic material extracted from biodegradable wood. 【Means for Solving the Problems】 【0006】 The present invention provides a method for impregnating a metal into a recalcitrant plastic material or a biodegradable plastic material (hereinafter, unless otherwise specified, both may be collectively referred to as plastic materials) and an inorganic impregnation apparatus for the same. 【0007】 The inorganic impregnation apparatus of this embodiment comprises a chamber for holding plastic material, a rotating means for rotating the chamber and agitating the plastic material, a chamber heater for heating the chamber and heating the plastic material, a vacuum pump for creating a vacuum state of 10 Pa or less inside the chamber, and a first precursor supply unit for supplying gaseous inorganic material into the chamber. The inorganic impregnation apparatus then creates a vacuum state for the plastic material inside the chamber, then supplies gaseous inorganic material into the chamber, heats and agitates the plastic material, and produces an organic-inorganic hybrid material. 【0008】 The inorganic infiltration apparatus of this embodiment may include a second precursor supply unit that provides gaseous oxidizing and reducing substances into the chamber. The system may also include an inert gas tank that supplies inert gas into the chamber. The plastic material preferably includes recalcitrant plastics and biodegradable plastics, and the inorganic material preferably includes metal compounds and silicon compounds. 【0009】 The manufacturing method of this embodiment includes a heating step of heating the plastic material placed in the chamber, a vacuum step of creating a vacuum of 10 Pa or less in the chamber, an inorganic material supply step of providing inorganic material in a gaseous state in the chamber, and an agitation step of agitating the plastic material in the chamber. With this manufacturing method, organic-inorganic hybrid materials can be produced by impregnating the plastic material with inorganic material in a gaseous state. 【0010】 The manufacturing method of this embodiment includes, after the above-mentioned oscillating step, an exhaust step of exhausting the chamber; after the exhaust step, an oxidation / reduction product supply step of providing oxidation / reduction products into the chamber; and an oscillating step of oscillating the organic-inorganic hybrid material within the chamber. The manufacturing method of this embodiment can produce an oxidation / reduction organic-inorganic hybrid material by oxidizing and reducing an organic-inorganic plastic material. Furthermore, the heating step preferably involves heating the plastic material to 80°C to 150°C, and the inorganic material supply step preferably involves supplying a gaseous inorganic material to a vacuum chamber to create a pressure of 100 Pa to 1000 Pa. [Effects of the Invention] 【0011】 The inorganic substance penetration apparatus and method of the present invention can impregnate a recalcitrant plastic material or a biodegradable plastic material with an inorganic substance such as a metal. [Brief explanation of the drawing] 【0012】 [Figure 1] This is a schematic cross-sectional view of an inorganic substance infiltration device. [Figure 2] Flowchart 1 shows a method for supplying metal to a plastic material. [Figure 3] Flowchart 2 shows a method for supplying metal to plastic materials. [Figure 4] This is a conceptual diagram illustrating the shift from plastic materials to organic-inorganic hybrid materials. [Figure 5] This is a conceptual diagram illustrating the shift from plastic materials to organic-inorganic hybrid materials. [Figure 6] Table 1 shows the results of the physical property evaluation of plastic materials and organic-inorganic hybrid materials. [Figure 7] Table 2 shows the results of the physical property evaluation of plastic materials and organic-inorganic hybrid materials. [Modes for carrying out the invention] 【0013】 Hereinafter, embodiments will be described with reference to the drawings. FIG. 1 used in the description schematically shows these embodiments to an extent that enables understanding, and the size, thickness, etc. may be exaggerated in some cases. 【0014】 <<Configuration of Inorganic Matter Penetration Device 100>> FIG. 1 is a schematic cross-sectional view of the inorganic matter penetration device 100 of the embodiment. The inorganic matter penetration device 100 is roughly composed of a precursor supply unit 10 and a chamber unit 20. The precursor supply unit 10 inputs two types of precursors into the chamber unit 20 in this embodiment. Although not shown, a configuration may be adopted in which three or more types of precursors are input into the chamber unit 20. 【0015】 <Configuration of Precursor Supply Unit 10> The precursor supply unit 10 includes a first precursor supply unit 11, a first precursor buffer tank 15, and a pipe 12 having a nozzle and a valve 18. The precursor supply unit 10 also includes a second precursor supply unit 13 and a pipe 14 having a nozzle and a valve 18. Although not shown, a second precursor buffer tank may be arranged on the pipe 14. 【0016】 The first precursor supply unit 11 is filled with a first precursor source in a solid or liquid state at room temperature, and generates a first precursor in a gaseous state. In order to generate the gaseous first precursor, the first precursor supply unit 11 has a heater 19. Although not shown, heaters may be arranged in the first precursor supply unit 11 and the first precursor buffer tank 15 to maintain the temperature of the gas, and heaters may be arranged at the nozzle at the tip of the pipe 12 and a part or all of the pipe 12. The gaseous first precursor is heated to 50°C to 150°C. The second precursor supply unit 13 is filled with a second precursor source in a solid, liquid or gaseous state, and generates a second precursor in a gaseous state. In order to sublimate or vaporize the second precursor, it is preferable that the second precursor supply unit 13 also has a heater 19. In order to maintain the temperature of the gas, heaters may be arranged at the nozzle at the tip of the pipe 14 and a part or all of the pipe 14. The valve 18 has the function of starting or stopping the supply of the gaseous first precursor or second precursor. 【0017】 The first precursor supply unit 11, the second precursor supply unit 13, the pipes 12 and 14, the first precursor buffer tank 15, etc. are preferably containers or pipes made of stainless steel or aluminum alloy so that precursors in a solid, liquid or gaseous state do not adhere. In the case of iron containers or pipes, it is preferable to apply a fluorine coating to the inside so that precursors do not adhere. 【0018】 The first precursor supply unit 11 is filled with a metal compound or a silicon compound (hereinafter, both may be collectively referred to as inorganic substances). The liquid or solid inorganic substance is heated by the heater 19, becomes a gas, and is sent to the chamber part 20 via the pipe 12 to the first precursor buffer tank 15. When the volume of the chamber part 20 described later is large, the gaseous first precursor may be insufficient, and it is preferable that the capacity of the first precursor buffer tank 15 is large. When the volume of the chamber part 20 is small, the first precursor buffer tank 15 may not be arranged. 【0019】 The second precursor supply section 13 contains distilled water, liquid ammonia, or gaseous hydrogen, etc., which generate a gas for oxidation, nitridation, or reduction. The liquid or gaseous solid second precursor is heated by the heater 19, becomes a gas, and is sent to the chamber section 20 via the piping 12. If the volume of the chamber section 20 is large, it is preferable to provide a second precursor buffer tank. 【0020】 <Configuration of Chamber Section 20> The chamber section 20 includes a resin container 26 in which plastic material can be placed, a rotating container 24 for rotating the resin container 26, a vacuum container 22 for creating a vacuum inside the resin container 26, and a lid section 21 for sealing the vacuum container 22 and the other components. The lid section 21, vacuum container 22, rotating container 24, and resin container 26 are made of stainless steel or aluminum, and their shape can be a box shape such as a rectangular parallelepiped or cylinder. It is preferable that the chamber section 20 is positioned at an angle θ (20 to 80 degrees) from the floor surface. This is because it makes it easier for workers to attach and detach the resin container 26, and to put plastic material in and out of the fixed resin container 26. 【0021】 The resin container 26 may be detachable from the rotating container 24, or it may be fixed to the rotating container 24. If the resin container 26 is detachable from the rotating container 24, it is easier for an operator to put plastic material into the resin container 26 after it has been removed from the chamber section 20, or to take out processed organic-inorganic hybrid material. The resin container 26 may be fixed to the rotating container 24 with fasteners such as screws or bolts. 【0022】 The rotating container 24 is connected to a rotating motor MT and a shaft 25 that transmits the rotation of the rotating motor MT in order to rotate the resin container 26. The rotating motor MT and the rotating container 24 may be directly connected via the shaft 25, or they may be indirectly connected via gears, belts and the shaft 25. The rotating container 24 only needs to be able to rotate at 5 rpm to 200 rpm by the rotating motor MT, and the rotation speed of the rotating container 24 may be constant or variable. In this embodiment, since the shaft 25 penetrates the vacuum container 22, it is possible to rotate even when the vacuum container 22 is under vacuum due to a magnetic fluid seal (not shown) attached to the vacuum container 22. 【0023】 A chamber heater 29 is attached to the bottom of the cylindrical rotating container 24. This is because the heat from the chamber heater 29 heats the resin container 26 via the rotating container 24. The heat from the chamber heater 29 heats the plastic material inside the resin container 26 to 80°C to 150°C. The chamber heater 29 may be attached to the side of the rotating container 24 or to the side of the resin container 26. If the resin container 26 is fixed to the rotating container 24, it is preferable that the chamber heater 29 be attached to the resin container 26. The chamber heater 29 may also be attached to the vacuum container 22 or to the lid 21. In this configuration, the heat from the chamber heater 29 is conducted to the resin container 26 via the vacuum container 22 and the lid 21. The chamber heater 29 may be attached to multiple locations, such as the rotating container 24 and the lid 21. 【0024】 The vacuum container 22 is a device that creates a vacuum inside the resin container 26. A pipe 27 is connected to the vacuum container 22, and a vacuum pump VP is connected to the pipe 27. The vacuum pump VP creates a vacuum inside the resin container 26. -3 It is preferable to be able to achieve a vacuum state of Pa to 10 Pa. The degree of vacuum can be increased by arranging various vacuum pumps VP in multiple stages. For example, if a turbomolecular pump is connected to the vacuum container 22 and a dry pump is connected to the turbomolecular pump, the inside of the resin container 26 can be reduced to 1 × 10 Pa. ―3It is possible to achieve a vacuum level of less than Pa. Furthermore, by connecting a mechanical booster pump to the vacuum container 22 and a rotary pump to the mechanical booster pump, it is possible to achieve a vacuum level of less than 10 Pa. Note that there are various types of vacuum pumps VP, but if the inside of the resin container 26 is 10 -3 The type of vacuum that can be created from Pa to 10 Pa is irrelevant. 【0025】 Furthermore, an exhaust gas removal unit GR is connected to piping 27. A gas of a metal compound or silicon compound generated from the first precursor supply unit 11 is supplied to the resin container 26, and these gases permeate the organic-inorganic hybrid material. The exhaust gas removal unit GR removes any metal compound or silicon compound gases that did not permeate completely. The exhaust gas removal unit GR is, for example, an adsorption filter, an activated carbon filter, or a carbon dioxide trap liquid, or a combination thereof. The gas that has passed through the exhaust gas removal unit GR becomes a safe gas and is released into the atmosphere. 【0026】 The lid 21 seals the inside of the vacuum container 22, and a sealing member such as an O-ring is placed on the lid 21 or on the vacuum container 22 in contact with the lid 21. Pipes 12 and 14 are attached to the lid 21, and it is preferable that when the lid 21 is closed, the nozzles of pipe 12 and pipe 14 reach into the resin container 26. 【0027】 Furthermore, a pipe 33 having a nozzle and a valve 38 is attached to the lid 21. An inert gas tank 31 is attached to the pipe 33. The inert gas tank 31 stores an inert gas, such as nitrogen gas or argon gas, in a gaseous state. The inert gas tank 31 is used to return the vacuum inside the chamber section 20 to atmospheric pressure. If air is used instead of an inert gas, the inert gas tank 31 and the like do not need to be provided. 【0028】 Figure 1 does not depict control devices such as timers, temperature sensors, and computers. However, valves 18 and 38, heater 19, chamber heater 29, rotary motor MT, and vacuum pump VP may be automatically controlled by the control device based on inputs from the timers and temperature sensors. 【0029】 <<Ingredients for Precasa>> The first precursor is a metal compound or a silicon compound (hereinafter, both may be collectively referred to as inorganic substances). Examples of metal compounds include transition metal compounds such as aluminum compounds, iron compounds, titanium compounds, nickel compounds, copper compounds, and zinc compounds. Examples of aluminum compounds include trimethylaluminum and aluminum chloride. Examples of iron compounds include bis(di-isopropylbutanamidinate)iron and bis(di-isopropylpropionamidinate)iron. Examples of silicon compounds include tris(dimethylamino)silane (TDMAS). 【0030】 Examples of the second precursor include oxidizing precursors such as water (H2O) or ozone (O3), and reducing precursors such as ammonia or hydrogen. 【0031】 <<Recalcitrant or biodegradable plastic materials>> Resistant plastic materials or biodegradable plastic materials are in the form of pellets with a diameter of 0.2-3 mm and a length of 0.2-5 mm, fibers with a diameter of less than 0.2 mm and a length of 5 mm or more, spherical particles with a diameter of 1 mm or more, or powders with a diameter of 1 mm or less. 【0032】 Resistant plastic materials include general-purpose plastics such as PP (polypropylene), PE (polyester), PET (polyethylene terephthalate), PC (polycarbonate), PMMA (polymethyl methacrylate), PS (polystyrene), COP (cycloolefin polymer), and COC (cycloolefin copolymer). 【0033】 Biodegradable plastic materials include polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxyalkanoic acid (PHA), polyhydroxybutyric acid (PHB), PHBH (a copolymer polyester consisting of R-3-hydroxybutanoic acid (3HB) and R-3-hydroxyhexanoic acid (3HH)), hemicellulose, or their derivative materials. 【0034】 The following details hemicellulose and hemicellulose derivatives. Hemicellulose is amorphous and has excellent uniformity, and the liquid after melting has good fluidity, making it suitable as an injection molding material. Wood is mainly composed of three components: cellulose, hemicellulose, and lignin. Cellulose is highly crystalline and fibrous, so it is not very suitable as the main component of an injection molding material in its own form. Similarly, lignin is also highly crystalline and has poor fluidity, so it is not very suitable as the main component of an injection molding material. 【0035】 Hemicellulose includes mannan, glucan, xylan, and xyloglucan. In this embodiment, mannan, glucan, xylan, and xyloglucan can be used as biodegradable amorphous resin materials. The best hemicellulose is xylan. The molecular weight of hemicellulose is 1,000 to 100,000, but when it is between 30,000 and 100,000, the strength of the plastic molded product after injection molding is good. Furthermore, hemicellulose may contain 50% cellulose or 50% lignin without any problem. 【0036】 Hemicellulose is characterized by its excellent biodegradability. It biodegrades faster than cellulose and lignin, and biodegrades at temperatures above 5°C. When buried in soil, hemicellulose is decomposed by microorganisms in the soil, and even at room temperature and in the atmosphere, it is decomposed by microorganisms into water and carbon dioxide after 3 months. Similarly, it is decomposed by microorganisms in seawater. 【0037】 The molecular formula for the basic structure of hemicellulose is shown in chemical formula 1. chemical formula 1 [ka] Here, R1 and R2 represent substituents. R1 or R2 may include, but is not limited to, hydrogen, nitrogen, alkyl groups, acetyl groups, acyl groups, aryl groups, phosphonyl groups, propenyl groups, acetonyl groups, carbonyl groups, carboxyl groups, etc. It may also be fluorine, bromine, chlorine, iodine, etc., or substituents containing these. It may also be an ionized substituent such as a cation or anion that forms an ionic liquid structure. Note that n is an integer of 2 or more. 【0038】 In hemicellulose raw materials extracted from wood, R1 and R2 are hydrogen. In this embodiment, hemicellulose derivatives are those in which R1 or R2 is substituted with a substituent other than hydrogen. Typical hemicellulose derivatives have R1 and R2 substituted with acetyl groups. The acetyl group is shown in chemical formula 2. This can be achieved by acetylating the hemicellulose raw material to change the hydrogen into acetyl groups. chemical formula 2 [ka] 【0039】 Hemicellulose raw materials or hemicellulose derivatives can be melt-mixed with other recalcitrant plastic materials. By feeding the resin pellets mixed in this way into an injection molding machine and changing the molding die, plastic molded products of various shapes can be obtained. In this embodiment, the resin material obtained by mixing hemicellulose raw materials or hemicellulose derivatives with other recalcitrant plastic materials is called hemicellulose mixed resin. When the hemicellulose mixed resin is placed in soil or seawater, the hemicellulose raw materials or hemicellulose derivatives themselves are mixed with the other recalcitrant plastic materials at a molecular level. Therefore, when the hemicellulose raw materials or hemicellulose derivatives are biodegraded by microorganisms, the other recalcitrant plastic materials are also decomposed at a molecular level, and biodegradation proceeds. In other words, the hemicellulose raw materials or hemicellulose derivatives play a role in making the other recalcitrant plastic materials themselves biodegradable. 【0040】 Other recalcitrant plastic materials include polymethyl methacrylate (PMMA, acrylic), polycarbonate (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), and polystyrene (PS), but are not limited to these resins. Other resin materials, such as those with molecular formulas like chemical formula 3, can also be mixed. chemical formula 3 [ka] Here, R3 represents a substituent, and is not limited to hydrogen, nitrogen, alkyl group, acetyl group, acyl group, aryl group, phosphonyl group, propenyl group, acetonyl group, carbonyl group, carboxyl group, etc. It may also be fluorine, bromine, chlorine, iodine, etc., or substituents containing these. It may also be an ionized substituent such as a cation or anion that forms an ionic liquid structure. A and Q each independently represent a single bond or a linking group. When Q is a linking group, Q may include groups containing alkylene, -O-, -NH2-, carbonyl group, etc. When A is a linking group, A may include groups containing alkylene, -O-, -C(=O)O-, etc. m is an integer of 1 or more. When m is 2 or more, R3 in the above structural formula may be the same or different, Q may be the same or different, and A and Q may be the same or different. 【0041】 Hemicellulose raw materials and hemicellulose derivatives can be subjected to either a methacrylate or acrylate reaction. When this reaction is applied, they become monomers called hemicellulose methacrylate or hemicellulose acrylate. These monomers have a molecular structure in which a methacrylic group or acryloyl group is attached to the hemicellulose raw material or hemicellulose derivative. Note that this is not limited to methacrylate or acrylate. In this embodiment, these are referred to as hemicellulose monomers. 【0042】 Hemicellulose polymers are obtained by polymerizing hemicellulose monomers to form resins. Hemicellulose polymers can be given various properties of resin materials. Polyhemicellulose methacrylate, obtained by polymerizing hemicellulose methacrylate, possesses the properties of both hemicellulose and polymethyl methacrylate (PMMA), and is a biodegradable plastic with high transparency and good strength. Some hemicellulose polymers have the basic molecular structure of chemical formula 4. The molecular weight (weight-average molecular weight Mw) of hemicellulose polymers is 1,000 to 10,000,000, but when the molecular weight is 30,000 to 1,000,000, the molded product has good strength when injection molded. R1, R2, R3, A, Q, m, and n are as described above. chemical formula 4 [ka] 【0043】 <<Inorganic penetration method>> Figure 2 is a flowchart illustrating the inorganic substance penetration method. The plastic material is placed in the resin container 26 (step S21). If the resin container 26 is detachable, the worker places the material in it after removing it from the rotating container 24; if the resin container 26 is fixed, the worker places the material in the resin container 26 inside the chamber section 20 which is tilted at an angle θ. 【0044】 The operator places the liquid or solid first precursor into the first precursor supply unit 11, and the first precursor supply unit is heated by the heater 19 (step S22). Due to the heating by the heater 19, the liquid first precursor vaporizes into a gas, and the solid first precursor sublimes into a gas. The first precursor in gaseous state is heated to between 50°C and 150°C. 【0045】 Simultaneously with or around the same time as the heating of the first precursor, the chamber section 20 is heated by the chamber heater 29, and the resin container 26 is heated to the set temperature (step S23). Inside the resin container 26, the plastic material is heated from 80°C to 150°C. The lid 21 is sealed by the worker (step S24). 【0046】 The vacuum pump VP creates a vacuum in the vacuum container 22, and also creates a vacuum in the resin container 26 inside the vacuum container 22 (step S25). The vacuum level inside the resin container 26 is preferably 10 Pa or less. When the vacuum level reaches 10 Pa or less, the vacuum pump VP stops and maintains that vacuum level. 【0047】 Next, valve 18 of piping 12 is opened, and the first precursor in gaseous state is supplied into the resin container 26 (step S26). As the first precursor in gaseous state is supplied, the gas pressure inside the resin container 26 increases from 100 Pa to 1000 Pa. Then, for example, when the gas pressure reaches 500 Pa, valve 18 is closed, and the supply of the first precursor is stopped (step S27). At the same time, heating of the first precursor supply section is stopped (step S28). Inside the resin container 26, the plastic material is heated, and the container is filled with the first precursor in gaseous state. 【0048】 Next, the plastic material is rotated within the resin container 26 (step S29). As the plastic material rotates, the gaseous first precursor penetrates from the material surface. The molecules of the penetrated first precursor attach to and bond with the molecules of the material. The plastic material changes from an organic material to an organic-inorganic hybrid material. 【0049】 After a predetermined time has elapsed, the gaseous first precursor has sufficiently permeated the plastic material. At this point, the rotation of the resin container 26 is stopped (step S30). In the above description, steps S26 and S29 were performed sequentially, but steps S26 and S29 may be started simultaneously. 【0050】 Since much of the first precursor in a gaseous state penetrates the plastic material, there is almost no first precursor in a gaseous state remaining in the resin container 26. However, in order to discharge all of the first precursor in a gaseous state from the resin container 26, the vacuum pump VP is activated, and the exhaust gas removal unit GR removes any gas from the first precursor that did not penetrate (step S31). 【0051】 Next, the inert gas in the inert gas tank 31 is supplied to the chamber section 20 when the valve 38 is opened (step S32). When the inert gas reaches atmospheric pressure, the valve 38 is closed. This allows the operator to open the lid 21. 【0052】 Simultaneously or around the same time, the chamber heater 29 stops, and the chamber 20 is cooled to room temperature (step S33). Then the lid 21 is opened, and the organic-inorganic hybrid material is removed from the resin container 26 (step S34). 【0053】 The above is an example of the first precursor penetrating the plastic material. From step S40 onward, the first and second precursors penetrate the plastic material. 【0054】 Following step S31, valve 18 of piping 14 is opened, and gaseous second precursor is supplied into the resin container 26 (step S41). As gaseous second precursor is supplied, the gas pressure inside the resin container 26 increases from 100 Pa to 1000 Pa. Then, for example, when it reaches 500 Pa, valve 18 is closed, and the supply of second precursor is stopped (step S42). Inside the resin container 26, the organic-inorganic hybrid material is heated, and the container is filled with gaseous second precursor. 【0055】 Next, the organic-inorganic hybrid material is rotated within the resin container 26 (step S43). As the organic-inorganic hybrid material rotates, the gaseous second precursor penetrates from the material surface. The molecules of the penetrated second precursor attach to and bond with the molecules of the organic-inorganic hybrid material. The organic-inorganic hybrid material becomes an oxidized and reduced organic-inorganic hybrid material. 【0056】 After a predetermined time has elapsed, the gaseous second precursor has sufficiently permeated the organic-inorganic hybrid material. At this point, the rotation of the resin container 26 is stopped (step S44). To discharge all of the gaseous second precursor from the resin container 26, the vacuum pump VP is activated, and the exhaust gas removal unit GR removes any remaining gas from the second precursor that could not be absorbed (step S45). 【0057】 Next, the inert gas in the inert gas tank 31 is supplied to the chamber section 20 when the valve 38 is opened (step S46). When the inert gas reaches atmospheric pressure, the valve 38 is closed. At the same time or before / after, the chamber heater 29 is stopped, and the chamber section 20 is cooled to room temperature (step S47). Then the lid 21 is opened and the hybrid material is removed from the resin container 26 (step S48). [Examples] 【0058】 Example 1 is an example in which a cellulose derivative was used as the plastic material. Commercially available cellulose acetate propionate (CAP) was used as the cellulose derivative. 20% of TPP (triphenyl phosphate) was kneaded into the cellulose derivative as a plasticizer, and the kneaded mixture was formed into pellets using an extruder, a cooling stage, and a pelletizer. 【0059】 One kilogram of this cellulose derivative pellet was supplied into the chamber section 20 of the inorganic material infiltration apparatus 100. The temperature of the chamber section 20 was set to 120°C. The chamber section 20 had a cylindrical structure and was rotated around the center of the bottom surface of the cylinder as the main axis. The rotation speed was set to 40 rpm. In addition, the inside of the chamber section 20 was evacuated using a vacuum pump VP, creating a vacuum state of 5 Pa inside the chamber section 20. 【0060】 Liquid trimethylaluminum at room temperature was placed in the first precursor supply section 11 as the first precursor. The liquid trimethylaluminum was heated to 130°C in the first precursor supply section 11, and trimethylaluminum gas was supplied into the chamber section 20. Trimethylaluminum gas was supplied until the gas pressure in the chamber section 20 reached 500 Pa, and the valve 18 of the piping 12 was closed. In this way, the trimethylaluminum gas was sealed inside the rotating resin container 26. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the trimethylaluminum gas permeated into the inside of the pellets, causing a chemical reaction between the cellulose derivative and the trimethylaluminum gas. In particular, a molecular structure was formed in which the metal was bonded to the carbonyl group of the cellulose derivative. The supply of trimethylaluminum gas lasted for 1000 seconds. After that, the chamber section 20 was removed by a vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction. 【0061】 Subsequently, water vapor (H2O) gas was supplied into the chamber section 20 as a second precursor, and the water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the piping 14 was closed. In this way, the water vapor gas was sealed inside the rotating chamber section 20. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the water vapor gas permeated into the inside of the pellets. Then, a chemical reaction occurred between the cellulose derivative and the water vapor gas. In particular, the portion of the cellulose derivative to which aluminum (Al) is bonded becomes an oxidized molecular structure, and substituents containing aluminum oxides, such as aluminum oxide and aluminum hydroxide, become formed. The water vapor gas was supplied for 250 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and then the lid 21 was opened and the pellets were removed. 【0062】 Figure 4(A) shows a conceptual diagram of the transformation from a cellulose derivative to an oxidized organic-inorganic hybrid material. n is an integer greater than or equal to 2, and M represents a metal element. In Example 1, it is aluminum. Test specimens were also prepared by injection molding using pellets of this oxidized organic-inorganic hybrid material and used together with the pellets for physical property evaluation. The results of the physical property evaluation are shown in Figure 6. As shown in the physical property evaluation of the cellulose derivative and Example 1, it can be seen that the organic-inorganic hybrid material is superior in strength, hardness, heat resistance, density, etc., when a metal element is bonded to the substituent. [Examples] 【0063】 Example 2 is an example in which polymethyl methacrylate (PMMA) was used as a persistent plastic material. PMMA was made into pellets using an extruder, a cooling stage, and a pelletizer. 【0064】 One kilogram of PMMA pellets was supplied into the chamber section 20 of the inorganic material infiltration apparatus 100. The temperature of the chamber section 20 was set to 100°C. The rotating container 24 was rotated at a speed of 20 rpm around the axis 25. In addition, the chamber section 20 was evacuated using a vacuum pump VP, creating a vacuum of 5 Pa inside the chamber section 20. 【0065】 Liquid trimethylaluminum at room temperature was placed in the first precursor supply section 11 as the first precursor. The liquid trimethylaluminum was heated to 130°C in the first precursor supply section 11, and trimethylaluminum gas was supplied into the chamber section 20. Trimethylaluminum gas was supplied until the gas pressure in the chamber section 20 reached 500 Pa, and the valve 18 of the piping 12 was closed. This sealed the trimethylaluminum gas inside the rotating resin container 26. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the trimethylaluminum gas permeated into the pellets, causing a chemical reaction between PMMA and the trimethylaluminum gas. In particular, a molecular structure was formed in which metal was bonded to the carbonyl group of PMMA. The supply of trimethylaluminum gas lasted for 1000 seconds. After that, the chamber section 20 was removed by a vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction. 【0066】 Subsequently, water vapor (H2O) gas was supplied into the chamber section 20 as a second precursor, and the water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the piping 14 was closed. In this way, the water vapor gas was sealed inside the rotating chamber section 20. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the water vapor gas permeated into the inside of the pellets. Then, a chemical reaction occurred between the PMMA and the water vapor gas. In particular, the molecular structure became oxidized at the part of the carbonyl group of PMMA to which the metal is bonded. The water vapor gas was supplied for 250 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and then the lid 21 was opened and the pellets were removed. 【0067】 Figure 4(B) shows a conceptual diagram of the transformation from PMMA to an oxidized organic-inorganic hybrid material. n is an integer greater than or equal to 2, and M represents a metallic element. Test specimens were created by injection molding using pellets of this oxidized organic-inorganic hybrid material and used together with the pellets for physical property evaluation. The results of the physical property evaluation are shown in Figure 6. As shown in the physical property evaluation of PMMA and Example 2, it can be seen that the organic-inorganic hybrid material is superior in strength, hardness, heat resistance, density, etc., due to the bonding of a metallic element to the carbonyl group. [Examples] 【0068】 Example 3 is an example in which polylactic acid (PLA) was used as the biodegradable plastic material. The PLA was made into pellets using an extruder, a cooling stage, and a pelletizer. 【0069】 One kilogram of PLA pellets was supplied into the chamber section 20 of the inorganic material infiltration apparatus 100. The temperature of the chamber section 20 was set to 120°C. The rotating container 24 was rotated around the axis 25 at a rotation speed of 80 rpm. In addition, the chamber section 20 was evacuated using a vacuum pump VP, creating a vacuum of 10 Pa inside the chamber section 20. 【0070】 Liquid trimethylaluminum at room temperature was placed in the first precursor supply section 11 as the first precursor. The liquid trimethylaluminum was heated to 130°C in the first precursor supply section 11, and trimethylaluminum gas was supplied into the chamber section 20. Trimethylaluminum gas was supplied until the gas pressure in the chamber section 20 reached 500 Pa, and the valve 18 of the piping 12 was closed. This sealed the trimethylaluminum gas inside the rotating resin container 26. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the trimethylaluminum gas permeated into the pellets, causing a chemical reaction between the PLA and the trimethylaluminum gas. In particular, a molecular structure was formed in which the metal was bonded to the carbonyl group of the PLA. The supply of trimethylaluminum gas lasted for 1000 seconds. After that, the chamber section 20 was removed by a vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction. 【0071】 Subsequently, water vapor (H2O) gas was supplied into the chamber 20 as a second precursor, and the water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the piping 14 was closed. In this way, the water vapor gas was sealed inside the rotating chamber 20. Inside the chamber 20, the pellets oscillated in accordance with the rotation, and the water vapor gas permeated into the inside of the pellets. Then, a chemical reaction occurred between the PLA and the water vapor gas. In particular, the molecular structure became oxidized at the part of the PLA carbonyl group to which the metal is bonded. The water vapor gas was supplied for 250 seconds. After that, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and then the lid 21 was opened and the pellets were removed. 【0072】 Figure 4(C) shows a conceptual diagram of the transformation from PLA to an oxidized organic-inorganic hybrid material. Test specimens were created using pellets of this oxidized organic-inorganic hybrid material by injection molding and used in the physical property evaluation along with the pellets. The results of the physical property evaluation are shown in Figure 6. n is an integer greater than or equal to 2, and M represents a metallic element. As shown in the physical property evaluation of PLA and Example 3, it can be seen that the bonding of a metallic element to the carbonyl group results in superior strength, hardness, heat resistance, density, etc., in the organic-inorganic hybrid material. [Examples] 【0073】 Example 4 is an example in which PHBH (a copolymer polyester consisting of R-3-hydroxybutanoic acid (3HB) and R-3-hydroxyhexanoic acid (3HH)) was used as a biodegradable plastic material. PHBH was made into pellets using an extruder, a cooling stage, and a pelletizer. 【0074】 One kilogram of PHBH pellets was supplied into the chamber section 20 of the inorganic infiltration apparatus 100. The temperature of the chamber section 20 was set to 110°C. The rotating container 24 was rotated at a speed of 60 rpm around the axis 25. In addition, the chamber section 20 was evacuated using a vacuum pump VP, creating a vacuum of 10 Pa inside the chamber section 20. 【0075】 Liquid trimethylaluminum at room temperature was placed in the first precursor supply section 11 as the first precursor. The liquid trimethylaluminum was heated to 130°C in the first precursor supply section 11, and trimethylaluminum gas was supplied into the chamber section 20. Trimethylaluminum gas was supplied until the gas pressure in the chamber section 20 reached 500 Pa, and the valve 18 of the piping 12 was closed. This sealed the trimethylaluminum gas inside the rotating resin container 26. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the trimethylaluminum gas permeated into the pellets, causing a chemical reaction between the PHBH and the trimethylaluminum gas. In particular, a molecular structure was formed in which metal was bonded to the carbonyl group of PHBH. The supply of trimethylaluminum gas lasted for 1000 seconds. After that, the chamber section 20 was removed by a vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction. 【0076】 Subsequently, water vapor (H2O) gas was supplied into the chamber 20 as a second precursor, and the water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the piping 14 was closed. In this way, the water vapor gas was sealed inside the rotating chamber 20. Inside the chamber 20, the pellets oscillated in accordance with the rotation, and the water vapor gas permeated into the inside of the pellets. Then, a chemical reaction occurred between the PHBH and the water vapor gas. In particular, the molecular structure in which the metal is bonded to the carbonyl group of the PHBH becomes oxidized. The water vapor gas was supplied for 250 seconds. After that, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and then the lid 21 was opened and the pellets were removed. 【0077】 Figure 5(A) shows a conceptual diagram of the transformation from PHBH to an oxidized organic-inorganic hybrid material. n and m are integers greater than or equal to 2, and M represents a metallic element. Test specimens were prepared by injection molding using pellets of this oxidized organic-inorganic hybrid material and used together with the pellets for property evaluation. The results of the property evaluation are shown in Figure 7. As shown in the property evaluation of PHBH and Example 4, it can be seen that the organic-inorganic hybrid material is superior in strength, hardness, heat resistance, density, etc., due to the bonding of a metallic element to the carbonyl group. [Examples] 【0078】 Example 5 is an example in which a hemicellulose derivative was used as a biodegradable plastic material. The hemicellulose derivative was kneaded with TPP (triphenyl phosphate) as a plasticizer, and the kneaded mixture was formed into pellets using an extruder, a cooling stage, and a pelletizer. 【0079】 One kilogram of hemicellulose derivative pellets was supplied into the chamber section 20 of the inorganic material infiltration apparatus 100. The temperature of the chamber section 20 was set to 120°C. The rotating container 24 was rotated at a speed of 30 rpm around the axis 25. In addition, the chamber section 20 was evacuated using a vacuum pump VP, creating a vacuum of 1 Pa inside the chamber section 20. 【0080】 Liquid trimethylaluminum at room temperature was placed in the first precursor supply section 11 as the first precursor. The liquid trimethylaluminum was heated to 130°C in the first precursor supply section 11, and trimethylaluminum gas was supplied into the chamber section 20. Trimethylaluminum gas was supplied until the gas pressure in the chamber section 20 reached 500 Pa, and the valve 18 of the piping 12 was closed. In this way, the trimethylaluminum gas was sealed inside the rotating resin container 26. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the trimethylaluminum gas permeated into the inside of the pellets, causing a chemical reaction between the hemicellulose derivative and the trimethylaluminum gas. In particular, a molecular structure was formed in which metal was bonded to the substituents of the hemicellulose derivative. The supply of this trimethylaluminum gas lasted for 1000 seconds. After that, the trimethylaluminum gas and the gas generated by the chemical reaction were removed from the chamber section 20 by a vacuum pump VP. 【0081】 Subsequently, water vapor (H2O) gas was supplied into the chamber 20 as a second precursor, and the water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the piping 14 was closed. In this way, the water vapor gas was sealed inside the rotating chamber 20. Inside the chamber 20, the pellets oscillated in accordance with the rotation, and the water vapor gas permeated into the inside of the pellets. Then, a chemical reaction occurred between the hemicellulose derivative and the water vapor gas. In particular, the molecular structure became oxidized at the parts of the hemicellulose derivative where metal was bonded to the substituents. The water vapor gas was supplied for 250 seconds. After that, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and then the lid 21 was opened and the pellets were removed. 【0082】 Figure 5(B) shows a conceptual diagram of the transformation from a hemicellulose derivative to an oxidized organic-inorganic hybrid material. n is an integer greater than or equal to 2, and M represents a metal element. Test specimens were prepared by injection molding using pellets of this oxidized organic-inorganic hybrid material and used together with the pellets for property evaluation. The results of the property evaluation are shown in Figure 7. As shown in the property evaluation of the hemicellulose derivative and Example 5, it can be seen that the organic-inorganic hybrid material is superior in strength, hardness, heat resistance, density, etc., when a metal element is bonded to the substituent. [Examples] 【0083】 Example 6 is an example in which a cellulose derivative and a hemicellulose derivative were used in a 50:50 ratio as the plastic material and biodegradable plastic material. The cellulose derivative and the hemicellulose derivative were kneaded together, and the mixture was formed into pellets using an extruder, a cooling stage, and a pelletizer. The hemicellulose derivative acts as a plasticizer for the cellulose derivative. 【0084】 One kilogram of pellets of the cellulose derivative and hemicellulose derivative was supplied into the chamber section 20 of the inorganic impregnation apparatus 100. The temperature of the chamber section 20 was set to 90°C. The rotating container 24 was rotated at a speed of 40 rpm around the axis 25. In addition, the chamber section 20 was evacuated using a vacuum pump VP, creating a vacuum of 10 Pa inside the chamber section 20. 【0085】 Liquid trimethylaluminum at room temperature was placed in the first precursor supply section 11 as the first precursor. The liquid trimethylaluminum was heated to 130°C in the first precursor supply section 11, and trimethylaluminum gas was supplied into the chamber section 20. Trimethylaluminum gas was supplied until the gas pressure in the chamber section 20 reached 500 Pa, and the valve 18 of the piping 12 was closed. In this way, the trimethylaluminum gas was sealed inside the rotating resin container 26. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the trimethylaluminum gas permeated into the inside of the pellets, causing a chemical reaction between the cellulose derivative and the hemicellulose derivative and the trimethylaluminum gas. In particular, a molecular structure was formed in which metal was bonded to the substituents of the cellulose derivative and the hemicellulose derivative. The supply of this trimethylaluminum gas lasted for 1000 seconds. After that, the chamber section 20 was removed by a vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction. 【0086】 Subsequently, water vapor (H2O) gas was supplied into the chamber section 20 as a second precursor, and the water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the piping 14 was closed. In this way, the water vapor gas was sealed inside the rotating chamber section 20. Inside the chamber section 20, the pellets oscillated in accordance with the rotation, and the water vapor gas permeated into the inside of the pellets. Then, a chemical reaction occurred between the cellulose derivative and the hemicellulose derivative and the water vapor gas. In particular, the molecular structure became oxidized in the parts where metal was bonded to the resin substitution. The water vapor gas was supplied for 250 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and then the lid 21 was opened and the pellets were removed. 【0087】 A conceptual diagram of the transformation from a mixture of cellulose derivatives and hemicellulose derivatives to an oxidized organic-inorganic hybrid material is shown in Figure 4(A) or Figure 5(B). Test specimens were prepared by injection molding using pellets of this oxidized organic-inorganic hybrid material and used together with the pellets for property evaluation. The results of the property evaluation are shown in Figure 7. As shown in the property evaluation of the mixture and Example 6, it can be seen that the organic-inorganic hybrid material exhibits superior strength, hardness, heat resistance, density, etc., due to the substitution of substituents with metal elements. [Industrial applicability] 【0088】 By using an inorganic impregnation apparatus or method, it is possible to manufacture organic-inorganic hybrid materials with dramatically improved strength and heat resistance. While examples of manufacturing pellet-shaped organic-inorganic hybrid materials used in injection molding are shown, the method can also be applied to manufacturing fibrous, particulate, and powder-type organic-inorganic hybrid materials. Furthermore, although the organic-inorganic hybrid materials in Examples 1-6 were oxidized to change their structure to a metal oxide, oxidation is not always necessary. 【0089】 Products that can be injection molded using pellets of organic-inorganic hybrid materials can be used for a wide range of applications, from beverage containers such as cups and food containers such as food trays, to industrial parts such as electrical appliances and automobile components. In particular, organic-inorganic hybrid materials have excellent strength, hardness, and heat resistance, making them suitable for products used in harsh environments. [Explanation of symbols] 【0090】 10…Preca Supply Department 11…First Pre-Casa Provision Department, 13…Second Pre-Casa Provision Department 15…First Precursor Buffer Tank 18…Valve, 19…Heater 20... Chamber section 21...Lid, 22...Vacuum container, 24...Rotating container, 26...Resin container 29... Chamber heater, 31... Inert gas tank MT...Rotating motor, GR...Exhaust gas removal unit, VP...Vacuum pump 100...Inorganic infiltration device

Claims

[Claim 1] A heating step in which a plastic material containing a non-degradable or biodegradable plastic placed in a chamber is heated to 80°C to 150°C, A vacuum step to bring the chamber to a vacuum state of 10 Pa or less, The inorganic material provisioning step involves providing an inorganic material in a gaseous state containing a metal compound or a silicon compound into the chamber portion, The first rocking step involves rocking the plastic material within the chamber, After the first oscillation step, an exhaust step is performed to exhaust the contents of the chamber, After the exhaust process, an oxidation precursor provisioning process is performed, in which an oxidation precursor is provided in the chamber section. The process includes a second rocking step in which the plastic material is rocked within the chamber, after the aforementioned oxidation precursor provisioning step. A manufacturing method for producing a hybrid material in which a gaseous inorganic substance is impregnated into the plastic material, and the inorganic substance is further oxidized. [Claim 2] The manufacturing method according to claim 1, wherein the inorganic material supply step involves supplying a gaseous inorganic material to the chamber in a vacuum state to raise the pressure from 100 Pa to 1000 Pa. [Claim 3] A chamber portion for holding a plastic material including a non-degradable plastic or a biodegradable plastic, A rotating means for rotating the chamber portion and oscillating the plastic material, A chamber heater that heats the chamber portion and heats the plastic material, A vacuum pump that creates a vacuum of 10 Pa or less inside the chamber, A first precursor supply unit that provides a gaseous inorganic substance containing a metal compound or a silicon compound into the chamber, The system comprises a second precursor supply unit that provides a gaseous oxidation precursor into the chamber, An inorganic impregnation apparatus for producing hybrid materials, comprising: heating the plastic material placed in the chamber to 80°C to 150°C; then creating a vacuum in the chamber; then providing a gaseous inorganic substance into the chamber; agitating the plastic material; and further providing an oxidation precursor into the chamber. [Claim 4] The inorganic material infiltration apparatus according to claim 3, further comprising an inert gas tank for supplying an inert gas into the chamber.

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