Method of infiltrating inorganic substance into plastic material, and inorganic substance infiltration apparatus

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 permeation device and method for permeating a hard-to-decompose or biodegradable plastic material with an inorganic substance such as a metal. [Background technology]

[0002] Plastic materials (including injection molding materials and fiber materials) such as PP (polypropylene) and polyamide are widely used. In general, plastic materials have problems such as low heat resistance and low strength. Although plastic materials with improved heat resistance and strength have been proposed, materials with even higher heat resistance and superior strength are required. For example, Patent Document 1 discloses a manufacturing method and manufacturing device for supplying metal to polylactic acid (PLA) having an L-lactide structure as a battery material for secondary batteries.

[0003] However, in Patent Document 1, a metal compound is supplied to the L-lactide structure of PLA to obtain modified polylactic acid (PLA), which is then polymerized. In addition, there is a drawback in that the modified polylactic acid is produced in a production device that uses a catalyst, etc. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2019 / 009286 Summary of the Invention [Problem to be solved by the invention]

[0005] The problem to be solved is that metals cannot be impregnated into hard-to-decompose plastic materials, and that metals cannot be impregnated into plastic materials extracted from biodegradable wood. [Means for solving the problem]

[0006] The present invention provides a method for impregnating a hard-to-degrade plastic material or a biodegradable plastic material (hereinafter, unless a distinction is required, both may be collectively referred to as plastic materials) with a metal, and an inorganic impregnation device for the method.

[0007] The inorganic substance permeation device of the embodiment includes a chamber part for putting a plastic material, a rotation means for rotating the chamber part and agitating the plastic material, a chamber heater for heating the chamber part and heating the plastic material, a vacuum pump for creating a vacuum state in the chamber part of 10 Pa or less, and a first precursor providing part for providing a gaseous inorganic substance into the chamber part. The inorganic substance permeation device creates a vacuum state in the plastic material in the chamber part, then provides the gaseous inorganic substance into the chamber part, and heats and agitates the plastic material to produce an organic-inorganic hybrid material.

[0008] The inorganic substance permeation device according to the embodiment may include a second precursor providing section that provides a gaseous oxidant or reductant into the chamber section. Also, an inert gas tank may be provided to supply an inert gas to the chamber. The plastic materials preferably include difficult to decompose plastics and biodegradable plastics, and the inorganic substances preferably include metal compounds and silicon compounds.

[0009] The manufacturing method according to the 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 substance providing step of providing a gaseous inorganic substance in the chamber, and a shaking step of shaking the plastic material in the chamber. This manufacturing method allows the inorganic substance in the gaseous state to permeate the plastic material, and produces an organic-inorganic hybrid material.

[0010] The manufacturing method of the embodiment includes an exhaust step of exhausting the inside of the chamber after the rocking step, an oxidation / reduction product providing step of providing an oxidation / reduction product into the chamber after the exhaust step, and a rocking step of rocking the organic-inorganic hybrid material in the chamber. The manufacturing method of the embodiment can produce an oxidized / reduced organic-inorganic hybrid material by permeating an organic-inorganic plastic material with oxidation / reduction. In addition, the heating step preferably heats the plastic material to 80° C. to 150° C., and the inorganic substance providing step preferably provides a gaseous inorganic substance to the vacuum chamber to bring the pressure therein to 100 Pa to 1000 Pa. Effect of the Invention

[0011] The inorganic substance permeation device and method of the present invention are capable of permeating inorganic substances such as metals into a hard-to-decompose plastic material or a biodegradable plastic material. [Brief description of the drawings]

[0012] [Figure 1] FIG. 2 is a schematic cross-sectional view of an inorganic permeation device. [Diagram 2] 1 is a flow chart 1 illustrating a method of providing metal to a plastic material. [Diagram 3] 2 is a flow chart 2 illustrating a method of providing metal to a plastic material. [Figure 4] This is a conceptual diagram of the transformation from a plastic material to an organic-inorganic hybrid material. [Diagram 5] This is a conceptual diagram of the transformation from a plastic material to an organic-inorganic hybrid material. [Figure 6] Table 1 shows the results of property evaluation of plastic materials and organic-inorganic hybrid materials. [Figure 7] Table 2 shows the results of property evaluation of plastic materials and organic-inorganic hybrid materials. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, the embodiments will be described with reference to the drawings. Fig. 1 used in the description shows the embodiments in a schematic manner to enable understanding, and the size, thickness, etc. may be exaggerated.

[0014] <<Configuration of inorganic substance permeation device 100>> 1 is a schematic cross-sectional view of an inorganic permeation device 100 according to an embodiment. The inorganic permeation device 100 is roughly composed of a precursor supply unit 10 and a chamber unit 20. In this embodiment, the precursor supply unit 10 supplies two types of precursors into the chamber unit 20. Although not shown, the precursor supply unit 10 may be configured to supply three or more types of precursors 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 disposed on the pipe 14.

[0016] The first precursor providing unit 11 is charged with a solid or liquid first precursor source at room temperature, and generates a gaseous first precursor. The first precursor providing unit 11 has a heater 19 to generate the gaseous first precursor. Although not shown, heaters may be provided in the first precursor providing unit 11 and the first precursor buffer tank 15 to maintain the temperature of the gas, and heaters may be provided in the nozzle at the end of the pipe 12 and in part or all of the pipe 12. The gaseous first precursor is heated to 50°C to 150°C. The second precursor providing unit 13 is charged with a solid, liquid, or gaseous second precursor source to generate a gaseous second precursor. It is preferable that the second precursor providing unit 13 also has a heater 19 to sublimate or vaporize the second precursor. Heaters may be provided in the nozzle at the end of the pipe 14 and in part or all of the pipe 14 to maintain the temperature of the gas. Valve 18 serves to start or stop the supply of the first or second gaseous precursor.

[0017] The first precursor providing unit 11, the second precursor providing 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 the precursor in a solid, liquid or gas state does not adhere to them. In the case of iron containers or pipes, the insides of them are preferably fluorine-coated so that the precursor does not adhere to them.

[0018] A metal compound or a silicon compound (hereinafter, both may be collectively referred to as an inorganic substance) is placed in the first precursor providing section 11. The liquid or solid inorganic substance is heated by a heater 19, turned into a gas, and sent to the first precursor buffer tank 15 via the pipe 12 to the chamber section 20. If the volume of the chamber section 20 described below is large, there may be a shortage of the first precursor in a gaseous state, and therefore it is preferable that the capacity of the first precursor buffer tank 15 is large. If the volume of the chamber section 20 is small, the first precursor buffer tank 15 does not need to be provided.

[0019] Distilled water, liquid ammonia, gaseous hydrogen, or the like that generates a gas for oxidation, nitridation, or reduction is placed in the second precursor providing section 13. The liquid or gaseous solid second precursor is heated by a heater 19, turned into a gas, and sent to the chamber section 20 via the pipe 12. When the volume of the chamber section 20 is large, it is preferable to place a second precursor buffer tank.

[0020] <Configuration of chamber section 20> The chamber section 20 has a resin container 26 in which a plastic material is 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 like. The lid section 21, the vacuum container 22, the rotating container 24, and the resin container 26 are containers made of stainless steel or aluminum, and may have a box shape such as a rectangular parallelepiped or cylinder. It is preferable that the chamber section 20 is arranged at an angle θ (20 degrees to 80 degrees) from the floor surface. This is because it is easy for an operator to attach and detach the resin container 26, and to put and take out the plastic material from the fixed resin container 26.

[0021] The resin container 26 may be detachable from the rotating container 24, or may be fixed to the rotating container 24. If the resin container 26 is detachable from the rotating container 24, it is easy for an operator to put plastic material into the resin container 26 removed from the chamber section 20, or to take out the treated 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 may be indirectly connected via a gear, a belt, and the shaft 25. The rotating container 24 may be rotated at 5 rpm to 200 rpm by the rotating motor MT, and the rotation speed of the rotating container 24 may be constant or may be variable. In this embodiment, the shaft 25 penetrates the vacuum container 22, and therefore can rotate even when the vacuum container 22 is evacuated by a magnetic fluid seal (not shown) attached to the vacuum container 22.

[0023] A chamber heater 29 is attached to the bottom surface of the cylindrical rotating vessel 24. This is because the heat of the chamber heater 29 heats the resin vessel 26 through the rotating vessel 24. The plastic material in the resin vessel 26 is heated to 80°C to 150°C by the heat of the chamber heater 29. The chamber heater 29 may be attached to the side of the rotating vessel 24 or the side of the resin vessel 26. If the resin vessel 26 is fixed to the rotating vessel 24, it is preferable that the chamber heater 29 is attached to the resin vessel 26. The chamber heater 29 may be attached to the vacuum vessel 22 or the lid 21. In this case, the heat of the chamber heater 29 is conducted to the resin vessel 26 through the vacuum vessel 22 and the lid 21. The chamber heater 29 may be attached to multiple locations such as the rotating vessel 24 and the lid 21.

[0024] The vacuum vessel 22 is a device for creating a vacuum in the resin vessel 26. A pipe 27 is connected to the vacuum vessel 22, and a vacuum pump VP is connected to the pipe 27. The vacuum pump VP evacuates the resin vessel 26 by 10 -3 It is preferable that the vacuum state can be made to a value between 1×10 Pa and 10 Pa. By arranging various vacuum pumps VP in multiple stages, the degree of vacuum can be increased. For example, if a turbo molecular pump is connected to the vacuum vessel 22 and a dry pump is connected to the turbo molecular pump, the inside of the resin vessel 26 can be evacuated to a value between 1×10 Pa and 10 Pa. ―3It is possible to achieve a vacuum of 10 Pa or less. Also, by connecting a mechanical booster pump to the vacuum vessel 22 and connecting a rotary pump to the mechanical booster pump, it is possible to achieve a vacuum of 10 Pa or less. There are various types of vacuum pumps VP, but the one that can evacuate the resin vessel 26 to 10 -3 As long as it is possible to create a vacuum of between 10 Pa and 10 Pa, the type of vacuum is not important.

[0025] In addition, an exhaust gas removal unit GR is connected to the pipe 27. Metal compound or silicon compound gas generated from the first precursor providing unit 11 is supplied to the resin container 26, and permeates the organic-inorganic hybrid material. The metal compound or silicon compound gas that has not permeated is removed by the exhaust gas removal unit GR. The exhaust gas removal unit GR is, for example, an adsorption filter, an activated carbon filter, 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 disposed on the lid 21 or on the vacuum container 22 that comes into contact with the lid 21. The pipes 12 and 14 are attached to the lid 21, and it is preferable that the nozzles of the pipes 12 and 14 are disposed so as to reach the inside of the resin container 26 when the lid 21 is closed.

[0027] Furthermore, a pipe 33 having a nozzle and a valve 38 is attached to the cover 21. An inert gas tank 31 is attached to the pipe 33. An inert gas, for example, nitrogen gas or argon gas, is stored in the inert gas tank 31 in a gaseous state. The inert gas tank 31 is used to return the inside of the chamber 20, which is in a vacuum state, to atmospheric pressure. When air is used instead of the inert gas, the inert gas tank 31 and the like may not be provided.

[0028] A timer, temperature sensors, a computer, and other control devices are not shown in Fig. 1. However, the valve 18, the valve 38, the heater 19, the chamber heater 29, the rotary motor MT, and the vacuum pump VP may be automatically controlled by a control device based on input from the timer and the temperature sensors.

[0029] <<Precursor materials>> The first precursor is a metal compound or a silicon compound (hereinafter, both may be collectively referred to as inorganic substances). Examples of the metal in the metal compound include transition metal compounds such as aluminum compounds, iron compounds, titanium compounds, nickel compounds, copper compounds, and zinc compounds. Examples of the aluminum compound include trimethylaluminum and aluminum chloride. Examples of the iron compound include bis(N,N'-diisopropylbutanamidinate)iron and bis(N,N'-diisopropylpropionamidinate)iron. Examples of the silicon compound include tris(dimethylamino)silane (TDMAS).

[0030] The second precursor may be an oxidizing precursor such as water (H2O) or ozone (O3), or a reducing precursor such as ammonia or hydrogen.

[0031] <<Hardly degradable or biodegradable plastic materials>> The difficult-to-degrade 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 powder with a diameter of 1 mm or less.

[0032] The difficult-to-decompose plastic materials are 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] The biodegradable plastic materials are polylactic acid (PLA), polybutylene succinate (PBS), trihydroxyalkanoic acid (PHA), polyhydroxybutyric acid (PHB), PHBH (copolyester composed of R-3-hydroxybutanoic acid (3HB) and R-3-hydroxyhexanoic acid (3HH)), hemicellulose or its derivative materials.

[0034] Hemicellulose and hemicellulose derivatives are described in detail below. Hemicellulose is amorphous and has very good 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. However, cellulose is highly crystalline and a fibrous substance, so it is not very suitable as the main component of injection molding materials as it is. Lignin is also highly crystalline and has poor fluidity, so it is not very suitable as the main component of injection molding materials.

[0035] Hemicellulose includes mannan, glucan, xylan, and xyloglucan. In this embodiment, these mannan, glucan, xylan, and xyloglucan can be used as the biodegradable amorphous resin material. The best hemicellulose is xylan. The molecular weight of hemicellulose is 1,000 to 100,000, but when it is 30,000 to 100,000, the strength of the plastic molded product when injection molding is performed is good. In addition, hemicellulose may contain 50% cellulose, and there is no problem even if it contains 50% lignin.

[0036] Hemicellulose is characterized by its good biodegradability. It biodegrades faster than cellulose and lignin, and is biodegradable at temperatures above 5°C. When buried in soil, hemicellulose is decomposed by microorganisms in the soil, and is also decomposed by microorganisms at room temperature and in the air, becoming water and carbon dioxide after three months. It is also 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 includes, but is not limited to, hydrogen, nitrogen, an alkyl group, an acetyl group, an acyl group, an aryl group, a phosphonyl group, a propenyl group, an acetonyl group, a carbonyl group, and a carboxyl group. In addition, R1 or R2 may be fluorine, bromine, chlorine, iodine, or a substituent containing these. In addition, R1 or R2 may be an ionized substituent such as a cation or an anion that forms an ionic liquid structure. In addition, n is an integer of 2 or more.

[0038] In the hemicellulose raw material extracted from wood, R1 and R2 are hydrogen. In this embodiment, hemicellulose derivatives are those in which R1 or R2 is replaced with a substituent other than hydrogen. In a representative hemicellulose derivative, R1 and R2 are replaced with acetyl groups. The acetyl group is shown in chemical formula 2. This can be achieved by subjecting the hemicellulose raw material to an acetylation reaction to change the hydrogen to an acetyl group. chemical formula 2 [ka]

[0039] The hemicellulose raw material or the hemicellulose derivative can be melt-kneaded with other difficult-to-degrade plastic materials. The resin pellets thus kneaded can be fed into an injection molding device and the molding die replaced to obtain plastic molded products of various shapes. In this embodiment, a resin material obtained by kneading the hemicellulose raw material or the hemicellulose derivative with other difficult-to-degrade plastic materials is called a hemicellulose mixed resin. When the hemicellulose mixed resin is placed in soil or seawater, the hemicellulose raw material or the hemicellulose derivative itself is mixed with the other difficult-to-degrade plastic materials at the molecular level, so that when the hemicellulose raw material or the hemicellulose derivative is biodegraded by microorganisms, the other difficult-to-degrade plastic materials are also decomposed at the molecular level, and biodegradation progresses. In other words, the hemicellulose raw material or the hemicellulose derivative plays a role of giving biodegradability to the other difficult-to-degrade plastic materials themselves.

[0040] Other difficult-to-decompose plastic materials include, but are not limited to, polymethyl methacrylate (PMMA, acrylic), polycarbonate (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polystyrene (PS), etc. As other resin materials, resins with molecular formulas such as Chemical Formula 3 can also be mixed. chemical formula 3 [ka] Here, R3 represents a substituent, and is not limited to hydrogen, nitrogen, an alkyl group, an acetyl group, an acyl group, an aryl group, a phosphonyl group, a propenyl group, an acetonyl group, a carbonyl group, a carboxyl group, etc. In addition, it may be fluorine, bromine, chlorine, iodine, etc., or a substituent containing them. It may also be an ionized substituent such as a cation or an anion that forms an ionic liquid structure. A and Q each independently represent a single bond or a linking group, and when Q is a linking group, Q may be a group containing an alkylene group, -O-, -NH2-, a carbonyl group, etc. In the case where A is a linking group, A may be a group containing an alkylene group, -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 a chemical reaction of methacrylation or acrylate. When this chemical reaction is applied, a monomer called hemicellulose methacrylate or hemicellulose acrylate is obtained. These monomers have a molecular structure in which a methacryl group or an acryloyl group is attached to the hemicellulose raw material or hemicellulose derivative. However, this is not limited to methacrylation or acrylate. In this embodiment, these are called hemicellulose monomers.

[0042] Hemicellulose polymers are obtained by polymerizing hemicellulose monomers to form resins. Hemicellulose polymers can be given the properties of various resin materials. Polyhemicellulose methacrylate obtained by polymerizing hemicellulose methacrylate has the properties of both hemicellulose and polymethyl methacrylate (PMMA), and is a plastic that is biodegradable, highly transparent, and has good strength. 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>> FIG. 2 is a flow chart illustrating the inorganic substance permeation method. A plastic material is poured into the resin container 26 (step S21). If the resin container 26 is detachable, the worker pours the material into the resin container 26 while it is removed from the rotating container 24. If the resin container 26 is fixed, the worker pours the material into the resin container 26 in the chamber section 20 which is tilted at an angle θ.

[0044] An operator puts the first precursor liquid or solid into the first precursor providing unit 11, and the first precursor providing unit is heated by the heater 19 (step S22). By the heating by the heater 19, the liquid first precursor is evaporated into a gas, and the solid first precursor is sublimated into a gas. The gaseous first precursor is heated to 50°C to 150°C.

[0045] At the same time as or around the time of heating the first precursor, the inside of the chamber 20 is heated by the chamber heater 29, and the resin container 26 is heated to a set temperature (step S23). In the resin container 26, the plastic material is heated to a temperature of 80°C to 150°C. The lid 21 is then sealed by an operator (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 degree of vacuum in the resin container 26 is preferably 10 Pa or less. When the degree of vacuum reaches 10 Pa or less, the vacuum pump VP is stopped and that degree of vacuum is maintained.

[0047] Next, the valve 18 of the pipe 12 is opened, and the first precursor in a gaseous state is supplied into the resin container 26 (step S26). As the first precursor in a gaseous state is supplied, the gas pressure in the resin container 26 increases from 100 Pa to 1000 Pa. When the gas pressure reaches, for example, 500 Pa, the valve 18 is closed, and the supply of the first precursor is stopped (step S27). At the same time, the heating of the first precursor providing unit is stopped (step S28). In the resin container 26, the plastic material is heated, and the resin container 26 is filled with the first precursor in a gaseous state.

[0048] Next, the plastic material is rotated in the resin container 26 (step S29). As the plastic material rotates, the first precursor in a gaseous state permeates from the surface of the material. The molecules of the first precursor that have permeated adhere 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 passed, the first precursor in gaseous state 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 are performed in order, but steps S26 and S29 may start simultaneously.

[0050] Since most of the first precursor in gaseous state permeates the plastic material, almost no first precursor in gaseous state remains in the resin container 26. However, in order to exhaust all of the first precursor in gaseous state from the resin container 26, the vacuum pump VP is started, and the gas of the first precursor that has not permeated is removed by the exhaust gas removal unit GR (step S31).

[0051] Next, the inert gas in the inert gas tank 31 is supplied to the chamber 20 by opening the valve 38 (step S32). When the inert gas reaches atmospheric pressure, the valve 38 is closed. This allows the operator to open the lid 21.

[0052] At the same time or around the same time, the chamber heater 29 is stopped and the chamber 20 is cooled to room temperature (step S33), and the lid 21 is opened and the organic-inorganic hybrid material is taken out of the resin container 26 (step S34).

[0053] The above is an example in which the first precursor permeates the plastic material. Step S40 and thereafter are examples in which the first precursor and the first precursor permeate the plastic material.

[0054] Following step S31, the valve 18 of the pipe 14 is opened, and the second precursor in a gaseous state is supplied into the resin container 26 (step S41). By supplying the second precursor in a gaseous state, the gas pressure in the resin container 26 increases from 100 Pa to 1000 Pa. When the pressure reaches, for example, 500 Pa, the valve 18 is closed, and the supply of the second precursor is stopped (step S42). In the resin container 26, the organic-inorganic hybrid material is heated, and the resin container 26 is filled with the second precursor in a gaseous state.

[0055] Next, the organic-inorganic hybrid material is rotated in the resin container 26 (step S43). As the organic-inorganic hybrid material rotates, the gaseous second precursor permeates from the surface of the material. The molecules of the permeated 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 second precursor in a gaseous state will have sufficiently permeated the organic-inorganic hybrid material, at which point the rotation of resin container 26 is stopped (step S44). In order to exhaust all of the second precursor in a gaseous state from within the resin container 26, the vacuum pump VP is started, and the gas of the second precursor that has not yet permeated is removed by the exhaust gas removal unit GR (step S45).

[0057] Next, the inert gas in the inert gas tank 31 is supplied to the chamber 20 by opening the valve 38 (step S46). When the inert gas reaches atmospheric pressure, the valve 38 is closed. At the same time or before or after this, the chamber heater 29 is stopped and the chamber 20 is cooled to room temperature (step S47). Then, the lid 21 is opened and the hybrid material is taken out from the resin container 26 (step S48). EXAMPLES

[0058] Example 1 is an example in which a cellulose derivative was used as a plastic material. The cellulose derivative was a commercially available cellulose acetate propionate (CAP). The cellulose derivative was mixed with 20% TPP (triphenyl phosphate) as a plasticizer, and the mixture was pelletized using an extruder, a cooling stage, and a pelletizer.

[0059] 1 kg of pellets of this cellulose derivative was fed into the chamber 20 of the inorganic permeation device 100. The temperature of the chamber 20 was set to 120°C. The chamber 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. The chamber 20 was evacuated by a vacuum pump VP, and the chamber 20 was placed in a vacuum state of 5 Pa.

[0060] As the first precursor, trimethylaluminum, which is liquid at room temperature, was placed in the first precursor providing section 11. The liquid trimethylaluminum was heated to 130°C in the first precursor providing 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 pipe 12 was closed. Trimethylaluminum gas was sealed inside the rotating resin container 26 in this way. In the chamber section 20, the pellets were oscillating in accordance with the rotation, and the trimethylaluminum gas penetrated into the pellets, causing a chemical reaction between the cellulose derivative and the trimethylaluminum gas. In particular, a molecular structure in which a metal is bonded to the carbonyl group of the cellulose derivative was formed. The time for which this trimethylaluminum gas was supplied was 1000 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction.

[0061] Then, water vapor (H2O) gas was supplied into the chamber 20 as the second precursor, and water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the pipe 14 was closed. Thus, water vapor gas was sealed inside the rotating chamber 20. In the chamber 20, the pellets oscillated with the rotation, and the water vapor gas penetrated into the pellets. Then, the cellulose derivative and the water vapor gas react chemically. In particular, the carbonyl group of the cellulose derivative was oxidized to a molecular structure where aluminum (Al) was bonded, and the resulting structure was a substituent containing aluminum oxide, which is a metal oxide, such as aluminum oxide or aluminum hydroxide. The time for supplying this water vapor gas was 250 seconds. Then, the chamber 20 was evacuated by the vacuum pump VP, and nitrogen gas was supplied, after which the lid 21 was opened and the pellets were taken out.

[0062] A conceptual diagram of the change from the cellulose derivative to the oxidized organic-inorganic hybrid material is shown in FIG. 4(A). n is an integer of 2 or more, and M represents a metal element. In Example 1, it is aluminum. Furthermore, a test piece was made by injection molding using pellets of this oxidized organic-inorganic hybrid material, and was used together with the pellets for the evaluation of physical properties. The results of the physical property evaluation are shown in FIG. 6. As shown in the evaluation of the physical properties of the cellulose derivative and Example 1, it can be seen that the organic-inorganic hybrid material is excellent in strength, hardness, heat resistance, density, etc., by bonding a metal element to the substituent. EXAMPLES

[0063] Example 2 is an example in which polymethyl methacrylate (PMMA) was used as the difficult-to-decompose plastic material. PMMA was pelletized using an extruder, a cooling stage, and a pelletizer.

[0064] 1 kg of these PMMA pellets was supplied into the chamber 20 of the inorganic substance permeation device 100. The temperature of the chamber 20 was set to 100° C. The rotating container 24 was rotated around the axis 25 at a rotation speed of 20 rpm. The inside of the chamber 20 was evacuated by the vacuum pump VP, and the inside of the chamber 20 was placed in a vacuum state of 5 Pa.

[0065] As the first precursor, trimethylaluminum, which is liquid at room temperature, was placed in the first precursor providing section 11. The liquid trimethylaluminum was heated to 130°C in the first precursor providing 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 pipe 12 was closed. This resulted in the trimethylaluminum gas being sealed inside the rotating resin container 26. In the chamber section 20, the pellets were oscillating in accordance with the rotation, and the trimethylaluminum gas penetrated into the pellets, causing a chemical reaction between PMMA and the trimethylaluminum gas. In particular, a molecular structure was formed in which a metal was bonded to the carbonyl group of PMMA. The time for which this trimethylaluminum gas was supplied was 1000 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction.

[0066] Then, water vapor (H2O) gas was supplied into the chamber 20 as the second precursor, and water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the pipe 14 was closed. In this way, water vapor gas was sealed inside the rotating chamber 20. In the chamber 20, the pellet oscillated in accordance with the rotation, and the water vapor gas penetrated into the pellet. Then, the PMMA and the water vapor gas react chemically. In particular, the part where the metal was bonded to the carbonyl group of PMMA became an oxidized molecular structure. The time for supplying this water vapor gas was 250 seconds. Then, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and the lid 21 was opened and the pellet was taken out.

[0067] A conceptual diagram of the change from PMMA to an oxidized organic-inorganic hybrid material is shown in Figure 4(B). n is an integer of 2 or more, and M represents a metal element. Furthermore, a test piece was made by injection molding using a pellet of this oxidized organic-inorganic hybrid material, and was used together with the pellet for evaluating the physical properties. 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 excellent in strength, hardness, heat resistance, density, etc., due to the metal element being bonded to the carbonyl group. EXAMPLES

[0068] Example 3 is an example in which polylactic acid (PLA) was used as the biodegradable plastic material. PLA was pelletized using an extruder, a cooling stage, and a pelletizer.

[0069] 1 kg of these PLA pellets was supplied into the chamber 20 of the inorganic permeation device 100. The temperature of the chamber 20 was set to 120° C. The rotating container 24 was rotated around the axis 25 at a rotation speed of 80 rpm. The inside of the chamber 20 was evacuated by the vacuum pump VP, and the inside of the chamber 20 was placed in a vacuum state of 10 Pa.

[0070] As the first precursor, trimethylaluminum, which is liquid at room temperature, was placed in the first precursor providing section 11. The liquid trimethylaluminum was heated to 130°C in the first precursor providing 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 pipe 12 was closed. This resulted in the trimethylaluminum gas being sealed inside the rotating resin container 26. In the chamber section 20, the pellets were oscillating in accordance with the rotation, and the trimethylaluminum gas penetrated into the pellets, causing a chemical reaction between the PLA and the trimethylaluminum gas. In particular, a molecular structure was formed in which a metal was bonded to the carbonyl group of the PLA. The time for which this trimethylaluminum gas was supplied was 1000 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction.

[0071] Then, water vapor (H2O) gas was supplied into the chamber 20 as the second precursor, and water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the pipe 14 was closed. Thus, water vapor gas was sealed inside the rotating chamber 20. In the chamber 20, the pellets oscillated in accordance with the rotation, and the water vapor gas penetrated into the pellets. Then, PLA and the water vapor gas react chemically. In particular, the part where the metal was bonded to the carbonyl group of PLA became an oxidized molecular structure. The time for supplying this water vapor gas was 250 seconds. Then, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and the lid 21 was opened and the pellets were taken out.

[0072] A conceptual diagram of the change from PLA to an oxidized organic-inorganic hybrid material is shown in Figure 4(C). Furthermore, a test piece was made by injection molding using pellets of this oxidized organic-inorganic hybrid material, and was used together with the pellets for the evaluation of physical properties. The results of the physical property evaluation are shown in Figure 6. n is an integer of 2 or more, and M represents a metal element. As shown in the physical property evaluation of PLA and Example 3, it can be seen that the organic-inorganic hybrid material has excellent strength, hardness, heat resistance, density, etc., due to the metal element being bonded to the carbonyl group. EXAMPLES

[0073] Example 4 is an example in which PHBH (copolyester composed of R-3-hydroxybutanoic acid (3HB) and R-3-hydroxyhexanoic acid (3HH)) was used as a biodegradable plastic material. PHBH was pelletized using an extruder, a cooling stage, and a pelletizer.

[0074] 1 kg of the PHBH pellets was supplied into the chamber 20 of the inorganic permeation device 100. The temperature of the chamber 20 was set to 110° C. The rotating container 24 was rotated around the axis 25 at a rotation speed of 60 rpm. The chamber 20 was evacuated by the vacuum pump VP, and the chamber 20 was placed in a vacuum state of 10 Pa.

[0075] As the first precursor, trimethylaluminum, which is liquid at room temperature, was placed in the first precursor providing section 11. The liquid trimethylaluminum was heated to 130° C. in the first precursor providing 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 pipe 12 was closed. This resulted in the trimethylaluminum gas being sealed inside the rotating resin container 26. In the chamber section 20, the pellets were oscillating in accordance with the rotation, and the trimethylaluminum gas penetrated into the pellets, causing a chemical reaction between PHBH and trimethylaluminum gas. In particular, a molecular structure in which a metal is bonded to the carbonyl group of PHBH was formed. The time for which this trimethylaluminum gas was supplied was 1000 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction.

[0076] Then, water vapor (H2O) gas was supplied into the chamber 20 as the second precursor, and water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the pipe 14 was closed. Thus, water vapor gas was sealed inside the rotating chamber 20. In the chamber 20, the pellet oscillated in accordance with the rotation, and the water vapor gas penetrated into the pellet. Then, PHBH and the water vapor gas react chemically. In particular, the part where the metal was bonded to the carbonyl group of PHBH became an oxidized molecular structure. The time for supplying this water vapor gas was 250 seconds. Then, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and the lid 21 was opened to remove the pellet.

[0077] The conceptual diagram of the change from PHBH to the oxidized organic-inorganic hybrid material is shown in FIG. 5(A). n and m are integers of 2 or more, and M represents a metal element. Furthermore, a test piece was made by injection molding using a pellet of this oxidized organic-inorganic hybrid material, and was used together with the pellet for the evaluation of physical properties. The results of the physical property evaluation are shown in FIG. 7. As shown in the evaluation of the physical properties of PHBH and Example 4, it can be seen that the organic-inorganic hybrid material is excellent in strength, hardness, heat resistance, density, etc., by bonding a metal 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 mixed with TPP (triphenyl phosphate) as a plasticizer, and the mixture was pelletized using an extruder, a cooling stage, and a pelletizer.

[0079] 1 kg of the hemicellulose derivative pellets was supplied into the chamber 20 of the inorganic permeation device 100. The temperature of the chamber 20 was set to 120° C. The rotating container 24 was rotated around the axis 25 at a rotation speed of 30 rpm. The inside of the chamber 20 was evacuated by the vacuum pump VP, and the inside of the chamber 20 was placed in a vacuum state of 1 Pa.

[0080] As the first precursor, trimethylaluminum, which is liquid at room temperature, was placed in the first precursor providing section 11. The liquid trimethylaluminum was heated to 130°C in the first precursor providing 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 pipe 12 was closed. Trimethylaluminum gas was thus sealed inside the rotating resin container 26. In the chamber section 20, the pellets were oscillating in accordance with the rotation, and the trimethylaluminum gas penetrated into the pellets, causing a chemical reaction between the hemicellulose derivative and the trimethylaluminum gas. In particular, a molecular structure in which a metal is bonded to the substituent of the hemicellulose derivative was formed. The time for which this trimethylaluminum gas was supplied was 1000 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction.

[0081] Then, water vapor (H2O) gas was supplied into the chamber 20 as the second precursor, and water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the pipe 14 was closed. Thus, water vapor gas was sealed inside the rotating chamber 20. In the chamber 20, the pellets oscillated in accordance with the rotation, and the water vapor gas penetrated into the pellets. Then, the hemicellulose derivative and the water vapor gas react chemically. In particular, the part where the metal was bonded to the substituent of the hemicellulose derivative became an oxidized molecular structure. The time for supplying this water vapor gas was 250 seconds. Then, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and the lid 21 was opened and the pellets were taken out.

[0082] A conceptual diagram of the change from the hemicellulose derivative to the oxidized organic-inorganic hybrid material is shown in Figure 5(B). n is an integer of 2 or more, and M represents a metal element. Furthermore, a test piece was made by injection molding using pellets of this oxidized organic-inorganic hybrid material, and was used together with the pellets for the evaluation of physical properties. The results of the physical property evaluation are shown in Figure 7. As shown in the evaluation of the physical properties of the hemicellulose derivative and Example 5, it can be seen that by bonding a metal element to the substituent, the organic-inorganic hybrid material is superior in strength, hardness, heat resistance, density, etc. EXAMPLES

[0083] Example 6 is an example in which a cellulose derivative and a hemicellulose derivative were used in a ratio of 50:50 as the plastic material and the biodegradable plastic material. The cellulose derivative and the hemicellulose derivative were mixed and the mixture was pelletized using an extruder, a cooling stage, and a pelletizer. The hemicellulose derivative acts as a plasticizer for the cellulose derivative.

[0084] 1 kg of pellets of the cellulose derivative and hemicellulose derivative were supplied into the chamber 20 of the inorganic permeation device 100. The temperature of the chamber 20 was set to 90° C. The rotating container 24 was rotated around the axis 25 at a rotation speed of 40 rpm. The inside of the chamber 20 was evacuated by the vacuum pump VP, and the inside of the chamber 20 was placed in a vacuum state of 10 Pa.

[0085] As the first precursor, trimethylaluminum, which is liquid at room temperature, was placed in the first precursor providing section 11. The liquid trimethylaluminum was heated to 130°C in the first precursor providing 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 pipe 12 was closed. Trimethylaluminum gas was thus sealed inside the rotating resin container 26. In the chamber section 20, the pellets were oscillating in accordance with the rotation, and the trimethylaluminum gas penetrated into the pellets, and the cellulose derivatives and hemicellulose derivatives reacted chemically with the trimethylaluminum gas. In particular, a molecular structure was formed in which a metal was bonded to the substituent of the cellulose derivatives and hemicellulose derivatives. The time for which this trimethylaluminum gas was supplied was 1000 seconds. After that, the chamber section 20 was evacuated by the vacuum pump VP to remove the trimethylaluminum gas and the gas generated by the chemical reaction.

[0086] Then, water vapor (H2O) gas was supplied into the chamber 20 as the second precursor, and water vapor was supplied until the gas pressure reached 250 Pa, after which the valve 18 of the pipe 14 was closed. Thus, water vapor gas was sealed inside the rotating chamber 20. In the chamber 20, the pellets oscillate in accordance with the rotation, and the water vapor gas penetrates into the pellets. Then, the cellulose derivatives and hemicellulose derivatives react chemically with the water vapor gas. In particular, the part where the metal is bonded to the resin is oxidized to form a molecular structure. The time for supplying this water vapor gas was 250 seconds. Then, the chamber 20 was evacuated by the vacuum pump VP, nitrogen gas was supplied, and the lid 21 was opened to remove the pellets.

[0087] The conceptual diagram of the change 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). In addition, a test piece was made by injection molding using pellets of this oxidized organic-inorganic hybrid material, and was used together with the pellets for the evaluation of physical properties. The results of the physical property evaluation are shown in Figure 7. As shown in the evaluation of the physical properties of the mixture and Example 6, it can be seen that the organic-inorganic hybrid material is superior in strength, hardness, heat resistance, density, etc., due to the substitution of the substituents with metal elements. [Industrial Applicability]

[0088] By using the inorganic infiltration device or inorganic infiltration method, it is possible to manufacture organic-inorganic hybrid materials with dramatically improved strength and heat resistance. In particular, an example of manufacturing pellet-shaped organic-inorganic hybrid materials used in injection molding, etc. has been shown, but it can also be applied to the manufacture of fibrous, particulate, or powdered organic-inorganic hybrid materials. In addition, in all of Examples 1 to 6, the organic-inorganic hybrid materials were oxidized to change them into a metal oxide structure, but oxidation is not necessarily required.

[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 or food containers such as food trays to industrial parts such as electrical appliances or automobile parts. 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…Precursor supply section 11: first precursor providing unit, 13: second precursor providing unit 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: Rotary motor, GR: Exhaust gas removal unit, VP: Vacuum pump 100...Inorganic infiltration device

Claims

1. a first step of introducing a first gas precursor into a chamber portion with a plastic material disposed inside the chamber portion; a second step of introducing a second gas precursor into the chamber portion with the plastic material disposed inside the chamber portion after the first step, At least a portion of the first gas precursor penetrates into the interior of the plastic material, and the first gas precursor is oxidized by the second gas precursor within the plastic material. A manufacturing method for producing hybrid materials.

2. a heating step of heating the plastic material placed in the chamber; a vacuum step of bringing the chamber into a vacuum state of 10 Pa or less; an inorganic substance providing step of providing a gaseous inorganic substance into the chamber; a first shaking step of shaking the plastic material in the chamber; an exhaust step of exhausting the chamber portion after the first swinging step; an oxidation precursor providing step of providing an oxidation precursor into the chamber after the exhausting step; a second shaking step of shaking the plastic material in the chamber after the oxidation precursor providing step, A method for producing a hybrid material, comprising the steps of: permeating the inorganic substance in a gaseous state into the plastic material; and producing a hybrid material in which the inorganic substance is oxidized.

3. The heating step heats the plastic material to a temperature of 80°C to 150°C, The method according to claim 2 , wherein the inorganic substance providing step provides a gaseous inorganic substance to the vacuum chamber to set the vacuum chamber to a pressure of 100 Pa to 1000 Pa.

4. a chamber portion for receiving a plastic material; a rotating means for rotating the chamber portion and agitating the plastic material; a chamber heater that heats the chamber portion and heats the plastic material; a vacuum pump that creates a vacuum state of 10 Pa or less inside the chamber; a first precursor providing unit that provides a gaseous inorganic substance into the chamber; a second precursor providing unit that provides a gaseous oxidation precursor into the chamber unit; An inorganic infiltration device for producing a hybrid material, which creates a vacuum in the plastic material in the chamber, then provides a gaseous inorganic material in the chamber, heats and agitates the plastic material, and further provides an oxidation precursor in the chamber.

5. 5. The inorganic matter permeation device according to claim 4, further comprising an inert gas tank for supplying an inert gas into the chamber portion.

6. The plastic material includes a hardly degradable plastic or a biodegradable plastic, The inorganic substance permeation device according to claim 4 or 5, wherein the inorganic substance includes a metal compound or a silicon compound.

7. An injection-moldable hybrid material produced by the method of claim 1 or 2.

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