Resin containing environmentally degradable ingredient, and molded article using the resin

Abstract

To provide an optimal production method for an environmentally friendly resin produced using an environmentally degradable ingredient, and an optimal processing method using the resin.SOLUTION: The present invention provides means for producing an injection-molded article or an extrusion-molded article using an environmentally friendly resin.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for producing a resin containing components to be decomposed in a natural environment and a molded article using the resin containing environmentally decomposable components, and provides means for reducing the environmental load and solving environmental problems.

Background Art

[0002] Patent Document 1 discloses a method for producing a resin for molding containing paper powder, in which the paper powder having a particle size of 50 μm or more and 150 μm or less is bound with a thermoplastic resin. However, there is no description regarding molding using the resin for molding containing paper powder, for example, foam molding, hollow molding, pressure-air molding, etc. in injection molding. Examples of the silane coupling agent, higher fatty acids such as stearic acid, maleic acid-modified polyolefin, and olefin-maleic anhydride copolymer are exemplified for the paper powder in order to enhance the kneadability of the resin. Although maleic acid-modified polyolefin and olefin-maleic anhydride copolymer show high compatibility (solubility) with the olefin resin to be blended, no specific implementation means are shown.

[0003] Patent Document 2 discloses that, similar to Patent Document 1, fine paper powder (however, the average particle size is changed to 10 μm to 50 μm) is bound using a thermoplastic resin in the same manner. In particular, it discloses that a compound having a maleic anhydride group is contained in an amount of 0.3 to 5 parts by weight. There is a description that the compatibility (solubility) is enhanced by containing a compound having a maleic anhydride group, but there is no specific explanation on how to use the compound having a maleic anhydride group. From the patent document, it only shows a process of simply putting paper powder, for example, polyolefin, and a compound having a maleic anhydride group into a twin-screw extruder and pelletizing. Although a compound having a maleic acid group is shown, no disclosure of halogenated polyolefin typified by chlorinated polyolefin is shown.

[0004] Patent Document 3 describes a method for producing a resin containing fine paper powder with an average particle size of 10 μm to 100 μm. Similar to Patent Document 2, it describes a compound having a maleic acid group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Disclosure of the Invention

Problems to be Solved by the Invention

[0006] These days, environmental pollution of plastic molded products has become a problem. Provided are a method for producing a molding resin mainly composed of an environmentally degradable component that easily decomposes in nature, and a processing method for a molded product using such resin. Means for Solving the Problems

[0007] Configuration, Action, and Effects of the Invention

[0008] (Configuration) The first invention according to claim 1 is such that an environmentally degradable substance and a maleic acid-modified polyolefin are mixed, and the maleic acid-modified polyolefin is supported on the powder surface of the environmentally degradable substance. (Action and Effect) In the first invention described in the claims, since maleic acid-modified polyolefin is supported on the surface of the powder of the environmentally degradable substance, the maleic acid-modified polyolefin exhibits high compatibility (solubility) with the polyolefin. Therefore, using the polyolefin obtained by melt-kneading the environmentally degradable substance containing the maleic acid-modified polyolefin and the polyolefin using a single-screw or multi-screw extruder, the resin for molding processing containing the environmentally degradable substance shows high compatibility (solubility) between the environmentally degradable component and the polyolefin due to the maleic acid-modified polyolefin. As a result, the physical strength of the obtained molding resin is higher than that when the maleic acid-modified polyolefin is not used.

[0009] (Configuration) In the case of the second invention described in claim 2, a resin for molding processing composed of an environmentally degradable substance, a maleic acid-modified polyolefin, and a polyolefin having compatibility (solubility) with the maleic acid-modified polyolefin. (Function and Effect) In the case of the second invention described in claim 2, since the maleic acid-modified polyolefin having compatibility (solubility) with the polyolefin is supported on the surface of the environmentally degradable component, using the resin for molding processing, a resin molded product obtained by molding has strength sufficient for use.

[0010] (Configuration) The third invention described in claim 3 is a resin molded product composed of an environmentally degradable component, maleic acid polyolefin, and polyolefin. (Function and Effect) In the third invention described in claim 3, the maleic acid-modified polyolefin showing high compatibility (solubility) with the polyolefin of the molding resin binds the environmentally degradable component and the polyolefin, so a molded product with high strength can be obtained.

[0011] (Configuration) In the fourth invention described in claim 4, the maleic acid-modified polyolefin described in claims 1 to 3 is changed to a chlorinated polyolefin that also shows high compatibility (solubility) with the polyolefin. (Function and Effect) Since chlorinated polyolefin exhibits high compatibility (solubility) with polyolefin, the chlorinated polyolefin binds the environmental degradation component and the polyolefin, so that a molded article with high strength can be obtained.

[0012] (Constitution) In the fourth invention according to claim 4, the maleic acid-modified polyolefin described in claims 1 to 3 is similarly made into a chlorinated polyolefin that exhibits high compatibility (solubility) with polyolefin. (Function and effect) Since chlorinated polyolefin exhibits high compatibility (solubility) with polyolefin, the chlorinated polyolefin binds the environmental degradation component and the polyolefin, so that a molded article with high strength can be obtained.

[0013] (Constitution) In the fifth invention according to claim 5, the environmental degradation component and the binding resin are replaced with a styrene-based resin, or a polymer alloy or polymer blend mainly composed of a styrene-based resin. (Function and effect) In the fifth invention according to claim 5, since it is a styrene-based resin, or a polymer alloy or polymer blend mainly composed of a styrene-based resin, the environmental degradation component and the styrene-based resin, or a polymer alloy or polymer blend mainly composed of a styrene-based resin are bound, so that a molded article with high strength can be obtained.

Brief description of the drawings

[0014]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0015] (Definition of Terms) First, the terms used in the present invention are defined. "Environmental resin" is a general term for a thermoplastic resin or a thermosetting resin containing the environmentally degradable component described below for the purpose of reducing the environmental load, and the content of the environmentally degradable component is 10% by weight (wt.%, %W / V) or more. When containing 10% W / V of the environmentally degradable component, for example, when it enters the soil, it is first biodegradated by microorganisms (bacteria, etc.), and since the remaining resin component is micronized, the decomposition rate by microorganisms is considered to be fast.

[0016] (Thermoplastic Resin) The resins (resins) that can be used in the present invention include all thermoplastic resins and thermosetting resins. First, the thermoplastic resin is described. The thermoplastic resins that can be used in the present invention include styrene resins typified by AS (polyviny cyanide), ABS (acrylonitrile-styrene-butadiene terpolymer), PS (polyphenylated vinyl), HIPS (high-impact PS), modified PPO (modified PPE); olefin resins typified by PE (polyhydrogenated vinyl), PP (polymethylated vinyl), polyolefin (polyalkylated vinyl); ester resins such as polyvinyl chloride (PVC), polyvinyl alcohol (PVAL), modified PVAL, polyvinyl butyral, polyvinyl acetal, PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate); amide resins such as 6-PA (polyamide), 6,6-PA; nitrocellulose, CMC (carboxymethyl cellulose), polylactic acid, polycaprolactone, polyhydroxyalkanoate, polyglycolic acid, casein, modified starch (starch), modified cellulose, low-degree polysaccharide derivatives (low-degree cellulose acetate), styrene-modified acrylic resins, acrylic resins, halogenated PPs typified by chlorinated polyolefins, halogenated PEs typified by chlorinated PEs, and polyolefins (PP, PE, etc.) modified with acids such as maleic acid. In the present invention, thermoplastic resins that are easily decomposed by biodegradation (decomposition by microorganisms), photodegradation, hydrolysis, oxidation, etc. are particularly preferred. These thermoplastic resins may also be in the form of a polymer alloy or a polymer blend. When forming a polymer alloy or a polymer blend, it is preferable that the resins are compatible with each other, but it is not necessary for them to be compatible if the strength of the molded article is not required.

[0017] (Thermosetting resin) Examples of the thermoplastic resins that can be used in the present invention include epoxy resins, phenolic resins, urea resins, etc. They can be used alone as in the case of the above-mentioned thermoplastic resins, or two or more of them can be mixed.

[0018] (Resins decomposed by microorganisms, etc.) Most of the above-mentioned thermoplastic resins and thermosetting resins will undergo biodegradation and the like if it takes a long time, but PET, PEN, polylactic acid, etc. have a fast rate of biodegradation and the like. If PP is also made finer, the rate of biodegradation will increase. A resin composition composed of environmental degradation components such as pulp powder, paper pieces, and paper powder, maleic acid-modified polyolefin, and PP will first have the pulp powder undergo biodegradation and the like and be decomposed into carbon dioxide gas and water. Next, the maleic acid modification will undergo biodegradation and the like. Finally, PP will undergo biodegradation and the like and be decomposed into carbon dioxide gas and water, so the environmental load is small. Similarly, styrene-modified acrylic resin and methoxymethylated PA also undergo biodegradation and the like in the same way. Naturally, nitrocellulose, cellulose acetate, CMC, polylactic acid, etc. have a faster rate of biodegradation and the like than PP, ABS, etc.

[0019] 〔Environmental degradation component {biomass}〕 In the present invention, the molded article contains substances that are decomposed by biodegradation, photodegradation, hydrolysis, thermo-oxidative decomposition, oxidative decomposition, ultraviolet decomposition, radiation decomposition, etc. This is called "environmental degradation component" and "environmental degradation material". Examples of environmental degradation components include paper pieces, pulp powder, for example, wood powder called sawdust (garbage), tree bark, rice straw (rice straw), straw of wheat, barley, rye, etc. (wheat straw), cotton, cotton, cellulose, konjac, seed coat of cacao beans, coffee grounds, eggshells, tempura scraps, buckwheat flour, bread, bread flour, soybeans, beans, okara, rapeseed, sake lees, koji, tea leaves, glutinous rice, glutinous wheat, mixed grain rice, brown rice, sugar, salt, mushrooms, meat, beef, pork, chicken, mutton, horse meat, soy meat, alternative meat, livestock products, livestock processed products, powdered milk, dairy products, fertilizers, feeds, production food ingredients (aquatic, agricultural), fish meal, fish, fish scales, fish bones, shells, vegetables, fruits, and their skins, leaves, seeds, cores, etc., food residues, discarded food, out-of-specification food, out-of-specification external materials, waste materials, waste oil, sand, mud, soil, leaves, flowers, charcoal, bamboo, weeds, titanium oxide, calcium carbonate, carbon black, pulp powder, lignocellulose, cellulose fine powder, cellulose nanofiber, hemp, cardboard, human hair, spirulina, amino acids, proteins, vitamins, sugarcane, starch, starch ChiExamples thereof include animal-derived bone meal, leather powder, etc. These can also be used in the present invention. Among thermoplastic resins, PET, PVAL, styrene-modified acrylic resin, maleic acid-modified polyolefin, halogenated polyolefin, etc. are easily biodegradable (decomposed by microorganisms). Since these mono-components derived from plants and animals are difficult to use as they are, they are used after being made fine (powdered). To make them fine, a rotary cutter or the like is used for fine pulverization, and then a dry jet mill, fine powder mill, roller mill of a fine crusher, etc. are used for further fine pulverization. After passing through processes such as sieving, the particle size (size) is selected. In addition to the physical means shown above, saccharification fermentation by microorganisms may also be used for fine pulverization. Fine pulverization using chemical agents is also possible. The environmental decomposition components may be used alone or in combination of several mono-components. The size (particle diameter) is not so important as long as it is 1,000 microns (μm) or less. Even if it is 1,000 μm or more, for example, it can be made into multiple layers by overlapping. The layers are bonded together using a thermoplastic. If the addition amount and content of the environmental decomposition components of the present invention are 10% W / V in the final molded product, the decomposition rate in nature will be high. If it is 51% W / V, it corresponds to a molded product that is environmentally friendly as required in the current industry.

[0020] (Pulp·Powder) The means for manufacturing pulp powder, which is an environmentally degradable component used in the present invention, will be described. It doesn't matter whether it is hardwood or softwood, but taking wood as an example, a chemical solution mainly composed of caustic soda {sodium hydroxide (NaOH)} and sodium sulfide is added to the chips obtained by pulverizing the wood, and heated at about 200°C or about 170°C to elute lignin and part of hemicellulose. This is called digestion or cooking. The chemical solution concentration and heating time vary depending on the type of raw material and the use of the pulp, and there are also some that can be pulped within 2 hours. After extracting cellulose in this way, it is pulverized. The pulp thus obtained is washed with water to remove the chemical solution, and then pulverized and refined without drying. It may also be refined after drying. The pulp powder thus obtained is one of the useful materials of the environmentally degradable substances used in the present invention, but it is not limited to pulp powder.

[0021] The process of manufacturing pulp powder using wood has been described, but it is not limited to wood, and it may also be the seed coat of cacao beans, coffee grounds, bamboo, grass, fallen leaves, etc. Citation Document 1 to Citation Document 3 state that paper powder is used and that it is an invention limited to paper powder. Since the paper powder recovered from the market is simply refined by physical force, in some cases, the cellulose fibers are cut and severed, so of course the strength is reduced. On the other hand, in the present invention, since pulp before making paper is used, there is no such cutting of cellulose using paper powder.

[0022] For example, many of the printed papers issued in the office are shredded, so the cellulose fibers are cut, making it difficult to recycle them as waste paper. Citation Document 1 to Citation Document 3 disclose means for binding paper powder made from waste paper with olefin resins, etc. as described above, but the present invention is different in that it uses a long pulp component in cellulose fibers instead of paper powder from waste paper. Of course, the pulp powder may be something unsuitable for paper manufacturing that is discarded as waste by a paper company.

[0023] (Compatibilizer) Since the environmental degradation component and the thermoplastic resin do not have much binding force, a compatibilizer is used to increase the binding force between the environmental degradation component and the thermoplastic resin. When the thermoplastic resin is an olefin resin typified by PP, effective compatibilizers are maleic acid-modified polyolefins and olefin - maleic anhydride copolymers. When the thermoplastic resin is a styrene resin typified by ABS, a polycarbonate ester typified by PC, or PVC (polyvinyl chloride), a styrene-modified acrylic resin is used, and when the thermoplastic resin is PA, a methoxymethylated polyamide is used. Since the addition amounts of these compatibilizers vary depending on the desired properties of the resin, the exact addition amounts are not shown.

[0024] (Reinforcing agent component, etc.) If necessary, a reinforcing agent is added. Additives include glass (glass) fibers, glass beads, carbon fibers, talc, carbon cal (calcium carbonate), calcium sulfate, stone powder, carbon powder, heat stabilizers, light absorbers, ultraviolet inhibitors, etc. Examples of properties that can be exemplified include rigidity and specific gravity (density). Naturally, these are also originally just substances that exist in nature and are simply refined into fine particles by physical means, so they are naturally environmentally friendly components. The non-biodegradable components remaining after the biodegradation of the environmental resin return to nature and become components that make up nature, so they do not have a great impact on the environment. Since pulp powder is fine, simply binding it with resin alone does not reach the desired strength. In this case, if cotton, thread, or cellulose nanofibers of the environmental degradation component are mixed, the strength can be increased. Naturally, the addition amount can be increased until the desired value is reached.

[0025] (Joining, binding) Environmental degradation components alone cannot be joined to each other, so other substances are used for joining. The main substances used for joining are thermoplastic resins and thermosetting resins, which are collectively called joining resins, also known as crimping resins, fusion resins, or adhesion resins. The case where the environmental degradation component is pulp powder and the bonding resin is PP will be described. When 51% W / V of pulp powder and 49% W / V of PP are mixed and melt-kneaded using a kneader, a short-axis extruder, or a multi-axis extruder and pelletized, PP acts as a bonding resin that bonds the pulp powder. In this case, since PP is once heated and melted, this case is particularly referred to as "melt bonding". Since the polyolefin modified with maleic acid is soluble in a solvent, the method of bonding pulp powder using a solvent-based varnish (a solution in which the resin is dissolved in a solvent) of maleic acid-modified polyolefin or an aqueous varnish obtained by suspending or emulsifying the solvent-based varnish in water is called "solution bonding". Patent Documents 1 to 3 disclose that a compound having a maleic anhydride group is contained at 0.3 to 55 W / V. There is a description that the compatibility (solubility) is enhanced by containing a compound having a maleic anhydride group, but no specific method of use is disclosed at all. The present invention describes specific means for modifying pulp powder using maleic acid-modified polyolefin. Originally, PP is a mono (resin) insoluble in a solvent, so it is necessary to modify it by some means to make it soluble in a solvent. Conventionally, halogens such as chlorine have been used. When halogens are used, a mono soluble in an organic solvent can be made, but not in an aqueous system (emulsion type). When regulations on environmental problems, particularly VOC (Volatile Organic Compounds), were started, the demand for providing aqueous mono increased. Therefore, maleic acid-modified mono (polyolefins typified by PE and PP) can be made not only in a solvent system but also in an aqueous system other than a halogenated one. The use of maleic acid-modified polyolefin includes applications as an adhesive for PP molded products. Even if an attempt is made to apply a two-component urethane paint to a PP molded product, sufficient adhesion of the paint film cannot be obtained. Therefore, if maleic acid-modified polyolefin is once applied to the PP molded product to make a primer, sufficient adhesion of the paint film of a heterogeneous two-component urethane paint can be ensured. Thus, maleic acid-modified polyolefin has the effect of enhancing the bonding force between PP and other mono.

[0026] Heat an aqueous solution (emulsion) containing maleic acid-modified polyolefin to about 40 °C, add the pulp powder described above, stir, impregnate the pulp powder with maleic acid-modified polyolefin, and then separate the aqueous solvent and the pulp powder containing maleic acid-modified polyolefin by filtration, centrifugation, etc., and dry to obtain a bulk (mass) in which maleic acid-modified polyolefin and pulp powder are mixed. Crush the bulk obtained in this way, mix it with PP, and pelletize it using a single (1)-screw extruder or, if necessary, a multi-screw (e.g., 2-screw) extruder. Since the pulp powder has been pretreated with maleic acid-modified polyolefin and has been plasticized in advance by maleic acid-modified polyolefin, it can be pelletized sufficiently even with a single-screw extruder. If necessary, one or more damages may be provided on the screw of the short-screw extruder to enhance the kneading property. In the case of a multi-screw extruder, the rotation direction of the screw is generally the same rotation (same direction), but it may also be reverse rotation (opposite direction). Of course, damages may be provided to enhance the kneading property. Also, make the flight (the groove of the screw) shallower to increase the compression ratio, or increase the ratio of the L (length) / D (diameter) of the screw. This can also be implemented with the screw of a single-screw extruder. Naturally, if the L / D is large and the flight is a double flight, the kneading property will be greatly improved.

[0027] The ignition point (ignition temperature) of paper is 450 °C for high-quality paper, 290 °C for newsprint, and about 400 °C - 470 °C for wood. Compared with maleic acid-modified polyolefin and the binding resin PP, it is higher, but if discoloration or burning is a concern, it can be avoided by replacing the air {oxygen (O2) that causes discoloration and burning and has a supporting combustion property} in the extruder hopper with inert nitrogen gas (N2). In practice, nitrogen gas (PSA or a product obtained by extracting nitrogen in the air using a separation membrane is sufficient) can be continuously introduced into the hopper.

[0028] The production of the above PP pellets may also use halogenated polyolefins such as halogenated PE or halogenated PP instead of maleic acid-modified polyolefin.

[0029] The case where the binding resin is AS, ABS, PS, HIPS, modified PPO, PC, etc. will be described. In this case, a styrene-modified acrylic resin may be used instead of the maleic acid-modified polyolefin. Styrene-modified acrylic resins are manufactured and sold, for example, under the trade name Acrylic (product name) by DIC Corporation, both in solvent-based and water-based systems. Similar to the case of maleic acid-modified polyolefins, pulp powder is immersed in these solutions (varnishes), dried, pulverized, and resin pellets showing thermoplasticity containing environmentally decomposable components are obtained using AS, ABS, PS, HIPS, modified PPO, PC, etc. as the binding resin with a single-screw or multi-screw extruder.

[0030] In addition to pulp powder, cocoa bean husks or coffee grounds may be used, or a mixture of these may be used. These may be used in combination with pulp powder.

[0031] Environmental decomposition components will be described using pulp powder for solution bonding. After putting a water (emulsion)-based varnish of maleic acid-modified polyolefin into pulp powder and stirring well, without adding any PP, a mono that has been dried and pelletized is heated and melted, and then, for example, put into a mold and heated (Heat) and compressed (Press) to form a shape (block). Of course, a mono using PP as the binding resin may also be used.

[0032] (Support of maleic acid-modified polyolefin, etc. on environmentally decomposable substances) Put pulp powder into a heatable and sprayable rocking mixer made by Aichi Machine Co., Ltd., rock while spraying a solvent-based maleic acid-modified polyolefin varnish, rotate, heat, and support maleic acid-modified polyolefin on the surface of the pulp powder. Mix the pulp powder carrying maleic acid-modified polyolefin with PP, melt-knead using an extruder or the like, and pelletize. Compared with the case of bonding only pulp powder and PP, maleic acid-modified polyolefin has a strong adhesive force to both pulp powder and PP, so the physical strength and mechanical strength of the resin are higher than when not using maleic acid-modified resin. In addition to pulp powder, the environmentally decomposable components exemplified above may be used. The resin may be not only PP but also PE, or a mixture of PP and PE may be used. In addition to maleic acid-modified polyolefin, halogenated polyolefin and halogenated PE can also be used. As described above, styrene-modified acrylic resin and methacrylated PA may be used.

[0033] (Coloring) When coloring of the raw material pellets is required, dyes and pigments are used for pelletization. Otherwise, coating may be performed. The purpose of coating is that since some of the environmentally decomposable components have high hygroscopicity and water absorbency, they cannot be used in liquids such as food containers and drinking water cups. Therefore, to improve moisture resistance and water resistance, the surface is coated by some method. One of the methods is coating. Air spray coating is common for coating, but wiping coating, brush coating, spin casting, etc. can also be performed. In the case of AS and ABS, the resin that forms the main component of the paint is AS or ABS varnish dissolved using organic solvents such as MEK (n-butanone) and ethyl acetate, or a paint mainly composed of a styrene-modified acrylic resin is used for painting. In the case of PS, HIPS, and modified PPO, a varnish with the above AS as PS or HIS, or a paint mainly composed of a styrene-modified acrylic resin is used for painting. In the case of PP, it is painted with a paint for PP mainly composed of a halogenated polyolefin or a maleic acid-modified polyolefin. After painting with a paint for PP mainly composed of a halogenated polyolefin or a maleic acid-modified polyolefin, if necessary, it may be painted with a two-component urethane paint.

[0034] Instead of painting, the surface may be laminated. In the case of injection molding, insert molding is mainly used for the lamination method. In the case of PET, the PET film is placed in the gap between the fixed side and the movable side of the injection molding die, the die is closed, and when the environmental resin is injected, the PET is heated by the temperature of the injected resin and is pressed against the fixed side by the force of filling the environmental resin, and heat-seals to the surface of the molded product using the environmental resin. To increase the bonding strength, an adhesive can be applied to the surface of the PET film in advance if necessary to increase the adhesive strength between the molded product and the lamination.

[0035] When the PET film is placed in the injection molding die and the environmental resin is injected, and the PET is attached to the surface of the injection molded product, there is excess PET film remaining around the circumference of the molded product, so this excess PET film is cut off. Means (PIM{( P ress I njection M ild) shown in Japanese Patent Application Laid-Open Nos. Sho 61-224223, Sho 62-211322, Sho 63-11873, Hei 1-184522, etc. may be used. After heating the PET film and using air pressure or vacuum pressure, for example, on the fixed side which is the design surface, pressure-air forming or vacuum forming is performed. Then, for example, a Thomson type or a press type die is incorporated into the injection molding machine die, cut using it, and then the environmental resin may be injected.

[0036] Using a multi-axis extruder, tableware such as bowls and plates can be made by drawing using pressure-air forming or vacuum forming from a sheet obtained by laminating PET on one side or both sides of an environmental resin. Of course, this can also be carried out using PP or PE instead of PET.

[0037] (Applicable products) All molded products using thermoplastic resins or thermosetting resins are applicable to the present invention. In particular, food packaging materials, food containers, food trays, vegetable and fruit bags, shopping bags, garbage bags, handbags, cutlery, amenities, films, fibers, building materials, electronic devices, electronic components, transportation, automobiles, automotive parts, agricultural materials, agricultural films, fishing nets, fishing-related items, sanitary products, pallets, tanks, bottles, stationery, packaging materials, and cushioning materials are exemplified. Considering environmental issues, it is expected that applying these molded products will have significant effects.

[0038] (Molding processing method) For the processing of resins containing environmentally degradable components in the present invention, methods such as injection molding processing, injection foam molding processing, injection blow molding, injection pressure-air molding processing, extrusion molding processing, vacuum molding processing, block molding processing, and calendar molding processing can be mentioned.

Example

[0039] (Manufacture of environmental resin) When sawing wood that was difficult to process at a lumber mill, the wood powder produced was sieved using a sieve to separate it into particles with a particle size of 1,000 μm or less. 49% W / V of PP resin powder was mixed with 51% W / V of wood powder with a particle size of 1,000 μm or less using a Henschel mixer, and the mixed powder was melt-kneaded using a twin-screw extruder. The extruded strands were air-cooled without being submerged in water for cooling and without absorbing water, and then cut using a pelletizer to produce ePlas001 containing 51 W / V of wood powder and having a binder resin (a resin component that connects environmentally degradable components, such as a thermoplastic resin or a thermosetting resin) of PP. A hole was drilled in the heating cylinder of the extruder, and 2% W / V of an emulsion of maleic acid-modified polyolefin {Arrow Base DA-1010 (trade name)} manufactured and sold by Unitika Ltd. was injected into the resin that was melting and plasticizing. The wood powder was impregnated with maleic acid-modified polyolefin, and the surface of the wood powder was supported by maleic acid-modified polyolefin, enhancing the binding property with PP. The same effect can be achieved by using halogenated polyolefin instead of maleic acid-modified polyolefin (Arrow Base DA-1010). If the powder of the environmentally degradable component that does not show any thermoplasticity at all is supported by maleic acid-modified polyolefin, styrene-modified acrylic resin, etc., since maleic acid-modified polyolefin, styrene-modified acrylic resin, and methoxymethylated polyamide show thermoplasticity, even if a large amount of the powder of the environmentally degradable component is included, it shows thermoplasticity. Therefore, when melt-kneading with ordinary thermoplastic resins such as PP, ABS, PA, etc., it can be easily kneaded and pelletized with a single-screw extruder by applying damage without using a multi-screw extruder with high kneading property. If the pellets thus selected are further highly kneaded, for example, in injection molding processing, when molding a molded product, damage can be applied to the screw and a mono can be used. This part, that is, the environmentally degradable component that does not show thermoplasticity, is immersed in a solution containing a substance showing thermoplasticity, dried, and the obtained mass (bulk) is pulverized. The pulverized mono contains the substance showing thermoplasticity (maleic acid-modified polyolefin, styrene-modified acrylic resin, methoxymethylated polyamide, etc.), so it shows thermoplasticity. The pulverized mono thus obtained may be bound with thermoplasticity. This is the difference in the manufacturing method part from Patent Document 1, Patent Document 2, and Patent Document 3.

Example

[0040] (Manufacture of environmental resin) While heating at 50 °C, 20% W / V of maleic acid-modified polyolefin ((Arrow Base DA-1010) was used with respect to 80% w / V of pulp powder. Using a rocking mixer (Figure 2), the maleic acid-modified polyolefin on the surface of the pulp powder was supported, and the inside was impregnated with the maleic acid-modified polyolefin and dried to show compatibility (solubility) with PP. Pulp powder that binds well with PP was obtained.

[0041] This pulp powder is pelletized using a single-screw extruder with damage incorporated into the screw, using 60% W / V of this pulp powder and 40% W / V of PP. In order to improve the melt kneading property during pelletization, holes were made in the heating cylinder of the single-screw extruder, and 2.5% W / V of ethanol (C2H5OH) was continuously injected into the molten resin containing the pulp powder of the environmental decomposition component in the heating cylinder using a plunger pump to lower the viscosity of the resin during melt kneading in the heating cylinder and enhance the kneading property. Instead of ethanol, propanol (C3H7OH) or a mixed solution of ethanol and propanol may also be used. Instead of ethanol, water (H2O) or a mixture of ethanol and water, for example, 50:50, may also be used.

[0042] A solution of chlorinated polyolefin may be used instead of the maleic acid-modified polyolefin. When the binding resin is a styrene-based resin such as ABS, a styrene-modified acrylic resin is used. The maleic acid-modified polyolefin acts as a reactive compatibilizer (solubilizer) with maleic acid and chemically reacts with PP. The chlorinated polyolefin physically binds (intermolecular force, van der Waals force) with the pulp powder, and the chlorinated polyolefin also physically binds with PP. The styrene-modified acrylic resin also shows physical binding and compatibility (solubility) with ABS.

Example

[0043] In Example 2 of this example, instead of the wood powder in Example 1, paper pieces and paper powder of 1,000 μm or less were used, and ePlas002 was produced using PP resin as the binder resin.

Example

[0044] In Example 1, the wood powder was simply melt-kneaded with PP resin as a binder resin without any treatment and pelletized. Therefore, the adhesion between the wood powder and PP was low. In a resin with low adhesion, it is inevitable that the strength of the molded product after molding processing, such as crack susceptibility (impact strength, etc.) and rigidity, will decrease. Therefore, in Example 3, maleic acid-modified polyolefin (maleic acid-modified polyolefin in a solvent mainly composed of water) was used as an emulsion to impregnate the wood powder with maleic acid-modified polyolefin, and the same melt-kneading was carried out using the one supported (coated) on the surface to produce ePlas003 by pelletization.

Example

[0045] In Example 4, the wood powder in Example 3 was changed to paper pieces and paper powder with a size of 1,000 μm or less to produce ePlas004.

Example

[0046] In Example 5, the PP of the binder resin in Example 1 was changed to ABS to produce ePlas005.

Example

[0047] In Example 6, the PP of the binder resin in Example 1 was changed to HIPS to produce ePlas006.

Example

[0048] In Example 7, the PP of the binder resin in Example 1 was changed to PPO {Noryl N190 (trade name)} modified with HIPS to produce ePlas007.

Example

[0049] In Example 8, the PP of the binder resin in Example 1 was changed to 6,6-PA (polyamide) to produce ePlas008.

Example

[0050] Example 9 produced ePlas009 by using the maleic acid-modified PP of Example 3 as a styrene-modified acrylic resin and using ABS as a binder resin.

Examples

[0051] Example 10 produced ePlas010 by using the binder resin of Example 9 as HIPS.

Examples

[0052] Example 10 produced ePlas011 by using the binder resin of Example 9 as PPO modified with HIPS.

Examples

[0053] Example 12 produced ePlas012 by changing the maleic acid-modified polyolefin of Example 3 to a methoxymethylated polyamide and using 6,6-PA as a binder resin.

Examples

[0054] Example 13 changed Examples 3, 9, 10, 11, and 12 from wood powder to paper pieces and paper powder.

Examples

[0055] Example 14 changed the wood powder of Examples 1 to 13 to pulp powder with a particle size of 1,000 μm or less.

Examples

[0056] Example 15 used each of the materials (environmental resin pellets) of ePlas001 to ePlas012 produced in the above examples and performed general molding of the molded product in Figure 3 using an injection molding machine with a clamping force of 180 tons. Compared with the case of only ordinary resins such as PP, ABS, HIPS, and 6,6-PA, there was no significant difference, and injection molding processing was possible.

Examples

[0057] The previous examples were general (ordinary) moldings, but Example 16 was a foam molding. A hole was drilled immediately before the compression zone on the lower side of the heating cylinder of an injection molding machine with a clamping force of 180 tons {an electric motor manufactured by Shibaura Machine Co., Ltd.} used in Example 15. During the resin plasticization stage, from the start of metering to the completion of metering, 1.5 volume% (vol.%, %V / V) of absolute ethanol was added and vaporized at the temperature of the heating cylinder, and ethanol vapor was used as a foaming gas to impart foamability to the molten resin.

[0058] It was injected into the mold of FIG. 3 to obtain a foam molded product using ethanol as a foaming agent. The foaming agents that can be used in the present invention are alcohols typified by the previously shown ethanol and propanol, and anhydrous ones are not necessarily required. In addition to alcohol, water may also be used, or a mixture of water and alcohol, for example, a mixture of ethanol containing 40%V / V of water, or a mixed solution of ethanol and propanol in a 1:1 ratio may be used.

[0059] Examples of foam molding using gas include MuCell, Amotec, and Soffit. It is also possible to implement a means of providing foamability to the molten resin in the nozzle with carbon dioxide gas when injecting the molten resin by providing a discharge port for liquefied carbon dioxide gas in the injection molding machine nozzle developed by Shinpo Akira.

[0060] Examples of solid foaming agents include inorganic chemical foaming agents such as sodium bicarbonate and potassium bicarbonate, organic chemical foaming agents such as ADCA (azo - di - carboxylic acid amide), HDCA (hydro - di - carboxylic acid amide), and DPT (di - nitroso - pentamethylene - tetramine), and hollow spheres such as Advancell (trade name) and Expancel (trade name). Of course, these foaming agents can be used alone or in combination.

Examples

[0061] In Example 15, since swirl marks (foam stripe patterns) peculiar to foam molding occur on the surface, a gas counter - pressure (GCP) method can be implemented to obtain a foam molded product with a beautiful surface without swirl marks. In addition to GCP, heat and cool, which raises the temperature of the mold surface, may also be used. Even when no foaming agent is used, the environmentally decomposable component absorbs moisture. If it is due to the moisture inside, drying can be done, but if GCP is performed without drying, the silver caused by the absorbed moisture can be eliminated.

Example

[0062] In addition to foam molding, it was confirmed that the environmentally friendly resin ePlas of the present invention can be used in hollow molding and pressure air molding to produce the molded product shown in Fig. 3, and it was confirmed that molding can be performed in the same manner as conventional PP and ABS. When discoloration or burning occurs in the environmentally decomposable component, in the case of injection molding or extrusion molding, nitrogen gas is introduced into the hopper to eliminate discoloration and burning. In the case of injection molding, it is advisable to perform nitrogen gas replacement inside the mold (cavity) before filling with the molten resin. Although Example 17 shows foam molding, a detailed description of this foam molding can be found in International Application No. PCT / JP2015 / 069216, Application No. Japanese Patent Application No. 2021-041312, etc. A detailed description of injection molding, extrusion molding, block molding, etc., and hollow molding and pressure air molding in the present invention can be found in International Application No. PCT / JP2016 / 086380, International Application No. PCT / JP2020 / 015536, International Application No. PCT / JP2020 / 015536, International Application No. PCT WO2005 / 018902, etc. The entire contents of the above-mentioned International Application No. PCT / JP2015 / 069216, Application No. Japanese Patent Application No. 2021-041312, International Application No. PCT / JP2016 / 086380, International Application No. PCT / JP2020 / 015536, International Application No. PCT / JP2020 / 015536, International Application No. PCT WO2005 / 018902 are incorporated in the specification of this patent.

[0063] The above-described examples and embodiments are examples illustrated for the purpose of explanation, and are not limited thereto as the present invention. Changes and additions are possible as long as they do not contravene the technical idea of the present invention that can be recognized by those skilled in the art from the claims, the detailed description of the invention, and the description in the drawings. Industrial Application Field

[0064] The present invention is applied to a molded article using a resin with a low environmental impact.

Explanation of reference numerals

[0065] 1. A resin pellet using PP in a binder resin containing 51% W / V of pulp powder.

Claims

1. A resin molded product made of a thermoplastic resin containing 10% W / V or more of an environmentally decomposable component, the environmentally decomposable substance is pulverized so that the average particle size is 1,000 μm or less, and the powder of the pulverized environmentally decomposable substance is immersed in a solvent-based or aqueous (emulsion-based) solution containing maleic acid-modified polyolefin, the temperature of the solution is heated to 25 degrees or more, stirred, and mixed, dried, and the obtained mass is pulverized to obtain an environmentally decomposable substance powder in which maleic acid-modified polyolefin is supported, which is an environmentally decomposable substance containing maleic acid-modified polyolefin.

2. A processing resin for molding obtained by melt-kneading the environmentally decomposable substance containing maleic acid-modified polyolefin according to Claim 1 with an olefin resin using a single-screw or multi-screw extruder.

3. A resin molded product obtained by performing molding processing using the molding resin according to Claim 2.

4. Claim 3 is a molding resin mainly composed of polyolefin containing an environmentally decomposable substance, in which the maleic acid-modified polyolefin described in Claims 1 to 3 is replaced with a halogenated polyolefin, or a resin molded product obtained by performing molding processing using the resin.

5. Claim 3 is a molding resin mainly composed of a styrene-based resin containing an environmentally decomposable substance, in which the maleic acid-modified polyolefin described in Claims 1 to 3 is replaced with a styrene-modified acrylic resin, a polyolefin with a styrene-based resin, or a polymer alloy or polymer blend mainly composed of a styrene-based resin, or a resin molded product obtained by performing molding processing using the resin.

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