Eggshell powder-containing resin composition and molded article

Abstract

The objective is to provide an eggshell powder-containing resin composition that can improve odor during heating and after cooling. [Solution] This technology provides an eggshell powder-containing resin composition that contains eggshell powder having a particle size D50 of 10 μm or more and 50 μm or less at a cumulative frequency of 50 volume percent in a volume-based particle size distribution measured by laser diffraction scattering, a thermoplastic resin, and a chemical reaction-type deodorizing component. This technology also provides an eggshell powder-containing resin composition that contains eggshell powder, a thermoplastic resin, an adsorption-type deodorizing component, and a chemical reaction-type deodorizing component.

Description

Technical Field

[0003]

[0001] The present invention relates to a resin composition containing eggshell powder and a molded body.

Background Art

[0002] In recent years, the depletion of resources has become a problem, and the reuse of industrial waste has been studied from the viewpoints of environmental protection and resource conservation. Such industrial waste includes waste-based biomass (food waste, livestock excrement, construction waste, waste paper, etc.). An example of such waste-based biomass is eggshells discarded at liquid egg factories and the like. Eggshells are substances derived from living organisms, and even if they are incinerated or disposed of as industrial waste, their environmental load becomes carbon neutral and the impact on the environment is small. In addition, since eggshells contain calcium, their development for various uses has been studied. Eggshells are powdered for use, and such eggshell powder, after washing eggshells with water, drying, and pulverizing, is used (Patent Document 1). Also, after firing eggshells, eggshell powder in the form of fine powder is used (Patent Document 2). Such eggshell powder is used to produce a resin composition by blending it with a thermoplastic resin (Patent Document 3).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, crushed eggshells have a distinctive odor derived from the eggshells, and this odor becomes particularly strong during heat treatment. Furthermore, when eggshell powder is used to manufacture resin compositions and molded products are produced from these compositions, the molded products also have an odor. While calcined eggshell powder has almost no odor, obtaining it requires a calcination process, which increases manufacturing costs.

[0005] The primary objective of this technology is to provide an eggshell powder-containing resin composition that can improve odor during heating and after cooling. [Means for solving the problem]

[0006] The inventors have found that an eggshell-containing resin composition having a specific configuration suppresses odor.

[0007] In other words, this technology provides an eggshell powder-containing resin composition comprising eggshell powder having a particle size D50 of 10 μm or more and 50 μm or less at a cumulative frequency of 50 volume percent in a volume-based particle size distribution measured by laser diffraction scattering, and a thermoplastic resin. The eggshell powder-containing resin composition may further contain an adsorbent deodorizing component. The adsorbent deodorizing component may be one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and zeolite-based deodorizers. This technology provides an eggshell powder-containing resin composition that contains eggshell powder, a thermoplastic resin, and an adsorbent deodorizing component. The adsorbent deodorizing component may be one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and zeolite-based deodorizers. The eggshell powder-containing resin composition may further contain a chemical reaction-type deodorizing component. This technology provides a molded article formed from the aforementioned eggshell powder-containing resin composition. This technology provides a molded body formed into the shape of a sheet. This technology provides a laminate in which the surface of the molded body is coated with a film. [Effects of the Invention]

[0008] This technology makes it possible to provide an odorless eggshell powder-containing resin composition. Furthermore, the effects of this technology are not necessarily limited to those described herein, but may include any of the effects described in this specification. [Modes for carrying out the invention]

[0009] The following describes preferred embodiments for implementing this technology. Note that the embodiments described below represent typical embodiments of this technology, and the scope of this technology is not limited to these embodiments.

[0010] This technology will be explained in the following order. 1. Description of this technology 2. First Embodiment (Example of an Eggshell Powder-Containing Resin Composition) (1) Composition of the eggshell powder-containing resin composition (2) Explanation of each component (3) Physical properties (4) Method for producing an eggshell powder-containing resin composition 3. Second Embodiment (Another Example of an Eggshell Powder-Containing Resin Composition) (1) Composition of the eggshell powder-containing resin composition (2) Explanation of each component (3) Physical properties (4) Method for producing an eggshell powder-containing resin composition 4. Third Embodiment (Example of a Molded Body) (1) Structure of the molded body (2) Explanation of each component (3) Method for manufacturing molded articles 5. Fourth Embodiment (Example of a Laminate) 6. Examples

[0011] 1. Description of this technology

[0012] The inventor has found that, in the volume-based particle size distribution measured by the laser diffraction scattering method, an eggshell powder having a particle diameter D50 of 10 μm or more and 50 μm or less with a cumulative frequency of 50% by volume, and a thermoplastic resin, can suppress the odor of the eggshell powder-containing resin composition. Further, the inventor has found that the odor of the eggshell powder-containing resin composition can be further suppressed by containing an adsorption-type deodorant component. Furthermore, the inventor has found that the odor of the eggshell powder-containing resin composition can be further suppressed when the adsorption-type deodorant component is one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and a zeolite-based deodorant.

[0013] 2. First Embodiment (Example of Eggshell Powder-Containing Resin Composition)

[0014] (1) Composition of Eggshell Powder-Containing Resin Composition

[0015] The eggshell powder-containing resin composition of the present embodiment contains an eggshell powder having a particle diameter D50 of 10 μm or more and 50 μm or less with a cumulative frequency of 50% by volume in the volume-based particle size distribution measured by the laser diffraction scattering method, and a thermoplastic resin. Further, the eggshell powder-containing resin composition of the present embodiment may further contain an adsorption-type deodorant component in addition to the eggshell powder and the thermoplastic resin.

[0016] (2) Explanation of Each Component

[0017] [Eggshell Powder]

[0018] Eggshell powder refers to eggshells that have been powdered. Eggshells, which are the raw material for eggshell powder, are the material that oviparous organisms such as birds form as the outer shell of their eggs. Eggshells from chickens raised as livestock are preferred because they are readily available and are discarded in large quantities after the liquid egg, including the egg white and yolk, is collected at liquid egg factories for use as raw materials for confectionery and dressings. To obtain eggshell powder from eggshells, the eggshell membrane is removed from the eggshells from which the egg white and yolk have been collected, and then the eggshells are crushed. Specifically, the eggshells from which the egg white and yolk have been collected are washed with hot water to remove any attached egg white, yolk, eggshell membrane, and debris, the eggshells are dried, and then crushed to obtain powder. Alkaline treatment may be performed during the removal of the eggshell membrane and washing. Such alkaline treatment can remove impurities such as proteins. Examples of eggshell drying methods include aerated drying, rotary drying, vacuum drying, fluidized bed drying, and freeze-drying. Methods for grinding eggshells include dry and wet methods. For grinding, for example, impact grinders, grinders using grinding media such as ball mills, and roller mills may be used. Alternatively, the eggshells may be first coarsely ground in a coarse grinder and then further ground in a fine grinder. Eggshell powder is mainly composed of calcium carbonate, and also contains small amounts of magnesium carbonate, calcium phosphate, and proteins.

[0019] From the viewpoint of suppressing odor and browning of the eggshell powder-containing resin composition and smoothing the surface roughness of the molded article obtained from the eggshell powder-containing resin composition, the eggshell powder may preferably have a particle size D50 at which the cumulative frequency is 50% by volume, measured by laser diffraction scattering, of 10 μm to 50 μm, more preferably 15 μm to 45 μm, even more preferably 20 μm to 40 μm, and even more preferably 25 μm to 35 μm. Various classification methods can be used to achieve a particle size D50 of 10 μm to 50 μm for the eggshell powder. Classification refers to the process of sieving the eggshell powder to be classified into those with a particle size greater than a specific value and those with a particle size less than or equal to that value. Various methods can be used to perform classification, such as using a dry classifier or a wet classifier. Examples of dry classifiers include vibrating sieve classifiers, air separators, DS separators, cyclone classifiers, turboclassifiers, and microseparators. On the other hand, examples of wet classifiers include centrifugal sedimentation machines, liquid cyclone classifiers, and hydrossilators. The method for measuring particle size D50 will be explained in section 2.(3) below.

[0020] The eggshell powder may be present in an amount of preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the eggshell-containing resin composition.

[0021] [Thermoplastic resin]

[0022] The thermoplastic resin contained in the eggshell powder-containing resin composition according to this embodiment is preferably a polyolefin resin, a polyester resin, or a mixture thereof. The thermoplastic resin may also be a polystyrene resin.

[0023] Polyolefin resins are polymers obtained by polymerization using olefins (e.g., α-olefins) as the main monomers. These polyolefin resins may be, for example, polyethylene (PE) resin, polypropylene (PP) resin, or a combination thereof.

[0024] The polyethylene resin may be, for example, low-density polyethylene (LDPE), high-density polyethylene (HDPE), very low-density polyethylene (VLDPE), linear low-density polyethylene (LLDPE), or ultra-high molecular weight polyethylene (UHMW-PE), or a combination thereof.

[0025] The polypropylene resin may be, for example, a homopolymer polypropylene resin, or a random copolymer or block copolymer polypropylene resin (e.g., an ethylene-propylene copolymer), or a combination thereof.

[0026] The polyolefin resin may preferably be a biomass-derived polyolefin resin (e.g., biomass-derived polyethylene resin), and may be, for example, a biomass polyethylene resin. The biomass polyethylene resin may be, for example, LDPE, LLDPE, or HDPE. This can reduce CO2 emissions.

[0027] The polyolefin resin may be a polyolefin resin produced using a metallocene catalyst. That is, the thermoplastic resin may be, for example, a metallocene catalyst-based polyethylene resin or polypropylene resin, or a combination thereof.

[0028] The aforementioned polystyrene resin may also be a metallocene catalyst-based polystyrene resin.

[0029] Polyester resins are polymers formed by the polymerization of monomers via ester bonds. Examples of such polyester resins include polyethylene terephthalate resin (PET), polyethylene naphthalate resin (PEN), polybutylene terephthalate resin (PBT), polylactic acid resin (PLA), or polycarbonate resin (PC), polybutylene adipate terephthalate resin (PBAT), polybutylene succinate resin (PBS), polyhydroxyalkanoate resin (PHA), or a combination of two or more of these.

[0030] Polystyrene resins are polymers formed by the polymerization of styrene monomers. These polystyrene resins may include, for example, polystyrene resin, rubber-reinforced polystyrene resin (high-impact polystyrene resin, HIPS), acrylonitrile-styrene copolymer (AS resin), methacrylic acid ester-styrene copolymer, acrylonitrile-acrylic rubber-styrene copolymer, and acrylonitrile-ethylene propylene-styrene copolymer, or any combination of two or more of these.

[0031] The type of thermoplastic resin contained in the eggshell powder-containing resin composition according to this embodiment may be appropriately selected by those skilled in the art depending on the type of molded article formed from the eggshell powder-containing resin composition, for example, but a thermoplastic resin with a low processing temperature is preferred. For example, when forming a film or sheet from the eggshell powder-containing resin composition, the thermoplastic resin may be, for example, preferably a polyolefin resin, more preferably a polyethylene resin or polypropylene resin, and even more preferably LLDPE or LDPE.

[0032] The thermoplastic resin contained in the eggshell powder-containing resin composition according to this embodiment preferably has a melting point of 90°C to 180°C, and more preferably 95°C to 170°C. By using a thermoplastic resin with a lower melting point, the temperature during molding can be lowered, and odors caused by heating the eggshell powder can be further suppressed.

[0033] According to one embodiment of this invention, the thermoplastic resin may be a biodegradable resin.

[0034] The thermoplastic resin may be in pellet or powder form, and is mixed and kneaded during molding using an extruder or injection molding to ensure uniform dispersion.

[0035] The thermoplastic resin may be preferably less than 90% by mass, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, based on 100% by mass of the eggshell-containing resin composition.

[0036] [Adsorbent deodorizing ingredients]

[0037] The adsorbent deodorizing component used in this embodiment refers to a deodorizing component that deodorizes odor-causing substances by chemical or physical adsorption, and its form may include powder, granules, or fine powder. In this embodiment, the adsorbent deodorizing component has the function of improving odors during heating and odors after cooling. When eggshell powder is mixed with a thermoplastic resin and heated to prepare an eggshell powder-containing resin composition, odors derived from residual proteins become a problem, and it is preferable to include an adsorbent deodorizing component to suppress such odors. Examples of adsorbent deodorizing components include zinc oxide, a mixture of silicon dioxide and zinc oxide, and zeolite-based deodorants. A commercially available mixture of silicon dioxide and zinc oxide is the product name "Shoe Cleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.). A commercially available zinc oxide is the product name "Kesmon (registered trademark) NS-30N" (manufactured by Toagosei Co., Ltd.). The mixture of silicon dioxide and zinc oxide may be preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, relative to the mass of the eggshell powder-containing resin composition. The zinc oxide may be preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the mass of the eggshell powder-containing resin composition. A commercially available zeolite-based deodorant is the product name "SP#2300" (manufactured by Nitto Funka Kogyo Co., Ltd.). The zeolite-based deodorant may be preferably 0.2% by mass or more, more preferably 0.7% by mass or more, and even more preferably 2% by mass or more, relative to the mass of the eggshell powder-containing resin composition.

[0038] Furthermore, in addition to the adsorption-type deodorizing component, a chemical reaction-type deodorizing component may also be included. A chemical reaction-type deodorizing component is a deodorizing component that deodorizes odor-causing substances through a chemical reaction, and examples include aqueous solutions of betaine compounds. Such chemical reaction-type deodorizing components are effective in suppressing odors generated when heating eggshell powder, and by using both the adsorption-type deodorizing component and the chemical reaction-type deodorizing component in combination, it is possible to improve odors during heating and after cooling. Examples of chemical reaction-type deodorizing components include betaine compounds. A commercially available chemical reaction-type deodorizing component is the product name "Epolion AL-152C" (manufactured by Kyoritsu Pharmaceutical Co., Ltd.). The amount of the chemical reaction-type deodorizing component may be preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.04% by mass or more, based on the mass of the eggshell powder-containing resin composition.

[0039] [Other additives]

[0040] The eggshell powder-containing resin composition according to this embodiment may contain additives other than adsorption-type deodorizing components and chemical reaction-type deodorizing components. As such additives, low-melting-point additives that have a melting point lower than the melting temperature of the thermoplastic resin and melt at a relatively low temperature may be used. Preferably, such low-melting-point additives melt at 100°C or lower, more preferably at 60 to 100°C. The low-melting-point additive may have a melting point of preferably 50 to 100°C, more preferably 55 to 90°C, and even more preferably 60 to 80°C. Specifically, examples of low-melting-point additives include glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, special fatty acid esters, and higher alcohol fatty acid esters. The glycerin fatty acid esters include monoglycerides, diglycerides, triglycerides, acetylated monoglycerides, organic acid monoglycerides, and medium-chain fatty acid monoglycerides.

[0041] According to this embodiment, the low-melting-point additive more preferably comprises a glycerin fatty acid ester, and even more preferably comprises a glycerin monostearate. The low-melting-point additive may preferably consist only of a glycerin fatty acid ester, and more preferably consist only of a glycerin monostearate. The low-melting-point additive may melt at a relatively low temperature, be viscous, and function to entangle and adhere to the eggshell powder.

[0042] The low-melting-point additive may be included in the eggshell resin powder-containing resin composition in a content ratio of, for example, preferably 0.1 to 3% by mass, and more preferably 0.5 to 0.8% by mass, relative to the mass of the eggshell powder-containing resin composition.

[0043] (3) Physical properties

[0044] [Eggshell powder particle size D50]

[0045] The particle size D50 of the eggshell powder contained in the eggshell powder-containing resin composition according to this embodiment is preferably 10 μm or more and 50 μm or less, more preferably 15 μm or more and 45 μm or less, even more preferably 20 μm or more and 40 μm or less, and even more preferably 25 μm or more and 35 μm or less. The method for measuring the particle size D50 will be described below.

[0046] A CILAS 1090 Liquid (manufactured by CILAS) laser scattering diffraction particle size distribution analyzer was used to measure the particle size D50 of eggshell powder with a measurement range of 0.04 to 500.00 μm / 100 Classes and water as the dispersion medium.

[0047] [Measurement of moisture content] Using a Laboplast Mill "Model: 4C150" (manufactured by Toyo Seiki Seisakusho Co., Ltd.), eggshell powder, thermoplastic resin, and additives are melt-kneaded at 185°C and 80 rpm for 4 minutes to prepare the sample. The moisture content of the obtained sample is measured at 105°C using a heat-drying type moisture meter "Product name: MS-70" (manufactured by A&D Co., Ltd.).

[0048] [Odor]

[0049] Using a Laboplast Mill "Model: 4C150" (manufactured by Toyo Seiki Seisakusho Co., Ltd.), eggshell powder, thermoplastic resin, and additives are melt-kneaded at 185°C and 80 rpm for 4 minutes, and the semi-molten resin is placed in a sealed container and sealed.

[0050] [Odor during heating]

[0051] The odor was checked four minutes after the start of melting and mixing, before sealing the container. The odor check was performed by seven panelists.

[0052] [Odor after cooling]

[0053] After cooling the semi-molten resin for 10 minutes, the lid of the sealed container was opened and the odor was checked. The odor was checked by seven panelists. Odor levels were evaluated using the following three-level criteria. ○: Acceptable △: Slightly smelly ×: smelly

[0054] (4) Method for producing an eggshell powder-containing resin composition

[0055] The method for producing the eggshell powder-containing resin composition according to this embodiment can employ various methods and can be selected according to the molding method of the molded article to be formed from the eggshell powder-containing resin composition. For example, the method for producing the eggshell powder-containing resin composition according to this embodiment may include a drying step, a kneading step, and an extrusion step. Each step will be described below.

[0056] <Drying process>

[0057] In the drying process, first, each component to be blended is weighed and the required amount of each component is prepared. Eggshell powder, a low-melting-point additive, and a chemical reaction-type deodorizing component are placed in a heated mixer and dried. The oil temperature of the heated mixer is preferably set to 100-200°C, more preferably 120-180°C, and even more preferably 140-160°C. Other additives and a thermoplastic resin are placed in the heated mixer and mixed. The mixing time is set as appropriate. After mixing, the mixture is transferred to a cooling mixer, and while the mixture is cooled, an adsorbent-type deodorizer is added and mixed. After mixing, the mixture in the cooling mixer is transferred to a stock tank.

[0058] <Mixing process>

[0059] In the kneading process, the mixture in the stock tank is transferred to an extruder such as a twin-screw extruder or a single-screw extruder. The mixture is heated and melted in the extruder, kneaded, and the components are uniformly dispersed. The melt-kneading temperature is preferably 130 to 220°C, more preferably 140 to 210°C, and even more preferably 150 to 200°C.

[0060] <Extrusion Process>

[0061] In the extrusion process, the molten mixture is continuously extruded from the extruder to obtain a primary processed product in the shape of a sheet or pellet.

[0062] In this embodiment, the eggshell powder and thermoplastic resin may be melt-kneaded and then transferred to a molding machine, or the eggshell powder and thermoplastic resin may be transferred to a molding machine and melt-kneaded simultaneously with molding. The melt-kneading may be performed using a single-screw kneader, a twin-screw kneader, or the like.

[0063] In this embodiment, the eggshell powder-containing resin composition may be in the form of pellets, and examples of pellet shapes include cylindrical, ellipsoidal, and spherical. The size of the pellets is not particularly limited but can be appropriately set depending on the extruder or molding machine used for transport.

[0064] 3. Second Embodiment (Another Example of an Eggshell Powder-Containing Resin Composition)

[0065] (1) Composition of the eggshell powder-containing resin composition

[0066] The eggshell powder-containing resin composition according to this embodiment contains eggshell powder, a thermoplastic resin, and an adsorption-type deodorizing component. The adsorption-type deodorizing component may be one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and a zeolite-based deodorant. In addition, the eggshell powder-containing resin composition according to this embodiment may further contain a chemical reaction-type deodorizing component in addition to the eggshell powder, the thermoplastic resin, and the adsorption-type deodorizing component.

[0067] (2) Explanation of each component

[0068] Since the descriptions of each component in the first embodiment apply to each component, the descriptions of each component will be omitted.

[0069] (3) Physical properties

[0070] Regarding the physical properties, the description of the physical properties in the first embodiment applies, so the description of the physical properties will be omitted.

[0071] (4) Method for producing an eggshell powder-containing resin composition The method for producing the eggshell powder-containing resin composition is described in the first embodiment, so the explanation of the method for producing the eggshell powder-containing resin composition will be omitted.

[0072] 4. Third Embodiment (Example of a Molded Body)

[0073] The molded article according to this embodiment is a molded article formed from the eggshell powder-containing resin composition.

[0074] (1) Structure of the molded body

[0075] The molded article according to this embodiment is formed from the eggshell powder-containing resin composition. The description of the eggshell powder-containing resin composition in the first embodiment applies, so the description of the eggshell powder-containing resin composition is omitted. The shape of the molded article according to this embodiment is not particularly limited, but examples include the shape of a sheet, a food container, etc. The sheet may have a thickness of 300 μm or more, and in particular, a thickness of 300 μm to 1.5 mm. The food container, etc. may have a wall thickness of 100 μm to 1.4 mm, for example.

[0076] According to one embodiment of the present invention, the sheet has a surface surface having an average roughness (Ra) measured in accordance with JIS B0031, preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 4 μm or less, and the said surface is the surface of a layer formed from the eggshell-containing resin composition. The average roughness may be measured using a surface roughness meter in accordance with JIS B0031. The eggshell-containing resin composition according to this technology makes it possible to provide a sheet having such a smooth surface. Such a sheet can be suitably used for cards, packaging, containers, separators, covers, dividers, laminates, and bags.

[0077] (2) Explanation of each component

[0078] The description of each component of the eggshell powder-containing resin composition that forms the molded article according to this embodiment is the same as the description of each component of the eggshell powder-containing resin composition in the first embodiment, so the description of each component of the eggshell powder-containing resin composition is omitted.

[0079] (3) Method for manufacturing molded articles

[0080] The molded article according to this embodiment may be further molded into a container or other molded article using a primary processed product in the shape of a sheet or pellet obtained in the extrusion step of the method for producing the eggshell powder-containing resin composition according to the first embodiment. Furthermore, ordinary molding techniques for petroleum-based plastics can be used to manufacture the molded article according to this embodiment. For example, eggshell powder and thermoplastic resin may be mixed in a mixer such as a Henschel mixer, tumbler mixer, Barber mixer, or kneader mixer, and a sheet may be molded using a T-die extruder or calender. Alternatively, the raw materials, such as eggshell powder and thermoplastic resin, may be kneaded and mixed directly and then molded, or the raw materials may be mixed in a mixer, then the strands may be extruded using a single-screw or twin-screw extruder, cut to produce pellets, and these pellets may be used as a masterbatch to mold a sheet.

[0081] When manufacturing sheets, the molding temperature range is preferably 150 to 200°C when the raw materials are directly kneaded and mixed for molding, from the viewpoint of suppressing burning and decomposition of the raw materials and seizing inside the cylinder, and from the viewpoint of suppressing the discharge of eggshell powder in an unmelted state, which can cause problems as the pressure rises. When manufacturing master pellets for molding, the temperature range is also preferably 150 to 200°C.

[0082] Furthermore, from the viewpoint of preventing burning and decomposition of the raw materials, it is preferable that the residence time in the cylinder be no more than 10 minutes.

[0083] The sheet extruded by the T-die extruder may be cooled by setting the take-up roll temperature to 95°C or lower, then taken up and wound up after being formed to a predetermined thickness.

[0084] Other molded products include, but are not limited to, containers (e.g., bottle containers), bottle caps, and corrugated plastic. For example, the eggshell powder-containing resin composition relating to this technology may be used for blow molding, injection molding, and shape extrusion molding. By blow molding, for example, a bottle container may be molded. By injection molding, for example, a bottle cap or container may be manufactured. By shape extrusion molding, for example, corrugated plastic may be molded.

[0085] 5. Fourth Embodiment (Example of a Laminate)

[0086] In this embodiment, the laminate is characterized by the surface of the molded body being covered with a film.

[0087] [Laminated structure]

[0088] In this embodiment, when the molded body is a sheet, a laminate is also provided in which the surface of the sheet is coated with a film. In this laminate, one side of the sheet surface may be coated with a film, or both sides of the sheet surface may be coated with a film. By coating the surface of the sheet with a film, bleed-out from the coated side surface can be suppressed. The film may be, for example, a polyolefin resin such as polyethylene (PE) resin, polypropylene (PP) resin, or a combination of two or more of these, or a polyester resin such as polylactic acid resin (PLA), polycarbonate resin (PC), polyethylene terephthalate resin (PET), polyethylene naphthalate resin (PEN), polybutylene terephthalate resin (PBT), polybutylene adipate terephthalate resin (PBAT), polybutylene succinate resin (PBS), polyhydroxyalkanoate resin (PHA), or a combination of two or more of these. An adhesive layer may be provided between the sheet and the film. As such an adhesive layer, a resin having a melting point lower than the melting point of the resin composition forming the sheet may be used. Examples of resins used in such an adhesive layer include epoxy resins and urethane resins.

[0089] In the laminate, the sheet may have a thickness of, for example, 300 μm or more, and more particularly, a thickness of 300 μm or more and 1.5 mm or less. The film may have a thickness of, for example, less than 60 μm, and more particularly, a thickness of 5 μm or more and less than 50 μm. The laminate according to this embodiment can be suitably used for cards, covers, packaging, containers, separators, dividers, bags, and lamination.

[0090] This technology can also employ the following configuration: [1] Eggshell powder in which, in the volume-based particle size distribution measured by laser diffraction scattering, the particle size D50 at which the cumulative frequency is 50% by volume is 10 μm or more and 50 μm or less, Thermoplastic resin and A resin composition containing eggshell powder, which includes the following: [2] Furthermore, the eggshell powder-containing resin composition according to [1] contains an adsorbent deodorizing component. [3] The eggshell powder-containing resin composition according to [2], wherein the adsorbent deodorizing component is one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and a zeolite-based deodorant. [4] Eggshell powder and Thermoplastic resin and Adsorbent deodorizing components, A resin composition containing eggshell powder, which includes the following: [5] The eggshell powder-containing resin composition according to [4], wherein the adsorbent deodorizing component is one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and a zeolite-based deodorant. [6] Furthermore, the eggshell powder-containing resin composition according to [1] or [4] contains a chemical reaction-type deodorizing component. [7] A molded article formed from an eggshell powder-containing resin composition described in any one of [1] to [6]. [8] A molded body as described in [7], formed into the shape of a sheet. [9] A laminate in which the surface of the molded article described in [8] is covered with a film. [Examples]

[0091] 6. Examples The present invention will be described in more detail below based on the examples. Note that the examples described below are representative examples of the present invention, and the scope of the present invention is not limited to these examples.

[0092] In this embodiment, the D50 particle size and odor of the eggshell powder were determined by the measurement method described in the above-mentioned embodiment.

[0093] [Example 1] Using a Laboplast Mill "Model: 4C150" (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a mixture was prepared with 100% by mass of eggshell powder-containing resin composition, 51% by mass of eggshell powder (D50 particle size 26 μm), 48.7% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.), and 0.3% by mass of product name "Shoe Cleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.). The mixture was melt-kneaded at 185°C and 80 rpm for 4 minutes to prepare a semi-molten eggshell powder-containing resin composition. The obtained eggshell powder-containing resin composition was placed in a sealed container and sealed.

[0094] The material exhibited the physical properties (odor suppression effect) shown in Table 1.

[0095] [Example 2] This method differs from Example 1 in that it uses 48.5% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.) and 0.5% by mass of product name "Shoe Cleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.), but all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0096] [Example 3] This eggshell powder-containing resin composition differs from Example 1 in that it was formulated with 48% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.) and 1% by mass of product name "Shoe Cleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.), but all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0097] [Example 4] This eggshell powder-containing resin composition differs from Example 1 in that it was formulated with 46% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.) and 3% by mass of product name "Shoe Cleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.), but all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0098] [Example 5] This eggshell powder-containing resin composition differs from Example 1 in that it was formulated with 44% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.) and 5% by mass of product name "Shoe Cleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.), but all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0099] [Example 6] This eggshell powder-containing resin composition differs from Example 1 in that it was formulated with 46% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.) and 3% by mass of product name "Kesmon (registered trademark) NS-30N" (manufactured by Toagosei Co., Ltd.), but all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0100] [Example 7] This eggshell powder-containing resin composition differs from Example 1 in that it was formulated with 44% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.) and 5% by mass of product name "Kesmon (registered trademark) NS-30N" (manufactured by Toagosei Co., Ltd.), but all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0101] [Example 8] This eggshell powder-containing resin composition differs from Example 1 in that it is formulated with 47.98% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.), 1% by mass of product name "Shoe Cleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.), and 0.02% by mass of product name "Epolion AL-152C" (manufactured by Kyoritsu Pharmaceutical Co., Ltd.) as a chemical reaction type deodorizing component. However, all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0102] [Example 9] This eggshell powder-containing resin composition differs from Example 1 in that it was formulated with 48% by mass of polypropylene resin "PM900C (registered trademark) MFR:30" (manufactured by Sun Allomer Co., Ltd.) and 1% by mass of product name "SP#2300" (manufactured by Nitto Funka Kogyo Co., Ltd.), but all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0103] [Comparative Example 1] This eggshell powder-containing resin composition differs from Example 1 in that it contains eggshell powder with a particle size of 135 μm, which was removed by classification in Example 1. However, all other conditions and methods were the same as in Example 1 to obtain the eggshell powder-containing resin composition. The composition and physical properties of the obtained eggshell powder-containing resin composition were as shown in Table 1.

[0104] The test results are shown in Table 1.

[0105] [Table 1]

[0106] From Table 1, the following can be seen:

[0107] In all of the eggshell powder-containing resin compositions of Examples 1 to 9, the D50 particle size of the eggshell powder was between 10 μm and 50 μm. Therefore, all of the eggshell powder-containing resin compositions of Examples 1 to 9 exhibited excellent odor improvement effects both during heating and after cooling.

[0108] Comparative Example 1, which uses eggshell powder with a D50 particle size larger than 50 μm, exhibits a severe odor during heating and cooling, demonstrating inferior odor improvement.

[0109] [Example 10] Using a twin-screw extruder "Model: PCM30" (manufactured by Ikegai Co., Ltd.), the following mixtures were prepared: 100% by mass of eggshell powder-containing resin composition, 53.5% by mass of eggshell powder (D50 particle size 26 μm), 44.48% by mass of polypropylene resin "Sumitomo Noblen FL6632G" (manufactured by Sumitomo Chemical Co., Ltd.), 1% by mass of product name "Shoecleanse (registered trademark) KD-211" (manufactured by Rasa Industries Co., Ltd.), and 0.02% by mass of product name "Epolion AL-152C" (manufactured by Kyoritsu Pharmaceutical Co., Ltd.). The mixture was melt-kneaded at 190°C to produce pellets of the eggshell powder-containing resin composition (hereinafter referred to as the eggshell powder-containing resin composition of Example 10).

[0110] The eggshell powder-containing resin composition pellets of Example 10 were transferred to a T-die single-screw extruder (model: LE-25-30 / CV, LCR-300) (manufactured by Labtech Engineering) and continuously extruded to form a sheet with a thickness of 460 μm. Both surfaces of the obtained sheet were coated with a 20 μm thick high-density polyethylene film (HDPE) (HD Film) (manufactured by Sumika Sekisui Film Co., Ltd.), and then heat-laminated using a vacuum laminator (LM-50X50-S, manufactured by NCP Co., Ltd.). This lamination process was performed at 120°C. This lamination process yielded a laminate with a thickness of 500 μm. The obtained laminate was further molded into a container with a wall thickness of 230 mm using a vacuum forming machine. The Ra value on the inside of the container was 3.6.

[0111] [Comparative Example 2] An eggshell powder-containing resin composition with the same composition as in Example 10, except that D50 uses eggshell powder with a particle size of 135 μm, was transferred to a T-die single-screw extruder and continuously extruded to form a sheet with a thickness of 460 μm. Both surfaces of the sheet obtained under the same conditions and methods as in Example 10 were coated with a 20 μm thick high-density polyethylene film (HDPE) "HD Film" (manufactured by Sumika Sekisui Film Co., Ltd.) and then heat-laminated. This lamination process was carried out at 120°C. This lamination process yielded a laminate with a thickness of 500 μm. The obtained laminate was further molded into a container with a wall thickness of 230 mm using a vacuum forming machine. The Ra value on the inside of the container was 6.7.

[0112] Comparing Example 10 with Comparative Example 2, the container molded from the eggshell powder-containing resin composition of Example 10, in which the D50 particle size of the eggshell powder was between 10 μm and 50 μm, had a lower Ra and was smoother than the container molded from the eggshell powder-containing resin composition of Comparative Example 2, which used eggshell powder with a D50 particle size greater than 50 μm.

[0113] Although embodiments and examples of this technology have been described in detail above, this technology is not limited to the embodiments and examples described above, and various modifications based on the technical concept of this technology are possible.

[0114] For example, the configurations, methods, processes, shapes, materials, and numerical values ​​mentioned in the above-described embodiments and examples are merely examples, and different configurations, methods, processes, shapes, materials, and numerical values ​​may be used as needed.

[0115] Furthermore, the configurations, methods, processes, shapes, materials, and numerical values ​​of the above-described embodiments and examples can be combined with each other, as long as they do not deviate from the spirit of this technology.

[0116] Furthermore, in this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of one step in the numerical range may be replaced with the upper or lower limit of another step in the numerical range. Unless otherwise specified, the materials exemplified in this specification may be used individually or in combination of two or more.

Claims

1. Eggshell powder in which, in the volume-based particle size distribution measured by laser diffraction scattering, the particle size D50 at a cumulative frequency of 50% by volume is 10 μm or more and 50 μm or less, Thermoplastic resin and It contains, Furthermore, an eggshell powder-containing resin composition containing a chemically reactive deodorizing component.

2. Furthermore, the eggshell powder-containing resin composition according to claim 1 contains an adsorbent deodorizing component.

3. The eggshell powder-containing resin composition according to claim 2, wherein the adsorbent deodorizing component is one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and a zeolite-based deodorant.

4. Eggshell powder and Thermoplastic resin and Adsorbent deodorizing components, It contains, Furthermore, an eggshell powder-containing resin composition containing a chemically reactive deodorizing component.

5. The eggshell powder-containing resin composition according to claim 4, wherein the adsorbent deodorizing component is one or more selected from the group consisting of zinc oxide, a mixture of silicon dioxide and zinc oxide, and a zeolite-based deodorant.

6. A molded article formed from the eggshell powder-containing resin composition according to any one of claims 1 to 5.

7. A molded article according to claim 6, which is formed into the shape of a sheet.

8. A laminate in which the surface of the molded article according to claim 7 is covered with a film.

Images