WO2018070086A1 - Multifunctional powder-containing resin composition - Google Patents

Multifunctional powder-containing resin composition Download PDF

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Publication number
WO2018070086A1
WO2018070086A1 PCT/JP2017/026376 JP2017026376W WO2018070086A1 WO 2018070086 A1 WO2018070086 A1 WO 2018070086A1 JP 2017026376 W JP2017026376 W JP 2017026376W WO 2018070086 A1 WO2018070086 A1 WO 2018070086A1
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Prior art keywords
powder
resin composition
containing resin
mass
antibacterial
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PCT/JP2017/026376
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French (fr)
Japanese (ja)
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丸尾茂明
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丸尾茂明
橋本君夫
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Publication of WO2018070086A1 publication Critical patent/WO2018070086A1/en

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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G19/00—Table service
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G19/00—Table service
    • A47G19/02—Plates, dishes or the like
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G19/00—Table service
    • A47G19/22—Drinking vessels or saucers used for table service
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G21/00—Table-ware
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02—Wrappers or flexible covers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a multifunctional powder-containing resin composition in which various fine powders are kneaded and contained in a resin composition to provide multifunctionality.
  • the problem to be solved by the present invention is to provide a multifunctional powder-containing resin composition having low raw material costs and high antibacterial performance.
  • the powder-containing resin composition according to the first aspect of the present invention comprises: A powder-containing resin composition comprising calcium hydroxide fine powder obtained by firing eggshell or shellfish at high temperature and hydrolyzing, fine calcium carbonate powder of eggshell or shellfish, and a resin composition,
  • the content of the calcium hydroxide fine powder is 0.5 mass% to 7.0 mass% with respect to the total mass of the powder-containing resin composition
  • the content of the calcium carbonate fine powder is the powder-containing resin composition. It is characterized by being 46.0 mass% to 65.0 mass% with respect to the total mass of the product.
  • the powder-containing resin composition according to the second aspect of the present invention A powder-containing resin composition comprising calcium hydroxide fine powder obtained by subjecting eggshells or shells to high-temperature firing and water addition, fine fiber powder such as wood chips or paper, and a resin composition,
  • the content of the calcium hydroxide fine powder is 0.5% by mass to 7.0% by mass with respect to the total mass of the powder-containing resin composition
  • the content of the fibrous raw material fine powder is a powder-containing resin. 46.0 mass% to 65.0 mass% with respect to the total mass of the composition.
  • the powder-containing resin composition according to the third aspect of the present invention is Powder-containing resin composition comprising calcium hydroxide fine powder obtained by subjecting eggshells or shells to high-temperature firing and water addition, calcium carbonate fine powder of eggshells or shells, fine fiber powder such as wood chips or paper, and a resin composition A thing,
  • the content of the calcium hydroxide fine powder is 0.5 mass% to 7.0 mass% with respect to the total mass of the powder-containing resin composition, and the content of the calcium carbonate fine powder is the powder-containing resin composition.
  • the content of the fine fiber material powder is 5.0% by mass to 60% by mass with respect to the total mass of the powder-containing resin composition. 0.0 mass%.
  • antibacterial tableware according to the fourth aspect of the present invention, Antibacterials such as antibacterial chopsticks, antibacterial spoons, antibacterial knives, antibacterial forks, antibacterial dishes, antibacterial trays, and antibacterial cups using the powder-containing resin composition described in the first to third aspects It is a characteristic tableware.
  • the effects listed below can be obtained by being composed of the aforementioned components.
  • (2) Calcium hydroxide is mixed for the purpose of antibacterial effect, but it is derived from organisms such as eggshells and shells, and there is no risk of causing allergies or side effects to the human body.
  • it has extremely high bactericidal power and can exhibit antibacterial and antiseptic effects comparable to conventional antibacterial agents using silver-based antibacterial agents and photocatalysts.
  • the resin base material may be a thermoplastic resin or a thermosetting resin.
  • It can be used to recycle wood chips and paper (pulp), which have been conventionally disposed of, and can contribute to resource recycling in society.
  • the calcium hydroxide according to the present invention uses biologically derived calcium carbonate such as eggshells and shells as its main raw material.
  • biologically derived calcium carbonate such as eggshells and shells
  • the production method of calcium hydroxide fine powder having high antibacterial, antiseptic and deodorizing performance used in the present invention from these main raw materials will be described.
  • the calcium hydroxide fine powder used in the present invention is pulverized from biologically derived calcium carbonate at high temperature, and then subjected to water addition to make it fine powder by a predetermined pulverization method. It is a thing.
  • bivalve shells such as scallop shells, clams shells, clams shells, sea shells, etc. can be used regardless of natural or aquaculture. Also good. However, in view of the fact that the composition of the shell is uniform and the supply amount is extremely stable, it is most desirable to use a scallop shell for aquaculture.
  • biological calcium carbonate (specifically using scallop shells) is not simply fired, but is fired within a range of 850 to 1,150 degrees Celsius in a special high temperature firing cracking furnace.
  • the firing time is desirably 1 hour or longer. Note that there is no problem if the firing temperature in the present invention is in the range of about 850 to 1,200 degrees, and it is usually desirable to perform high-temperature firing for about 1 hour at a set temperature of about 1,000 degrees Celsius. However, optimally, high-temperature baking for about 1 to 2 hours at a set temperature of about 1,000 degrees Celsius is most preferable.
  • Such high-temperature baking treatment may be performed in the air, or may be performed in the range of an inert gas such as nitrogen or carbon dioxide. Incidentally, by performing such high-temperature baking treatment, organic matter other than calcium carbonate contained in biological calcium carbonate is removed by thermal decomposition.
  • the composition of biological calcium carbonate is (CaCO 3 ), and calcium oxide (CaO) can be obtained by baking it at a high temperature (850 ° C. or more for 1 hour or more).
  • the calcium oxide (CaO) can be obtained by being modified by subjecting it to a predetermined hydration treatment.
  • generated in the present Example is shown in the chart of Fig.1 (a).
  • Calcium hydroxide (Ca (OH) 2 ) has an extremely high ability to reduce alkali ions, and its pH (pH) ranges from 12.0 to 13.8.
  • pH pH ranges from 12.0 to 13.8.
  • strong alkali strong base properties exhibit performance such as antibacterial effect, antiseptic effect, and deodorant effect.
  • the alkaline pH (pH) differs greatly depending on the high-temperature firing, the firing time, the amount of water added during hydration, and the method of adding water.
  • the particle size (miniaturization) of the powder has a great influence on the alkaline pH (pH).
  • the biological calcium carbonate has a probability of denaturation from calcium oxide (CaO) generated by firing to calcium hydroxide (Ca (OH) 2 ). to differ greatly.
  • the concentration of calcium hydroxide (Ca (OH) 2 ) is an extremely important point, and it has been confirmed and verified that it has a great influence on the alkaline pH (pH).
  • the strong alkali (strong base) pH (pH) is increased to about 13.8, the antibacterial effect, antiseptic, deodorizing effect, etc. are exerted extremely strongly, and silver antibacterial It can be produced at an extremely low cost as compared with agents.
  • the particle size of the pulverized fine particles becomes 5 ⁇ m or less, recombination of the fine particles frequently occurs during the pulverization, the particle sizes of the fine particles become irregular and the particle size becomes uniform. Problems such as inability to plan occur. Therefore, in this example, in the pulverization treatment of calcium hydroxide (Ca (OH) 2 ) after high-temperature firing / hydration, silica fine powder (SiO 2 ) is converted to calcium hydroxide (SiO 2 ) in order to prevent recombination of fine particles. 0.5 to 5.0 mass% (preferably 0.7 to 1.5 mass%) is blended with respect to the total mass of Ca (OH) 2 ). As a result, the average particle diameter of the pulverized particles can be made uniform to 0.5 to 3.0 ⁇ m.
  • the particle size homogenization process by the above-mentioned process is not particularly desired, in order to prevent recombination of fine particles in the pulverization process of calcium hydroxide (Ca (OH) 2 ) after high-temperature firing and hydration, It is preferable to perform the drying step again for 3 to 4 hours in a forced dryer so that the moisture content of the powder is in the range of 2700 ppm to 3500 ppm.
  • the calcium hydroxide produced by the above treatment is set in a special pulverizer (for example, an air jet mill), and a fine powder having an average particle size of about 0.5 to 3.0 ⁇ m. Is generated.
  • a special pulverizer for example, an air jet mill
  • eggshells contain less impurities in the raw materials, so that it is possible to obtain almost pure calcium hydroxide compared to the aforementioned shells.
  • the fine pulverization step after firing and various parameters such as the pulverized particle size are the same as the manufacturing process in the case of the shell described above.
  • Calcium carbonate based on the present invention is calcium carbonate such as eggshells and shells derived from living organisms as its main raw material. Below, the production
  • sea shells such as sea shells
  • the calcium carbonate derived from living organisms for example, scallop shells, clams shells, clams shells, sea shells such as sea shells
  • scallop shells for example, scallop shells, clams shells, clams shells
  • sea shells such as sea shells
  • composition of biological calcium carbonate is (CaCO 3 ), and the calcium carbonate fine powder used in the present invention can be obtained by pulverizing it to a particle size of about 80 to 100 ⁇ m using a mill pulverizer or the like.
  • the calcium carbonate fine powder used in the present invention is obtained by finely pulverizing biological calcium carbonate by a predetermined pulverization method.
  • the manufacturing process of calcium carbonate powder when eggshell is used as the main raw material the pulverization process when shells shown above are used as the main raw material, and various parameters such as the pulverized particle size, etc. This is the same as the manufacturing process.
  • fine fiber material powder such as wood chips and paper (pulp)
  • the fine fiber material powder used in the present invention can be used as long as it is a safe and secure substance that does not have specificity in its main raw materials. Is possible.
  • a method for producing a piece of wood and paper (pulp) fine powder will be described.
  • the wood pieces are dried to reduce the water content to 15 to 35% in a forced dryer.
  • the preferable water content is 15 to 25%.
  • wood having a moisture content of 30% or less is used because about 30% or less is the fiber saturation point of the wood pieces.
  • the mechanical performance (longitudinal compression / transverse compression / hardness longitudinal tension / transverse tension / bending / shear) is remarkably improved.
  • the fiber material fine powder using the wood piece as a main raw material can be obtained by pulverizing the wood piece that has undergone the drying step to a particle size of about 80 to 100 ⁇ m with a mill pulverizer or the like.
  • the drying process of the piece of paper is less than that of wood pieces.
  • the moisture content varies depending on the storage condition, but in normal storage, the moisture content is 8 to 20%. In this case, the moisture content is forcibly dried to 8 to 10% in the dryer.
  • the fiber material fine powder can be obtained by pulverizing the paper piece obtained in the drying step to a particle size of 80 to 100 ⁇ m with a mill pulverizer or the like.
  • Powder-containing resin composition based on the present invention
  • the calcium hydroxide fine powder obtained by the production process of (1) above and the calcium carbonate fine powder obtained by the production process of (2), or (3) Mixing fiber material fine powder such as wood chips and paper (pulp) obtained in the manufacturing process with the resin has antibacterial properties and also reduces the blending ratio of the resin (the amount of the resin decreased is (2 ) Supplement with calcium carbonate fine powder obtained by the production process of (3) and fibrous raw material fine powder such as wood chips and paper (pulp).), Multifunctional powder-containing resin composition with reduced production cost Obtainable.
  • the content ratio of the calcium hydroxide fine powder is 0.5% by mass to 7.0% by mass with respect to the total mass of the powder-containing resin composition regardless of which raw material is used as a base. It is desirable to set within the range of%.
  • the fine powder which is another mixture is a fine powder of calcium carbonate obtained by the production process of (2) or a fine fiber powder of fiber material such as wood chips and paper (pulp) obtained by the production process of (3).
  • a fine powder of fiber material such as wood chips and paper (pulp) obtained by the production process of (3).
  • the content ratio of each fine powder is preferably set in the range of 46.0 mass% to 65.0 mass% with respect to the total mass of the powder-containing resin composition.
  • a polymer resin such as a polypropylene resin or a polyethylene resin
  • the selection of the resin is not particularly limited.
  • a thermoplastic resin and a thermosetting resin can also be used.
  • the multi-functional powder-containing resin composition based on the present invention has strong antibacterial and bactericidal properties, and is a human body. Therefore, it is optimal to use as a tableware material such as chopsticks, spoons, forks, knives, plates, trays, cups.
  • one-way disposable chopsticks are the mainstream. Some of these are made of materials such as wood and bamboo, but they are treated with high-risk chemicals for disinfection.
  • Use of the application product of the multifunctional powder-containing resin composition according to the present invention provides various tableware with excellent cost performance, high safety at the same price range, and easy disposal as flammables can do.
  • the chopsticks made of the multifunctional powder-containing resin composition according to the present invention have sufficient physical properties and high antibacterial performance. It can be used as an alternative.
  • the calcium hydroxide obtained by the production process of (1) has a bacteriostatic activity value of 3.6 and a bactericidal activity value of 1. 3 for Escherichia coli, indicating that the bacteriostatic activity value is 5.3 and the bactericidal activity value is 3.2.
  • both the bacteriostatic activity value and the bactericidal activity value are parameters that represent the effect of inhibiting the growth of antibacterial agents against bacteria.
  • FIG. 2 shows the case where the test bacterium is Escherichia coli
  • FIG. 3 shows the case where the test bacterium is Staphylococcus aureus.
  • the multifunctional powder-containing resin composition according to the present invention uses calcium hydroxide as a raw material derived from natural organisms such as shells and eggshells, adverse side effects and allergic reactions are also harmful to the human body. It can realize excellent antibacterial and antiseptic effects on foods.
  • the ratio of the resin composition used is as small as about half of the whole, the cost performance of the product is high, and the CO 2 emission is low in the combustion incineration process at the time of disposal, and consideration is given to the environment. .
  • the configuration and method of the present invention described above are not limited to the tableware field, but can be used in fields that require antibacterial and antiseptic effects.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention provides a multifunctional powder-containing resin composition that has no adverse effect on the human body, has significant antimicrobial and antiseptic effects, and exhibits extremely high material cost-effectiveness. This powder-containing resin composition is formed by mixing/kneading, in a resin composition, a calcium hydrate fine powder obtained by firing egg shells or seashells at high temperature and adding water thereto, with a calcium carbonate fine powder derived of eggs shells or seashells, or a fine powder of a fiber material, such as wood chips and paper (pulp), in a predetermined ratio. Such a powder-containing resin composition has excellent antimicrobial activity and is highly safe to the human body, and thus can be used as a material for production of antimicrobial eating utensils such as chopsticks and spoons.

Description

多機能性粉末含有樹脂組成物Multifunctional powder-containing resin composition
本発明は、各種の微小粉体を樹脂組成物に混練含有させ、多機能性を持たせた多機能性粉末含有樹脂組成物に関するものである。 The present invention relates to a multifunctional powder-containing resin composition in which various fine powders are kneaded and contained in a resin composition to provide multifunctionality.
近年、私たちを取り巻く日用品等においては、石油由来の化学合成樹脂による製品が大半を占めている。また、これらの製品の生産量及び廃棄量の急激な増大が大きな社会問題となっている。これらの樹脂成型品は、そのほとんどが熱可塑性樹脂や熱硬化性樹脂により構成されており、製品の廃棄時における焼却処理や埋立て処理が地球温暖化や土壌汚染の原因にもなっている。 In recent years, most of the daily necessities surrounding us are made of petroleum-derived chemical synthetic resins. In addition, the rapid increase in production and disposal of these products has become a major social problem. Most of these resin molded products are composed of a thermoplastic resin or a thermosetting resin, and the incineration process and the landfill process at the time of disposal of the product also cause global warming and soil contamination.
人々の環境に対しての意識の高まりや、リサイクル法の厳正化に伴う廃棄処理方法の高度化から、業者や消費者の問題意識も高まっている。そのため、可燃物としての廃棄処理が容易な紙素材、木素材等への関心が集中している。また、人々の衛生概念の高まりから、製品素材に銀粉末等を含有させ抗菌性能を有した日用品も製造されているが、製品のコスト高や耐水性、耐熱性、耐久性などが十分ではない。 Business people and consumers are becoming more aware of problems due to the growing awareness of the environment and the sophistication of disposal methods associated with stricter recycling laws. For this reason, there is a focus on paper materials, wood materials, etc. that can be easily disposed of as combustible materials. In addition, due to the rise in people's hygiene concept, daily commodities that contain antibacterial performance by including silver powder etc. in the product material are also manufactured, but the cost of the product, water resistance, heat resistance, durability, etc. are not sufficient .
そのため、近年、可燃物としての廃棄処理が容易であり、かつ素材に抗菌性、殺菌性等の多機能性を有した低コストの粉末含有樹脂組成物による成形品が注目を集め、その研究開発が活発化している（特許文献１、２を参照のこと）。 Therefore, in recent years, molded products made of low-cost powder-containing resin compositions, which are easy to dispose of as combustible materials and have multi-functionality such as antibacterial and bactericidal properties, have attracted attention. (See Patent Documents 1 and 2).
しかしながら、従来の紙やパルプ、あるいは木材等の素材、および銀粉末等を樹脂に含有させた混合材は、製造工程の複雑化や銀粉末等の配合によるコスト高を招くという欠点があった。また、係る混合剤を用いた製品の人体に対する安全性の面においても問題があった。 However, conventional materials such as paper, pulp, or wood, and a mixed material containing silver powder or the like in a resin have disadvantages that the manufacturing process becomes complicated and the cost increases due to the combination of silver powder and the like. There is also a problem in terms of the safety of products using such a mixture with respect to the human body.
特開２００９－２８５２３号公報JP 2009-28523 A 特開２００９－２９１２１号公報JP 2009-29121 A
本発明が解決しようとする課題は、原料費が安価で、かつ高い抗菌性能を有した多機能性粉末含有樹脂組成物を提供することを目的としている。 The problem to be solved by the present invention is to provide a multifunctional powder-containing resin composition having low raw material costs and high antibacterial performance.
上記の目的を達成するため、本発明の第一の観点による粉末含有樹脂組成物は、
卵殻もしくは貝殻を高温焼成し加水を施した水酸化カルシウム微粉末と、卵殻もしくは貝殻の炭酸カルシウム微粉末と、樹脂組成物とを含む粉末含有樹脂組成物であって、
前記水酸化カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して０．５質量％～７．０質量％であり、前記炭酸カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して４６．０質量％～６５．０質量％であることを特徴とする。 In order to achieve the above object, the powder-containing resin composition according to the first aspect of the present invention comprises:
A powder-containing resin composition comprising calcium hydroxide fine powder obtained by firing eggshell or shellfish at high temperature and hydrolyzing, fine calcium carbonate powder of eggshell or shellfish, and a resin composition,
The content of the calcium hydroxide fine powder is 0.5 mass% to 7.0 mass% with respect to the total mass of the powder-containing resin composition, and the content of the calcium carbonate fine powder is the powder-containing resin composition. It is characterized by being 46.0 mass% to 65.0 mass% with respect to the total mass of the product.
また、本発明の第二の観点による粉末含有樹脂組成物は、
卵殻もしくは貝殻を高温焼成し加水を施した水酸化カルシウム微粉末と、木片または紙等の繊維質素材微粉末と、樹脂組成物とを含む粉末含有樹脂組成物であって、
前記水酸化カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して０．５質量％～７．０質量％であり、前記繊維質素材微粉末の含有量は、粉末含有樹脂組成物の総質量に対して４６．０質量％～６５．０質量％であることを特徴とする。 Moreover, the powder-containing resin composition according to the second aspect of the present invention,
A powder-containing resin composition comprising calcium hydroxide fine powder obtained by subjecting eggshells or shells to high-temperature firing and water addition, fine fiber powder such as wood chips or paper, and a resin composition,
The content of the calcium hydroxide fine powder is 0.5% by mass to 7.0% by mass with respect to the total mass of the powder-containing resin composition, and the content of the fibrous raw material fine powder is a powder-containing resin. 46.0 mass% to 65.0 mass% with respect to the total mass of the composition.
また、本発明の第三の観点による粉末含有樹脂組成物は、
卵殻もしくは貝殻を高温焼成し加水を施した水酸化カルシウム微粉末と、卵殻もしくは貝殻の炭酸カルシウム微粉末と、木片または紙等の繊維質素材微粉末と、樹脂組成物とを含む粉末含有樹脂組成物であって、
前記水酸化カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して０．５質量％～７．０質量％であり、前記炭酸カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して５．０質量％～６０．０質量％であり、前記繊維質素材微粉末の含有量は、粉末含有樹脂組成物の総質量に対して５．０質量％～６０．０質量％であることを特徴とする。 The powder-containing resin composition according to the third aspect of the present invention is
Powder-containing resin composition comprising calcium hydroxide fine powder obtained by subjecting eggshells or shells to high-temperature firing and water addition, calcium carbonate fine powder of eggshells or shells, fine fiber powder such as wood chips or paper, and a resin composition A thing,
The content of the calcium hydroxide fine powder is 0.5 mass% to 7.0 mass% with respect to the total mass of the powder-containing resin composition, and the content of the calcium carbonate fine powder is the powder-containing resin composition. The content of the fine fiber material powder is 5.0% by mass to 60% by mass with respect to the total mass of the powder-containing resin composition. 0.0 mass%.
また、本発明の第四の観点による抗菌性食器は、
前記第一ないし第三の観点に記載された粉末含有樹脂組成物を用いた抗菌性箸、抗菌性スプーン、抗菌性ナイフ、抗菌性フォーク、抗菌性皿、抗菌性トレー、抗菌性カップ等の抗菌性食器であることを特徴とする。 In addition, the antibacterial tableware according to the fourth aspect of the present invention,
Antibacterials such as antibacterial chopsticks, antibacterial spoons, antibacterial knives, antibacterial forks, antibacterial dishes, antibacterial trays, and antibacterial cups using the powder-containing resin composition described in the first to third aspects It is a characteristic tableware.
本発明による粉末含有樹脂組成物においては、前述の成分から構成されることによって次に列挙する効果が得られる。
（１）石油由来の合成樹脂製品とは違い可燃物として処理が可能である。
（２）抗菌効果を目的とした水酸化カルシウムを混合しているが、これは卵殻や貝殻などの生物由来の物であり、人体に対してアレルギーや副作用などを生じさせるおそれがない。また、殺菌力も極めて高く、銀系抗菌剤や光触媒を用いた従来の抗菌剤に勝るとも劣らない抗菌・防腐効果を発揮することができる。 In the powder-containing resin composition according to the present invention, the effects listed below can be obtained by being composed of the aforementioned components.
(1) Unlike petroleum-derived synthetic resin products, it can be treated as a combustible material.
(2) Calcium hydroxide is mixed for the purpose of antibacterial effect, but it is derived from organisms such as eggshells and shells, and there is no risk of causing allergies or side effects to the human body. In addition, it has extremely high bactericidal power and can exhibit antibacterial and antiseptic effects comparable to conventional antibacterial agents using silver-based antibacterial agents and photocatalysts.
（３）水酸化カルシウムは、消臭効果も高いために、水酸化カルシウムを樹脂母材に混合した時に樹脂母材の樹脂臭も軽減することができる。因みに、樹脂母材は、熱可塑性樹脂であっても良いし、あるいは熱硬化性樹脂であっても良い。
（４）従来、廃棄処分とされていた木片や紙（パルプ）などの再利用に役立ち、社会における資源リサイクルに貢献することが出来る。 (3) Since calcium hydroxide has a high deodorizing effect, the resin odor of the resin base material can be reduced when calcium hydroxide is mixed with the resin base material. Incidentally, the resin base material may be a thermoplastic resin or a thermosetting resin.
(4) It can be used to recycle wood chips and paper (pulp), which have been conventionally disposed of, and can contribute to resource recycling in society.
以下、本発明を実施するための最良の形態である実施例について、本願の明細書に添付した各図面を参照しつつ以下に説明を行う。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments that are the best mode for carrying out the present invention will be described below with reference to the drawings attached to the specification of the present application.
（１）  水酸化カルシウム微粉末の生成
　本発明に基づく水酸化カルシウムは、その主原料として生物由来である卵殻や貝殻等の炭酸カルシウムを使用する。それらの主原料から本発明において使用される抗菌・防腐・消臭性能が高い水酸化カルシウム微粉末の生成方法の説明を行う。 (1) Production of calcium hydroxide fine powder The calcium hydroxide according to the present invention uses biologically derived calcium carbonate such as eggshells and shells as its main raw material. The production method of calcium hydroxide fine powder having high antibacterial, antiseptic and deodorizing performance used in the present invention from these main raw materials will be described.
（１－１）主原料として貝殻を使用する場合
　本発明に用いられる水酸化カルシウム微粉末は、生物由来の炭酸カルシウムを高温焼成した後に、加水を施しこれを所定の微粉砕方法によって微細粉末化したものである。 (1-1) When shellfish is used as the main raw material The calcium hydroxide fine powder used in the present invention is pulverized from biologically derived calcium carbonate at high temperature, and then subjected to water addition to make it fine powder by a predetermined pulverization method. It is a thing.
　ここで生物由来の炭酸カルシウムとしては、天然或いは養殖を問わず、例えばホタテの貝殻、ハマグリ貝殻、アサリ貝殻、ホッキ貝殻等の二枚貝の貝殻を利用することができるが、その他の珊瑚などを用いてもよい。但し、貝殻の組成分が均一であること、並びに供給量が極めて安定していることなどの点に鑑みれば、養殖用のホタテの貝殻を用いることが最も望ましい。 As biological calcium carbonate here, bivalve shells such as scallop shells, clams shells, clams shells, sea shells, etc. can be used regardless of natural or aquaculture. Also good. However, in view of the fact that the composition of the shell is uniform and the supply amount is extremely stable, it is most desirable to use a scallop shell for aquaculture.
　生物由来の炭酸カルシウムを用いて焼成し生成された酸化カルシウムやそれに加水を施した水酸化カルシウムには殺菌力、防腐、消臭等の効果があることは周知の事実である。係る効果を最大限に発揮させるには、その焼成方法並びに粉砕方法が極めて重要な要素となる。すなわち、生物由来の炭酸カルシウムを焼成、粉砕して生成された水酸化カルシウム微粉末のアルカリイオン還元能力は、その焼成方法並びに微粉末化工程によって得られる粉末粒径によって大きく異なる。 It is a well-known fact that calcium oxide produced by firing with calcium carbonate derived from living organisms and calcium hydroxide with water added thereto have effects such as bactericidal power, antiseptic and deodorizing. In order to maximize the effect, the firing method and pulverization method are extremely important factors. That is, the alkali ion reduction ability of the calcium hydroxide fine powder produced by firing and pulverizing biological calcium carbonate varies greatly depending on the firing method and the powder particle size obtained by the fine powdering step.
　因みに、水酸化カルシウムではなく、水酸化カルシウム生成前の酸化カルシウムを使用すると、酸化カルシウムはその水和時に発熱を起こす特性を有するので、樹脂混錬時において樹脂成型温度に不具合が生じるため、本発明に酸化カルシウムを使用することはできない。 By the way, if calcium oxide before calcium hydroxide formation is used instead of calcium hydroxide, calcium oxide generates heat during its hydration, which causes problems in resin molding temperature during resin kneading. Calcium oxide cannot be used in the invention.
　本実施例では、生物由来の炭酸カルシウム（具体的にはホタテ貝殻を用いる）を単に焼成するだけではなく、特殊高温焼成分解炉において摂氏８５０～１，１５０度の範囲内において焼成を施し、その焼成時間は１時間以上が望ましい。なお本発明における焼成温度は、８５０～１，２００度程度の範囲内であれば問題はなく、通常では摂氏１，０００度程度の設定温度で、約１時間にわたり高温焼成を行うことが望ましい。但し、最適には摂氏１，０００度程度の設定温度で、約１時間から２時間までの高温焼成が最も好ましい。 In this embodiment, biological calcium carbonate (specifically using scallop shells) is not simply fired, but is fired within a range of 850 to 1,150 degrees Celsius in a special high temperature firing cracking furnace. The firing time is desirably 1 hour or longer. Note that there is no problem if the firing temperature in the present invention is in the range of about 850 to 1,200 degrees, and it is usually desirable to perform high-temperature firing for about 1 hour at a set temperature of about 1,000 degrees Celsius. However, optimally, high-temperature baking for about 1 to 2 hours at a set temperature of about 1,000 degrees Celsius is most preferable.
　このような高温焼成処理は、空気中で行なってもよいが、或いは、窒素や炭酸ガス等の不活性ガスの範囲気内で行うようにしても良い。因みに、係る高温焼成処理を施すことによって、生物由来の炭酸カルシウム中に含まれる炭酸カルシウム以外の有機物などが熱分解により除去されることになる。 Such high-temperature baking treatment may be performed in the air, or may be performed in the range of an inert gas such as nitrogen or carbon dioxide. Incidentally, by performing such high-temperature baking treatment, organic matter other than calcium carbonate contained in biological calcium carbonate is removed by thermal decomposition.
　生物由来の炭酸カルシウムの組成は（CaCO３）であり、これを高温焼成（８５０度以上で１時間以上）することによって酸化カルシウム（CaO）が得られる。本実施例においては、前記酸化カルシウム（CaO）に所定の水和処理を施すことにより変性されて得ることができる。なお、本実施例で生成した水酸化カルシウムの組成成分を図１（ａ）の図表に示す。 The composition of biological calcium carbonate is (CaCO 3 ), and calcium oxide (CaO) can be obtained by baking it at a high temperature (850 ° C. or more for 1 hour or more). In this embodiment, the calcium oxide (CaO) can be obtained by being modified by subjecting it to a predetermined hydration treatment. In addition, the composition component of the calcium hydroxide produced | generated in the present Example is shown in the chart of Fig.1 (a).
　水酸化カルシウム（Ca（OH）２）は、アルカリイオン還元能力が極めて高く、そのpH（ペーハー）は、１２．０～１３．８にも及ぶものである。係る強アルカリ（強塩基）性によって、抗菌効果や防腐、消臭効果等の性能が発揮されることになる。 Calcium hydroxide (Ca (OH) 2 ) has an extremely high ability to reduce alkali ions, and its pH (pH) ranges from 12.0 to 13.8. Such strong alkali (strong base) properties exhibit performance such as antibacterial effect, antiseptic effect, and deodorant effect.
　本実施例では、高温焼成及びその焼成時間、ならびに水和時の水分添加量、水分添加方法によって上記アルカリ性pH（ペーハー）に大きな相違が生じる。また、粉末の粒径（微細化）によってもアルカリ性pH（ペーハー）に大きな影響あることが確認・実証されている。 In this example, the alkaline pH (pH) differs greatly depending on the high-temperature firing, the firing time, the amount of water added during hydration, and the method of adding water. In addition, it has been confirmed and verified that the particle size (miniaturization) of the powder has a great influence on the alkaline pH (pH).
　また、上記において、水和時の水分添加量及び添加方法によって、生物由来の炭酸カルシウムが、焼成によって生成された酸化カルシウム（CaO）から水酸化カルシウム（Ca（OH）２）への変性確率が大きく異なる。本発明においては、水酸化カルシウム（Ca（OH）２）の濃度が極めて重要なポイントになり、アルカリ性pH（ペーハー）に大きな影響あることが確認・実証されている。 In addition, in the above, depending on the amount of water added during hydration and the addition method, the biological calcium carbonate has a probability of denaturation from calcium oxide (CaO) generated by firing to calcium hydroxide (Ca (OH) 2 ). to differ greatly. In the present invention, the concentration of calcium hydroxide (Ca (OH) 2 ) is an extremely important point, and it has been confirmed and verified that it has a great influence on the alkaline pH (pH).
　以上の処理を施すことによって、強アルカリ（強塩基）性pH（ペーハー）は１３．８程度までに上昇し、抗菌効果や防腐、消臭効果等が極めて強力に発揮され、しかも、銀系抗菌剤等と比較して極めて低コストで生成することができる。 By applying the above treatment, the strong alkali (strong base) pH (pH) is increased to about 13.8, the antibacterial effect, antiseptic, deodorizing effect, etc. are exerted extremely strongly, and silver antibacterial It can be produced at an extremely low cost as compared with agents.
ところで、粉砕工程において、粒子の微細化は粉砕された微粒子の粒径が５μｍ以下になると粉砕中に微粒子同士の再結合が頻繁に発生し、微粒子の粒径が不揃いとなり粒子径の均一化が図れない等不具合が生ずる。そのため本実施例では、高温焼成・水和後の水酸化カルシウム（Ca（OH）２）の粉砕処理において、微粒子同士の再結合を防止すべく、シリカ微粉末（SiO２）を水酸化カルシウム（Ca（OH）２）の総質量に対して０．５～５．０質量％（好適には、０．７～１．５質量％）配合する。これによって、粉砕処理後の粒子の平均粒径を０．５～３．０μｍに均一化することができる。 By the way, in the pulverization step, when the particle size of the pulverized fine particles becomes 5 μm or less, recombination of the fine particles frequently occurs during the pulverization, the particle sizes of the fine particles become irregular and the particle size becomes uniform. Problems such as inability to plan occur. Therefore, in this example, in the pulverization treatment of calcium hydroxide (Ca (OH) 2 ) after high-temperature firing / hydration, silica fine powder (SiO 2 ) is converted to calcium hydroxide (SiO 2 ) in order to prevent recombination of fine particles. 0.5 to 5.0 mass% (preferably 0.7 to 1.5 mass%) is blended with respect to the total mass of Ca (OH) 2 ). As a result, the average particle diameter of the pulverized particles can be made uniform to 0.5 to 3.0 μm.
前述の工程による粒径の均一化工程を特に望まない場合は、高温焼成・水和後の水酸化カルシウム（Ca（OH）２）の粉砕処理において、微粒子同士の再結合を防止すべく、同粉体の含水率を２７００ppm～３５００ppmの範囲になるよう強制乾燥機にて３～４時間乾燥工程を再度行うことが好ましい。 If the particle size homogenization process by the above-mentioned process is not particularly desired, in order to prevent recombination of fine particles in the pulverization process of calcium hydroxide (Ca (OH) 2 ) after high-temperature firing and hydration, It is preferable to perform the drying step again for 3 to 4 hours in a forced dryer so that the moisture content of the powder is in the range of 2700 ppm to 3500 ppm.
本実施例においては、上記の処理によって生成された水酸化カルシウムを、特殊微粉砕機（例えば、エアジェットミル装置）にセットして、平均粒径が０．５～３．０μｍ程度の微細粉末を生成する。 In this example, the calcium hydroxide produced by the above treatment is set in a special pulverizer (for example, an air jet mill), and a fine powder having an average particle size of about 0.5 to 3.0 μm. Is generated.
（１－２）主原料として卵殻を使用する場合
　主原料として卵殻を用いた場合の水酸化カルシウム粉末の製造プロセスも、上記に示した貝殻を主原料として用いた場合の製造プロセスとほぼ同様である。但し、卵殻の場合は前述の貝殻の場合と異なり、殻の厚みが非常に薄く質量も小さいため、焼成温度を低く設定し、また焼成時間も短く設定する。本実施例において主原料として卵殻を用いた場合は、焼成温度を摂氏９００度程度にし、焼成時間は５～１０分間程度（好適には６分間程度）とすることが望ましい。 (1-2) When eggshell is used as the main raw material The manufacturing process of calcium hydroxide powder when eggshell is used as the main raw material is almost the same as the manufacturing process when the shell shown above is used as the main raw material. is there. However, in the case of eggshell, unlike the case of shells described above, the thickness of the shell is very thin and the mass is small, so the firing temperature is set low and the firing time is also set short. When eggshell is used as the main raw material in this embodiment, it is desirable that the baking temperature is about 900 degrees Celsius and the baking time is about 5 to 10 minutes (preferably about 6 minutes).
　また、卵殻の場合は貝殻と異なり原材料に含まれる不純物が少ないため、前述の貝殻の場合に比較して、ほぼ純粋な水酸化カルシウムを得ることが可能となる。なお、焼成後における微粉砕工程や、粉砕粒径などの各種のパラメータに関しては、前述した貝殻の場合の製造プロセスと同様である。 Also, unlike eggshells, eggshells contain less impurities in the raw materials, so that it is possible to obtain almost pure calcium hydroxide compared to the aforementioned shells. Note that the fine pulverization step after firing and various parameters such as the pulverized particle size are the same as the manufacturing process in the case of the shell described above.
（２）  炭酸カルシウム微粉末の生成
　本発明に基づく炭酸カルシウムは、その主原料として生物由来である卵殻や貝殻等の炭酸カルシウムである。以下に、その炭酸カルシウム微粉末の生成方法の説明を行う。
（２－１）主原料として貝殻を使用する場合
　本発明に用いられる炭酸カルシウム微粉末は、生物由来の炭酸カルシウムを所定の微粉砕方法によって微細粉末化したものである。 (2) Production of calcium carbonate fine powder Calcium carbonate based on the present invention is calcium carbonate such as eggshells and shells derived from living organisms as its main raw material. Below, the production | generation method of the calcium carbonate fine powder is demonstrated.
(2-1) When shells are used as the main raw material The calcium carbonate fine powder used in the present invention is obtained by finely pulverizing biological calcium carbonate by a predetermined pulverization method.
　ここで生物由来の炭酸カルシウムとしては、天然或いは養殖を問わず、例えばホタテの貝殻、ハマグリ貝殻、アサリ貝殻、ホッキ貝殻等の二枚貝との貝殻を利用することができるが、その他の珊瑚などを用いてもよい。但し、貝殻の組成物が均一であること、並びに供給量が極めて安定していることなどの点に鑑みれば、養殖用のホタテの貝殻を用いることが好ましい。 Here, as the calcium carbonate derived from living organisms, for example, scallop shells, clams shells, clams shells, sea shells such as sea shells can be used regardless of natural or aquaculture, but other shellfish etc. are used. May be. However, in view of the fact that the composition of the shell is uniform and the supply amount is extremely stable, it is preferable to use a scallop shell for aquaculture.
　生物由来の炭酸カルシウムの組成は（CaCO３）であり、本発明に用いられる炭酸カルシウム微粉末は、これをミル粉砕装置等により粒径を８０～１００μｍ程度に粉砕することによって得ることができる。 The composition of biological calcium carbonate is (CaCO 3 ), and the calcium carbonate fine powder used in the present invention can be obtained by pulverizing it to a particle size of about 80 to 100 μm using a mill pulverizer or the like.
　（２－２）主原料として卵殻を使用する場合
　本発明に用いられる炭酸カルシウム微粉末は、生物由来の炭酸カルシウムを所定の微粉砕方法によって微細粉末化したものである。 (2-2) When eggshell is used as the main raw material The calcium carbonate fine powder used in the present invention is obtained by finely pulverizing biological calcium carbonate by a predetermined pulverization method.
　主原料として卵殻を用いた場合の炭酸カルシウム粉末の製造プロセスも、上記に示した貝殻を主原料として用いた場合の微粉砕工程や、粉砕粒径などの各種のパラメータに関しても、上記した貝殻の場合の製造プロセスと同様である。 The manufacturing process of calcium carbonate powder when eggshell is used as the main raw material, the pulverization process when shells shown above are used as the main raw material, and various parameters such as the pulverized particle size, etc. This is the same as the manufacturing process.
（３）  木片及び紙（パルプ）等の繊維質素材微粉末の生成
　本発明に用いられる繊維質素材微粉末は、その主原料に特定性を持たず安全・安心である物質であればその使用が可能である。ここでは、木片及び紙（パルプ）微粉末の生成方法の説明を行う。 (3) Production of fine fiber material powder such as wood chips and paper (pulp) The fine fiber material powder used in the present invention can be used as long as it is a safe and secure substance that does not have specificity in its main raw materials. Is possible. Here, a method for producing a piece of wood and paper (pulp) fine powder will be described.
（３－１）主原料として木片を使用する場合
　本発明に用いられる繊維質素材微粉末において、木片を使用する場合は木片チップの乾燥工程が重要になる。木片の含水率は、一般に極めて高く乾燥材を除いては８０％を超えるものがほとんどである。含水率が高いままの木片チップ等を用いての微粉砕化は困難であり、粉砕された木片粉をそのまま樹脂へ混錬かると、樹脂の物性を低下させる等の不具合を生ずるため強制的な乾燥工程が必要とされる。 (3-1) When using wood chips as the main raw material When using wood chips in the fine fiber material powder used in the present invention, the drying process of the wood chip becomes important. The moisture content of the wood pieces is generally extremely high, and most of them exceed 80% except for the desiccant. It is difficult to pulverize with wood chips with a high moisture content, and if the crushed wood powder is kneaded into resin as it is, it will cause problems such as lowering the physical properties of the resin. A drying step is required.
　木片の乾燥は、強制的な乾燥機において含水率を１５～３５％まで低下させるべく乾燥を行う。因みに、好適な含水率は１５～２５％である。木材の樹種により異なるが、約３０％以下が木片の繊維飽和点であることから含水率が３０％以下のものを使用する。因みに、木片は繊維飽和点に達すると力学的性能（縦圧縮・横圧縮・硬さ縦引張・横引張・曲げ・せん断）が著しく向上する。 The wood pieces are dried to reduce the water content to 15 to 35% in a forced dryer. Incidentally, the preferable water content is 15 to 25%. Although it differs depending on the wood species, wood having a moisture content of 30% or less is used because about 30% or less is the fiber saturation point of the wood pieces. Incidentally, when the wood piece reaches the fiber saturation point, the mechanical performance (longitudinal compression / transverse compression / hardness longitudinal tension / transverse tension / bending / shear) is remarkably improved.
木片の粉砕においては、上記乾燥工程を経た木片をミル粉砕装置等により、粒径８０～１００μｍ程度に粉砕することによって、木片を主原料とした繊維質素材微粉末を得ることができる。 In the pulverization of the wood piece, the fiber material fine powder using the wood piece as a main raw material can be obtained by pulverizing the wood piece that has undergone the drying step to a particle size of about 80 to 100 μm with a mill pulverizer or the like.
（３－２）主原料として紙片（パルプ）を使用する場合
　本発明に用いられる繊維質素材微粉末として、紙片（パルプ）を使用する場合、紙片の乾燥工程は木片と比較して少なく、その含水率は保存状態により異なるが、通常で保存の場合は含水率が８～２０％である。この場合、やはり強制的に乾燥機において含水率を８～１０％まで乾燥を行う。粉砕においては、上記乾燥工程を得た紙片をミル粉砕装置等により、粒径を８０～１００μｍに粉砕することによって繊維質素材微粉末を得ることができる。 (3-2) When using a piece of paper (pulp) as the main raw material When using a piece of paper (pulp) as the fine fiber material powder used in the present invention, the drying process of the piece of paper is less than that of wood pieces. The moisture content varies depending on the storage condition, but in normal storage, the moisture content is 8 to 20%. In this case, the moisture content is forcibly dried to 8 to 10% in the dryer. In the pulverization, the fiber material fine powder can be obtained by pulverizing the paper piece obtained in the drying step to a particle size of 80 to 100 μm with a mill pulverizer or the like.
（４）本発明に基づく粉末含有樹脂組成物
　上記（１）の製造プロセスで得られた水酸化カルシウム微粉末と、（２）の製造プロセスで得られた炭酸カルシウム微粉末、あるいは（３）の製造プロセスで得られた木片及び紙（パルプ）等の繊維質素材微末を樹脂に混合することにより、抗菌性を有し、なおかつ樹脂の配合割合を減らし（樹脂を減少させた分は、（２）（３）の製造プロセスで得られた炭酸カルシウム微粉末や、木片及び紙（パルプ）等の繊維質素材微粉末で補う。）、製造コストを減少させた多機能性粉末含有樹脂組成物を得ることができる。 (4) Powder-containing resin composition based on the present invention The calcium hydroxide fine powder obtained by the production process of (1) above and the calcium carbonate fine powder obtained by the production process of (2), or (3) Mixing fiber material fine powder such as wood chips and paper (pulp) obtained in the manufacturing process with the resin has antibacterial properties and also reduces the blending ratio of the resin (the amount of the resin decreased is (2 ) Supplement with calcium carbonate fine powder obtained by the production process of (3) and fibrous raw material fine powder such as wood chips and paper (pulp).), Multifunctional powder-containing resin composition with reduced production cost Obtainable.
　本実施例においては、何れの原料をベースとした場合であっても、水酸化カルシウム微粉末の含有比率は、粉末含有樹脂組成物の総質量に対して０．５質量％～７．０質量％の範囲内に設定することが望ましい。 In this example, the content ratio of the calcium hydroxide fine powder is 0.5% by mass to 7.0% by mass with respect to the total mass of the powder-containing resin composition regardless of which raw material is used as a base. It is desirable to set within the range of%.
また、他の混合物である微粉末は（２）の製造プロセスで得られた炭酸カルシウム微粉末、或いは（３）の製造プロセスで得られた木片及び紙（パルプ）等の繊維質素材微粉末の一方、或いはその両方を含むものであっても良い。なお、各微粉末の含有比率は、粉末含有樹脂組成物の総質量に対して４６．０質量％～６５．０質量％の範囲内に設定することが好ましい。 In addition, the fine powder which is another mixture is a fine powder of calcium carbonate obtained by the production process of (2) or a fine fiber powder of fiber material such as wood chips and paper (pulp) obtained by the production process of (3). One or both of them may be included. The content ratio of each fine powder is preferably set in the range of 46.0 mass% to 65.0 mass% with respect to the total mass of the powder-containing resin composition.
本実施例で用いられる樹脂組成物としては、ポリプロピレン樹脂またはポリエチレン樹脂などの高分子樹脂を用いることが可能であり、特に樹脂の選別は問わない。また、樹脂の性質に関しても特に限定するものではなく、例えば熱可塑性樹脂や、熱硬化性樹脂も使用することが可能である。 As the resin composition used in this example, a polymer resin such as a polypropylene resin or a polyethylene resin can be used, and the selection of the resin is not particularly limited. Moreover, it does not specifically limit regarding the property of resin, For example, a thermoplastic resin and a thermosetting resin can also be used.
（５）  本発明に基づく多機能性粉末含有樹脂組成物の応用製品
　前述のように、本発明に基づく多機能性粉末含有樹脂組成物は、強力な抗菌性・殺菌性を有し、かつ人体に対し極めて高い安全性を有しているので、箸、スプーン、フォーク、ナイフ、皿、トレー、カップ等の食器素材として用いることが最適である。 (5) Application product of multi-functional powder-containing resin composition based on the present invention As described above, the multi-functional powder-containing resin composition based on the present invention has strong antibacterial and bactericidal properties, and is a human body. Therefore, it is optimal to use as a tableware material such as chopsticks, spoons, forks, knives, plates, trays, cups.
例えば、現在、外食産業や仕出し弁当、コンビニ弁当においては、ワンウエイの割り箸が主流となっている。一部には、木製や竹製といった素材によるものも見受けられるが、雑菌消毒処理として危険性の高いケミカル処理がなされている。本発明による多機能性粉末含有樹脂組成物の応用製品を利用すれば、コストパフォーマンスに優れ、同等の価格帯で安全性が高く、かつ可燃物としても廃棄処理が容易な様々の食器類を提供することができる。 For example, in the restaurant industry, catered lunches and convenience store lunches, one-way disposable chopsticks are the mainstream. Some of these are made of materials such as wood and bamboo, but they are treated with high-risk chemicals for disinfection. Use of the application product of the multifunctional powder-containing resin composition according to the present invention provides various tableware with excellent cost performance, high safety at the same price range, and easy disposal as flammables can do.
　また、本発明に基づく多機能性粉末含有樹脂組成物から成る箸は、その物性強度も十分に兼ね備えており、かつ高い抗菌性能も有しているため、外食産業において、現在の樹脂製箸の代わりとしても使用が可能である。 In addition, the chopsticks made of the multifunctional powder-containing resin composition according to the present invention have sufficient physical properties and high antibacterial performance. It can be used as an alternative.
（６）  本発明に用いられる水酸化カルシウム微粉末の抗菌・防腐効果
　次に、本発明に基づく生物由来からなる水酸化カルシウムの抗菌・防腐効果の実証例について説明を行う。添付図面の図１（ｂ）に（１）の製造プロセスで得られた水酸化カルシウム微粉末を用いた多機能性粉末含有樹脂組成物の抗菌効果に関する抗菌性試験（JIS-Z ２８０１）の結果を示す。 (6) Antibacterial and antiseptic effect of calcium hydroxide fine powder used in the present invention Next, a demonstration example of the antibacterial and antiseptic effect of calcium hydroxide composed of organisms based on the present invention will be described. Results of antibacterial test (JIS-Z 2801) on the antibacterial effect of the multifunctional powder-containing resin composition using the calcium hydroxide fine powder obtained by the manufacturing process of (1) in FIG. Indicates.
図１（ｂ）の図表によれば、（１）の製造プロセスで得られた水酸化カルシウムは、黄色ブドウ球菌に対しては、その静菌活性値が３．６、殺菌活性値が１．３を示し、大腸菌に対しては、その静菌活性値が５．３、殺菌活性値が３．２という極めて高い数値を有することが示されている。因みに、静菌活性値および殺菌活性値とは、共に抗菌剤の細菌類に対する繁殖抑止効果を表したパラメータであり、一般に、
静菌活性値≧２．０　　　殺菌活性値≧０．０
であれば、その抗菌・防腐効果が有効であると認証されている。 According to the chart of FIG. 1B, the calcium hydroxide obtained by the production process of (1) has a bacteriostatic activity value of 3.6 and a bactericidal activity value of 1. 3 for Escherichia coli, indicating that the bacteriostatic activity value is 5.3 and the bactericidal activity value is 3.2. Incidentally, both the bacteriostatic activity value and the bactericidal activity value are parameters that represent the effect of inhibiting the growth of antibacterial agents against bacteria.
Bacteriostatic activity value ≧ 2.0 Bactericidal activity value ≧ 0.0
If so, it is certified that its antibacterial and antiseptic effects are effective.
　また、本発明に基づく多機能性粉末含有樹脂組成物の細菌類に対する繁殖抑止効果を視認できるデータとして、ＪＩＳ・Ｌ１９０２：２００８の菌液吸収法試験による試験結果写真を図２および図３に示す。因みに、図２は供試菌が大腸菌の場合を示すものであり、図３は供試菌が黄色ブドウ球菌の場合を示すものである。 Moreover, as data which can visually recognize the reproduction suppression effect with respect to bacteria of the multifunctional powder containing resin composition based on this invention, the test result photograph by the microbial liquid absorption test of JIS * L1902: 2008 is shown in FIG. 2 and FIG. . Incidentally, FIG. 2 shows the case where the test bacterium is Escherichia coli, and FIG. 3 shows the case where the test bacterium is Staphylococcus aureus.
これらの写真からも明らかなように、本発明に基づく多機能性粉末含有樹脂組成物を添加した培養地（各写真の左側シャーレ）においては、培養後１８時間を経過しても細菌によるコロニーの発生は全く認められなかった。なお、同図表の数値ならびに試験結果写真は、一般財団法人「カケンテストセンター」（大阪府）による平成２８年２月１２日付の試験報告書の記載に基づいている。 As is clear from these photographs, in the culture place to which the multifunctional powder-containing resin composition based on the present invention was added (the left petri dish in each photograph) No outbreak was observed. The figures and test result photos in the chart are based on the test report dated February 12, 2016 by the general foundation “Kaken Test Center” (Osaka Prefecture).
　以上に説明したように本発明に基づく多機能性粉末含有樹脂組成物は、貝殻や卵殻などの天然生物由来の原料とした水酸化カルシウムを用いるので、人体に対しても有害な副作用やアレルギー反応を引き起こすことなく、食品類に対して優れた抗菌・防腐効果が実現できる。また、使用される樹脂組成物の比率が全体の半分程度と少ないため、製品のコストパフォーマンスが高く、かつ、その廃棄時における燃焼焼却処理においてもCO２排出量が少なく環境に対する配慮がなされている。 As described above, since the multifunctional powder-containing resin composition according to the present invention uses calcium hydroxide as a raw material derived from natural organisms such as shells and eggshells, adverse side effects and allergic reactions are also harmful to the human body. It can realize excellent antibacterial and antiseptic effects on foods. In addition, since the ratio of the resin composition used is as small as about half of the whole, the cost performance of the product is high, and the CO 2 emission is low in the combustion incineration process at the time of disposal, and consideration is given to the environment. .
　なお、本発明の実施形態は、以上に説明した実施例に限定されるものではなく、例えば、各々の実施例を構成する各部位の形状や配置、或いはその素材などは、本発明の趣旨を逸脱することなく、現実の実施形態様に即して適宣変更ができるものであることは言うまでもない。 The embodiments of the present invention are not limited to the examples described above. For example, the shape and arrangement of each part constituting each of the examples, or the material thereof is the gist of the present invention. It goes without saying that appropriate changes can be made in accordance with the actual embodiment without departing.
以上に説明した本発明の構成並びに方法は食器類の分野に限らず、抗菌・防腐効果を必要とする分野においてその利用が可能である。 The configuration and method of the present invention described above are not limited to the tableware field, but can be used in fields that require antibacterial and antiseptic effects.
本発明に用いられる水酸化カルシウムの成分一覧、及びその抗菌効果の試験結果を示す図表である。It is a table | surface which shows the component list of the calcium hydroxide used for this invention, and the test result of the antibacterial effect. 本発明に用いられる水酸化カルシウムの細菌類（大腸菌）に対する繁殖抑止効果を示す写真である。It is a photograph which shows the reproduction inhibitory effect with respect to bacteria (E. coli) of the calcium hydroxide used for this invention. 本発明に用いられる水酸化カルシウムの細菌類（黄色ブドウ球菌）に対する繁殖抑止効果を示す写真である。It is a photograph which shows the reproduction inhibitory effect with respect to bacteria (Staphylococcus aureus) of the calcium hydroxide used for this invention.

Claims (4)

  1. 卵殻もしくは貝殻を高温焼成し加水を施した水酸化カルシウム微粉末と、卵殻もしくは貝殻の炭酸カルシウム微粉末と、樹脂組成物とを含む粉末含有樹脂組成物であって、
    前記水酸化カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して０．５質量％～７．０質量％であり、前記炭酸カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して４６．０質量％～６５．０質量％であることを特徴とする粉末含有樹脂組成物。     A powder-containing resin composition comprising calcium hydroxide fine powder obtained by firing eggshell or shellfish at high temperature and hydrolyzing, fine calcium carbonate powder of eggshell or shellfish, and a resin composition,
    The content of the calcium hydroxide fine powder is 0.5 mass% to 7.0 mass% with respect to the total mass of the powder-containing resin composition, and the content of the calcium carbonate fine powder is the powder-containing resin composition. A powder-containing resin composition characterized by being 46.0% by mass to 65.0% by mass with respect to the total mass of the product.
  2. 卵殻もしくは貝殻を高温焼成し加水を施した水酸化カルシウム微粉末と、木片または紙等の繊維質素材微粉末と、樹脂組成物とを含む粉末含有樹脂組成物であって、
    前記水酸化カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して０．５質量％～７．０質量％であり、前記繊維質素材微粉末の含有量は、粉末含有樹脂組成物の総質量に対して４６．０質量％～６５．０質量％であることを特徴とする粉末含有樹脂組成物。     A powder-containing resin composition comprising calcium hydroxide fine powder obtained by subjecting eggshells or shells to high-temperature firing and water addition, fine fiber powder such as wood chips or paper, and a resin composition,
    The content of the calcium hydroxide fine powder is 0.5% by mass to 7.0% by mass with respect to the total mass of the powder-containing resin composition, and the content of the fibrous raw material fine powder is a powder-containing resin. A powder-containing resin composition, comprising 46.0% by mass to 65.0% by mass with respect to the total mass of the composition.
  3. 卵殻もしくは貝殻を高温焼成し加水を施した水酸化カルシウム微粉末と、卵殻もしくは貝殻の炭酸カルシウム微粉末と、木片または紙等の繊維質素材微粉末と、樹脂組成物とを含む粉末含有樹脂組成物であって、
    前記水酸化カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して０．５質量％～７．０質量％であり、前記炭酸カルシウム微粉末の含有量は、粉末含有樹脂組成物の総質量に対して５．０質量％～６０．０質量％であり、前記繊維質素材微粉末の含有量は、粉末含有樹脂組成物の総質量に対して５．０質量％～６０．０質量％であることを特徴とする粉末含有樹脂組成物。     Powder-containing resin composition comprising calcium hydroxide fine powder obtained by subjecting eggshells or shells to high-temperature firing and water addition, calcium carbonate fine powder of eggshells or shells, fine fiber powder such as wood chips or paper, and a resin composition A thing,
    The content of the calcium hydroxide fine powder is 0.5 mass% to 7.0 mass% with respect to the total mass of the powder-containing resin composition, and the content of the calcium carbonate fine powder is the powder-containing resin composition. The content of the fine fiber material powder is 5.0% by mass to 60% by mass with respect to the total mass of the powder-containing resin composition. A powder-containing resin composition, characterized by being 0.0% by mass.
  4. 請求項１ないし請求項３の何れか一項に記載された粉末含有樹脂組成物を用いた抗菌性箸、抗菌性スプーン、抗菌性ナイフ、抗菌性フォーク、抗菌性皿、抗菌性トレー、抗菌性カップ等の抗菌性食器。 Antibacterial chopsticks, antibacterial spoon, antibacterial knife, antibacterial fork, antibacterial dish, antibacterial tray, antibacterial using the powder-containing resin composition according to any one of claims 1 to 3 Antibacterial tableware such as cups.
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