JP6293389B2 - Microbicide control agent and acaricide composition - Google Patents

Microbicide control agent and acaricide composition Download PDF

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JP6293389B2
JP6293389B2 JP2017550306A JP2017550306A JP6293389B2 JP 6293389 B2 JP6293389 B2 JP 6293389B2 JP 2017550306 A JP2017550306 A JP 2017550306A JP 2017550306 A JP2017550306 A JP 2017550306A JP 6293389 B2 JP6293389 B2 JP 6293389B2
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particles
platinum
resin
control agent
algae
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JPWO2017082201A1 (en
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正信 大北
正信 大北
楠 呉
楠 呉
甲 貴傳名
甲 貴傳名
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Osaka Gas Chemicals Co Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10Macromolecular compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12Powders or granules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • A01N59/20Copper
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles

Description

本発明は、微生物防除剤、抗菌剤、防藻剤、バイオフィルム形成抑制剤、微生物防除方法、抗菌方法、防藻方法、バイオフィルム形成抑制方法、殺ダニ組成物、防ダニ部材及び防ダニ方法に関する。   The present invention relates to a microbial control agent, an antibacterial agent, an algal control agent, a biofilm formation inhibitor, a microbial control method, an antibacterial method, an algae control method, a biofilm formation suppression method, an acaricide composition, an acaricide member and an acaricidal method. About.

食品、水、生活用品、動物、植物、汚泥等に付着している微生物やダニ等を除去する技術は、環境衛生の観点や耐久性等の観点から極めて重要である。従来、空気浄化技術、水処理技術、植物工場、食品工業においては、精密ろ過膜、逆浸透膜等のろ過膜によって微生物を制御する方法、あるいは、銀、銅、亜鉛などの金属、抗生物質又はイミダゾール・チアゾール等の農薬に代表される有機系化合物等の抗菌物質を利用する方法によって、微生物を除去することが行われている。これら一例として、銀(銀イオンおよび銀コロイド粒子のうち少なくとも1つを含む)含有液と繊維製品を接触させ、液体成分を除去することで繊維製品に抗菌効果を付与する技術が提案されている(例えば、特許文献1を参照)。   Techniques for removing microorganisms and mites adhering to food, water, daily necessities, animals, plants, sludge, etc. are extremely important from the viewpoint of environmental hygiene and durability. Conventionally, in air purification technology, water treatment technology, plant factories, food industry, methods for controlling microorganisms by filtration membranes such as microfiltration membranes and reverse osmosis membranes, metals such as silver, copper, zinc, antibiotics or Removal of microorganisms is performed by a method using an antibacterial substance such as an organic compound typified by agricultural chemicals such as imidazole and thiazole. As an example of these, a technique has been proposed in which an antibacterial effect is imparted to a fiber product by bringing the liquid containing silver (including at least one of silver ions and silver colloid particles) into contact with the fiber product and removing the liquid component. (For example, see Patent Document 1).

特開2007−31857号公報JP 2007-31857 A

しかしながら、上述したろ過膜によって微生物の量を制御する方法では、高圧損や目詰まり等の問題が発生し、効率的に微生物等を除去することが困難であった。また、上記特許文献1に開示のように銀イオンによって抗菌を行う技術では、銀イオンが溶出し、抗菌効果の持続性に問題があり、また、銀イオンの溶出により環境に影響を与えるという問題があった。その上、このような銀イオンが用いられる微生物防除剤では、抗菌性能の点においてもさらなる向上が求められていた。   However, in the method of controlling the amount of microorganisms using the above-described filtration membrane, problems such as high pressure loss and clogging occur, and it is difficult to efficiently remove microorganisms and the like. In addition, in the technique of performing antibacterial action using silver ions as disclosed in Patent Document 1, there is a problem in that silver ions are eluted and there is a problem in the durability of the antibacterial effect, and the environment is affected by the elution of silver ions. was there. In addition, the microorganism control agent using such silver ions has been required to further improve the antibacterial performance.

本発明は、上記に鑑みてなされたものであり、微生物防除性能、特に抗菌性能、防藻性能やバイオフィルム形成抑制性能に優れ、しかも、金属の溶出が抑制された微生物防除剤を提供することを目的とする。また、本発明は、ダニの発生及び増加を抑制する性能に優れ、殺ダニ組成物、防ダニ部材及び防ダニ方法を提供することを目的とする。   The present invention has been made in view of the above, and provides a microbial control agent that is excellent in microbial control performance, in particular, antibacterial performance, algal control performance and biofilm formation suppression performance, and in which metal elution is suppressed. With the goal. Moreover, this invention is excellent in the performance which suppresses generation | occurrence | production and increase of a tick, and it aims at providing an acaricide composition, an acaricide member, and an acaricidal method.

本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、特定の金属粒子の組み合わせにより、上記目的を達成できることを見出し、本発明を完成するに至った。   As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by a combination of specific metal particles, and has completed the present invention.

すなわち、本発明は、例えば以下の項に記載の主題を包含する。
項1.白金粒子と、白金以外の金属粒子とを含む、微生物防除剤。
項2.前記金属粒子が銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子からなる群より選ばれる少なくとも1種を含む、上記項1に記載の微生物防除剤。
項3.前記金属粒子が銀粒子及び銅粒子からなる群より選ばれる少なくとも1種を含む、上記項1に記載の微生物防除剤。
項4.前記白金粒子及び前記金属粒子の平均粒子径が0.1〜1000nmである、上記項1〜3のいずれか1項に記載の微生物防除剤。
項5.前記白金粒子及び前記金属粒子が基材上に担持されている、上記項1〜4のいずれか1項に記載の微生物防除剤。
項6.前記白金粒子及び前記金属粒子が0.01〜20,000ng/cmで前記基材に担持されている、上記項5に記載の微生物防除剤。
項7.前記基材が樹脂で形成されている、上記項5又は6に記載の微生物防除剤。
項8.前記樹脂がポリスチレン樹脂、塩化ビニル樹脂、フッ素樹脂、ABS樹脂、PET樹脂、ポリカーボネート樹脂、尿素樹脂、オレフィン樹脂及びフェノール樹脂からなる群より選ばれる少なくとも1種を含む、上記項7に記載の微生物防除剤。
項9.前記基材が、シート状、板状、ブロック状、ネット状、パンチングシート状、粒状、ロッド状、破砕状及びディッシュ状のいずれかの形状に形成されている、上記項5〜8のいずれか1項に記載の微生物防除剤。
項10.上記項1〜9のいずれか1項に記載の微生物防除剤を含む、抗菌剤。
項11.上記項1〜9のいずれか1項に記載の微生物防除剤を含む、防藻剤。
項12.上記項1〜9のいずれか1項に記載の微生物防除剤を含む、バイオフィルム形成抑制剤。
項13.上記項1〜9のいずれか1項に記載の微生物防除剤を用いて対象物に微生物防除機能を付与させる、微生物防除方法。
項14.上記項1〜9のいずれか1項に記載の微生物防除剤を用いて対象物に抗菌性を付与させる、抗菌方法。
項15.上記項1〜9のいずれか1項に記載の微生物防除剤を用いて対象物に防藻性を付与させる、防藻方法。
項16.上記項1〜9のいずれか1項に記載の微生物防除剤を用いて対象物にバイオフィルム形成抑制効果を付与させる、バイオフィルム形成抑制方法。
項17.白金粒子と、白金以外の金属粒子とを含む、殺ダニ組成物。
項18.前記金属粒子が銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子からなる群より選ばれる少なくとも1種を含む、上記項17に記載の殺ダニ組成物。
項19.前記金属粒子が銀粒子及び銅粒子からなる群より選ばれる少なくとも1種を含む、上記項17又は18に記載の殺ダニ組成物。
項20.前記白金粒子及び前記金属粒子の平均粒子径が0.1〜1000nmである、上記項17〜19のいずれか1項に記載の殺ダニ組成物。
項21.上記項17〜20のいずれか1項に記載の殺ダニ組成物を使用した、防ダニ部材(但し、養蜂部材を除く)。
項22.上記項17〜20のいずれか1項に記載の殺ダニ組成物を用いて対象物(但し、養蜂部材を除く)に防ダニ機能を付与させる、防ダニ方法。
That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1. A microbial control agent comprising platinum particles and metal particles other than platinum.
Item 2. Item 2. The microorganism control agent according to Item 1, wherein the metal particles include at least one selected from the group consisting of silver particles, copper particles, nickel particles, and zinc particles.
Item 3. Item 2. The microorganism control agent according to Item 1, wherein the metal particles include at least one selected from the group consisting of silver particles and copper particles.
Item 4. Item 4. The microorganism control agent according to any one of Items 1 to 3, wherein an average particle size of the platinum particles and the metal particles is 0.1 to 1000 nm.
Item 5. Item 5. The microorganism control agent according to any one of Items 1 to 4, wherein the platinum particles and the metal particles are supported on a substrate.
Item 6. Microbial control agent according to said platinum particles and the metal particles are supported on the substrate in 0.01~20,000ng / cm 2, Item 5.
Item 7. Item 7. The microorganism control agent according to Item 5 or 6, wherein the substrate is formed of a resin.
Item 8. The microorganism control according to Item 7, wherein the resin includes at least one selected from the group consisting of polystyrene resin, vinyl chloride resin, fluorine resin, ABS resin, PET resin, polycarbonate resin, urea resin, olefin resin, and phenol resin. Agent.
Item 9. Any of the above items 5 to 8, wherein the substrate is formed into any one of a sheet shape, a plate shape, a block shape, a net shape, a punching sheet shape, a granular shape, a rod shape, a crushed shape, and a dish shape. The microorganism control agent according to Item 1.
Item 10. Item 10. An antibacterial agent comprising the microorganism control agent according to any one of items 1 to 9.
Item 11. The algae control agent containing the microorganism control agent of any one of said items 1-9.
Item 12. A biofilm formation inhibitor comprising the microorganism control agent according to any one of Items 1 to 9.
Item 13. A microorganism control method for imparting a microorganism control function to an object using the microorganism control agent according to any one of Items 1 to 9.
Item 14. The antibacterial method of giving antimicrobial property to a target object using the microorganism control agent of any one of said items 1-9.
Item 15. An algae control method for imparting alga control to an object using the microorganism control agent according to any one of items 1 to 9.
Item 16. The biofilm formation suppression method of giving a biofilm formation inhibitory effect to a target object using the microorganism control agent of any one of said items 1-9.
Item 17. An acaricidal composition comprising platinum particles and metal particles other than platinum.
Item 18. Item 18. The acaricidal composition according to Item 17, wherein the metal particles include at least one selected from the group consisting of silver particles, copper particles, nickel particles, and zinc particles.
Item 19. Item 19. The acaricidal composition according to Item 17 or 18, wherein the metal particles include at least one selected from the group consisting of silver particles and copper particles.
Item 20. Item 20. The acaricidal composition according to any one of Items 17 to 19, wherein an average particle size of the platinum particles and the metal particles is 0.1 to 1000 nm.
Item 21. The tick-proof member (however, a beekeeping member is excluded) using the acaricide composition of any one of said item | term 17-20.
Item 22. 21. A tick-proof method for imparting an anti-mite function to an object (excluding beekeeping members) using the acaricidal composition according to any one of items 17 to 20.

本発明に係る微生物防除剤は、白金粒子と、白金以外の金属粒子とを含むことで、それぞれの金属粒子単独では到底なし得ない微生物防除性能、特に抗菌性能、防藻性能、およびバイオフィルムの形成抑制性能に優れ、しかも、金属の溶出も抑制される。そのため、上記微生物防除剤は、優れた微生物防除性能、特に抗菌性、防藻性能およびバイオフィルムの形成抑制性能を発揮すると共に、金属の溶出が抑制されることで耐久性や持続性が向上し、環境に与える影響も抑えることができる。また、本発明に係る微生物防除剤で基材を処理することにより、抗菌効果と防藻効果とバイオフィルム形成抑制効果の3つの異なる効果を併せ得ることができる。本発明に係る微生物防除剤を使用することにより、処理労力を半減することができ、また、処理コストも低減できるので、非常に有用である。   The microbial control agent according to the present invention contains platinum particles and metal particles other than platinum, so that the microbial control performance, especially antibacterial performance, anti-algae performance, Excellent formation suppression performance, and metal elution is also suppressed. Therefore, the above-mentioned microbial control agent exhibits excellent microbial control performance, in particular, antibacterial property, anti-algae performance and biofilm formation suppression performance, and also improves durability and sustainability by suppressing metal elution. The impact on the environment can also be reduced. In addition, by treating the substrate with the microorganism control agent according to the present invention, three different effects of an antibacterial effect, an algal control effect, and a biofilm formation inhibitory effect can be obtained together. By using the microorganism control agent according to the present invention, the processing effort can be halved and the processing cost can be reduced, which is very useful.

本発明に係る殺ダニ組成物は、白金粒子と、白金以外の金属粒子とを含むことで、白金粒子及び上記金属粒子単独では到底なし得ないダニの発生抑制機能及びダニの増加抑制機能を発揮することが可能となる。上記殺ダニ組成物を使用した防ダニ部材は、ダニの発生及び増加を抑制する性能に優れるので、防ダニや殺ダニを必要とする資材全般に対して使用でき、例えば、生活関連資材として、タタミ、カーペット、壁材、床材、天井材、家具、家電製品、食品容器、食品包装材、台所製品などに適しており、また例えば、産業用資材として、植物、動物、昆虫等を育成したり、保管したりする部材(但し、養蜂部材を除く)として適している。   The acaricidal composition according to the present invention includes a platinum particle and a metal particle other than platinum, thereby exhibiting a tick generation suppressing function and a tick increase suppressing function that cannot be achieved with platinum particles and the above metal particles alone. It becomes possible to do. The mite-preventing member using the mite-killing composition is excellent in the performance of suppressing the occurrence and increase of mites, so it can be used for all materials that require mite-prevention and mite-killing, for example, as life-related materials, Suitable for tatami, carpets, wall materials, floor materials, ceiling materials, furniture, home appliances, food containers, food packaging materials, kitchen products, etc. Or as a member to be stored (excluding beekeeping members).

参考試験例1の結果であり、飼育時間とミツバチヘギイタダニの生存数との関係を示している。It is the result of the reference test example 1, and has shown the relationship between breeding time and the number of living honeybee mites. 参考試験例2の結果であり、飼育時間とミツバチヘギイタダニの生存数との関係を示している。It is the result of the reference test example 2, and has shown the relationship between breeding time and the number of living honeybee mites.

以下、本発明の実施形態について詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail.

(微生物防除剤および殺ダニ組成物)
本実施形態の微生物防除剤および殺ダニ組成物は、白金粒子と、白金以外の金属粒子とを含む。以下、上記の「白金以外の金属粒子」を単に「金属粒子」と略記することがある。
(Microbicide control agent and acaricide composition)
The microorganism control agent and acaricide composition of this embodiment contain platinum particles and metal particles other than platinum. Hereinafter, the above “metal particles other than platinum” may be simply abbreviated as “metal particles”.

白金粒子は、白金(Pt)で構成される粒子である。白金粒子としては、通常は、白金元素で形成されるが、白金の酸化物が含まれていてもよい。その他、白金粒子は、白金と他の金属元素との合金が含まれていてもよい。   The platinum particles are particles composed of platinum (Pt). The platinum particles are usually formed of platinum element, but may contain platinum oxide. In addition, the platinum particles may contain an alloy of platinum and another metal element.

上記金属粒子は、特に限定されないが、銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子のからなる群より選ばれる少なくとも1種であることが好ましい。この場合、毒性が低い上に抗菌性能及び殺ダニ性能に優れるので、微生物の発生を防止又は除去する効果やダニの発生及び増加を抑制する効果が大きくなる。   The metal particles are not particularly limited, but are preferably at least one selected from the group consisting of silver particles, copper particles, nickel particles, and zinc particles. In this case, since the toxicity is low and the antibacterial performance and the acaricidal performance are excellent, the effect of preventing or removing the generation of microorganisms and the effect of suppressing the generation and increase of mites are increased.

金属粒子は、白金粒子と同様、通常は、例えば、銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子のからなる群より選ばれる少なくとも1種の金属元素で形成される。金属粒子には、該金属元素の酸化物が含まれていてもよい。その他、上記金属粒子は、前記金属元素と他の金属元素で構成さされる合金が含まれていてもよい。   The metal particles are usually formed of at least one metal element selected from the group consisting of silver particles, copper particles, nickel particles, and zinc particles, for example, like the platinum particles. The metal particles may contain an oxide of the metal element. In addition, the metal particles may include an alloy composed of the metal element and another metal element.

上記金属粒子は、例えば、銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子のうちの1種のみで構成されていてもよいし、あるいは、2種以上を含んで構成されていてもよい。   For example, the metal particles may be composed of only one of silver particles, copper particles, nickel particles, and zinc particles, or may be composed of two or more.

上記金属粒子としては、銀粒子及び銅粒子からなる群より選ばれる少なくとも1種を含むことが好ましい。この場合、特に抗菌性能に優れるので、微生物の発生を防止又は除去する効果がよりいっそう大きくなる。また、上記金属粒子としては、銀粒子であることが特に好ましい。この場合、優れた微生物防除性能及び殺ダニ性能に加え、安全性の高い金属粒子を使用し、かつ極めて低濃度で上記効果を発現するため、一般的に他の微生物防除剤が有するような毒性や刺激性等が極めて低くなる。   The metal particles preferably include at least one selected from the group consisting of silver particles and copper particles. In this case, since the antibacterial performance is particularly excellent, the effect of preventing or removing the generation of microorganisms is further increased. The metal particles are particularly preferably silver particles. In this case, in addition to excellent microbial control performance and acaricidal performance, metal particles with high safety are used and the above effects are exhibited at an extremely low concentration. And irritation are extremely low.

白金粒子及び前記金属粒子の平均粒子径は特に限定的ではなく、例えば、0.1nm以上、また例えば、1000nm以下のナノ粒子とすることができる。この場合、抗菌性能及び殺ダニの効果が発揮されやすくなり、また、白金粒子及び前記金属粒子を基材に担持させて使用する場合に、白金粒子及び前記金属粒子が基材に担持されやすくなる。また、当該粒子径が0.1nm以上であることで、これら金属の微粒子化をさせやすく、当該粒子径が1000nm以下であることで、液剤とする場合や、担体に担持させるための水分散液作製工程で金属粒子の沈降を抑制しやすく、ハンドリング等が困難になりくい。なお、ここでいう白金粒子及び前記金属粒子の平均粒子径とは、ゼータ電位測定装置(ゼータサイザーナノZS90、Malvern社製)で測定した結果をいう。   The average particle diameter of the platinum particles and the metal particles is not particularly limited, and can be, for example, nanoparticles of 0.1 nm or more, for example, 1000 nm or less. In this case, the antibacterial performance and the effect of acaricide are easily exhibited, and when the platinum particles and the metal particles are supported on the base material, the platinum particles and the metal particles are easily supported on the base material. . In addition, when the particle diameter is 0.1 nm or more, these metals can be easily formed into fine particles, and when the particle diameter is 1000 nm or less, the liquid dispersion or the aqueous dispersion for supporting the carrier It is easy to suppress sedimentation of metal particles in the production process, and handling is difficult. In addition, the average particle diameter of platinum particle | grains and the said metal particle here means the result measured with the zeta potential measuring device (Zeta Sizer nano ZS90, product made by Malvern).

白金粒子及び前記金属粒子の形状は特に限定的ではなく、球状粒子、多角状粒子、繊維状粒子、針状粒子、フレーク状粒子、多孔質粒子等が例示される。なお、白金粒子及び前記金属粒子は、凝集した状態であってもよい。   The shapes of the platinum particles and the metal particles are not particularly limited, and examples thereof include spherical particles, polygonal particles, fibrous particles, needle-like particles, flake-like particles, and porous particles. The platinum particles and the metal particles may be in an aggregated state.

微生物防除剤及び殺ダニ組成物において、白金粒子及び上記金属粒子の含有量は制限されない。微生物防除剤の抗菌性能及び殺ダニ性能がより高まるという観点から、白金粒子及び上記金属粒子の含有割合は、白金粒子と上記金属粒子との質量合計を100とした場合、白金粒子は、例えば5以上、好ましくは10以上、更に好ましくは20以上、特に好ましくは30以上であり、また例えば、白金粒子は、95以下、好ましくは90以下、更に好ましくは80以下、特に好ましくは70以下である。   In the microbial control agent and the acaricide composition, the content of the platinum particles and the metal particles is not limited. From the viewpoint that the antibacterial performance and the acaricidal performance of the microbial control agent are further increased, the platinum particles and the metal particles have a content ratio of 100 when the total mass of the platinum particles and the metal particles is 100. The number of platinum particles is 95 or less, preferably 90 or less, more preferably 80 or less, and particularly preferably 70 or less, preferably 10 or more, more preferably 20 or more, and particularly preferably 30 or more.

本実施形態の微生物防除剤及び殺ダニ組成物は、白金粒子と、上記金属粒子とを含む限りは、その形態は特に限定されない。例えば、微生物防除剤及び殺ダニ組成物は、白金粒子と、上記金属粒子とが媒体に分散した形態(分散液)であってもよい。この場合、前記媒体としては、通常は液体であり、水、低級アルコール、あるいは、これらの混合溶媒が例示される。   The form of the microbial control agent and the acaricide composition of the present embodiment is not particularly limited as long as it contains platinum particles and the metal particles. For example, the microorganism control agent and the acaricide composition may be in a form (dispersion) in which platinum particles and the metal particles are dispersed in a medium. In this case, the medium is usually a liquid, and water, lower alcohol, or a mixed solvent thereof is exemplified.

本実施形態の微生物防除剤及び殺ダニ組成物は、白金粒子及び前記金属粒子が基材上に担持されていてもよい。この場合、簡易な方法(例えば後述する液への浸漬及びマイクロ波処理)で基材に抗菌性、防藻性、バイオフィルムの形成抑制性能、殺ダニや防ダニの機能等を付与することができる。微生物防除剤及び殺ダニ組成物は、白金粒子及び前記金属粒子が基材上に担持されている形態を「微生物防除部材」といってもよい。   In the microbial control agent and the acaricide composition of this embodiment, platinum particles and the metal particles may be supported on a substrate. In this case, a simple method (for example, immersion in a liquid and microwave treatment described later) may impart antibacterial properties, algae-proofing properties, biofilm formation inhibition performance, acaricidal and anti-mite functions, etc. to the substrate. it can. In the microorganism controlling agent and the acaricidal composition, the form in which the platinum particles and the metal particles are supported on the base material may be referred to as “microorganism controlling member”.

基材の種類は特に制限されない。白金粒子及び前記金属粒子がより担持しやすく、種々の製品の微生物防除剤として適用させやすいという観点から、前記基材が樹脂で形成されていることが好ましい。   The type of substrate is not particularly limited. From the viewpoint that the platinum particles and the metal particles are more easily supported and can be easily applied as a microbial control agent for various products, the base material is preferably formed of a resin.

前記基材が樹脂で形成されている場合、前記樹脂としては、ポリスチレン樹脂、塩化ビニル樹脂、フッ素樹脂、ABS樹脂、PET樹脂、ポリカーボネート樹脂、尿素樹脂、ポリ乳酸樹脂、オレフィン樹脂及びフェノール樹脂からなる群より選ばれる少なくとも1種を含むことが好ましい。前記基材がこれらのいずれかの樹脂を含んで形成されている場合は、白金粒子及び前記金属粒子が基材に担持されやすく、しかも、高い抗菌性能及び殺ダニ性能を発揮することができる。上記フッ素樹脂としては、例えば、PTFE(ポリテトラフルオロエチレン)等が例示される。上記オレフィン樹脂としては、例えば、ポリエチレン、ポリプロピレン樹脂等が例示される。   When the substrate is formed of a resin, the resin is made of polystyrene resin, vinyl chloride resin, fluorine resin, ABS resin, PET resin, polycarbonate resin, urea resin, polylactic acid resin, olefin resin, and phenol resin. It is preferable to include at least one selected from the group. When the base material is formed by including any of these resins, the platinum particles and the metal particles are easily carried on the base material, and high antibacterial performance and acaricidal performance can be exhibited. Examples of the fluororesin include PTFE (polytetrafluoroethylene). Examples of the olefin resin include polyethylene and polypropylene resin.

前記基材が樹脂で形成されている場合、前記樹脂として、ポリカーボネート樹脂は、白金粒子及び前記金属粒子の担持量が少なくても十分な微生物防除効果及び殺ダニ効果を示すため、使用する金属粒子に係る経済性の点においては好ましい。   When the substrate is formed of a resin, the polycarbonate resin is a metal particle to be used because the polycarbonate resin exhibits a sufficient microbial control effect and acaricidal effect even if the supported amount of platinum particles and the metal particles is small. This is preferable in terms of economic efficiency.

白金粒子及び前記金属粒子の前記基材への担持量に制限はないが、例えば、0.001ng/cm以上とすることができ、好ましくは0.01ng/cm以上、より好ましくは0.1ng/cm以上であり、また、例えば、100,000ng/cm以下とすることができ、好ましくは50,000ng/cm以下、より好ましくは20,000ng/cm以下の量で前記基材に担持されていることが好ましい。このような担持量で白金粒子及び前記金属粒子を前記基材に担持させることにより、微生物防除剤の抗菌性能及び殺ダニ組成物の殺ダニ性能が十分に発揮され得る。なお、本明細書でいう基材への担持量(ng/cm)とは、白金粒子の担持量(ng/cm)と前記金属粒子の担持量(ng/cm)の総担持量を示す。The amount of platinum particles and metal particles supported on the substrate is not limited, but may be, for example, 0.001 ng / cm 2 or more, preferably 0.01 ng / cm 2 or more, more preferably 0.00. and at 1 ng / cm 2 or more, and is, for example, be a 100,000ng / cm 2 or less, preferably 50,000ng / cm 2 or less, more preferably the group in an amount of 20,000 ng / cm 2 or less It is preferable to be carried on a material. By supporting the platinum particles and the metal particles on the substrate in such a loading amount, the antibacterial performance of the microorganism control agent and the acaricidal performance of the acaricide composition can be sufficiently exhibited. In addition, the carrying amount (ng / cm 2 ) on the substrate referred to in this specification is the total carrying amount of the carrying amount of platinum particles (ng / cm 2 ) and the carrying amount of the metal particles (ng / cm 2 ). Indicates.

前記基材の形状としては、シート状、板状、ブロック状、ネット状、パンチングシート状、粒状、ロッド状、破砕状、ディッシュ状および用途に応じた様々な製品形状が例示される。これらのいずれかの形状であれば、微生物防除剤や殺ダニ組成物を適用できる範囲がより広くなり、抗菌性能や殺ダニ性能を付与しやすくなる。例えば、前記基材の形状がシート状であれば、その厚みに何ら制限はなく、用途に応じた厚みに形成することができる。なお、前記基材は、中空状又は多孔質状等、内部に細孔を有していてもよい。   Examples of the shape of the substrate include a sheet shape, a plate shape, a block shape, a net shape, a punching sheet shape, a granular shape, a rod shape, a crushed shape, a dish shape, and various product shapes according to applications. If it is any of these shapes, the range which can apply a microbe control agent and an acaricide composition will become wider, and it will become easy to provide antibacterial performance and acaricide performance. For example, if the shape of the base material is a sheet shape, the thickness is not limited at all, and the substrate can be formed to a thickness according to the application. The base material may have pores inside such as a hollow shape or a porous shape.

本実施形態の微生物防除剤及び殺ダニ組成物では、本発明の効果が阻害されない程度であれば、その他の材料が添加されていてもよい。その他の材料としては、例えば、白金粒子及び前記金属粒子以外の金属元素で構成される粒子、その他の微生物防除剤(抗菌剤、殺菌剤、防腐剤、防藻剤、防カビ剤等)、pH調整剤、酸化防止剤、光安定剤、消泡剤、分散安定剤、滑剤等が例示される。   In the microorganism control agent and the acaricide composition of the present embodiment, other materials may be added as long as the effects of the present invention are not inhibited. Other materials include, for example, platinum particles and particles composed of metal elements other than the metal particles, other microorganism control agents (antibacterial agents, bactericides, antiseptics, algae control agents, fungicides, etc.), pH Examples thereof include regulators, antioxidants, light stabilizers, antifoaming agents, dispersion stabilizers, and lubricants.

上記その他の微生物防除剤としては、例えば、イソチアゾリン系化合物、ベンゾイミダゾール系化合物、トリアゾール系化合物、ニトロアルコール系化合物、ジチオール系化合物、チオフェン系化合物、ハロアセチレン系化合物、フタルイミド系化合物、ハロアルキルチオ系化合物、フェニルウレア系化合物、トリアジン系化合物、グアニジン系化合物、四級アンモニウム塩系化合物等が挙げられる。   Examples of the other microorganism control agents include, for example, isothiazoline compounds, benzimidazole compounds, triazole compounds, nitroalcohol compounds, dithiol compounds, thiophene compounds, haloacetylene compounds, phthalimide compounds, haloalkylthio compounds. , Phenylurea compounds, triazine compounds, guanidine compounds, quaternary ammonium salt compounds, and the like.

イソチアゾリン系化合物としては、具体的には、2−メチル−4−イソチアゾリン−3−オン、2−n−オクチル−4−イソチアゾリン−3−オン、5−クロロ−2−メチル−4−イソチアゾリン−3−オン、5−クロロ−2−n−オクチル−4−イソチアゾリン−3−オン、4−クロロ−2−n−オクチル−4−イソチアゾリン−3−オン、4,5−ジクロロ−2−n−オクチル−4−イソチアゾリン−3−オン、2−メチル−4,5−トリメチレン−4−イソチアゾリン−3−オン、1,2−ベンゾイソチアゾリン−3−オン、N−n−ブチル−1,2−ベンゾイソチアゾリン−3−オン等が挙げられる。   Specific examples of the isothiazoline-based compound include 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazoline-3. -One, 5-chloro-2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl -4-isothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, Nn-butyl-1,2-benzisothiazoline -3-one etc. are mentioned.

ベンゾイミダゾール系化合物としては、具体的には、メチル−2−ベンゾイミダゾールカルバメート(慣用名:カルベンダジム)、エチル−2−ベンゾイミダゾールカルバメート、2−(4−チアゾリル)ベンゾイミダゾール等が挙げられる。   Specific examples of the benzimidazole compound include methyl-2-benzimidazole carbamate (common name: carbendazim), ethyl-2-benzimidazole carbamate, 2- (4-thiazolyl) benzimidazole, and the like.

トリアゾール系化合物としては、具体的には、α−ブチル−α−(2,4−ジクロロフェニル)−1H−1,2,4−トリアゾール−1−エタノール(慣用名:ヘキサコナゾール)、α−[2−(4−クロロフェニル)エチル]−α−(1,1−ジメチルエチル)−1H−1,2,4−トリアゾール−1−エタノール(慣用名:テブコナゾール)、及びα−(4−クロロフェニル)−α−(1−シクロプロピルエチル)−1H−1,2,4−トリアゾール−1−エタノール(慣用名:シプロコナゾール)、1−[[2−(2,4−ジクロロフェニル)−4−n−プロピル−1,3−ジオキソラン−2−イル]メチル]−1H−1,2,4−トリアゾール(慣用名:プロピコナゾール)等が挙げられる。   Specific examples of triazole compounds include α-butyl-α- (2,4-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol (common name: hexaconazole), α- [ 2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (common name: tebuconazole), and α- (4-chlorophenyl)- α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol (common name: cyproconazole), 1-[[2- (2,4-dichlorophenyl) -4-n- Propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (common name: propiconazole) and the like.

ニトロアルコール系化合物としては、具体的には、2−ブロモ−2−ニトロプロパン−1,3−ジオール、2,2−ジブロモ−2−ニトロ−1−エタノール等が挙げられる。   Specific examples of the nitroalcohol compound include 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro-1-ethanol, and the like.

ジチオール系化合物としては、具体的には、4,5−ジクロロ−1,2−ジチオール−3−オン等が挙げられる。   Specific examples of the dithiol-based compound include 4,5-dichloro-1,2-dithiol-3-one.

チオフェン系化合物としては、具体的には、3,3,4−トリクロロテトラヒドロチオフェン−1,1−ジオキシド、3,3,4,4−テトラクロロテトラヒドロチオフェン−1,1−ジオキシド等が挙げられる。   Specific examples of the thiophene compound include 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and the like.

ハロアセチレン系化合物としては、具体的には、N−ブチル−3−ヨードプロピオール酸アミド、3−ヨード−2−プロピニル−N−ブチルカルバメート等が挙げられる。   Specific examples of the haloacetylene compound include N-butyl-3-iodopropiolic acid amide, 3-iodo-2-propynyl-N-butylcarbamate, and the like.

フタルイミド系化合物としては、具体的には、N−1,1,2,2−テトラクロロエチルチオ−テトラヒドロフタルイミド(Captafol)、N−トリクロロメチルチオ−テトラヒドロフタルイミド(Captan)、N−ジクロロフルオロメチルチオフタルイミド(Fluorfolpet)、N−トリクロロメチルチオフタルイミド(Folpet)等が挙げられる。   Specific examples of the phthalimide-based compound include N-1,1,2,2-tetrachloroethylthio-tetrahydrophthalimide (Captafol), N-trichloromethylthio-tetrahydrophthalimide (Captan), and N-dichlorofluoromethylthiophthalimide (Fluorolpet). N-trichloromethylthiophthalimide (Folpet) and the like.

ハロアルキルチオ系化合物としては、具体的には、N−ジメチルアミノスルホニル−N−トリル−ジクロロフルオロメタンスルファミド(Tolylfluanide)、N−ジメチルアミノスルホニル−N−フェニル−ジクロロフルオロメタンスルファミド(Dichlofluanide)等が挙げられる。   Specific examples of the haloalkylthio compounds include N-dimethylaminosulfonyl-N-tolyl-dichlorofluoromethanesulfamide (Tolylfluoride), N-dimethylaminosulfonyl-N-phenyl-dichlorofluoromethanesulfamide (Dichlofluoride). ) And the like.

フェニルウレア系化合物としては、具体的には、3−(3,4−ジクロロフェニル)−1,1−ジメチルウレア等が挙げられる。   Specific examples of the phenylurea compound include 3- (3,4-dichlorophenyl) -1,1-dimethylurea.

トリアジン系化合物としては、具体的には、2−メチルチオ−4−t−ブチルアミノ−6−シクロプロピルアミノ−s−トリアジン等が挙げられる。   Specific examples of the triazine compound include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine.

グアニジン系化合物としては、具体的には、1,6−ジ−(4’−クロロフェニルジグアニド)−ヘキサン、ポリヘキサメチレンビグアニジン塩酸塩等が挙げられる。   Specific examples of the guanidine-based compound include 1,6-di- (4'-chlorophenyldiguanide) -hexane, polyhexamethylene biguanidine hydrochloride and the like.

四級アンモニウム塩系化合物としては、具体的には、ヘキサデシルトリメチルアンモニウムブロマイド、ヘキサデシルトリメチルアンモニウムクロライド、塩化ベンザルコニウム、ジ−n−デシル−ジメチルアンモニウムクロライド、1−ヘキサデシルピリジニウムクロライド等が挙げられる。   Specific examples of the quaternary ammonium salt compound include hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, benzalkonium chloride, di-n-decyl-dimethylammonium chloride, 1-hexadecylpyridinium chloride and the like. It is done.

これらその他の微生物防除剤は、1種を単独で使用でき、又は必要に応じて2種以上を混合して使用することができる。好ましくは、ベンゾイミダゾール系化合物、トリアゾール系化合物、ハロアセチレン系化合物及びこれらの塩からなる群より選択される1種又は2種以上の化合物であり、特に好ましくは、メチル−2−ベンゾイミダゾールカルバメート、2−(4−チアゾリル)ベンゾイミダゾール、α−[2−(4−クロロフェニル)エチル]−α−(1,1−ジメチルエチル)−1H−1,2,4−トリアゾール−1−エタノール、α−ブチル−α−(2,4−ジクロロフェニル)−1H−1,2,4−トリアゾール−1−エタノール及び3−ヨード−2−プロピニル−N−ブチルカルバメートからなる群より選択される1種又は2種である。   These other microorganism control agents can be used alone or in combination of two or more as required. Preferably, it is one or two or more compounds selected from the group consisting of benzimidazole compounds, triazole compounds, haloacetylene compounds and salts thereof, particularly preferably methyl-2-benzimidazole carbamate, 2- (4-thiazolyl) benzimidazole, α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, α- One or two selected from the group consisting of butyl-α- (2,4-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol and 3-iodo-2-propynyl-N-butylcarbamate It is.

また、その他の微生物防除剤を含有させる場合、その配合割合は、特に制限されず、剤型、目的及び用途によって適宜選択されるが、例えば、白金粒子と白金以外の金属粒子の総量100重量部に対して、微生物防除剤の総量1〜10000重量部、好ましくは10〜1000重量部で含有させる。   In addition, when other microbial control agents are included, the blending ratio is not particularly limited and is appropriately selected depending on the dosage form, purpose and application. For example, the total amount of platinum particles and metal particles other than platinum is 100 parts by weight. The total amount of the microorganism control agent is 1 to 10000 parts by weight, preferably 10 to 1000 parts by weight.

pH調整剤としては、例えば、酸、塩基等が挙げられる。酸としては、具体的には、塩酸、硝酸、硫酸、乳酸、酢酸、クエン酸等が挙げられる。塩基としては、具体的には、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、トリエチルアミン、トリメチルアミン、アンモニア等が挙げられる。これらのpH調整剤は、1種を単独で使用でき、又は必要に応じて2種以上を混合して使用することができる。   Examples of the pH adjuster include acids and bases. Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, lactic acid, acetic acid, citric acid and the like. Specific examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, triethylamine, trimethylamine, ammonia and the like. These pH adjusters can be used individually by 1 type, or can be used in mixture of 2 or more types as needed.

酸化防止剤としては、例えば、フェノール系酸化防止剤、アミン系酸化防止剤等が挙げられる。フェノール系酸化防止剤としては、具体的には、2,6−ジ−t−ブチル−4−メチルフェノール、2,2’−メチレンビス(4−メチル−6−t−ブチルフェノール)等が挙げられる。また、アミン系酸化防止剤としては、具体的には、アルキルジフェニルアミン、N,N’−ジ−s−ブチル−p−フェニレンジアミン等が挙げられる。これらの酸化防止剤は、1種を単独で使用でき、又は必要に応じて2種以上を混合して使用することができる。   Examples of the antioxidant include phenolic antioxidants and amine antioxidants. Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol and 2,2'-methylenebis (4-methyl-6-t-butylphenol). Specific examples of amine-based antioxidants include alkyldiphenylamine and N, N′-di-s-butyl-p-phenylenediamine. These antioxidants can be used individually by 1 type, or can be used in mixture of 2 or more type as needed.

光安定剤としては、例えば、ビス(2,2,6,6−テトラメチル−4−ピペリジル)セバケート等のヒンダードアミン系光安定剤等が挙げられる。光安定剤は、1種を単独で使用でき、又は必要に応じて2種以上を混合して使用することができる。   Examples of the light stabilizer include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. A light stabilizer can be used individually by 1 type, or can mix and use 2 or more types as needed.

消泡剤としては、例えば、シリコーン系消泡剤、有機系消泡剤等が挙げられる。有機系消泡剤としては、具体的には、界面活性剤、ポリエーテル、高級アルコール等が挙げられる。消泡剤は、1種を単独で使用でき、又は必要に応じて2種以上を混合して使用することができる。   As an antifoamer, a silicone type antifoamer, an organic type antifoamer, etc. are mentioned, for example. Specific examples of the organic antifoaming agent include surfactants, polyethers and higher alcohols. An antifoamer can be used individually by 1 type, or can mix and use 2 or more types as needed.

微生物防除剤及び殺ダニ組成物を製造する方法は特に限定されない。例えば、微生物防除剤及び殺ダニ組成物が白金粒子及び前記金属粒子が上述の媒体に分散した形態である場合、白金粒子、前記金属粒子及び媒体を準備し、これらを所定の配合量で混合させることで、微生物防除剤及び殺ダニ組成物を調製することができる。この微生物防除剤及び殺ダニ組成物を調製するにあたり、適宜、市販の混合機や分散機を使用してもよい。また、このような微生物防除剤及び殺ダニ組成物の場合、白金粒子及び前記金属粒子の合計の配合量は、媒体100質量部に対して、0.00001重量部以上、好ましくは0.0001重量部以上、更に好ましくは0.001重量部以上であり、また例えば50重量部以下、好ましくは10重量部以下、さらに好ましくは1質量部以下とすることができる。この場合、白金粒子と前記金属粒子との混合比(白金粒子の質量:金属粒子の質量)は、白金粒子と上記金属粒子との質量合計を100とした場合、白金粒子は、例えば5以上、好ましくは10以上、更に好ましくは20以上であり、特に好ましくは30以上であり、また例えば、95以下、好ましくは90以下、更に好ましくは80以下、特に好ましくは70以下である。   The method for producing the microbial control agent and the acaricide composition is not particularly limited. For example, when the microbial control agent and the acaricidal composition are in a form in which platinum particles and the metal particles are dispersed in the above-mentioned medium, platinum particles, the metal particles and the medium are prepared and mixed in a predetermined blending amount. Thus, a microbial control agent and an acaricidal composition can be prepared. In preparing the microbial control agent and the acaricide composition, a commercially available mixer or disperser may be used as appropriate. In the case of such a microorganism control agent and acaricide composition, the total amount of platinum particles and the metal particles is 0.00001 parts by weight or more, preferably 0.0001 parts by weight with respect to 100 parts by weight of the medium. Part or more, more preferably 0.001 part by weight or more, for example, 50 parts by weight or less, preferably 10 parts by weight or less, more preferably 1 part by weight or less. In this case, the mixing ratio of the platinum particles and the metal particles (the mass of the platinum particles: the mass of the metal particles) is, for example, 5 or more when the total mass of the platinum particles and the metal particles is 100. The number is preferably 10 or more, more preferably 20 or more, particularly preferably 30 or more, and for example, 95 or less, preferably 90 or less, more preferably 80 or less, and particularly preferably 70 or less.

一方、白金粒子及び前記金属粒子が基材に担持されてなる微生物防除剤及び殺ダニ組成物の製造方法も特に限定されない。例えば、白金粒子及び前記金属粒子の分散液をあらかじめ調製しておき、この分散液を用いて、白金粒子及び前記金属粒子を基材に担持させることで、白金粒子及び前記金属粒子が基材に担持されてなる微生物防除剤及び殺ダニ組成物を製作することができる。前記分散液から白金粒子及び前記金属粒子を基材に担持させる方法としては、分散液に基材を浸漬させる方法、あるいは、基材に分散液を噴霧又は塗布等する方法、蒸着法等が例示されるが、これらに限定されるわけではない。   On the other hand, the method for producing a microbial control agent and an acaricidal composition in which platinum particles and the metal particles are supported on a substrate is not particularly limited. For example, a dispersion of platinum particles and the metal particles is prepared in advance, and the platinum particles and the metal particles are supported on the substrate by using the dispersion to support the platinum particles and the metal particles on the substrate. A microbial control agent and an acaricide composition which are supported can be produced. Examples of the method for supporting the platinum particles and the metal particles from the dispersion on the substrate include a method of immersing the substrate in the dispersion, a method of spraying or applying the dispersion to the substrate, a vapor deposition method, and the like. However, it is not limited to these.

上記のように、前記分散液に基材を浸漬させる方法で微生物防除剤及び殺ダニ組成物を製造する場合、前記基材を前記分散液に浸漬させた状態において、マイクロ波を照射することにより、前記基材に白金粒子及び前記金属粒子を定着させてもよい。同様に、前記基材に前記分散液を噴霧又は塗布する方法で微生物防除剤及び殺ダニ組成物を製造する場合、噴霧又は塗布等して分散液の被膜を形成した後にマイクロ波を照射することにより、前記基材に白金粒子及び前記金属粒子を定着させてもよい。   As described above, when producing a microbial control agent and an acaricide composition by a method of immersing a substrate in the dispersion, by irradiating microwaves in a state where the substrate is immersed in the dispersion. The platinum particles and the metal particles may be fixed to the base material. Similarly, when producing a microorganism control agent and an acaricide composition by spraying or applying the dispersion to the substrate, microwaves are irradiated after forming a coating of the dispersion by spraying or application. Thus, the platinum particles and the metal particles may be fixed to the substrate.

上記のようにマイクロ波を照射することで、比較的短時間で均一にコーティングでき、基材への白金粒子及び前記金属粒子の担持がより強固になり、バインダーを使用せずとも基材に白金粒子及び前記金属粒子を担持させることが可能となる。これにより、微生物防除剤及び殺ダニ組成物がより優れた抗菌効果及び殺ダニ効果を発揮することが可能になる。しかも、基材への白金粒子及び前記金属粒子の担持がより強固になることで、金属元素の外部への溶出もさらに抑制されるという利点もある。   By irradiating with microwaves as described above, uniform coating can be achieved in a relatively short time, and the support of the platinum particles and the metal particles on the substrate becomes stronger, and platinum can be applied to the substrate without using a binder. It becomes possible to carry the particles and the metal particles. Thereby, it becomes possible for a microorganism control agent and an acaricide composition to exhibit the more excellent antibacterial effect and acaricide effect. In addition, since the platinum particles and the metal particles are more firmly supported on the base material, there is an advantage that elution of the metal element to the outside is further suppressed.

マイクロ波を照射する場合、照射強度は、0.005〜0.1W/cmとすることができる。マイクロ波の照射は、例えば、市販のマイクロ波照射装置を使用してもよいし、あるいは、電子レンジを使用してもよい。また、マイクロ波を照射するにあたっては、適宜、加熱を行ってもよい。マイクロ波の照射時間は、マイクロ波の照射強度に応じて適宜設定すればよく、例えば、0.1〜60分とすることができる。In the case of irradiation with microwaves, the irradiation intensity can be 0.005 to 0.1 W / cm 3 . For microwave irradiation, for example, a commercially available microwave irradiation apparatus may be used, or a microwave oven may be used. Moreover, when irradiating a microwave, you may heat suitably. What is necessary is just to set the irradiation time of a microwave suitably according to the irradiation intensity | strength of a microwave, for example, can be 0.1 to 60 minutes.

本実施形態の微生物防除剤及び殺ダニ組成物は、上述のように、白金粒子と、前記金属粒子とを含んで構成されるものであり、抗菌性能及び殺ダニ性能に優れるものである。   As described above, the microorganism control agent and the acaricide composition of the present embodiment are composed of platinum particles and the metal particles, and are excellent in antibacterial performance and acaricide performance.

例えば、本実施形態の微生物防除剤では、JIS Z2801の準拠する抗菌性試験における黄色ブドウ球及び大腸菌に対する各々の抗菌活性値がいずれも2.0以上となり得る。   For example, in the microorganism control agent of this embodiment, each antibacterial activity value against S. aureus and Escherichia coli in an antibacterial test according to JIS Z2801 can be 2.0 or more.

抗菌性能の評価は、上記JIS Z2801に準拠することができ、一般的に知られている、フィルム密着法を採用することができる。このフィルム密着法では、測定サンプル表面に細菌を含む液体を滴下し、その上をフィルムで覆って24時間が経過後に試料から細菌を回収し、生菌数の測定を行う。この測定結果を、無加工品の生菌数と比較し、抗菌活性値を算出する。   The antibacterial performance can be evaluated in accordance with the above JIS Z2801, and a generally known film adhesion method can be employed. In this film contact method, a liquid containing bacteria is dropped on the surface of a measurement sample, and the liquid is covered with a film. After 24 hours, bacteria are collected from the sample, and the number of viable bacteria is measured. The measurement result is compared with the number of viable bacteria in the unprocessed product to calculate the antibacterial activity value.

上記フィルム密着法の他、シェーク法を採用してもよい。この方法では、試料を細菌の懸濁液に浸漬し、振とうすることにより細菌と試料を接触させて生菌数の測定を行う。この測定結果を、無加工品の生菌数と比較し、抗菌活性値を算出する。上記フィルム密着法が適用できない試料に対しては、このようなシェーク法を採用することができる。   In addition to the film adhesion method, a shake method may be employed. In this method, the sample is immersed in a suspension of bacteria and shaken to bring the bacteria into contact with the sample and measure the number of viable bacteria. The measurement result is compared with the number of viable bacteria in the unprocessed product to calculate the antibacterial activity value. Such a shake method can be adopted for a sample to which the film adhesion method cannot be applied.

本実施形態の微生物防除剤では、上記フィルム密着法によって測定された黄色ブドウ球及び大腸菌に対する各々の抗菌活性値がいずれも2.0以上となり得る。   In the microorganism control agent of the present embodiment, each antibacterial activity value against S. aureus and Escherichia coli measured by the film adhesion method can be 2.0 or more.

本実施形態の微生物防除剤(白金粒子と、白金以外の金属粒子とを含む分散液)は、例えば、シャーレー等の細胞を培養する容器(以下、「細胞培養容器」という)を抗菌処理及び殺菌処理をするために使用することができる。   The microorganism control agent (dispersion liquid containing platinum particles and metal particles other than platinum) according to the present embodiment is, for example, an antibacterial treatment and sterilization of a container for culturing cells such as a petri dish (hereinafter referred to as “cell culture container”). Can be used for processing.

本実施形態の微生物防除剤により表面処理した細胞培養容器は抗菌性能に優れている。それゆえ、従来は細胞を培養する前処理として、細胞培養容器を加熱又は紫外線照射等の方法によって抗菌処理等をすることが必要であったが、本実施形態の微生物防除剤で抗菌処理等をした細胞培養容器を用いる場合、そのような前処理がなくとも細胞を培養できるので、前処理等の手間を省くことが可能である。   The cell culture container surface-treated with the microorganism control agent of this embodiment is excellent in antibacterial performance. Therefore, conventionally, as a pretreatment for culturing cells, it has been necessary to carry out antibacterial treatment by a method such as heating or ultraviolet irradiation of a cell culture container. When the cell culture container is used, the cells can be cultured without such pretreatment, so that it is possible to save time and labor for the pretreatment.

また、本実施形態の微生物防除剤により抗菌処理等をした細胞培養容器を用いたとしても、細胞の増殖に影響を及ぼすことなく細胞の培養を行うことができる。   Further, even when a cell culture container subjected to antibacterial treatment or the like with the microorganism control agent of the present embodiment is used, cells can be cultured without affecting cell proliferation.

また、本実施形態の微生物防除剤により抗菌処理等をした細胞培養容器を用いることで、培養の前後及び培養中に他の菌が混入することも抑制されるので、細胞の培養に影響を与えにくく、効率よく細胞を培養することができる。即ち、培養中のバクテリア等のコンタミネーション防止に用いる抗生物質の添加を省くことも可能である。   In addition, by using a cell culture container that has been antibacterial treated with the microorganism control agent of the present embodiment, it is possible to prevent other bacteria from being mixed before and after culturing and during culturing. It is difficult and can culture cells efficiently. That is, it is possible to omit the addition of antibiotics used to prevent contamination of bacteria during cultivation.

細胞培養容器は、細胞を培養する直前に本実施形態の微生物防除剤で抗菌処理等を行ってもよい。あるいは、細胞培養容器が生産された後又は細胞培養容器の生産と同時に本実施形態の微生物防除剤で抗菌処理等を行ってもよい。また、本抗菌処理は、加熱処理又は紫外線照射処理の影響を受けにくい。   The cell culture container may be subjected to antibacterial treatment or the like with the microorganism control agent of this embodiment immediately before culturing the cells. Alternatively, after the cell culture container is produced or simultaneously with the production of the cell culture container, an antibacterial treatment or the like may be performed with the microorganism control agent of the present embodiment. Further, the antibacterial treatment is not easily affected by heat treatment or ultraviolet irradiation treatment.

本実施形態の微生物防除剤で抗菌処理等された細胞培養容器では、各種の細胞を培養することができる。細胞の種類は限定されない。   Various types of cells can be cultured in the cell culture container that has been antibacterial treated with the microorganism control agent of the present embodiment. The type of cell is not limited.

本実施形態の微生物防除剤では、藻類発生抑制性能があり、その効果は、後述の実施例で示すように植物栽培容器での試験で目視確認できる。   The microorganism control agent of this embodiment has algae generation suppression performance, and the effect can be visually confirmed by a test in a plant cultivation container as shown in Examples described later.

本実施形態の微生物防除剤はバイオフィルム形成抑制性能があり、後述の実施例で示すようにサンプルプレートによる試験により、バイオフィルム形成が顕著に少ないこと(目視で全く確認できないレベル)が確認できる。なお、バイオフィルムとは生物膜やスライムとも言われ、一般に水系で微生物が物質の表面に付着・増殖することによって微生物細胞内から多糖やタンパク質、核酸などの高分子物質を産生して、微生物と微生物産生物質とが構造体を形成したものをいう。バイオフィルムの形成は、様々な産業において、設備や流路(パイプライン、樋、等)の汚染や腐食、系の閉塞、製品不良、およびエネルギー損失等により、大きな悪影響を及ぼす原因となりうる。   The microorganism control agent of the present embodiment has a biofilm formation inhibitory performance, and it can be confirmed that biofilm formation is remarkably small (a level that cannot be visually confirmed at all) by a test using a sample plate as shown in Examples described later. Biofilms are also called biofilms or slimes. Generally, microorganisms adhere to and grow on the surface of substances in the aqueous system to produce high-molecular substances such as polysaccharides, proteins, and nucleic acids from inside microbial cells. A product produced by a microorganism is a structure. Biofilm formation can cause significant adverse effects in various industries due to contamination and corrosion of equipment and flow paths (pipelines, dredging, etc.), system blockages, product defects, and energy loss.

本実施形態の殺ダニ組成物は殺ダニや防ダニ性能があり、後述の実施例で示すように、樹脂等で形成される基材に対して殺ダニ組成物で処理することでダニの増殖を抑制することができる。このように本実施形態の殺ダニ組成物は、対象物に防ダニ機能を付与することができる。   The acaricidal composition of this embodiment has acaricidal and acaricidal performance, and as shown in the examples described later, the growth of mites is achieved by treating the substrate formed of resin or the like with the acaricidal composition. Can be suppressed. Thus, the acaricide composition of this embodiment can provide an acaricidal function to an object.

本実施形態の微生物防除剤及び殺ダニ組成物では、白金粒子と、前記金属粒子とを含むことで、抗菌性能及び殺ダニ性能に優れるものであるので、例えば、微生物防除剤及び殺ダニ組成物において、白金粒子及び前記金属粒子が低濃度であっても、良好な抗菌性能及び殺ダニ性能を示すことができる。それゆえ、上記のように白金粒子及び前記金属粒子が基材に担持された微生物防除剤及び殺ダニ組成物では、担持量が従来よりも少量であっても、高い抗菌性能、高い防藻性能、高いバイオフィルム形成抑制能及び殺ダニ性能を発現させることが可能である。金属粒子が、銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子のからなる群より選ばれる少なくとも1種を含む場合には特に抗菌性能及び殺ダニ性能が優れ、担持量がより少量であっても、高い抗菌性能、高い防藻性能、高いバイオフィルム形成抑制能及び高い殺ダニ性能が発現する。つまり、本発明に係る微生物防除剤又は殺ダニ組成物で基材を処理することにより、抗菌効果と防藻効果とバイオフィルム形成抑制効果と殺ダニ効果の4つの異なる効果を併せ得ることができる。しかも、これらの金属粒子であれば、極めて安全性が高いという利点も有する。   In the microorganism control agent and the acaricide composition of the present embodiment, since the platinum particles and the metal particles are included, the antibacterial performance and the acaricide performance are excellent. In the above, even if the platinum particles and the metal particles have a low concentration, good antibacterial performance and acaricidal performance can be exhibited. Therefore, as described above, the microbial control agent and the miticide composition in which the platinum particles and the metal particles are supported on the base material have high antibacterial performance and high algal control performance even if the supported amount is smaller than before. It is possible to develop high biofilm formation inhibiting ability and acaricidal performance. Especially when the metal particles contain at least one selected from the group consisting of silver particles, copper particles, nickel particles and zinc particles, antibacterial performance and acaricidal performance are excellent, even if the loading amount is smaller, High antibacterial performance, high antialgae performance, high biofilm formation suppression capability and high acaricidal performance are manifested. That is, by treating the substrate with the microorganism control agent or the acaricide composition according to the present invention, it is possible to obtain four different effects of the antibacterial effect, the algae control effect, the biofilm formation inhibitory effect, and the acaricide effect. . In addition, these metal particles have the advantage of extremely high safety.

白金やその他金属を単独で施工したことを謳う抗菌製品が市販されていることから、白金粒子単独、あるいは前記金属粒子単独でも、一定の抗菌作用があると考えられていたが、本発明の完成過程で実施した試験においては、各金属粒子単独では効果がみられなかった。これに対し、本実施形態の微生物防除剤及び殺ダニ組成物のように、白金粒子及び前記金属粒子の両方を含むことで、それぞれの金属粒子単独では到底なし得ない優れた微生物防除性能が発揮され、相乗的に抗菌性能が向上する。   Since antibacterial products that demand the construction of platinum and other metals alone are commercially available, platinum particles alone or the metal particles alone were considered to have a certain antibacterial effect, but the present invention was completed. In the tests conducted in the process, each metal particle alone had no effect. In contrast, by including both the platinum particles and the metal particles as in the microbial control agent and the acaricide composition of the present embodiment, excellent microbial control performance that cannot be achieved with each metal particle alone is achieved. And synergistically improves antibacterial performance.

さらに、微生物防除剤及び殺ダニ組成物は、白金粒子と前記金属粒子とを含んで構成されているので、従来のような金属イオンが溶出するおそれが非常に小さいものである。そのため、上記微生物防除剤及び殺ダニ組成物は、環境に与える影響も低減することができる。   Furthermore, since the microbial control agent and the acaricide composition are configured to contain platinum particles and the metal particles, there is a very low possibility that conventional metal ions will be eluted. Therefore, the microbial control agent and the acaricide composition can also reduce the influence on the environment.

本実施形態の微生物防除剤によれば、優れた抗菌性能を有し、金属の溶出も低減されることから、対象物に微生物防除機能を付与させることが容易であり、微生物を防除する方法としての使用に適している。また、上記微生物防除剤を使用することにより、処理労力を半減することができ、また、処理コストも低減できるので、非常に有用である。そのため、上記微生物防除剤は、工業的な用途(例えば、含水パルプ、塗工紙、紙用塗工液、塗料、バインダー、接着剤、ラテックス、インキ、エッチ液、浸し水、木材、繊維、木粉、プラスチック、セメント混和剤、シーリング剤、樹脂エマルション、建材原料等の多くの工業製品又は工業用原材料)に加え、特に安全性等が重視される植栽培等の農業分野、抗菌ボトル等の食品分野、細胞培養基材等の理化学資材等、各種の用途にも適用することが可能であり、特に、抗菌剤、防藻剤、バイオフィルム形成抑制剤として有用である。   According to the microorganism control agent of the present embodiment, since it has excellent antibacterial performance and metal elution is also reduced, it is easy to impart a microorganism control function to an object, and as a method for controlling microorganisms Suitable for use. In addition, the use of the above-mentioned microorganism control agent is very useful because the processing effort can be halved and the processing cost can be reduced. Therefore, the above microorganism control agent is used for industrial purposes (for example, hydrous pulp, coated paper, paper coating liquid, paint, binder, adhesive, latex, ink, etchant, soaking water, wood, fiber, wood In addition to flour, plastics, cement admixtures, sealing agents, resin emulsions, building materials, etc., many industrial products or industrial raw materials), especially agricultural fields such as planting where safety is a priority, foods such as antibacterial bottles, etc. It can be applied to various fields such as fields, physics and chemistry materials such as cell culture substrates, and is particularly useful as an antibacterial agent, an algaeproofing agent, and a biofilm formation inhibitor.

また、本実施形態の殺ダニ組成物によれば、これを対象物に適用して防ダニ部材を形成することができる。このような防ダニ部材は、殺ダニ組成物に含まれる白金粒子及び白金以外の金属粒子を有して形成されているため、ダニの発生及び増加を抑制する性能に優れるので、防ダニや殺ダニを必要とする資材全般に対して使用でき、例えば、生活関連資材として、タタミ、カーペット、壁材、床材、天井材、家具、家電製品、食品容器、食品包装材、台所製品などに適しており、また、例えば、産業用資材として、植物、動物、昆虫等を育成したり、保管したりする部材(但し、養蜂部材を除く)として適している。   Moreover, according to the acaricide composition of this embodiment, this can be applied to a target object to form an acaricidal member. Such a tick-proof member is formed with platinum particles and metal particles other than platinum contained in the mite-killing composition, and therefore has excellent performance in suppressing the occurrence and increase of mites, so Can be used for all materials that require ticks, for example, suitable for life-related materials such as tatami, carpets, wall materials, flooring materials, ceiling materials, furniture, household appliances, food containers, food packaging materials, kitchen products, etc. For example, as an industrial material, it is suitable as a member for growing or storing plants, animals, insects, etc. (excluding beekeeping members).

以下、実施例により本発明をより具体的に説明するが、本発明はこれら実施例の態様に限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to the aspect of these Examples.

1.抗菌効果の確認
(調製例1)白金粒子分散液の調製
0.212gの塩化白金酸カリウム(KPtCl)を50mLの純水に溶解して、塩化白金酸カリウム水溶液を調製した。別途、0.129gのクエン酸ナトリウムを50mLの純水に溶解して0.01mol/Lのクエン酸ナトリウム水溶液を、また、0.881gのアスコルビン酸を50mLの純水に溶解して0.1mol/Lのアスコルビン酸水溶液をそれぞれ調製した。上記の塩化白金酸カリウム水溶液50mLを850mLの純水に加えた後、さらに0.01mol/Lクエン酸ナトリウム水溶液50mLと0.1mol/Lアスコルビン酸水溶液50mLをそれぞれ加え、約5分間100rpmで撹拌して反応させた。次にイオン交換膜処理を行い、白金粒子分散液中のイオン性の不純物を除去して、白金粒子を含むコロイド溶液を得た。ゼータ電位測定装置(ゼータサイザーナノZS90、Malvern社製)で測定した白金粒子の粒子径は130nmであった。また、TEM/EDS(HITACHI H−7100、加速電圧100kV)にて測定した白金粒子中の白金の純度は100%であった。
1. Confirmation of Antibacterial Effect (Preparation Example 1) Preparation of Platinum Particle Dispersion Solution 0.212 g of potassium chloroplatinate (K 2 PtCl 4 ) was dissolved in 50 mL of pure water to prepare a potassium chloroplatinate solution. Separately, 0.129 g of sodium citrate was dissolved in 50 mL of pure water to dissolve a 0.01 mol / L sodium citrate aqueous solution, and 0.881 g of ascorbic acid was dissolved in 50 mL of pure water to give 0.1 mol. / L ascorbic acid aqueous solution was prepared respectively. After adding 50 mL of the above potassium chloroplatinate aqueous solution to 850 mL of pure water, 50 mL of 0.01 mol / L sodium citrate aqueous solution and 50 mL of 0.1 mol / L ascorbic acid aqueous solution were added, respectively, and stirred at 100 rpm for about 5 minutes. And reacted. Next, ion exchange membrane treatment was performed to remove ionic impurities in the platinum particle dispersion, and a colloidal solution containing platinum particles was obtained. The particle diameter of the platinum particles measured with a zeta potential measuring device (Zeta Sizer Nano ZS90, manufactured by Malvern) was 130 nm. Moreover, the purity of platinum in the platinum particles measured by TEM / EDS (HITACHI H-7100, acceleration voltage 100 kV) was 100%.

上記方法で得られた分散液の白金濃度をICP−MS(パーキンエルマー社製ElanDRCII)で確認し、更に水で希釈して、白金粒子濃度が100mg/Lの分散液(分散液1)を得た。   The platinum concentration of the dispersion obtained by the above method was confirmed by ICP-MS (ElanDRCII manufactured by Perkin Elmer) and further diluted with water to obtain a dispersion (dispersion 1) having a platinum particle concentration of 100 mg / L. It was.

(調製例2)銀粒子分散液の調製
0.157gの硝酸銀(AgNO)を50mLの純水に溶解して硝酸銀水溶液を調製した。別途、10wt%のアンモニア水を、また、0.881gのアスコルビン酸を50mLの純水に溶解して0.1mol/Lのアスコルビン酸水溶液をそれぞれ調製した。上記の0.01mol/L硝酸銀水溶液50mLを900mLの純水に加えた後、10wt%のアンモニア水でpH11に調整した。さらに0.1mol/L、アスコルビン酸水溶液1mLを加え、約5分間100rpmで撹拌して反応させた。次にイオン交換膜処理を行い、銀粒子分散液中のイオン性の不純物を除去して、銀粒子を含むコロイド溶液を得た。ゼータ電位測定装置(ゼータサイザーナノZS90、Malvern社製)で測定した粒子径は130nmであった。また、TEM/EDS(HITACHI H-7100、加速電圧100kV)にて測定した銀粒子中の銀の純度は100%であった。
Preparation Example 2 Preparation of Silver Particle Dispersion Solution 0.157 g of silver nitrate (AgNO 3 ) was dissolved in 50 mL of pure water to prepare a silver nitrate aqueous solution. Separately, 10 wt% ammonia water and 0.881 g of ascorbic acid were dissolved in 50 mL of pure water to prepare 0.1 mol / L ascorbic acid aqueous solutions. 50 mL of the above 0.01 mol / L silver nitrate aqueous solution was added to 900 mL of pure water, and then adjusted to pH 11 with 10 wt% ammonia water. Furthermore, 0.1 mol / L and 1 mL of ascorbic acid aqueous solution were added, and it was made to react by stirring at 100 rpm for about 5 minutes. Next, an ion exchange membrane treatment was performed to remove ionic impurities in the silver particle dispersion, thereby obtaining a colloidal solution containing silver particles. The particle diameter measured by a zeta potential measuring device (Zeta Sizer Nano ZS90, manufactured by Malvern) was 130 nm. Further, the purity of silver in the silver particles measured by TEM / EDS (HITACHI H-7100, acceleration voltage 100 kV) was 100%.

上記方法で得られた分散液の銀濃度をICP−MS(パーキンエルマー社製ElanDRCII)で確認し、更に水で希釈して、銀粒子濃度が100mg/Lの分散液(分散液2)を得た。   The silver concentration of the dispersion obtained by the above method is confirmed by ICP-MS (ElanDRCII manufactured by Perkin Elmer), and further diluted with water to obtain a dispersion (dispersion 2) having a silver particle concentration of 100 mg / L. It was.

(調製例3〜7)
調製例1及び調製例2で得られた分散液1及び分散液2をそれぞれ、表1に示す配合割合で混合することで、後述する実施例で使用するための白金粒子と銀粒子の混合液(それぞれ調製例3〜7)を得た。
(Preparation Examples 3 to 7)
By mixing the dispersion liquid 1 and the dispersion liquid 2 obtained in Preparation Example 1 and Preparation Example 2 at the blending ratios shown in Table 1, respectively, a mixed liquid of platinum particles and silver particles for use in Examples described later. (Preparation Examples 3 to 7, respectively) were obtained.

Figure 0006293389
Figure 0006293389

(調製例8)
調製例1で得られた分散液1(白金粒子分散液)と、分散液3としてナノ銅(シグマ社製、カタログ品番774111、粒子径40〜60nm、99%)を水分散した液とを所定量混合し、白金粒子と銅粒子の配合割合が質量比で70/30、両金属粒子合計の濃度が100mg/Lの混合液を調製した。
(Preparation Example 8)
Dispersion liquid 1 (platinum particle dispersion liquid) obtained in Preparation Example 1 and dispersion liquid 3 in which nano copper (manufactured by Sigma, catalog number 774111, particle diameter 40-60 nm, 99%) is dispersed in water The mixture was quantitatively mixed to prepare a mixed solution in which the mixing ratio of platinum particles and copper particles was 70/30 by mass ratio and the total concentration of both metal particles was 100 mg / L.

(調製例9)
調製例1で得られた分散液1(白金粒子分散液)と、分散液4としてニッケル粒子(シグマ社製、カタログ品番577995、粒子径<100nm、99%)を水分散した液とを所定量混合し、白金粒子とニッケル粒子の配合割合が質量比で70/30、両金属粒子合計の濃度が100mg/Lの混合液を調製した。
(Preparation Example 9)
A predetermined amount of the dispersion 1 (platinum particle dispersion) obtained in Preparation Example 1 and a dispersion 4 in which nickel particles (manufactured by Sigma, catalog part number 577995, particle size <100 nm, 99%) are dispersed in water The mixture was mixed to prepare a mixed solution in which the mixing ratio of platinum particles and nickel particles was 70/30 in mass ratio, and the total concentration of both metal particles was 100 mg / L.

(調製例10)
調製例1で得られた分散液1(白金粒子分散液)と、分散液5として酸化亜鉛粒子(シグマ社製、カタログ品番721085、粒子径<130nm、40%)を所定量混合し、白金粒子と酸化亜鉛粒子の配合割合が質量比で70/30、両金属粒子合計の濃度が100mg/Lの混合液を調製した。
(Preparation Example 10)
A predetermined amount of the dispersion 1 (platinum particle dispersion) obtained in Preparation Example 1 and zinc oxide particles (manufactured by Sigma, catalog part number 721085, particle size <130 nm, 40%) as the dispersion 5 were mixed to obtain platinum particles. And a mixture of zinc oxide particles in a mass ratio of 70/30 and a total concentration of both metal particles of 100 mg / L.

表2には、調製例8〜10の配合組成を示している。   Table 2 shows the compositions of Preparation Examples 8 to 10.

Figure 0006293389
Figure 0006293389

(実施例1)
ポリテトラフルオロエチレン樹脂(PTFE樹脂)製の基材(2×3cmのネット状で開口部が1mm角)8質量部を採取し、純水で洗浄してから、上記調製例3で調製した混合液に浸漬させた。その後、基材が浸漬した混合液を、試験用マイクロ波装置(PerkinElmer製Multiwave3000)に設置し、マイクロ波の照射処理を行った。マイクロ波の照射条件は、照射波長2.45GHz、照射パワー400W、照射時間7minとして1回の処理を行った。その後、基材を引き上げ、純水で洗浄し、一昼夜室温で乾燥することにより、微生物防除剤を得た。
Example 1
8 parts by mass of a base material made of polytetrafluoroethylene resin (PTFE resin) (2 × 3 cm net shape and 1 mm square opening), washed with pure water, and mixed in Preparation Example 3 above It was immersed in the liquid. After that, the mixed solution in which the base material was immersed was placed in a test microwave device (Multiwave 3000 manufactured by PerkinElmer) and subjected to microwave irradiation treatment. Microwave irradiation conditions were as follows: irradiation wavelength 2.45 GHz, irradiation power 400 W, irradiation time 7 min. Thereafter, the base material was pulled up, washed with pure water, and dried overnight at room temperature to obtain a microorganism control agent.

(実施例2〜8)
調製例3で調製した混合液を調製例4〜10で調製した混合液に代えた以外は(それぞれ実施例2〜8)、実施例1と同様の方法でそれぞれ微生物防除剤を得た。
(Examples 2 to 8)
A microorganism control agent was obtained in the same manner as in Example 1 except that the mixed solution prepared in Preparation Example 3 was replaced with the mixed solution prepared in Preparation Examples 4 to 10 (Examples 2 to 8 respectively).

(比較例1)
調製例3で調製した混合液を調製例1で得られた分散液1に代えた以外は、実施例1と同様の方法で微生物防除剤を得た。
(Comparative Example 1)
A microorganism control agent was obtained in the same manner as in Example 1, except that the mixed solution prepared in Preparation Example 3 was replaced with the dispersion 1 obtained in Preparation Example 1.

(比較例2)
調製例3で調製した混合液を調製例2で得られた分散液2に代えた以外は、実施例1と同様の方法で微生物防除剤を得た。
(Comparative Example 2)
A microorganism control agent was obtained in the same manner as in Example 1 except that the mixed liquid prepared in Preparation Example 3 was replaced with the dispersion 2 obtained in Preparation Example 2.

(抗菌性評価)
各実施例及び比較例で得られた試験検体に対し、JIS Z2801の準拠する測定方法に従い、フィルム密着法で抗菌性試験を行った。また、菌体としては、黄色ブドウ球及び大腸菌のそれぞれを用いて試験を行った。結果を表3に示す。
(Antimicrobial evaluation)
The test specimens obtained in each Example and Comparative Example were subjected to an antibacterial test by a film adhesion method according to a measurement method based on JIS Z2801. Moreover, as a microbial cell, it tested using each of yellow staphylococcus and colon_bacillus | E._coli. The results are shown in Table 3.

Figure 0006293389
Figure 0006293389

(実施例9)
PTFE樹脂製の基材の代わりにポリカーボネート(PC樹脂)製の基材に変更したこと以外は実施例2と同様の手順で白金粒子及び銀粒子が基材に担持された微生物防除剤を得た。
Example 9
A microbial control agent in which platinum particles and silver particles were supported on a base material was obtained in the same procedure as in Example 2 except that the base material was made of polycarbonate (PC resin) instead of the base material made of PTFE resin. .

(実施例10)
調製例4で得られた混合液を水で1/10の濃度に希釈して使用したこと以外は実施例2と同様の手順で微生物防除剤を得た。
(Example 10)
A microorganism control agent was obtained in the same procedure as in Example 2 except that the mixture obtained in Preparation Example 4 was diluted to 1/10 with water and used.

(実施例11)
PTFE樹脂製の基材の代わりにポリカーボネート(PC樹脂)製の基材に変更したこと以外は実施例10と同様の手順で微生物防除剤を得た。
(Example 11)
A microorganism control agent was obtained in the same procedure as in Example 10 except that the base material was made of polycarbonate (PC resin) instead of the base material made of PTFE resin.

(実施例12)
マイクロ波の照射条件として、照射波長2.45GHz、照射パワー400W、照射時間7minの処理を1回に代えて3回行った以外は、実施例2と同様の手順で微生物防除剤を得た。
(Example 12)
As a microwave irradiation condition, a microorganism control agent was obtained in the same procedure as in Example 2, except that the treatment with an irradiation wavelength of 2.45 GHz, an irradiation power of 400 W, and an irradiation time of 7 min was performed three times instead of once.

(実施例13)
PTFE樹脂製の基材の代わりにポリカーボネート(PC樹脂)製の基材に変更したこと以外は、実施例12と同様の手順で微生物防除剤を得た。
(Example 13)
A microorganism control agent was obtained in the same procedure as in Example 12 except that the substrate was made of polycarbonate (PC resin) instead of the PTFE resin substrate.

(実施例14)
PTFE樹脂製の基材の代わりにポリスチレン(PS樹脂)製の基材に変更したこと、及びマイクロ波の照射条件として、照射波長2.45GHz、照射パワー400W、照射時間7minの処理を1回に代えて5回行った以外は、実施例2と同様の手順で微生物防除剤を得た。
(Example 14)
Change to a polystyrene (PS resin) base material instead of a PTFE resin base material, and as a microwave irradiation condition, treatment with an irradiation wavelength of 2.45 GHz, an irradiation power of 400 W, and an irradiation time of 7 min at a time Instead, the microorganism control agent was obtained in the same procedure as in Example 2, except that the procedure was performed 5 times.

なお、実施例1〜5、実施例9〜14において、マイクロ波の照射前、照射後の白金/銀微粒子混合液をサンプリングし、銀イオン測定器(日本イオン社製、AGT−131)にて銀イオン濃度を確認したところ、何れも検出限界以下であった。   In Examples 1 to 5 and Examples 9 to 14, the platinum / silver fine particle mixed solution before and after microwave irradiation was sampled, and a silver ion measuring instrument (AGT-131, manufactured by Nippon Ion Co., Ltd.) was used. When the silver ion concentration was confirmed, all were below the detection limit.

<評価方法>
(金属担持量の測定)
上記各実施例及び比較例で作製した微生物防除剤について、硫酸灰化法に従い、金属担持量を測定した。具体的には、(1)試料に硫酸を添加し、炭化および灰化を実施し、(2)王水溶解、(3)灰化後、王水を加え、溶解処理を実施し、(4)パーキンエルマー社製ElanDRCIIを使用して、得られた溶液の金属量を計測した。
<Evaluation method>
(Measurement of metal loading)
About the microorganism control agent produced by said each Example and comparative example, the metal carrying amount was measured according to the sulfuric acid ashing method. Specifically, (1) sulfuric acid is added to the sample, carbonization and ashing are carried out, (2) aqua regia dissolution, (3) after ashing, aqua regia is added and dissolution treatment is carried out, (4 ) The amount of metal in the resulting solution was measured using ElanDRCII manufactured by PerkinElmer.

(金属溶出量の測定)
100mL三角フラスコにイオン交換水10mLと、実施例2で作製した微生物防除剤を加え、35℃の恒温振とう機に設置し、振幅30mm、水平方向振とう数150rpmの条件で24時間にわたって振とうした。得られた浸とう液の金属量をIPC−MS(パーキンエルマー社製ElanDRCII)で計測し、これにより、基材からの金属溶出量を定量した。
(Measurement of metal elution amount)
Add 10 mL of ion-exchanged water and the microorganism control agent prepared in Example 2 to a 100 mL Erlenmeyer flask, place in a constant temperature shaker at 35 ° C., and shake for 24 hours under conditions of an amplitude of 30 mm and a horizontal shake of 150 rpm. did. The amount of metal in the obtained immersion liquid was measured by IPC-MS (ElanDRCII manufactured by Perkin Elmer Co.), thereby quantifying the amount of metal elution from the substrate.

(抗菌活性値の測定)
JIS Z2801の準拠する測定方法に従い、フィルム密着法及びシェーク法の各々の方法で抗菌性試験を行った。また、菌体としては、黄色ブドウ球及び大腸菌のそれぞれを用いて試験を行った。
(Measurement of antibacterial activity value)
According to the measurement method based on JIS Z2801, the antibacterial property test was done by each of the film adhesion method and the shake method. Moreover, as a microbial cell, it tested using each of yellow staphylococcus and colon_bacillus | E._coli.

各実施例で得られた微生物防除剤の抗菌活性値を測定するに先立って、調製例4で得られた分散液の抗菌活性試験を実施したところ、18時間培養後に3.9の抗菌活性値を示した。この結果を考慮すると、白金粒子と銀粒子とを含む分散液自体にも、優れた抗菌作用があることがわかる。   Prior to measuring the antibacterial activity value of the microbial control agent obtained in each Example, the antibacterial activity test of the dispersion obtained in Preparation Example 4 was carried out. showed that. Considering this result, it can be seen that the dispersion itself containing platinum particles and silver particles also has an excellent antibacterial action.

Figure 0006293389
Figure 0006293389

Figure 0006293389
Figure 0006293389

Figure 0006293389
Figure 0006293389

表4には、各実施例及び比較例で作製した微生物防除剤において、基材に担持された金属量(白金及び銀)を示している。いずれの実施例においても、基材状に白金及び銀が一定の量で担持されていることがわかる。   Table 4 shows the amount of metal (platinum and silver) supported on the base material in the microbial control agents produced in each Example and Comparative Example. In any of the examples, it can be seen that platinum and silver are supported in a certain amount on the substrate.

表5には、実施例2で作成した微生物防除剤からの金属溶出量の測定結果を示している。この結果、実施例2の微生物防除剤は単体からの金属溶出量が検出限界以下であった。また、それにもかかわらず、後述の通り、実施例2の微生物防除剤は優れた抗菌効果を発現している。   Table 5 shows the measurement results of the metal elution amount from the microorganism control agent prepared in Example 2. As a result, the amount of metal elution from the single substance of the microorganism control agent of Example 2 was below the detection limit. Nevertheless, as described later, the microorganism control agent of Example 2 exhibits an excellent antibacterial effect.

表6にはフィルム密着法における菌体(黄色ブドウ球及び大腸菌)に対する抗菌活性値を示している。PC樹脂製の基材(実施例9,11,13)はPTFE樹脂製の基材(実施例)に比べて金属担持量が少ないにもかかわらず、同等の優れた抗菌性能を発現した。   Table 6 shows the antibacterial activity value against bacterial cells (yellow staphylococci and Escherichia coli) in the film adhesion method. Although the base material made of PC resin (Examples 9, 11, and 13) had a smaller metal loading than the base material made of PTFE resin (Example), the same excellent antibacterial performance was exhibited.

2.防藻効果の確認
(実施例15)
植物栽培容器(アズワン ビオラモポリカーボネイト角型ボトル、材質:ポリカーボネート、容量:150mL)内部を純水で洗浄後、調製例4で調製した混合液(白金/銀粒子分散液)の純水による100倍希釈液を入れた。その後、試験用マイクロ波装置(PerkinElmer製Multiwave3000)に設置し、マイクロ波の照射処理を行った。マイクロ波の照射条件は、照射波長2.45GHz、照射パワー400W、照射時間7minとして1回の処理を行った。容器内の白金/銀粒子分散液を除去し、容器内部を純水で洗浄後、一昼夜室温で乾燥することにより、内面に白金粒子及び銀粒子が担持された植物栽培容器を得た。
2. Confirmation of anti-algae effect (Example 15)
Plant cultivation container (As One Violamo polycarbonate square bottle, material: polycarbonate, capacity: 150 mL) After washing the interior with pure water, the mixture (platinum / silver particle dispersion) prepared in Preparation Example 4 is 100 times with pure water. Diluent was added. Then, it installed in the test microwave apparatus (Multiwave3000 by PerkinElmer), and performed the microwave irradiation process. Microwave irradiation conditions were as follows: irradiation wavelength 2.45 GHz, irradiation power 400 W, irradiation time 7 min. The platinum / silver particle dispersion in the container was removed, the interior of the container was washed with pure water, and then dried overnight at room temperature to obtain a plant cultivation container having platinum particles and silver particles supported on the inner surface.

(実施例16)
マイクロ波の照射条件として、照射波長2.45GHz、照射パワー400W、照射時間7minの処理を1回に代えて2回行った以外は、実施例15と同様の手順で内面に白金粒子及び銀粒子が担持された植物栽培容器を得た。
(Example 16)
As the microwave irradiation conditions, platinum particles and silver particles were formed on the inner surface in the same procedure as in Example 15 except that the treatment with an irradiation wavelength of 2.45 GHz, an irradiation power of 400 W, and an irradiation time of 7 min was performed twice instead of once. A plant cultivation container on which was supported was obtained.

(比較例3)
分散液を、銀粒子を含まず白金粒子のみを含む分散液1(調製例1)に変更したこと以外は実施例15と同様の手順で内面に白金粒子が担持された植物栽培容器を得た。
(Comparative Example 3)
A plant cultivation container having platinum particles supported on the inner surface was obtained in the same procedure as in Example 15 except that the dispersion was changed to Dispersion 1 (Preparation Example 1) containing only platinum particles but not silver particles. .

(比較例4)
分散液を、白金粒子を含まず銀粒子のみを含む分散液2(調製例2)に変更したこと以外は実施例15と同様の手順で内面に銀粒子が担持された植物栽培容器を得た。
(Comparative Example 4)
A plant cultivation container having silver particles supported on the inner surface was obtained in the same procedure as in Example 15 except that the dispersion was changed to Dispersion 2 (Preparation Example 2) containing only silver particles but not platinum particles. .

(防藻試験)
実施例15〜16、比較例3〜4で作製した容器に植物培養液(OATアグリオ製 OATハウス8号の100倍希釈液)を入れ、そこでキュウリの苗を8日間栽培し、培養液中の藻の発生状況を目視で確認した。
(Algae prevention test)
The plant culture solution (100-fold diluted solution of OAT House No. 8 manufactured by OAT Agrio) was put into the containers prepared in Examples 15 to 16 and Comparative Examples 3 to 4, where cucumber seedlings were cultivated for 8 days, The occurrence of algae was confirmed visually.

表7には、上記防藻試験結果の結果を示す。   Table 7 shows the results of the algae control results.

Figure 0006293389
Figure 0006293389

表7から、実施例15,16では藻の発生がなく、この結果から、白金と銀粒子が基材に担持された微生物防除剤では、防藻効果が発現していることが確認された。   From Table 7, there was no generation of algae in Examples 15 and 16, and from this result, it was confirmed that the microbial control agent in which platinum and silver particles were supported on the base material exhibited an algal control effect.

3.バイオフィルム形成抑制効果の確認
(実施例17)
実施例2で作製した微生物防除剤(白金と銀粒子が担持されたPTFE基材)を5cm×5cmにカットして試験片を得た。
3. Confirmation of biofilm formation inhibitory effect (Example 17)
The microorganism control agent (PTFE base material carrying platinum and silver particles) produced in Example 2 was cut into 5 cm × 5 cm to obtain test pieces.

(実施例18)
調製例4で調製した混合液を純水で10倍希釈した白金銀粒子分散液を用いた以外は、実施例2と同様の方法で、白金と銀粒子が基材に担持された微生物防除剤(白金と銀粒子が担持されたPTFE基材)を作製し、これを5cm×5cmにカットして試験片を得た。
(Example 18)
A microorganism control agent in which platinum and silver particles are supported on a substrate in the same manner as in Example 2, except that a platinum-silver particle dispersion obtained by diluting the mixed solution prepared in Preparation Example 4 with pure water 10 times was used. (PTFE base material carrying platinum and silver particles) was prepared and cut into 5 cm × 5 cm to obtain a test piece.

(実施例19)
調製例4で調製した混合液を純水で100倍希釈した混合液を用いた以外は、実施例2と同様の方法で、白金と銀粒子が基材に担持された微生物防除剤(白金と銀粒子が担持されたPTFE基材)を作製し、これを5cm×5cmにカットして試験片を得た。
(Example 19)
A microorganism control agent (platinum and platinum) in which platinum and silver particles are supported on a substrate in the same manner as in Example 2 except that the mixed solution prepared in Preparation Example 4 was diluted 100 times with pure water. A PTFE base material carrying silver particles was prepared, and this was cut into 5 cm × 5 cm to obtain test pieces.

(比較例5)
白金及び金属粒子のいずれも担持させず、PTFE基材を5cm×5cmにカットして試験片を得た。
(Comparative Example 5)
Neither platinum nor metal particles were supported, and a PTFE base material was cut into 5 cm × 5 cm to obtain a test piece.

(バイオフィルム抑制効果の確認試験)
水道水10Lを、外部循環装置付恒温水槽の恒温水槽に入れ、外部循環対象に循環させることなく、自己循環させた。この恒温水槽中に実施例17〜19および比較例5のいずれかの試験片を浸漬し、毎日9時〜17時までの8時間を運転時間とし、運転温度は、室温から40℃の範囲として、10日間運転した。その後、各試験片表面のバイオフィルム(膜状の物質)の形成について、目視で評価した。
(Confirmation test of biofilm suppression effect)
10 L of tap water was put into a constant temperature water tank of a constant temperature water tank with an external circulation device, and self-circulated without being circulated to an external circulation target. The test piece of any of Examples 17 to 19 and Comparative Example 5 is immersed in this constant temperature water bath, and 8 hours from 9:00 to 17:00 every day is set as the operating time, and the operating temperature is in the range from room temperature to 40 ° C. I drove for 10 days. Thereafter, the formation of a biofilm (film-like substance) on the surface of each test piece was visually evaluated.

表8は、バイオフィルム抑制効果の確認試験を示している。   Table 8 shows a confirmation test of the biofilm suppression effect.

Figure 0006293389
Figure 0006293389

表8から、実施例17〜19ではバイオフィルムの形成がなく、この結果から、白金と銀粒子が基材に担持された微生物防除剤では、バイオフィルム形成抑制効果が発現していることが確認された。   From Table 8, in Examples 17-19, there was no formation of a biofilm, and from this result, it was confirmed that a biofilm formation inhibitory effect was manifested in the microbial control agent in which platinum and silver particles were supported on a substrate. It was done.

4.殺ダニ、防ダニ効果の確認(1)
(実施例20)
JIS L1920:2007に準じて試験を行った。具体的には、サンプル瓶に加工試料または未加工試料を敷き詰め、50〜80匹/0.1gのダニ培地(ヤケヒョウヒダニ)を各々の試料にばらまいた後、4、6および8週間放置後、サンプル管瓶内の生存ダニを計数することで、ダニの増殖抑制率を算出した。上記加工試料は、基材であるPE製樹脂ペレット(Φ10mm×L10mm)を、表9に示す組成割合の殺ダニ組成物の水分散液(No.1〜4)で処理することで調製した。なお、いずれの試料もマイクロ波照射(出力400W、時間14min)処理によって調製した。
4). Confirmation of mite killing and mite prevention effect (1)
(Example 20)
The test was conducted according to JIS L 1920: 2007. Specifically, a processed or unprocessed sample is spread on a sample bottle, 50 to 80 animals / 0.1 g of mite medium (Yake leopard mite) is dispersed in each sample, and then left for 4, 6 and 8 weeks, By counting the number of surviving ticks in the tube bottle, the growth inhibition rate of ticks was calculated. The processed sample was prepared by treating PE resin pellets (Φ10 mm × L10 mm) as a substrate with an aqueous dispersion (No. 1 to 4) of the acaricide composition having the composition ratio shown in Table 9. All samples were prepared by microwave irradiation (output 400 W, time 14 min).

そして、下記の計算式により、ダニの忌避率を算出した。
忌避率(%)=[(A−B)/A]×100
ここで、Aは未加工試料の誘引ダニ数、Bは加工試料の誘引ダニ数を表す。
Then, the mite repellent rate was calculated by the following formula.
Repelling rate (%) = [(A−B) / A] × 100
Here, A represents the number of attracted ticks of the unprocessed sample, and B represents the number of attracted ticks of the processed sample.

Figure 0006293389
Figure 0006293389

表10には、表9に示すNo.1〜No.4の試料で処理した加工試料における忌避率を示している。   Table 10 shows the No. shown in Table 9. 1-No. The repelling rate in the processed sample processed with the sample of 4 is shown.

Figure 0006293389
Figure 0006293389

この結果から、白金及び銀粒子が基材に担持された防ダニ部材では、優れた防ダニ効果が発現していることが確認された。   From this result, it was confirmed that an excellent mite-preventing effect was exhibited in the mite-proof member in which platinum and silver particles were supported on the base material.

5.殺ダニ、防ダニ効果の確認(2)
(参考試験例1)
PLA(ポリ乳酸樹脂)製ハニカム(クニムネ社製)を、表9の試料No.1(白金粒子と銀粒子の混合分散液)に浸漬することで、白金粒子及び銀粒子を担持するPLA製ハニカムを防ダニ巣脾として得た。
5. Confirmation of mite killing and mite prevention effect (2)
(Reference Test Example 1)
A PLA (polylactic acid resin) honeycomb (manufactured by Kunimune Co., Ltd.) was used. By immersing in 1 (mixed dispersion of platinum particles and silver particles), a PLA honeycomb carrying platinum particles and silver particles was obtained as a spleen-proof spleen.

得られた防ダニハニカムをアクリル製ケージ(幅40cm、奥行10cm、高さ20cm)内に設置し、ミツバチヘギイタダニを5匹入れ、インキュベーター(パナソニック社製)にて30℃、70%湿度の条件に調整して飼育をした。飼育してから2時間、4時間、6時間及び24時間後にミツバチヘギイタダニの生存率を測定した。この操作を反復6回行って生存率の平均値を算出した。   The obtained tick-proof honeycomb was placed in an acrylic cage (width 40 cm, depth 10 cm, height 20 cm), and five bee wings were placed in an incubator (manufactured by Panasonic) at 30 ° C. and 70% humidity. The animals were reared after adjusting to the conditions. The survival rate of the honeybee mite was measured 2 hours, 4 hours, 6 hours and 24 hours after the breeding. This operation was repeated 6 times to calculate the average survival rate.

図1は、飼育時間とミツバチヘギイタダニの生存数との関係を示している。また、比較として、未処理のPLA製ハニカム、すなわち、白金粒子及び銀粒子を担持していないハニカム(以下、「ブランク巣脾」という)についても防ダニ巣脾と同様の試験をした結果を合わせて示している(図1棒グラフの各経過時間において、左側棒グラフが防ダニ巣脾の生存ダニ数、右側棒グラフがブランク巣脾生存ダニ数を示している)。   FIG. 1 shows the relationship between rearing time and the number of living honey bee mites. For comparison, the results of tests similar to those for anti-tick nest spleens were also applied to untreated PLA honeycombs, that is, honeycombs not carrying platinum particles and silver particles (hereinafter referred to as “blank nest spleens”). (In each elapsed time of FIG. 1 bar graph, the left bar graph shows the number of surviving ticks of the mite-preventing spleen, and the right bar graph shows the number of surviving ticks of the blank nest spleen).

この結果から、防ダニ巣脾ではブランク巣脾と比べると、飼育時間の経過に伴ってミツバチヘギイタダニの生存数が減少していることが認められる。よって、白金粒子と銀粒子を含む殺ダニ組成物で処理されたハニカムは、殺ダニ効果及び防ダニ効果を有しているといえる。   From this result, it can be seen that the number of honey bee mite ticks decreased with the passage of breeding time in the tick-proof nest spleen compared with the blank nest spleen. Therefore, it can be said that the honeycomb treated with the acaricide composition containing platinum particles and silver particles has an acaricidal effect and an acaricidal effect.

6.殺ダニ、防ダニ効果の確認(3)
(参考試験例2)
殺ダニ、防ダニ効果の確認(2)で得た防ダニ巣脾と、ブランク巣脾とをアクリル製ケージ(幅40cm、奥行10cm、高さ20cm)内に設置し、ミツバチヘギイタダニを10匹入れ、インキュベーター(パナソニック社製)にて30℃、70%湿度の条件に調整して飼育をした。飼育してから2時間、4時間、6時間及び24時間後にミツバチヘギイタダニがいずれの巣脾に存在しているかを確認した。この操作を反復6回行ってミツバチヘギイタダニの各々の巣脾における存在数平均値を算出した。
6). Confirmation of mite killing and mite prevention effect (3)
(Reference Test Example 2)
The mite-preventing spleen obtained in the confirmation of the mite-killing and mite-preventing effect (2) and the blank nest spleen are placed in an acrylic cage (width 40 cm, depth 10 cm, height 20 cm). The animals were housed and reared in an incubator (manufactured by Panasonic) under conditions of 30 ° C. and 70% humidity. After 2 hours, 4 hours, 6 hours, and 24 hours after breeding, it was confirmed in which nest spleen the honeybee mite was present. This operation was repeated 6 times to calculate the average number of honey bee mites in each nest spleen.

図2は、飼育時間とミツバチヘギイタダニの生存数との関係を示している(図2棒グラフの各経過時間において、左側棒グラフが防ダニ巣脾の生存ダニ数、右側棒グラフがブランク巣脾生存ダニ数を示している)。   FIG. 2 shows the relationship between breeding time and the number of honey bee mite survivals (the left bar graph shows the number of mite-preventing spleen survival ticks and the right bar graph shows blank nest spleen survival at each elapsed time in FIG. 2). Shows the number of ticks).

この結果から、飼育時間の経過と共に、防ダニ巣脾におけるミツバチヘギイタダニの生存数はブランク巣脾に比べて大きな減少がみられることがわかる。よって、白金粒子と銀粒子を含む殺ダニ組成物で処理されたハニカムは、ダニに対する忌避効果を有しているといえる。   From this result, it can be seen that, as the breeding time elapses, the number of honey bee mite survivors in the mite-preventing spleen is greatly reduced compared to the blank nest spleen. Therefore, it can be said that the honeycomb treated with the acaricide composition containing platinum particles and silver particles has a repellent effect against mites.

7.細胞培養の確認
(実施例21)
細胞培養容器であるポリスチレン樹脂(PS樹脂)製ディッシュ(組織培養用ディッシュ「FALCON3001」、直径35mm)を純水で洗浄した後、表9に示す試料No.2の白金粒子及び銀粒子を含む分散液に浸漬させることでディッシュの抗菌処理を行った。その後、ディッシュが浸漬した混合液を、試験用マイクロ波装置(PerkinElmer製Multiwave3000)に設置し、マイクロ波の照射処理を行った。マイクロ波の照射条件は、照射波長2.45GHz、照射パワー400W、照射時間7minとして1回の処理を行った。その後、ディッシュを引き上げ、さらに、70%EtOHに数分間浸漬し、ディッシュを引き上げた後、紫外線を約1時間照射することで滅菌処理を行った。これにより、抗菌処理された細胞培養容器を得た。
7). Confirmation of cell culture (Example 21)
After washing a polystyrene resin (PS resin) dish (tissue culture dish “FALCON3001”, diameter 35 mm), which is a cell culture container, with pure water, the sample No. shown in Table 9 was obtained. The dish was subjected to antibacterial treatment by being immersed in a dispersion containing platinum particles and silver particles. Thereafter, the mixed solution in which the dish was immersed was placed in a test microwave device (Multiwave 3000 manufactured by PerkinElmer) and subjected to microwave irradiation treatment. Microwave irradiation conditions were as follows: irradiation wavelength 2.45 GHz, irradiation power 400 W, irradiation time 7 min. Thereafter, the dish was pulled up, further immersed in 70% EtOH for several minutes, the dish was pulled up, and then sterilized by irradiation with ultraviolet rays for about 1 hour. Thereby, an antimicrobially treated cell culture container was obtained.

上記細胞培養容器を用いて、次の条件で細胞の培養を行った。
細胞の条件
・HepG2細胞(ヒト肝芽腫細胞)
・培地:WE+10%FBS
・培養期間:5日間(培地交換無)
細胞播種密度
・1.5×10cells/dish
(1.6×10cells/cm
培養条件
・培養液量:2ml/dish(35mm)
・培養:37℃、5%CO雰囲気下とした。
Using the cell culture vessel, cells were cultured under the following conditions.
Cell conditions-HepG2 cells (human hepatoblastoma cells)
-Medium: WE + 10% FBS
・ Culture period: 5 days (without medium change)
Cell seeding density 1.5 × 10 5 cells / dish
(1.6 × 10 4 cells / cm 2 )
Culture conditions-Volume of culture solution: 2 ml / dish (35 mm)
Culture: 37 ° C., 5% CO 2 atmosphere.

(実施例22)
白金粒子及び銀粒子を含む分散液を表9に示す試料No.1に変更したこと以外は、実施例21と同様の条件で細胞培養容器を得て、細胞の培養を行った。
(Example 22)
A dispersion containing platinum particles and silver particles was prepared as Sample No. A cell culture vessel was obtained under the same conditions as in Example 21 except that the cells were changed to 1, and cells were cultured.

(ブランク試験)
白金粒子及び銀粒子を含む分散液による抗菌処理を行わなかったこと以外は、実施例21と同様の条件で、細胞の培養を行った。
(Blank test)
Cells were cultured under the same conditions as in Example 21 except that the antibacterial treatment with the dispersion containing platinum particles and silver particles was not performed.

表11には、細胞培養容器への白金及び銀の担持量を示しており、あわせて、抗菌性の結果及びアルブミン分泌活性の値も示している。   Table 11 shows the amounts of platinum and silver supported on the cell culture container, and also shows the antibacterial results and the value of albumin secretion activity.

白金及び銀の担持量は、ディッシュを溶解して金属を含む液を得た後、ICP−MSを用いて定量した。白金及び銀の担持量は、前述の「金属担持量の測定」と同様の方法で行った。   The supported amounts of platinum and silver were quantified using ICP-MS after dissolving the dish to obtain a metal-containing liquid. The supported amounts of platinum and silver were measured in the same manner as the above-mentioned “Measurement of metal supported amount”.

アルブミン分泌活性の値は、細胞の活性を示す指標である。アルブミン分泌活性の値は、次の方法により計測した。まず、培養培地中に分泌されたアルブミン量を酵素標識免疫測定法(ELISA)により定量し、この定量値から単位細胞数当りのアルブミン分泌速度に換算した。細胞数の測定は、DNA−DAPI(4,6−diaminodino−2−phenylindole、和光純薬工業社製)蛍光法により算出した。すなわち、一定細胞から抽出したDNAとDNA−DAPIの蛍光強度間の検量線を作製し、この関係をもとに培養した細胞の細胞数を算出した。この細胞数をもとに、前述の単位細胞当りのアルブミン分泌速度を算出した。   The value of albumin secretion activity is an index indicating the activity of cells. The value of albumin secretion activity was measured by the following method. First, the amount of albumin secreted into the culture medium was quantified by enzyme-labeled immunoassay (ELISA), and the albumin secretion rate per unit cell number was converted from this quantified value. The number of cells was calculated by DNA-DAPI (4,6-diaminodino-2-phenylindole, manufactured by Wako Pure Chemical Industries, Ltd.) fluorescence method. That is, a calibration curve between DNA extracted from certain cells and the fluorescence intensity of DNA-DAPI was prepared, and the number of cells cultured was calculated based on this relationship. Based on the number of cells, the albumin secretion rate per unit cell was calculated.

抗菌性の評価は、JIS Z2801の準拠する測定方法に従い、シェーク法(35℃±1℃)による抗菌活性値から、下記基準で判断した。菌体としては、大腸菌を用いた。
○:抗菌活性値が2.0以上であり、優れた抗菌性を有していた。
×:抗菌活性値が2.0未満であり、抗菌性を有していなかった。
The antibacterial evaluation was judged according to the following criteria from the antibacterial activity value by the shake method (35 ° C. ± 1 ° C.) according to the measurement method in accordance with JIS Z2801. E. coli was used as the microbial cell.
◯: The antibacterial activity value was 2.0 or more and had excellent antibacterial properties.
X: The antibacterial activity value was less than 2.0, and it did not have antibacterial properties.

Figure 0006293389
Figure 0006293389

表11から、実施例21〜22の細胞培養容器は、高い抗菌性を有していると共に、細胞の活性もブランク試験と同等であることから、抗菌処理が細胞の培養に影響を与えていないことがわかる。   From Table 11, since the cell culture container of Examples 21-22 has high antibacterial property, since the activity of a cell is equivalent to a blank test, antibacterial treatment does not affect the culture of a cell. I understand that.

さらに、実施例22で得た細胞培養容器を用いて、同条件でNIH3T3細胞(マウス繊維芽細胞)、HeLa細胞(ヒト子宮頸癌細胞)、hMSC(ヒト間葉系幹細胞)の培養を行ったところ、これら細胞の培養への影響は見られなかった(これら細胞が問題なく培養されることが確認された)。   Furthermore, using the cell culture vessel obtained in Example 22, NIH3T3 cells (mouse fibroblasts), HeLa cells (human cervical cancer cells), and hMSCs (human mesenchymal stem cells) were cultured under the same conditions. However, no influence on the culture of these cells was observed (it was confirmed that these cells were cultured without problems).

Claims (14)

生物防除剤を含む、防藻剤であって、
前記微生物防除剤は、白金粒子と、銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子からなる群より選ばれる少なくとも1種の金属粒子とを含み、
白金粒子と上記金属粒子との質量合計を100とした場合、白金粒子が10以上90以下である、防藻剤
Including the micro-biological control agent, a Bomozai,
The microorganism control agent includes platinum particles and at least one metal particle selected from the group consisting of silver particles, copper particles, nickel particles and zinc particles,
An anti-algae agent wherein the platinum particles are 10 or more and 90 or less when the total mass of the platinum particles and the metal particles is 100 .
前記金属粒子が銀粒子及び銅粒子からなる群より選ばれる少なくとも1種を含む、請求項1に記載の防藻剤。The algae deterrent according to claim 1, wherein the metal particles include at least one selected from the group consisting of silver particles and copper particles. 前記白金粒子及び前記金属粒子の平均粒子径が0.1〜1000nmである、請求項1又は2に記載の防藻剤。The anti-algae agent according to claim 1 or 2, wherein the platinum particles and the metal particles have an average particle diameter of 0.1 to 1000 nm. 前記白金粒子及び前記金属粒子が基材上に担持されている、請求項1〜3のいずれか1項に記載の防藻剤。The anti-algae agent of any one of Claims 1-3 with which the said platinum particle and the said metal particle are carry | supported on the base material. 前記白金粒子及び前記金属粒子が0.01〜20,000ng/cmThe platinum particles and the metal particles are 0.01 to 20,000 ng / cm. 2 で前記基材に担持されている、請求項4に記載の防藻剤。The algae-proofing agent according to claim 4, which is carried on the substrate. 前記基材が樹脂で形成されている、請求項4又は5に記載の防藻剤。The anti-algae agent of Claim 4 or 5 in which the said base material is formed with resin. 前記樹脂がポリスチレン樹脂、塩化ビニル樹脂、フッ素樹脂、ABS樹脂、PET樹脂、ポリカーボネート樹脂、尿素樹脂、オレフィン樹脂及びフェノール樹脂からなる群より選ばれる少なくとも1種を含む、請求項6に記載の防藻剤。The algae according to claim 6, wherein the resin includes at least one selected from the group consisting of polystyrene resin, vinyl chloride resin, fluorine resin, ABS resin, PET resin, polycarbonate resin, urea resin, olefin resin, and phenol resin. Agent. 前記基材が、シート状、板状、ブロック状、ネット状、パンチングシート状、粒状、ロッド状、破砕状及びディッシュ状のいずれかの形状に形成されている、請求項4〜7のいずれか1項に記載の防藻剤。The base material according to any one of claims 4 to 7, wherein the base material is formed into any one of a sheet shape, a plate shape, a block shape, a net shape, a punching sheet shape, a granular shape, a rod shape, a crushed shape, and a dish shape. The algae preventer according to item 1. 生物防除剤を用いて対象物に防藻性を付与させる、防藻方法であって、
前記微生物防除剤は、白金粒子と、銀粒子、銅粒子、ニッケル粒子及び亜鉛粒子からなる群より選ばれる少なくとも1種の金属粒子とを含み、
白金粒子と上記金属粒子との質量合計を100とした場合、白金粒子が10以上90以下である、防藻方法。
Thereby imparting antialgal the object using microbial control agent, a algae method,
The microorganism control agent includes platinum particles and at least one metal particle selected from the group consisting of silver particles, copper particles, nickel particles and zinc particles,
An anti-algae method wherein the platinum particles are 10 or more and 90 or less when the total mass of the platinum particles and the metal particles is 100.
前記白金粒子及び前記金属粒子が基材上に担持されている、請求項9に記載の防藻方法。The algae prevention method according to claim 9, wherein the platinum particles and the metal particles are supported on a base material. 白金粒子と、銀粒子とを含み、白金粒子と銀粒子との質量合計を100とした場合、白金粒子が10以上90以下である、殺ダニ組成物。 Comprising platinum particles, and silver particles child, when the total mass of platinum particles and the silver particles 100, the platinum particles is 10 or more and 90 or less, acaricidal composition. 前記白金粒子及び前記銀粒子の平均粒子径が0.1〜1000nmである、請求項11に記載の殺ダニ組成物。 The acaricidal composition according to claim 11, wherein the platinum particles and the silver particles have an average particle diameter of 0.1 to 1000 nm. 請求項11又は12に記載の殺ダニ組成物を使用した、防ダニ部材(但し、養蜂部材を除く)。 A tick-proof member (excluding a beekeeping member) using the acaricidal composition according to claim 11 or 12 . 請求項11又は12に記載の殺ダニ組成物を用いて対象物(但し、養蜂部材を除く)に防ダニ機能を付与させる、防ダニ方法。 The mite prevention method which provides a target object (however, except a beekeeping member) the mite prevention function using the acaricide composition of Claim 11 or 12 .
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