JP7214936B1 - Antibacterial/antiviral composition and method for producing the same - Google Patents
Antibacterial/antiviral composition and method for producing the same Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 20
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 title abstract description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 63
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 63
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001246 colloidal dispersion Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 239000001509 sodium citrate Substances 0.000 claims abstract description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 3
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
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- 238000000576 coating method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 2
- 229940108928 copper Drugs 0.000 claims 4
- 239000000084 colloidal system Substances 0.000 claims 1
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000005749 Copper compound Substances 0.000 abstract description 5
- 150000001880 copper compounds Chemical class 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 3
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
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- 238000004062 sedimentation Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000282552 Chlorocebus aethiops Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
【課題】本発明は、亜酸化銅を原料として得られる沈殿物の無い透明なコロイド分散液であって、抗菌・抗ウィルス性組成物およびその製造方法である。【解決手段】亜酸化銅を分散させた亜酸化銅懸濁溶液（スラリー溶液）に有機酸を加え加熱して溶解し、更に塩酸を加えて清澄化した溶液に、クエン酸３ナトリウムを用いてpH調整して得られた平均粒子径が１０～１００ｎｍの沈殿物の無い水溶液であって、CuイオンやＣｕ２Ｏ・ＣｕＯ・ＣｕＣｌ・ＣｕＣｌ２などの銅化合物が混在する有色透明な分散液であり、長期間に亘って凝集沈殿せず、適切な無機バインダーを選定して配合すれば、優れた密着性のある、高い抗菌・抗ウィルス及び防藻性の水系組成物を提供することである。【選択図】図１Kind Code: A1 The present invention relates to an antibacterial/antiviral composition, which is a transparent colloidal dispersion free from precipitates obtained using cuprous oxide as a raw material, and a method for producing the same. SOLUTION: An organic acid is added to a cuprous oxide suspension solution (slurry solution) in which cuprous oxide is dispersed, heated and dissolved, and further hydrochloric acid is added to clarify the solution, and trisodium citrate is added to the solution. It is an aqueous solution with an average particle size of 10 to 100 nm obtained by adjusting the pH without precipitation, and is a colored and transparent dispersion in which copper compounds such as Cu ions and CuO, CuO, CuCl, and CuCl are mixed. To provide a highly antibacterial, antiviral and antialgal water-based composition which does not aggregate and precipitate over a period of time and has excellent adhesion when an appropriate inorganic binder is selected and blended. [Selection drawing] Fig. 1
Description
本発明は、亜酸化銅を原料として、Ｃｕイオンおよび、コロイド粒子の主成分として、Ｃｕ２（Ｃ６Ｈ４Ｏ７）、Ｃｕ２０、ＣｕＣｌやＣｕＯなどの銅化合物を含有する有色透明な溶液であって、優れた密着性を有する溶液であり、抗菌・抗ウイルス性組成物に関するものである。 The present invention uses cuprous oxide as a raw material, Cu ions, and as the main components of colloidal particles, a colored and transparent liquid containing copper compounds such as Cu 2 (C 6 H 4 O 7 ) , Cu 2 O , CuCl and CuO. The present invention relates to an antibacterial/antiviral composition, which is a solution having excellent adhesiveness.
従来、亜酸化銅分散液の凝集を抑え、分散性を向上させるためには、界面活性剤を使用する事が一般的であり、特許文献１のＷＯ２０１４／１３２６０６公報の３頁目の段落００１５にはリン酸エステル型アニオン界面活性剤を用い、当該分散液にはリン酸エステル型アニオン界面活性剤を含有することが記載されている。特許文献２のＷＯ２０１９／０４５１１０公報の６頁目の１３行目から１７行目には、分散剤として可溶な界面活性剤等を使用して凝集を防ぐことが記載されている。また、特許文献３の特開２０１３－０８２６５４号公報、特許文献４の特開２０１６－００３２３４号公報および特許文献５の特開２０１７－０５２８８０号公報の何れにも界面活性剤の使用が記載されている。
Conventionally, in order to suppress the aggregation of the cuprous oxide dispersion and improve the dispersibility, it is common to use a surfactant. uses a phosphate ester type anionic surfactant, and describes that the dispersion contains the phosphate ester type anionic surfactant. Patent Document 2, WO2019/045110, page 6, lines 13 to 17, describes the use of a soluble surfactant or the like as a dispersant to prevent aggregation. Further, Japanese Patent Application Laid-Open No. 2013-082654 of Patent Document 3, Japanese Patent Application Laid-Open No. 2016-003234 of
しかし、特許文献１の４頁目の段落００１７によれば、界面活性剤の含有量が少ない場合には、分散液が凝集沈降して抗菌・抗ウィルス性能が低下し、逆に界面活性剤の含有量が多い場合にも、界面活性剤の残存量が多くなり、やはり抗菌・抗ウィルス性能が低下するという欠点が生じると言うことであった。
However, according to paragraph 0017 on
その改善策として、界面活性剤を使用しないで、亜酸化銅を原料とする凝集・沈降しない、高い抗菌・抗ウィルス性能を有する分散液およびその製造方法を提供することで、銅イオンや銅化合物の有する抗菌・抗ウィルス性を高める効果である。 As an improvement measure, by providing a dispersion liquid having high antibacterial and antiviral performance that does not aggregate or precipitate from cuprous oxide as a raw material without using a surfactant and a method for producing the same, copper ions and copper compounds It is an effect that enhances the antibacterial and antiviral properties of
解決しようとする問題点は、界面活性剤を使用しないで、亜酸化銅すなわちＣｕ２Ｏを原料とした沈殿物の無い透明なコロイド分散液の製造は非常に難しい点である。 The problem to be solved is that it is very difficult to prepare a sediment-free transparent colloidal dispersion from cuprous oxide, ie Cu 2 O, without the use of surfactants.
本発明は、酸化第１銅を主原料として、還元性の高い有機酸を用いて溶解し、少量の無機酸を添加して清澄化した後、有機酸のアルカリ塩でｐH調整した、Cu２＋イオン、Ｃｕ+イオンや、Ｃｕ２Ｏやクエン酸銅やＣｕＣｌやＣｕＯなどの銅化合物が混在する透明な水溶液であって、各種基板に優れた密着性を持ち、界面活性剤を含有しない分散液であり、高い抗菌・抗ウィルス性を有することを最も主要な特徴とする。 The present invention uses cuprous oxide as the main raw material, dissolves it using a highly reducing organic acid, adds a small amount of inorganic acid to clarify it, and then adjusts the pH with an alkali salt of an organic acid. Cu 2+ A transparent aqueous solution in which ions, Cu + ions, and copper compounds such as Cu 2 O, copper citrate, CuCl, and CuO are mixed, and has excellent adhesion to various substrates, and does not contain a surfactant. The most important feature is that it has high antibacterial and antiviral properties.
本発明の亜酸化銅（古河ケミカル社製「微粒子亜酸化銅 FRC-０５」：Ｃｕ２Ｏ含有量９８．８重量％、乾燥減量０．１重量％、比表面積２．８ｍ２／ｇ）を主原料とした分散液（以下、「亜酸化銅分散液」と称する）は、長期間に亘って凝集沈殿せず、塗装基板に対して適切な水性無機バインダーを使用すれば形成される塗膜は優れた密着性を有し、鉛筆硬度で７Ｈ～８Ｈ以上を有する強靱な膜となるため、耐久性に優れているという利点および、黄色ブドウ球菌に対する２４時間後の抗菌活性値が４．６～４．９以上を有し、ウィルスに対する開始から１０時間後のTCID５０/ｍLが検出限界未満となるほどの高い抗ウィルス性能を有する利点がある。 The cuprous oxide of the present invention (Furukawa Chemical Co., Ltd. “Fine cuprous oxide FRC-05”: Cu 2 O content 98.8% by weight, loss on drying 0.1% by weight, specific surface area 2.8 m 2 /g) The dispersion used as the main raw material (hereinafter referred to as "cuprous oxide dispersion") does not coagulate and precipitate over a long period of time, and a coating film can be formed by using an appropriate aqueous inorganic binder for the coated substrate. Has excellent adhesion and forms a tough film with a pencil hardness of 7H to 8H or more, so it has the advantage of being excellent in durability, and the antibacterial activity value against Staphylococcus aureus after 24 hours is 4.6. ∼4.9 or higher, and has the advantage of having such a high antiviral performance that the TCID 50 /mL after 10 hours against the virus is below the limit of detection.
（亜酸化銅分散液の製造方法）
図１に示す様な製造工程に基づいて、基本的な製造方法を説明する。
〔Ｓ１〕亜酸化銅（Cu２O）５ｇを水（H２O）２００ｍLに入れて、さらに水（H２O）を３００ｍL加えて、２０℃～４０℃で５００ｒｐｍの回転数で撹拌して（ｐH６～７）、亜酸化銅懸濁液（スラリー溶液）を作る。
〔Ｓ２〕還元性のある有機酸であるクエン酸３ｇを加えて溶解させ、ｐH４のほぼ透明な水溶液を作る。
〔Ｓ３〕濃度３５％の塩酸を６ｇ加えて、６０℃に温度を上げて、ｐH２～２．５の透明で赤色の水溶液とし、静置して清澄液を得る。
〔Ｓ４〕ｐH調整のため、還元機能のあるアルカリ性のクエン酸３ナトリウム３ｇを加えて溶解させ、ｐH４～５の透明な青緑色から緑色を帯びた水溶液とし、９５℃以上で２～３分間沸騰させる。
〔Ｓ５〕約４８０ｍLの水（H２O）を加えて、１０００ｍLの亜酸化銅分散液であって、ｐH３．５～４．５の透明な水溶液が得られる。ただし、水溶液の色は、青みがかった緑色である青緑から緑色を帯びたものとなっている。
〔Ｓ６〕不純物を濾過する。
以上の工程では、界面活性剤などの分散剤が不要であり、当該工程で製造された亜酸化銅分散液は、当然界面活性剤の成分を含有しない透明なコロイド分散液であり、長期間に凝集しない分散水溶液が得られたが、当該分散液の発色が青緑色から緑色までの多様性を有している。尚、当該分散液の原料として使用した「微粒子亜酸化銅 FRC-０５」の特定粒子径以下・以上の粒子量のパーセンテージを示す積分分布１０％径であるD１０は、０．４７μｍ、５０％径であるD５０は０．７５μｍ、９０％径であるＤ９０は１．５７μｍとなっている。また、上記の工程〔Ｓ２〕の有機酸としてアスコルビン酸やリンゴ酸を用いても構わないので、クエン酸にこだわるものではない。
(Method for producing cuprous oxide dispersion)
A basic manufacturing method will be described based on the manufacturing process shown in FIG.
[S1] Put 5 g of cuprous oxide (Cu 2 O) into 200 mL of water (H 2 O), add 300 mL of water (H 2 O), and stir at 500 rpm at 20° C. to 40° C. (pH 6-7), making cuprous oxide suspension (slurry solution).
[S2] 3 g of citric acid, which is a reducing organic acid, is added and dissolved to prepare an almost transparent aqueous solution of
[S3] Add 6 g of hydrochloric acid having a concentration of 35% and raise the temperature to 60° C. to make a transparent red aqueous solution of pH 2 to 2.5.
[S4] To adjust the pH, add and dissolve 3 g of alkaline trisodium citrate, which has a reducing function, to make a clear bluish-green to greenish aqueous solution with a pH of 4 to 5, and boil at 95°C or higher for 2 to 3 minutes. Let
[S5] About 480 mL of water (H 2 O) is added to obtain 1000 mL of cuprous oxide dispersion with a pH of 3.5-4.5 and a clear aqueous solution. However, the color of the aqueous solution changes from bluish green to greenish green.
[S6] Impurities are filtered.
In the above steps, a dispersant such as a surfactant is not required, and the cuprous oxide dispersion produced in this step is naturally a transparent colloidal dispersion that does not contain a surfactant component, and can be used for a long time. A non-agglomerated dispersed aqueous solution was obtained, and the color of the dispersed solution varied from bluish green to green. In addition, D10, which is the 10% diameter of the integral distribution indicating the percentage of the amount of particles having a specific particle diameter or less of "fine particle cuprous oxide FRC-05" used as a raw material of the dispersion, is 0.47 μm, 50% diameter D50, which is 0.75 μm, and D90, which is 90% diameter, is 1.57 μm. In addition, since ascorbic acid or malic acid may be used as the organic acid in step [S2], citric acid is not limited.
（本願発明の分散液が凝集しない理由の推定）
本コロイド溶液が凝集・造粒して沈殿を生じないメカニズムの推定として、コロイド粒子の主な組成と考えられる亜酸化銅Cu２O、塩化第一銅ＣｕＣｌ、クエン酸銅Ｃｕ２（Ｃ６Ｈ４Ｏ７）を含有しているものと考えられる。
そして、これらの混在した微粒子を形成するのは、成分のクエン酸第二銅の構造に起因するものと思われる。このように形成されたコロイド微粒子に存在するクエン酸銅の1分子中に配位するＣｕ２＋が２個、更にクエン酸が持つ３個のヒドロキシル基からＨが脱離したＣ＝Ｏ－が他の粒子のそれらと電荷で相互に反発し合うためであると考えられる。
以上のことから、本願発明の亜酸化銅分散液は、クエン酸第二銅をコロイドの主成分とする水系分散液であり、あるいは、Ｃｕ２Ｏ、ＣｕＣｌ、Ｃｕ２（Ｃ６Ｈ４Ｏ７）などの銅化合物が混在したコロイド粒子を主成分とした銅含有分散水溶液であるとも考えている。
(Presumption of the reason why the dispersion liquid of the present invention does not aggregate)
As a presumption of the mechanism that this colloidal solution aggregates and granulates and does not cause precipitation, cuprous oxide Cu 2 O, cuprous chloride CuCl, copper citrate Cu 2 (C 6 H 4 O 7 ).
It is believed that the formation of these mixed fine particles is due to the structure of the cupric citrate component. In the colloidal fine particles formed in this way, there are two Cu 2+ coordinated in one molecule of copper citrate, and C=O- , in which H is eliminated from the three hydroxyl groups of citric acid. This is thought to be due to mutual repulsion with those of the particles of .
From the above, the cuprous oxide dispersion of the present invention is an aqueous dispersion containing cupric citrate as a main colloidal component, or Cu 2 O, CuCl, Cu 2 (C 6 H 4 O 7 ) is considered to be a copper-containing dispersed aqueous solution mainly composed of colloidal particles mixed with copper compounds such as ).
亜酸化銅分散液（１）を５倍に希釈した水溶液の粒度分布を測定した結果が図２であり、その自己相関関数を図３に示している。また、図１０の右側は分散工程実施前の亜酸化銅懸濁溶液（スラリー溶液）であり、左側は当該亜酸化銅分散液のサンプルを示した代用写真であり、右側の水溶液は混濁しているが、左側の分散液は有色透明な水溶液となっている。当該亜酸化銅分散液（１）は、Ｃｕ２+と、かすかに存在するかもしれないCu＋などのＣｕイオンと、Ｃｕ２ＯやＣｕＯやＣｕＣｌやＣｕ２（Ｃ６Ｈ４Ｏ７）などのＣｕ化合物が混在した状態であり、１００Ｗの超音波を２分間照射して分散させた後、動的光散乱法で測定した。平均粒子径はキュムラント法によって算出した結果を表１に示している。当該測定は、某社に委託し、測定機器は、スペクトリス（株）製の「ゼータサイザーPro」を使用した。 FIG. 2 shows the result of measuring the particle size distribution of an aqueous solution obtained by diluting the cuprous oxide dispersion (1) 5 times, and FIG. 3 shows its autocorrelation function. In addition, the right side of FIG. 10 is a cuprous oxide suspension solution (slurry solution) before the dispersion step is performed, the left side is a substitute photograph showing a sample of the cuprous oxide dispersion, and the right side aqueous solution is turbid. However, the dispersion on the left is a colored and transparent aqueous solution. The cuprous oxide dispersion (1) contains Cu 2+ , Cu ions such as Cu + which may exist slightly, and Cu 2 O, CuO, CuCl, Cu 2 (C 6 H 4 O 7 ) , etc. The Cu compound was mixed, and was dispersed by irradiation with 100 W ultrasonic waves for 2 minutes, and then measured by the dynamic light scattering method. Table 1 shows the average particle size calculated by the cumulant method. The measurement was outsourced to a certain company, and the measuring instrument used was "Zetasizer Pro" manufactured by Spectris Co., Ltd.
上記の表１から、平均粒子径は６５．１９ｎｍであり、自己相関関数は０．４０４１となっている。第１ピークの平均粒子径は２２．８２ｎｍであり、第２ピークの平均粒子径は２０７．８ｎｍであり、第３ピークの平均粒子径は５０８３ｎｍの３つのピークを示す混合分散液であり、緩やかな減衰成分と急激な減衰成分が混じった自己相関関数を示している。 From Table 1 above, the average particle size is 65.19 nm and the autocorrelation function is 0.4041. The average particle size of the first peak is 22.82 nm, the average particle size of the second peak is 207.8 nm, and the average particle size of the third peak is 5083 nm. It shows an autocorrelation function with a mixture of smooth decay components and sharp decay components.
亜酸化銅分散液（１）と異なる日に製造した亜酸化銅分散液（２）を５倍に希釈した水溶液の粒度分布を測定した結果が図４であり、その自己相関関数を図５に示している。
表２の結果から、当該亜酸化銅分散液（２）の平均粒径は４３．６４ｎｍであり、自己相関関数は０．６１９１である。また、第１ピークの平均粒子径は２２．８ｎｍであり、第２ピークの平均粒子径は２１１.３ｎｍであり、第３ピークの平均粒子径は４３１６ｎｍの３つのピークを示す混合分散液であり、やはり緩やかな減衰成分と急激な減衰成分が混じった自己相関関数を示している。
The result of measuring the particle size distribution of an aqueous solution obtained by diluting the cuprous oxide dispersion (2) produced on a different day from the cuprous oxide dispersion (1) by 5 times is shown in FIG. 4, and the autocorrelation function is shown in FIG. showing.
From the results in Table 2, the cuprous oxide dispersion (2) has an average particle size of 43.64 nm and an autocorrelation function of 0.6191. In addition, the average particle size of the first peak is 22.8 nm, the average particle size of the second peak is 211.3 nm, and the average particle size of the third peak is 4316 nm. , again shows an autocorrelation function with a mixture of gradual and rapid decay components.
亜酸銅分散液（１）、（２）と異なる日に製造した亜酸化銅分散液（３）を５倍に希釈した水溶液の粒度分布を測定した結果が図６であり、その自己相関関数を図７に示している。
表３の結果から、当該亜酸化銅分散液（３）の平均粒径は７５．９１ｎｍであり、自己相関関数は０．４５２５である。また、第１ピークの平均粒子径は２１．２３ｎｍであり、第２ピークの平均粒子径は２０８．１ｎｍであり、第３ピークの平均粒子径は５１１４ｎｍの３つのピークを示す混合分散液であり、やはり緩やかな減衰成分と急激な減衰成分が混じった自己相関関数を示している。
FIG. 6 shows the result of measuring the particle size distribution of an aqueous solution obtained by diluting the cuprous oxide dispersion (3) produced on a different day from the cuprous oxide dispersion (1) and (2) by 5 times, and the autocorrelation function is shown in FIG. is shown in FIG.
From the results in Table 3, the cuprous oxide dispersion (3) has an average particle size of 75.91 nm and an autocorrelation function of 0.4525. In addition, the average particle size of the first peak is 21.23 nm, the average particle size of the second peak is 208.1 nm, and the average particle size of the third peak is 5114 nm. , again shows an autocorrelation function with a mixture of gradual and rapid decay components.
亜酸銅分散液（１）、（２）、（３）と異なる日に製造した亜酸化銅分散液（４）を５倍に希釈した水溶液の粒度分布を測定した結果が図８であり、その自己相関関数を図９に示している。
表４の結果から、当該亜酸化銅分散液（３）の平均粒径は３４．２７ｎｍであり、自己相関関数は０．５９６６ である。また、第１ピークの平均粒子径は２３．５ｎｍであり、第２ピークの平均粒子径は１６５．６ｎｍであり、第３ピークの平均粒子径は４９６９ｎｍの３つのピークを示す混合分散液であり、やはり緩やかな減衰成分と急激な減衰成分が混じった自己相関関数を示している。
The result of measuring the particle size distribution of an aqueous solution obtained by diluting the cuprous oxide dispersion (4) produced on a different day from the cuprous oxide dispersion (1), (2), (3) by 5 times is shown in FIG. Its autocorrelation function is shown in FIG.
From the results in Table 4, the cuprous oxide dispersion (3) has an average particle size of 34.27 nm and an autocorrelation function of 0.5966. Moreover, the average particle size of the first peak is 23.5 nm, the average particle size of the second peak is 165.6 nm, and the average particle size of the third peak is 4969 nm. , again shows an autocorrelation function with a mixture of gradual and rapid decay components.
実施例１～実施例４の結果から、本願発明の亜酸化銅分散液を５倍に希釈した水溶液は、全体の平均粒子径が３４ｎｍ～７５ｎｍであり、３つの粒度分布を有する有色透明な水溶液であることが判明した。また、第１のピークの平均粒径は、２１．２３～２３．５ｎｍの範囲にあり、平均値は．５９ｎｍであり、第２のピークの平均粒径は、１６５．６～２１１．３ｎｍの範囲にあり、平均値は１９８．２ｎｍであり、第３のピークの平均粒径は、４３１６～５１１４ｎｍの範囲にあり、平均値は４８７９．５ｎｍであることを特徴とした分散液である。このように、３つの粒度ピークを有することを特徴とする本願発明の亜酸化銅分散液は、使用する有機酸や無機酸の組み合わせで、粒度ピークが１つになる場合もあり、２つになる場合がある。 From the results of Examples 1 to 4, the aqueous solution obtained by diluting the cuprous oxide dispersion of the present invention 5 times has an overall average particle size of 34 nm to 75 nm, and has three particle size distributions. turned out to be. Also, the average particle size of the first peak is in the range of 21.23 to 23.5 nm, and the average value is . 59 nm, the average particle size of the second peak ranges from 165.6 to 211.3 nm, the average value is 198.2 nm, and the average particle size of the third peak ranges from 4316 to 5114 nm. and an average value of 4879.5 nm. Thus, the cuprous oxide dispersion of the present invention, which is characterized by having three particle size peaks, may have one particle size peak depending on the combination of organic acids and inorganic acids used, and may have two. may become.
製造から半年以上経過した出願当時においても、何れの亜酸化銅分散液は、凝集・沈殿物が観察されないことから、界面活性剤を助剤として用いなくても分散効果が維持されていることも判明した。
尚、実施例１～４の亜酸化銅分散液の製造日は異なるが、凝集沈降しないため、粒度解析は同じ日に行なった。
Even at the time of filing, which had been more than half a year since the manufacture, no aggregation or sedimentation was observed in any of the cuprous oxide dispersions. found.
Although the production dates of the cuprous oxide dispersions of Examples 1 to 4 were different, the particle size analysis was performed on the same day because they did not coagulate and sediment.
（抗菌試験）
黄色ブドウ球菌を使って抗菌活性試験を「ＪＩＳ Ｚ ２８０１：２０１０ ５」に準用して実施例１で作成した亜酸化銅分散液（１）を使用して行なった。実施例１の亜酸化銅分散液（１）の濃度を１００とした場合、試料Ａは１／１００に希釈した水溶液を５ｃｍ角の試験片Ａに塗布して乾燥させた表面に０．４ｍLの黄色ブドウ球菌を接種して４ｃｍ角のフィルムで被覆し、温度３５±１℃、相対湿度９０％以上で２４時間培養した後の生菌数（個/ｃｍ２）を測定した。同様に、試料Ｂは、亜酸化銅分散液を１／５０に希釈した水溶液を５ｃｍ角の試験片Ｂに塗布して乾燥させて試験を行ない、試料Ｃは、亜酸化銅分散液を１／２０に希釈した水溶液を５ｃｍ角の試験片Ｃに塗布して乾燥させて試験を行った。比較対象として、無加工試験片としてポリエチレンフィルムを使用した。結果として、表５で示す様に、試料Ａでは、２４時間後の生菌数が０.１１なので、抗菌活性値は４．６となり、試料Ｂおよび試料Ｃでは生菌数が-０．２以下なので、抗菌活性値は４．９以上という数値を示し、抗菌性能基準が２．０以上とされていることから、当該試験において、試料Ａ～Ｃはいずれも高い抗菌性能を有している。尚、抗菌活性値は、次式（数１）で算出した。
(Antibacterial test)
An antibacterial activity test using Staphylococcus aureus was performed using the cuprous oxide dispersion (1) prepared in Example 1 according to "JIS Z 2801:2010 5". When the concentration of the cuprous oxide dispersion (1) of Example 1 is 100, sample A is a 1/100 diluted aqueous solution applied to a 5 cm square test piece A and dried. Staphylococcus aureus was inoculated, covered with a 4 cm square film, cultured at a temperature of 35±1° C. and a relative humidity of 90% or higher for 24 hours, and then the number of viable bacteria (cells/cm 2 ) was measured. Similarly, for sample B, an aqueous solution diluted to 1/50 of the cuprous oxide dispersion was applied to a 5 cm square test piece B and dried for testing. An aqueous solution diluted to 20 was applied to a 5 cm square test piece C, dried, and tested. A polyethylene film was used as an unprocessed test piece for comparison. As a result, as shown in Table 5, in sample A, the viable count after 24 hours is 0.11, so the antibacterial activity value is 4.6, and in samples B and C, the viable count is -0.2. Therefore, the antibacterial activity value is 4.9 or more, and the antibacterial performance standard is 2.0 or more, so in the test, samples A to C all have high antibacterial performance. . The antibacterial activity value was calculated by the following formula (Equation 1).
（被膜強度）
実施例１の亜酸化銅分散液（１）を塗装基板に対し、適切な水性無機バインダー（例として、日産化学製コロイダルシリカＸＳ等）を選定し適量を配合して塗布すれば、形成される乾燥塗膜は優れた密着性を有し、鉛筆硬度試験（ＪＩＳ Ｋ５４００）に準じて手書き法で測定したところ、鉛筆強度で７Ｈ～８Ｈ以上を有する強靱な膜となるため、耐久性に優れている。
(Coating strength)
The cuprous oxide dispersion (1) of Example 1 is applied to a coated substrate by selecting an appropriate aqueous inorganic binder (eg, colloidal silica XS manufactured by Nissan Chemical Industries, Ltd.) and applying an appropriate amount. The dry coating film has excellent adhesion, and when measured by a handwriting method according to the pencil hardness test (JIS K5400), it becomes a tough film with a pencil strength of 7H to 8H or more, so it has excellent durability. there is
（抗ウィルス試験）
本願発明の亜酸化銅分散液のウィルスの不活化効果試験を某衛生研究所に委託して行なった。供試微生物は、人の唾液からｖｅｒｏ細胞（アフリカミドリザルの腎臓上皮由来株化細胞）を用いて培養した人由来分離株で、分離培養後、リアルタイムＰＣＲ検査を用いてSARS-CoV-2遺伝子の増幅を確認（厚生労働省通知法）したウィルス株を用いた。段落００１１に記載の本願発明の亜酸化銅分散液の濃度を１００とした場合、ウィルス不活化試験に用いた亜酸化銅分散液は２５倍に希釈した水溶液を使用して、試験資材（１）～（４）としてそれぞれ１０ｍL使用した。再現性の確認のため、製造日が異なる４つの亜酸化銅分散液（１）～（４）を用意して、同じ日に当該試験を行なうこととした。その試験結果を表６に示している。
比較対照として、リン酸緩衝液１０ｍL使用して対照区とした。試験区１～４および対照区の水溶液から各１ｍLを分取して、１０６TCID５０／ｍL以上の濃度のウィルス液を添加して、室温（２５℃）で１０時間静置した。
(Antiviral test)
A virus inactivation effect test of the cuprous oxide dispersion of the present invention was entrusted to a certain health research institute. The test microorganism is a human-derived isolate cultured from human saliva using vero cells (a cell line derived from the kidney epithelium of African green monkeys). A virus strain whose amplification was confirmed (Ministry of Health, Labor and Welfare notification method) was used. When the concentration of the cuprous oxide dispersion of the present invention described in paragraph 0011 is 100, the cuprous oxide dispersion used in the virus inactivation test is a 25-fold diluted aqueous solution, and the test material (1) 10 mL each was used as (4). In order to confirm reproducibility, four cuprous oxide dispersions (1) to (4) with different production dates were prepared and the test was performed on the same day. Table 6 shows the test results.
As a control, 10 mL of phosphate buffer was used as a control group. A 1 mL portion was taken from each of the aqueous solutions of
１０時間経過後の試験区のウィルス混合液をさらにそれぞれ１０倍希釈し、９６ウェルプレートに培養した細胞に各１００μL接種して、室温３７℃、ＣＯ２濃度５％で５日間培養した。培養細胞を顕微鏡観察し、培養細胞に現れる細胞変異効果（ Cytopathic effect： CPE）をもって、ウィルスの増殖を確認し、数２で示す計算式に基づいて、その濃度を算出したものを表６に示している。 After 10 hours, the virus mixture in the test group was further diluted 10-fold, and 100 μL each was inoculated into cells cultured in a 96-well plate and cultured at room temperature of 37° C. and CO 2 concentration of 5% for 5 days. The cultured cells were observed under a microscope, and the proliferation of the virus was confirmed by the cytopathic effect (CPE) that appeared in the cultured cells. ing.
表６の結果から、リン酸緩衝液を使った対照区では試験開始から１０時間の経過までに、１０７．３から１０６．５ＴＣＩＤ５０／ｍLへウィルス量が自然減退しているが、その原因はつかめていない。一方、亜酸化銅分散液を用いた試験区１、３および４でのウィルス濃度は、検出限界濃度である１０２．５ＴＣＩＤ５０/ｍＬとなり、９９．９９％以上の減少率が確認され、試験区２でもウィルス濃度は１０３.３ＴＣＩＤ５０/ｍＬとなり９９．９３％の減少率が確認され、対照区の自然減少以上の効果があることが分かった。そこで、表６の結果をグラフとして示した図１１からも、当該ウィルス不活化試験の減少していることが判明した。当該不活化試験の結果として、本願発明の亜酸化銅分散液は、高い抗ウィルス性組成物であることが確認された。
From the results in Table 6, in the control group using the phosphate buffer, the virus amount spontaneously decreased from 10 7.3 to 10 6.5 TCID 50 /mL within 10 hours from the start of the test, I haven't found the cause. On the other hand, the virus concentration in
本願発明の亜酸化銅分散液は、沈殿物のない有色透明なコロイド分散溶液であって、適切な無機バインダーを配合すれば、優れた密着性を有し、ガラス等の硬い塗装基板に塗布してできた塗装薄膜の硬度は、鉛筆硬度７H以上であることから、抗菌・抗ウイルス性能を必要とする用途として、医療現場や介護施設の施設内の装材として利用することができる。また、常温で半年以上の長期間に亘って、凝集沈殿が観察されない分散液であることから、保管が容易であり、高い抗菌性と高い抗ウイルス不活化性能を有する塗装材として利用することが可能である。本願発明の亜酸化銅分散液の色は緑色や青色などの有色透明な分散液であるが、一般社団法人日本銅センターHPの「安全な銅」によれば、緑青すなわち青水が安全であることは昭和５９年８月には、厚生省（現 厚生労働省）が緑青猛毒説を間違いであることを認めていたとの記載からも安全である。
The cuprous oxide dispersion of the present invention is a colored and transparent colloidal dispersion without sediment, and if an appropriate inorganic binder is blended, it has excellent adhesion and can be applied to a hard coated substrate such as glass. Since the hardness of the coating thin film produced by this method is 7H or higher, it can be used as a material in medical facilities and nursing care facilities for applications that require antibacterial and antiviral performance. In addition, since it is a dispersion in which no coagulation and sedimentation is observed for a long period of half a year or more at room temperature, it is easy to store and can be used as a coating material with high antibacterial and antiviral inactivation properties. It is possible. The color of the cuprous oxide dispersion of the present invention is a colored and transparent dispersion such as green or blue. is safe from the statement that in August 1984, the Ministry of Health and Welfare (currently the Ministry of Health, Labor and Welfare) admitted that the verdigris deadly poison theory was wrong.
Claims (3)
界面活性剤を含有しない分散水溶液であって、
動的散乱法で測定し、キュムラント法によって算出した結果、３つの粒度分布（第１ピークの平均粒子径：２１．２３ｎｍ～２３．５ｎｍ、第２ピークの平均粒子径：１６５．６ｎｍ～２１１．３ｎｍ、第３ピークの平均粒子径：４３１６ｎｍ～５１１４ｎｍ）を有し、全体の平均粒子径が３４ｎｍ～７５ｎｍであることを特徴とする分散水溶液であって、
常温で長期間に亘って凝集沈殿しない、ｐH３．５～４．５の銅含有コロイド分散水溶液。 Cuprous oxide, cuprous chloride, and copper citrate are the main components of the colloid, and is a colored and transparent copper-containing dispersed aqueous solution,
A dispersed aqueous solution containing no surfactant,
As a result of measuring by the dynamic scattering method and calculating by the cumulant method, three particle size distributions (average particle size of the first peak: 21.23 nm to 23.5 nm, average particle size of the second peak: 165.6 nm to 211.0 nm). 3 nm, the average particle size of the third peak: 4316 nm to 5114 nm), and the overall average particle size is 34 nm to 75 nm,
A copper-containing colloidal dispersion aqueous solution with a pH of 3.5 to 4.5 that does not coagulate and precipitate at room temperature for a long period of time .
請求項１に記載の界面活性剤を含有しない銅含有コロイド分散液を塗布して乾燥させた塗装表面と、A coated surface on which the surfactant-free copper-containing colloidal dispersion according to claim 1 is applied and dried;
からなる抗菌・抗ウイルス塗装材。An antibacterial and antiviral coating material consisting of.
〔Ｓ２〕還元性のある有機酸であるクエン酸３ｇを加えて溶解させ、ｐH４のほぼ透明な水溶液を作る工程を第２工程とし、
〔Ｓ３〕濃度３５％の塩酸を６ｇ加えて、６０℃に温度を上げて、ｐH２～２．５の透明で赤色の水溶液とし、静置して清澄液を得る工程を第３工程とし、
〔Ｓ４〕ｐH調整のため、還元機能のあるアルカリ性のクエン酸３ナトリウム３ｇを加えて溶解させ、ｐH４～５の透明な青緑色から緑色を帯びた水溶液とし、９５℃以上で２～３分間沸騰させる工程を第４工程とし、
〔Ｓ５〕約４８０ｍLの水（H２O）を加えて、１０００ｍLの亜酸化銅分散液であって、ｐH３．５～４．５の有色透明な水溶液が得られる工程を第５工程とし、
〔Ｓ６〕不純物を濾過する工程を第６工程とからなる、
界面活性剤を含有しない、亜酸化銅と塩化第一銅とクエン酸銅をコロイドの主成分とする有色透明な銅含有分散水溶液の製造方法。 [S1] Put 5 g of cuprous oxide (Cu 2 O) into 200 mL of water (H 2 O), add 300 mL of water (H 2 O), and stir at 500 rpm at 20° C. to 40° C. , with the step of making a cuprous oxide suspension as the first step,
[S2] The second step is the step of adding and dissolving 3 g of citric acid, which is a reducing organic acid, to prepare an almost transparent aqueous solution with a pH of 4.
[S3] The third step is the step of adding 6 g of hydrochloric acid having a concentration of 35%, raising the temperature to 60° C. to form a transparent red aqueous solution with a pH of 2 to 2.5, and allowing the solution to stand still to obtain a clear liquid.
[S4] To adjust the pH, add and dissolve 3 g of alkaline trisodium citrate, which has a reducing function, to make a clear bluish-green to greenish aqueous solution with a pH of 4 to 5, and boil at 95°C or higher for 2 to 3 minutes. The step of causing is the fourth step,
[S5] The step of adding about 480 mL of water (H 2 O) to obtain 1000 mL of a cuprous oxide dispersion having a pH of 3.5 to 4.5 and a colored and transparent aqueous solution is the fifth step.
[S6] a step of filtering impurities, comprising a sixth step;
A method for producing a colored and transparent copper-containing dispersion aqueous solution containing no surfactant and containing cuprous oxide, cuprous chloride and copper citrate as main colloidal components.
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| WO2005007328A1 (en) | 2003-07-17 | 2005-01-27 | Asahi Kasei Medical Co., Ltd. | Metal colloid solution |
| WO2014132606A1 (en) | 2013-02-27 | 2014-09-04 | パナソニック株式会社 | Cuprous oxide particle dispersion, coating agent composition, and antibacterial/antiviral member |
| JP2015147987A (en) | 2014-02-07 | 2015-08-20 | 石原ケミカル株式会社 | Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method |
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| WO2005007328A1 (en) | 2003-07-17 | 2005-01-27 | Asahi Kasei Medical Co., Ltd. | Metal colloid solution |
| WO2014132606A1 (en) | 2013-02-27 | 2014-09-04 | パナソニック株式会社 | Cuprous oxide particle dispersion, coating agent composition, and antibacterial/antiviral member |
| JP2015147987A (en) | 2014-02-07 | 2015-08-20 | 石原ケミカル株式会社 | Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method |
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