TW202043491A - Powder of metallic copper fine particles and method for producing the same - Google Patents

Powder of metallic copper fine particles and method for producing the same Download PDF

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TW202043491A
TW202043491A TW109111441A TW109111441A TW202043491A TW 202043491 A TW202043491 A TW 202043491A TW 109111441 A TW109111441 A TW 109111441A TW 109111441 A TW109111441 A TW 109111441A TW 202043491 A TW202043491 A TW 202043491A
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metal copper
copper
fatty acid
powder
boiling point
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小金井章子
大橋和彰
小坂泰啓
生田目大輔
濱野亮介
石河明
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日商東洋製罐集團控股股份有限公司
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Abstract

The present invention relates to a powder of metallic copper fine particles capable of efficiently exhibiting antiviral properties, a method for producing the powder of metallic copper fine particles, and an antiviral agent. More specifically, the present invention is characterized in that the antiviral agent includes a powder of metallic copper fine particles coated with fatty acid and/or an ester compound.

Description

金屬銅微粒粉末及其製造方法Metal copper particulate powder and manufacturing method thereof

本發明係關於金屬銅微粒粉末及其製造方法，更詳細而言，係關於可有效率地展現之抗病毒性之金屬銅微粒粉末及其製造方法、以及從該金屬銅微粒粉末製得之抗病毒劑。The present invention relates to metallic copper particulate powder and its manufacturing method, and more specifically, to metallic copper particulate powder capable of efficiently exhibiting antiviral properties, its manufacturing method, and the antiviral properties obtained from the metallic copper particulate powder. Viral agent.

以往，就具有抗菌性或抗病毒性之材料而言，有著使用銀離子或銅(II)離子作為有效成分，使此等金屬離子擔載於沸石或矽膠等物質，或者使其分散於溶劑中製成抗病毒材料之各種提案。 然而，上述金屬離子可展現對於如流感病毒般之具有外套膜(envelope)構造之病毒的抗病毒性，但無法展現對於如諾羅病毒般之不具有外套膜構造之病毒的抗病毒性。In the past, for materials with antibacterial or antiviral properties, silver ions or copper (II) ions were used as active ingredients, and these metal ions were supported on zeolite or silica gel, or dispersed in a solvent Various proposals for making antiviral materials. However, the above-mentioned metal ions can exhibit antiviral properties against viruses with an envelope structure like influenza viruses, but cannot exhibit antiviral properties against viruses without an envelope structure like norovirus.

作為可展現無關乎有無外套膜構造之抗病毒性的金屬化合物，已知一價銅化合物，例如下述專利文獻1中，記載一種抗病毒組成物，其特徵為含有一價之銅化合物微粒、還原劑、及分散介質，且pH6以下。下述專利文獻2中，記載一種抗菌抗病毒性組成物，其特徵為含有BET比表面積為5~100m2 /g之氧化亞銅粒子、具有醛基之醣類、及光觸媒物質。下述專利文獻3中，記載一種抗病毒性塗膜，具有將銅粒子及銅化合物粒子之至少一者擔持於氧化物粒子之平均二次粒徑為80nm~600nm之銅擔持氧化物、平均二次粒徑為1μm~15μm之硫酸鋇及撥水性之樹脂黏接劑。 [先前技術文獻] [專利文獻]As a metal compound that can exhibit antiviral properties regardless of the presence or absence of a mantle structure, a monovalent copper compound is known. For example, in Patent Document 1 below, an antiviral composition is described, which is characterized by containing monovalent copper compound particles, Reducing agent, and dispersion medium, and pH 6 or less. Patent Document 2 below describes an antibacterial and antiviral composition characterized by containing cuprous oxide particles with a BET specific surface area of 5-100 m 2 /g, sugars having aldehyde groups, and a photocatalyst substance. The following Patent Document 3 describes an antiviral coating film having a copper-supported oxide having at least one of copper particles and copper compound particles supported on oxide particles with an average secondary particle diameter of 80 nm to 600 nm. Barium sulfate with an average secondary particle size of 1μm~15μm and water-repellent resin adhesive. [Prior Art Document] [Patent Document]

[專利文獻1]日本專利第5194185號公報 [專利文獻2]日本特開2013-82654號公報 [專利文獻3]日本特開2015-205998號公報[Patent Document 1] Japanese Patent No. 5194185 [Patent Document 2] JP 2013-82654 A [Patent Document 3] JP 2015-205998 A

[發明所欲解決之課題][The problem to be solved by the invention]

然而，一價銅化合物之微粒容易凝聚，不易使一價銅化合物均勻地分散，在將分散液用來作為抗病毒組成物，或與塗料混合用來作為經塗層之抗病毒成形體的情況，難以有效率地展現一價銅化合物之微粒具有的抗病毒性。 此外，在使用如上述專利文獻中列舉般之粒徑大之一價銅化合物時，則粒子表面積變小，與病毒之接觸機會減少而抗病毒性降低。此外，有著經塗層粒徑大之一價銅化合物的抗病毒成形體的霧度或光穿透率變差而損害透明性之問題。 另外，一價銅化合物之微粒雖也可藉由進行粉碎而獲得，但因為沒有被膜劑或安定劑，故也有著容易凝聚，容易產生從氧化亞銅氧化為氧化銅(II)之氧化的問題。However, the particles of the monovalent copper compound are easy to agglomerate, and it is not easy to uniformly disperse the monovalent copper compound. When the dispersion is used as an antiviral composition or mixed with a paint to be used as a coated antiviral molded body , It is difficult to efficiently demonstrate the antiviral properties of the monovalent copper compound particles. In addition, when a monovalent copper compound having a large particle diameter as listed in the above patent document is used, the particle surface area becomes smaller, the chance of contact with the virus is reduced, and the antiviral property is reduced. In addition, there is a problem that the haze or light transmittance of the antiviral molded body of the coated monovalent copper compound with a large particle size deteriorates and the transparency is impaired. In addition, although the particles of the monovalent copper compound can also be obtained by pulverization, since there is no coating agent or stabilizer, there is also a problem that it is easy to agglomerate, and it is easy to oxidize from cuprous oxide to copper(II) oxide. .

本案發明者們，為了解決如此問題，針對可有效率地展現高抗病毒性之微粒持續地深入研究之結果，發現金屬銅相較於一價銅化合物可展現更高之抗病毒性，且發現藉由將金屬銅微粒之表面被覆脂肪酸及該脂肪酸之酯化合物，即使在於低沸點溶劑中以高濃度含有之情況也不會凝聚而均勻地分散。 然而，上述金屬銅微粒雖然在分散液之狀態可不凝聚而成為均勻之分散液，但在沒有介質之單獨金屬銅微粒之狀態下容易凝聚，不易有效率地展現抗病毒性。此外，有著下述問題：因為凝聚而金屬銅微粒之每個二次粒子之有機物(脂肪酸及酯化合物)的被覆量變多，無法獲得具有如於分散液所獲得般之高抗病毒性的微粒粉末。 因此，本發明之目的係提供一種可有效率地展現抗病毒性之金屬銅微粒粉末、及該金屬銅微粒粉末之製造方法。 本發明之其他目的係提供一種抗病毒劑，在可有效率地展現抗病毒性的同時，為有效成分的金屬銅的抗氧化性優良，可長期間展現之優良的抗病毒性。 [解決課題之手段]In order to solve such a problem, the inventors of the present case have conducted in-depth research on particles that can efficiently exhibit high antiviral properties. They found that metallic copper can exhibit higher antiviral properties than monovalent copper compounds. By coating the surface of the metallic copper particles with fatty acid and the fatty acid ester compound, even if it is contained in a low boiling point solvent at a high concentration, it does not aggregate and is uniformly dispersed. However, although the above-mentioned metal copper particles may not aggregate in the state of the dispersion liquid and become a uniform dispersion liquid, they tend to aggregate in the state of separate metal copper particles without a medium, and it is difficult to efficiently exhibit antiviral properties. In addition, there is a problem that the amount of coating of the organic matter (fatty acid and ester compound) per secondary particle of the metal copper particles increases due to aggregation, and it is impossible to obtain a particle powder with high antiviral properties as obtained in a dispersion liquid. . Therefore, the object of the present invention is to provide a metal copper particulate powder that can efficiently exhibit antiviral properties and a method for manufacturing the metal copper particulate powder. Another object of the present invention is to provide an antiviral agent that can efficiently exhibit antiviral properties, and at the same time, metal copper, which is an active ingredient, has excellent antioxidant properties and can exhibit excellent antiviral properties for a long time. [Means to solve the problem]

根據本發明，提供一種金屬銅微粒粉末，其特徵在於，由被覆有脂肪酸及/或酯化合物之金屬銅微粒構成。 本發明之金屬銅微粒粉末適宜為： 1.上述金屬銅微粒之平均二次粒徑為100nm~500μm； 2.上述酯化合物係脂肪酸與多元醇的酯化合物； 3.上述脂肪酸係碳數10~22之高級脂肪酸； 4.上述金屬銅微粒之平均一次粒徑為10~500nm之範圍； 5.上述脂肪酸及/或酯化合物對於上述金屬銅微粒之被覆量係0.1~20質量%。According to the present invention, there is provided a metal copper particle powder characterized by being composed of metal copper particles coated with fatty acid and/or ester compound. The metal copper particulate powder of the present invention is suitably: 1. The average secondary particle size of the above metal copper particles is 100nm~500μm; 2. The above-mentioned ester compound is an ester compound of fatty acid and polyhydric alcohol; 3. The above fatty acids are higher fatty acids with carbon number 10-22; 4. The average primary particle size of the above metal copper particles is in the range of 10~500nm; 5. The coating amount of the fatty acid and/or ester compound to the metal copper particles is 0.1-20% by mass.

根據本發明之第一製造方法，提供一種金屬銅微粒粉末之製造方法，其特徵在於，具有下述步驟： 藉由於多元醇中添加脂肪酸銅，將其進行加熱混合，製備分散有經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆之金屬銅微粒的分散液； 將該分散液與低沸點溶劑混合後，將該多元醇及低沸點溶劑二相分離，且使多元醇中之游離脂肪酸及酯化合物移動至低沸點溶劑中； 除去該二相分離後之低沸點溶劑； 回收除去了低沸點溶劑之多元醇中的經脂肪酸及/或酯化合物被覆的金屬銅微粒。According to the first manufacturing method of the present invention, there is provided a manufacturing method of metal copper particulate powder, which is characterized in that it has the following steps: By adding fatty acid copper to the polyol, heating and mixing it to prepare a dispersion liquid of metal copper particles coated with fatty acid and/or the fatty acid and polyol ester compound; After mixing the dispersion with a low-boiling point solvent, the polyol and the low-boiling point solvent are separated into two phases, and the free fatty acids and ester compounds in the polyol are moved to the low-boiling point solvent; Remove the low boiling point solvent after the two-phase separation; The fatty acid and/or ester compound coated metal copper particles in the polyol from which the low boiling point solvent has been removed are recovered.

根據本發明之第二製造方法，提供一種金屬銅微粒粉末之製造方法，其特徵在於，具有下述步驟： 藉由於多元醇中添加脂肪酸及銅化合物，將其進行加熱混合，製備分散有經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆之金屬銅微粒的分散液； 將該分散液與低沸點溶劑混合後，將該多元醇及低沸點溶劑進行二相分離，且使多元醇中之游離脂肪酸及酯化合物移動至低沸點溶劑中； 除去該二相分離後之低沸點溶劑； 回收除去了低沸點溶劑之多元醇中的經脂肪酸及/或酯化合物被覆的金屬銅微粒。According to the second manufacturing method of the present invention, there is provided a manufacturing method of metal copper particulate powder, which is characterized in that it has the following steps: By adding fatty acids and copper compounds to the polyols, heating and mixing them to prepare a dispersion of metal copper particles coated with fatty acids and/or ester compounds of the fatty acids and polyols; After mixing the dispersion with a low boiling point solvent, the polyol and the low boiling point solvent are subjected to two-phase separation, and the free fatty acids and ester compounds in the polyol are moved to the low boiling point solvent; Remove the low boiling point solvent after the two-phase separation; The fatty acid and/or ester compound coated metal copper particles in the polyol from which the low boiling point solvent has been removed are recovered.

在本發明之金屬銅微粒粉末之製造方法中，宜為： 1.上述銅化合物係乙酸銅、氯化銅、溴化銅之任一者； 2.上述多元醇係二乙二醇、乙二醇、三乙二醇、丙二醇、聚乙二醇、聚丙二醇、甘油之任一者。In the manufacturing method of the metallic copper particulate powder of the present invention, it is preferable that: 1. The above-mentioned copper compound is any one of copper acetate, copper chloride, and copper bromide; 2. The above-mentioned polyol is any one of diethylene glycol, ethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and glycerin.

根據本發明，提供一種抗病毒劑，其特徵在於：係由上述金屬銅微粒粉末構成，藉由X射線光電子能譜法測定該金屬銅微粒集合體之表面時，相對於最先測得金屬銅成分深度中之全部銅成分，金屬銅之比率維持在10%以上。 在本發明之抗病毒劑中，宜為 1.係上述金屬銅微粒粉末分散於溶劑中而得之分散液； 2.係上述金屬銅微粒粉末分散於樹脂中而得之樹脂組成物； 3.含有0.01~2.0質量%之上述金屬銅微粒粉末之抗病毒劑的抗病毒活性值為3.0以上。 [發明之效果]According to the present invention, there is provided an antiviral agent, which is characterized in that it is composed of the above-mentioned metal copper particle powder, and when the surface of the metal copper particle assembly is measured by X-ray photoelectron spectroscopy, compared with the first measured metal copper The ratio of all the copper components in the composition depth, and the metal copper is maintained above 10%. Among the antiviral agents of the present invention, it is preferably 1. A dispersion obtained by dispersing the above metal copper particles in a solvent; 2. A resin composition obtained by dispersing the above metal copper particles in a resin; 3. The antiviral activity value of the antiviral agent containing 0.01~2.0% by mass of the metal copper particulate powder is 3.0 or more. [Effects of Invention]

在本發明之金屬銅微粒粉末中，維持平均二次粒子之粒徑係100nm~500μm之範圍的粉末狀態因而表面積大，且由脂肪酸及/或酯化合物構成的對於構成粉末之金屬銅微粒之二次粒子之被膜量減低，因而能以粉末狀態展現優良的抗病毒性。 此外，本發明之金屬銅微粒粉末，不僅具有抗病毒性，亦具有抗菌性、導電性、紫外線遮蔽性、抗污性等特性。尤其，可展現無關乎外套膜構造之有無的抗病毒性，即使對於諾羅病毒等不具有外套膜構造之病毒亦可展現抗病毒性。 本發明之金屬銅微粒粉末即使在空氣環境下亦能以金屬銅之狀態安定地存在。 在本發明之金屬銅微粒粉末之製造方法中，可有效率地除去在金屬銅微粒形成時所生成之過多的游離脂肪酸或酯化合物、或者未反應之脂肪酸銅等成分，可有效率地製造為粉末狀態的金屬銅微粒。In the metal copper particulate powder of the present invention, the average secondary particle size is maintained in the powder state in the range of 100nm~500μm, so the surface area is large, and it is composed of fatty acid and/or ester compound. The coating amount of the secondary particles is reduced, so it can exhibit excellent antiviral properties in a powder state. In addition, the metal copper particulate powder of the present invention not only has antiviral properties, but also has antibacterial properties, electrical conductivity, ultraviolet shielding properties, antifouling properties and the like. In particular, it can exhibit antiviral properties regardless of the presence or absence of the mantle structure, even for viruses that do not have a mantle structure such as norovirus. The metallic copper particulate powder of the present invention can exist stably in the state of metallic copper even in an air environment. In the method for producing metal copper particulate powder of the present invention, excessive free fatty acids or ester compounds, or unreacted fatty acid copper and other components generated during the formation of metal copper particulates can be efficiently removed, and the production can be efficiently made. Metal copper particles in powder state.

本發明之抗病毒劑藉由以脂肪酸及/或酯化合物被覆為抗病毒性之有效成分的金屬銅微粒，而可有效地防止金屬銅微粒之氧化及凝聚，可長期間展現優良的抗病毒性。亦即，在本發明中，發現只要藉由X射線光電子能譜法測定金屬銅微粒集合體表面時，相對於最先測得金屬銅成分之深度中之全部銅成分，金屬銅之比率維持在10%以上，則可充分地展現抗病毒性，且發現了就不妨害抗病毒性且抑制上述金屬銅之氧化及凝聚而言所必須之足夠的脂肪酸及/或酯化合物的被覆量。The antiviral agent of the present invention can effectively prevent the oxidation and aggregation of the metal copper particles by coating the metal copper particles with fatty acids and/or ester compounds as the effective components of antiviral properties, and can exhibit excellent antiviral properties for a long time. . That is, in the present invention, it has been found that as long as the surface of the metallic copper particle assembly is measured by X-ray photoelectron spectroscopy, the ratio of metallic copper to all the copper components in the depth of the first measured metallic copper component is maintained at 10% or more, the antiviral property can be fully exhibited, and a sufficient amount of the fatty acid and/or ester compound coating is found to prevent the antiviral property from harming the antiviral property and inhibit the oxidation and aggregation of the copper metal.

本發明之抗病毒劑之上述效果，從後述之實施例之結果可明瞭。亦即，可知由實施例1~8所製備之金屬銅微粒粉末構成之抗病毒劑，係表面組成為金屬銅100%，針對實施例1及6進行之抗病毒性評價也高。另一方面，可知如比較例6般，脂肪酸銅熱分解，未被覆有脂肪酸及/或酯化合物之金屬銅微粒係金屬銅容易氧化(比較例6)。此外，由實施例10所製備之金屬銅微粒粉末構成之抗病毒劑係表面組成為金屬銅46%，可獲得與金屬銅100%之實施例6同等的抗病毒性。此外，從圖3可明瞭，本發明之抗病毒劑即使在於空氣中保存8個月的情況，金屬銅仍不會氧化而存在46%，可知本發明之抗病毒劑可長期間展現優良的抗病毒性。The above-mentioned effects of the antiviral agent of the present invention are clear from the results of the examples described later. That is, it can be seen that the antiviral agent composed of the metallic copper particulate powder prepared in Examples 1 to 8 has a surface composition of 100% metallic copper, and the antiviral evaluation performed on Examples 1 and 6 is also high. On the other hand, as in Comparative Example 6, fatty acid copper is thermally decomposed, and the metal copper particulate-based metal copper that is not covered with fatty acid and/or ester compound is easily oxidized (Comparative Example 6). In addition, the surface composition of the antiviral agent system composed of the metallic copper particulate powder prepared in Example 10 is metallic copper 46%, and the antiviral properties equivalent to that of Example 6 with 100% metallic copper can be obtained. In addition, it can be seen from Fig. 3 that even if the antiviral agent of the present invention is stored in the air for 8 months, the metallic copper still does not oxidize and exists 46%. It can be seen that the antiviral agent of the present invention can exhibit excellent antiviral properties for a long time. Viral.

本發明之抗病毒劑可展現無關乎外套膜構造之有無的抗病毒性，即使對於諾羅病毒等不具有外套膜構造之病毒仍可展現抗病毒性。The antiviral agent of the present invention can exhibit antiviral properties irrespective of the presence or absence of the mantle structure, even for viruses that do not have a mantle structure such as norovirus.

(金屬銅微粒粉末) 本發明之金屬銅微粒粉末係由被覆有脂肪酸及/或酯化合物之金屬銅微粒構成之為乾燥狀態的粉末，展現抗病毒性之有效成分即金屬銅可吸附病毒而使病毒失活，可展現無關乎外套膜構造之有無的優良的抗病毒性。亦即，據認為金屬銅微粒具有之優良之抗病毒性，係藉由從金屬銅產生之活性氧的氧化力，使由微小蛋白質構成之病毒的蛋白質變性，且藉由金屬銅與病毒之蛋白質之硫醇基進行反應而使蛋白質變性，可使病毒失活。另外，經脂肪酸及/或酯化合物被覆之金屬銅微粒展現抗病毒性之機制雖尚未明瞭，據認為係藉由病毒附著在存在於金屬銅微粒表面之被覆，且與被覆進行置換，而與金屬銅接觸。(Metal copper particle powder) The metal copper particle powder of the present invention is a dry powder composed of metal copper particles coated with fatty acid and/or ester compounds. The effective ingredient that exhibits antiviral properties, that is, metal copper can adsorb viruses and inactivate viruses, and can show Excellent antiviral properties regardless of the structure of the mantle. That is, it is believed that metal copper particles have excellent antiviral properties. The oxidizing power of active oxygen generated from metal copper denatures virus proteins composed of tiny proteins, and metal copper and virus proteins The thiol group reacts to denature the protein and inactivate the virus. In addition, although the mechanism by which metal copper particles coated with fatty acid and/or ester compounds exhibit antiviral properties is not yet clear, it is believed that the virus attaches to the coating existing on the surface of the metal copper particles and replaces the coating with the metal. Copper contacts.

本發明之金屬銅微粒粉末中，據認為在金屬銅微粒之周圍之脂肪酸或酯化合物係各別進行配位，另一方面，酯化合物具有與脂肪酸之親和性，故以脂肪酸之周圍或經與脂肪酸混合之狀態進行配位。因此，可防止起因於金屬銅微粒之表面活性提高所致的微粒表面的氧化，且可抑制微粒的凝聚，可長期間展現優良的抗病毒性。 本發明之金屬銅微粒粉末，藉由充分地被覆酯化合物，而展現特別優良的抗病毒性。In the metal copper particle powder of the present invention, it is considered that the fatty acid or ester compound around the metal copper particle is coordinated separately. On the other hand, the ester compound has affinity with fatty acid, so the fatty acid is surrounded by Coordination is carried out in the state of mixing fatty acids. Therefore, it is possible to prevent the oxidation of the surface of the particles due to the increase in the surface activity of the metal copper particles, and it is possible to inhibit the aggregation of the particles, and to exhibit excellent antiviral properties for a long time. The metal copper particulate powder of the present invention exhibits particularly excellent antiviral properties by sufficiently covering the ester compound.

在本發明中，將金屬銅微粒粉末用來作為抗病毒劑時，重要的是：藉由X射線光電子能譜法測定金屬銅微粒集合體之表面時，相對於最先測得金屬銅成分之深度中之全部銅成分，金屬銅之比率維持在10%以上。亦即，藉由脂肪酸及/或酯化合物覆蓋金屬銅微粒表面，可抑制金屬銅微粒之氧化及凝聚，但考慮有效率地展現抗病毒性之觀點，該被覆與金屬銅微粒之界面中之金屬銅之存在量為重要事項，故在本發明之抗病毒劑中發現，於最先測得金屬銅成分之深度(相當於被覆之厚度)測定金屬銅成分的存在量，該金屬銅成分若維持在全部銅成分之10%以上，宜為20%以上，尤其宜為40%以上，則可獲得優良之抗病毒性。此外，上述值係藉由X射線光電子能譜法測定金屬銅微粒集合體之全部表面，從其平均而得之結果，故可近似於存在於集合體表面之各個金屬銅微粒的狀態。In the present invention, when the metal copper particle powder is used as an antiviral agent, it is important that when the surface of the metal copper particle assembly is measured by X-ray photoelectron spectroscopy, compared with the first measured metal copper composition For all copper components in the depth, the ratio of metallic copper is maintained above 10%. That is, by covering the surface of the metal copper particles with fatty acid and/or ester compounds, the oxidation and aggregation of the metal copper particles can be inhibited. However, considering the viewpoint of effective antiviral performance, the metal at the interface between the coating and the metal copper particles The amount of copper is an important matter. Therefore, it is found in the antiviral agent of the present invention that the depth of the metallic copper component (equivalent to the thickness of the coating) is measured at the first measurement of the metallic copper component. If the metallic copper component is maintained More than 10% of the total copper content, preferably more than 20%, especially more than 40%, can obtain excellent antiviral properties. In addition, the above-mentioned value is measured by X-ray photoelectron spectroscopy on the entire surface of the metal copper particle assembly, and the result is obtained from the average, so it can approximate the state of each metal copper particle existing on the surface of the assembly.

另外，在本發明之金屬銅微粒粉末中，如後述，因為在金屬銅微粒粉末之製造時，有效率地除去過多之脂肪酸或酯化合物、或者未反應之脂肪酸銅等，故容易過濾、清洗，而維持平均二次粒徑小，表面積大之金屬銅微粒之粉末狀態。其結果，可獲得優良之抗病毒性。此外，如上述，若在金屬銅微粒中之脂肪酸及/或酯化合物所為之被覆量為0.1~20質量%，尤其為0.1~10質量%，係與以往藉由從分散液除去溶劑回收而得之金屬銅微粒同等，或比其更少量，因此可有效率地展現金屬銅微粒所具有之抗病毒性等特性。In addition, in the metal copper particulate powder of the present invention, as described later, since excessive fatty acids or ester compounds, or unreacted fatty acid copper, etc., are efficiently removed during the production of the metal copper particulate powder, it is easy to filter and clean. It maintains the powder state of metallic copper particles with small average secondary particle size and large surface area. As a result, excellent antiviral properties can be obtained. In addition, as described above, if the coating amount of the fatty acid and/or ester compound in the metal copper particles is 0.1-20% by mass, especially 0.1-10% by mass, it is obtained by removing the solvent from the dispersion liquid and recovering it in the past. The metal copper particles are the same or smaller than that, so it can effectively display the antiviral properties of the metal copper particles.

就被覆於金屬銅微粒表面之脂肪酸而言，可例示肉豆蔻酸、硬脂酸、油酸、棕櫚酸、正癸酸、對甲苯甲酸、琥珀酸、丙二酸、酒石酸、蘋果酸、戊二酸、己二酸、乙酸等，此等亦可為多種之組合，尤其宜為碳數10~22之高級脂肪酸，其中適宜為硬脂酸。 被覆於金屬銅微粒表面之酯化合物適宜為後述本發明之金屬銅微粒粉末之製造方法中之來自為原料之脂肪酸及多元醇的酯化合物，亦可摻合來自原料以外之酯化合物，此等雖可為不同之酯化合物，期望為與來自原料之酯化合物相同種類較適合。 就被覆於金屬銅微粒表面之適宜的酯化合物而言，係上述脂肪酸與後述多元醇之酯化合物，並非限定為此等，可舉例如二乙二醇二硬脂酸酯、乙二醇二硬脂酸酯、丙二醇二硬脂酸酯、聚乙二醇二硬脂酸酯、聚丙二醇二硬脂酸酯等。As for the fatty acid coated on the surface of the metallic copper particles, myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, p-toluic acid, succinic acid, malonic acid, tartaric acid, malic acid, and glutaric acid can be exemplified. Acid, adipic acid, acetic acid, etc., these can also be a combination of multiple, especially a higher fatty acid with a carbon number of 10-22, among which stearic acid is suitable. The ester compound coated on the surface of the metallic copper particles is suitably the ester compound derived from the fatty acid and polyhydric alcohol as the raw materials in the method for producing the metallic copper particle powder of the present invention described later, and ester compounds derived from other than raw materials may also be blended. It may be a different ester compound, and it is desirable that the same type as the ester compound derived from the raw material is suitable. The suitable ester compound coated on the surface of the metallic copper particles is an ester compound of the above-mentioned fatty acid and the polyhydric alcohol mentioned below, and is not limited to these. Examples include diethylene glycol distearate and ethylene glycol distearate. Fatty acid ester, propylene glycol distearate, polyethylene glycol distearate, polypropylene glycol distearate, etc.

本發明中之金屬銅微粒之平均一次粒徑適宜為10~500nm，尤其為10~200nm之範圍。藉由金屬銅微粒之平均一次粒子為上述範圍，可有效率地展現優良之抗病毒性能。亦即，如此之平均一次粒徑小的金屬銅微粒，因為金屬銅微粒之與氧的接觸率高，而可有效率地產生活性氧，可展現優良之抗病毒性能。此外，本說明書中的平均一次粒徑係將金屬銅微粒與金屬銅微粒之間沒有空隙者設為一個粒子，求其平均者，關於測定方法係如後述。 本發明之金屬銅微粒粉末係由具有上述平均一次粒徑之一次粒子構成，平均二次粒徑適宜為100nm~500μm，尤其為100nm~100μm之範圍，藉此，能以粉末狀態展現優良之抗病毒性，且塗布性等操作性亦明顯地優良。The average primary particle size of the metallic copper particles in the present invention is suitably 10~500nm, especially in the range of 10~200nm. Since the average primary particles of the metallic copper particles are in the above range, excellent antiviral performance can be effectively exhibited. That is, the metal copper particles with such a small average primary particle size can efficiently generate active oxygen because of the high contact rate of the metal copper particles with oxygen, and can exhibit excellent antiviral performance. In addition, the average primary particle diameter in this specification is that the metal copper microparticles|fine-particles and the metal copper microparticles without voids are made into one particle, and the average is calculated|required, and the measurement method is as follows. The metal copper particulate powder of the present invention is composed of primary particles having the above-mentioned average primary particle size, and the average secondary particle size is suitably 100nm~500μm, especially in the range of 100nm~100μm, whereby the powder state can exhibit excellent resistance. Viral properties and workability such as coating properties are also remarkably excellent.

(第一製造方法) 本發明之金屬銅微粒粉末可藉由以下製造方法進行製備。 (1)第一步驟 藉由將脂肪酸銅添加至多元醇中，將其進行加熱，製備分散有表面經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆之金屬銅微粒的多元醇分散液。此時，在金屬銅微粒之表面，被覆有脂肪酸與多元醇之酯化合物較為理想。 加熱溫度係未達使用之脂肪酸銅之開始分解之溫度，具體而言宜為160~230℃之範圍。加熱混合之時間適宜為60~360分鐘。(First manufacturing method) The metal copper particulate powder of the present invention can be prepared by the following manufacturing method. (1) The first step The fatty acid copper is added to the polyol and heated to prepare a polyol dispersion in which metal copper particles are dispersed on the surface of the fatty acid and/or the ester compound of the fatty acid and the polyol. At this time, it is preferable to coat the surface of the metallic copper particles with an ester compound of fatty acid and polyhydric alcohol. The heating temperature does not reach the temperature at which the fatty acid copper starts to decompose. Specifically, it is preferably in the range of 160~230℃. The suitable time for heating and mixing is 60~360 minutes.

脂肪酸銅之摻合量係相對於多元醇宜為0.1~5質量%。在脂肪酸銅之量比上述範圍少的情況，相較於為上述範圍之情況係金屬銅微粒粉末回收的效率低，經濟性差。在脂肪酸銅之量比上述範圍多的情況，金屬銅微粒之生成效率降低，且雜質之生成量也增加，不易回收金屬銅微粒粉末。只要能製造則摻合量之範圍沒有特別之限制，但在脂肪酸銅之量少的情況，與為上述範圍之情況相比有無法賦予分散液充分之抗病毒性之虞。另一方面，在脂肪酸銅之量多的情況，與為上述範圍之情況相比，有經濟性差，且損害塗布性或成形性之虞。 就多元醇而言，可列舉乙二醇、二乙二醇、三乙二醇、聚乙二醇、聚丙二醇、甘油，就與後述之低沸點溶劑的組合適當地選擇。The blending amount of fatty acid copper is preferably 0.1 to 5% by mass relative to the polyol. In the case where the amount of fatty acid copper is less than the above range, the recovery efficiency of the metal copper particulate powder is lower than the case in the above range, and the economy is poor. When the amount of fatty acid copper is larger than the above range, the production efficiency of metal copper particles is reduced, and the amount of impurities produced is also increased, making it difficult to recover metal copper particles. The range of the blending amount is not particularly limited as long as it can be manufactured. However, when the amount of fatty acid copper is small, there is a possibility that sufficient antiviral properties cannot be imparted to the dispersion liquid compared to the case where it is in the above range. On the other hand, when the amount of fatty acid copper is large, compared with the case in the above-mentioned range, economic efficiency may be inferior, and coatability or moldability may be impaired. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and glycerin, and are appropriately selected from the combination with the low boiling point solvent described below.

(2)第二步驟 然後，將分散有經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆之金屬銅微粒的多元醇分散液與低沸點溶劑混合，製備混合液。 低沸點溶劑宜添加相對於多元醇為10~200質量%的量。 就低沸點溶劑而言，可例示乙酸甲酯、乙酸乙酯、乙酸丁酯等酯類、己烷、庚烷、甲苯、二甲苯、環己烷等烴類、甲基異丁基酮、甲基乙基酮、環己酮等酮類等低沸點溶劑，宜為酯系溶劑，其中，適宜使用乙酸丁酯、乙酸乙酯、甲基異丁酮。低沸點溶劑重要的是不與多元醇相溶，以多元醇與低沸點溶劑之溶解度參數(Sp值)之差為3以上的方式組合較為理想。 就適宜之情況而言，在使用了二乙二醇(Sp值：12.6)作為多元醇時，期望使用乙酸丁酯(Sp值：8.4)作為低沸點溶劑。(2) The second step Then, a polyol dispersion in which metal copper particles coated with a fatty acid and/or an ester compound of the fatty acid and a polyol are dispersed is mixed with a low boiling point solvent to prepare a mixed liquid. The low boiling point solvent is preferably added in an amount of 10 to 200% by mass relative to the polyol. As for low boiling point solvents, esters such as methyl acetate, ethyl acetate, butyl acetate, hydrocarbons such as hexane, heptane, toluene, xylene, and cyclohexane, methyl isobutyl ketone, methyl Low-boiling solvents such as ketones such as methyl ethyl ketone and cyclohexanone are preferably ester-based solvents. Among them, butyl acetate, ethyl acetate, and methyl isobutyl ketone are suitably used. It is important that the low-boiling point solvent is not compatible with the polyol, and it is ideal to combine the polyol and the low-boiling point solvent with a solubility parameter (Sp value) difference of 3 or more. As far as it is appropriate, when diethylene glycol (Sp value: 12.6) is used as a polyol, it is desirable to use butyl acetate (Sp value: 8.4) as a low boiling point solvent.

在本發明之金屬銅微粒粉末之製造方法中，重要的是於低沸點溶劑中不摻合分散劑。藉此，經脂肪酸及/或酯化合物被覆之金屬銅微粒不會移動至低沸點溶劑而殘留沉澱於多元醇中。另一方面，存在於多元醇中之過量的脂肪酸銅、或者游離之脂肪酸或酯化合物、以及雜質會移動至低沸點溶劑中。其結果，在雜質等經減低的多元醇中，存在有經脂肪酸及/或酯化合物被覆之金屬銅微粒。In the manufacturing method of the metallic copper particulate powder of the present invention, it is important that a dispersant is not blended in the low boiling point solvent. Thereby, the metal copper particles coated with the fatty acid and/or the ester compound will not migrate to the low boiling point solvent and remain and precipitate in the polyol. On the other hand, the excessive fatty acid copper, or free fatty acid or ester compound, and impurities present in the polyol will move to the low boiling point solvent. As a result, in the polyol with reduced impurities and the like, there are metallic copper particles coated with fatty acid and/or ester compound.

在本發明之金屬銅微粒之製造方法中，據認為被覆於金屬銅微粒之脂肪酸及/或酯化合物量係可防止金屬銅之氧化及凝聚所需要最低限度的量，就有效率地發揮抗病毒性等之特性上而言為重要，且於上述第一步驟生成之脂肪酸與多元醇之酯化合物被覆於金屬銅微粒的量為足夠，故沒有必要還於低沸點溶劑中摻合酯化合物，但取決於第一步驟中的被覆量，也可進行摻合。In the method for producing metallic copper particles of the present invention, it is believed that the amount of fatty acid and/or ester compound coated on the metallic copper particles is the minimum amount required to prevent the oxidation and aggregation of metallic copper, thereby effectively exerting disease resistance Characteristics such as toxicity are important, and the amount of the fatty acid and polyol ester compound produced in the first step above to coat the metallic copper particles is sufficient, so it is not necessary to blend the ester compound in the low boiling point solvent, but Depending on the amount of coating in the first step, blending can also be performed.

(3)第三步驟 藉由將上述混合液於0~40℃之溫度靜置30~120分鐘，使多元醇與低沸點溶劑相分離。若混合液相分離，則混合液中存在之過量之脂肪酸銅、游離脂肪酸或脂肪酸之酯化合物、或者雜質會萃取至低沸點溶劑側，而經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆的金屬銅微粒係以沉澱於多元醇中之狀態殘留。 然後，藉由從經相分離之混合液除去低沸點溶劑，可獲得於多元醇中沉澱有經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆之金屬銅微粒的分散液。 低沸點溶劑之除去，可藉由單蒸餾、減壓蒸餾、精密蒸餾、薄膜蒸餾、萃取等以往公知的分離方法來進行。 此外，從多元醇回收金屬銅微粒粉末可藉由膜分離、離心分離、蒸發、倒出等以往公知之分離方法進行，但不限定為此等，適宜藉由膜分離。 經分離之金屬銅微粒以水清洗後，藉由於40~50℃加熱乾燥60~360分鐘，將水分充分地除去，可獲得乾燥狀態之金屬銅微粒粉末。(3) The third step By allowing the above-mentioned mixed liquid to stand at a temperature of 0-40°C for 30-120 minutes, the polyol is separated from the low-boiling solvent. If the mixed liquid phase is separated, the excess fatty acid copper, free fatty acids or fatty acid ester compounds, or impurities present in the mixed liquid will be extracted to the low boiling point solvent side, and be coated with fatty acids and/or fatty acid and polyol ester compounds The metal copper particles are left in the state of precipitation in the polyol. Then, by removing the low-boiling point solvent from the phase-separated mixed liquid, a dispersion liquid in which metal copper particles coated with fatty acid and/or an ester compound of the fatty acid and the polyol precipitated in the polyol can be obtained. The removal of low boiling point solvents can be performed by conventionally known separation methods such as single distillation, vacuum distillation, precision distillation, thin film distillation, and extraction. In addition, the recovery of the metal copper particulate powder from the polyol can be carried out by conventionally known separation methods such as membrane separation, centrifugal separation, evaporation, and decanting, but it is not limited to these, and separation by membrane is suitable. After the separated metal copper particles are washed with water, they are heated and dried at 40~50°C for 60 to 360 minutes to fully remove the water and obtain a dry metal copper particle powder.

(第二製造方法) 於低沸點溶劑中經脂肪酸及/或脂肪酸之酯化合物被覆之金屬銅微粒的製造方法除了上述製造方法之外，亦可藉由以下方法製備。 亦即，在上述第一製造方法中之第一步驟，添加脂肪酸及銅化合物之組合來替代脂肪酸銅，除此以外，以與第一製造方法同樣的方式進行，藉此可製備分散有經脂肪酸及/或該脂肪酸之酯化合物被覆的金屬銅微粒的分散液，然後藉由經上述第二步驟及第三步驟，可同樣地獲得乾燥狀態之金屬銅微粒粉末。(Second manufacturing method) The method for producing metal copper particles coated with fatty acid and/or fatty acid ester compound in a low boiling point solvent can also be produced by the following method in addition to the above-mentioned production method. That is, in the first step of the above-mentioned first production method, a combination of fatty acid and copper compound is added instead of fatty acid copper, except that it is carried out in the same manner as in the first production method, whereby it is possible to prepare dispersed fatty acid And/or the dispersion liquid of the metal copper particles coated with the fatty acid ester compound, and then through the second step and the third step described above, a dry metal copper particle powder can be obtained in the same manner.

(第三製造方法) 本發明之金屬銅微粒粉末，可藉由上述第一製造方法及第二製造方法，有效率地製造以脂肪酸及/或該脂肪酸與多元醇之酯化合物的被覆量為0.1~20質量%的量經被覆的金屬銅微粒，藉由以下方法亦可製造經脂肪酸及/或酯化合物被覆之金屬銅微粒粉末。亦即，不限於上述液相法，將脂肪酸銅於空氣或氮氣環境等惰性環境下予以加熱並還原後，添加上述酯化合物，藉由將其粉碎混合之氣相法，可製造至少經酯化合物被覆的金屬銅微粒粉末。(Third manufacturing method) The metal copper particulate powder of the present invention can be efficiently produced by the above-mentioned first manufacturing method and second manufacturing method with a coating amount of a fatty acid and/or an ester compound of the fatty acid and a polyhydric alcohol of 0.1-20% by mass The coated metal copper particles can also be produced by the following method to produce a fatty acid and/or ester compound coated metal copper particle powder. That is, not limited to the above-mentioned liquid phase method, the fatty acid copper is heated and reduced in an inert environment such as air or nitrogen atmosphere, and then the above-mentioned ester compound is added. Coated metal copper particle powder.

(金屬銅微粒粉末之用途) 本發明之金屬銅微粒粉末及由該金屬銅微粒構成之抗病毒劑，係如同前述，具有優良之抗病毒性，藉由固定於成形體表面，或使其含於成形體中，金屬銅化合物微粒粉末與氧反應使活性氧產生，藉此可發揮優良之抗病毒性能。 例如，亦可使金屬銅微粒分散於純水、離子交換水等水；甲醇、乙醇、丙醇、異丙醇、丁醇等低級醇；甲醇改性、苯改性、三元醇改性、甲乙酮改性、苯甲酸地那銨(denatonium benzoate)改性、香料改性等一般改性醇等中製成分散液，或者亦可再分散於上述低沸點溶劑中，製成經調整了脂肪酸及/或該脂肪酸與多元醇之酯化合物的被覆量的金屬銅微粒的分散液。 此外，製備分散液時，為了改善金屬銅微粒粉末之於分散介質中的分散性，宜摻合分散劑。分散劑之摻合量係取決於分散液中之經脂肪酸及/或該脂肪酸之酯化合物被覆之金屬銅微粒的量而不同，相對於分散介質宜為0.01~2質量%之量。 就分散劑而言，可使用於吸附基具有1級、2級、3級胺或中和其抗衡離子而得之胺鹽、羧酸或羧酸鹽、羥基之任一者之1種以上，且於主鏈及側鏈具有脂肪酸、聚醚、聚酯、聚胺甲酸酯、聚芳酯之高分子分散劑。 此等分散劑藉由具有吸附基而吸附於上述銅化合物微粒的表面，藉由主鏈或側鏈而改善與非水系溶劑的相容性，高分子鏈之立體障礙所產生的斥力使銅化合物微粒之凝聚受到抑制，均勻地分散於非水系溶劑中，可消除隨時間經過而導致之凝聚。 就高分子分散劑而言，可使用僅以主鏈構成之類型，或具有側鏈之梳型結構之類型、具有星型結構之類型。(Use of metal copper particles) The metal copper particle powder and the antiviral agent composed of the metal copper particles of the present invention have excellent antiviral properties as described above. By fixing on the surface of the formed body or being contained in the formed body, the metal copper compound The particle powder reacts with oxygen to generate active oxygen, which can exert excellent antiviral performance. For example, metal copper particles can also be dispersed in pure water, ion exchange water and other water; lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol; methanol modification, benzene modification, triol modification, Methyl ethyl ketone modification, denatonium benzoate modification, perfume modification and other general modified alcohols, etc. are made into dispersions, or can be redispersed in the above low boiling point solvents to make adjusted fatty acids and /Or a dispersion liquid of metal copper particles covering the amount of the ester compound of fatty acid and polyol. In addition, when preparing the dispersion, in order to improve the dispersibility of the metal copper particulate powder in the dispersion medium, a dispersant is preferably blended. The blending amount of the dispersant depends on the amount of the fatty acid and/or the fatty acid ester compound in the dispersion and the amount of metal copper particles coated with the fatty acid ester compound, and is preferably 0.01-2% by mass relative to the dispersion medium. As for the dispersant, one or more of any one of amine salt, carboxylic acid or carboxylate, and hydroxyl group can be used for adsorbing group having 1, 2, 3 amine or neutralizing its counter ion, And in the main chain and side chain there are fatty acid, polyether, polyester, polyurethane, polyarylate polymer dispersant. These dispersants are adsorbed on the surface of the copper compound particles by having an adsorbing group, and the main chain or side chain improves the compatibility with the non-aqueous solvent. The repulsive force generated by the steric obstacle of the polymer chain makes the copper compound The aggregation of the particles is suppressed and dispersed evenly in the non-aqueous solvent to eliminate the aggregation caused by the passage of time. As for the polymer dispersant, a type composed only of the main chain, a type having a comb structure with side chains, or a type having a star structure can be used.

含有如此之金屬銅微粒粉末的分散液適合使用來作為塗料組成物或樹脂組成物之稀釋溶劑，藉此，不會損害塗料組成物或樹脂組成物之透明性，可對於由該塗料組成物構成之塗膜、或者由樹脂組成物構成之樹脂成形體賦予抗病毒性能。 就如此之塗料組成物而言，可列舉將酚醛樹脂、環氧樹脂、胺甲酸酯樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂、不飽和聚酯樹脂、聚矽氧樹脂等熱硬化性樹脂、或光硬化型丙烯酸系樹脂等作為基礎樹脂者。 此外，就樹脂組成物而言，在上述熱硬化性樹脂之外，可列舉由低-、中-、高-密度聚乙烯、線狀低密度聚乙烯、線狀超低密度聚乙烯、同排聚丙烯、對排聚丙烯、丙烯-乙烯共聚物、聚丁烯-1、乙烯-丁烯-1共聚物、丙烯-丁烯-1共聚物、乙烯-丙烯-丁烯-1共聚物等烯烴樹脂、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯樹脂、尼龍6、尼龍6,6、尼龍6,10等聚醯胺樹脂、聚碳酸酯樹脂等熱塑性樹脂構成者。The dispersion liquid containing such a metal copper particle powder is suitable for use as a diluting solvent for a coating composition or a resin composition, so that the transparency of the coating composition or the resin composition will not be impaired, and it can be used for the coating composition The coating film or the resin molded body composed of resin composition impart antiviral performance. Such coating compositions include thermosetting resins such as phenol resins, epoxy resins, urethane resins, melamine resins, urea resins, alkyd resins, unsaturated polyester resins, and silicone resins. , Or light-curing acrylic resin as the base resin. In addition, in terms of resin composition, in addition to the above-mentioned thermosetting resins, examples include low-, medium-, and high-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, and Polypropylene, parallel polypropylene, propylene-ethylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer and other olefins Resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamide resins such as nylon 6, nylon 6, 6, and nylon 6, 10, Constructed of thermoplastic resin such as polycarbonate resin.

就更具體之用途而言，可例示將不織布或樹脂薄膜或者纖維製品等作為基材，於該基材表面塗布含有抗病毒性組成物之塗料組成物形成塗膜而成之成形體、從含有抗病毒性組成物之樹脂組成物直接成形薄膜、片材、不織布、纖維等成形體而成之成形體等。 [實施例]For more specific uses, a non-woven fabric, resin film, or fiber product is used as a substrate, and a coating composition containing an antiviral composition is applied to the surface of the substrate to form a coating film. The resin composition of the antiviral composition is directly molded into a molded body such as a film, sheet, non-woven fabric, fiber, etc. [Example]

[實施例1] 對於二乙二醇添加硬脂酸銅2.5質量%，邊攪拌邊進行加熱。自到達190℃的時間點算起加熱2小時後，冷卻至120℃以下，添加乙酸丁酯並攪拌約1分鐘。靜置使二乙二醇層與乙酸丁酯層分離後，除去乙酸丁酯層，獲得含有金屬銅微粒之二乙二醇分散液。 將該二乙二醇分散液藉由孔徑10μm之膜過濾器抽濾，以水清洗後，於50℃乾燥2小時獲得金屬銅微粒粉末。獲得之金屬銅微粒粉末之X射線繞射測定結果表示於圖1。[Example 1] 2.5% by mass of copper stearate was added to diethylene glycol, and the mixture was heated while stirring. After heating for 2 hours from the point of time when it reached 190°C, it was cooled to 120°C or less, and butyl acetate was added and stirred for about 1 minute. After standing to separate the diethylene glycol layer and the butyl acetate layer, the butyl acetate layer was removed to obtain a diethylene glycol dispersion liquid containing metal copper particles. The diethylene glycol dispersion was suction filtered through a membrane filter with a pore diameter of 10 μm, washed with water, and dried at 50° C. for 2 hours to obtain metal copper particulate powder. The X-ray diffraction measurement results of the obtained metallic copper particulate powder are shown in FIG. 1.

[實施例2] 將加熱溫度變更為210℃，除此以外，以與實施例1同樣的方式製作金屬銅微粒粉末。[Example 2] Except having changed the heating temperature to 210°C, in the same manner as in Example 1, a metal copper fine particle powder was produced.

[實施例3] 將硬脂酸銅變更為月桂酸銅，除此以外，以與實施例1同樣的方式製作金屬銅微粒粉末。[Example 3] Except that copper stearate was changed to copper laurate, in the same manner as in Example 1, a metal copper fine particle powder was produced.

[實施例4] 將硬脂酸銅變更為硬脂酸及乙酸銅，除此以外，以與實施例1同樣的方式製作金屬銅微粒粉末。[Example 4] Except that copper stearate was changed to stearic acid and copper acetate, the same procedure as in Example 1 was carried out to produce metal copper fine particles.

[實施例5] 將二乙二醇變更為乙二醇，除此以外，以與實施例1同樣的方式製作金屬銅微粒粉末。[Example 5] Except that diethylene glycol was changed to ethylene glycol, the metal copper microparticle powder was produced in the same manner as in Example 1.

[實施例6] 將二乙二醇變更為甘油，除此以外，以與實施例1同樣的方式製作金屬銅微粒粉末。[Example 6] Except that diethylene glycol was changed to glycerin, in the same manner as in Example 1, a metal copper fine particle powder was produced.

[參考例1] 於蒸餾水加入為分散劑之DISPERBYK-2060(BYK Japan KK.製)0.5質量%進行攪拌。然後，以金屬銅成分成為0.5質量%之方式，添加藉由實施例1獲得之金屬銅微粒粉末並進行攪拌。進行10分鐘超音波處理獲得含金屬銅微粒之分散液。[Reference example 1] 0.5% by mass of DISPERBYK-2060 (manufactured by BYK Japan KK.) as a dispersant was added to distilled water and stirred. Then, the metallic copper particulate powder obtained in Example 1 was added and stirred so that the metallic copper component became 0.5% by mass. Perform ultrasonic treatment for 10 minutes to obtain a dispersion liquid containing metal copper particles.

[參考例2] 於乙酸丁酯加入為分散劑之DISPERBYK-2090(BYK Japan KK.製)0.5質量%進行攪拌。然後，以金屬銅成分成為0.5質量%之方式添加藉由實施例1獲得之金屬銅微粒粉末並進行攪拌。進行10分鐘超音波處理獲得含金屬銅微粒之分散液。[Reference example 2] 0.5% by mass of DISPERBYK-2090 (manufactured by BYK Japan KK.) as a dispersant was added to butyl acetate and stirred. Then, the metallic copper particulate powder obtained in Example 1 was added and stirred so that the metallic copper component became 0.5% by mass. Perform ultrasonic treatment for 10 minutes to obtain a dispersion liquid containing metal copper particles.

[比較例1] 將硬脂酸銅變更為硫酸銅，除此以外，以與實施例1同樣的方式進行製作。[Comparative Example 1] Except that copper stearate was changed to copper sulfate, it was produced in the same manner as in Example 1.

[比較例2] 將加熱溫度變更為150℃，除此以外，以與實施例1同樣的方式進行製作。[Comparative Example 2] Except having changed the heating temperature to 150°C, it was produced in the same manner as in Example 1.

[比較例3] 將乾燥溫度變更為120℃，除此以外，以與實施例1同樣的方式進行製作。獲得之金屬銅微粒粉末之X射線繞射測定結果表示於圖1。[Comparative Example 3] Except having changed the drying temperature to 120°C, it was produced in the same manner as in Example 1. The X-ray diffraction measurement results of the obtained metallic copper particulate powder are shown in FIG. 1.

[比較例4] 對於乙酸丁酯添加金屬銅微粒試藥(Sigma-Aldrich Co. LLC製)為0.05質量%及DISPERBYK-2090為1.0重量%，藉由超音波振動裝置進行攪拌獲得分散液。[Comparative Example 4] To butyl acetate, a metal copper particle reagent (manufactured by Sigma-Aldrich Co. LLC) was added at 0.05% by weight and DISPERBYK-2090 at 1.0% by weight, and a dispersion was obtained by stirring with an ultrasonic vibration device.

[比較例5] 不進行加入乙酸丁酯並於靜置後除去乙酸丁酯層之步驟，除此以外，以與實施例1同樣的方式進行製作。[Comparative Example 5] The production was performed in the same manner as in Example 1 except that the step of adding butyl acetate and removing the butyl acetate layer after standing still was not performed.

[實施例7] 對於二乙二醇添加硬脂酸銅2.5質量%，邊攪拌邊進行加熱。從到達190℃之時間點算起加熱2小時後，將二乙二醇分散液冷卻至60℃。 然後，加入溶解了為分散劑之DISPERBYK-2090(BYK Japan KK.製)1.0質量%及二乙二醇二硬脂酸酯1.0質量%的乙酸丁酯進行攪拌。靜置約1小時後，收集乙酸丁酯層，製作金屬銅微粒分散液。將該金屬銅微粒分散液以孔徑0.1μm之膜過濾器抽濾，以水清洗後，於50℃乾燥2小時獲得金屬銅微粒粉末。[Example 7] 2.5% by mass of copper stearate was added to diethylene glycol, and the mixture was heated while stirring. After heating for 2 hours from the point of reaching 190°C, the diethylene glycol dispersion was cooled to 60°C. Then, butyl acetate in which 1.0% by mass of DISPERBYK-2090 (manufactured by BYK Japan KK.) and 1.0% by mass of diethylene glycol distearate as a dispersant were dissolved was added and stirred. After standing for about 1 hour, the butyl acetate layer was collected to prepare a metal copper particle dispersion. The metal copper particle dispersion was suction filtered through a membrane filter with a pore diameter of 0.1 μm, washed with water, and dried at 50° C. for 2 hours to obtain metal copper particle powder.

(實施例8) 對於甘油添加硬脂酸銅2.5質量%，邊攪拌邊進行加熱。從到達190℃之時間點算起加熱2小時後，將甘油分散液冷卻至室溫。添加與甘油等量之乙醇進行攪拌，藉由孔徑10μm之膜過濾器抽濾。以己烷、乙酸丁酯清洗，獲得金屬銅微粒粉末。(Example 8) 2.5% by mass of copper stearate was added to glycerin, and the mixture was heated while stirring. After heating for 2 hours from the point of reaching 190°C, the glycerin dispersion was cooled to room temperature. Add the same amount of ethanol as glycerin, stir, and filter with a membrane filter with a pore size of 10 μm. It was washed with hexane and butyl acetate to obtain metal copper particulate powder.

(實施例9) 將實施例8之金屬銅微粒粉末於空氣中保存2個月。(Example 9) The metal copper particulate powder of Example 8 was stored in the air for 2 months.

(實施例10) 將實施例9之金屬銅微粒粉末於空氣中保存6個月。(Example 10) The metal copper particulate powder of Example 9 was stored in the air for 6 months.

(比較例6) 將加熱溫度變更為250℃，除此以外，以與實施例1同樣的方式製作。(Comparative Example 6) Except having changed the heating temperature to 250°C, it was produced in the same manner as in Example 1.

(比較例7) 將實施例8之清洗藉由乙醇來進行，除此以外，以同樣方式製作金屬銅微粒粉末。(Comparative Example 7) Except that the washing in Example 8 was performed with ethanol, the metal copper particulate powder was produced in the same manner.

(微粒之金屬組成的鑑定) 將製得之金屬銅微粒粉末之金屬組成以Rigaku Corporation製粉末X射線繞射裝置測定。測定範圍係2θ=30°~60°，若為金屬銅，則於43°、50°之位置出現峰部。(Identification of metal composition of particles) The metal composition of the obtained metal copper particulate powder was measured with a powder X-ray diffraction apparatus manufactured by Rigaku Corporation. The measurement range is 2θ=30°~60°. If it is metallic copper, peaks will appear at 43° and 50°.

(金屬銅微粒之表面組成評價) 將約0.1g之金屬銅微粒粉末藉由KBr錠劑成形器成形為直徑約5mm之圓形狀。將該成形物藉由X射線光電子能譜裝置K-Alpha(Thermo Fisher Scientific K.K.製)，以測定徑：0.4mmφ、X射線源：Al單色儀、測定元素：Cu2p、O1s、C1s、步輻(step size)：0.1eV之條件測定。從獲得之圖譜之來自金屬銅之峰部(約933eV)、來自氧化銅等峰部(約935eV)之面積，算出各別之成分比。(Evaluation of the surface composition of metallic copper particles) About 0.1 g of metallic copper particulate powder was formed into a circular shape with a diameter of about 5 mm by a KBr tablet shaper. The molded product was subjected to X-ray photoelectron spectroscopy device K-Alpha (manufactured by Thermo Fisher Scientific KK) to measure diameter: 0.4mmφ, X-ray source: Al monochromator, measurement elements: Cu2p, O1s, C1s, step radiation (step size): Measured under 0.1eV conditions. From the area of the peak from metallic copper (about 933 eV) and the peak from copper oxide (about 935 eV) in the obtained spectrum, the respective component ratios were calculated.

(抗病毒性評價) [水系分散液之情況] 將經調整成為相對於黏結樹脂金屬銅成分濃度為0.05質量%的分散液90質量%、與作為黏結樹脂之丙烯酸樹脂9.95質量%混合製成塗布液。將未加工之不織布浸漬於塗布液，取出並將多餘的液體以滾筒式絞擰機除去後，於80℃之乾燥機乾燥5分鐘。之後於150℃之乾燥機乾燥2分鐘，使金屬銅微粒粉末固定而獲得不織布。(Antiviral Evaluation) [In the case of aqueous dispersion] 90% by mass of the dispersion liquid adjusted to have a concentration of 0.05% by mass relative to the metallic copper component of the binder resin, and 9.95% by mass of acrylic resin as the binder resin were mixed to prepare a coating liquid. The unprocessed non-woven fabric is immersed in the coating liquid, taken out and the excess liquid is removed with a drum wringer, and dried in a dryer at 80°C for 5 minutes. Then, it was dried in a dryer at 150°C for 2 minutes to fix the metal copper particles to obtain a non-woven fabric.

[溶劑系分散液之情況] 將經調整成相對於黏結樹脂，金屬銅成分濃度為0.05質量%之分散液90質量%、作為黏結樹脂之光硬化性丙烯酸樹脂9.9質量%、及光聚合起始劑0.1質量%混合製成塗布液。將未加工之不織布浸漬於塗布液，取出並將多餘之液體以滾筒式絞擰機除去後，於90℃之乾燥機乾燥2分鐘。之後，進行UV照射10分鐘，使金屬銅微粒粉末固定而獲得不織布。[In the case of solvent-based dispersions] Coating is prepared by mixing 90% by mass of a dispersion liquid adjusted to a concentration of 0.05% by mass of the metallic copper component relative to the binder resin, 9.9% by mass of a photocurable acrylic resin as a binder, and 0.1% by mass of a photopolymerization initiator liquid. The unprocessed non-woven fabric is immersed in the coating liquid, taken out and the excess liquid is removed with a drum wringer, and dried in a dryer at 90°C for 2 minutes. After that, UV irradiation was performed for 10 minutes to fix the metal copper fine particles to obtain a non-woven fabric.

(不織布之抗病毒性評價方法) 1.使宿主細胞感染病毒，培養後，將經藉由離心分離除去細胞殘渣者作為病毒懸浮液。 2.將上述1之病毒懸浮液經以滅菌蒸餾水10倍稀釋而得者作為試驗病毒懸浮液。 3.將試驗病毒懸浮液0.2mL接種至不織布之試驗片0.4g。 4.25℃放置2小時後，添加SCDLP培養基20mL以旋渦混合器進行攪拌，從檢體洗出病毒。 5.藉由噬菌斑測定法測定病毒感染價，算出抗病毒活性值。 6.若抗病毒活性值為3.0以上，則可判定對於該病毒有充分之抗病毒性。(Evaluation method of antiviral property of non-woven fabric) 1. Infect a host cell with a virus, and after culturing, the cell residue removed by centrifugation is used as a virus suspension. 2. The virus suspension of 1 above was diluted 10-fold with sterilized distilled water as the test virus suspension. 3. Inoculate 0.2 mL of the test virus suspension to 0.4 g of the non-woven test piece. 4. After standing at 25°C for 2 hours, add 20 mL of SCDLP medium and stir with a vortex mixer to wash out the virus from the specimen. 5. Measure the virus infection price by the plaque assay method and calculate the antiviral activity value. 6. If the antiviral activity value is 3.0 or more, it can be judged that the virus has sufficient antiviral properties.

(脂肪酸及/或酯化合物之總量之測定方法) 藉由示差-熱重量同時測定裝置(TG/DTA7220 Hitachi High-Technologies Corporation製)，將粉末試料約10mg於氮氣環境下以10℃/min升溫至600℃。從獲得之譜圖將重量減少份作為脂肪酸及酯化合物之總量。(Method for measuring the total amount of fatty acids and/or ester compounds) Using a differential-thermogravimetry simultaneous measuring device (TG/DTA7220 Hitachi High-Technologies Corporation), about 10 mg of the powder sample was heated to 600°C at 10°C/min in a nitrogen atmosphere. From the obtained spectrum, the weight reduction is regarded as the total amount of fatty acid and ester compound.

(金屬銅微粒之平均一次粒徑及平均二次粒徑之測定方法) 平均一次粒徑之測定方法：藉由掃描式電子顯微鏡(S-4800 Hitachi High-Technologies Corporation製)觀察粉末試料，獲得圖像。使用圖像解析式粒度分布測定軟體Mac-View算出平均一次粒徑。 粉末金屬銅微粒之平均二次粒徑之測定方法：使用雷射繞射式粒度分布測定裝置(SALD-3100 島津製作所(股)製)，藉由濕式法測定平均二次粒徑。(Method for measuring average primary particle size and average secondary particle size of metallic copper particles) The method of measuring the average primary particle size: Observe the powder sample with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) to obtain an image. The average primary particle size is calculated using the image analysis type particle size distribution measurement software Mac-View. Method for measuring the average secondary particle size of powdered metal copper particles: Using a laser diffraction particle size distribution analyzer (SALD-3100 manufactured by Shimadzu Corporation), the average secondary particle size was measured by a wet method.

於表1展示關於實施例1~7及比較例1~5之金屬銅微粒(分散液)能否製作、及藉由實施例1及7、比較例5獲得之金屬銅微粒之脂肪酸及/或酯化合物之被覆量。 於表2展示關於實施例8~10及比較例6~7之金屬銅微粒能否製作、及X射線光電子能譜法所為之金屬銅微粒集合體之表面組成測定結果。 於表3展示使用了將於實施例1、6、10及比較例5、7獲得之金屬銅微粒粉末藉由參考例1所示之方法經調整而得的金屬銅微粒分散液、及使用了藉由比較例4獲得之金屬銅微粒分散液之不織布的對於流感病毒及貓杯狀病毒之抗病毒性評價結果。Table 1 shows whether the metal copper particles (dispersions) of Examples 1 to 7 and Comparative Examples 1 to 5 can be produced, and the fatty acids and/or the metal copper particles obtained by Examples 1 and 7 and Comparative Example 5 The coating amount of the ester compound. Table 2 shows whether the metal copper particles of Examples 8-10 and Comparative Examples 6-7 can be produced, and the measurement results of the surface composition of the metal copper particle aggregates by X-ray photoelectron spectroscopy. Table 3 shows the use of the metallic copper particulate powder obtained in Examples 1, 6, 10 and Comparative Examples 5 and 7 by the method shown in Reference Example 1, and the use of the metallic copper particulate dispersion liquid The antiviral evaluation result of the non-woven fabric of the metal copper particle dispersion liquid obtained in Comparative Example 4 against influenza virus and feline calicivirus.

各別將實施例1之金屬銅微粒集合體之X射線光電子能譜法的譜圖展示於圖2，實施例10之金屬銅微粒集合體之X射線光電子能譜法的譜圖展示於圖3。The X-ray photoelectron spectroscopy of the metal copper particle assembly of Example 1 is shown in Fig. 2 respectively, and the X-ray photoelectron spectroscopy of the metal copper particle assembly of Example 10 is shown in Fig. 3 .

[表1] 　 能否製作金屬銅微粒或分散液 銅粒子之組成 被覆量 (質量%) 平均一次粒徑 (nm) 平均二次粒徑 (μm) 實施例1 ○ 金屬銅 7.6 80 100 實施例2 ○ 金屬銅 ※ 100 ※ 實施例3 ○ 金屬銅 ※ ※ ※ 實施例4 ○ 金屬銅 ※ ※ ※ 實施例5 ○ 金屬銅 ※ ※ ※ 實施例6 ○ 金屬銅 ※ 150 ※ 實施例7 ○ 金屬銅 2.0 80 0.2 比較例1 × 粒徑1μm以上 金屬銅 ※ ※ ※ 比較例2 × 無法形成粒子 - ※ ※ ※ 比較例3 ○ 金屬銅+氧化亞銅 ※ ※ ※ 比較例4 ○ 金屬銅 ※ ※ ※ 比較例5 ○ 金屬銅 30 80 ※ ※係未測定[Table 1] Can make metal copper particles or dispersions Composition of copper particles Coverage (mass%) Average primary particle size (nm) Average secondary particle size (μm) Example 1 ○ Metallic copper 7.6 80 100 Example 2 ○ Metallic copper ※ 100 ※ Example 3 ○ Metallic copper ※ ※ ※ Example 4 ○ Metallic copper ※ ※ ※ Example 5 ○ Metallic copper ※ ※ ※ Example 6 ○ Metallic copper ※ 150 ※ Example 7 ○ Metallic copper 2.0 80 0.2 Comparative example 1 × Particle size 1μm or more Metallic copper ※ ※ ※ Comparative example 2 × Cannot form particles - ※ ※ ※ Comparative example 3 ○ Copper metal + cuprous oxide ※ ※ ※ Comparative example 4 ○ Metallic copper ※ ※ ※ Comparative example 5 ○ Metallic copper 30 80 ※ ※Not determined

[表2] 能否製作金屬銅微粒或分散液 藉由X射線光電子能譜法所測之銅微粒集合體之表面組成有機物被膜量 實施例8 ○ 金屬銅：100% 有機物被膜：金屬銅微粒之2.0質量% 實施例9 ○ 金屬銅：50% 氧化銅等：50% 實施例10 ○ 金屬銅：46% 氧化銅等：54% 比較例6 ○ 氧化銅：100% 比較例7 ○ 金屬銅：100% 有機物被膜：金屬銅微粒之30質量% [Table 2] Can make metal copper particles or dispersions The amount of organic coating on the surface of the copper particle assembly measured by X-ray photoelectron spectroscopy Example 8 ○ Copper metal: 100% organic coating: 2.0% by mass of metal copper particles Example 9 ○ Copper metal: 50% Copper oxide, etc.: 50% Example 10 ○ Copper metal: 46% Copper oxide, etc.: 54% Comparative example 6 ○ Copper oxide: 100% Comparative example 7 ○ Copper metal: 100% organic coating: 30% by mass of metal copper particles

[表3] 　 抗病毒活性值 (流感病毒) 抗病毒活性值 (貓杯狀病毒) 實施例1 ≧3.9 4.1 實施例6 ≧3.9 3.2 實施例10 ≧3.9 3.2 比較例4 1.2 0.3 比較例5 2.8 1.4 比較例7 2.8 1.4 [產業上利用性][table 3] Antiviral activity value (influenza virus) Antiviral activity value (feline calicivirus) Example 1 ≧3.9 4.1 Example 6 ≧3.9 3.2 Example 10 ≧3.9 3.2 Comparative example 4 1.2 0.3 Comparative example 5 2.8 1.4 Comparative example 7 2.8 1.4 [Industrial availability]

本發明之金屬銅微粒粉末作為分散液之形態，藉由作為稀釋劑含有於構成纖維製品等之樹脂組成物中、或直接塗布或含浸於纖維製品等，可對於紙製品、口罩、濕紙巾、空調過濾器、空氣清淨機用過濾器、衣服、作業服、窗簾、地毯、汽車用構件、包裝構件、保鮮材料、床單、毛巾、浴墊、尿布套、填充娃娃、拖鞋、鞋墊、雨刷等清掃用品等纖維製品賦予抗病毒性。 此外，藉由使用低沸點溶劑作為分散液之分散介質，也可用來作為塗料組成物或樹脂組成物之稀釋劑，藉此可對於塗膜或樹脂成形物賦予抗病毒性。 另外，也可使用於醫療用具、醫療用具之包裝薄膜、廢棄容器、垃圾袋、療養院或醫院、學校等公共設施之牆壁材料或地板材料、蠟塗層材料、嘔吐物的處理用具等。 另外，除了衛生製品以外，也可使用於導電膜、薄膜、金屬板、玻璃板、船舶用塗料、熱交換器散熱片、或餐具等陶瓷製品、橡膠製品、水龍頭等金屬製品、加濕器用添加劑、液體洗劑、離子吸附劑等各種用途中。The metal copper particulate powder of the present invention is in the form of a dispersion liquid, and can be used for paper products, masks, wet tissues, paper products, masks, wet tissues, etc., by being contained as a diluent in resin compositions constituting fiber products, or directly coated or impregnated in fiber products Air-conditioning filters, filters for air purifiers, clothing, work clothes, curtains, carpets, automotive components, packaging components, fresh-keeping materials, sheets, towels, bath mats, diaper covers, stuffed dolls, slippers, insoles, wipers, etc. Fiber products such as supplies impart antiviral properties. In addition, by using a low-boiling point solvent as the dispersion medium of the dispersion liquid, it can also be used as a diluent for a coating composition or a resin composition, thereby imparting antiviral properties to the coating film or resin molded product. In addition, it can also be used for medical appliances, packaging films for medical appliances, waste containers, garbage bags, wall materials or floor materials for nursing homes, hospitals, schools and other public facilities, wax coating materials, and vomit disposal tools. In addition to sanitary products, it can also be used for conductive films, films, metal plates, glass plates, paints for ships, heat exchanger fins, ceramic products such as tableware, rubber products, metal products such as faucets, and additives for humidifiers. , Liquid lotion, ion adsorbent and other applications.

無no

[圖1]展示藉由實施例1及比較例3獲得之金屬銅微粒粉末的X射線繞射測定結果的圖。 [圖2]展示藉由實施例1獲得之抗病毒劑之X射線光電子能譜法之譜圖的圖。 [圖3]展示藉由實施例10獲得之抗病毒劑之X射線光電子能譜法之譜圖的圖。[Fig. 1] A graph showing the results of X-ray diffraction measurement of metal copper fine particles obtained in Example 1 and Comparative Example 3. [FIG. 2] A diagram showing the spectrum of the antiviral agent obtained in Example 1 by X-ray photoelectron spectroscopy. [Figure 3] A diagram showing the spectrum of the antiviral agent obtained in Example 10 by X-ray photoelectron spectroscopy.

Claims (14)

一種金屬銅微粒粉末，其特徵在於：由被覆有脂肪酸及/或酯化合物之金屬銅微粒構成。A metal copper particle powder, characterized in that it is composed of metal copper particles coated with fatty acid and/or ester compound. 如請求項1之金屬銅微粒粉末，其中，該金屬銅微粒之平均二次粒徑為100nm~500μm。Such as the metal copper particle powder of claim 1, wherein the average secondary particle size of the metal copper particle is 100nm~500μm. 如請求項1或2之金屬銅微粒粉末，其中，該酯化合物係脂肪酸與多元醇之酯化合物。According to claim 1 or 2, the metal copper particulate powder, wherein the ester compound is an ester compound of fatty acid and polyhydric alcohol. 如請求項1或2之金屬銅微粒粉末，其中，該脂肪酸係碳數10~22之高級脂肪酸。Such as the metal copper particulate powder of claim 1 or 2, wherein the fatty acid is a higher fatty acid with carbon number 10-22. 如請求項1或2之金屬銅微粒粉末，其中，該金屬銅微粒之平均一次粒徑係10~500nm之範圍。Such as the metal copper particle powder of claim 1 or 2, wherein the average primary particle size of the metal copper particle is in the range of 10 to 500 nm. 如請求項1或2之金屬銅微粒粉末，其中，該脂肪酸及/或酯化合物對於該金屬銅微粒之被覆量係0.1~20質量%。The metal copper particle powder of claim 1 or 2, wherein the coating amount of the fatty acid and/or ester compound to the metal copper particle is 0.1-20% by mass. 一種金屬銅微粒粉末之製造方法，其特徵在於，具有下述步驟： 藉由於多元醇中添加脂肪酸銅，將其進行加熱混合，製備分散有經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆之金屬銅微粒的分散液； 將該分散液與低沸點溶劑混合後，將該多元醇及低沸點溶劑二相分離，且使多元醇中之游離脂肪酸及酯化合物移動至低沸點溶劑中； 除去該二相分離後之低沸點溶劑； 回收除去了低沸點溶劑之多元醇中的經脂肪酸及/或酯化合物被覆的金屬銅微粒。A method for manufacturing metal copper particulate powder, characterized in that it has the following steps: By adding fatty acid copper to the polyol, heating and mixing it to prepare a dispersion liquid of metal copper particles coated with fatty acid and/or the fatty acid and polyol ester compound; After mixing the dispersion with a low-boiling point solvent, the polyol and the low-boiling point solvent are separated into two phases, and the free fatty acids and ester compounds in the polyol are moved to the low-boiling point solvent; Remove the low boiling point solvent after the two-phase separation; The fatty acid and/or ester compound coated metal copper particles in the polyol from which the low boiling point solvent has been removed are recovered. 一種金屬銅微粒粉末之製造方法，其特徵在於，具有下述步驟： 藉由於多元醇中添加脂肪酸及銅化合物，將其進行加熱混合，製備分散有經脂肪酸及/或該脂肪酸與多元醇之酯化合物被覆之金屬銅微粒的分散液； 將該分散液與低沸點溶劑混合後，將該多元醇及低沸點溶劑進行二相分離，且使多元醇中之游離脂肪酸及酯化合物移動至低沸點溶劑中； 除去該二相分離後之低沸點溶劑； 回收除去了低沸點溶劑之多元醇中的經脂肪酸及/或酯化合物被覆的金屬銅微粒。A method for manufacturing metal copper particulate powder, characterized in that it has the following steps: By adding fatty acids and copper compounds to the polyols, heating and mixing them to prepare a dispersion of metal copper particles coated with fatty acids and/or ester compounds of the fatty acids and polyols; After mixing the dispersion with a low boiling point solvent, the polyol and the low boiling point solvent are subjected to two-phase separation, and the free fatty acids and ester compounds in the polyol are moved to the low boiling point solvent; Remove the low boiling point solvent after the two-phase separation; The fatty acid and/or ester compound coated metal copper particles in the polyol from which the low boiling point solvent has been removed are recovered. 如請求項8之金屬銅微粒粉末之製造方法，該銅化合物係乙酸銅、氯化銅、溴化銅之任一者。According to the method for producing metal copper particulate powder of claim 8, the copper compound is any one of copper acetate, copper chloride, and copper bromide. 如請求項7至9中任一項之金屬銅微粒粉末之製造方法，該多元醇係二乙二醇、乙二醇、三乙二醇、丙二醇、聚乙二醇、聚丙二醇、甘油之任一者。Such as the method for producing metal copper particulate powder of any one of claims 7 to 9, the polyol is any of diethylene glycol, ethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and glycerin One. 一種抗病毒劑，其特徵在於：係由如請求項1至6中任一項之金屬銅微粒粉末構成，藉由X射線光電子能譜法測定該金屬銅微粒集合體之表面時，相對於在最先測得金屬銅成分之深度中之全部銅成分，金屬銅之比率維持在10%以上。An antiviral agent, which is characterized in that it is composed of metal copper particle powder as claimed in any one of claims 1 to 6, and when the surface of the metal copper particle assembly is measured by X-ray photoelectron spectroscopy, it is The first measurement of all copper components in the depth of the metallic copper component, the ratio of metallic copper is maintained above 10%. 如請求項11之抗病毒劑，係金屬銅微粒粉末經分散於溶劑中之分散液。For example, the antiviral agent of claim 11 is a dispersion in which metal copper particulate powder is dispersed in a solvent. 如請求項11或12之抗病毒劑，係金屬銅微粒粉末經分散於樹脂中之樹脂組成物。For example, the antiviral agent of claim 11 or 12 is a resin composition in which metal copper particles are dispersed in a resin. 如請求項11或12之抗病毒劑，其中，該金屬銅微粒粉末之含量為0.01~2.0質量%之抗病毒劑的抗病毒活性值為3.0以上。For example, the antiviral agent of claim 11 or 12, wherein the antiviral activity value of the antiviral agent whose content of the metal copper particulate powder is 0.01~2.0% by mass is 3.0 or more.
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