TWI738826B - Antimicrobial, antiviral and/ or antialgal material comprising inorganic/ organic hybrid compound and process for producing the same - Google Patents

Abstract

Conventional antimicrobials, antivirals and/ or antialgal materials of the type in which active ingredients are fixed to solids are the type in which the active ingredients are kneaded into ordinary plastics (organic polymers), but in such a case, the active ingredients tend to desorb on the surface, and if they are embedded in the interior, there is a problem that the action can not be sufficiently expressed.

The present invention relates to an antimicrobial, an antiviral, and/ or antialgal material comprising an inorganic/ organic hybrid compound in which an inorganic oxide or a derivative thereof and a hydroxyl group-containing organic polymer are chemically bonded to each other. The hybrid compound has both water resistance and water absorption, and since the active ingredients stably fixed thereon are fine and highly active particles such as nanoparticles, it is possible to obtain a high antimicrobial, antiviral and/ or antialgal material effect without excessive elimination and release of active ingredients, and to fully use up all fixed active ingredients.

Description

包含無機/有機混成化合物之抗微生物、抗病毒及/或防藻材料以及其製造方法 Anti-microbial, anti-viral and/or anti-algae material containing inorganic/organic hybrid compound and its manufacturing method

本發明是關於新穎的抗微生物、抗病毒、及/或防藻材料。 The present invention relates to novel anti-microbial, anti-viral, and/or anti-algae materials.

向來，以改善家庭、建築物等居住環境為目的，而實施殺菌、抗菌處理。例如針對住宅設備儀器，有使用紫外線燈的紫外線照射法、臭氧氧化法、次亞氯酸鈉溶液清洗法等各種方法，視目的而各分別加以選擇。於具有殺菌性、抗菌性的製品中，使用有機系抗菌劑或銀、銅等的殺菌、抗菌材料，為了提供清潔的環境而實施賦予殺菌或抗菌性的種種方案。 Traditionally, for the purpose of improving the living environment of homes, buildings, etc., sterilization and antibacterial treatments have been implemented. For example, for residential equipment and instruments, there are various methods such as ultraviolet irradiation using ultraviolet lamps, ozone oxidation, and sodium hypochlorite solution cleaning methods, which can be selected according to the purpose. In products with bactericidal and antibacterial properties, organic antibacterial agents or antibacterial and antibacterial materials such as silver and copper are used, and various proposals for imparting sterilization or antibacterial properties are implemented in order to provide a clean environment.

該等方法之中，屬於物理性手法的照射γ線、電子線，紫外線、微波等電磁波(光)的方法非常有效，但需要有用於此目的之裝置及電源，而只能在工場的專用設備內或住宅設備儀器之中等原本即有限的場所使用。關 於臭氧氧化法，也是需要有用於產生臭氧的裝置及電源，情況沒有甚麼不同。又，做為較簡單的方法而言有加熱殺菌法，但是還是需要有用於加熱之某種設備。該等電磁波照射、臭氧氧化、加熱等方法都不只是有抗微生物效果，多半會附帶引起對象物的劣化，由這一點而言無法適用的情況也很多。 Among these methods, irradiating electromagnetic waves (light) such as gamma rays, electron rays, ultraviolet rays, microwaves, etc., which are physical methods, are very effective. However, devices and power sources for this purpose are required, and special equipment in the workshop can only be used. It can be used in limited places such as indoor or residential equipment. shut In the ozone oxidation method, a device and power source for ozone generation are also required, and the situation is no different. In addition, as a simpler method, there is a heat sterilization method, but some kind of equipment for heating is still required. These methods such as electromagnetic wave irradiation, ozone oxidation, and heating do not only have an antimicrobial effect, but also cause deterioration of the object. In this regard, there are many cases where they cannot be applied.

間接利用光的方法而言，也有利用氧化鈦等光觸媒，對其照射光線而使其顯現抗微生物或抗病毒作用的方法。此時可以由自然光或居住環境中的照明而使其顯現效果，並不一定需要專用裝置及電源，但是就需要某種光源之點而言，在使用場所、用途上還是有限制。 In the method of indirect use of light, there is also a method of using a photocatalyst such as titanium oxide to irradiate it with light to show an antimicrobial or antiviral effect. At this time, natural light or lighting in the residential environment can be used to make the effect appear. It does not necessarily require a dedicated device and power supply. However, as far as a certain light source is required, there are still restrictions on the place of use and purpose.

由化學物質(藥劑)所致的抗微生物、抗病毒、防藻，不需要特別的裝置、電源、光源，對於使用場所的限制少，因而是被廣泛使用的方法。菌類最容易增殖的環境是儲存水、循環水、用水環境(如廚房、浴室、洗手間等)、濕潤環境等，例如，對於自來水的殺菌從以前就使用氯。又，為了工場及建築物的冷卻水、游泳池、溫浴設施的浴缸水，使用水的紙‧紙漿工業的抄紙製程的水等的抗菌，有使用氯或氯系化合物、異噻唑啉系化合物等，而採取直接溶解於水中的方法。關於該等方法，由於溶解於水之故抗菌作用會廣布於全域，就此點而言是有效的，但為了要得到更高的抗菌效果而溶解高濃度時，有產生對健康有害的疑慮之外，排水時對環境有不好的影響的疑慮。又，該等藥劑所具有的氧化性、對pH的影響，也有促進 設備的構件及儀器的腐蝕的疑慮。 Anti-microbial, anti-virus, and anti-algae caused by chemical substances (medicaments) do not require special equipment, power supply, or light source, and have few restrictions on the place of use, so they are widely used methods. The environment where fungi are most likely to proliferate is storage water, circulating water, water environment (such as kitchens, bathrooms, toilets, etc.), humid environments, etc. For example, chlorine has been used for the sterilization of tap water since before. In addition, for the antibacterial use of cooling water in factories and buildings, swimming pools, bath water in warm bathing facilities, paper using water, and water used in the papermaking process of the pulp industry, there are chlorine or chlorine compounds, isothiazoline compounds, etc. , And take the method of directly dissolving in water. Regarding these methods, the antibacterial effect is widespread in the whole area due to the dissolution in water, which is effective in this regard, but in order to obtain a higher antibacterial effect, the high concentration of dissolution may be harmful to health. In addition, there is a concern that the drainage will have a bad impact on the environment. In addition, the oxidizing properties of these agents and the effect on pH also promote Concerns about corrosion of equipment components and instruments.

另一方面，作為門窗、家具、文具、玩具、美容用具等日常與皮膚接觸的部分的抗微生物、抗病毒的方法而言，會採取在構成材料中將有效成分揉入，或在材料表面進行覆蓋等方法。亦即，有效成分是成為固定在固形材料上的狀態。例如，有將涕必靈(thiabendazole)系化合物或銀等有效成分承載於氧化矽、氧化鋁、沸石、磷酸鋯等的抗微生物、抗病毒組成物揉入於構成材料中，或覆蓋在材料表面的方法等。該等方法可以適用於有需要抗微生物、抗病毒作用的全部固形物，例如，也可適用於具備抗微生物、抗病毒作用的過濾器(口罩)、網、薄片、膜、纖維等。該等抗微生物、抗病毒有效成分固定在固形物上的型態，也適用於如前述的儲水、循環水、用水環境、濕潤環境等，不需要將藥劑溶解於水中也有實現抗微生物、抗病毒效果的可能性。 On the other hand, as an anti-microbial and anti-viral method for the parts that come into contact with the skin on a daily basis, such as doors and windows, furniture, stationery, toys, and beauty appliances, the effective ingredients are kneaded in the constituent materials or applied on the surface of the material. Covering and other methods. That is, the active ingredient is in a state of being fixed to the solid material. For example, there are antimicrobial and antiviral compositions that carry active ingredients such as thiabendazole compounds or silver on silica, alumina, zeolite, zirconium phosphate, etc., knead into the constituent material, or cover the surface of the material Method and so on. These methods can be applied to all solids that require antimicrobial and antiviral effects. For example, they can also be applied to filters (masks), nets, sheets, membranes, fibers, etc., that have antimicrobial and antiviral effects. These anti-microbial and anti-viral active ingredients are fixed on solids, and are also suitable for the aforementioned water storage, circulating water, water environment, humid environment, etc., without the need to dissolve the drug in water, it can also achieve anti-microbial and anti-microbial properties. Possibility of viral effects.

將抗微生物、抗病毒成分固定而形成的固形物之例，以如以下所述者加以說明。 Examples of solids formed by fixing antimicrobial and antiviral ingredients are described below.

例如，在塑膠薄片或樹脂成形物的情況，係將二苯基醚系殺菌劑或洛赫西定(chlorhexidine)系殺菌劑等有機系抗菌劑揉入於樹脂，或塗裝在表面，而使其保持殺菌性或抗菌性(參照專利文獻1)。 For example, in the case of plastic sheets or resin moldings, organic antibacterial agents such as diphenyl ether fungicides or chlorhexidine fungicides are kneaded into the resin or coated on the surface to make It maintains bactericidal or antibacterial properties (see Patent Document 1).

此外，在沸石或氧化矽凝膠、及玻璃等礦物承載體上承載銀、銅、及鋅等金屬材料的無機系抗菌劑，將此無機系抗菌劑揉入於樹脂或塗裝在表面而形成膜或塑膠薄片、 纖維，而使其保持殺菌性或抗菌性(參照專利文獻2、專利文獻3、專利文獻4)。 In addition, an inorganic antibacterial agent containing metallic materials such as silver, copper, and zinc is carried on a mineral carrier such as zeolite, silica gel, and glass, and the inorganic antibacterial agent is kneaded into resin or coated on the surface to form it. Film or plastic sheet, Fibers maintain sterilization or antibacterial properties (see Patent Document 2, Patent Document 3, and Patent Document 4).

此外，揭示有：在二軸延伸PET膜上，將銀離子以離子蒸鍍法蒸鍍成為抗菌層，再將聚酯等塗布在抗菌層上而成的膜狀抗菌性積層體(參照專利文獻5)。 In addition, it is disclosed that on a biaxially stretched PET film, silver ions are vapor-deposited by ion vapor deposition to form an antibacterial layer, and then polyester or the like is coated on the antibacterial layer. 5).

此外揭示有：將纖維素系衍生物、胺基甲酸乙酯樹脂、丙烯酸樹脂及聚乙烯醇樹脂等高分子化合物做為黏合劑，併用銀、銀奈米粒子、銅、鋅、及金等有抗菌性的無機化合物，及洛赫西定或三氯沙(triclosan)等有機系抗菌劑，以及防腐劑或抗生劑等而形成的抗菌積層構造體(參照專利文獻6)。 In addition, it was revealed that polymer compounds such as cellulose derivatives, urethane resins, acrylic resins, and polyvinyl alcohol resins are used as binders, and silver, silver nanoparticles, copper, zinc, and gold are used as binders. An antibacterial multilayer structure formed by an antibacterial inorganic compound, an organic antibacterial agent such as loxidine or triclosan, and an antiseptic or biocide (see Patent Document 6).

此外揭示有：將在丙烯酸系樹脂承載有銀的氧化矽或氧化鋁粒子在膜表面進行塗裝處理，而得防藻性膜(參照專利文獻7)。 In addition, it is disclosed that an anti-algae film is obtained by coating silica or alumina particles carrying silver on an acrylic resin on the film surface (see Patent Document 7).

該等先前文獻中，保有抗微生物、抗病毒作用的固形物，亦即，將有效成分固定化的基材，全都是既有的有機聚合物(塑膠)。 In these previous documents, the solids that retain the antimicrobial and antiviral effects, that is, the substrates on which the active ingredients are immobilized, are all existing organic polymers (plastics).

順帶一提，本發明的發明者的一部分至今為止係揭示了與純粹的有機聚合物及純粹的無機氧化物都不一樣的新穎素材之無機/有機混成化合物。該物係具有羥基的聚乙烯醇與無機氧化物在分子水平上經化學鍵結而成的無機/有機混成化合物，反映無機氧化物的性質，雖是低價格但化學的安定性及耐熱性優異，可適用於數個領域(不包括抗微生物、抗病毒、及/或防藻材料)。 By the way, part of the inventors of the present invention so far have disclosed inorganic/organic hybrid compounds of novel materials that are different from pure organic polymers and pure inorganic oxides. The compound is an inorganic/organic hybrid compound formed by chemically bonding polyvinyl alcohol with hydroxyl groups and inorganic oxides at the molecular level. It reflects the properties of inorganic oxides. Although it is low-priced, it has excellent chemical stability and heat resistance. It can be applied to several fields (excluding anti-microbial, anti-viral, and/or anti-algae materials).

例如，該等無機/有機混成化合物，可做為質子(或氫氧化物離子)傳導性固體電解質使用，而有對燃料電池、各種電解裝置、感測器、電池、電致變色裝置(electrochromic device)、除濕機等種種用途的應用之提案。該等可做為固體電解質使用的無機/有機混成化合物，詳細而言是矽氧化合物與聚乙烯醇所成之無機/有機混成化合物(參照專利文獻8)，鋯氧化物與聚乙烯醇所成之無機/有機混成化合物(參照專利文獻9、10)等。或又揭示鋯氧化物與聚乙烯醇所成之無機/有機混成化合物含有鈀等金屬奈米粒子的有機合成用觸媒(參照專利文獻11)。由該等混成化合物所成的固體電解質，是在無機氧化物的鹽與聚乙烯醇共存的狀態下，經由將無機氧化物的鹽以酸或鹼中和的製程而製造。 For example, these inorganic/organic hybrid compounds can be used as proton (or hydroxide ion) conductive solid electrolytes, and are useful for fuel cells, various electrolysis devices, sensors, batteries, and electrochromic devices (electrochromic device). ), dehumidifiers and other applications for various purposes. These inorganic/organic hybrid compounds that can be used as solid electrolytes, in detail, are inorganic/organic hybrid compounds formed by silicon oxide compounds and polyvinyl alcohol (refer to Patent Document 8), and zirconium oxides and polyvinyl alcohol. The inorganic/organic hybrid compound (refer to Patent Documents 9, 10) and so on. Or, it is disclosed that the inorganic/organic hybrid compound of zirconium oxide and polyvinyl alcohol contains metal nanoparticles such as palladium as a catalyst for organic synthesis (see Patent Document 11). The solid electrolyte composed of these mixed compounds is manufactured through a process of neutralizing the salt of the inorganic oxide with an acid or alkali in a state where the salt of the inorganic oxide and polyvinyl alcohol coexist.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]特表2010-510819號公報 [Patent Document 1] JP 2010-510819 Gazette

[專利文獻2]特表2011-500306號公報 [Patent Document 2] Special Form 2011-500306 Bulletin

[專利文獻3]國際公開第2012/098742號 [Patent Document 3] International Publication No. 2012/098742

[專利文獻4]特表2011-530400號公報 [Patent Document 4] Special Form 2011-530400 Bulletin

[專利文獻5]國際公開第2007/132919號 [Patent Document 5] International Publication No. 2007/132919

[專利文獻6]特表2010-509791號公報 [Patent Document 6] Special Form No. 2010-509791 Bulletin

[專利文獻7]特開2003-327730號公報 [Patent Document 7] JP 2003-327730 A

[專利文獻8]專利第4832670號 [Patent Document 8] Patent No. 4832670

[專利文獻9]專利第3848882號 [Patent Document 9] Patent No. 3848882

[專利文獻10]專利第4081343號 [Patent Document 10] Patent No. 4,083,343

[專利文獻11]PCT/JP2011/065129 [Patent Document 11] PCT/JP2011/065129

本申請案的課題，是提供新穎的抗微生物、抗病毒、及/或防藻材料。理想是提供解決下述課題的抗微生物、抗病毒、及/或防藻材料。 The subject of this application is to provide novel anti-microbial, anti-viral, and/or anti-algae materials. The ideal is to provide anti-microbial, anti-viral, and/or anti-algae materials that solve the following problems.

如上所述，以電磁波(光)照射、臭氧氧化，加熱等物理方法的殺菌，需要有專用的裝置及電源、光源等，本來可使用的場所及用途即受限定。因此，可使用的場所或環境的限制少的使用化學物質(藥劑)的抗微生物、抗病毒處理被廣泛使用，但使用於儲水、循環水等的藥劑是以溶解於水的型態為主，有對人體及環境的不良影響的疑慮之外，與其接觸的構件、儀器的腐蝕亦可能成為問題。因此之故，為了適用於儲水、循環水等，以使用將有效成分固定於固形物的抗微生物、抗病毒材料為理想。亦即，將與水接觸的構件本身以具有抗微生物、抗病毒作用者構成，也有以將有效成分固定於固形物而形成的材料來形成過濾器等，使其與水接觸而進行抗微生物、抗病毒處理的方法。 As described above, sterilization by physical methods such as electromagnetic wave (light) irradiation, ozone oxidation, heating, etc., requires a dedicated device, power supply, light source, etc., and the places and uses that can be used are limited. Therefore, antimicrobial and antiviral treatments using chemical substances (medicaments) with few restrictions on the usable place or environment are widely used, but the medicaments used in water storage and circulating water are mainly dissolved in water. In addition to doubts about adverse effects on the human body and the environment, corrosion of components and equipment in contact with it may also become a problem. Therefore, in order to be suitable for water storage, circulating water, etc., it is ideal to use antimicrobial and antiviral materials that fix active ingredients in solids. That is, the member itself that comes into contact with water is composed of an antimicrobial and antiviral effect, and there is also a material formed by fixing the active ingredient to a solid substance to form a filter, etc., which is brought into contact with water for antimicrobial, antiviral, Methods of anti-viral treatment.

就固定在固形物的抗微生物、抗病毒有效成分而言，有涕必靈系化合物等有機化合物，及銀、銅等金屬、金屬微粒子(奈米粒子)、或鹽、氧化物、錯合物等 金屬化合物。又，在金屬的情況，常在被承載在氧化矽、氧化鋁、沸石、磷酸鋯等無機固體粒子的狀態下，將此無機固體粒子承載體固定於固形物而使用。要在與水接觸的構件本身保持抗微生物、抗病毒作用時，可考慮將該等有效成分揉入於構件的方法。但是，此時對於構件可使用的構成材料的選擇產生某種程度的限制，實際上將固定有效成分的覆蓋膜形成在構件表面係較為簡單。或者也可考慮將固定了有效成分的膜狀物黏貼在構件表面的方法。另一方面，在以將有效成分固定於固形物而形成的材料來形成過濾器，使其與水接觸而實施抗微生物、抗病毒處理的情況，將有效成分揉入屬於過濾器的網、網篩、不織布等多孔質體的構成構件本身，或在構件表面形成固定了有效成分的覆蓋膜即可。 As far as the antimicrobial and antiviral active ingredients fixed in solid matter are concerned, there are organic compounds such as chlorhexidine compounds, metals such as silver and copper, metal particles (nanoparticles), or salts, oxides, and complexes. Wait Metal compounds. Furthermore, in the case of metals, the inorganic solid particle carrier is often used by fixing the inorganic solid particle carrier to a solid in a state where it is supported on inorganic solid particles such as silica, alumina, zeolite, and zirconium phosphate. To maintain the antimicrobial and antiviral effects of the component itself in contact with water, a method of kneading these active ingredients into the component can be considered. However, at this time, the selection of the constituent materials that can be used for the member is somewhat restricted, and it is actually relatively simple to form a coating film that fixes the active ingredient on the surface of the member. Alternatively, a method of sticking a film with an active ingredient fixed on the surface of the member can also be considered. On the other hand, when a filter is formed with a material formed by fixing the active ingredient to a solid substance, and it is brought into contact with water to perform antimicrobial and antiviral treatment, the active ingredient is kneaded into the net and net belonging to the filter. The constituent member itself of a porous body such as a sieve or a non-woven fabric, or a covering film to which the active ingredient is fixed may be formed on the surface of the member.

順便一提，採取將抗微生物、抗病毒有效成分揉入固形物的構件的方法時，由可容易進行揉入過程之點而言，構成材料幾乎被限定於塑膠(有機聚合物)。又，在固形物表面形成固定了有效成分的覆蓋膜的情況時，其覆蓋膜需要是可彎曲性的，所以會由有機聚合物來形成。將固定有效成分的膜狀物黏貼於固形物的情況時，其膜狀物也需要是可彎曲性的，也是需要由有機聚合物來形成。例如在專利文獻1至7中，固定了有效成分者也是聚酯等通常的有機聚合物。將前述的有抗微生物、抗病毒作用的金屬成分承載在氧化矽、氧化鋁、沸石、磷酸鋯等無機固體粒子者，有效成分是直接固定在無機固體粒子，但最後 是將該粒子整個揉入於有機聚合物而使用。 By the way, when the method of kneading antimicrobial and antiviral active ingredients into a solid component is adopted, the material is almost limited to plastic (organic polymer) in terms of the ease of the kneading process. In addition, when forming a cover film to which an active ingredient is fixed on the surface of a solid object, the cover film needs to be flexible, so it is formed of an organic polymer. In the case of sticking the film material that fixes the active ingredient to the solid material, the film material also needs to be flexible, and it also needs to be formed of an organic polymer. For example, in Patent Documents 1 to 7, those having an active ingredient immobilized are also ordinary organic polymers such as polyester. Where the aforementioned metal components with antimicrobial and antiviral effects are carried on inorganic solid particles such as silica, alumina, zeolite, zirconium phosphate, etc., the effective components are directly fixed on the inorganic solid particles, but at the end The whole particle is kneaded into an organic polymer and used.

該等有效成分在被揉入於有機聚合物時，有效成分被有機聚合物包埋而被固定。在固形物表面形成的覆蓋膜中，結果還是有效成分被構成覆蓋膜的有機聚合物包埋而被固定。順帶一提，為了顯現抗微生物、抗病毒、或防藻作用，微生物、病毒、藻等需要與有效成分接觸，咸認為在多數情況，經固定的有效成分會有微量溶出，與微生物、病毒、藻接觸而顯現效力。因此，有效成分即便被固形物的有機聚合物包埋，也需要有露出的部分。但是，在水中的話，露出部分的有效成分的溶出、脫離速度大，所以露出度過大時容易引起有效成分的減損，在初期雖可得較大的抗微生物、抗病毒效果，但效果不會持續。或又，由於有效成分以高濃度溶出，也會導致周圍環境的污染，更因有效成分多量平白地溶出，從材料成本之點而言也不理想。但是，反過來以有效成分不容易脫離之方式形成過度包埋的狀態時，不能得到充分的抗微生物、抗病毒作用，還是變成平白揉入多量有效成分而使用的結果。在固定了有效成分的型態中，需要將該等相反的條件調節於適度的狀態，但實際上其調節不容易。 When the active ingredients are kneaded into the organic polymer, the active ingredients are embedded and fixed by the organic polymer. In the covering film formed on the surface of the solid material, as a result, the active ingredient is embedded and fixed by the organic polymer constituting the covering film. By the way, in order to show anti-microbial, anti-virus, or anti-algae effects, microorganisms, viruses, algae, etc. need to be in contact with active ingredients. It is believed that in most cases, the fixed active ingredients will dissolve in a small amount, and it will interact with microorganisms, viruses, Algae contact and show effectiveness. Therefore, even if the active ingredient is embedded in the solid organic polymer, it needs to have an exposed part. However, in water, the elution and release rate of the active ingredients in the exposed part is high, so if the exposure is too large, it is easy to cause the loss of the active ingredients. Although a large anti-microbial and anti-viral effect can be obtained in the initial stage, the effect will not last. . Or, since the active ingredients are eluted at a high concentration, it will also cause pollution to the surrounding environment, and because the active ingredients are eluted in a large amount, it is not ideal from the point of material cost. However, conversely, when the active ingredient is not easily detached from the over-embedded state, sufficient antimicrobial and antiviral effects cannot be obtained, and it is still the result of rubbing in a large amount of active ingredient and using it. In the form of fixed active ingredients, it is necessary to adjust the opposite conditions to an appropriate state, but in fact, the adjustment is not easy.

如前所述，固定了有效成分的固形物在多數情況下是有機聚合物，但所使用的通常的有機聚合物是疏水性，不溶於水且不吸收水。由於使用水溶性的有機聚合物時在水中其本身會溶解，所以由水中的安定性而言自然會選擇疏水性的通常的有機聚合物。但是，包埋而固定 在疏水性的有機聚合物中的有效成分，因為與水的接觸受阻，實質上對於抗微生物、抗病毒、或防藻作用會變成較為不活性。有效成分在露出的部分溶出、脫離速度非常大，將該等的相反的條件調節於適度的狀態係不容易，使抗微生物、抗病毒、或防藻作用的高活性與抑制有效成分的脫離(耐久性)兩者並存係極為困難。又，無法避免本來由於包埋部分的有效成分的活性消失而必然會自然大量發生的有效成分浪費問題。該等問題對於儲水、循環水、用水環境、濕潤環境等的水環境的抗微生物、抗病毒、或防藻處理全盤適用。 As mentioned above, the solid matter to which the active ingredient is immobilized is in most cases an organic polymer, but the usual organic polymer used is hydrophobic, insoluble in water, and does not absorb water. When a water-soluble organic polymer is used, it dissolves in water itself, so in terms of stability in water, a normal organic polymer that is hydrophobic is naturally selected. However, embedded and fixed The effective ingredients in hydrophobic organic polymers are substantially less active for antimicrobial, antiviral, or anti-algae effects due to hindered contact with water. The active ingredients dissolve and detach at a very high rate in the exposed part, and it is not easy to adjust these opposite conditions to a proper state, so that the high activity of antimicrobial, antiviral, or anti-algae effects and inhibits the detachment of the active ingredients ( Durability) The coexistence of the two is extremely difficult. In addition, it is inevitable to avoid the problem of waste of active ingredients that inevitably occurs naturally due to the disappearance of the activity of the active ingredients in the embedded part. These problems are fully applicable to the anti-microbial, anti-viral, or anti-algae treatment of water environments such as storage water, circulating water, water environment, and humid environment.

不只是在水環境，通常的乾燥環境中的門窗、家具、文具、玩具、美容用品等日常跟皮膚接觸的東西也被要求要有抗微生物、抗病毒作用。在這個情況時也與上述同樣，有將抗微生物、抗病毒有效成分揉入於構成構件，或在表面形成固定了有效成分的覆蓋膜，或黏貼固定了有效成分的膜的方法，而通常經固定者是有機聚合物。如前所述，咸認為抗微生物、抗病毒作用係因為經固定的有效成分微量溶出，其與微生物、病毒接觸之故而顯現效力。因此，與水環境不同，在通常的乾燥狀態下使用時本來就不容易有效果出現。雖然藉由來自大氣中的濕氣、或入身體發散的濕氣、分泌的汗等的有機聚合物表面的微量吸附水分會發揮作用，但如前所述，通常使用的有機聚合物是疏水性，本來就容易潑除吸附水，所以抗微生物、抗病毒作用不容易顯現。 Not only in the water environment, but also in the usual dry environment such as doors and windows, furniture, stationery, toys, beauty products and other things that come in contact with the skin on a daily basis, are also required to have antimicrobial and antiviral effects. In this case, similarly to the above, there are methods of kneading antimicrobial and antiviral active ingredients into constituent members, or forming a covering film fixed on the surface of the active ingredient, or pasting a film fixed on the active ingredient. The fixer is an organic polymer. As mentioned earlier, Xian believes that the antimicrobial and antiviral effects are due to the microdissolution of the fixed active ingredients and their effectiveness when they come into contact with microorganisms and viruses. Therefore, unlike the water environment, it is not easy to have an effect when used in a normal dry state. Although the moisture from the atmosphere, the moisture that enters the body, the secreted sweat, etc., the surface of the organic polymer absorbs moisture in a small amount, it will play a role, but as mentioned above, the commonly used organic polymer is hydrophobic , It is easy to splash off the adsorbed water, so the anti-microbial and anti-viral effects are not easy to show.

在表面形成有固定了有效成分的覆蓋膜的抗微生物、抗病毒材料的情況，基材的構成構件是有機聚合物時親和性良好、黏合安定性良好，但想要適用的東西之構成材料不一定是有機聚合物。例如，由玻璃、磁磚、便器等陶器製品、水泥材料等無機材料構成時，與由有機聚合物所成的覆蓋膜的親和性不良，會在覆蓋膜本身的長期黏合安定性上產生問題。 In the case of antimicrobial and antiviral materials with a coating film immobilized on the surface of active ingredients, when the constituent member of the base material is an organic polymer, the affinity and adhesion stability are good, but the constituent material of the thing to be applied is not It must be an organic polymer. For example, when it is composed of ceramic products such as glass, tiles, and toilets, or inorganic materials such as cement materials, poor affinity with the cover film made of organic polymer may cause problems in the long-term adhesion stability of the cover film itself.

本發明的特徵，是由無機氧化物或其衍生物與具有羥基的有機聚合物經化學鍵結而成的無機/有機混成化合物所成，該無機/有機混成化合物係內部含有銀或銅的金屬或其化合物並且不溶解於水的固體，並且能吸收水。 The feature of the present invention is an inorganic/organic hybrid compound formed by chemical bonding of an inorganic oxide or its derivative and an organic polymer having a hydroxyl group. The inorganic/organic hybrid compound is a metal or metal containing silver or copper inside The compound is a solid that is insoluble in water and can absorb water.

關於無機/有機混成化合物，特別是，無機氧化物或其衍生物係含有鋯的氧化物或該等的衍生物，具有羥基的有機聚合物係含有聚乙烯醇者。在無機/有機混成化合物含有的銀或銅的金屬或其化合物是含有直徑10nm以下的粒子，又，利用CuK α線的X線繞射法所得的繞射強度-繞射角圖中，歸屬於銀或銅的金屬或其化合物的最高尖峰的半峰寬度在2(2 θ°)以上，或無尖峰為特徵。 Regarding inorganic/organic hybrid compounds, in particular, inorganic oxides or their derivatives are zirconium-containing oxides or derivatives thereof, and organic polymers having hydroxyl groups contain polyvinyl alcohol. The silver or copper metal or its compound contained in the inorganic/organic hybrid compound contains particles with a diameter of 10 nm or less. In addition, the diffraction intensity-diffraction angle diagram obtained by the X-ray diffraction method of CuK α rays belongs to The half-width of the highest peak of silver or copper metal or its compound is more than 2 (2 θ°), or it is characterized by no peak.

本發明的抗微生物、抗病毒及/或防藻材料的特徵，以使其中的銀或銅的量相對於常溫的水成為1mg/L以上的方式將材料投入後浸漬24小時以上時，由材料溶出於水中的銀或銅的濃度未達0.05mg/L。 The antimicrobial, antiviral and/or algae-preventing material of the present invention is characterized in that when the material is immersed for more than 24 hours after being immersed in the material so that the amount of silver or copper is 1 mg/L or more relative to water at room temperature, the material The concentration of silver or copper dissolved in the water does not reach 0.05 mg/L.

本發明的抗微生物、抗病毒及/或防藻材料可以是膜狀物，膜狀物可以是覆蓋在固形物表面的塗布膜。塗布膜可以覆蓋在門窗、家具、文具、玩具、美容用具、垃圾容器、排水口構件、便器、塑膠溫室用聚乙烯薄片、儀器的開關、醫療用具、船底外面等固形物表面。覆蓋塗布膜的固形物是多孔質材料，可以是網、網篩、紡織物、不織布，可做為過濾器或口罩使用。再者，本發明的材料是膜狀的情況時，其特徵為，在無機/有機混成化合物含有的銀或銅的金屬或其化合物對於膜狀物的厚度方向有濃度梯度。 The anti-microbial, anti-virus and/or anti-algae material of the present invention can be a membrane, and the membrane can be a coating film covering the surface of a solid object. The coating film can cover the surface of solid objects such as doors and windows, furniture, stationery, toys, beauty appliances, garbage containers, drainage ports, toilets, polyethylene sheets for plastic greenhouses, instrument switches, medical appliances, and outside the bottom of ships. The solid material covering the coating film is a porous material, which can be a net, mesh, woven fabric, or non-woven fabric, which can be used as a filter or a mask. Furthermore, when the material of the present invention is in the form of a film, it is characterized in that the metal or compound of silver or copper contained in the inorganic/organic hybrid compound has a concentration gradient in the thickness direction of the film.

本發明的抗微生物、抗病毒及/或防藻材料與液體接觸時，可抑制該液體中的微生物、病毒的個體數增加，或可減少個體數。此時，可一面使液體強制循環一面使其與液體接觸，又，經適用的液體是使用於游泳池、澡堂、集合住宅用儲水槽、飼養用水槽、工業用儲水槽、工業用循環水、自來水、淨化槽、冷卻塔、運輸船的壓艙水(ballast water)的水。本材料與氣體接觸時，可抑制該氣體中的微生物、病毒的個體數增加，或減少個體數，此時可一面使氣體強制循環一面使其與氣體接觸。 When the anti-microbial, anti-viral and/or anti-algae material of the present invention is in contact with a liquid, the number of individuals of microorganisms and viruses in the liquid can be inhibited from increasing, or the number of individuals can be reduced. At this time, the liquid can be forced to circulate while making it contact with the liquid. In addition, the applied liquid is used in swimming pools, bathhouses, multi-household water storage tanks, breeding water tanks, industrial water storage tanks, industrial circulating water, and tap water. , Johkasou, cooling towers, ballast water of transport ships. When this material is in contact with gas, the number of microorganisms and viruses in the gas can be inhibited from increasing, or the number of individuals can be reduced. In this case, the gas can be forced to circulate and contact with the gas.

本發明的抗微生物、抗病毒及/或防藻材料係在聚乙烯醇及銀或銅的鹽共存之狀態下，將鋯鹽或氧化鋯鹽以鹼中和，經由鋯氧化物與聚乙烯醇進行化學鍵結而形成無機/有機混成化合物的過程而製造者。此時，鋯氧化物與聚乙烯醇進行化學鍵結而形成無機/有機混成化 合物的過程，是由鋯鹽或氧化鋯鹽與聚乙烯醇及銀或銅的鹽共存的溶液除去溶媒而形成固形物，使其與鹼接觸而將固形物中的鋯鹽或氧化鋯鹽中和而實施者。 The anti-microbial, anti-virus and/or anti-algae material of the present invention is based on the coexistence of polyvinyl alcohol and silver or copper salt, the zirconium salt or zirconia salt is neutralized with alkali, and the zirconium oxide and polyvinyl alcohol Produced by the process of chemical bonding to form an inorganic/organic hybrid compound. At this time, zirconium oxide and polyvinyl alcohol are chemically bonded to form an inorganic/organic hybrid The process of compounding is to remove the solvent from a solution in which a zirconium salt or a zirconium oxide salt and a polyvinyl alcohol and a silver or copper salt coexist to form a solid substance, and contact it with an alkali to remove the zirconium salt or zirconium oxide salt in the solid substance Neutralization and implementation.

在本發明的抗微生物、抗病毒及/或防藻材料的製造方法中，形成含有銀或銅的化合物之鋯氧化物與聚乙烯醇進行化學鍵結的無機/有機混成化合物之後，可將銀或銅的化合物以還原劑還原而成為金屬狀態的銀或銅。 In the manufacturing method of the antimicrobial, antiviral and/or algae-preventing material of the present invention, after forming an inorganic/organic mixed compound chemically bonded between zirconium oxide containing silver or copper compound and polyvinyl alcohol, silver or The copper compound is reduced with a reducing agent to become metallic silver or copper.

重複上述，將本發明提示如下。 Repeating the above, the present invention is presented as follows.

[發明1] [Invention 1]

一種抗微生物、抗病毒、及/或防藻材料，是由無機氧化物或其衍生物與具有羥基的有機聚合物進行化學鍵結而成的無機/有機混成化合物所構成，該無機/有機混成化合物係在內部含有銀或銅的金屬或其化合物並且不溶解於水的固體，且能吸收水。 An anti-microbial, anti-viral, and/or anti-algae material, which is composed of an inorganic/organic hybrid compound formed by chemical bonding of an inorganic oxide or its derivative and an organic polymer with a hydroxyl group. The inorganic/organic hybrid compound It is a solid that contains silver or copper metal or its compound inside and is insoluble in water and can absorb water.

[發明2] [Invention 2]

如發明1所述的的抗微生物、抗病毒、及/或防藻材料，其中，無機氧化物是鋯、矽、鈦、或鎢的氧化物。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 1, wherein the inorganic oxide is an oxide of zirconium, silicon, titanium, or tungsten.

[發明3] [Invention 3]

如發明2所述的抗微生物、抗病毒、及/或防藻材料，其中，無機氧化物是鋯的氧化物。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 2, wherein the inorganic oxide is zirconium oxide.

[發明4] [Invention 4]

如發明1所述的抗微生物、抗病毒、及/或防藻材料，其中，具有羥基的有機聚合物是聚乙烯醇。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 1, wherein the organic polymer having a hydroxyl group is polyvinyl alcohol.

[發明5] [Invention 5]

如發明1至4中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，在無機/有機混成化合物含有的銀或銅的金屬或其化合物含有直徑10nm以下的粒子。 The antimicrobial, antiviral, and/or anti-algae material according to any one of Inventions 1 to 4, wherein the metal or compound of silver or copper contained in the inorganic/organic hybrid compound contains particles with a diameter of 10 nm or less.

[發明6] [Invention 6]

如發明1至4中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，利用Cu K α線的X線繞射法所得的繞射強度-繞射角圖中歸屬於無機/有機混成化合物含有的銀或銅的金屬或其化合物的尖峰之中，最高尖峰的半峰寬度是2(2 θ°)以上，或無尖峰。 The antimicrobial, antiviral, and/or algae-preventing material according to any one of Inventions 1 to 4, wherein the diffraction intensity-diffraction angle diagram obtained by the X-ray diffraction method of Cu K α rays is attributed Among the spikes of the silver or copper metal or its compound contained in the inorganic/organic hybrid compound, the half-value width of the highest spike is 2 (2θ°) or more, or there is no spike.

[發明7] [Invention 7]

如發明1至4中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，將抗微生物、抗病毒、及/或防藻材料以其中的銀或銅的量成為1mg/L以上的量之方式浸漬於常溫水中24小時以上時，溶出於水中的銀或銅的濃度未達0.05mg/L。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of Inventions 1 to 4, wherein the amount of silver or copper in the anti-microbial, anti-viral, and/or anti-algae material is 1 mg When immersed in water at room temperature for more than 24 hours, the concentration of silver or copper dissolved in the water does not reach 0.05 mg/L.

[發明8] [Invention 8]

如發明1至4中任一項所述的抗微生物、抗病毒、及/或防藻材料，其為膜狀物。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of Inventions 1 to 4, which is a membrane.

[發明9] [Invention 9]

如發明8所述的抗微生物、抗病毒、及/或防藻材料，其中，膜狀物是覆蓋在固形物表面的塗布膜。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 8, wherein the membrane is a coating film covering the surface of the solid.

[發明10] [Invention 10]

如發明9所述的抗微生物、抗病毒、及/或防藻材料， 其中，表面被塗布膜覆蓋的固形物是門窗、家具、文具、玩具、美容用具、垃圾容器、排水口構件，便器、塑膠溫室用聚乙烯薄片、儀器的開關、醫療用具。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 9, Among them, the solid objects covered by the coating film are doors and windows, furniture, stationery, toys, beauty appliances, garbage containers, drain components, toilets, polyethylene sheets for plastic greenhouses, switches for instruments, and medical appliances.

[發明11] [Invention 11]

如發明9所述的抗微生物、抗病毒、及/或防藻材料，其中，固形物是多孔質材料。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 9, wherein the solid material is a porous material.

[發明12] [Invention 12]

發明11所述的抗微生物、抗病毒、及/或防藻材料，其中，多孔質材料是網、網篩、紡織物、不織布。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 11, wherein the porous material is a net, a mesh screen, a woven fabric, or a non-woven fabric.

[發明13] [Invention 13]

如發明11所述的抗微生物、抗病毒、及/或防藻材料，其中，多孔質材料是過濾器或口罩。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 11, wherein the porous material is a filter or a mask.

[發明14] [Invention 14]

如發明8所述的抗微生物、抗病毒、及/或防藻材料，其中，在無機/有機混成化合物所含的銀或銅的金屬或其化合物對於膜狀物的厚度方向具有濃度梯度。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 8, wherein the metal or compound of silver or copper contained in the inorganic/organic hybrid compound has a concentration gradient in the thickness direction of the film.

[發明15] [Invention 15]

如發明1至5中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，藉由使抗微生物、抗病毒、及/或防藻材料與液體接觸，而抑制該液體中的微生物、病毒的個體數的增加，或減少個體數。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of Inventions 1 to 5, wherein the liquid is inhibited by contacting the anti-microbial, anti-viral, and/or anti-algae material with the liquid Increase or decrease the number of individuals in the microorganisms and viruses.

[發明16] [Invention 16]

如發明15所述的抗微生物、抗病毒、及/或防藻材料，其中，一面使液體強制循環一面使抗微生物、抗病毒、 及/或防藻材料與液體接觸。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 15, wherein the liquid is forced to circulate while the anti-microbial, anti-viral, And/or the anti-algae material is in contact with the liquid.

[發明17] [Invention 17]

如發明15所述的抗微生物、抗病毒、及/或防藻材料，其中，液體是使用在游泳池、澡堂、集合住宅用儲水槽、飼養用水槽、工業用儲水槽、工業用循環水、自來水、淨化槽、冷卻塔、運輸船的壓艙水的水。 The antimicrobial, antiviral, and/or algae-preventing material according to Invention 15, wherein the liquid is used in swimming pools, bathhouses, water storage tanks for residential complexes, breeding water tanks, industrial water storage tanks, industrial circulating water, and tap water , Johkasou, cooling tower, ballast water of transport ships.

[發明18] [Invention 18]

如發明1至4中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，藉由使抗微生物、抗病毒、及/或防藻材料與氣體接觸，而抑制該氣體中的微生物、病毒的個體數的增加，或減少個體數。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of Inventions 1 to 4, wherein the gas is inhibited by contacting the anti-microbial, anti-viral, and/or anti-algae material with the gas Increase or decrease the number of individuals in the microorganisms and viruses.

[發明19] [Invention 19]

如發明18所述的抗微生物、抗病毒、及/或防藻材料，其中，一面使氣體強制循環一面使抗微生物、抗病毒、及/或防藻材料與氣體接觸。 The anti-microbial, anti-viral, and/or anti-algae material according to Invention 18, wherein the gas is forced to circulate while the anti-microbial, anti-viral, and/or anti-algae material is in contact with the gas.

[發明20] [Invention 20]

一種抗微生物、抗病毒、及/或防藻材料的製造方法，係經由下述過程而製得如發明3或4所述的抗微生物、抗病毒、及/或防藻材料：在聚乙烯醇及銀或銅的鹽共存的狀態下，將鋯鹽或氧化鋯鹽以鹼中和，由鋯氧化物與聚乙烯醇進行化學鍵結形成無機/有機混成化合物的過程。 An anti-microbial, anti-viral, and/or anti-algae material is prepared through the following process to prepare the anti-microbial, anti-viral, and/or anti-algae material according to Invention 3 or 4: The process of neutralizing the zirconium salt or zirconium oxide salt with an alkali in the presence of a silver or copper salt, and chemically bonding the zirconium oxide and polyvinyl alcohol to form an inorganic/organic hybrid compound.

[發明21] [Invention 21]

一種獲得如發明20所述的抗微生物、抗病毒，及/或防藻材料的製造方法，其中，鋯氧化物與聚乙烯醇進行化 合而形成無機/有機混成化合物的過程，是藉由從鋯鹽或氧化鋯鹽與聚乙烯醇以及銀或銅的鹽共存的溶液除去溶媒形成固形物，使此固形物與鹼接觸而中和固形物中的鋯鹽或氧化鋯鹽，藉此而施行者。 A method for obtaining the anti-microbial, anti-viral, and/or anti-algae material according to Invention 20, wherein the zirconium oxide is chemically combined with polyvinyl alcohol The process of combining to form an inorganic/organic hybrid compound is to form a solid by removing the solvent from a solution in which a zirconium salt or a zirconia salt, a polyvinyl alcohol, and a silver or copper salt coexist, and contacting the solid with an alkali to neutralize The zirconium salt or zirconium oxide salt in the solid substance, by which it is performed.

[發明22] [Invention 22]

一種獲得如發明20所述的抗微生物、抗病毒、及/或防藻材料的製造方法，其特徵為：在含有銀或銅的化合物之鋯氧化物與聚乙烯醇進行化學鍵結形成無機/有機混成化合物之後，將銀或銅的化合物以還原劑還原製成金屬狀態的銀或銅。 A manufacturing method for obtaining the antimicrobial, antiviral, and/or anti-algae material according to Invention 20, which is characterized in that: the zirconium oxide of a compound containing silver or copper is chemically bonded with polyvinyl alcohol to form an inorganic/organic After the compound is mixed, the silver or copper compound is reduced with a reducing agent to produce silver or copper in a metallic state.

本發明的材料發揮抗微生物、抗病毒及/或防藻效果。理想是，本發明的抗微生物、抗病毒及/或防藻材料的特徵為不溶解於水的固體，且可吸收水。本發明是藉由可以容易控制銀或銅等有效成分的放出速度而抑制過度的放出，不浪費有效成分而能活用，所以可在長期間維持效果，且成本效益也大。又，無機/有機混成化合物中，銀或銅等有效成分是以奈米粒子等微細而有活性的狀態存在，在表面的粒子由於直接接觸而顯現高的抗微生物、抗病毒及/或防藻作用，也能夠將小的病毒等取入於材料中進行攻撃。再者，作為覆蓋膜使用時，不論是有機材料或無機材料，對廣範圍的材料均顯現安定的黏合性。 The material of the present invention exerts anti-microbial, anti-virus and/or anti-algae effects. Ideally, the anti-microbial, anti-viral and/or anti-algae material of the present invention is characterized by solids that are insoluble in water and can absorb water. The present invention can easily control the release rate of effective ingredients such as silver or copper, thereby suppressing excessive release, and can be utilized without wasting the effective ingredients, so the effect can be maintained for a long period of time, and the cost-effectiveness is also great. In addition, in the inorganic/organic hybrid compound, active ingredients such as silver or copper exist in a fine and active state such as nano particles, and the particles on the surface exhibit high anti-microbial, anti-viral and/or anti-algae properties due to direct contact. Function, it is also possible to take small viruses etc. into the material for attack. Furthermore, when used as a cover film, whether it is an organic material or an inorganic material, it exhibits stable adhesion to a wide range of materials.

亦即，首先，無機氧化物與有機聚合物進行化學鍵結形成的無機/有機混成化合物，可將具有抗微 生物、抗病毒及/或防藻效果的銀及銅的金屬、金屬化合物等有效成分，做成如奈米粒子般的微細粒子安定的加以固定。該等銀及銅的有效成分，是在混成化合物生成之同時在其固體內部生成之故，多數是停留於奈米粒子等微細的狀態，不會長大而不活性化，而能維持活性的狀態。本發明的無機/有機混成化合物具有在內部吸收水的性質，環境中有水分時，成為將其吸收於混成化合物的分子間隙的狀態。在該狀態下，銀及銅的有效成分會經由吸收了水的混成化合物的分子間隙在化合物內部擴散，也會緩緩地被供給到表面。到達表面的銀及銅的有效成分，是在此處與微生物、病毒等接觸，而顯現抗微生物、抗病毒及/或防藻作用，此時對表面的有效成分的供給，是受到在混成化合物內緩慢的內部擴散的速度控制，因此速度受到適度的控制，可避免有效成分的過多放出。藉此，可消除有效成分的浪費。關於這種效果，雖然在有機聚合物之情況時若使用以水溶性的有機聚合物為基質的親水性高的有機聚合物亦有可能實現，但此時不容易得到在水環境中安定的材料。本發明的材料係藉由使用具有高親水性但不溶解於水、在水中也維持高安定性的無機/有機混成化合物而可實現如此的效果。 That is, first of all, the inorganic/organic hybrid compound formed by the chemical bonding of inorganic oxide and organic polymer can have anti-microbial properties. Active ingredients such as silver and copper metals and metal compounds that have biological, anti-viral and/or anti-algae effects are stabilized and fixed as fine particles like nanoparticles. The active ingredients of silver and copper are generated inside the solid at the same time as the mixed compound is formed. Most of them stay in a fine state such as nano particles, do not grow up and become inactivated, but can maintain an active state. . The inorganic/organic hybrid compound of the present invention has the property of absorbing water inside, and when moisture is present in the environment, it will be absorbed in the molecular gap of the hybrid compound. In this state, the active ingredients of silver and copper diffuse in the compound through the molecular gaps of the mixed compound that has absorbed water, and are also gradually supplied to the surface. The effective ingredients of silver and copper that reach the surface come in contact with microorganisms, viruses, etc., and exhibit anti-microbial, anti-viral and/or anti-algae effects. At this time, the supply of effective ingredients to the surface is affected by the mixed compounds. The speed of internal diffusion is controlled slowly, so the speed is moderately controlled to avoid excessive release of active ingredients. Thereby, the waste of effective ingredients can be eliminated. Regarding this effect, in the case of organic polymers, it is possible to use a highly hydrophilic organic polymer based on a water-soluble organic polymer, but it is not easy to obtain a material that is stable in a water environment. . The material of the present invention can achieve this effect by using an inorganic/organic hybrid compound that has high hydrophilicity but is insoluble in water and maintains high stability in water.

又，在混成化合物內部，有效成分是在如奈米粒子般的微細而恆常地如在活性高的狀態，因而可以活用有效成分而不會剩下，可在長期間維持安定的高抗微生物、抗病毒及/或防藻作用。如前所述，在以往的將有 效成分固定於固形物的型態的抗微生物、抗病毒及/或防藻材料，在有效成分的露出部分會產生過度的脫離、溶出，在包埋部分則相反的有完全不活性的問題。另一方面，在本材料係由無機/有機混成化合物所構成，在水中也是安定的材料，同時是親水性而可吸收水，可以將有效成分藉由在材料內的內部擴散以受到速度控制的狀態供給至表面，可解消以往之材料的問題。具有這樣的效果，同時混成化合物也兼具有如有機聚合物般可彎曲性的物性。 In addition, in the mixed compound, the active ingredients are as fine as nano-particles and are constantly in a highly active state, so the active ingredients can be utilized without leaving behind, and the high antimicrobial stability can be maintained for a long period of time. , Anti-virus and/or anti-algae effect. As mentioned earlier, in the past there will be Antimicrobial, antiviral, and/or algae-preventing materials in which the active ingredients are fixed to solids will cause excessive detachment and elution in the exposed part of the active ingredients, and the opposite has the problem of complete inactivity in the embedded part. On the other hand, this material is composed of an inorganic/organic hybrid compound. It is also a stable material in water. At the same time, it is hydrophilic and can absorb water. It can control the speed of the active ingredients by diffusing inside the material. The state is supplied to the surface, which can solve the problem of previous materials. With such an effect, the compound compound also has physical properties that are flexible like organic polymers.

銀或銅的有效成分，不只在混成化合物內部，在表面也有存在，而與微生物、病毒等直接接觸，但在該等表面的有效成分也是奈米粒子而處在活性高的狀態，所以會發揮高抗微生物、抗病毒及/或防藻作用。再者，混成化合物的格子間隙會因為吸收水而擴大，而小的病毒可進入其內部，在內部與奈米粒子接觸而受到攻撃。亦即，即便沒有將有效成分放出也可得到抗病毒效果。 The effective ingredients of silver or copper exist not only in the compound compound, but also on the surface, but also in direct contact with microorganisms, viruses, etc. However, the effective ingredients on the surface are also nano particles and are in a highly active state, so they will exert High anti-microbial, anti-virus and/or anti-algae effect. In addition, the lattice gaps of the mixed compounds will expand due to the absorption of water, and small viruses can enter the interior and come into contact with the nanoparticles in the interior and be attacked. That is, the antiviral effect can be obtained even if the active ingredient is not released.

無機/有機混成化合物具有吸水性一事，不僅於水環境，在通常環境中的門窗、家具、文具、玩具、美容用品等日常會與皮膚接觸的東西之抗微生物、抗病毒處理上也是重要的。如前述，通常有效成分係被固定在有機聚合物，但有機聚合物是疏水性，在不是水環境、濕潤環境的普通乾燥環境中不容易顯現抗微生物、抗病毒作用。相對於此，本發明的無機/有機混成化合物具有吸水性，會吸收大氣中的濕氣，或人身體發散的濕氣、分泌的汗等由來的水分，在通常的乾燥環境中也可實現保水狀 態。無機/有機混成化合物的一部分在某種程度可維持類似在水環境、濕潤狀態的容易顯現抗微生物、抗病毒作用的狀態，由此可得高效果。 Inorganic/organic hybrid compounds have water absorption properties, not only in the water environment, but also in the antimicrobial and antiviral treatment of things that come in contact with the skin, such as doors and windows, furniture, stationery, toys, and beauty products in normal environments. As mentioned above, the effective ingredients are usually fixed in organic polymers, but organic polymers are hydrophobic, and it is not easy to exhibit antimicrobial and antiviral effects in ordinary dry environments that are not water or humid environments. In contrast, the inorganic/organic hybrid compound of the present invention has water absorption properties and absorbs moisture derived from atmospheric moisture, moisture emitted by the human body, sweat secreted, etc., and can retain water in a normal dry environment. shape state. A part of the inorganic/organic hybrid compound can maintain the antimicrobial and antiviral effects similar to that in a water environment and in a humid state to a certain extent, so that high effects can be obtained.

以往在有機聚合物固定有效成分的方法中，也有使有效成分盡可能露出於表面，而可提高活性的方法，但此時若在使用中被水沾濕，則有效成分會容易被除去。又，不被水沾濕但是在人碰觸的用途時有效成分會容易掉落。但是，在本發明的材料中，由於係以下述機制發揮作用：原本在內部存在的有效成分係經由無機/有機混成化合物的吸濕性而向表面擴散，因此有效成分的表面露出雖少也可顯現效果。或者，將病毒取入於內部而加以攻撃的情況時，原本的有效成分也不需要露出於表面。 In the conventional method of fixing effective ingredients with organic polymers, there is also a method of exposing the effective ingredients on the surface as much as possible to increase the activity. However, in this case, if it gets wet with water during use, the effective ingredients are easily removed. In addition, it is not wetted by water, but the active ingredients will easily fall when touched by humans. However, in the material of the present invention, since the active ingredient originally present in the interior diffuses to the surface via the hygroscopicity of the inorganic/organic hybrid compound, the surface of the active ingredient may be exposed to a small amount. Show the effect. Or, when the virus is taken inside and attacked, the original active ingredient does not need to be exposed on the surface.

銀或銅是做為抗微生物、抗病毒及/或防藻材料的通常的有效成分而常被使用，在本發明中也利用此等，但此等的氧化物等化合物之氧化性非常強。但是，一般而言，有機聚合物對氧化之耐性弱，承載銀或銅的化合物時，由於此等的氧化作用而有劣化的可能性。相對於此，本發明的無機/有機混成化合物係反映出無機氧化物的極高的耐氧化性的性質，承載氧化作用強的銀或銅的化合物時也不容易引起劣化。 Silver or copper is often used as an effective ingredient for antimicrobial, antiviral and/or algae-preventing materials. These are also used in the present invention, but these oxides and other compounds are very oxidizing. However, in general, organic polymers have weak resistance to oxidation, and when a compound of silver or copper is supported, there is a possibility of deterioration due to such oxidation. In contrast, the inorganic/organic hybrid compound of the present invention reflects the extremely high oxidation resistance properties of inorganic oxides, and it is not easy to cause deterioration when supporting silver or copper compounds with strong oxidation.

又，本發明的材料是由對無機物及有機物雙方親和性高的無機/有機混成化合物所構成。因此之故，在固形物的表面形成覆蓋膜時，固形物的構成材料不論是有機聚合物，亦或是如陶瓷等無機物，都可安定的黏 合。 In addition, the material of the present invention is composed of an inorganic/organic hybrid compound having high affinity for both inorganic and organic substances. Therefore, when a coating film is formed on the surface of a solid object, whether the constituent material of the solid object is an organic polymer or an inorganic material such as ceramics, it can be stably adhered. combine.

第1圖係本發明的抗微生物、抗病毒及/或防藻材料以利用Cu K α線的X線繞射法測得的繞射強度-繞射角圖(45kV，40mA，掃描速度0.002°s^-1) The first figure is the diffraction intensity-diffraction angle graph of the antimicrobial, antiviral and/or algae-preventing material of the present invention measured by the X-ray diffraction method of Cu K α rays (45kV, 40mA, scanning speed 0.002° s ^-1 )

(a)含銀的材料，(b)含銅的材料 (a) Silver-containing materials, (b) Copper-containing materials

第2圖係概略表示本發明的抗微生物、抗病毒及/或防藻材料的代表性實施形態(第1實施形態)的系統圖。 Fig. 2 is a system diagram schematically showing a representative embodiment (first embodiment) of the antimicrobial, antiviral, and/or anti-algae material of the present invention.

第3圖係概略表示本發明的抗微生物、抗病毒及/或防藻材料的代表性實施形態(第2實施形態)的系統圖。 Fig. 3 is a system diagram schematically showing a representative embodiment (the second embodiment) of the antimicrobial, antiviral, and/or anti-algae material of the present invention.

在本申請案中，「由…所成」(或「由…所構成」、「由…所形成」)是表示可以含有所述成分以外的成分之意。 In this application, "made by" (or "made by", "made by") means that it may contain ingredients other than the above-mentioned ingredients.

以下說明本發明的抗微生物、抗病毒及/或防藻材料的實施形態。本發明是，無機氧化物或其衍生物與有羥基的有機聚合物進行化學鍵結而成的無機/有機混成化合物所構成，該無機/有機混成化合物係以在內部含有銀或銅的金屬或其化合物並且不溶解於水的固體、且可以吸收水者做為基本。在本發明中，無機氧化物或其衍生物，理想是鋯的氧化物或該等的衍生物。這裡的鋯的氧化物或其衍生物就是含有ZrO₂做為基本單元的化合物，係指氫氧化鋯及通式ZrO₂‧xH₂O表示的鋯酸、或該等的衍生 物全部。又，就其他的無機氧化物而言，可使用矽的氧化物或其衍生物等，但此時矽的氧化物或其衍生物是含SiO₂做為基本單元的化合物，係指以通式SiO₂‧xH₂O表示的矽酸、或該等的衍生物全部。除此以外也可使用鈦、鎢等的氧化物作為無機氧化物。在該等的無機氧化物或其衍生物中也可以有一部分被別的金屬元素取代，也容許偏離化學量論組成，或添加添加物。 Hereinafter, embodiments of the antimicrobial, antiviral and/or algae-preventing material of the present invention will be described. The present invention is composed of an inorganic/organic hybrid compound formed by chemically bonding an inorganic oxide or its derivative and an organic polymer having a hydroxyl group. The inorganic/organic hybrid compound is a metal or its Compounds and solids that do not dissolve in water and can absorb water are the basic ones. In the present invention, the inorganic oxide or its derivatives are desirably zirconium oxides or derivatives thereof. The zirconium oxide or its derivative here is a compound containing ZrO ₂ as a basic unit, which refers to zirconium hydroxide and zirconic _{acid represented by the general formula ZrO 2 ‧xH 2} O, or all of these derivatives. In addition, for other inorganic oxides, silicon oxides or their derivatives, etc. can be used, but in this case, silicon oxides or their derivatives are _{compounds containing SiO 2} as the basic unit. Silicic acid represented by SiO _{2 ‧xH 2} O, or all of these derivatives. In addition to this, oxides such as titanium and tungsten can also be used as inorganic oxides. Some of these inorganic oxides or their derivatives may be substituted by other metal elements, and it is also allowed to deviate from the stoichiometric composition or to add additives.

在本發明中的無機/有機混成化合物，是上述無機氧化物或其衍生物與有機聚合物分子進行化學鍵結而成者。因此，在有機聚合物分子需要有與無機氧化物鍵結的鍵，做為其鍵結的鍵者可使用具有羥基的有機聚合物。例如，無機氧化物或其衍生物與具有羥基的有機聚合物形成無機/有機混成化合物時，兩者以分子階層互相纏繞，並經由有機聚合物的羥基藉由氫鍵結、脫水縮合而堅固地鍵結。混成化合物可以與有機聚合物及無機氧化物或其衍生物經物理性混合的混合物區別。亦即，與混合物不同，構成混成化合物的各成分的化學性質在混成化後並不一定保持不變。例如，具有羥基的有機聚合物單獨時是水溶性的時候，與無機氧化物或其衍生物形成混成化合物的狀態時基本上不溶解於水。如此由在混成化後化學的性質有變化一事，可以表示其為與由物理性混合的混合物不同的混成化合物。又，該無機/有機混成化合物不溶解於水，但親水性高，具有吸水性。如前所述，由於固定了有效成分的該無機/有機混成化合物的耐水性及吸水性併存，本 發明會產生關於抗微生物、抗病毒及/或防藻材料的高活性、有效成分放出速度的控制等種種效果。 The inorganic/organic hybrid compound in the present invention is formed by chemically bonding the above-mentioned inorganic oxide or its derivative and organic polymer molecules. Therefore, the organic polymer molecule needs to have a bond with the inorganic oxide, and as the bond for the bond, an organic polymer with a hydroxyl group can be used. For example, when an inorganic oxide or its derivative and an organic polymer with a hydroxyl group form an inorganic/organic hybrid compound, the two are entangled with each other at a molecular level, and the hydroxyl group of the organic polymer is hydrogen-bonded and dehydrated and condensed to form an inorganic/organic hybrid compound. Bond. The mixed compound can be distinguished from a mixture in which organic polymers and inorganic oxides or their derivatives are physically mixed. That is, unlike a mixture, the chemical properties of the components constituting the mixed compound do not necessarily remain unchanged after being mixed. For example, when an organic polymer having a hydroxyl group is water-soluble alone, it is basically insoluble in water when it forms a mixed compound with an inorganic oxide or a derivative thereof. In this way, the change in the chemical properties after the mixing can indicate that it is a mixed compound that is different from the mixture that is physically mixed. In addition, this inorganic/organic hybrid compound does not dissolve in water, but has high hydrophilicity and water absorption. As mentioned above, due to the coexistence of water resistance and water absorption of the inorganic/organic hybrid compound with fixed active ingredients, this The invention will produce various effects regarding the high activity of antimicrobial, antiviral and/or algae-preventing materials, and the control of the release rate of active ingredients.

關於做為抗微生物、抗病毒及/或防藻材料的有效成分而常被使用的銀或銅的氧化物等，由於該等的化合物因氧化性非常強，因此承載該等的通常的有機聚合物有劣化的可能性。相對於此，本發明的無機/有機混成化合物反映出其無機氧化物的極高耐氧化性的性質，在承載氧化作用強的銀或銅的化合物時也不容易引起劣化。亦即，使用無機/有機混成化合物作為固定有效成分的物質時，除了如上所述的耐水性與吸水性可以併存之點以外，在能耐銀或銅的化合物的強氧化作用之點上也是重要的。 Regarding silver or copper oxides, which are often used as effective ingredients for antimicrobial, antiviral, and/or anti-algae materials, since these compounds are very oxidizing, they carry the usual organic polymerizations. There is a possibility of deterioration. In contrast, the inorganic/organic hybrid compound of the present invention reflects the extremely high oxidation resistance properties of its inorganic oxide, and it is unlikely to cause deterioration when supporting silver or copper compounds with strong oxidation. That is, when an inorganic/organic hybrid compound is used as a substance for fixing the effective ingredient, in addition to the above-mentioned water resistance and water absorption can coexist, it is also important to withstand the strong oxidation of silver or copper compounds. .

在本發明中，構成無機/有機混成化合物的具有羥基的有機聚合物的聚合度並無特別限定。例如為500至100000，理想是1000至20000，較理想是2000至5000。聚合度是遵照例如JIS K 6726：1994進行測定。 In the present invention, the degree of polymerization of the organic polymer having a hydroxyl group constituting the inorganic/organic hybrid compound is not particularly limited. For example, it is 500 to 100,000, preferably 1,000 to 20,000, and more preferably 2,000 to 5,000. The degree of polymerization is measured according to, for example, JIS K 6726:1994.

在本發明中，構成無機/有機混成化合物的具有羥基的有機聚合物，較理想是聚乙烯醇。這裡的聚乙烯醇並不需要是完整的，本質上可以做為聚乙烯醇發揮功能者即可使用。例如羥基的一部份經由其他的基團取代者，一部分與其他的聚合物共聚者也可做為聚乙烯醇發揮功能。例如，屬於本發明的有機聚合物之聚乙烯醇，理想是由50莫耳%以上、較理想是70莫耳%以上、更理想是90莫耳%以上的乙烯醇或其衍生物的單體單元所構成。例 如，該乙烯醇或其衍生物的單體單元，其羥基的至少70%、理想是至少80%、較理想是至少85%沒有被其他的基團取代。又，在本發明的製造過程中，如經由聚乙烯醇則可得同樣的效果，所以可將做為聚乙烯醇的原料之聚乙酸乙烯酯等做為出發原料。例如，可使用聚乙酸乙烯酯的至少70%、理想是至少80%、較理想是至少85%被皂化而得的聚乙烯醇。皂化度是遵照例如JIS K 6726：1994進行測定。 In the present invention, the organic polymer having a hydroxyl group constituting the inorganic/organic hybrid compound is preferably polyvinyl alcohol. The polyvinyl alcohol here does not need to be complete, it can be used as a polyvinyl alcohol in essence. For example, part of the hydroxyl group is substituted by other groups, and part of the hydroxyl group is copolymerized with other polymers, which can also function as polyvinyl alcohol. For example, the polyvinyl alcohol belonging to the organic polymer of the present invention is preferably composed of monomers of vinyl alcohol or its derivatives at 50 mol% or more, more preferably 70 mol% or more, and more preferably 90 mol% or more. Constituted by the unit. example For example, in the monomer unit of the vinyl alcohol or its derivative, at least 70%, ideally at least 80%, and more ideally at least 85% of the hydroxyl groups are not substituted by other groups. In addition, in the manufacturing process of the present invention, the same effect can be obtained through polyvinyl alcohol, so polyvinyl acetate, etc., which is a raw material of polyvinyl alcohol, can be used as a starting raw material. For example, polyvinyl alcohol obtained by saponification of at least 70%, desirably at least 80%, and more desirably at least 85% of polyvinyl acetate can be used. The degree of saponification is measured according to, for example, JIS K 6726:1994.

關於聚乙烯醇，只要在其功能可充分顯現的範圍，則也可混合其他的聚合物，例如聚乙烯、聚丙烯等聚烯烴系聚合物，聚丙烯酸系聚合物，聚氧化乙烯、聚氧化丙烯等聚醚系聚合物，聚對酞酸乙二酯、聚對酞酸丁二酯；PET等聚酯系聚合物，聚四氟乙烯、聚氟化亞乙烯等氟系聚合物，甲基纖維素等醣鏈系聚合物，聚乙酸乙烯酯系聚合物，聚苯乙烯系聚合物，聚碳酸酯系聚合物，環氧樹脂系聚合物或其他有機、無機添加物等。例如，本發明的有機聚合物理想是含有50重量%以上、較理想是70重量%以上、更理想是90重量%以上的聚乙烯醇。 Regarding polyvinyl alcohol, as long as its function can be fully developed, other polymers can also be mixed, such as polyethylene, polypropylene and other polyolefin polymers, polyacrylic polymers, polyethylene oxide, and polypropylene oxide. Polyether polymers such as polyethylene terephthalate, polybutylene terephthalate; polyester polymers such as PET, fluorine polymers such as polytetrafluoroethylene, polyvinylidene fluoride, methyl fiber Sugar chain polymer such as element, polyvinyl acetate polymer, polystyrene polymer, polycarbonate polymer, epoxy resin polymer or other organic and inorganic additives, etc. For example, the organic polymer of the present invention desirably contains 50% by weight or more, more desirably 70% by weight or more, and more desirably 90% by weight or more of polyvinyl alcohol.

在本發明的抗微生物、抗病毒及/或防藻材料中，相對於無機/有機混成化合物中的有機聚合物，無機氧化物或其衍生物的量過少時，耐水性、耐氧化性會不充分。相反的，無機氧化物或其衍生物過多時，水分的吸收量降低，膨潤也會變小，有效成分及病毒的擴散速度變小，抗微生物、抗病毒及/或防藻效果降低等，無機/ 有機混成化合物變硬、脆，容易引起破損。因此，較宜將混成化合物中的無機氧化物或其衍生物重量之相對於有機聚合物重量的重量比控制在0.1至10。 In the anti-microbial, anti-viral and/or anti-algae material of the present invention, when the amount of inorganic oxide or its derivative is too small relative to the organic polymer in the inorganic/organic hybrid compound, the water resistance and oxidation resistance will be poor. full. Conversely, when inorganic oxides or their derivatives are too much, the amount of water absorption will decrease, the swelling will also decrease, the diffusion rate of active ingredients and viruses will decrease, and the antimicrobial, antiviral and/or anti-algae effects will decrease. / The organic compound compound becomes hard and brittle, and it is easy to cause damage. Therefore, it is better to control the weight ratio of the inorganic oxide or its derivative in the mixed compound to the weight of the organic polymer to be 0.1-10.

在本發明中，無機/有機混成化合物含有做為抗微生物、抗病毒及/或防藻作用的有效成分之銀或銅的金屬或其化合物。銀的情況時，除了金屬狀態之外，可使用銀氧化物、氯化銀等銀鹽、銀的錯合物等化合物。銅的情況時，除了金屬狀態之外，可使用銅氧化物、銅的錯合物等化合物。此等可以被含有單獨一種，亦可同時被含有多數種。又，此等以固體粒子被包含在無機/有機混成化合物中時，此等是以奈米粒子為理想，特別是含有直徑10nm以下的粒子為理想。如此，因為恆常地處在活性高的狀態，有效成分藉由在無機/有機混成化合物內的內部擴散而供給至表面時可活用無餘，在長期間安定的維持高抗微生物、抗病毒及/或防藻作用。又，由於為微細的奈米粒子，故在表面存在的粒子直接接觸微生物及病毒進行攻撃時，可顯現高的活性，又取入病毒等進行攻撃時也顯現高活性。該等銀或銅的金屬或其化合物以充分小的粒子存在一事，可藉由下述狀態而顯示：利用Cu K α線的X線繞射法所得的繞射強度-繞射角圖中，歸屬於該等金屬或化合物的尖峰中之最高尖峰的半峰寬度在2(2 θ°)以上，或無尖峰的狀態。在本發明的抗微生物、抗病毒及/或防藻材料中，所含有的銀或銅的金屬或其化合物換算為金屬原子宜在0.1wt%以上、較理想是0.5wt%以上、更理想是1wt %以上。雖沒有上限，但換算為金屬原子時較宜為含有例如15wt%以下，由可以抑制金屬溶出的觀點以含有5wt%以下為理想。 In the present invention, the inorganic/organic hybrid compound contains silver or copper metal or its compound as an effective ingredient for antimicrobial, antiviral, and/or anti-algae effects. In the case of silver, in addition to the metallic state, compounds such as silver salts such as silver oxide and silver chloride, and silver complexes can be used. In the case of copper, in addition to the metallic state, compounds such as copper oxides and copper complexes can be used. These can be contained in a single species or in multiple species at the same time. In addition, when these solid particles are contained in an inorganic/organic hybrid compound, these are preferably nano-particles, especially particles with a diameter of 10 nm or less. In this way, because the active ingredient is constantly in a state of high activity, the active ingredient can be utilised when supplied to the surface by internal diffusion in the inorganic/organic mixed compound, and it can stably maintain high antimicrobial, antiviral and/ Or anti-algae effect. In addition, since they are fine nanoparticles, the particles present on the surface directly contact microorganisms and viruses to attack, and they exhibit high activity, and they also exhibit high activity when viruses or the like are taken in for attack. The existence of these silver or copper metals or their compounds as sufficiently small particles can be shown by the following state: the diffraction intensity-diffraction angle diagram obtained by the X-ray diffraction method of Cu K α rays, The half-width of the highest peak among the peaks attributable to the metals or compounds is above 2 (2 θ°), or there is no peak. In the anti-microbial, anti-virus and/or anti-algae material of the present invention, the silver or copper metal or its compound contained in the metal atom is preferably 0.1wt% or more, more preferably 0.5wt% or more, more preferably 1wt %above. Although there is no upper limit, when converted into metal atoms, it is preferably contained, for example, 15 wt% or less, and it is desirable to contain 5 wt% or less from the viewpoint that metal elution can be suppressed.

繞射強度-繞射角圖就是作為X線繞射的結果通常可得的圖，是表示X線的計數值相對於繞射角2 θ的關係的圖。物質是結晶性的情況時，由於結晶面的規則性積層而產生X線的繞射現象，在對應於結晶面的面間隔的特定繞射角中X線的計數值會顯著升高，在繞射強度-繞射角圖中其繞射角位置可得尖銳的尖峰。粒子小、結晶面的積層數不多時，尖峰的高度低而寬度大，所以半峰寬度(繞射尖峰頂點高度的一半位置的尖峰寬度以2 θ的角度單位2 θ°表示的數值)會變大。又，物質為微小的不能形成結晶程度的微粒子(奈米粒子)時，在本來該物質是結晶時應該會有尖峰的繞射角也完全不會有繞射尖峰出現。亦即，半峰寬度變成無限大。因此，半峰寬度可視為表示微粒子(奈米粒子)程度的尺度，其值愈大結晶性愈低，表示是愈小的微粒子。在本發明中，在無機/有機混成化合物的繞射強度-繞射角圖中，在可歸屬於在其中所含的銀或銅的金屬或其化合物的尖峰之中，最高尖峰的半峰寬度在2(2 θ°)以上，或成為無繞射尖峰的狀態。在第1圖表示含有本發明的銀及銅的材料的X線繞射的典型繞射強度-繞射角圖(PANalytical社製X’Pert Pro，使用Cu K α線)。任一種材料的繞射強度-繞射角圖都沒有看到尖銳的繞射尖峰，沒有半峰寬度未達2(2 θ°)者。 The diffraction intensity-diffraction angle graph is a graph generally available as a result of X-ray diffraction, and is a graph showing the relationship between the count value of the X-ray and the diffraction angle 2 θ. When the substance is crystalline, the X-ray diffraction phenomenon occurs due to the regular layering of crystal planes. The X-ray count value will increase significantly at a specific diffraction angle corresponding to the interplanar spacing of the crystal planes. The position of the diffraction angle in the radiation intensity-diffraction angle diagram can be a sharp peak. When the particles are small and the number of layers of crystal planes is small, the height of the peak is low and the width is large, so the half-width (the peak width at half the height of the peak of the diffraction peak is expressed in the angle unit 2 θ° of 2 θ). Get bigger. In addition, when the substance is tiny and cannot form crystalline particles (nanoparticles), when the substance is originally crystalline, there should be a peak diffraction angle and no diffraction peak appears at all. That is, the width at half maximum becomes infinite. Therefore, the half-value width can be regarded as a scale indicating the degree of fine particles (nanoparticles), and the larger the value, the lower the crystallinity, which means that the smaller the fine particles. In the present invention, in the diffraction intensity-diffraction angle diagram of the inorganic/organic hybrid compound, among the peaks attributable to the silver or copper metal or its compound contained therein, the half-width of the highest peak Above 2 (2 θ°), or a state of no diffraction peak. Fig. 1 shows a typical diffraction intensity-diffraction angle diagram of X-ray diffraction of a material containing silver and copper of the present invention (X'Pert Pro manufactured by PANalytical, using Cu K α line). In the diffraction intensity-diffraction angle diagram of any material, no sharp diffraction peaks are seen, and there is no one with a half-peak width less than 2 (2 θ°).

在本發明中之特徵為，屬於有效成分之銀或銅的金屬或其化合物，是以微粒子(奈米粒子)的狀態被包含在具有吸水性的無機/有機混成化合物中，由此之故，可控制該等有效成分擴散至材料表面及被放出的速度。亦即，對於抗微生物、抗病毒及/或防藻作用所需要的最小限度的有效成分被緩緩放出，內包的有效成分為微粒子(奈米粒子)的狀態之故，可維持固定的有效成分供給至其用盡為止，耐久性優異。加之，對周圍環境的污染，及對接觸的人的污染可抑制在最小限度。又，由於在表面固定化的有效成分的粒子成為活性高的微粒子(奈米粒子)，與微生物、病毒等直接接觸而顯現高的抗微生物、抗病毒及/或防藻作用。再者，由於取入病毒等而進行攻撃時也顯現高活性，也可以將有效成分的放出降低至極限程度而獲得效果。該等有效成分的放出速度，是以本發明的抗微生物、抗病毒及/或防藻材料中的銀或銅的量成為1mg/L以上的量之方式將抗微生物、抗病毒及/或防藻材料浸漬於常溫的水中24小時以上，測定在水中溶出的銀或銅的濃度而可數值化。在本發明中理想是其數值未達0.05mg/L。 The feature of the present invention is that the metal or compound of silver or copper, which is an active ingredient, is contained in a water-absorbent inorganic/organic hybrid compound in the form of fine particles (nanoparticles). Therefore, The speed at which the active ingredients diffuse to the surface of the material and be released can be controlled. That is, the minimum effective ingredients required for antimicrobial, antiviral, and/or algae prevention effects are slowly released, and the contained effective ingredients are in the state of fine particles (nanoparticles), so it can maintain a fixed effect. The ingredients are supplied until they are used up, and the durability is excellent. In addition, the pollution to the surrounding environment and the pollution to the people in contact can be suppressed to a minimum. In addition, since the particles of the active ingredient immobilized on the surface become highly active microparticles (nanoparticles), and direct contact with microorganisms, viruses, etc., exhibits high antimicrobial, antiviral, and/or algae prevention effects. Furthermore, it exhibits high activity even when attacking by taking in viruses and the like, and it is also possible to reduce the release of active ingredients to the limit to obtain an effect. The release rate of these active ingredients is based on the method that the amount of silver or copper in the antimicrobial, antiviral and/or antialgae material of the present invention becomes 1 mg/L or more. The algae material is immersed in water at room temperature for more than 24 hours, and the concentration of silver or copper eluted in the water is measured and quantified. In the present invention, it is ideal that its value does not reach 0.05 mg/L.

本發明的抗微生物、抗病毒及/或防藻材料，可製成適當形態的固形物，將其直接浸漬於想要處理的水中等使用。理想形態是膜狀。此時，例如可將膜狀物直接浸漬於水、或可裝配於某種支持材、或可捲起來***於管柱內使用。又，也可細切成小片使用，將其小片裝填 於管柱使用。又，亦可將膜狀物黏貼在對象固形物的表面使用。 The anti-microbial, anti-viral and/or anti-algae material of the present invention can be made into a solid material in an appropriate form and directly immersed in the water to be treated for use. The ideal form is film-like. At this time, for example, the membrane-like substance can be directly immersed in water, or it can be assembled to a certain support material, or it can be rolled up and inserted into a pipe column for use. Also, it can be used by cutting into small pieces and filling the small pieces Used in the pipe string. Moreover, it is also possible to stick the film-like object on the surface of the target solid object and use it.

本發明的抗微生物、抗病毒及/或防藻材料亦可覆蓋於對象固形物的表面使用。此時在表面還是成為膜狀物。覆蓋時，對象固形物的形態可以是任何形態，所有的東西都可成為對象。又，本材料是以兼備無機物、有機物雙方性質的無機/有機混成化合物做為基質而成，所以不論是無機物、有機物，可以與所有的東西安定的黏合，在有機聚合物(塑膠)、木材、紙、玻璃、陶瓷、金屬等可安定的覆蓋。例如，在屬於多孔質材之網、網篩、紡織物、不織布等的表面覆蓋本發明的材料，可做為具有抗微生物、抗病毒及/或防藻作用的過濾器使用。或者，亦可做成在珠等粒狀物或其他固形物的表面覆蓋本發明的材料後沉入於儲水中的型態的抗微生物、抗病毒及/或防藻材料。 The anti-microbial, anti-viral and/or anti-algae material of the present invention can also be used to cover the surface of a solid object. At this time, it still becomes a film on the surface. When covering, the shape of the object solid can be any shape, and everything can become the object. In addition, this material is made of an inorganic/organic hybrid compound that has both inorganic and organic properties as a matrix. Therefore, whether it is inorganic or organic, it can be stably bonded to everything. In organic polymer (plastic), wood, Stable covering with paper, glass, ceramics, metal, etc. For example, the material of the present invention can be used as a filter with anti-microbial, anti-virus and/or anti-algae effects by covering the surface of a mesh, mesh screen, woven fabric, non-woven fabric, etc. belonging to a porous material with the material of the present invention. Alternatively, it can also be made into an antimicrobial, antiviral and/or antialgae material in which the surface of granular or other solid objects such as beads is covered with the material of the present invention and then submerged in storage water.

本材料是膜狀物的情況時，在無機/有機混成化合物含有的有效成分銀或銅的金屬或其化合物可對於膜狀物的厚度方向有濃度梯度。例如，在水環境使用的情況時，容易引起有效成分的過度放出之故，藉由使膜狀物表面側的有效成分濃度比內部側低以抑制放出速度的方法係為有效者。另一方面，在通常的乾燥環境使用的情況時，反而不容易引起有效成分的放出、效果不容易顯現之故，反而是使膜狀物表面側的有效成分濃度比內部側高乃為有效者。 When the material is a membrane material, the active ingredient silver or copper metal or its compound contained in the inorganic/organic hybrid compound may have a concentration gradient in the thickness direction of the membrane material. For example, when used in a water environment, it is easy to cause excessive release of active ingredients. Therefore, it is effective to suppress the release rate by making the concentration of the active ingredient on the surface side of the membrane lower than that on the inner side. On the other hand, when used in a normal dry environment, it is not easy to cause the release of active ingredients and the effect is not easy to manifest. Instead, it is effective to make the active ingredient concentration on the surface side of the membrane higher than the inner side.

本發明的材料，做為抗微生物、抗病毒及/或防藻材料可在所有的用途上使用。菌及藻容易增殖的場所有儲水、循環水，本發明是如前所述，不會因多餘的有效成分溶出而污染水並能有效顯現抗微生物、抗病毒及/或防藻作用，因此對所有的儲水、循環水都可以使用。例如，游泳池、溫浴設施的浴缸水、集合住宅用儲水槽的水、自來水等是直接與人體接觸，或攝取到人的體內的東西，所以是極力不希望使用藥劑的用途。又，養殖用或鑑賞用的飼養用水槽，也有對魚類等飼養生物的影響，所以不希望使用藥劑，或不能使用藥劑的用途。運輸船的壓艙水最後被廢棄於海中，所以由環境污染的觀點還是希望能避免藥劑的使用之用途。其他，例如紙‧紙漿工業的造紙製程所使用的水等工業用儲水‧循環水，工場及建築物的冷卻塔的水等，使用藥劑時該藥劑的氧化性、對pH的影響，有促進對設備的構件及儀器的腐蝕的疑慮。又，工業用水的情況也有對藥劑混入製品的疑慮。在該等用途上，可活用本發明的材料的特徵，亦即，抑制多餘的有效成分的溶出。 The material of the present invention can be used in all applications as an anti-microbial, anti-viral and/or anti-algae material. For the storage and circulating water where bacteria and algae are prone to proliferate, the present invention will not pollute the water due to the elution of redundant active ingredients and can effectively exhibit antimicrobial, antiviral and/or anti-algae effects, as mentioned above. It can be used for all storage and circulating water. For example, bath water in swimming pools, warm bathing facilities, water storage tanks for residential houses, tap water, etc., are things that directly contact the human body or are ingested into the human body, so the use of medicines is highly undesirable. In addition, the water tank for breeding or appreciation also has an effect on the breeding organisms such as fish, so it is not desirable to use medicines, or the use of medicines cannot be used. The ballast water of the transport ship is finally discarded in the sea, so from the viewpoint of environmental pollution, it is still hoped that the use of chemicals can be avoided. Others, such as industrial water used in the papermaking process of the paper and pulp industry, circulating water, water in the cooling towers of factories and buildings, etc., the oxidizing property of the chemical and the effect on pH when using the chemical are promoted Concerns about corrosion of equipment components and instruments. In addition, there are concerns about the mixing of chemicals into products in the case of industrial water. In these applications, the characteristics of the material of the present invention can be utilized, that is, the elution of unnecessary active ingredients can be suppressed.

在該等用途上適用本發明的材料時，基本上如本材料與水接觸，則可得抗微生物、抗病毒及/或防藻效果，所以甚麼樣的使用形態都可以。最簡單的是將本發明的材料直接浸漬於水。由有效成分能有效作用的觀點而言以比表面積比較大的膜狀、纖維狀為理想，但由製造的容易度、使用後回收的簡單度、強度等之點而言以膜狀 最為理想。又，在與水接觸的構件黏貼本發明的材料的膜狀物，或也有在構件表面覆蓋的方法。又，在儲水的情況，在玻璃珠、石、陶瓷塊、陶瓷片等固形物覆蓋本發明的材料後將其沈入，或亦有覆蓋在塑膠球等使其漂浮等方法。例如在養殖用或鑑賞用的飼養用水槽，有必要防止魚類等飼養生物感染病毒、或在不讓藻(苔)生長飼養箱的玻璃等，因而需要以不影響飼養生物之方式實施抗微生物、抗病毒及/或防藻處理。例如有將本發明的材料覆蓋的小石舖滿水槽底，或在飼養箱的玻璃內面事先覆蓋本發明的材料等方法。 When the material of the present invention is applied to these applications, basically, if the material is in contact with water, it can obtain anti-microbial, anti-viral and/or anti-algae effects, so it can be used in any form. The simplest is to directly immerse the material of the present invention in water. From the point of view that the active ingredients can effectively function, the film shape and fibrous shape with a relatively large specific surface area are ideal, but in terms of ease of manufacture, ease of recycling after use, and strength, the film shape is preferred. The most ideal. In addition, there is a method of sticking a film of the material of the present invention to a member in contact with water, or covering the surface of the member. In addition, in the case of water storage, solid objects such as glass beads, stones, ceramic blocks, ceramic sheets, etc. are covered with the material of the present invention and then sunk, or there are methods such as covering plastic balls to float them. For example, in the breeding water tank for breeding or appreciation, it is necessary to prevent the infection of virus by breeding organisms such as fish, or the glass of the breeding tank that does not allow algae (moss) to grow. Therefore, it is necessary to implement antimicrobial, Anti-virus and/or anti-algae treatment. For example, there are methods such as covering the bottom of the water tank with small stones covered with the material of the present invention, or covering the material of the present invention on the glass inner surface of the terrarium in advance.

但是，在水中溶解藥劑的方法是可使有效成分普遍達到水全域，而與此不同，本發明的材料的情況是其效果僅及於與材料接觸的水而已。亦即，僅在受限定的場所設置本材料，且水不太動的情況時，抗微生物、抗病毒及/或防藻效果不會遍及水全體。於是，有需要在底面全面舖滿覆蓋本材料的東西，或在與水接觸的構成材料的全面覆蓋本材料等，此時也會有需要相當多成本的情況。因此，將本材料使用於儲水時以使水全體循環為有效。此時，將本材料以適當的形態充填而構成管柱，使水通過此管柱，或在攪拌裝置的攪拌翼表面黏貼或覆蓋本材料，則可進行有效處理。 However, the method of dissolving the medicament in the water allows the effective ingredients to reach the entire water in general. Unlike this, in the case of the material of the present invention, its effect is only as good as the water in contact with the material. That is, when the material is only installed in a restricted place and the water is not too mobile, the anti-microbial, anti-viral and/or anti-algae effects will not spread over the entire water. Therefore, it is necessary to cover the entire bottom surface of the material, or to cover the entire surface of the constituent material in contact with water. In this case, a considerable amount of cost may be required. Therefore, when this material is used for water storage, it is effective to circulate the entire water. At this time, the material is filled in an appropriate form to form a pipe column, and water is passed through the pipe column, or the material is pasted or covered on the surface of the stirring wing of the stirring device for effective treatment.

本發明的抗微生物、抗病毒及/或防藻材料，可使用於防止在船的船底外面有藤壺等的貝類及藻附著、成長，而使推進時的阻力增大。此時，有在船底外面 覆蓋本材料，或黏貼膜的方法。如以往的方法，也可有將銅化合物等有效成分混合於塗料進行塗布的方法，但這樣容易引起有效成分的過度溶出之故，容易引起海洋、河川、湖水等的環境污染。本發明的材料在沒有多餘成分的溶出下仍可得效果，因而可減少污染。 The anti-microbial, anti-virus and/or anti-algae material of the present invention can be used to prevent shellfish and algae such as barnacles from attaching and growing on the outside of the bottom of a ship, thereby increasing the resistance during propulsion. At this time, there is outside the bottom of the ship The method of covering this material or pasting film. As in the conventional method, there may also be a method of mixing active ingredients such as copper compounds in the paint and coating, but this is likely to cause excessive elution of the active ingredients, and it is easy to cause environmental pollution such as oceans, rivers, and lakes. The material of the present invention can still obtain effects without the dissolution of redundant components, thereby reducing pollution.

本發明的材料不僅是對儲水、循環水等恆常地浸漬於水的環境，也可做為在用水環境、濕潤環境中的抗微生物、抗病毒及/或防藻材料使用。在該等的用途上，係以在該等環境中的物品表面覆蓋本材料的方法為中心。例如，浴室的牆壁、地板、排水口，或在該處使用的所有東西係為對象。該等的大半通常是由有機聚合物(塑膠)所成，但針對該等的表面，本材料可形成安定的覆蓋膜。又，本發明的材料是由無機/有機混成化合物所形成，由於對無機物也有高的親和性，牆壁、地板、浴缸，窗等由水泥、磁磚、陶器，玻璃等無機物質所形成時也可將本材料安定的覆蓋。其他在廚房、洗手間、廁所的用水環境中使用的所有物件，如臉盆、桶、水盆、水桶、垃圾容器等也為對象。這種情況時，對無機物質的陶器所形成的洗手間的水槽、便器等也可形成安定的覆蓋膜。對調理器具、其他所謂的廚房用品也可使用，對水壺、便當容器等的密封襯墊(packing)也可使用。 The material of the present invention is not only for the environment that is constantly immersed in water such as water storage and circulating water, but also can be used as an antimicrobial, antiviral and/or anti-algae material in a water environment and a humid environment. In these uses, it is centered on the method of covering the surface of articles in these environments with this material. For example, bathroom walls, floors, drains, or everything used there are objects. Most of these are usually made of organic polymers (plastics), but for these surfaces, this material can form a stable covering film. In addition, the material of the present invention is formed by an inorganic/organic hybrid compound, and because it has a high affinity for inorganic substances, walls, floors, bathtubs, windows, etc. can also be formed by inorganic substances such as cement, tiles, pottery, and glass. Cover this material stably. All other objects used in the water environment of kitchens, washrooms, and toilets, such as washbasins, buckets, basins, buckets, garbage containers, etc., are also targeted. In this case, a stable cover film can also be formed on the sink, toilet, etc. of the toilet made of ceramics made of inorganic substances. It can also be used for conditioning appliances and other so-called kitchen products, and it can also be used for packing such as kettles and lunch containers.

又，做為在濕潤環境使用的東西之在塑膠溫室使用的聚乙烯薄片容易長藻，有妨礙植物的生育所需要的光的供給的問題，可考慮在此聚乙烯薄片上覆蓋本材 料的方法。 In addition, polyethylene sheets used in plastic greenhouses, which are used in humid environments, tend to grow algae, which hinders the supply of light necessary for the growth of plants. Consider covering this polyethylene sheet with this material. Material method.

本發明的材料在不是特別濕潤的環境、在通常的大氣環境下也可做為抗微生物、抗病毒及/或防藻材料使用。例如門窗、家具、文具、玩具、美容用品、儀器的開關類等，對日常與皮膚接觸的東西中任何東西都可適用。特別是適用於醫院內的該等東西時，對院內感染的抑制有效。又，亦可利用於各種醫療器具。對於該等用途，可將本發明的材料的膜狀物黏貼在該等的表面、或將本發明的材料覆蓋在該等的表面使用。 The material of the present invention can also be used as an anti-microbial, anti-viral and/or anti-algae material in an environment that is not particularly humid or in a normal atmospheric environment. For example, doors and windows, furniture, stationery, toys, beauty products, equipment switches, etc., can be applied to anything that comes in contact with the skin on a daily basis. Especially when it is applied to such things in a hospital, it is effective in suppressing nosocomial infection. In addition, it can also be used in various medical devices. For these applications, the film of the material of the present invention can be pasted on these surfaces, or the material of the present invention can be covered on these surfaces for use.

例如在家畜、鳥、其他動物的飼養場中，對在其中使用的所有東西將本材料預先覆蓋在表面、或預先黏貼在表面，則有用於防止菌、病毒的感染。特別是對帶菌或病毒的鳥由外面飛來而引起的禽流感等疾病的感染，係有可能藉由採用以覆蓋了本材料的網來圍起來等方法來防止。 For example, in livestock, bird, and other animal farms, pre-covering or pre-adhering this material on the surface of everything used in it can be used to prevent bacterial and virus infection. In particular, the infection of bird flu and other diseases caused by birds with bacteria or viruses flying from outside may be prevented by using a net covered with this material to enclose it.

在多孔質材的網、網篩、紡織物、不織布等的表面覆蓋本發明的材料，可做為具有抗微生物、抗病毒及/或防藻作用的過濾器使用。在將氣體強制地循環下，使其通過該過濾器而使其接觸，藉此可使空氣中的菌、病毒不會增加，或可使其減少。因此，可以做為空氣清淨機的空氣過濾器使用。又，由同樣的作用可做為口罩使用。 Covering the surface of porous material nets, mesh screens, woven fabrics, non-woven fabrics, etc. with the material of the present invention can be used as a filter with antimicrobial, antiviral and/or anti-algae effects. When the gas is forcedly circulated, it is allowed to pass through the filter to make it contact, so that bacteria and viruses in the air will not increase or can be reduced. Therefore, it can be used as an air filter of an air cleaner. In addition, it can be used as a mask by the same function.

其次，說明本發明的抗微生物、抗病毒及/或防藻材料的製造製程。第2圖是表示本材料的製造製程的第1實施形態的概略系統圖。首先，作為原料者而在 步驟1準備溶媒，在步驟2準備銀或銅的鹽，在步驟3準備銀或銅的鹽以外的無機鹽或含氧酸鹽，在步驟4準備有羥基的有機聚合物，在步驟5將該等原料混合，而得溶媒中有銀或銅的鹽、及其以外的無機鹽或含氧酸鹽及具有羥基的有機聚合物共存的混合溶液。步驟1至4的準備製程的順序並無限定，在步驟5中混合該等原料的順序也沒有限定。溶媒是以含有水為理想。又，銀或銅的鹽、其以外的無機鹽、含氧酸鹽、或含有羥基的有機聚合物可以是任一組成的東西，但以能溶解於水者為理想。例如，在步驟2中，就銀或銅的鹽而言可使用硝酸銀、氯化銅等，也可以為該等的水合物。在步驟3中，就銀或銅的鹽以外的無機鹽或含氧酸鹽而言，可使用鋯鹽、氧化鋯鹽、矽酸鹽等。又，例如做為步驟4的具有羥基的有機聚合物而使用聚乙烯醇時，為了要使在後製程中將水除去而成形的製程，可以在生產上的實際時間範圍內實行起見，在步驟5的混合溶液中，理想是使聚乙烯醇的濃度為5重量%以上，較理想為10重量%以上。又，使用銀鹽時，為了要防止由光造成的銀鹽的還原，較宜為在此製程中把光遮斷後實施。 Next, the manufacturing process of the anti-microbial, anti-viral and/or anti-algae material of the present invention will be described. Figure 2 is a schematic system diagram showing the first embodiment of the manufacturing process of this material. First of all, as the raw material Prepare solvent in step 1, prepare silver or copper salt in step 2, prepare inorganic salt or oxo acid salt other than silver or copper salt in step 3, prepare organic polymer with hydroxyl in step 4, and prepare it in step 5. Such raw materials are mixed to obtain a mixed solution in which a salt of silver or copper, other inorganic salts or oxo acid salts, and an organic polymer having a hydroxyl group coexist in the solvent. The order of the preparation process of steps 1 to 4 is not limited, and the order of mixing the raw materials in step 5 is also not limited. The solvent is ideally containing water. In addition, silver or copper salts, other inorganic salts, oxo acid salts, or hydroxyl-containing organic polymers may have any composition, but those that are soluble in water are preferred. For example, in step 2, silver or copper salts may be silver nitrate, copper chloride, etc., or may be hydrates of these. In step 3, for inorganic salts or oxo acid salts other than silver or copper salts, zirconium salts, zirconium oxide salts, silicates, etc. can be used. In addition, for example, when polyvinyl alcohol is used as the organic polymer having a hydroxyl group in step 4, the process of shaping in order to remove water in the subsequent process can be carried out within the actual production time range. In the mixed solution of step 5, it is desirable that the concentration of polyvinyl alcohol is 5% by weight or more, more desirably 10% by weight or more. In addition, when silver salt is used, in order to prevent the reduction of silver salt caused by light, it is better to cut off the light during this process.

其次，在步驟3的銀或銅的鹽以外的無機鹽或含氧酸鹽是鋯鹽、氧化鋯鹽等能以鹼中和者的情況時，在步驟6係將混合溶液中的銀或銅的鹽及其以外的無機鹽或含氧酸鹽以鹼中和，在步驟7得到中和後的原料溶液。在步驟3的銀或銅的鹽以外的無機鹽或含氧酸鹽是矽酸鹽等能以酸中和者的情況時，在步驟6係將混合溶液中的銀 或銅的鹽以外的無機鹽或含氧酸鹽以酸中和，在步驟7得到中和後的原料溶液。然後在步驟8將溶媒除去，在步驟9得到本發明的材料的成形體。在步驟7的中和後的原料液有由中和生成的不要的鹽存在時，在步驟9得到成形物之後，可將其水洗而除去不要的鹽。 Secondly, when the inorganic salt or oxo acid salt other than the silver or copper salt in step 3 is a zirconium salt or a zirconia salt that can be neutralized with alkali, step 6 is to remove the silver or copper in the mixed solution. The salt and other inorganic salts or oxo acid salts are neutralized with alkali, and a neutralized raw material solution is obtained in step 7. When the inorganic salt or oxo acid salt other than the silver or copper salt in step 3 is a silicate that can be neutralized with acid, step 6 is to remove the silver in the mixed solution. Or inorganic salts or oxo acid salts other than copper salts are neutralized with an acid, and a neutralized raw material solution is obtained in step 7. Then, in step 8, the solvent is removed, and in step 9, a molded body of the material of the present invention is obtained. When the raw material liquid after neutralization in step 7 contains unnecessary salt produced by neutralization, after the molded product is obtained in step 9, it can be washed with water to remove the unnecessary salt.

在第2圖的步驟5的原料液中，銀或銅的鹽及其以外的無機鹽或含氧酸鹽以及具有羥基的有機聚合物係溶解而以分子層級混合。在此狀態中，在步驟6實施中和操作時，無機鹽或含氧酸鹽被中和，成為無機氧化物或其衍生物。剛產生的小的無機氧化物或其衍生物是不安定的，如附近有具有羥基的有機聚合物時，會與其羥基鍵合。如此，無機氧化物或其衍生物與有機聚合物形成經化學鍵結的無機/有機混成化合物。此時，無機氧化物或其衍生物因與有機聚合物進行化學鍵結而成長受阻，停留於奈米粒子。銀或銅的鹽，在步驟6的中和操作以鹼實施時，係成為以氧化物、氫氧化物等形態被攝入於無機/有機混成化合物的狀態，或成為其本身也與有機聚合物進行化學鍵結的狀態，但不論哪一種情況都會停留於奈米粒子。步驟6的中和操作是以酸實施時，銀或銅的鹽在中和後也以鹽的狀態被攝入於無機/有機混成化合物中。因此，在這個情況時銀或銅的鹽不只在中和操作之前，在之後添加也可以。不論哪一種情況銀或銅的化合物都在無機/有機混成化合物中生成，所以不會變成大的粒子。 In the raw material liquid of step 5 in Fig. 2, the salt of silver or copper, other inorganic salts or oxo acid salts, and the organic polymer system having a hydroxyl group are dissolved and mixed at a molecular level. In this state, when the neutralization operation is performed in step 6, the inorganic salt or oxo acid salt is neutralized to become an inorganic oxide or its derivative. The newly produced small inorganic oxide or its derivative is unstable, and if there is an organic polymer having a hydroxyl group nearby, it will bond with its hydroxyl group. In this way, the inorganic oxide or its derivative and the organic polymer form a chemically bonded inorganic/organic hybrid compound. At this time, the inorganic oxide or its derivative is chemically bonded to the organic polymer, which hinders the growth and stays in the nanoparticle. The salt of silver or copper, when the neutralization operation of step 6 is carried out with an alkali, is in a state of being taken up in the inorganic/organic mixed compound in the form of oxides, hydroxides, etc., or it is also in a state of being combined with an organic polymer. It is in the state of chemical bonding, but in either case it will stay in the nanoparticle. When the neutralization operation in step 6 is carried out with an acid, the silver or copper salt is also taken into the inorganic/organic mixed compound as a salt after neutralization. Therefore, in this case, the silver or copper salt can be added not only before the neutralization operation, but also afterwards. In either case, silver or copper compounds are generated in the inorganic/organic hybrid compound, so they will not become large particles.

在步驟6中和原料溶液中的無機鹽或含氧 酸鹽的酸，只要是能實施該等的中和的酸則甚麼樣的酸都可以。例如，可使用鹽酸、硫酸、硝酸、磷酸、乙酸、質子型的陽離子交換性樹脂等。在步驟6中和原料溶液中的無機鹽或含氧酸鹽的鹼，只要能實施該等的中和的鹼則甚麼樣的鹼都可以。例如，可使用氫氧化鈉、氫氧化鉀、氫氧化鋰、氨、氫氧化鈣、氫氧化鍶、氫氧化鋇、碳酸鹽、氫氧化物離子型的陰離子交換性樹脂等。該等的酸、鹼可以單獨使用，亦可多數混合的狀態使用。 In step 6, neutralize the inorganic salt or oxygen in the raw material solution The acid of the acid salt may be any acid as long as it can perform such neutralization. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, proton-type cation exchange resin, etc. can be used. In step 6, the base of the inorganic salt or oxo acid salt in the raw material solution is neutralized, and any base can be used as long as the base can be neutralized. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, calcium hydroxide, strontium hydroxide, barium hydroxide, carbonate, hydroxide ion type anion exchange resin, etc. can be used. These acids and bases can be used alone or in a mixed state.

在既有的固形物表面覆蓋本材料時，將步驟7的原料溶液在對象物表面塗布之後，在步驟8除去溶媒(乾燥)，在步驟9得到本材料的覆蓋膜。例如，在網的表面形成本材料的覆蓋膜時，可將步驟7的原料溶液直接塗布或噴霧，或將網浸漬於原料液後拉出等之後，加熱除去溶媒(乾燥)等方法實施。 When covering this material on the surface of an existing solid object, after applying the raw material solution of step 7 to the surface of the object, the solvent is removed in step 8 (drying), and a covering film of this material is obtained in step 9. For example, when forming a coating film of this material on the surface of the net, the raw material solution of step 7 may be directly applied or sprayed, or the net may be immersed in the raw material liquid and drawn out, and then heated to remove the solvent (drying).

第3圖是表示本材料的製造製程的第2實施形態的概略系統圖。經由與第2圖同樣的製程，在步驟5得到銀或銅的鹽及其以外的無機鹽或含氧酸鹽以及具有羥基的有機聚合物共存的混合溶液。其次，在步驟6除去溶媒。在步驟7做成銀或銅的鹽及其以外的無機鹽或含氧酸鹽以及具有羥基的有機聚合物的混合物所成形的固形物。在步驟8使其與酸或鹼接觸而將無機鹽或含氧酸鹽中和。在步驟9得到本材料的成形體。在步驟8中，使其與酸或鹼接觸的方法而言，有在酸或鹼的溶液浸漬、或將酸或鹼溶液在步驟7的混合物塗布或噴霧、或暴露於蒸氣等方 法。第3圖的步驟8的中和製程中也與第2圖時的原理同樣進行混成化，銀或銅的化合物或其以外的無機氧化物或其衍生物停留於如奈米粒子般的微細粒子。 Fig. 3 is a schematic system diagram showing the second embodiment of the manufacturing process of this material. Through the same process as in Fig. 2, in step 5, a mixed solution in which a silver or copper salt, other inorganic salts or oxo acid salts, and an organic polymer having a hydroxyl group coexist is obtained. Next, in step 6, the solvent is removed. In step 7, a solid formed of a mixture of a silver or copper salt, other inorganic salts or oxo acid salts, and an organic polymer having a hydroxyl group is formed. In step 8, it is brought into contact with an acid or a base to neutralize the inorganic salt or oxo acid salt. In step 9, a molded body of this material is obtained. In step 8, the method of bringing it into contact with an acid or alkali includes dipping in an acid or alkali solution, coating or spraying the mixture of the acid or alkali solution in step 7, or exposing to steam. Law. In the neutralization process of step 8 in Fig. 3, mixing is carried out in the same principle as in Fig. 2, and silver or copper compounds or other inorganic oxides or derivatives thereof stay in fine particles like nanoparticles. .

根據第2實施形態在既有的固形物的表面覆蓋本材料時，將步驟5的混合溶液在對象物表面塗布之後，在步驟6除去溶媒(乾燥)，在步驟7將銀或銅的鹽及其以外的無機鹽或含氧酸鹽以及具有羥基的有機聚合物的混合物的覆蓋膜在對象物表面上成形。在步驟8使其與酸或鹼接觸而中和無機鹽或含氧酸鹽，在步驟9得到本材料的覆蓋膜。在步驟8，與酸或鹼接觸的方法而言，有浸漬於酸或鹼的溶液、或將酸或鹼溶液在步驟7的混合物的覆蓋膜塗布或噴霧、或暴露於蒸氣等方法。 When covering the surface of an existing solid object with this material according to the second embodiment, the mixed solution of step 5 is applied to the surface of the object, the solvent is removed (drying) in step 6, and the silver or copper salt and The coating film of the mixture of the other inorganic salt or oxyacid salt and the organic polymer having a hydroxyl group is formed on the surface of the object. In step 8, it is brought into contact with an acid or alkali to neutralize the inorganic salt or oxo acid salt, and in step 9, a covering film of this material is obtained. In step 8, the method of contacting with acid or alkali includes immersing in an acid or alkali solution, coating or spraying the cover film of the mixture of the acid or alkali solution in step 7, or exposing to steam.

以如第2圖或第3圖的方法可製造無機氧化物或其衍生物與具有羥基的有機聚合物進行化學鍵結而成的無機/有機混成化合物。此混成化合物是有機聚合物由無機氧化物或其衍生物的奈米粒子交聯所以不溶解於水。然後，由無機氧化物或其衍生物的奈米粒子、或有機聚合物的未鍵結的殘留羥基等的作用而親水性高，有吸水的性質。如前所述，由於此耐水性及吸水性兩者兼具，而可實現良好的抗微生物、抗病毒及/或防藻作用。又，採取將既成的銀、銅或其化合物在之後揉入的方法時，無法將該等的粒子製成那麼細小，但如本發明的方法，將銀、銅的成分從原料液的階段導入，在無機/有機混成化合物的生成過程同時該等的化合物也生成，而可製成如奈米粒子般 非常微細的粒子。如前所述，由此可得到最後為止把有效成分完全用完，或提高固定在表面的粒子直接攻撃微生物、病毒時的活性，或提高將病毒攝入於內部進行攻撃時的活性等效果。銀或銅的金屬或化合物的微粒子(奈米粒子)的程度，係成為比如無機/有機混成化合物的無機氧化物是鋯的氧化物的情況般，在第2圖的步驟6或第3圖的步驟8的中和操作是由鹼實施、銀或銅的鹽也受中和的情況更微細的東西。由此點考量，做為無機氧化物而言特別是以鋯的氧化物為理想，此時做為製造方法而言以第3圖的第2實施形態較為理想。 By the method shown in Figure 2 or Figure 3, an inorganic/organic hybrid compound formed by chemically bonding an inorganic oxide or its derivative and an organic polymer having a hydroxyl group can be produced. This hybrid compound is an organic polymer cross-linked by nanoparticles of inorganic oxide or its derivatives, so it is insoluble in water. Then, the nano particles of inorganic oxides or derivatives thereof, or the unbonded residual hydroxyl groups of organic polymers, etc., have high hydrophilicity and have water-absorbing properties. As mentioned above, due to the combination of water resistance and water absorption, good anti-microbial, anti-viral and/or anti-algae effects can be achieved. Also, when the method of kneading the existing silver, copper or its compound later, the particles cannot be made so small, but like the method of the present invention, the silver and copper components are introduced from the stage of the raw material liquid , In the process of the formation of inorganic/organic hybrid compounds, these compounds are also generated, and can be made into nano-particles. Very fine particles. As mentioned above, it is possible to obtain the effect of completely using up the active ingredients until the end, or improving the activity when the particles fixed on the surface directly attack microorganisms and viruses, or improving the activity when the virus is taken into the inside to attack. The degree of fine particles (nanoparticles) of silver or copper metal or compound is like the case where the inorganic oxide of the inorganic/organic hybrid compound is zirconium oxide. The neutralization operation in step 8 is carried out by alkali, and the situation where the salt of silver or copper is also neutralized is more subtle. From this point of view, as an inorganic oxide, zirconium oxide is particularly preferable. In this case, as a manufacturing method, the second embodiment shown in Fig. 3 is preferable.

在第2圖或第3圖的步驟9的階段，藉由成為成形體之後又在80至170℃繼續加熱，將混成化的反應更推進，可提高本材料的強度。又，以第2圖或第3圖的方法製造的無機/有機混成化合物中的銀或銅的化合物，以適當的還原劑還原，亦可成為金屬狀態。 At the stage of step 9 in Fig. 2 or Fig. 3, by continuing to heat at 80 to 170°C after forming a molded body, the reaction of mixing is further advanced, and the strength of the material can be improved. In addition, the silver or copper compound in the inorganic/organic hybrid compound produced by the method shown in FIG. 2 or FIG. 3 may be reduced with a suitable reducing agent to become a metallic state.

要獲得本材料的膜狀物時，將在第2圖的步驟7的原料液或第3圖的步驟5的混合溶液在平面的基材上澆下、或在要覆蓋的對象物表面塗布而製造。此時，在某種程度將溶媒揮發的狀態再澆下或塗布第二層，將其反覆操作而可覆蓋多數層。也可以改變各層的組成，例如由改變各層的銀或銅的濃度，可對於膜狀物的厚度方向產生濃度梯度。在水環境下使用的情況時，容易引起有效成分的過度放出之故，使膜狀物表面側的有效成分濃度比內部側低以抑制放出速度的方法係為有效者。該狀態可藉由使 表面側層的銀或銅成分的濃度比內部側層低而實現。另一方面，在通常的乾燥環境中使用的情況時，反過來不容易引起有效成分的放出、效果不容易顯現之故，反而使膜狀物的表面側層的有效成分濃度比內部側高乃為有效者。該狀態可藉由使表面側層的銀或銅成分的濃度比內部側層高而實現。 To obtain a film of this material, the raw material solution in step 7 in Figure 2 or the mixed solution in step 5 in Figure 3 is poured on a flat substrate or coated on the surface of the object to be covered. manufacture. At this time, the solvent is volatilized to a certain extent, and then the second layer is poured or coated, and the operation is repeated to cover many layers. The composition of each layer can also be changed. For example, by changing the concentration of silver or copper in each layer, a concentration gradient can be generated in the thickness direction of the film. When used in a water environment, it is easy to cause excessive release of the active ingredient. Therefore, it is effective to reduce the concentration of the active ingredient on the surface side of the membrane material than the inner side to suppress the rate of release. This state can be The concentration of the silver or copper component of the surface side layer is lower than that of the inner side layer. On the other hand, when used in a normal dry environment, it is not easy to cause the release of effective ingredients and the effect is not easy to manifest. On the contrary, the concentration of effective ingredients on the surface side layer of the membrane is higher than that on the inner side. Effective. This state can be achieved by making the concentration of the silver or copper component of the surface side layer higher than that of the inner side layer.

[實施例] [Example]

以下說明本發明的抗微生物、抗病毒及/或防藻材料的實施例。又，本申請發明不受該等實施例所述內容的任何限定。 Examples of the anti-microbial, anti-viral and/or anti-algae material of the present invention will be described below. In addition, the invention of this application is not limited in any way by the content described in these embodiments.

例1 example 1

將含有銀做為有效成分的本發明的抗微生物、抗病毒及/或防藻材料膜依據第3實施形態製作，製成對於膜狀物的厚度方向有銀成分的濃度梯度、銀成分的濃度在內部比在表面高的膜。 The antimicrobial, antiviral and/or algae-preventing material film of the present invention containing silver as an active ingredient is produced according to the third embodiment, and the thickness direction of the film is made to have a silver component concentration gradient and a silver component concentration A film that is higher on the inside than on the surface.

在聚合度為3100至3900、皂化度為86至90%的聚乙烯醇10重量%水溶液90g添加硝酸銀(AgNO₃)0.7g及氧化氯化鋯八水合物(ZrCl₂O‧8H₂O)4g，為了防止硝酸銀的光還原而在以鋁箔遮光的狀態下攪拌同時在50℃加熱1小時，調製混合溶液A。又，在聚合度為3100至3900、皂化度為86至90%的聚乙烯醇10重量%水溶液90g添加氧化氯化鋯八水合物(ZrCl₂O‧8H₂O)4g，攪拌同時在50℃加熱1小時，調製混合溶液B。亦即在混合溶液A中加入銀化合物，在混合溶液B中未加入銀化合物。 _{Add 0.7g of silver nitrate (AgNO 3} ) and 4g of zirconium oxychloride octahydrate (ZrCl ₂ O‧8H ₂ O) to 90 g of a 10% by weight aqueous solution of polyvinyl alcohol with a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90%. In order to prevent the photoreduction of silver nitrate, the mixed solution A was prepared by heating at 50° C. for 1 hour while stirring with the aluminum foil shielded from light. In addition, 4 g of _{zirconium oxide chloride octahydrate (ZrCl 2} O‧8H ₂ O) was added to 90 g of a 10% by weight aqueous solution of polyvinyl alcohol with a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90%. Heat for 1 hour to prepare mixed solution B. That is, the silver compound is added to the mixed solution A, and the silver compound is not added to the mixed solution B.

其次，將此混合溶液，在裝配有刀片(其係使用微測距計而可調節其與台座之間的間隙者)的覆蓋(coating)裝置(R K Print Coat Instruments Ltd.製K Control coater 202)的平滑台座上所舖平的聚酯膜上澆下混合溶液B。此時將台座加熱控制成為70℃。將混合溶液B在台座的上澆下之後，即刻將間隙調節為0.4mm的刀片以一定速度在混合溶液B上掃平而成為一定厚度。再者，在70℃加熱下放置而使水分揮發，在流動性大約消失的階段將混合溶液A從上面重疊澆下，再度即刻將間隙調節為0.6mm的刀片以一定速度在混合溶液A上掃平。再在70℃加熱下放置使水分揮發，在流動性大約消失的階段再度將混合溶液B由上面重疊澆下，即刻將間隙調節為0.4mm的刀片以一定速度在原料溶液B上掃平。在70℃加熱下放置使水分揮發，在流動性大約消失的階段將台座的溫度升高至130℃，保持該狀態實施1.5小時的加熱處理。然後，將台座上生成的膜剝離，在0.2N的氫氧化鈉水溶液中常溫浸漬18小時後，在60℃至70℃的熱水中清洗30分鐘左右。在室溫下乾燥後，在120℃加熱處理1小時，再度在90℃的熱水中清洗1小時左右，製成膜1。膜1含有平均1.3wt%的銀。 Secondly, apply this mixed solution to a coating device (K Control coater 202 made by RK Print Coat Instruments Ltd.) equipped with a blade (which uses a micro distance meter to adjust the gap between it and the pedestal). Pour mixed solution B on the flat polyester film on the smooth pedestal. At this time, the heating of the pedestal was controlled to 70°C. After the mixed solution B is poured on the pedestal, the blade with the gap adjusted to 0.4 mm is immediately leveled on the mixed solution B at a certain speed to become a certain thickness. In addition, place it under heating at 70°C to volatilize the water. At the stage when the fluidity is about to disappear, the mixed solution A is poured over from above, and the blade with the gap adjusted to 0.6mm is immediately leveled on the mixed solution A at a certain speed. . Then place it under heating at 70°C to volatilize the water. At the stage when the fluidity is about to disappear, the mixed solution B is poured again from the top, and the blade with the gap adjusted to 0.4mm is immediately leveled on the raw material solution B at a certain speed. It was left under heating at 70°C to volatilize water, the temperature of the pedestal was raised to 130°C at the stage when the fluidity was about to disappear, and the heat treatment was performed for 1.5 hours while maintaining this state. Then, the film formed on the pedestal was peeled off, and after being immersed in a 0.2N sodium hydroxide aqueous solution at room temperature for 18 hours, it was washed in hot water at 60°C to 70°C for about 30 minutes. After drying at room temperature, it was heat-treated at 120°C for 1 hour, and then washed in hot water at 90°C for about 1 hour to form a film 1. Film 1 contains an average of 1.3 wt% silver.

如本例，由本材料塗布三層而製作，由於只有內部層為具有銀化合物的混合溶液A，而可製造內部的銀成分濃度高、在表面附近的濃度低的膜狀物。 As in this example, it is made by coating three layers of this material. Since only the inner layer is the mixed solution A containing the silver compound, it is possible to produce a film with a high concentration of the silver component inside and a low concentration near the surface.

例2 Example 2

將含有銀做為有效成分的本發明的抗微生物、抗病毒及/或防藻材料的膜依據第3實施形態製作，並且對於膜狀物的厚度方向具有銀成分的濃度梯度，製成表面的銀成分濃度比內部高的膜。 The film of the antimicrobial, antiviral and/or algae-preventing material of the present invention containing silver as an active ingredient is produced according to the third embodiment, and has a concentration gradient of the silver component in the thickness direction of the film, and is made into a surface A film with a higher concentration of silver content than the inside.

在聚合度為3100至3900、皂化度為86至90%的聚乙烯醇10重量%水溶液90g添加氧化氯化鋯八水合物(ZrCl₂O‧8H₂O)2g及硝酸銀0.05g，為了防止硝酸銀的光還原而在以鋁箔遮光的狀態下攪拌同時在50℃加熱1小時，調製成混合溶液A。又，在聚合度為3100至3900、皂化度為86至90%的聚乙烯醇10重量%水溶液90g添加氧化氯化鋯八水合物(ZrCl₂O‧8H₂O)2g，攪拌同時在50℃加熱1小時，調製成混合溶液B。即在混合溶液A中加入銀化合物、在混合溶液B中未加入銀化合物。 _{Add 2} g of zirconium oxide chloride octahydrate (ZrCl 2 O‧8H ₂ O) and 0.05 g of silver nitrate to 90 g of a 10% by weight aqueous solution of polyvinyl alcohol with a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90% to prevent silver nitrate The light was reduced and heated at 50°C for 1 hour while stirring in a state where the aluminum foil was shielded from light, to prepare a mixed solution A. _{In addition, 2} g of zirconium oxide chloride octahydrate (ZrCl 2 O‧8H ₂ O) was added to 90 g of a 10% by weight aqueous solution of polyvinyl alcohol with a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90%. Heat for 1 hour to prepare mixed solution B. That is, the silver compound is added to the mixed solution A, and the silver compound is not added to the mixed solution B.

其次，將此混合溶液，在裝配有刀片(其係使用微測距計而可調節其與台座之間的間隙者)的覆蓋裝置(R K Print Coat Instruments Ltd.製K Control coater 202)的平滑台座上所舖平的聚酯膜上澆下混合溶液A。此時將台座加熱控制成為70℃。將混合溶液A在台座上澆下之後，即刻將間隙調節成為0.3mm的刀片以一定的速度在混合溶液A上掃平而成為一定的厚度。再者，在70℃加熱同時放置使水分揮發，在流動性大約消失的階段將混合溶液B從上面重疊澆下，再度即刻將間隙調節為0.6mm的刀片以一定的速度在混合溶液B上掃平。再者，在70℃加熱同時放置使水分揮發，在流動性大約消失的階段再度將混合 溶液A從上面重疊澆下，即刻將間隙調節為0.4mm的刀片以一定的速度在混合溶液A上掃平。在70℃加熱同時放置使水分揮發，在流動性大約消失的階段將台座的溫度提高至130℃，保持該狀態1.5小時實施加熱處理。然後，將在台座上生成的膜剝離，在0.2N的氫氧化鈉水溶液中常溫浸漬18小時之後，在60℃至70℃的熱水中清洗30分鐘左右。在室溫乾燥後，在120℃實施加熱處理1小時，再度在90℃的熱水中清洗1小時左右，製成膜2。 Next, apply this mixed solution to a smooth base equipped with a covering device (K Control coater 202 made by RK Print Coat Instruments Ltd.) equipped with a blade (which uses a micro distance meter to adjust the gap between it and the base) Pour mixed solution A on the flat polyester film. At this time, the heating of the pedestal was controlled to 70°C. After pouring the mixed solution A on the pedestal, the blade with the gap adjusted to 0.3 mm is immediately flattened on the mixed solution A at a certain speed to become a certain thickness. In addition, heat at 70°C while leaving the water to volatilize. At the stage when the fluidity disappears, the mixed solution B is poured from above, and the blade with the gap adjusted to 0.6mm is immediately leveled on the mixed solution B at a certain speed. . In addition, heat at 70°C while leaving it to volatilize the water, and mix again at the stage when the fluidity is about to disappear. Solution A was poured down from above, and the blade with the gap adjusted to 0.4mm was immediately leveled on the mixed solution A at a certain speed. Heat at 70°C while leaving it to volatilize water, raise the temperature of the pedestal to 130°C when the fluidity is about to disappear, and keep this state for 1.5 hours to perform heat treatment. Then, the film formed on the pedestal was peeled off, and after being immersed in a 0.2N sodium hydroxide aqueous solution at room temperature for 18 hours, it was washed in hot water at 60°C to 70°C for about 30 minutes. After drying at room temperature, heat treatment was performed at 120°C for 1 hour, and then washed in hot water at 90°C for about 1 hour to form a film 2.

如本例，由本材料塗布三層而製作，由於只有表面側的層為具有銀化合物的混合溶液A，而可製造表面附近的銀成分濃度高、在內部的濃度低的膜狀物。 As in this example, it is made by coating three layers of this material. Since only the layer on the surface side is the mixed solution A containing the silver compound, it is possible to produce a film with a high concentration of silver near the surface and a low concentration inside.

例3 Example 3

將含有銅做為有效成分的本發明的抗微生物、抗病毒及/或防藻材料膜依照第3實施形態製作。 The antimicrobial, antiviral and/or antialgae material film of the present invention containing copper as an active ingredient is produced in accordance with the third embodiment.

在聚合度為3100至3900、皂化度為86至90%的聚乙烯醇10重量%水溶液90g添加氧化氯化鋯八水合物(ZrCl₂O‧8H₂O)6g及氯化銅二水合物(CuCl₂‧2H₂O)0.3g，攪拌同時在50℃加熱1小時，調製成混合溶液。其次，將此混合溶液，在裝配有刀片(其係使用微測距計而可調節其與台座之間的間隙者)的覆蓋裝置(R K Print Coat Instruments Ltd.製K Control coater 202)的平滑台座上所舖平的聚酯膜上將混合溶液澆下。此時將台座加熱控制成為70℃。將混合溶液在台座上澆下之後，即刻將間隙調節為0.5mm的刀片以一定的速度在混合溶液上掃平而成為一定 的厚度。再者，在70℃加熱同時放置使水分揮發，在流動性大約消失的階段將台座的溫度提高到130℃，保持該狀態實施加熱處理1.5小時。然後，將在台座上生成的膜剝離，在0.1N的氫氧化鈉水溶液中常溫浸漬18小時之後，在60℃至70℃的熱水中清洗30分鐘左右。在室溫乾燥後，在120℃實施加熱處理1小時，再度在90℃的熱水中清洗1小時左右，製成膜3。膜3平均含有1.2wt%的銅。 Add 6 g of zirconium oxide chloride octahydrate (ZrCl ₂ O‧8H ₂ O) and copper chloride dihydrate ( CuCl ₂ ‧2H ₂ O) 0.3g, heated at 50°C for 1 hour while stirring, to prepare a mixed solution. Next, apply this mixed solution to a smooth base equipped with a covering device (K Control coater 202 made by RK Print Coat Instruments Ltd.) equipped with a blade (which uses a micro distance meter to adjust the gap between it and the base) Pour the mixed solution on the flat polyester film. At this time, the heating of the pedestal was controlled to 70°C. After pouring the mixed solution on the pedestal, the blade with the gap adjusted to 0.5mm is immediately flattened on the mixed solution at a certain speed to become a certain thickness. Furthermore, heating was carried out at 70°C while leaving it to volatilize water, the temperature of the pedestal was raised to 130°C at a stage when the fluidity was about to disappear, and the heat treatment was performed for 1.5 hours while maintaining this state. Then, the film formed on the pedestal was peeled off, and after immersing in a 0.1N sodium hydroxide aqueous solution at room temperature for 18 hours, it was washed in hot water at 60°C to 70°C for about 30 minutes. After drying at room temperature, heat treatment was performed at 120°C for 1 hour, and then washed in hot water at 90°C for about 1 hour to form a film 3. The film 3 contains 1.2wt% copper on average.

例4 Example 4

將含有銀做為有效成分的本發明的抗微生物、抗病毒及/或防藻材料的膜依照第3實施形態製作，製成在聚丙烯製的網篩(網)表面覆蓋的東西。 The film of the antimicrobial, antiviral and/or algae-preventing material of the present invention containing silver as an active ingredient is produced in accordance with the third embodiment, and is made to be covered on the surface of a polypropylene mesh (net).

在聚合度為3100至3900、皂化度為86至90%的聚乙烯醇10重量%水溶液90g添加氧化氯化鋯八水合物(ZrCl₂O‧8H₂O)4g及硝酸銀0.4g，為了防止硝酸銀的光還原而在以鋁箔遮光的狀態下攪拌同時在50℃加熱1小時，調製成混合溶液。在此混合溶液將聚丙烯製的網篩(紗門用網)浸漬1小時。取出之後，以吹風機將多餘的混合溶液除去，在130℃實施加熱處理1小時。然後，在0.2N的氫氧化鈉水溶液中常溫浸漬18小時之後，在60℃至70℃的熱水中清洗30分鐘左右。在室溫乾燥後，在120℃實施加熱處理1小時，再度在90℃的熱水中清洗1小時左右，製成以本發明的膜覆蓋的聚丙烯製的網篩(PP網篩)。 _{Add 4 g of zirconium oxide chloride octahydrate (ZrCl 2} O‧8H ₂ O) and 0.4 g of silver nitrate to 90 g of a 10% by weight aqueous solution of polyvinyl alcohol with a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90% to prevent silver nitrate The light was reduced and heated at 50°C for 1 hour while stirring in a state where the aluminum foil was shielded from light, to prepare a mixed solution. In this mixed solution, a polypropylene mesh (net for screen doors) was immersed for 1 hour. After taking it out, the excess mixed solution was removed with a hair dryer, and heat treatment was performed at 130°C for 1 hour. Then, after immersing in a 0.2N sodium hydroxide aqueous solution at room temperature for 18 hours, it is washed in hot water at 60°C to 70°C for about 30 minutes. After drying at room temperature, heat treatment was performed at 120°C for 1 hour, and then washed in hot water at 90°C for about 1 hour to prepare a polypropylene mesh (PP mesh) covered with the film of the present invention.

例5 Example 5

(試驗例1 溶出試驗) (Test Example 1 Dissolution test)

將本發明的膜，添加於各試驗水而以ICP發光分析測定銀、及銅的溶出量。 The film of the present invention was added to each test water, and the elution amount of silver and copper was measured by ICP emission analysis.

調製滅菌水、磷酸緩衝液、及使菌數成為10⁵CFU/mL的方式添加含有黄色葡萄球菌及大腸菌的菌液之磷酸緩衝液(磷酸緩衝液+菌)等各試驗水800mL。將膜1或膜3添加於各試驗水使銀或銅的含量成為約1mg/L以上並攪拌。然後，測定在膜投入前及膜投入3小時後、6小時後、24小時後各試驗水中的銀或銅的濃度。在膜1、膜3的任一種皆未檢出銀、及銅，表示在膜上被安定的固定化。將該測定結果示於第1表、第2表。又，將膜1、膜3浸漬在任一種水時都看到膜的膨張，且變得柔軟，在測定後取出在大氣中放置乾燥時，恢復到原來的大小、硬度。由此確認，該等的膜會明顯的吸水。又，膜1及膜3浸漬在任一種水時，都會吸水但不會溶解，沒有看到膜的劣化。 Prepare sterilized water, phosphate buffer solution, and add 800 mL of each test water such as phosphate buffer solution (phosphate buffer solution + bacteria) containing Staphylococcus aureus and coliform bacteria solution ^{so that the number of bacteria becomes 10 5 CFU/mL.} The film 1 or the film 3 was added to each test water so that the content of silver or copper was about 1 mg/L or more, and stirred. Then, the concentration of silver or copper in each test water was measured before film input and 3 hours, 6 hours, and 24 hours after film input. No silver or copper was detected in either of the film 1 or the film 3, indicating that it was stabilized and immobilized on the film. The measurement results are shown in Table 1 and Table 2. In addition, when the film 1 and the film 3 were immersed in any water, the film swelled and became soft, and when it was taken out after the measurement and left to dry in the air, it returned to its original size and hardness. From this, it was confirmed that these films obviously absorb water. In addition, when the film 1 and the film 3 are immersed in any type of water, they both absorb water but do not dissolve, and no deterioration of the film is seen.

例6 Example 6

(試驗例2 抗菌力試驗) (Test Example 2 Antibacterial power test)

將所製作的膜依照抗菌製品技術協議會的試驗法，實施由振盪燒瓶法的抗菌力評估試驗。 The produced film was subjected to the antibacterial power evaluation test by the shaking flask method in accordance with the test method of the Antibacterial Products Technical Council.

將Staphylococcus aureus、Escherichia coli分別在滅菌過的磷酸緩衝生理食鹽水(KH₂PO₄)添加菌液使菌數成為10⁴至10⁵CFU/mL左右，製成試驗菌液30mL。將其添加於200mL的滅菌過的三角瓶，將膜1或膜3切片後投入使銀或銅成為1mg/L以上，在25±5℃、320至340rpm的條件振盪。然後，在各經過時間(0小時、1小時、3小時、24小時、72小時、168小時)測定活菌數，實施抗菌力的評估。又，在上述操作以沒有添加菌液的處理做為對照。又，製作不含銀及銅的比較膜，做為膜重量投入與膜1或膜3大約同樣的量，對其進行評估(比較例1)。將該等的結 果示於第3表、第4表。膜1及膜3都顯現優異的殺菌效果。 Staphylococcus aureus and Escherichia coli were respectively added to sterilized phosphate buffered saline (KH ₂ PO ₄ ) to make the bacteria count to about 10 ⁴ to 10 ⁵ CFU/mL to prepare 30 mL of test bacteria solution. This was added to a 200 mL sterilized Erlenmeyer flask, the film 1 or film 3 was sliced, and the film 1 or film 3 was sliced and put in so that silver or copper would become 1 mg/L or more, and shaken under the conditions of 25±5° C. and 320 to 340 rpm. Then, the number of viable bacteria was measured at each elapsed time (0 hour, 1 hour, 3 hours, 24 hours, 72 hours, 168 hours), and the antibacterial activity was evaluated. In addition, in the above operation, the treatment without adding bacterial liquid was used as a control. In addition, a comparative film containing no silver and copper was produced, and approximately the same amount as that of the film 1 or the film 3 was added as the film weight, and this was evaluated (Comparative Example 1). These results are shown in Table 3 and Table 4. Both film 1 and film 3 exhibited excellent sterilization effects.

又，試驗使用的菌株是如下2種。 In addition, the strains used in the test were the following two types.

Staphylococcus aureus NBRC12732 Staphylococcus aureus NBRC12732

Escherrichia coli NBRC3972 Escherrichia coli NBRC3972

例7 Example 7

(試驗例3 殺藻試驗) (Test Example 3 Algae Killing Test)

綠藻類是使用Chlorella vulgarris C-135(以下，稱為綠藻)評估膜1及膜3的殺藻效果。 For the green algae, Chlorella vulgarris C-135 (hereinafter referred to as green algae) was used to evaluate the algae killing effect of the membrane 1 and the membrane 3.

將MDM培養基的綠藻前培養液，以蒸餾水稀釋使吸光度O.D.₄₂₀的值成為0.25至0.28，在此投入HEPES(N-2-羥乙基哌嗪-N’-2-乙烷磺酸)使其溶解，HEPES的濃度設成50mM。在此添加苛性鈉，調整pH為8.5。將此試驗液10mL分注於L字型試管，設置在光照射型振盪-恒溫水槽中。將膜1及膜3切片，分別投入使銀或銅成為6mg/L。又，製作與在例6所製作的同樣的比較膜，切片，做為膜重量投入與膜1或膜3同樣的量，對其進行評估。 在30℃，10KLx(明：12小時，暗：12小時)的條件下振盪培養，以目視觀察2日。殺藻效果是依據第5表所述的判定基準評估，將試驗結果示於第6表。 Dilute the green algae pre-culture solution of the MDM medium with distilled water to make the absorbance OD ₄₂₀ value of 0.25 to 0.28, and put in HEPES (N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid). It dissolves, and the concentration of HEPES is set to 50 mM. Add caustic soda here to adjust the pH to 8.5. Dispense 10 mL of this test solution into an L-shaped test tube, and set it in a light-irradiated shaking-thermostat water tank. The film 1 and the film 3 were sliced, and the silver or copper was injected into 6 mg/L, respectively. In addition, the same comparative film as that produced in Example 6 was prepared, sliced, and the same amount as the film 1 or the film 3 was added as the film weight, and the evaluation was performed. The culture was shaken under the conditions of 30°C and 10 KLx (bright: 12 hours, dark: 12 hours), and visual observation was performed for 2 days. The algae killing effect was evaluated based on the criteria described in Table 5, and the test results are shown in Table 6.

例8 Example 8

(試驗例4 病毒不活化試驗) (Test Example 4 Virus inactivation test)

其次實施以例4製作的銀奈米膜處理後的PP製網篩的病毒不活化性能的評估。 Next, the evaluation of the virus inactivation performance of the PP mesh sieves treated with the silver nanomembrane prepared in Example 4 was carried out.

將例4的PP網篩切成約3cm×3cm的大小，將其重疊4張，做為評估對象的PP網篩試驗片。又，做 為比較對照使用玻璃板的試驗片。將流感病毒(influenza A virus(H1N1)A/PR/8/34 ATCC VR-1469)的細胞培養後的流感病毒培養液離心分離，將所得的上澄液以精製水稀釋10倍，製成病毒液。在各試驗片接種病毒液0.2mL，在室溫保存3小時、6小時、24小時。保存後，測定病毒感染價(TCID₅₀/mL)。將該等的結果示於第7表。 The PP mesh sieve of Example 4 was cut into a size of about 3 cm×3 cm, and 4 sheets were stacked to form a PP mesh sieve test piece for evaluation. In addition, a test piece of a glass plate was used as a comparative control. The influenza virus culture solution after cell culture of influenza virus (influenza A virus (H1N1) A/PR/8/34 ATCC VR-1469) is centrifuged, and the resulting supernatant is diluted 10 times with purified water to prepare a virus liquid. Each test piece was inoculated with 0.2 mL of virus solution and stored at room temperature for 3 hours, 6 hours, and 24 hours. After storage, the virus infection price (TCID ₅₀ /mL) was determined. The results are shown in Table 7.

又，病毒感染價的評估，以[R=logB-logA](A：做為比較對照的玻璃板試驗片的病毒感染價，B：評估對象的PP網篩試驗片的病毒感染價)表示的不活化效果R在2以上時，判斷為具有不活化效果。其結果顯示與試驗片接觸24小時後顯現病毒不活化效果。 In addition, the evaluation of the virus infection price is expressed in [R=logB-logA] (A: virus infection price of the glass plate test piece as a comparative control, B: virus infection price of the PP mesh test piece to be evaluated) When the inactivation effect R is 2 or more, it is judged that there is an inactivation effect. The result showed that the virus inactivation effect appeared after being in contact with the test piece for 24 hours.

[產業上的利用可能性] [Industrial Utilization Possibility]

本發明的抗微生物、抗病毒、及/或防藻材料，是活用不會附帶有效成分的多餘放出而可得高效果 的特徵，可做為用在游泳池、澡堂、集合住宅用儲水槽、飼養用水槽、工業用儲水槽、工業用循環水、自來水、淨化槽、冷卻塔、運輸船的壓艙水使用的水的抗微生物、抗病毒、及/或防藻材料。又，也可使用做為覆蓋門窗、家具、文具、玩具、美容用具、垃圾容器、排水口構件、便器、塑膠溫室用聚乙烯薄片、儀器的開關、醫療用具、空氣過濾器、口罩等的抗微生物、抗病毒、及/或防藻材料。 The anti-microbial, anti-viral, and/or anti-algae material of the present invention can achieve high effects without excessive release of active ingredients. It can be used as water used in swimming pools, bathhouses, multi-household water storage tanks, breeding water tanks, industrial water storage tanks, industrial circulating water, tap water, Johkasou, cooling towers, and ballast water for transport ships. Anti-microbial, anti-viral, and/or anti-algae materials. In addition, it can also be used as a protective covering for doors and windows, furniture, stationery, toys, beauty appliances, garbage containers, drain components, toilets, polyethylene sheets for plastic greenhouses, equipment switches, medical appliances, air filters, masks, etc. Microbial, anti-viral, and/or anti-algae materials.

Claims (21)

一種抗微生物、抗病毒、及/或防藻材料，其特徵為：由無機氧化物或其衍生物與具有羥基的有機聚合物進行化學鍵結而成的無機/有機混成化合物所構成，該無機/有機混成化合物係在內部含有銀或銅的金屬或其化合物並且不溶解於水的固體，且可吸收水，其中，無機氧化物是鋯、矽、鈦或鎢的氧化物。 An anti-microbial, anti-viral, and/or anti-algae material, which is characterized in that it is composed of an inorganic/organic hybrid compound formed by chemical bonding of an inorganic oxide or its derivative and an organic polymer having a hydroxyl group. The organic hybrid compound is a solid that contains silver or copper metal or its compound inside and is insoluble in water and can absorb water. Among them, the inorganic oxide is an oxide of zirconium, silicon, titanium, or tungsten. 如申請專利範圍第1項所述的抗微生物、抗病毒、及/或防藻材料，其中，無機氧化物為鋯的氧化物。 The anti-microbial, anti-viral, and/or anti-algae material according to item 1 of the scope of patent application, wherein the inorganic oxide is zirconium oxide. 如申請專利範圍第1項所述的抗微生物、抗病毒、及/或防藻材料，其中，具有羥基的有機聚合物是聚乙烯醇。 The anti-microbial, anti-viral, and/or anti-algae material according to item 1 of the scope of patent application, wherein the organic polymer having a hydroxyl group is polyvinyl alcohol. 如申請專利範圍第1項至第3項中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，在無機/有機混成化合物含有的銀或銅的金屬或其化合物含有直徑10nm以下的粒子。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of items 1 to 3 in the scope of the patent application, wherein the silver or copper metal or its compound contained in the inorganic/organic hybrid compound contains Particles below 10nm in diameter. 如申請專利範圍第1項至第3項中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，在利用CuK α線的X線繞射法所得的繞射強度-繞射角圖中，歸屬於在無機/有機混成化合物含有的銀或銅的金屬或其化合物的尖峰之中，最高尖峰的半峰寬度為2(2 θ°)以上，或無尖峰。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of items 1 to 3 of the scope of patent application, wherein the diffraction strength obtained by the X-ray diffraction method using CuK α rays is − In the diffraction angle diagram, among the spikes of the silver or copper metal or its compound contained in the inorganic/organic hybrid compound, the half-width of the highest spike is 2 (2 θ°) or more, or there is no spike. 如申請專利範圍第1項至第3項中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，將抗微生物、 抗病毒、及/或防藻材料以其中的銀或銅的量成為1mg/L以上的量之方式浸漬於常溫水中24小時以上時，在水中溶出的銀或銅的濃度未達0.05mg/L。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of items 1 to 3 in the scope of the patent application, wherein the anti-microbial, anti-viral, and/or anti-algae material When the anti-viral and/or anti-algae material is immersed in water at room temperature for more than 24 hours so that the amount of silver or copper in it becomes 1 mg/L or more, the concentration of silver or copper eluted in the water does not reach 0.05 mg/L . 如申請專利範圍第1項至第3項中任一項所述的抗微生物、抗病毒、及/或防藻材料，其為膜狀物。 The anti-microbial, anti-viral, and/or anti-algae material described in any one of items 1 to 3 of the scope of the patent application is a membrane. 如申請專利範圍第7項所述的抗微生物、抗病毒、及/或防藻材料，其中，膜狀物是覆蓋在固形物表面的塗布膜。 The anti-microbial, anti-viral, and/or anti-algae material according to item 7 of the scope of patent application, wherein the membrane is a coating film covering the surface of the solid. 如申請專利範圍第8項所述的抗微生物、抗病毒、及/或防藻材料，其中，表面被塗布膜覆蓋的固形物是門窗、家具、文具、玩具、美容用具、垃圾容器、排水口構件、便器、塑膠溫室用聚乙烯薄片、儀器的開關、醫療用具。 The anti-microbial, anti-viral, and/or anti-algae material described in item 8 of the scope of the patent application, wherein the solid objects covered by the coating film are doors and windows, furniture, stationery, toys, beauty appliances, garbage containers, and drains Components, toilets, polyethylene sheets for plastic greenhouses, switches for instruments, and medical appliances. 如申請專利範圍第8項所述的抗微生物、抗病毒、及/或防藻材料，其中，固形物是多孔質材料。 The anti-microbial, anti-viral, and/or anti-algae material according to item 8 of the scope of patent application, wherein the solid material is a porous material. 如申請專利範圍第10項所述的抗微生物、抗病毒、及/或防藻材料，其中，多孔質材料是網、網篩、紡織物、不織布。 The anti-microbial, anti-viral, and/or anti-algae material according to item 10 of the scope of patent application, wherein the porous material is a net, a mesh screen, a woven fabric, or a non-woven fabric. 如申請專利範圍第10項所述的抗微生物、抗病毒、及/或防藻材料，其中，多孔質材料是過濾器或口罩。 The anti-microbial, anti-viral, and/or anti-algae material according to item 10 of the scope of patent application, wherein the porous material is a filter or a mask. 如申請專利範圍第7項所述的抗微生物、抗病毒、及/或防藻材料，其中，在無機/有機混成化合物含有的銀或銅的金屬或其化合物對於膜狀物的厚度方向具有濃度梯度。 The anti-microbial, anti-viral, and/or anti-algae material according to item 7 of the scope of patent application, wherein the metal or compound of silver or copper contained in the inorganic/organic hybrid compound has a concentration in the thickness direction of the film gradient. 如申請專利範圍第1項至第3項中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，藉由使抗微生物、抗病毒、及/或防藻材料與液體接觸，而抑制該液體中的微生物、病毒的個體數增加，或減少個體數。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of items 1 to 3 in the scope of the patent application, wherein the anti-microbial, anti-viral, and/or anti-algae material is combined with the liquid Contact, and inhibit the increase in the number of microorganisms and viruses in the liquid, or decrease the number of individuals. 如申請專利範圍第14項所述的抗微生物、抗病毒、及/或防藻材料，其中，一面使液體強制循環一面使抗微生物、抗病毒、及/或防藻材料與液體接觸。 The anti-microbial, anti-viral, and/or anti-algae material according to item 14 of the scope of patent application, wherein the liquid is forced to circulate while the anti-microbial, anti-viral, and/or anti-algae material is brought into contact with the liquid. 如申請專利範圍第14項所述的抗微生物、抗病毒、及/或防藻材料，其中，液體是使用在游泳池、澡堂、集合住宅用儲水槽、飼養用水槽、工業用儲水槽、工業用循環水、自來水、淨化槽、冷卻塔、運輸船的壓艙水的水。 For example, the antimicrobial, antiviral, and/or anti-algae material described in item 14 of the scope of patent application, wherein the liquid is used in swimming pools, bathhouses, residential water storage tanks, breeding water tanks, industrial water storage tanks, industrial use Circulating water, tap water, Johkasou, cooling tower, ballast water of transport ships. 如申請專利範圍第1項至第3項中任一項所述的抗微生物、抗病毒、及/或防藻材料，其中，藉由使抗微生物、抗病毒、及/或防藻材料與氣體接觸，而抑制該氣體中的微生物、病毒的個體數增加，或減少個體數。 The anti-microbial, anti-viral, and/or anti-algae material according to any one of items 1 to 3 in the scope of the patent application, wherein the anti-microbial, anti-viral, and/or anti-algae material is combined with the gas The number of individuals that suppress the microorganisms and viruses in the gas increases or decreases the number of individuals. 如申請專利範圍第17項所述的抗微生物、抗病毒、及/或防藻材料，其中，一面使氣體強制循環一面使抗微生物、抗病毒、及/或防藻材料與氣體接觸。 The anti-microbial, anti-viral, and/or anti-algae material according to item 17 of the scope of patent application, wherein the gas is forced to circulate while the anti-microbial, anti-viral, and/or anti-algae material is in contact with the gas. 一種抗微生物、抗病毒、及/或防藻材料的製造方法，其為經由下述過程之申請專利範圍第2項或第3項所述的抗微生物、抗病毒、及/或防藻材料的製造方法： 在聚乙烯醇及銀或銅的鹽共存的狀態下，將鋯鹽或氧化鋯鹽以鹼中和，鋯氧化物與聚乙烯醇進行化學鍵結形成無機/有機混成化合物的過程。 An anti-microbial, anti-viral, and/or anti-algae material manufacturing method, which is an anti-microbial, anti-viral, and/or anti-algae material described in item 2 or 3 of the scope of patent application through the following process Production method: In a state where polyvinyl alcohol and silver or copper salts coexist, the zirconium salt or zirconia salt is neutralized with an alkali, and the zirconium oxide and polyvinyl alcohol are chemically bonded to form an inorganic/organic hybrid compound. 如申請專利範圍第19項所述的抗微生物、抗病毒、及/或防藻材料的製造方法，其中，前述形成無機/有機混成化合物的過程，是藉由從鋯鹽或氧化鋯鹽與聚乙烯醇及銀或銅的鹽共存的溶液除去溶媒而形成固形物，使此固形物與鹼接觸而中和固形物中的鋯鹽或氧化鋯鹽，藉此而施行者。 The method for manufacturing antimicrobial, antiviral, and/or algae-preventing materials as described in item 19 of the scope of patent application, wherein the aforementioned process of forming an inorganic/organic compound compound is obtained by combining zirconium salt or zirconium oxide The solution in which vinyl alcohol and silver or copper salt coexist removes the solvent to form a solid substance, and the solid substance is brought into contact with an alkali to neutralize the zirconium salt or zirconia salt in the solid substance, thereby performing the procedure. 如申請專利範圍第19項所述的抗微生物、抗病毒、及/或防藻材料的製造方法，其中，在形成前述無機/有機混成化合物之後，藉由將銀或銅的化合物以還原劑還原而製成金屬狀態的銀或銅。 The method for manufacturing an antimicrobial, antiviral, and/or algae-preventing material as described in item 19 of the scope of the patent application, wherein after forming the aforementioned inorganic/organic hybrid compound, the silver or copper compound is reduced with a reducing agent And it is made into metallic silver or copper.

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