TW201124085A - Antibacterial composition, antibacterial articles and antibacterial method - Google Patents

Antibacterial composition, antibacterial articles and antibacterial method Download PDF

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TW201124085A
TW201124085A TW99101147A TW99101147A TW201124085A TW 201124085 A TW201124085 A TW 201124085A TW 99101147 A TW99101147 A TW 99101147A TW 99101147 A TW99101147 A TW 99101147A TW 201124085 A TW201124085 A TW 201124085A
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antibacterial
resin
composition
antibacterial composition
resins
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TW99101147A
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Chinese (zh)
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Shigeaki Maruo
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Shigeaki Maruo
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Abstract

Disclosed is an antibacterial composition comprising calcium hydroxide and an element of boron, in which the content of the element of boron is above about 0.05%, preferably above about 0.2%, in the total mass of the antibacterial composition. Also disclosed is an antibacterial product containing the antibacterial composition. The product of the present application has a high safety and can be prepared at a lower price.

Description

201124085 六、發明說明: 【發明所屬之技術領域】 剛本㈣料抗餘合㈣含#抗8以㈣抗菌製品, 所述的抗菌組合物含有氫氧化鈣及硼元素。 【先前技術】 [_-直以來,人們已採用各種方法及其心料㈣製品 抗菌性。例如,已經提出過咖有機類抗_'銀離子 或鋅離子的減脆_'錢❹生物提取物或殼聚 糖等天然成分的天然抗菌劑來獲得的抗菌。 。口 闕其中,有機抗_具有㈣性㈣—面。但是,一般來 說,由於其在製品中的溶出速度快,_所制得的製品 缺乏持續祕肢果。μ,在符衫純要求前提下 所選擇的有機抗菌劑报難達到所希望的抗菌效果。 _]另外,抗菌劑在合成樹脂中的溶解性低時,會產生白濁 或使光澤度下降而汗損轉_品__卜觀。 师]利祕離子或鋅離子的無機抗㈣,因其安全性相對較 高’可以對廣譜的細菌發揮抗菌性,並已經以不同形式 用在各種合成樹脂製品中。 闺但是’為了將這樣的無機抗8_抗菌性賦予樹脂,在 向樹脂混人的過程巾,作為抗g成分㈣離子等會弓I起 樹脂的透明度降低、變色’或者容易引起樹脂劣化等問 題。此外’ ^向整個樹脂中混人銀離子類抗菌劑,則存 在於鎮模成型製品内部的抗菌職乎不能發揮抗菌性。 另-方面’由於無機抗菌劑本身也不便宜,這就造成生 099101147 表單編號A0101 第3頁/共27頁 09920023] 201124085 產費用增高的問題。 [0007] 為了解決這些問題,有人已提議將微粉體無機抗菌劑分 散在乙醇等溶劑中,通過向成型品表面喷霧、塗布,或 是鍍上一層含有該抗菌劑的表面鍍膜來賦予製品抗菌性 。而且,一直以來都主要採取這樣的方法,例如:專利 公開號:平成6-80528號公報,專利公開號:平成 8-283452號公報,以及專利公開號:平成1 1-12478號 公報所公開。 [0008] 雖然上述利用銀離子或辞離子的無機抗菌劑具有比較高 的安全性,但是不能否認仍存在由於慢性攝取而危害人 體健康的可能性,而且應謹慎對待使用之後的廢棄處理 問題(由於焚燒所造成的大氣污染、填埋地的土壤污染、 再利用的可能性等)。 [0009] 此外,對於在合成樹脂成型品表面進行鍍膜而賦予抗菌 性的方法,若該產品出現傷痕或經過較長時間後,其抗 菌性難免會降低。 [0010] 此外,一直以來主要作為填充劑及穩定劑而使用的氫氧 化鈣,由於具有抗菌性,也有人提議將其混合入合成樹 脂,以製成含有氫氧化鈣的樹脂組成物。但是,為達到 期望的抗菌效果,需要添加相當數量的氫氧化鈣(相對於 100重量份的合成樹脂通常需加入16重量份以上)。但是 這樣會有損製品的機械強度、表面外觀等之虞(如專利公 開號:2001-1 23071號公報)。 [00113 本發明為基於上述情況,為解決上述問題而進行的課題 099101147 表單編號A0101 第4頁/共27頁 0992002311-0 201124085 [0012] Ο [0013] [0014]Ο [0015] 099101147 ,其提供了安全性高、價廉、容易製造的抗菌性樹脂製 品及抗菌組合物。本發明的樹脂製品不會因混入所述抗 菌組合物後而降低其本身的各種特性(如機械性能等)。 【發明内容】 本發明人為解決上述問題進行了專心研究。發明人意想 不到地發現,含有硼元素0. 05重量%以上的、以氫氧化鈣 為主要成分的抗菌組合物具有很好的抗菌性能。同時, 以含有硼元素0.05重量%以上的、以氫氧化鈣為主要成分 的適當量的抗菌組合物,與熱塑性樹脂或熱固性樹脂混 合,可得到抗菌效果非常好的樹脂製品,而且不會降低 其機械強度等物理性質。 因此,本發明的一方面涉及抗菌組合物,其包含氫氧化 鈣和硼元素,並且所述硼元素的含量占所述抗菌組合物 總重量的約0. 05%以上,優選約0. 2%以上。 本發明另一方面涉及抗菌組合物,其通過如下方法制得 :將貝殼煆燒;向煆燒產物中加入水,制得以氫氧化鈣 為主要成分的組合物;如果需要,向所制得的粉末中加 入硼元素,使硼元素的含量占所述組合物總重量約0. 05% 以上,優選约0. 2 %以上。 本發明的再一方面涉及抗菌製品,其包括約100重量份 的熱塑性樹脂和約0. 02-2. 99重量份的抗菌組合物或者 包括約100重量份的熱固性樹脂和約0.卜5. 0重量份的抗 菌組合物,其中所述抗菌組合物,其包含氫氧化妈和删 元素,並且所述硼元素的含量占所述抗菌組合物總重量 的約0. 05%以上,優選約0. 2 %以上,或者所述抗菌組合 表單編號Α0101 第5頁/共27頁 0992002311-0 201124085 物通過如下方法制得:將貝殼煆燒;向煆燒產物中加入 水,制得以氫氧化鈣為主要成分的組合物;如果需要, 向所制得的粉末中加入硼元素,使硼元素的含量占所述 組合物總重量約0. 0 5 %以上,優選約0. 2 %以上。 [0016] 在上述抗菌組合物中,硼元素的量占抗菌組合物的重量 通常可為約0. 0 5-10%,優選為0. 2-8%,較優選為1-5% 。通常硼元素在組合物中,以氧化硼形式存在。 [0017] 本發明的其他方面涉及抗菌方法,其包括對需要抗菌的 製品施用有效量的上述抗菌組合物,所述抗菌組合物包 含氫氧化鈣和硼元素,並且所述硼元素的含量占該抗菌 組合物總重量的0. 0 5 %以上。 [0018] 在本發明的某些實施方案中,所述抗菌組合物可被製成 粉末形式,優選地,所述抗菌組合物製成平均粒徑為0. 5 以m-lOvm的微粉。含有此種粉末的抗菌製品較為令人滿 意。 [0019] 在本發明抗菌組合物的某些實施方案中,可以含有鐵, 但是鐵含量需占在抗菌組合物總重量的0. 8%以下,優選 0. 4%以下。在本發明的某些實施方案中,制得的抗菌組 合物中不含有鐵。 [0020] 用於本發明的抗菌製品的抗菌組合物,因以作為食品添 加劑使用的氫氧化鈣為主要成分,與常規方法中主流的 塑膠添加用的含有銀離子或辞離子的抗菌劑相比,具有 穩定性高且廉價的特點。 [0021] 即使向樹脂中添加的抗菌組合物的添加量很少,本發明 099101147 表單編號A0101 第6頁/共27頁 0992002311-0 201124085 的抗菌製品也可以充分發揮餐具所要求的較高的抗菌性 政果,而且不破壞樹脂的機械特性及其外觀。 [0022]在本發明的抗菌製品的某些實施方案中,使用的抗菌組 合物,特別是微粉化抗菌組合物在材料中均勻分佈,可 以更南地發揮抗菌性效果。在此情況下,即使製品表面 被劃傷,其抗菌性能也不會降低。 [0023] 而且’本發明的抗菌製品,由於使用了上述的安全性高 且廉價的抗菌材料,因此可以用於包括曰 用品在内的各201124085 VI. Description of the invention: [Technical field to which the invention pertains] The original (four) material anti-surge (4) contains #抗8 to (4) antibacterial products, and the antibacterial composition contains calcium hydroxide and boron. [Prior Art] [_- Straight, people have adopted various methods and their minds (4) antibacterial properties. For example, antibacterial agents have been proposed which have been obtained from natural antibacterial agents such as silver ions or zinc ions, which are natural antibacterial agents such as citrus extracts or chitosan. . Among them, organic resistance _ has (four) sex (four) - face. However, in general, due to its fast dissolution rate in the product, the resulting product lacks sustained secrets. μ, the organic antibacterial agent selected under the premise of pure requirements of the shirt is difficult to achieve the desired antibacterial effect. _] In addition, when the solubility of the antibacterial agent in the synthetic resin is low, white turbidity may occur or the gloss may be lowered and the sweat may be converted to a product. The inorganic anti-seismic or zinc-based inorganic anti-(four), because of its relatively high safety, can exert antibacterial properties against a wide spectrum of bacteria and has been used in various forms in various synthetic resin products. However, in order to impart such an inorganic anti-bacterial property to the resin, in the process towel mixed with the resin, as the anti-g component (tetra) ion or the like, the transparency of the resin is lowered, the discoloration is caused, or the resin is easily deteriorated. . Further, when the silver ion-based antibacterial agent is mixed into the entire resin, the antibacterial property existing in the molded product of the molded article cannot exhibit antibacterial properties. The other side is because the inorganic antibacterial agent itself is not cheap, which causes the birth. 099101147 Form No. A0101 Page 3 of 27 09920023] 201124085 The problem of increased production costs. [0007] In order to solve these problems, it has been proposed to disperse a fine powder inorganic antibacterial agent in a solvent such as ethanol, and to impart antibacterial property to the product by spraying, coating, or plating a surface coating film containing the antibacterial agent onto the surface of the molded article. Sex. In addition, the method of the publication of the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [0008] Although the above-mentioned inorganic antibacterial agent using silver ions or reciprocating ions has relatively high safety, it is not denied that there is still a possibility of endangering human health due to chronic ingestion, and the disposal problem after use should be treated with caution (due to Air pollution caused by incineration, soil pollution in landfills, possibility of reuse, etc.). Further, in the method of imparting antibacterial properties to a surface of a synthetic resin molded article by coating, if the product is scratched or a long period of time, the antibacterial property is inevitably lowered. Further, calcium hydroxide which has been mainly used as a filler and a stabilizer has been proposed to be mixed into a synthetic resin to form a resin composition containing calcium hydroxide because of its antibacterial property. However, in order to achieve the desired antibacterial effect, it is necessary to add a considerable amount of calcium hydroxide (it is usually necessary to add 16 parts by weight or more with respect to 100 parts by weight of the synthetic resin). However, this may impair the mechanical strength, surface appearance, and the like of the product (for example, Patent Publication No. 2001-1 23071). [00113] The present invention is based on the above-mentioned situation, and the problem to solve the above problem is 099101147. Form No. A0101, Page 4/27, 0992002311-0, 201124085 [0012] [0013] [0014] 99 [0015] 099101147, which provides An antibacterial resin product and an antibacterial composition which are safe, inexpensive, and easy to manufacture. The resin product of the present invention does not reduce its own various characteristics (e.g., mechanical properties, etc.) after being mixed into the antibacterial composition. SUMMARY OF THE INVENTION The present inventors conducted intensive studies to solve the above problems. The inventors have unexpectedly found that an antibacterial composition containing more than 0.05% by weight of boron element and having calcium hydroxide as a main component has excellent antibacterial properties. At the same time, an appropriate amount of the antibacterial composition containing 0.05% by weight or more of boron element and containing calcium hydroxide as a main component is mixed with a thermoplastic resin or a thermosetting resin to obtain a resin product having an excellent antibacterial effect without lowering it. Physical properties such as mechanical strength. 0%, preferably about 0.2%, more than about 0. 25%, preferably about 0.2% the above. Another aspect of the present invention relates to an antibacterial composition which is obtained by calcining a shell; adding water to the calcined product to prepare a composition having calcium hydroxide as a main component; if necessary, preparing the shell 0以上以上。 Preferably, the amount of the composition is about 0. 05% or more, preferably about 0.2% or more. A further aspect of the invention relates to an antibacterial article comprising about 100 parts by weight of a thermoplastic resin and about 0. 02-2. 99 parts by weight of the antimicrobial composition or comprising about 100 parts by weight of a thermosetting resin and about 0. 0 5%以上以上优选优选0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2% or more, or the antibacterial combination form number Α0101 5th page/total 27 pages 0992002311-0 201124085 The object is obtained by the following method: simmering the shell; adding water to the simmered product to obtain calcium hydroxide 5%以上以上。 Preferably, the composition of the composition of the composition of the composition of the total weight of the composition of the composition of the total weight of the composition of about 0. 0 5% or more, preferably about 0.2% or more. 8%,优选优选为1-5%。 In the above-mentioned antibacterial composition, the amount of boron may be from about 0. 0 5-10%, preferably 0. 2-8%, more preferably 1-5%. Typically boron is present in the composition in the form of boron oxide. [0017] A further aspect of the invention relates to an antibacterial method comprising applying an effective amount of the above-described antimicrobial composition to an article in need of antibacterial composition, the antibacterial composition comprising calcium hydroxide and boron, and the content of the boron element is 0以上以上。 The total weight of the antibacterial composition of 0. 0 5 % or more. The micro-powder of m-lOvm. The micro-powder having an average particle size of 0.5 m-lOvm. Antibacterial products containing such powders are more satisfactory. 8%以下。 Preferably, the amount of the antibacterial composition is less than 0.8%, preferably 0.4% or less. In certain embodiments of the invention, the antibacterial composition produced does not contain iron. [0020] The antibacterial composition used in the antibacterial article of the present invention contains calcium hydroxide as a food additive as a main component, and is superior to an antibacterial agent containing silver ions or reciprocating ions for the main plastic addition in the conventional method. It has the characteristics of high stability and low cost. [0021] Even if the amount of the antibacterial composition added to the resin is small, the antibacterial product of the present invention 099101147 Form No. A0101 Page 6 / 27 pages 0992002311-0 201124085 can also fully exert the high antibacterial required for tableware. Sexuality, without destroying the mechanical properties of the resin and its appearance. [0022] In certain embodiments of the antimicrobial articles of the present invention, the antimicrobial compositions used, particularly the micronized antimicrobial compositions, are evenly distributed throughout the material to provide an antibacterial effect more southerly. In this case, even if the surface of the product is scratched, the antibacterial property is not lowered. Further, the antibacterial article of the present invention can be used for each of the articles including the diaper article because the above-mentioned highly safe and inexpensive antibacterial material is used.

種製品。特別是可提供直接與手或皮膚直接接觸的安全 &菌製品’如電腦等的鍵盤,各種機械器具的機箱和遙 控器等按鍵,餐具類,切菜板或金屬碗等烹調用具,座 便器’浴室/盥洗室用地板材料或牆壁材料,以及其他如 吊環或電梯的牆壁材料等。 【實施方式】 [0024] 本發明的抗菌製品包括含有氫氧化鈣及硼化物的抗菌組 合物及熱塑性樹脂或熱固,樹脂。Kind of products. In particular, it can provide safe & fungus products directly in direct contact with hands or skin, such as keyboards for computers, etc., buttons for various mechanical devices, remote control buttons, tableware, cutting boards or metal bowls, etc., toilets 'Bathroom/washroom floor materials or wall materials, as well as other wall materials such as rings or elevators. [Embodiment] The antibacterial article of the present invention comprises an antibacterial composition containing calcium hydroxide and a boride, and a thermoplastic resin or a thermosetting resin.

[00¾]以下以具體實施方式和/或實施例對本發明進行更詳細的 說明。 [0027] 099101147 [0026][0034] The invention is described in more detail below in terms of specific embodiments and/or examples. 099101147 [0026]

適於本發明抗菌製品的“抗菌組合物,,(本文中又稱“抗 菌劑’除非另有說說明,兩者具有相同含義)中的氫氧 化鈣,為本領域中常規的氫氧化鈣。 在本發明的某些實施方案中,氫氧化鈣通過本領域所屬 技術人員已知的方法,如煆燒碳酸鈣制得氧化鈣後,再 表單編號A0101 第7頁/共27頁 0992002311-0 [0028] 201124085 水合制得。 [0029] 在本發明的某些實施方案中,可採用動物性來源的妈作 為碳_的來源。能夠用於本發明的示例性的動物性約 原1括i_不限於扇貝殼、餘魚殼、海螺殼、衝浪給殼、 海膽殼等天然或養i的貝類的殼,或義外殼等為原料 。在本發明的某些實施方案t,使用扇貝殼作為本發明 的動物㈣源。由於制殼具有組成均—且供應量足的 特點’而且使肖這些殼原、料在煆燒後,不需要其他處理 ’可直接將輯所得的產物水合,制得抗I組合物的原 料。 [0030]An "antibacterial composition," (also referred to herein as "antibacterial agent", unless otherwise stated, both of which have the same meaning) of calcium hydroxide, is a conventional calcium hydroxide in the art. In certain embodiments of the invention, the calcium hydroxide is prepared by methods known to those skilled in the art, such as calcined calcium carbonate to obtain calcium oxide, and then Form No. A0101, page 7 / total 27 pages 0992002311-0 [ 0028] 201124085 Hydration. [0029] In certain embodiments of the invention, an animal-derived mother may be employed as a source of carbon. Exemplary animal species that can be used in the present invention include i_ not limited to scallop shells, remnant shells, conch shells, surf shells, sea urchin shells, and the like, or shells of shellfish, or shells. As raw materials. In certain embodiments t of the invention, scallop shells are used as the source of the animal (iv) of the invention. Since the shell has the characteristics of uniform composition and sufficient supply, and the shells and the shells are simmered, no other treatment is required, and the obtained product can be directly hydrated to prepare a raw material of the anti-I composition. [0030]

在本發明的某些實施方案巾,將貝殼糾製成貝殼粉末( 或顆粒狀物),在8〇〇°C-l,20(TC,優選850。(:-1,000°C 進仃煆燒,其間可通入二氧化碳。煆燒既可以在空氣中 進订’又可以在氮氣等惰性氣體中進行。可根據煆燒溫 度设定適當的假燒時間,但是通常為空氣溫度到達預定 煆燒溫度後的1〇分鐘_12〇分鐘,優遷15分鐘_9〇分鐘。 通過这樣的處理’可通過熱分解去徐不需要的有機物。 [0031] [0032] 煆燒後水合,可制得以氫氧化鈣為主體的粉末。 在本發明的某些實施方案中,在煆燒和水合的過程中, 可依據需要進行進—步粉碎製成微粉,微粉的最終平均 粒杈可為0*1 Vm~500从m,優選為0.5 gm-100 ,更優選為0.5 yra-4〇 ,最優選為0.5 /zm-l〇 β m。通過將微粒的粒徑進一步微粉化,制得的粉末抗菌組 合物在與熱塑性樹脂或熱固性樹脂混合時,可實現均勻 099101147 表單編號A0101 第8頁/共27頁 0992002311-0 201124085 [0033] [0034] Ο [0035] [0036]In certain embodiments of the invention, the shell is corrected into a shell powder (or granule) at 8 ° C, 20 (TC, preferably 850. (: - 1,000 ° C) In the meantime, carbon dioxide can be introduced. The smoldering can be ordered in the air and can be carried out in an inert gas such as nitrogen. The appropriate smoldering time can be set according to the simmering temperature, but usually the air temperature reaches the predetermined sinter temperature. After 1 minute _12 〇 minutes, excellent mobilization 15 minutes _9 〇 minutes. Through such a treatment 'can be used to decompose unwanted organic matter by heat. [0032] [0032] After simmering, it can be hydrated Calcium hydroxide is the main powder. In some embodiments of the present invention, in the process of calcining and hydrating, the powder may be further pulverized as needed to prepare a fine powder, and the final average particle size of the fine powder may be 0*1. Vm~500 is from m, preferably from 0.5 gm to 100, more preferably from 0.5 yra to 4 Å, and most preferably from 0.5 /zm to 〇β m. The powder antibacterial combination is obtained by further micronizing the particle size of the particles. When mixed with thermoplastic resin or thermosetting resin, it can achieve uniformity 099101147 Form No. A0101 Page 8 of 27 0992002311-0 201124085 [0033] [0036] [0036]

[0037] 099101147 分散,即充分賦予製品抗菌能力。 在本發明的某些實施方案中,若從動物性鈣源制得的粉 末中硼元素的濃度較低,可根據需要,向制得的以氫氧 化鈣為主體的微粉中,加入氧化硼等含有硼元素的微粉 ,充分混合均勻後,制得粉末抗菌組合物。 這樣制得的粉末抗菌組合物是以氫氧化鈣為主體、以硼 元素為必須成份的粉末抗菌組合物,其中硼的含量在粉 末抗菌組合物總重量的0. 0 5重量% (重量百分比)以上,優 選0. 2重量%以上。在某些實施方式中,所述抗菌組合物 中硼元素的量占抗菌組合物的重量通常可為約0. 05-10% ,優選為0. 2-8%,較優選為卜5%。 在本發明的某些實施方案中,如果抗菌組合物成分來源 於含鐵原料,則在抗菌組合物中,鐵含量需占抗菌組合 物總重量的0. 8%以下,優選0. 4%以下。在本發明的某 些實施方案中,制得的抗菌組合物中不含有鐵。 埶朔性施十脂 本發明的某些實施方案中,能夠與所述抗菌組合物混合 的熱塑性樹脂的示例性實例包括但不限於聚乙烯樹脂、 聚丙烯樹脂、聚苯乙烯樹脂、聚氯乙烯樹脂、聚醯胺樹 脂、聚碳酸酯樹脂、聚縮醛樹脂、PET(聚對苯二甲酸乙 二酯)樹脂、PBT(聚對苯二甲酸丁二酯)樹脂、ABS(丙烯 腈-丁二烯-苯乙烯)樹脂等。 在本發明的某些實施方案中,用於切菜板等烹調用具或 電腦等的鍵盤的熱塑性樹脂選自聚乙烯樹脂、聚丙烯樹 表單編號A0101 第9頁/共27頁 0992002311-0 [0038] 201124085 [0039] [0040] [0041] [0042] [0043] [0044] 脂、ABS樹脂或PBT樹脂。 在本發明的某些實施方案中,所述抗菌組合物的混合量 為:相對於100重量份熱塑性樹脂添加〇. 02重量份-2. 99 重量份’優選至少〇. 1重量份,更優選重量份以上。 1.0重量份_2. 9重量份尤為優選’通常使用2.0重量份_ 2. 5重量份。 本發明的某些實施方案中,能夠與所述抗菌組合物混合 的熱固性樹脂的示例性實例包括但不限於不飽和聚酯樹 曰環氧樹脂、酚酿樹脂、密胺樹脂、丙埽酸樹脂、尿 素樹脂、聚醯亞胺樹脂、矽樹脂等。 本發月的某些實施方案中,所述抗菌組合物的混合量 為相對於100重量份熱塑性樹脂添加〇}重量份_5〇重 里伤’更優選〇. 15重量份-3重量份。 抗菌 在本發明的某些實施方案巾,齡實際需要,可在本發 的k菌製品中添加常規的、慣用於由熱塑性樹脂或熱 樹月曰製成的成型品中的添加劑,如:可塑劑、穩定 劑抗氧化劑、填充劑、紫外吸收劑、著色劑(顏料、, 料等)、替.I μ i 士, 发九增白劑、抗炎劑、粘度調節劑等。 本發明的抗_製品中,可通過本領域技術人員已知的裝 單料堡出機、二軸壓出機、捏和機、授拌器、雙 機將上述粉末抗菌組合物與所述熱塑性樹脂混練[0037] 099101147 Dispersion, that is, sufficient to impart antibacterial ability to the product. In some embodiments of the present invention, if the concentration of boron element in the powder prepared from the animal calcium source is low, boron oxide or the like may be added to the prepared fine powder mainly composed of calcium hydroxide as needed. The fine powder containing boron element is thoroughly mixed and uniformly, and a powder antibacterial composition is obtained. 0重量重量的重量重量的重量的重量重量的质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量重量2重量百分比以上。 The above, preferably 0.2% by weight or more. 8%,优选优选为五重量。 In some embodiments, the amount of the boron compound in the antibacterial composition may be from about 0.05 to 10%, preferably from 0. 2-8%, more preferably 5%. The 8% or less, preferably 0.4% or less, of the total weight of the antibacterial composition. . In some embodiments of the invention, the resulting antimicrobial composition does not contain iron. In some embodiments of the present invention, illustrative examples of thermoplastic resins that can be mixed with the antimicrobial composition include, but are not limited to, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride. Resin, polyamide resin, polycarbonate resin, polyacetal resin, PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, ABS (acrylonitrile-butadiene) An ene-styrene resin or the like. In some embodiments of the present invention, the thermoplastic resin for a cooking utensil such as a cutting board or a keyboard of a computer or the like is selected from the group consisting of polyethylene resin, polypropylene tree form No. A0101, page 9 / total 27 pages 0992002311-0 [0038 [0044] [0044] [0044] A grease, an ABS resin or a PBT resin. In some embodiments of the present invention, the antibacterial composition is blended in an amount of from 0.2 part by weight to 2.99 parts by weight 'preferably at least 0.1 part by weight, more preferably 100 parts by weight of the thermoplastic resin. More than the weight. 1.0 parts by weight to 1.9 parts by weight is particularly preferred 'usually 2.0 parts by weight to 2.5 parts by weight. In certain embodiments of the present invention, illustrative examples of thermosetting resins that can be mixed with the antimicrobial composition include, but are not limited to, unsaturated polyester dendritic epoxy resins, phenolic resin, melamine resins, and acrylic acid resins. , urea resin, polyimide resin, enamel resin, and the like. In some embodiments of the present month, the antibacterial composition is added in an amount of 重量 5 parts by weight to 5% by weight of the thermoplastic resin, more preferably 15 15 parts by weight to 3 parts by weight. Antibacterial In some embodiments of the present invention, it is practically necessary to add an additive conventionally used in a molded article made of a thermoplastic resin or a hot tree, such as a plastic, to the k-product of the present invention. Agents, stabilizers, fillers, UV absorbers, colorants (pigments, materials, etc.), .I μ i, nin brighteners, anti-inflammatory agents, viscosity modifiers, etc. In the anti-product of the present invention, the above-mentioned powder antibacterial composition and the thermoplastic can be obtained by a single-loading machine, a two-axis extruder, a kneader, a stirrer, and a double machine known to those skilled in the art. Resin kneading

099101147 表單編號A〇l〇i 第10頁/共27頁 0992002311-0 [0045] 201124085 ,充分混合使其均勻化後,使用注入成型、壓出成型、 吹塑成型等方式,製成所期望的形狀。或通過曰曆處理 法或鑄造方法等,製成臈/紙狀,或根據用途製成發泡製 品0 [0046] 此外,在使用熱固性樹脂的情況下,用攪拌器等充分混 合’形成均勻混合物’並將其灌入期望成形的模具中, 按照選定的樹脂固有的固化條件,使其固化後,脫模即 可。 [0047] 本發明的抗菌製品及抗菌組合物可用於各種用途。 [0048] 本發明的抗菌組合物與常規的作為塑膠用抗菌劑使用的 銀離子或鋅離子不同,是一種廉價且安全性高的材料, 可用於包含日用品在内的廣泛製品。 [0049] 因此,可很好地用於與手或皮膚直接接觸的製品。具體 來說,如製成電腦等的鍵盤、各種機械器具和遙控器等 的主體或按鍵、餐具類、切菜板或金屬碗等的烹調用具 、座便器、浴室/盥洗室用地板材料或牆壁材料、其他如 吊環或電梯的四壁材料等。 [0050] 特別是本發明的抗菌製品,由於抗菌組合物在材料中均 句地分佈並發揮其效果,在用於如切菜板的等的場合, 即使切菜板表面被菜刀劃傷,也能夠充分發揮抗菌性能 ,並長期維持抗菌功效。 []以下舉出實施例,更詳細地說明本發明,但是本發明並 不局限在這些實施例中。 099101147 表單編號A0101 第U頁/共27頁 0992002311-0 201124085 [0052] 製備例1 :抗菌組合物的製備 _]將扇貝的貝殼粉碎後,在100(rc下假燒j小時。向假燒 產物中加入水,消化後,用粉碎機將制得的氫氧化鈣粉 末進一步粉碎,制得平均粒徑為10 的粉末。並向^ 中混入氧化硼,制得抗菌組合物。 [0054] 表1示出了所得抗菌組合物的組成分析。 [0055] 表1 -抗菌組合物的組成 [0056] 成份(元素) 含量(重量%) ~~~~~~~ Ca(OH)2 ~~~ -—~ C 5.6 S〇3 ~~ ~~ 0.41 -- Na2〇 0. 39 ~~ Α1Ω ~~ „-~~~~~~~—_ 2 3 0.35 Fe2°3 ~〇?34~~ ~~~~~~~ SrO ——---- „,. —-——______ 0.20 ....' ΡΛ ' ----------- f 0. 14 > MgO 0. 11 B2°3 ’ —" 一 , ------— 0. 11 貫例1 :抗菌性測試1 "~~--- [0057] [0058] 099101147 [測試片(抗菌製品)的製備(1 )] 將上述抗菌組合物按照相對於聚丙稀總f量的(K02重量% ,0. 5重Ϊ%、丨· 〇重量%、2. Q重量%或2 重量%混合, 製成大小約為5〇随X 40_、厚度為2-3 mm的測試片。 表單編號A0101 第12頁/共27頁 0992002311-0 201124085 [0059] [0060] [0061] Ο [0062] [抗菌性測試及結果] 按照JIS Ζ 2801:2000 “抗菌加工製品-抗菌性測試方 法抗菌效果” 5. 2塑膠製品等的測試方法,對按照上述 製造的加入抗菌組合物的測試片(測試片1-測試片5)進行 抗菌性測試。 即將所制的5種測試片及未加工的聚乙烯薄膜的表面用乙 醇擦拭並充分乾燥後,接種0.3 mL含有下面所述的3種菌 株的任意一種的菌液後,覆蓋聚乙烯薄膜,在35°C下, 培養24小時(相對濕度為90%)後,測量細菌的生菌數。 所用的測試片、被覆薄膜、菌液的概要列於表2,24小時 培養後的生菌數測量結果列於表3。此外,測試片5)和未 加工的測試片的菌液培養結果的照片示於第一圖-第三圖099101147 Form No. A〇l〇i Page 10 of 27 Page 0992002311-0 [0045] 201124085, after mixing thoroughly to homogenize, using injection molding, extrusion molding, blow molding, etc., to achieve the desired shape. Or by a calendar process or a casting method, etc., it is made into a crepe/paper shape, or a foamed product is made according to the use. [0046] Further, in the case of using a thermosetting resin, a mixture is sufficiently mixed with a stirrer or the like to form a homogeneous mixture. 'Pour it into a mold that is desired to be formed, and then solidify it according to the curing conditions inherent to the selected resin. The antibacterial and antimicrobial compositions of the present invention are useful in a variety of applications. The antibacterial composition of the present invention is an inexpensive and highly safe material unlike conventional silver ion or zinc ion used as an antibacterial agent for plastics, and can be used for a wide range of products including daily necessities. [0049] Therefore, it can be suitably used for articles that are in direct contact with hands or skin. Specifically, it is a keyboard such as a computer, a main body such as a computer tool or a remote controller, a cooking utensil such as a button, a tableware, a cutting board or a metal bowl, a toilet bowl, a floor material or a wall for a bathroom/washroom. Materials, other four-wall materials such as rings or elevators. [0050] Particularly, in the antibacterial product of the present invention, since the antibacterial composition is uniformly distributed in the material and exerts its effect, in the case of being used for, for example, a cutting board, even if the surface of the cutting board is scratched by a kitchen knife, It can fully exert antibacterial properties and maintain antibacterial effects for a long time. [The present invention will now be described in more detail by way of examples, but the invention is not limited thereto. 099101147 Form No. A0101 Page U/Twenty-seventh page 0992002311-0 201124085 [Preparation Example 1 : Preparation of antibacterial composition _] After smashing the shell of scallop, it was simmered at 100 (rc for 1 hour). Water was added thereto, and after digesting, the obtained calcium hydroxide powder was further pulverized by a pulverizer to obtain a powder having an average particle diameter of 10. The boron oxide was mixed into the mixture to prepare an antibacterial composition. [0054] The composition analysis of the obtained antibacterial composition is shown. [0055] Table 1 - Composition of Antibacterial Composition [0056] Ingredient (Element) Content (% by Weight) ~~~~~~~ Ca(OH)2 ~~~ - —~ C 5.6 S〇3 ~~ ~~ 0.41 -- Na2〇0. 39 ~~ Α1Ω ~~ „-~~~~~~~__ 2 3 0.35 Fe2°3 ~〇?34~~ ~~~ ~~~~ SrO ——---- „,. —————______ 0.20 ....' ΡΛ ' ----------- f 0. 14 > MgO 0. 11 B2° 3 '-" I, ------- 0. 11 Example 1: Antibacterial test 1 "~~--- [0058] [0058] 099101147 [Preparation of test piece (antibacterial product) (1 The above antibacterial composition is in an amount relative to the total amount of polypropylene (K02% by weight, 0.5% by weight, 丨·〇 weight) 2. Q% by weight or 2% by weight of the mixture, and a test piece having a size of about 5 〇 with X 40 _ and a thickness of 2-3 mm. Form No. A0101 Page 12 of 27 0992002311-0 201124085 [0059] [0061] [Antibacterial Test and Results] According to JIS Ζ 2801:2000 "Antibacterial Processed Products - Antibacterial Test Method Antibacterial Effect" 5. 2 Test methods for plastic products, etc., manufactured according to the above The test piece (test piece 1 - test piece 5) to which the antibacterial composition was added was subjected to an antibacterial test. The surface of the prepared 5 test pieces and the unprocessed polyethylene film was wiped with ethanol and sufficiently dried, and 0.3 mL was inoculated. The bacterial solution of any of the three strains described below was covered with a polyethylene film, and cultured at 35 ° C for 24 hours (relative humidity of 90%), and the number of bacteria in the bacteria was measured. The summary of the coating film and the bacterial liquid is shown in Table 2, and the results of measuring the number of bacteria after 24 hours of cultivation are shown in Table 3. In addition, photographs of the results of the bacterial culture of the test piece 5) and the unprocessed test piece are shown in the first. Figure - the third picture

099101147 表單編號A0101 第13頁/共27頁 0992002311-0 201124085 C〇〇63] 表2-測試片、被覆薄膜、菌液的概要099101147 Form No. A0101 Page 13 of 27 0992002311-0 201124085 C〇〇63] Table 2 - Summary of test piece, coated film, and bacterial solution

分類 抗菌加工 無菌加工 測試片 種類 測試片 1)-5)*1 聚乙烯薄 膜 大小 約 50 mm X 40 咖 約 50 mm X 40 ram 形狀 長方形 長方形 厚度 約 2-3 mm 約 0. 09 ram 被覆薄膜 種類 未加工的聚乙烯薄膜 大小 約 40 mm X 30 mm 形狀 長方形 厚度 約 0. 09 ram 菌液ί2攝取量 大腸桿菌 0. 3 mL 金黃色葡萄球菌 0. 3 mL 大腸桿菌 (0157:Η7) 0. 3 mL 菌液中細菌數 大腸桿菌 8. lxlOVmL 金黃色葡萄球菌 6. 6xl〇VmL 大腸桿菌 (0157:Η7) 7. OxlOVmL * 1 : 測試片1)-測試片5) [0064] 1 )加入抗菌組合物的聚丙烯樹脂片含有抗菌組合物0. 02%Classification Antibacterial processing Aseptic processing test piece type test piece 1)-5)*1 Polyethylene film size about 50 mm X 40 Coffee approx. 50 mm X 40 ram Shape Rectangular rectangular thickness about 2-3 mm About 0. 09 ram Covered film type The raw polyethylene film is about 40 mm X 30 mm in shape and has a rectangular shape thickness of about 0. 09 ram bacteria liquid ί2 intake Escherichia coli 0. 3 mL Staphylococcus aureus 0. 3 mL Escherichia coli (0157: Η7) 0. 3 The number of bacteria in the mL solution was 8. ExlOVmL Staphylococcus aureus 6. 6xl〇VmL Escherichia coli (0157: Η7) 7. OxlOVmL * 1 : Test piece 1) - Test piece 5) [0064] 1) Adding an antibacterial combination 02%% of the polypropylene resin sheet containing the antibacterial composition 0. 02%

[0065] [0066] [0067] [0068] 2) 加入抗菌組合物的聚丙烯樹脂片 3) 加入抗菌組合物的聚丙浠樹脂片 4) 加入抗菌組合物的聚丙烯樹脂片 5) 加入抗菌組合物的聚丙稀樹脂片 2. 99% 含有抗菌組合物0. 5% 含有抗菌組合物1. 0% 含有抗菌組合物2. 0% 含有抗菌組合物 099101147 表單編號A0101 第14頁/共27頁 0992002311-0 201124085 [0069] *2 :菌液所含菌種 [0070] 大腸桿菌:Escherichia col i [0071] 金黃色葡萄菌:Staphy 1 ococcus aureussub-sp.AureusNBRC 12732 [0072] 大腸桿菌(血清型0157 : H7,非產志贺(Vero)毒素菌株) •Escherichia coliATCC 43888 [0073][0068] 2) a polypropylene resin sheet to which an antibacterial composition is added 3) a polypropylene resin sheet to which an antibacterial composition is added 4) a polypropylene resin sheet to which an antibacterial composition is added 5) an antibacterial combination is added Polypropylene resin sheet 2. 99% Containing antibacterial composition 0. 5% Antibacterial composition 1. 0% Antibacterial composition 2. 0% Antibacterial composition 099101147 Form No. A0101 Page 14 of 27 0992002311 -0 201124085 [0069] *2: bacteria contained in bacterial liquid [0070] Escherichia col i [0071] Staphylococcus aureus: Staphy 1 aureussub-sp. AureusNBRC 12732 [0072] Escherichia coli (serotype 0157) : H7, a non-Shiga toxin strain) • Escherichia coliATCC 43888 [0073]

表3-測試片生菌數的測量結果 菌種 測試片 每測試 片生菌 數 接種後不久 未加工 2. 7x105 未加工 1.6xl07 大腸桿菌 35 2C,培養 24 測試片3) 30 小時後 測試片4) <10 測試片5) <10 接種後不久 未加工 1.5χ106 未加工 6. 2x106 金黃色葡萄球菌 35 SC,培養 24 測試片1) 50 小時後 測試片3) <10 測試片4) <10 測試片5) <10 接種後不久 未加工 2. 5x105 未加工 6. 8x106 大腸桿菌 0Γ,+立矣 9/1 測試片1) <10 (0157 : H7) /In δϋέ — 測試片3) <10 ’J、町攸 測試片4) <10 測試片5) <10 [0074] 如表3所示,未加工的測試片(聚乙烯薄膜)在35°C培養24 小時後,全部呈現細菌增殖的結果,但是,含有本發明 099101147 表單編號A0101 第15頁/共27頁 0992002311-0 201124085 的抗菌組合物的測試片1)-測試片5)對3種菌的任音—種 都發揮了優良的抗菌性能。特別是,通過顯示培養結果 的第一圖-第三圖可以明確,與未加工的測試片(第一圖 (A) 、第二圖(A)、第二圖(A))相比’測試片5)(第—圖 (B) 、第一圖(B)、第二圖(B))對3種菌中的任意一種^ 發揮了良好的抗菌性能。 [0075] 實施例2 :抗菌性測試2 [〇〇76][測試片(抗菌製品)的製備(2)] [0077]將在“製備例1 :抗菌組合物的製備” +製備的抗菌組合 物,以相對於密胺總重量的〇. 2重量%混合,製成大小约 為45 mm X 45 mm、厚度為2随的正方形測試片。 [〇〇78][抗菌性測試及結果] [0079] 如前所述,按照JIS Z 2801 :2000測試方法,對測試片 進行抗菌性測試。 [0080] 即將所制的測試片6)及未加工的聚乙錄薄膜的表面用乙 醇擦拭並充分乾燥後,接種0. 4 mL含有下面所述的2種菌 株的任意一種的菌液後,覆蓋聚乙烯薄膜,在35。(3下, 培養24小時(相對濕度為90%)後,測量細菌的生菌數。 [0081] 所用的測試片、被覆薄膜、菌液的概要列於表4,24小時 培養後的生菌數測量結果列於表5。 099101147 表單編號A0101 第16頁/共27頁 201124085 [0082] Ο [0083] [0084] [0085] [0086]G [0087] [0088]Table 3 - Measurement results of the number of test pieces of bacteria. Test sample of the test piece. The number of bacteria per test piece was not processed shortly after inoculation 2. 7x105 Unprocessed 1.6xl07 Escherichia coli 35 2C, culture 24 test piece 3) Test piece 4 after 30 hours <10 test piece 5) <10 Not processed shortly after inoculation 1.5χ106 Unprocessed 6. 2x106 Staphylococcus aureus 35 SC, culture 24 test piece 1) Test piece after 50 hours 3) <10 test piece 4) <10 Test piece 5) <10 Not processed shortly after inoculation 2. 5x105 Unprocessed 6. 8x106 Escherichia coli 0Γ, +立矣9/1 Test piece 1) <10 (0157 : H7) /In δϋέ - Test Sheet 3) <10 'J, machi test piece 4) <10 test piece 5) <10 [0074] As shown in Table 3, the unprocessed test piece (polyethylene film) was cultured at 35 ° C 24 After the hour, all showed the result of bacterial proliferation, but the test piece containing the antibacterial composition of the invention 099101147 Form No. A0101, page 15 / 27 pages 0992002311-0 201124085 1) - test piece 5) - All have excellent antibacterial properties. In particular, it can be clarified by displaying the first to third pictures of the culture results, compared with the unprocessed test pieces (first figure (A), second figure (A), second figure (A)) Sheet 5) (Fig. (B), Fig. 1 (B), and Fig. 2 (B)) exhibited good antibacterial properties against any of the three types of bacteria. Example 2: Antibacterial property test 2 [〇〇76] [Preparation of test piece (antibacterial preparation) (2)] [0077] Antibacterial combination prepared in "Preparation Example 1: Preparation of antibacterial composition" The mixture was mixed with 〇. 2% by weight based on the total weight of melamine to prepare a square test piece having a size of about 45 mm X 45 mm and a thickness of 2. [〇〇78] [Antibacterial Test and Results] As described above, the test piece was subjected to an antimicrobial test in accordance with the JIS Z 2801:2000 test method. [0080] Immediately after the surface of the test piece 6) and the unprocessed polyimprint film produced by the test, the substrate was inoculated with ethanol and inoculated with 0.4 ml of the bacterial solution containing any of the two strains described below. Cover the polyethylene film at 35. (3 times, after culturing for 24 hours (relative humidity: 90%), the number of bacteria in the bacteria was measured. [0081] The test pieces, the coated film, and the bacterial liquid used are summarized in Table 4, and the bacteria after 24 hours of cultivation were used. The number measurement results are shown in Table 5. 099101147 Form No. A0101 Page 16 of 27 201124085 [0082] [0084] [0085] [0086] [0088]

表4-測試片、被覆^ ^膜、菌液的概卷 _ 分類 抗菌加工 無菌加 測試片 種類 測試片6)-9)” 聚乙烯薄_塵_ 大小 約 45 咖 X 45 mm 約45咖X 45 tom 形狀 大致正方形 大致正方座一 厚度 約2_醒 約0. 01卹 被覆薄膜 種類 未加工的聚乙烯薄膜 大小 約 35 ram X 3_5 mm 形狀 大致長方形 _____ 厚度 約 0.1 mm 菌液β攝取量 大腸桿菌 0. 4 mL 金黃色葡萄球 菌 0. 4 mL 菌液中細菌數 大腸桿菌 3.5xl〇VmL 金黃色葡萄球 菌 5. 8xl05/mL *1:測試片6)Table 4 - Test sheet, coated ^ ^ film, bacterial liquid volume _ classification antibacterial processing aseptic plus test piece type test piece 6) -9)" polyethylene thin _ dust _ size about 45 coffee X 45 mm about 45 coffee X 45 tom shape roughly square roughly square seat a thickness about 2_ wake up about 0. 01 shirt coated film type unprocessed polyethylene film size about 35 ram X 3_5 mm shape roughly rectangular _____ thickness about 0.1 mm bacteria liquid β intake large intestine Bacillus 0. 4 mL Staphylococcus aureus 0. 4 mL Bacterial bacteria in the bacterial cell E. coli 3.5xl 〇 VmL Staphylococcus aureus 5. 8xl05 / mL *1: test piece 6)

抗菌組合物的密胺樹脂片含有抗菌組合物0.2% *2 :菌液所含菌種 大腸桿菌:The melamine resin sheet of the antibacterial composition contains the antibacterial composition 0.2% *2: the strain contained in the bacterial liquid Escherichia coli:

Escherichia coliATCC 8739 金黃色_ :Staphy1ococcus aureusATCC 6538 表5-測試片生菌數的測量結果Escherichia coliATCC 8739 Golden Yellow _ : Staphy1ococcus aureusATCC 6538 Table 5 - Measurement Results of Test Bacteria

大勝棹_ 測試片 金黃色葡萄球菌 接種後不久 35SC,培養 24小時後 接種後不久 35eC,培養 24小時後 未加工 未加工 測試片6) 未加工 未加工 測試片6) 每測試片生菌 數 1.6x10s 1.3xlQ7 <10 2.0xl05 3. 2x105 <10 099101147 表單鴆衆A〇l〇1 第17頁/共27頁 0992002311-0 201124085 ⑴089]如表5所示,未加工的測試片(聚乙婦薄膜)在3 5。(3培養2 4 小時候後’全部呈現細菌增殖的結果,但是,含有本發 明的抗菌組合物的測s式片6 )對兩種菌的任意一種都發揮 了優良的抗菌性能。 [0〇9〇]實施例3 :水提取物的pH值測試及測試結果 [0091 ]從實施例1 [測試片(抗菌製品)的製備(1)]中製備的測試 片(將加入相對於聚丙烯總重量的〇 2重量%抗菌組合物的 測試片作為樣品)切取10 mm X 10 _大小做成測試片 7)。 [0092] 按照JIS K 7371 :2000 “塑谬聚氣乙烯均聚物及共聚 物-水提取物p Η值的測量方法”,對測試片7 )的水提取物 的pH值進行測量。 [0093] 由此測出水提取物的pH值為8. 1,該值處於自來水pH值的 5.8-8.6範圍内,因此確定即使將本發明的抗菌製品用於 佐用具或餐具等情況,仍然.是安全的。 [0094] 實施例4 :機械物理性質測試及測鳞結果 [〇〇95]與實施例1[測試片(抗菌製品)的製備(1)] 一樣,仿“製 備例1 :抗菌組合物的製備”,將所述抗菌組合物按照相 對於聚丙稀總重量的0. 5重量%、1. 0重量%、1. 5重量%、 2. 0重量%、2. 5重量%或2. 99重量%混合,製成大小約為 50 mm X 40 mm、厚度為2-3 mm的長方形測試片8)-測 試片13)。再製備無添加抗菌組合物的測試片作為對照。 [0096]對制得的測試片進行軟化點溫度測試、撞擊測試及流動 099101147 表單編號A0101 第18頁/共27頁 0992002311-0 201124085 性測試’以此來評價測試片的機械物理性質 [0097]在物理性質評價中所使用的測量裝置列於表6,所得結果 列於表7。 [0098] 表6-測量裴置 [0099] 測量項目 測量儀器* _ VI CAT軟化點溫度 測試大胜棹_ Test strips Staphylococcus aureus 35SC shortly after inoculation, cultured for 24 hours, 35eC shortly after inoculation, unprocessed untested test pieces after 24 hours of culture 6) Unprocessed unprocessed test pieces 6) Number of bacteria per test piece 1.6 X10s 1.3xlQ7 <10 2.0xl05 3. 2x105 <10 099101147 Forms of the public A〇l〇1 Page 17 of 27 0992002311-0 201124085 (1)089] As shown in Table 5, the unprocessed test piece (poly B Women's film) at 3 5 . (3) After the culture was carried out for 24 hours, all of the bacteria were proliferated. However, the sigmoid sheet 6 containing the antibacterial composition of the present invention exhibited excellent antibacterial properties against either of the two bacteria. [0〇9〇] Example 3: pH test and test result of water extract [0091] Test piece prepared from Example 1 [Preparation of test piece (antibacterial product) (1)] (will be added relative to A test piece of 抗菌2% by weight of the total weight of the polypropylene as a sample) was cut to a size of 10 mm X 10 _ to make a test piece 7). The pH of the water extract of the test piece 7) was measured in accordance with JIS K 7371:2000 "Measuring method for measuring the p Η value of the plastic condensed polyethylene homopolymer and the copolymer-water extract". [0093] The pH of the water extract was determined to be 8.1, and the value was in the range of 5.8 to 8.6 of the pH value of the tap water, thereby determining that even if the antibacterial article of the present invention is used for the case of utensils or tableware, It is safe. Example 4: Mechanical physical property test and scale measurement result [〇〇95] As in Example 1 [Preparation of test piece (antibacterial product) (1)], "Preparation Example 1: Preparation of antibacterial composition" 5重量%, 2. 0重量%, 2. 5重量百分比或2. 99重量。 The weight of the total weight of the polypropylene relative to the total weight of the polypropylene is 0.5% by weight, 1.0% by weight, 1. 5重量%, 2. 0% by weight, 2. 5重量% or 2.99 weight % mixing, making a rectangular test piece 8)-test piece 13) having a size of approximately 50 mm X 40 mm and a thickness of 2-3 mm. A test piece without the added antimicrobial composition was prepared as a control. [0096] The prepared test piece was subjected to a softening point temperature test, an impact test, and a flow. 099101147 Form No. A0101 Page 18/27 pages 0992002311-0 201124085 Sexual test 'This is used to evaluate the mechanical physical properties of the test piece [0097] The measuring devices used in the evaluation of physical properties are shown in Table 6, and the results obtained are shown in Table 7. Table 6 - Measurement Devices [0099] Measurement Items Measuring Instruments * _ VI CAT Softening Point Temperature Test

Charpy衝擊測試 HDT VICAT測試機 測量條件 -------- —___ 測量負荷5kg 衝擊試驗機 ❹ [0100] [0101] 錘子15 J(帶缺 熔體流動速率測試 熔體指數儀F-F01 51(1 ·均為(株式會社)東洋精械製造所製造 表7-機械物理性質評價結果Charpy Impact Test HDT VICAT Tester Measurement Conditions -------- —___ Measurement Load 5kg Impact Tester ❹ [0100] [0101] Hammer 15 J (With Melt Flow Rate Test Melt Indexer F-F01 51 (1) All products manufactured by Toyo Seiki Machinery Co., Ltd. Table 7 - Evaluation results of mechanical and physical properties

測量負荷2. 16 kg ’測量溫度230°C 〇 測試片w 對照(無添加) VICAT軟化點 溫度(°C) 103.1 Charpy衝擊 測試(KJ/m2) 7——————--- 3. 1 熔體流動速率 (g/ΙΟ分鐘 10. 9 測試片8 ) -----— 105. 3 3. 2 10. 7 測試片9) ----- 103. 1 3. 2 10. 2 測試片10) 「106. 4 3. 2 10. 2 測試片11) 105. 5 3. 2 9. 9 測試片12) 105. 7 3. 2 9. 7 測試片13) -----__ :扣,…u 〇、 105. 7 3. 2 9.5 *單·編號A0101 第19頁/共27頁 099101147 0992002311-0 201124085 [0102] 8)加入抗菌組合物的聚丙烯樹脂片含有抗菌組合物0. 5% [0103] 9)加入抗菌組合物的聚丙烯樹脂片含有抗菌組合物1. 0% [0104] 10)加入抗菌組合物的聚丙烯樹脂片含有抗菌組合物1. 5% [0105] 11)加入抗菌組合物的聚丙烯樹脂片含有抗菌組合物2. 0% [0106] 12)加入抗菌組合物的聚丙烯樹脂片含有抗菌組合物2. 5% [0107] 1 3)加入抗菌組合物的聚丙烯樹脂片含有抗菌組合物 2. 99% [0108] 如表7所示,得到結果顯示,含有上述抗菌組合物的測試 f〖 片8)-測試片13)的軟化點溫度測試、衝擊測試值與未添 加的測試片的測試值基本相同,二者數值的差異可認定 在誤差範圍内。 [0109] 此外,流動性隨抗菌組合物添加量的增加有減小趨勢, 但是與無添加的情況相比減少量很小,流動性基本保持 〇Measuring load 2. 16 kg 'Measurement temperature 230 °C 〇 Test piece w Control (no addition) VICAT softening point temperature (°C) 103.1 Charpy impact test (KJ/m2) 7——————--- 3. 1 Melt flow rate (g/ΙΟ minutes 10.9 test piece 8) ------ 105. 3 3. 2 10. 7 Test piece 9) ----- 103. 1 3. 2 10. 2 Test piece 10) "106. 4 3. 2 10. 2 Test piece 11) 105. 5 3. 2 9. 9 Test piece 12) 105. 7 3. 2 9. 7 Test piece 13) -----__ : buckle, ...u 〇, 105. 7 3. 2 9.5 *单·编号 A0101 Page 19 of 27 099101147 0992002311-0 201124085 [0102] 8) Polypropylene resin sheet containing antibacterial composition contains antibacterial composition0 5% [0105] 5% [0105] The polypropylene resin sheet containing the antibacterial composition contains the antibacterial composition 1. 5% [0105] 5% [0107] 1 3) Adding an antibacterial combination. The polypropylene resin sheet to which the antibacterial composition is added contains the antibacterial composition 2. 0% [0106] 12) The polypropylene resin sheet to which the antibacterial composition is added contains the antibacterial composition 2. 5% [0107] 1 3) The polypropylene resin sheet containing the antimicrobial composition 2. 99% [0108] As shown in Fig. 7, the results show that the softening point temperature test and the impact test value of the test containing the above-mentioned antibacterial composition are substantially the same as those of the unadded test piece, and the values of the two are The difference can be considered to be within the error range. [0109] In addition, the fluidity decreases with an increase in the amount of the antimicrobial composition added, but the amount of reduction is small compared to the case of no addition, and the fluidity is substantially maintained.

[0110] 可見,符合本發明的抗菌性製品與無添加的測試片相比 II ,基本保持了同樣的機械物理性質。 [0111] 實施例5 :合成樹脂製品的抽提測試 [0112] 將在“製備例1 :抗菌組合物的製備”中製備的上述抗菌 組合物,以相對於聚丙稀總重量的2. 9 9重量%進行混合, 製成大小約40 cm X 24 cm、厚約13 mm的切菜板。 [0113] 根據食品衛生法-食品/添加劑等的規格基準(昭和3 4年厚 生省告示第370號)以聚乙烯及聚丙烯為主要成分的合成 099101147 表單編號A0101 第20頁/共27頁 0992002311-0 201124085 樹脂制器具,或容器包裝(平成18年厚生勞動省告示第 201號)進行材質測試(鉛 '鎘)及抽提測試(重金屬(鉛) 、過能酸鉀消耗量、蒸發殘留物(水、4%醋酸' 2〇%乙醇 、庚燒)) 據此,結果顯示,任一項測試結果都符合食品衛生法一食 m/添加劑等的規格基準昭和34年厚生省告示第37〇號), 因此可以確認,本發明的抗菌性製品即使用於切菜板等 時也是安全的。 【圖式簡單說明】 〇 [0114] [0115] ❾ [0116] [0117] 第-圖為顯示用含有大腸桿菌的溶液在測試片5 )(含有 2. 99%抗菌組合物的聚丙烯樹脂片)(第一圖⑻)和不含 抗菌組合物的(未加工)測試片(第一圖⑴)上培養⑷、 時後的結果的照片。 第二圓為顯示用含有金黃色葡萄球菌的溶液在測試片 5)(含有2. 99%抗菌組合物的聚丙稀樹脂片)(第二圖⑻) 和不含抗菌組合物的(未加工)測試片(第二圖(a))上培養 24小時後的結果的照片。 第三圖A顯示用含有大腸桿菌(0157:H7)的溶液在測試 片5)(含有2."%抗菌組合物的聚丙烯樹脂片)(第二圖 ⑽和不含抗菌組合物的(未加工)測試片(第三圖⑼ 上培養24小時後的結果的照片。 【主要元件符號說明】 無 099101147 表單編號A0101 第21頁/共27頁 0992002311-0It can be seen that the antibacterial article according to the present invention substantially maintains the same mechanical and physical properties as compared with the test piece without added II. 5 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 The % by weight was mixed to make a cutting board having a size of about 40 cm X 24 cm and a thickness of about 13 mm. [0113] According to the food hygiene law - food / additive and other specifications (Showa 34th, Ministry of Health and Welfare Notice No. 370), polyethylene and polypropylene as the main component of the synthesis 099101147 Form No. A0101 Page 20 / 27 pages 0992002311- 0 201124085 Resin-made appliance, or container packaging (Heisei 18 Ministry of Health, Labour and Welfare Notice No. 201) for material testing (lead 'cadmium) and extraction test (heavy metal (lead), peracid potassium consumption, evaporation residue ( Water, 4% acetic acid '2〇% ethanol, heptane)) According to this, the results show that any of the test results are in line with the food hygiene law, a food m / additive and other specifications, the Showa 34 years of the Ministry of Health and Welfare Notice No. 37) Therefore, it was confirmed that the antibacterial product of the present invention is safe even when used for a cutting board or the like. [Simple Description of the Drawings] 〇 [0114] [0115] [0117] The first figure shows a test piece 5) containing a solution containing Escherichia coli (a polypropylene resin sheet containing 2.99% of the antimicrobial composition) (Photograph of the first figure (8)) and the (unprocessed) test piece (the first figure (1)) containing no antibacterial composition (4), after the time. The second circle is shown in a test piece 5) containing a solution containing Staphylococcus aureus (a polypropylene resin sheet containing 2.99% of the antimicrobial composition) (second figure (8)) and an antibacterial composition (raw) A photograph of the results of the test piece (Fig. 2 (a)) after 24 hours of cultivation. Figure 3A shows a test piece 5) containing a solution containing Escherichia coli (0157:H7) (a polypropylene resin sheet containing 2. "% antibacterial composition) (second figure (10) and without antimicrobial composition ( Unprocessed test piece (photograph of the result after 24 hours of incubation on the third figure (9). [Explanation of main component symbols] None 099101147 Form No. A0101 Page 21 of 27 0992002311-0

Claims (1)

201124085 七、申請專利範圍: 1 . 一種抗菌組合物,其包含氫氧化鈣和硼元素,並且所述硼 元素的含量占所述抗菌組合物總重量的約0. 05%以上,優 選約0. 2 %以上。 2 .如請求項1所述的抗菌組合物,其中所述抗菌組合物中蝴 元素以氧化硼形式存在。 3 .如請求項2所述的抗菌組合物,其中所述組合物為粉末形 式存在。 4 .如請求項3所述的抗菌組合物,其中抗菌組合物的平均粒 徑約為0.1 /zm-500 /zm,優選約為0.5 /zm-100 /im ,更優選約為0. 5 # m-40私m,最優選約為0.5 /zm-10 /z m。 5 .如請求項2所述的抗菌組合物,其更包含鐵元素,鐵含量 占在抗菌組合物總重量的約0. 8%以下,優選約0. 4°/。以下 〇 6 . —種抗菌組合物,其通過如下方法制得:將貝殼煆燒;向 煆燒產物中加入水,制得以氫氧化鈣為主要成分的組合物 ;向所制得的粉末中加入硼元素,使硼元素的含量占所述 .組合物總重量約0.05°/»以上,優選約0.2 %以上。 7 .如請求項6所述的抗菌組合物,其中所述氫氧化妈來自動 物性約源,例如扇貝殼、鮑魚殼、海螺殼、衝浪蛤殼、海 膽殼等天然或養殖的貝類的殼,或珊瑚外殼,優選扇貝殼 〇 8 .如請求項7所述的抗菌組合物,其中所述抗菌組合物中獨 元素以氧化硼形式存在。 099101147 表單編號A0101 第22頁/共27頁 0992002311-0 201124085 如 請求項8所述的抗菌級入式存在。 勿’其中所述組合物為耠 末形 ίο . 11 · Ο 1213 14 . Ο 15 . 16 . 如請求項9所述的抗菌級入 仫、,勺為0. 1 /zm-500 “扣,優選 的平岣 ,更優選約為 0. 5 em、4〇 '' °'5 ^m^l〇〇 4〇 一最優選約為0.5广 从®〜1 〇 如請求項8所述的抗菌組合物, 占在抗菌組合物總重量的約〇 8。/ 、 δ几,',織含量 。 下’優選約。,以下 一種抗菌方法,包括對_抗菌的;施 料項W1中任—請求項的抗“合:。,效量的 一種抗菌製品,其包括約1〇 n n9 0 重量伤的熱塑性槲2.99重量份的請求曰和約 組合物或者包括約100重量 月、項的抗 番吾八 量㈣熱固性樹脂和約0】 重1份的請求項卜11中的任 ^0*1 叫未項的抗菌組合物。 形述的抗菌製品,其·述抗菌組合物以粉末 二::刀散於所述熱塑性辦脂或熱固性樹脂中。 、驾、、項13或14所述的抗菌製品,其中所述熱塑性樹脂 '^聚乙烯树脂、聚丙烯樹脂、聚苯乙烯樹脂、聚氣乙烯 樹月曰、聚酿胺樹脂 '聚碳酸樹脂、聚縮祕脂、ΡΕΤ( 聚對笨一甲酸乙二酯)樹脂、ΡΒΤ(聚對苯二甲酸丁二酯) 樹脂和ABS(丙稀腈-丁二烯_苯乙稀)樹脂。 如》月求項15所述的抗菌製品,其中所述熱固性樹脂選自不 飽和聚酯樹脂、環氧樹脂、酚醛樹脂、密胺樹脂、丙烯酸 樹脂、尿素樹脂、聚醯亞胺樹脂和矽樹脂 % 約菌 5. f 099101147 如清求項13或14所述的抗菌製品,其中所述熱固性樹脂 表單編蚝ΑΟίοι 第23頁/共27頁 0992002311-0 17 . 201124085 選自不飽和聚酯樹脂、環氧樹脂、酚醛樹脂、密胺樹脂、 丙稀酸樹脂、尿素樹脂、聚酸亞胺樹脂和碎樹脂。 099101147 表單編號A0101 第24頁/共27頁5%以上以上优选优选0. 0. More than 0. 05%, preferably about 0. The total weight of the antibacterial composition is about 0. 05% or more, preferably about 0. 2% or more. The antibacterial composition according to claim 1, wherein the butterfly element in the antibacterial composition is present in the form of boron oxide. 3. The antibacterial composition of claim 2, wherein the composition is in the form of a powder. I. The antibacterial composition of claim 3, wherein the antibacterial composition has an average particle size of from about 0.1 / zm to about 500 / zm, preferably from about 0.5 / zm to about 100 / im, more preferably about 0. 5 # M-40 is m, most preferably about 0.5 / zm - 10 / zm. The 5% or less, preferably about 0. 4 ° /. The following antibacterial composition is prepared by calcining a shell; adding water to the calcined product to prepare a composition having calcium hydroxide as a main component; adding to the obtained powder The boron element has a boron content of about 0.05%/» or more, preferably about 0.2% or more, based on the total weight of the composition. The antibacterial composition according to claim 6, wherein the hydroxide mother is derived from an animal origin, such as a shell of a scallop, an abalone shell, a conch shell, a surf shell, a sea urchin shell, or the like. Or a coral shell, preferably a scallop shell. The antimicrobial composition according to claim 7, wherein the sole element in the antimicrobial composition is present in the form of boron oxide. 099101147 Form No. A0101 Page 22 of 27 0992002311-0 201124085 The antibacterial grade entry as described in claim 8 exists. / 其中 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 The antibacterial composition as described in claim 8 is more preferably about 0.5 mil, 4 〇 '' ° '5 ^ m ^ l 〇〇 4 〇 最 最 最 最 最 最 最 最 最 最 最 最 最 最 最 最, occupies about 8% of the total weight of the antibacterial composition, δ, ', weaving content. The lower 'preferred about., the following one antibacterial method, including the antibacterial; the application item W1 in the request - Anti-": An antibacterial preparation comprising: about 1〇n n90 weight of thermoplastic 槲 2.99 parts by weight of the desired bismuth and about composition or comprising about 100 weights of the item, the anti-Panwu (four) thermosetting resin and about 0] Any one of the claims 1 of the claim 1 is called the unantibacterial composition. The antibacterial product described above, wherein the antibacterial composition is dispersed in the thermoplastic resin or thermosetting resin in a powder two:: knife. The antibacterial article according to the item 13, wherein the thermoplastic resin is a polyethylene resin, a polypropylene resin, a polystyrene resin, a polystyrene tree, a polyamine resin, a polycarbonate resin, Polycondensation, bismuth (poly(ethylene terephthalate)) resin, bismuth (polybutylene terephthalate) resin and ABS (acrylonitrile-butadiene-styrene) resin. The antibacterial article according to the above item 15, wherein the thermosetting resin is selected from the group consisting of unsaturated polyester resins, epoxy resins, phenol resins, melamine resins, acrylic resins, urea resins, polyimide resins, and oxime resins. The antibacterial article of claim 13 or 14, wherein the thermosetting resin form is edited ίοι Page 23 of 27 0992002311-0 17 . 201124085 is selected from the group consisting of unsaturated polyester resins, Epoxy resin, phenolic resin, melamine resin, acrylic resin, urea resin, polyimidate resin and crushed resin. 099101147 Form No. A0101 Page 24 of 27 0992002311-00992002311-0
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI797752B (en) * 2021-09-17 2023-04-01 鄒智揮 Manufacturing method of long-acting bio-based multifunctional additive

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI797752B (en) * 2021-09-17 2023-04-01 鄒智揮 Manufacturing method of long-acting bio-based multifunctional additive

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