CN100453691C - Method for manufacturing bathroom product with surface antibacterial film and product thereof - Google Patents

Abstract

The invention provides a method for manufacturing a bathroom product with a surface antibacterial film and a product thereof, wherein the manufacturing method comprises the following steps: placing a bathroom body in a reaction chamber having a reactant gas selected from the group consisting of nitrogen, methane, acetylene, and combinations thereof; (B) plating on one surface of the bathroom body by a closed non-equilibrium magnetic sputtering method at a certain reaction temperature and working pressure to form an antibacterial film on the surface of the bathroom body. Wherein the step (B) uses a pair of first metal targets made of silver and a pair of second metal targets. The second metal target is selected from the following metal materials: zirconium, titanium and chromium. The invention can prepare bathroom products meeting the antibacterial requirement and has the characteristics of good coating compactness, high-quality wear resistance, excellent corrosion resistance, good antibacterial effect and the like.

Description

Translated fromChinese

具有表面抗菌膜的卫浴产品的制作方法及其制品Manufacturing method and product of bathroom product with surface antibacterial film

【技术领域】【Technical field】

本发明是有关于一种具有表面镀膜的卫浴产品的制作方法及其制品，特别是指一种具有表面抗菌膜(anti-microbialfilm)的卫浴产品的制作方法及其制品。The present invention relates to a manufacturing method of a bathroom product with a surface coating and its products, in particular to a manufacturing method of a bathroom product with an anti-microbial film on the surface and its products.

【背景技术】【Background technique】

参阅图1，一种习知具有表面镀膜的卫浴产品1，包含：一卫浴本体11及一形成在该卫浴本体11的一表面上的镀膜12。Referring to FIG. 1 , a conventional bathroom product 1 with surface coating includes: abathroom body 11 and acoating 12 formed on a surface of thebathroom body 11 .

该镀膜12可以是由一氮化物(nitride)或一碳化物(carbide)所制成。借助在该卫浴本体11上所形成的镀膜12以提供该卫浴产品1一抗磨耗(antifriction)的机械性质，使该卫浴产品11不但可以具有较好的耐磨耗性，并使该卫浴产品11的表面的光泽度提高。Thecoating 12 can be made of nitride or carbide. By virtue of thecoating 12 formed on thesanitary body 11 to provide the sanitary product 1 with an anti-friction mechanical property, thesanitary product 11 can not only have better wear resistance, but also make thesanitary product 11 The glossiness of the surface is improved.

此种镀膜12虽然可提供该卫浴本体11耐磨耗等特点，但是，对于时下因应抗菌功效的使用市场而言，则无法符合抗菌的需求。再者，该镀膜12一般是借助溅镀(sputtering)法或非平衡磁式溅控(Unbalanced magnetron sputtering；简称UBMS)等方式制作。其中，利用前面所提及的溅镀等方法制作的镀膜12具有镀膜组成不均等问题。Although this kind ofcoating 12 can provide characteristics such as wear resistance of thebathroom body 11, it cannot meet the antibacterial demand for the current market that needs antibacterial effect. Furthermore, thecoating film 12 is generally fabricated by means of sputtering or unbalanced magnetron sputtering (UBMS for short). Wherein, thecoating film 12 produced by the above-mentioned methods such as sputtering has problems such as uneven composition of the coating film.

针对抗菌功效的镀膜，在以往常见的用于医疗用品(medical device)的抗菌镀膜的相关文献中，有的是利用电池作用(galvanic action)或电解质(electrolyte)等湿式方法释放出抗菌离子(如：银离子或铜离子等)来达成抗菌的功效。另外，又有如金属制品的抗菌化技术则是借助添加抗菌性金属、以含抗菌剂的涂料进行涂装(coating)、以及涂布氧化钛(TiO₂)溶液后烘烤等方式来达成抗菌的功效。Aiming at the coating with antibacterial effect, in the relevant literature of the antibacterial coating that is commonly used in medical devices (medical device) in the past, some use wet methods such as battery action (galvanic action) or electrolyte (electrolyte) to release antibacterial ions (such as: silver ions or copper ions, etc.) to achieve antibacterial effect. In addition, the antibacterial technology of metal products is achieved by adding antibacterial metals, coating with antibacterial agent coatings, and coating titanium oxide (TiO₂ ) solutions and then baking. effect.

由上所述，如何开发出符合抗菌需求的卫浴产品，是当前研究开发卫浴产品的相关业者所需克服的一大难题。From the above, how to develop sanitary products that meet the antibacterial requirements is a major problem that current research and development of sanitary products needs to overcome.

【发明内容】【Content of invention】

因此，本发明的目的即是提供一种具有表面抗菌膜的卫浴产品的制作方法，可制得符合抗菌需求的卫浴产品。Therefore, the object of the present invention is to provide a method for manufacturing a sanitary product with an antibacterial film on the surface, which can produce a sanitary product that meets antibacterial requirements.

本发明的另一目的是提供一种具有表面抗菌膜的卫浴产品，具有良好的镀膜致密性、高品质的耐磨耗性、优异的抗腐蚀性及抗菌效果佳等特点。Another object of the present invention is to provide a bathroom product with an antibacterial film on the surface, which has the characteristics of good coating compactness, high-quality wear resistance, excellent corrosion resistance and good antibacterial effect.

基于上述目的，本发明提供一种具有表面抗菌膜的卫浴产品的制作方法，其特征在于：其包含以下步骤：Based on the above purpose, the present invention provides a method for making a bathroom product with a surface antibacterial film, which is characterized in that: it comprises the following steps:

将一卫浴本体放置于一具有反应气体的反应腔体中，该反应气体是选自于下列气体所构成的群组中的一种：氮气、甲烷、乙炔及其组合；及placing a bathroom body in a reaction chamber with a reactive gas selected from the group consisting of nitrogen, methane, acetylene and combinations thereof; and

在一定的反应温度及工作压力下，利用一封闭式非平衡磁式溅控法于该卫浴本体的一表面进行一定时间的施镀，以在该卫浴本体的表面上形成一抗菌膜；Under a certain reaction temperature and working pressure, a closed unbalanced magnetic sputtering method is used to perform plating on a surface of the bathroom body for a certain period of time, so as to form an antibacterial film on the surface of the bathroom body;

其中，该步骤(B)是使用一对第一金属靶材及一对第二金属靶材，该第一金属靶材是由银所制成，该第二金属靶材是由选自于下列金属材料所构成的群组所制成：锆、钛及铬，于该第一金属靶材上施加一预定电流值，并于该卫浴本体上提供一负偏压以形成该抗菌膜。Wherein, the step (B) is to use a pair of first metal target and a pair of second metal target, the first metal target is made of silver, the second metal target is selected from the following It is made of a group composed of metal materials: zirconium, titanium and chromium. A predetermined current value is applied to the first metal target, and a negative bias voltage is provided on the sanitary body to form the antibacterial film.

在一具体实施例中，该反应气体是氮气，该第二金属靶材的金属材料是锆。In a specific embodiment, the reaction gas is nitrogen, and the metal material of the second metal target is zirconium.

较佳地，该步骤(B)中的预定电流值是介于0.4A至0.45A，该反应温度是介于80℃至180℃，该工作压力是介于20mTorr至0.1mTorr，该施镀时间是介于3min至13min，该负偏压的绝对值是低于80V。Preferably, the predetermined current value in the step (B) is between 0.4A and 0.45A, the reaction temperature is between 80°C and 180°C, the working pressure is between 20mTorr and 0.1mTorr, and the plating time is is between 3min and 13min, and the absolute value of the negative bias voltage is lower than 80V.

适用于本发明的该步骤(A)中的该卫浴本体是由选自于下列所构成的群组中的材料所制成：铜合金(copper alloy)、锌合金(zinc alloy)、不锈钢(stainless steel)、塑料(plastic)及陶瓷(ceramic)。在一具体实施例中，该卫浴本体是由铜合金所制成。The bathroom body suitable for the step (A) of the present invention is made of a material selected from the group consisting of: copper alloy, zinc alloy, stainless steel steel), plastic and ceramic. In a specific embodiment, the bathroom body is made of copper alloy.

适用于本发明的该步骤(A)中的该卫浴本体是选自于下列所所构成的群组：毛巾杆架、门把、挂勾、水龙头、莲蓬头、置物架、肥皂架、卫生纸架及牙刷杯架。The bathroom body suitable for the step (A) of the present invention is selected from the group consisting of: towel bar rack, door handle, hook, faucet, shower head, shelf, soap holder, toilet paper holder and Toothbrush cup holder.

利用本发明的方法可制作出一种具有表面抗菌膜的卫浴产品，包含一卫浴本体；其特征在于：Utilize the method of the present invention to produce a kind of bathroom product with surface antibacterial film, comprise a bathroom body; It is characterized in that:

在该卫浴本体的一表面上形成有抗菌膜，该抗菌膜是由一抗菌组成物所制成，该抗菌组成物包含有一母材及纳米级银粒子，该母材是选自于下列化合物所构成的群组：氮化物及碳化物。An antibacterial film is formed on a surface of the bathroom body, the antibacterial film is made of an antibacterial composition, the antibacterial composition includes a base material and nano-scale silver particles, the base material is selected from the following compounds Constituent groups: nitrides and carbides.

该抗菌膜是由一抗菌组成物所制成。该抗菌组成物包含有一母材及纳米级银粒子。该母材是选自于下列所构成的群组的化合物：氮化物及碳化物。The antibacterial film is made of an antibacterial composition. The antibacterial composition includes a base material and nanometer silver particles. The base material is a compound selected from the group consisting of nitrides and carbides.

适用于本发明的该化合物为氮化物。较佳地，该氮化物是选自于下所构成的群组：氮化锆(ZrN)、氮化铬(CrN)及氮化钛(TiN)。在一具体实施例中，该氮化物是氮化锆。The compounds suitable for use in the present invention are nitrides. Preferably, the nitride is selected from the group consisting of zirconium nitride (ZrN), chromium nitride (CrN) and titanium nitride (TiN). In a specific embodiment, the nitride is zirconium nitride.

适用于本发明的该卫浴本体是由选自于下列所构成的群组中的材料所制成：铜合金、锌合金、不锈钢、塑料及陶瓷。在一具体实施例中，该卫浴本体是由铜合金所制成。The bathroom body suitable for the present invention is made of materials selected from the group consisting of copper alloy, zinc alloy, stainless steel, plastic and ceramics. In a specific embodiment, the bathroom body is made of copper alloy.

适用于本发明的该卫浴本体是选自于下列所构成的群组：毛巾杆架、门把、挂勾、水龙头、莲蓬头、置物架、肥皂架、卫生纸架及牙刷杯架。The bathroom body suitable for the present invention is selected from the group consisting of towel bar holder, door handle, hook, faucet, shower head, storage rack, soap holder, toilet paper holder and toothbrush cup holder.

有关本发明的前述及其它技术内容、特点与功效，在以下配合参考图式的一具体实施例的详细说明中，将可清楚的明白。The foregoing and other technical contents, features and effects of the present invention will be clearly understood in the following detailed description of a specific embodiment with reference to the drawings.

【附图说明】【Description of drawings】

图1是一正视剖面示意图，说明一种习知具有表面镀膜的卫浴产品；Fig. 1 is a front sectional schematic diagram illustrating a conventional bathroom product with a surface coating;

图2是一流程图，说明本发明的制作具有表面抗菌膜的卫浴产品的方法；及Fig. 2 is a flow chart, illustrates the method for making the bathroom product with surface antibacterial film of the present invention; And

图3是一正视剖面示意图，说明本发明的具有表面抗菌膜的卫浴本体。Fig. 3 is a front sectional schematic diagram illustrating the bathroom body with an antibacterial film on the surface of the present invention.

【具体实施方式】【Detailed ways】

<实施例一><Example 1>

利用研磨(milling)及抛光(polish)等制造程序对一材料为铜合金的卫浴本体进行表面平坦化处理。另外，以去离子水(deionize water)清洗该完成平坦化的卫浴本体，并利用乙醇擦拭该卫浴本体。接着，以超音波震荡法清洁该卫浴本体并加以烘干。The surface planarization treatment is carried out on a bathroom body made of copper alloy through manufacturing processes such as milling and polishing. In addition, the flattened bathroom body was cleaned with deionized water, and the bathroom body was wiped with ethanol. Then, the body of the bathroom is cleaned by ultrasonic vibration method and dried.

放置该卫浴本体于一具有氮气的反应气体及氩气(Ar₂)的缓冲气体的反应腔体中。在180℃的反应温度及1.1mTorr的工作压力下，利用CFUBMS法于该卫浴本体的一表面实施13分钟的施镀时间，以在该卫浴本体的表面上形成一抗菌膜。The bathroom body is placed in a reaction chamber with nitrogen reaction gas and argon (Ar₂ ) buffer gas. Under the reaction temperature of 180° C. and the working pressure of 1.1 mTorr, the CFUBMS method was used to implement a plating time of 13 minutes on a surface of the bathroom body to form an antibacterial film on the surface of the bathroom body.

在该具体实施例一中，是使用一对由银制成的靶材及一对由锆制成的靶材。于该银靶材上施加一0.45A的电流值，并于该卫浴本体上提供一负偏压量(-50V)以形成一含有纳米级银粒子的氮化锆(Ag-ZrN)的抗菌膜。In the first embodiment, a pair of targets made of silver and a pair of targets made of zirconium are used. Apply a current value of 0.45A to the silver target, and provide a negative bias (-50V) on the bathroom body to form an antibacterial film of zirconium nitride (Ag-ZrN) containing nano-scale silver particles .

利用该具体实施例一的方法，可制作出本发明的具有表面抗菌膜的卫浴产品。参阅图3，由该具体实施例一所制作的卫浴产品，包含：一材料为铜合金的卫浴本体2，及一形成在该卫浴本体2的一表面上的抗菌膜3。Utilize the method of this specific example 1, can make the bathroom product with surface antibacterial film of the present invention. Referring to FIG. 3 , the bathroom product produced by the first embodiment includes: a bathroom body 2 made of copper alloy, and an antibacterial film 3 formed on a surface of the bathroom body 2 .

该抗菌膜3是由一抗菌组成物所制成。该抗菌组成物包含有一材料为氮化锆(ZrN)的母材及纳米级银粒子。The antibacterial film 3 is made of an antibacterial composition. The antibacterial composition includes a base material of zirconium nitride (ZrN) and nanometer silver particles.

<抗菌度分析><Analysis of Antibacterial Degree>

本发明的具有表面抗菌膜的卫浴产品是送至食品工业发展研究所(Food Industry Research & Development Institute)进行大肠杆菌(Escherichia coli)及金黄色葡萄球菌(Staphylococcus aureus)等抑菌试验。此处所采用的试验方式为日本工业标准(Japanese Industry Standard；JIS)的JIS Z2801：2000法，所得分析结果如表一及表二所示：The bathroom product with surface antibacterial film of the present invention is sent to the Food Industry Research & Development Institute (Food Industry Research & Development Institute) for antibacterial tests on Escherichia coli and Staphylococcus aureus. The test method used here is the JIS Z2801:2000 method of the Japanese Industry Standard (JIS), and the analysis results obtained are shown in Table 1 and Table 2:

表一、抗菌镀膜对大肠杆菌的抑菌情形Table 1. Antibacterial effect of antibacterial coating on Escherichia coli

抑菌值＝log(对照组24小时菌数/样品组24小时菌数)Bacterial inhibition value = log (the number of bacteria in the control group in 24 hours/the number of bacteria in the sample group in 24 hours)

表二、抑菌值与抑菌率的参考对照表Table 2. Reference table of antibacterial value and antibacterial rate

^**NA：因样品组菌数大于对照组菌数，无法计算其抑菌值^** NA: Since the number of bacteria in the sample group is greater than the number of bacteria in the control group, the antibacterial value cannot be calculated

其中，抗菌镀膜试片S17是利用本发明的具体实施例一的方法所制备而得的卫浴产品。由表一及表二可得，本发明的卫浴产品具有99.999％的抑菌率。另外，本发明的卫浴产品对于金黄色葡萄球菌及绿浓杆菌(Pseudomonas aeruginosa)的抑菌率也可达99％(表未示)。Among them, the antibacterial coating test piece S17 is a sanitary product prepared by the method of the first embodiment of the present invention. It can be obtained from Table 1 and Table 2 that the bathroom product of the present invention has a bacteriostatic rate of 99.999%. In addition, the antibacterial rate of the bathroom product of the present invention to Staphylococcus aureus and Pseudomonas aeruginosa can reach 99% (not shown).

由于，本发明利用CFUBMS法可于该反应腔体内形成一连续封闭式磁场，使该卫浴本体的中心区域被此连续封闭式磁场所包围。因此，有效地防止电浆(plasma)粒子(氮离子、银离子、氩离子等)逃逸，并将电浆粒子局限于该连续封闭式磁场内以提高离子的碰撞机率并增加离化(ionization)率，从而产生电浆密集区并增加薄膜中等离子(plasma)沉积密度。如此，可增加卫浴产品表面的载银抗菌镀膜致密性，并可提高抗腐蚀(corrosion resistance)性及耐磨耗性。Because the present invention uses the CFUBMS method to form a continuous closed magnetic field in the reaction chamber, so that the central area of the bathroom body is surrounded by the continuous closed magnetic field. Therefore, effectively prevent plasma (plasma) particles (nitrogen ions, silver ions, argon ions, etc.) rate, thereby creating a plasma-dense region and increasing the plasma (plasma) deposition density in the film. In this way, the compactness of the silver-loaded antibacterial coating on the surface of the bathroom product can be increased, and the corrosion resistance and wear resistance can be improved.

另外，材料对于抗菌机制大致上有干扰细胞壁(cell wall)的合成、损坏细胞膜(cell membrane)、抑制蛋白质(protein)的合成及干扰核酸(nucleic acid)的合成等机制。由于离化率的增加致使银粒子的外层轨域被游离掉的电子数目提高，因而使得银离子的尺寸可微小化。由此，带有正电荷的微小化银离子与细菌的间借助异性相吸引的方式，使细胞膜破裂而导致细菌发生溶解死亡，并破坏细菌内的酵素系统(enzymesystem)影响细菌正常的新陈代谢。In addition, the antibacterial mechanism of materials generally includes mechanisms such as interfering with the synthesis of cell walls, damaging cell membranes, inhibiting protein synthesis, and interfering with nucleic acid synthesis. As the ionization rate increases, the number of electrons that are dissociated from the outer orbital domain of the silver particle increases, thereby making the size of the silver ion miniaturized. Thus, the positively charged miniaturized silver ions and the bacteria are attracted by the opposite sex, causing the cell membrane to rupture, causing the bacteria to dissolve and die, and destroying the enzyme system (enzymesystem) in the bacteria to affect the normal metabolism of the bacteria.

本发明的制作具有表面抗菌膜的卫浴产品的方法及其制品，具有良好的镀膜致密性、高品质的耐磨耗性、优异的抗腐蚀性及抗菌效果佳等特点，确实达到本发明的目的。The method for making sanitary products with surface antibacterial film and its products of the present invention have the characteristics of good coating compactness, high-quality wear resistance, excellent corrosion resistance and good antibacterial effect, and indeed achieve the purpose of the present invention .

以上所述仅为本发明的较佳实施例而已，当不能以此限定本发明实施的范围，实际上，根据本发明所作的各种等效变化与修饰，皆应仍属于本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and should not limit the scope of the present invention. In fact, various equivalent changes and modifications made according to the present invention should still belong to the protection scope of the present invention. within.

Claims (6)

Translated fromChinese

1.一种具有表面抗菌膜的卫浴产品的制作方法，其特征在于：其包含以下步骤：1. A method for making a sanitary product with a surface antibacterial film, characterized in that: it comprises the following steps:(A)将一卫浴本体放置于一具有反应气体的反应腔体中，该反应气体是选自于下列气体所构成的群组中的一种：氮气、甲烷、乙炔及其组合；及(A) placing a bathroom body in a reaction chamber with a reactive gas selected from the group consisting of nitrogen, methane, acetylene and combinations thereof; and(B)在一定的反应温度及工作压力下，利用一封闭式非平衡磁式溅控法于该卫浴本体的一表面进行一定时间的施镀，以在该卫浴本体的表面上形成一抗菌膜；(B) Under a certain reaction temperature and working pressure, use a closed non-equilibrium magnetic sputtering method to perform plating on a surface of the bathroom body for a certain period of time to form an antibacterial film on the surface of the bathroom body ;其中，该步骤(B)是使用一对第一金属靶材及一对第二金属靶材，该第一金属靶材是由银所制成，该第二金属靶材是由选自于下列金属材料所构成的群组所制成：锆、钛及铬，于该第一金属靶材上施加一预定电流值，并于该卫浴本体上提供一负偏压以形成该抗菌膜；Wherein, the step (B) is to use a pair of first metal target and a pair of second metal target, the first metal target is made of silver, the second metal target is selected from the following It is made of a group composed of metal materials: zirconium, titanium and chromium, applying a predetermined current value on the first metal target, and providing a negative bias voltage on the bathroom body to form the antibacterial film;该步骤(B)中的预定电流值是介于0.4A至0.45A，该步骤(B)中的反应温度是介于80℃至180℃，该步骤(B)中的工作压力是介于20mTorr至0.1mTorr，该步骤(B)中的施镀时间是介于3min至13min，该步骤(B)中的负偏压的绝对值是低于80V。The predetermined current value in the step (B) is between 0.4A and 0.45A, the reaction temperature in the step (B) is between 80°C and 180°C, and the working pressure in the step (B) is between 20mTorr To 0.1mTorr, the plating time in the step (B) is between 3min to 13min, and the absolute value of the negative bias voltage in the step (B) is lower than 80V.2.如权利要求1所述的具有表面抗菌膜的卫浴产品的制作方法，其特征在于：该反应气体是氮气。2. The manufacturing method of the bathroom product with surface antibacterial film as claimed in claim 1, characterized in that: the reaction gas is nitrogen.3.如权利要求2所述的具有表面抗菌膜的卫浴产品的制作方法，其特征在于：该第二金属靶材的金属材料是锆。3. The manufacturing method of a bathroom product with an antibacterial film on the surface according to claim 2, wherein the metal material of the second metal target is zirconium.4.如权利要求1所述的具有表面抗菌膜的卫浴产品的制作方法，其特征在于：该步骤(A)中的该卫浴本体是由选自于下列材料所构成的群组中的任一种材料所制成：铜合金、锌合金、不锈钢及塑料。4. The manufacturing method of a bathroom product having an antibacterial film on the surface as claimed in claim 1, wherein the bathroom body in the step (A) is any one selected from the group consisting of the following materials Made of various materials: copper alloy, zinc alloy, stainless steel and plastic.5.如权利要求1所述的具有表面抗菌膜的卫浴产品的制作方法，其特征在于：该步骤(A)中的该卫浴本体是选自于下列所构成的群组：门把、挂勾、水龙头和置物架。5. The manufacturing method of a bathroom product with an antibacterial film on the surface as claimed in claim 1, wherein the bathroom body in the step (A) is selected from the group consisting of: door handle, hook , faucets and shelves.6.如权利要求1所述的具有表面抗菌膜的卫浴产品的制作方法，其特征在于：该步骤(A)中的该卫浴本体是选自于下列所构成的群组：毛巾杆架、莲蓬头、肥皂架、卫生纸架及牙刷杯架。6. The manufacturing method of the bathroom product with surface antibacterial film as claimed in claim 1, characterized in that: the bathroom body in the step (A) is selected from the group consisting of: towel bar frame, shower head , soap holder, toilet paper holder and toothbrush cup holder.

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