TW200813252A - A method to produce a wear resistant, corrosion resistant and transparent coating - Google Patents
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200813252 九、發明說明： 【發明所屬之技術領域】 本發明是有關於-種耐磨耗抗腐蝕之鍍膜的製作方、、去 ，特別是指-種耐磨耗抗腐餘且透明度高之鍍膜的製作方 法。 【先前技術】 -般而言，在衛浴用品的領域中，由於此等用品所處 的使用環境不但渔度高，此外，„需承受清潔劑等酸驗200813252 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for producing a coating for abrasion resistance and corrosion resistance, and particularly for a coating having high abrasion resistance and high transparency. Production method. [Prior Art] In general, in the field of sanitary ware, the use environment of these products is not only high in fishing, but also, it is necessary to withstand the acid test such as detergent.
溶液的清洗與沖刷，因&，衛浴用品至少必須能夠達到耐 磨耗、抗腐蝕等特性。 以現有的技術中，大多數是使用如喷漆等技術以在衛 浴用品的底材上塗裝一透明塑膠的拉克鍍膜（Cleaning and scouring of the solution, due to &, toiletries must at least be resistant to wear and corrosion. Most of the prior art techniques use a technique such as painting to apply a transparent plastic lacquer coating to the substrate of the bathroom article (
Elastic Lacquer Coating) ’藉以防止衛浴用品的底材與環境 中的水分、或清潔劑直接接觸。雖然施予前述技術之衛浴 用品可藉由此透明塑膠的拉克鍍膜阻止外界水氣的侵蝕， 然而，經由此技術所構成的拉克鍍膜之硬度值僅為astm 3363-05中的F等級，且其本身不耐高溫、冷熱循環低、易 沾指紋、耐磨耗性不足，此外，於製程中需夾雜地使用到 許多毒性物質，亦造成製程上的污染。 與抗腐钱之鐘膜相關的技術，可見於Us 5,437,725中 所揭示之一種用以於移動中的金屬材料連續地披覆一具有 組成梯度之聚合沉積物的裝置，其裝置提供一種電漿輔助 化學氣相、/儿積（plasma enhanced CVD，簡稱PECVD)之連續 鍍膜方法，包含： 5 200813252 ⑷於-低壓腔體中引入-氣態之高分子單體(如，六甲 基二石夕氧烧，HDMSO)以維持、約l〇pa〜i〇〇pa(〇 3 mbar)的工作壓力； w於該低廢腔體中利用一第第二及一第三捲筒 連續地帶動-帶狀金屬’其中，與該第一、第二及 第三捲筒對應處分別設置有一與一電源供應器電性 連接的第 第二及-第三電極，且料電極分 別與該帶狀金屬共同界定出_第___第二及一第Elastic Lacquer Coating) ‘ to prevent the substrate of the bathroom from coming into direct contact with moisture or detergent in the environment. Although the sanitary article to which the above-mentioned technology is applied can prevent the external moisture from being eroded by the Lac coating of the transparent plastic, the hardness of the Lac coating formed by the technology is only the F grade in astm 3363-05, and It is not resistant to high temperature, low cycle of cold and heat, easy to fingerprint, and insufficient wear resistance. In addition, many toxic substances are used in the process, which also causes pollution in the process. A technique relating to the anti-corrosion film can be seen in U.S. Patent No. 5,437,725, the disclosure of which is incorporated herein incorporated by reference in its entire entire entire entire entire entire disclosure A continuous coating method for chemical vaporization or plasma enhanced CVD (PECVD), comprising: 5 200813252 (4) introduction of a gaseous monomer in a low pressure chamber (eg, hexamethyldiazepine) , HDMSO) to maintain, about l〇pa~i〇〇pa (〇3 mbar) working pressure; w in the low waste cavity using a second and a third reel continuously moving - strip metal Wherein, the second and third electrodes electrically connected to the power supply are respectively disposed corresponding to the first, second and third reels, and the material electrodes are respectively defined together with the strip metal _第___ second and one
三空間； (C)定義該等電極分別作為一晤 、 卞电4刀⑺讣苟除極，並以該帶狀金屬作 為一陰極； (晴該電源供應器施予80 w及％他的工作條件， 藉該等空間中所構成的電位差致使該高分子單體產 =裂解並分別構成三區的低溫電漿，進而於該帶狀 金屬表面依序形成一趨近有機特性的第—層、一趨 近無機特性的第二層及—趨近有機特性的第三層。 於^的聚合物沉積裝置中’該第二捲筒内四周财 L:r(permanent magnets)，藉該等永久磁鐵以在該 的單==持则G的磁場強度，並使得該第二空間内 性的第::速裂解而於該第-層上形成該趨近無機特 一利用揭示於us 5,437,725之裝置所取得的第—、二及 一層’其目的主要是在於，藉由低溫電漿聚合 以在金屬材料表面± 门刀子材科 仏成H，猎該保護膜提 6 200813252 鍅的特性。 另’一般用途廣泛的商用塑膠及高分子等 聚碳酸抑♦▲畔因具财優異的抗破損（b咖如e 咖e)能力而可取代破璃材料並常被應用於車頭燈或窗 然而’對於某些需具傷有耐磨耗、抗紫外線老化 特性的應利域而言，此等商職膠材料仍存在有耐磨耗 性差以及無法承受長時間的紫外線照射等缺點，因此，1 應用範圍仍大受限制。 'Three spaces; (C) define the electrodes as a single, 4 4 (7) 讣苟 depolarization, and use the strip metal as a cathode; (the power supply is given 80 w and % of his work) Conditions, by the potential difference formed in the spaces, the polymer monomer is produced = cracked and respectively constitutes a low temperature plasma of the three regions, and a first layer which is close to the organic property is sequentially formed on the surface of the strip metal, a second layer that is closer to the inorganic property and a third layer that is closer to the organic property. In the polymer deposition apparatus of the ^, the second reel is surrounded by permanent magnets, by means of the permanent magnets Using the magnetic field strength of the single == holding G, and making the second spatial intrinsic:: speed cracking to form the approaching inorganic specificity on the first layer, the device disclosed in us 5,437,725 The first, second and first layers obtained are mainly aimed at the characteristics of the coating film on the surface of the metal material by low-temperature plasma polymerization, and the characteristics of the protective film 6 200813252 另. A wide range of commercial plastics and polymers, such as polycarbonate It has the ability to resist damage (b coffee such as e-ca) and can replace broken glass materials and is often used in headlights or windows. However, for some need to have wear resistance and UV aging resistance In terms of the field, these commercial rubber materials still have shortcomings such as poor wear resistance and long-term ultraviolet radiation. Therefore, the scope of application is still limited.
US 6,737’121則是有鑑於此等商用塑膠仍存在有前述的 缺失’因而揭示一種利用電孤電漿沉積如c Plasma deposition)製備多層膜製品的方法包含以下步驟： ⑴連接有—_室的電漿產生室内引人一電聚 孔體’該〉儿積室具有較該電漿產生室更低的壓力 ，該製品是沉積於該沉積室内； (ii)於該電裝產生宮肉a 生至内引入一電弧以製造一流入該沉 積室内的電漿； 有機石夕材料的中間層； (111)將一含有一第-氧化劑、至少-可聚合之烴類及 一第一有機矽材料的第一材料注入該電紫中，並 反應該第一材料以在-基材上形成-含有一聚合 (iv)將 3有一第二氧化劑、至少一主要金屬及一有 機二屬化合物的第二材料注入該電漿中，並反應 該第二材料以在該中間層上形成—含有無機的紫 外線吸收材料之第二層。 7 200813252 此外，於該步驟（iv)之後更包含一步驟⑺ (V)是將一合右一笼一 e w δ亥步驟 有弟二乳化刎及一第二有機矽材料的 料注入該電赞中，廿昂~材 电水中，並反應該弟三材料以在該第二屑 一含有耐磨耗材料之第三層。 " >成 由前述說明可知，US 6,737，121主要是利用高溫的電弧 電漿迫使該第三材料產生較完整的裂解，&而在該第二層 上形成具備有耐磨耗性的第三層。 曰US 6,737 '121 is in view of the fact that such commercial plastics still have the aforementioned defects, thus revealing a method for preparing a multilayer film article by using electro-plasma deposition such as c plasma deposition, comprising the following steps: (1) Connecting a chamber The plasma generating chamber introduces an electric polycolloid. The accumulating chamber has a lower pressure than the plasma generating chamber, and the product is deposited in the deposition chamber; (ii) the meat is produced in the electric appliance. Introducing an arc to produce a plasma flowing into the deposition chamber; an intermediate layer of the organic stone material; (111) comprising a first oxidizing agent, at least a polymerizable hydrocarbon, and a first organic germanium material a first material is injected into the electro violet, and the first material is reacted to form on the substrate - a second material comprising a polymer (iv) 3 to have a second oxidant, at least one main metal and an organic dimer compound The plasma is injected and the second material is reacted to form a second layer comprising an inorganic UV absorbing material on the intermediate layer. 7 200813252 In addition, after step (iv), a step (7) (V) is further included in which a material of a right-cage, an ew, and a second organic cerium material is injected into the electric tribute. , 廿昂~材电水, and reacts the three materials to the third layer containing the wear resistant material in the second chip. "> As can be seen from the foregoing description, US 6,737,121 mainly uses high temperature arc plasma to force the third material to produce a relatively complete cracking, & and on the second layer is formed with wear resistance the third floor.曰
對於衛浴用品等相關領域而言，鍍膜尚需具備有高透 明度的特點以符合美觀性的要求。然而，us 5，们及 US 6,737，121兩篇美國前案之方法所提供的鍍膜特性，僅考 里到耐磨耗及抗腐蝕等功效，因此，由此等方法所製得的 鍍膜仍無法符合衛浴用品中對於透明度高之美觀性的要求 【發明内容】 <發明概要> 由於一般透過PECVD以使得位於反應環境中的石夕氧燒 類（sil〇xanes)產生反應裂解，雖然可提供抗磨耗性高的鍍膜 ’但由此法所製得的鍍膜，經光源照射之下仍可由其外觀 顯示出大量的干涉條紋，因此，透明度不佳。 而利用PECVD於反應環境中額外引入氧化劑，雖然有 利於結合經過裂解的氧化劑與矽離子並降低矽離子與碳的 結合機率，進而增加鍍膜的無機化並改善鍍膜的透明度。 然而，最終所取得的鍍膜之透明度仍嫌不足。 前述透明度不足的原因乃是在於矽氧烷類於裂解反應 8 200813252 過程中游離化的程度不夠所致。因此，有鏗於鍍膜需同時 達到财磨耗抗腐链及高透明度的要求，首要之技街則是在 於增加矽氧烷類於形成電漿態時的游離化程度。然而，其 於PECVD本身反應環境的限制，雖然經由增加工作電壓以 將電能全部地導引到電漿中可增加反應氣體源的游離化， 但最終所形成之鍍膜屬於電性絕緣的材質，極容易因為在 鍍膜表面累積過量的電荷而產生放電打弧（arc)的現象，致 使最終所製得的鍍膜仍存在有鍍膜不均的問題。 • 因此，本發明是利用直流雙極脈衝電壓（Bipolar pulse DC)並配合製程以調整出恰當的直流雙極脈衝電屢之鑛膜週 期[即’占空比（duty CyCle)]，在減少累積於鍍膜表面的電荷 量的情況下仍可提高鍍膜週期以增加氣體反應源的游離化 並提高最終鑛膜之透明度。 士圖1所示，在決定雙極脈衝電壓頻率之後以取得雙 極脈衝私壓的週期為t〇。利用工作電壓在—V維持q的時間 以作為產生電漿的錢膜時間，並以+v的反向電壓維持h的 ⑩ ％間以作為移除累積電荷的媳*時間日夺，則[VtoJxlOOo/o被 定義為占空比。 值待 ^的疋’考慮反應氣體源的游離化程度將決定 鑛膜的無機化程度與透明度。因此，在反應環境中不產生 放電打弧的現象下，占空比應盡量維持在高比例的狀態以 提供反應氣體源具備有足夠的電能產生游離化，其中，占 二比至乂而间於4〇 % ;然而，在顧及適度地將累積於鍍膜 表面的電荷予以排除，占空比將不超過95%。 9 200813252 〈發明目的〉 因此，本發明之㈣，即在提供一種耐磨餘腐钱且 透明度高之鍍膜的製作方法。 於是，本發明耐磨耗抗腐蝕且透明度高之鍍膜的製作 方法，包含以下步驟： (a)於一反應腔體中引入一含有一呈氣態之矽氧烷類、 一氧化劑（可為氧氣）及一輸送氣體（可為氬氣）之反應 源；及 ~ φ (b)對該反應腔體之一陰極板（或稱作掛具）施予一雙極 脈衝電壓，以使該反應源裂解成一電漿氣體並於一 設置於該陰極板（或稱作掛具）之基材上形成一耐磨 耗抗腐蝕且透明度高之鍍膜； 其中，該雙極脈衝電壓的占空比（duty cycle)是介於 %至95 %之間。 【實施方式】 <發明詳細說明> _ 本發明耐磨耗抗腐蝕且透明度高之鍍膜的製作方法， 包含以下步驟·· (a) 於一反應腔體中引入一含有一呈氣態之矽氧烷類、 一氧化劑及一輸送氣體之反應源；及 (b) 對該反應腔體之一陰極板施予一雙極脈衝電壓，以 使5亥反應源裂解成一電漿氣體並於一設置於該陰極 板之基材上形成一耐磨耗抗腐蝕且透明度高之鑛膜 10 200813252 %至95 %之 其中，該雙極脈衝電壓的占空比是介於4〇 間。 由前揭發明概要的說明可知，較適合於本發明該步驟 (b)之雙極脈衝電壓的占空比是介於6〇 %至95 %之間。而適 用於本务明该步驟（b)之雙極脈衝電壓的頻率是介於1 〇 j^Hz 至250 kHz之間；該步驟卬)之雙極脈衝電壓的工作電壓是 介於-100 V至-400 V之間；該步驟（b)之反應腔體的工作壓 力是介於1 PaS 1〇〇 Pa之間；該步驟⑷之呈氣態的石夕氧烧For related fields such as toiletries, the coating needs to have high transparency to meet the aesthetic requirements. However, the coating properties provided by us 5, US and US 6,737,121 in the US method of the previous case only have the effects of abrasion resistance and corrosion resistance. Therefore, the coatings obtained by such methods are still unable to Compliance with the requirements for high transparency in sanitary articles [Summary of the Invention] <Summary of the Invention> Since the reaction cracking is generally carried out by PECVD to cause sil〇xanes in the reaction environment, although The coating with high abrasion resistance', but the coating produced by this method can still exhibit a large amount of interference fringes by its light source, and therefore, the transparency is not good. The use of PECVD to additionally introduce an oxidizing agent into the reaction environment, while facilitating the combination of the cleavage oxidant and cerium ions and reducing the probability of binding of cerium ions to carbon, thereby increasing the inorganicization of the coating and improving the transparency of the coating. However, the transparency of the final coating obtained is still insufficient. The reason for the lack of transparency mentioned above is due to insufficient degree of dissociation of the oxane in the cleavage reaction 8 200813252. Therefore, there is a need to simultaneously achieve the requirements of the anti-corrosion chain and high transparency of the coating, and the primary technology street is to increase the degree of dissociation of the oxane in the formation of the plasma state. However, its limitation on the reaction environment of PECVD itself, although the introduction of the working voltage to fully guide the electrical energy into the plasma can increase the release of the reactive gas source, but the final formed coating is an electrically insulating material. It is easy to cause a discharge arcing phenomenon due to accumulation of an excessive amount of electric charge on the surface of the plating film, so that the coating film finally obtained still has a problem of uneven coating. • Therefore, the present invention utilizes a bipolar pulse DC and a process to adjust the proper DC bipolar pulse current to the membrane cycle [ie, duty cycle (duty CyCle)], reducing accumulation In the case of the amount of charge on the surface of the coating, the plating cycle can be increased to increase the freeness of the gas reaction source and increase the transparency of the final mineral film. As shown in Fig. 1, the period of obtaining the bipolar pulse private voltage after determining the bipolar pulse voltage frequency is t〇. Use the working voltage to maintain q for -V as the film time to generate the plasma, and maintain the 10% of h with the reverse voltage of +v as the time to remove the accumulated charge. [VtoJxlOOo /o is defined as the duty cycle. The degree of freeness of the reaction gas source will determine the degree of mineralization and transparency of the mineral film. Therefore, under the phenomenon that no discharge arcing occurs in the reaction environment, the duty ratio should be maintained as high as possible to provide a source of reactive gas with sufficient electrical energy to generate dissociation, wherein the ratio is equal to 4〇%; however, the duty ratio will not exceed 95%, taking into account the proper elimination of the charge accumulated on the surface of the coating. 9 200813252 <Object of the Invention> Therefore, (4) of the present invention provides a method for producing a coating film having high wear resistance and high transparency. Therefore, the method for preparing a coating film with high abrasion resistance and corrosion resistance and high transparency comprises the following steps: (a) introducing a gas phase-containing oxane gas and an oxidizing agent (which may be oxygen) into a reaction chamber. And a reaction source for transporting gas (which may be argon); and ~ φ (b) applying a bipolar pulse voltage to a cathode plate (or a rack) of the reaction chamber to cleave the reaction source Forming a plasma gas and forming a coating resistant to corrosion and high transparency on a substrate disposed on the cathode plate (or called a hanger); wherein the duty cycle of the bipolar pulse voltage (duty cycle) ) is between % and 95%. [Embodiment] <Detailed Description of the Invention> _ The method for producing a coating film having high abrasion resistance and corrosion resistance and high transparency comprises the following steps: (a) introducing a gas containing a gas in a reaction chamber a reaction source of an oxane, an oxidant, and a transport gas; and (b) applying a bipolar pulse voltage to one of the cathode plates of the reaction chamber to cause the 5-gal reaction source to be cracked into a plasma gas and set in a plasma A corrosion-resistant and highly transparent mineral film 10 is formed on the substrate of the cathode plate, wherein the duty cycle of the bipolar pulse voltage is between 4 。. It is apparent from the description of the foregoing summary of the invention that the duty cycle of the bipolar pulse voltage which is more suitable for the step (b) of the present invention is between 6〇% and 95%. The frequency of the bipolar pulse voltage for this step (b) is between 1 〇j^Hz and 250 kHz; the operating voltage of the bipolar pulse voltage of this step 卬) is between -100 V Between -400 V; the working pressure of the reaction chamber of the step (b) is between 1 PaS and 1 〇〇 Pa; the gas-phase shixi oxygen burning of the step (4)
類疋四甲基二矽氧烷（tetramethyldisiloxane ;簡稱TMDSO ; 化學式為C4Hu〇Si2)‘或六曱基二矽氧燒 (heXamethyldiSil〇Xane ;簡稱 HMDS〇 ;化學式為 caw叫) ;該步驟⑷之氧化劑是氧氣(〇2)或臭氧（〇3);該步称⑷之輸 送氣體是氬氣㈣；且呈氣態㈣氧絲是於丨域壓及室 溫的條件下經由該輸送氣體引入該反應腔體中。Tetramethyldisiloxane (TMDSO; chemical formula is C4Hu〇Si2)' or hexamethyldiSil〇Xane (referred to as HMDS〇; chemical formula is called caw); oxidant of this step (4) Is oxygen (〇2) or ozone (〇3); the transport gas of the step (4) is argon (four); and the gaseous (tetra) oxygen filament is introduced into the reaction chamber via the transport gas under the conditions of pressure and room temperature. In the body.
值得-提的是，在顧及適度地排除累積於該步驟⑻之 鑛膜表面的電荷並使得該步驟⑻之反應源獲取足夠的電处 :乂產生游離化的狀況下，較佳地，該步驟(b)之雙極脈衝； Μ的占空Q介於8G%至之間；該步驟⑻之雙極脈衝 電壓的反向電壓是介於0 V至+75 V之間；配合介於的％ 至95 %之間的占空比，該步驟⑻之雙極脈衝電壓的頻率 介於30 kHzS 25〇 kHz之間；該步驟⑻之雙極脈衝電壓的 工作電壓是介於-100 v至_300 V之間；該 體的工作壓力是介於丨Pa i 1Q ρ ^ α腔 上以至1〇 Pa之間；該步驟 烧類及氧化劑分別是四甲基二石夕氧烧及氧氣。 乳 200813252 另，值得一提的是，當該步驟（a)之反應源中之氧氣流 量對氬氣流量的比值過小時，將使得引入該反應·腔體中的 氧氣量相對下降，並影響該步驟（b)之鐘膜的透明度；反之 ，當該步驟（a)之反應源中之氧氣流量對氬氣流量的比值過 大時，將使得本發明之鍍率下降。因此，該步驟之反應 源中的氧氣流量對氬氣流量之比值是介於〇_5至2.0之間。 又更佳地，該步驟（a)之反應源中的氧氣流量對氬氣流量之 比值是介於0.5至1.0之間。 又，值付一提的是，本發明前面所述之工作電壓並不 限於-120 V至_4〇〇 V之間的範圍。由於當工作電壓越大時 ，不僅可提高實施於該反應源之電能以辅助該反應源之游 離化，此外，亦可增加設置於該陰極之基材的工作溫度， 以提供經游離化的反應源在沉積過程中得到較高的擴散能 里，並增加該步驟（b)之鍍膜結構的緻密性及附著性。 因此’在本發明中，涉及與工作電壓有關的細部條件 要是與設置在該陰極上的基材材質有關。當該基材的 材質屬於高分子材料時，則應適度地降低工作電壓以避免 無法承受高溫條件的高分子材料產生損壞。反之，當該基 材的材質屬於陶瓷材料時，在不產生放電打弧的情況下， ::可適度地增加工作電壓’藉以提高實施於該反應源的電 月b ^使件該反應源之游離化得到適度的優化。$，需注意 :疋虽工作電壓增加時，需適度的調降占空比以避免過 ®的電荷累積於該鍍膜上。 有關本發明之前述及其他技術内容、特點與功效，在 12 200813252 以下配合參考圖式之兩個具體例的詳細說明中，將可清楚 的呈現。 <具體例一> 在本發明耐磨耗抗腐蝕且透明度高之鍍膜的製作方法 之一具體例一中，首先，是提供一材質為丙烯腈-丁二烯_苯 乙烯共聚合物（acrylonitrile - butadiene-styrene，簡稱 ABS)的浴室用蓮蓬頭（Sh〇wer head)以作為該具體例一之基 材，並依序地於該基材上形成一厚度約1〇 μιη的鎳（Ni)鍍膜 及一厚度約為0.1 μπι〜0.2 μπι的鉻（Cr)鑛膜。 進一步地，利用氧電漿施予表面處理以移除形成於該 鉻鍍膜表面的污染物，並利用PECVD於該鉻鍍膜上形成一 厚度約3·8 μπι〜4·0 μιη的耐磨耗抗腐蝕且透明度高之鍍膜 〇 在該具體例一中，該反應源含有TMDS〇、〇2及Ar ·， 〇2的流量/Ar的流量等於！，且丁MDS〇是在1大氣壓及室 溫的條件下經由流量為250 %(^1的Ar引入該反應腔體中以 維持7 Pa的工作壓力；該具體例一之工作電壓、反向電壓 、雙極脈衝電壓的頻率及鍍膜時間分別是_1〇〇 V、+乃V、 250 kHz及90分鐘。 再參閱圖1’以實施於本發明該具體例一的頻率為25〇 kHz計算，其雙極脈衝電壓的週期（^)為4微秒（叫）；且， 在該具體例-中，可產生電聚的鍍膜時間⑹為3597毫微秒 ㈣’可移除累積電荷的媳火時間⑹為4〇3 ns。因此，由 [(tr^VWxiOO%所算得，該具體例一之占空比約為9〇%。 13 200813252 <具體例二> 在本發明耐磨耗抗腐蝕且透明度高之鍍膜的製作方法 之一具體例二中，大致上是與該具體例一相同，其不同處 僅在於，提供一材質為黃銅（brass)之水龍頭用中元盤 (middle escutcheon)以作為該具體例二之基材，且該工作電 壓及鍍膜時間分別是_280 V及120分鐘，以使得該具體例 二最終所製得的鑛膜厚度約為7 μηι。 <特性分析> . 本發明該具體例一、二所製得的鍍膜，不但具備有透 明度高、冷熱循環佳及優異-的耐磨耗性等特點。此外，經 抗腐蝕性、硬度及附著性等標準規範的測試，亦有顯著的 功效。再者，因該具體例二之鑛膜的接觸角（contact angle) 約為100度而具備有良好的疏水性，亦更適用於溼度高的 衛浴環境中。茲整理該具體例一及二之抗腐蝕性、硬度、 附著性等標準規範測試結果於下列表1.中。 表1.It is worth mentioning that, in consideration of moderately excluding the electric charge accumulated on the surface of the mineral film of the step (8) and causing the reaction source of the step (8) to obtain sufficient electric power: in the case where the helium is dissociated, preferably, the step (b) Bipolar pulse; 占's duty Q is between 8G% and between; the reverse voltage of the bipolar pulse voltage of step (8) is between 0 V and +75 V; To a duty ratio of 95%, the frequency of the bipolar pulse voltage of the step (8) is between 30 kHz and 25 kHz; the operating voltage of the bipolar pulse voltage of the step (8) is between -100 v and _300. Between V; the working pressure of the body is between 丨Pa i 1Q ρ ^ α cavity and even 1 〇 Pa; the burning and oxidizing agent in this step are respectively tetramethyl oxalate and oxygen. Milk 200813252 In addition, it is worth mentioning that when the ratio of the oxygen flow rate to the argon flow rate in the reaction source of the step (a) is too small, the amount of oxygen introduced into the reaction chamber is relatively decreased, and the effect is affected. The transparency of the clock film of the step (b); conversely, when the ratio of the oxygen flow rate to the argon gas flow rate in the reaction source of the step (a) is too large, the plating rate of the present invention is lowered. Therefore, the ratio of the oxygen flow rate to the argon flow rate in the reaction source of this step is between 〇5 and 2.0. Still more preferably, the ratio of the oxygen flow rate to the argon flow rate in the reaction source of the step (a) is between 0.5 and 1.0. Further, it is worth mentioning that the operating voltage previously described in the present invention is not limited to the range between -120 V and _4 〇〇 V. Since the electric energy applied to the reaction source can be increased to assist the dissociation of the reaction source when the operating voltage is increased, the operating temperature of the substrate disposed on the cathode can be increased to provide a free reaction. The source obtains higher diffusion energy during the deposition process and increases the compactness and adhesion of the coating structure of the step (b). Thus, in the present invention, the details relating to the operating voltage are related to the material of the substrate disposed on the cathode. When the material of the substrate is a polymer material, the operating voltage should be appropriately lowered to avoid damage to the polymer material which cannot withstand high temperature conditions. On the other hand, when the material of the substrate belongs to a ceramic material, in the case where no discharge arcing occurs, :: the operating voltage can be appropriately increased, so that the electricity source b ^ is made to be used in the reaction source The freeing is moderately optimized. $, need to pay attention to: 疋 Although the working voltage increases, it is necessary to moderate the duty cycle to avoid the accumulation of charge on the coating. The foregoing and other technical contents, features, and advantages of the present invention will be apparent from the following detailed description of FIG. <Specific Example 1> In a specific example 1 of the method for producing a coating film having high abrasion resistance and corrosion resistance and high transparency, firstly, a material is provided as an acrylonitrile-butadiene-styrene copolymer ( A acrylonitrile-butadiene-styrene (ABS) bathroom shower head (Sh〇wer head) is used as the substrate of the specific example 1, and a nickel (Ni) having a thickness of about 1 μm is sequentially formed on the substrate. The coating and a chromium (Cr) mineral film having a thickness of about 0.1 μm to 0.2 μm. Further, a surface treatment is performed by using an oxygen plasma to remove contaminants formed on the surface of the chrome plating film, and a wear resistance of about 3·8 μm to 4·0 μm is formed on the chrome plating film by PECVD. Corrosion and high transparency coating 〇 In this specific example 1, the reaction source contains TMDS〇, 〇2 and Ar·, and the flow rate of 〇2/Ar flow is equal to! And DDS is at a flow rate of 250% at a pressure of 1 atm and room temperature (I is introduced into the reaction chamber to maintain a working pressure of 7 Pa; the working voltage and reverse voltage of the specific example 1) The frequency of the bipolar pulse voltage and the coating time are respectively _1 〇〇 V, + is V, 250 kHz, and 90 minutes. Referring again to FIG. 1 ', the frequency of the specific example 1 implemented in the present invention is 25 〇 kHz, The period (^) of the bipolar pulse voltage is 4 microseconds (called); and, in this specific example, the coating time (6) at which electropolymerization can be generated is 3,597 nanoseconds (four) 'the bonfire of the accumulated accumulated charge The time (6) is 4 〇 3 ns. Therefore, the duty ratio of the specific example 1 is about 9〇% calculated by [(tr^VWxiOO%. 13 200813252 < specific example 2> One of the specific examples of the method for producing a highly corrosive and highly transparent coating is substantially the same as the specific example 1. The only difference is that a middle escutcheon for a faucet made of brass is provided. ) as the substrate of the specific example 2, and the working voltage and coating time are _280 V and 120 minutes, respectively. The bell is such that the thickness of the mineral film finally obtained in the second embodiment is about 7 μm. <Characteristics Analysis> The coating film produced by the specific examples 1 and 2 of the present invention has high transparency and thermal cycle. Good and excellent - wear resistance and other characteristics. In addition, the test of the standard specifications such as corrosion resistance, hardness and adhesion, also has significant effects. Moreover, due to the contact angle of the mineral film of the specific example 2 ( Contact angle) is about 100 degrees and has good hydrophobicity. It is also suitable for use in high humidity sanitary environments. The standard test results of corrosion resistance, hardness and adhesion of the specific examples 1 and 2 are compiled. In Listing 1. Table 1.
標準規範 具體例一 具體例二 抗腐#性1 ASTM B287 (hr) - 96 硬度& ASTM 3363-05 9H 9H 附著性# ASTM D3359-B 5B 5B 14 1 酷酸鹽水喷霧試驗（Acetic acid salt spray test)。 &錯筆硬度測試（Pencil test)。 # 百格測試（Cross-Cut adhesion test)。 綜上所述，本發明耐磨耗抗腐蝕且透明度高之鍍膜的 製作方法，不但可製得耐磨耗性佳、硬度高、抗腐蝕性良 200813252 浴用 之目的 好、高附著性及耐冷熱循環的鍍膜，且其㈣亦可符合衛 一品中對於透明度高之美觀性的要求，確實達到本發明 惟以上所述者，僅為本發明之較佳實施例而已，當不 旎以此限定本發明實施之範圍，即大凡依本發主 ^ T #專利 範圍及發明說明内容所作之簡單的等效變化舆修飾，比 屬本發明專利涵蓋之範圍内。 白仍 【圖式簡單說明】Standard Specification Specific Example 1 Specific Example 2 Anticorrosion #1 1 ASTM B287 (hr) - 96 Hardness & ASTM 3363-05 9H 9H Adhesion # ASTM D3359-B 5B 5B 14 1 Acid Salt Spray Test (Acetic acid Salt spray test). &Pencil test. #Cross-Cut adhesion test. In summary, the method for producing a coating film with high abrasion resistance, corrosion resistance and high transparency can not only obtain good wear resistance, high hardness and good corrosion resistance, but also has good purpose, high adhesion and heat resistance. Circulating coating, and (4) can also meet the requirements for high transparency in the Weiyi product, and it is only the preferred embodiment of the present invention that is only the preferred embodiment of the present invention. The scope of the invention, that is, the simple equivalent changes and modifications made by the present invention in the scope of the invention and the scope of the invention are within the scope of the invention. White still [schematic description]
圖1是一電壓對時間曲線圖，說明鍍膜時‘ 時間(t2)的關係。 · 1 #熄火 【主要元件符號說明】Figure 1 is a voltage versus time graph illustrating the relationship of time (t2) during coating. · 1 #断火 [Main component symbol description]
1515
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