TWI272135B - Precoated metal sheet and process for producing the same - Google Patents
Precoated metal sheet and process for producing the same Download PDFInfo
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- TWI272135B TWI272135B TW95103188A TW95103188A TWI272135B TW I272135 B TWI272135 B TW I272135B TW 95103188 A TW95103188 A TW 95103188A TW 95103188 A TW95103188 A TW 95103188A TW I272135 B TWI272135 B TW I272135B
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/24094—Indication parts or information parts for identification
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
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- Engineering & Computer Science (AREA)
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Abstract
Description
1272135 (1) 九、發明說明 【發明所屬之技術領域】 本發明是關於使用於家電製品或汽車用車載 外板材或構造構件,進一步使用於建材、屋頂材 途之預塗覆金屬板及其製造方法。 【先前技術】 P 以鋼板、鋁板或鋁合金板爲代表之金屬薄板 優良之強度與加工性,藉由實施各種的加工,可 電製品、汽車用車載零件、進一步於建材等的各 使用於這些用途之金屬板的加工品,會有以提昇 蝕性等爲目的,進行表面處理。此表面處理,以 係以將金屬板加工成預定的形狀後來進行之後塗 coat )方式爲主流,但在最近,以改善工作場所 工製程的簡單化與減低成本等爲目的,將預先在 φ 行表面處理之預塗覆金屬板成形加工成預定形狀 方式也逐漸被使用。且,近年,該預塗覆金屬板 製品-機械的多樣化與高品質化,而賦予各種功; 指紋性、耐受損性、接地連接性 '散熱性、遮熱 • 性等之功能性預塗覆金屬板被開發,且廣泛普及 • 近年,這樣的預塗覆金屬板爲了因應製品-機械丨 與高品質化,而賦予各種功能例如耐指紋性、耐 接地連接性 '散熱性、遮熱性、抗菌性等之功能 金屬板被開發,且廣泛普及中。 零件等的 等各種用 材係具有 適用於家 種用途。 外觀或耐 往以來, 覆(post 環境或加 金屬板進 之預塗覆 爲了因應 能例如耐 性、抗菌 中。且, 的多樣化 受損性、 性預塗覆 -4- (2) (2)1272135 在預塗覆金屬板’因在實施了表面塗裝之狀態下進行 成形加工,所以不僅對於塗膜要求優良之成形加工性,並 且由於沖壓成形後的外觀直接成爲製品外觀,故也被要求 優良之表面外觀及性狀等。例如在日本發明專利第 3 3 3 8 1 5 6號公報(段落〜0017 ),揭示有:對於鋁合 金板材,以環氧樹脂、胺甲酸乙酯(urethane )樹脂及丙 烯酸樹脂的單獨或其混合物做爲基礎樹脂,且包含5〜 4 0 %之粒徑0.1 μ m以下的S i Ο 2、及 5〜6 0 %的潤滑劑之塗 料,以〇 · 5〜1 0 μπι之厚度進行塗裝,而將摩擦係數控制成 〇 · 1 5以下之具有優良的成形性與耐受損性之預塗覆金屬板 〇 在日本發明專利第 3 3 3 8 1 5 6號公報(段落000 8.〜 0 0 1 7 )所揭示之預塗覆金屬板,係由錦合金板材所構成, 但一般以鋁爲材料之預塗覆金屬板經常被使用於被要求輕 量之用途,例如,被使用於筆記型電腦搭載用的光碟機( 驅動器)之蓋類、或液晶顯示器之框架、背蓋類、車載用 電裝品之 ECU (Electronic Control Unit)或汽車音響、 汽車導航系統、自動換片器(disk auto changer)等的蓋 類或構造構件。在這些之中,使用於光碟驅動器或自動換 片器之情況,搭載有CD或DVD等的碟片。在最近,受 到寫入型驅動器的普及,個人性編輯音樂CD,製作自作 碟片1 0也逐漸變多。又,如圖4 ( a )所示,這樣的自作 碟片1 0會有在碟片D的表面接著識別用的識別標籤L之 狀態下加以使用之情事。 -5- (3) (3)1272135 【發明內容】 但,如前述光碟驅動器或自動換片器,在會有將識別 標籤L這樣的黏著物插入到裝置內之可能性的用途上,需 要預先防備受到由裝置所產生的熱等,造成識別標籤L的 一部分剝離,然後,成爲剝離出來之黏著部Ln會有在附 著到裝置內的各部位之危險性。 做爲防止這樣的危險性之方法之一,在黏著物(識別 標籤L )有可能附著之部位,實施此黏著物不易附著之表 面處理的方法爲有效的。例如,如圖4 ( b )所示,在光 碟驅動器20之情況,承載有自作碟片10的托盤21之上 側表面、或覆蓋自作碟片1 0的蓋22之內側表面等,鄰接 於自作碟片1 〇且面積越大之構件,黏著物附著之危險性 越大。因此,在對於這些零件加工使用之預塗覆金屬板, 預先實施表面處理,使得識別標籤L這種的黏著物不易附 著,有助於迴避附著物附著。又,這種的黏著物之不易附 著的性質,實際上不僅黏著物,亦兼具抗油或污垢等的各 種物質之性質,故即使在長期間使用於建材、汽車用車載 零件、屋內機器等的用途上,在能夠減低維修之頻率的這 一點上能加以期待。 又,加上前述課題,如圖4 ( b )所示,以往的光碟 驅動器20,一般爲在自作碟片10置入取出之際,將安裝 自作碟片10的托盤21本身由光碟驅動器20中取出、置 入到光碟驅動器20中之抽屜(drawer )方式。 -6 - (4) 1272135 相對於此,最近,並非如上所述之 盤來取出置入光碟者,而是開發出將光 於光碟驅動器蓋之開口部般的吸入式( 動器。在這種吸入式的光碟驅動器,會 擦於光碟驅動器蓋內面之狀態下取出置 出置入之際,光碟面與光碟驅動器蓋內 造成滑動傷痕之問題點。 在吸入式的光碟驅動器,當將光碟 了防止光碟表面受到損傷,以往,在與 觸之部位,以噴霧塗裝等的方法實施防 這種方法係必須針對每一個沖壓加工後 行處理。因此,存在有製程變得繁雜, 本也變得非常大等之問題點。藉由預先 施傷痕防止處理,可期待製程的簡單化 減低成本。 因此,本發明之發明者們爲了達到 案了,藉由將組合了特定的氟樹脂與硬 塗佈烘烤,在金屬板的表面形成樹脂皮 行烘烤的最適當化,使樹脂皮膜的皮膜 變濃,確保黏著物之非黏著性,同時降 度,良好地保持金屬板與樹脂皮膜之接 非黏著特性的預塗覆金屬板與其製造方 本發明之目的係在於提供一種成形 金屬板及其製造方法,其不僅具有優良 使用安裝光碟的托 碟本身插入至設置 slot-in )的光碟驅 有由於在將光碟摩 入,故在將光碟取 面產生摩擦而容易 置入取出之際,爲 容易與光碟滑動接 止受損處理。但, 的光碟驅動器蓋進 生產性降低,且成 在成形前的鋁板實 、生產力之提昇及 上述般的要求,考 化劑之氟系塗料的 膜,且利用配合進 最外表面之氟濃度 低皮膜內部之氟濃 著力的具有優良之 法。 加工使用之預塗覆 之成形性、潤滑性 (5) 1272135 '外觀’並且兼具即使使用於倂用黏著物之用途上, 物也不易附著,污垢或由也不易附著之特性。 本發明的另一目的係在於提供一種成形加工使用 塗覆金屬板及其製造方法,其不僅具有優良之成形性 滑性 '外觀’並且兼具即使使用於倂用黏著物之用途 黏著物也不易附著,污垢或由也不易附著,且與光碟 觸’也不易在其表面造成傷痕之特性。 在本發明的第1實施形態,係爲一種預塗覆金屬 具備金屬板、及藉由形成於其表面的氟系樹脂所構成 脂皮膜之預塗覆金屬板,其特徵爲:當以方程式(1 算在前述樹脂皮膜的最外表面之氟濃度的比例時,前 濃度的比例爲2 0 %以上,並且以方程式(1 )計算在 樹脂皮膜的皮膜內部之皮膜厚度大約1/2的位置之氟 的比例時,前述氟濃度的比例爲1 5 %以下, A(%) = {F/(F + C + 0+N)}xlOO … (1) 其中,在前述方程式(1 ) ,A爲氟濃度的比例£ 爲氟質量%,C爲碳質量%,0爲氧質量%,N爲氮質 〇 藉由作成如此結構的話,由於樹脂皮膜的氟在最 面變濃,故可將樹脂皮膜的黏著物之剝離強度維持於 狀態。又,同時在除了最外表面之皮膜內部,可將氟 抑制成低,故即使未形成樹脂系底層或接著劑層,亦 樹脂皮膜與金屬板強固地接著。 又,在預塗覆金屬板,前述樹脂皮膜係以胺甲酸 黏著 之預 、潤 上, 等接 板, 的樹 )計 述氟 前述 濃度 /〇,F 量% 外表 低的 濃度 可使 乙酯 -8- (6) 1272135 結合、醯胺結合、尿素結合中之至少一 將具有氫氧基、羧基及胺基中至少一種 具有2個以上之異氰酸酯基(isocyan 酸酯化合物予以結合加以構成。若作成 於氟系樹脂的分子利用以這些化學結合 成三次元網眼構造,故可使樹脂皮膜更 著。 又,在預塗覆金屬板,前述氟系樹 量平均分子量,爲20萬以下。若作成 得氟系樹脂、與具有2個以上的異氰酸 合之相溶性提昇,所獲得之氟系樹脂皮 在6 0度鏡面光澤度測定,超過8 0,而 光澤性之外觀。 又,在預塗覆金屬板,在前述金屬 之間,具備耐鈾性皮膜。若作成這種結 塗覆金屬板之耐蝕性,並且可使得樹脂 與金屬板接著。 又,在預塗覆金屬板,前述金屬板 。若作成這種結構的話,比起使用其他 謀求輕量化。 又,在前述第1實施形態之預塗覆 ,其特徵爲:包含:在前述金屬板的表 第1製程;與在200°C以上2 8 0°C以下 進行烘烤,以形成氟系樹脂皮膜之第2 種的化學結合,來 類的氟系樹脂;與 ate group ) 的異氰 這種結構的話,由 產生交聯反應而形 強固地與金屬板接 脂的分子量,在重 這種結構的話,使 酯基的異氰酸酯化 膜的表面光澤度, 能獲得具有優良的 板與前述樹脂皮膜 構的話,可提升預 皮膜更加以強固地 爲錦板或銘合金板 金屬板之情況,可 金屬板的製造方法 面塗佈氟系塗料之 ,將前述氟系塗料 製程。若作成這種 -9 - (7) (7)1272135 結構的話,藉由預定溫度的烘烤處理,能夠使樹脂皮膜的 氟濃度在皮膜最外表面變濃,並且可在皮膜內部被抑制成 低,因此可進一步將樹脂皮膜的黏著物之剝離強度維持更 低,又,可使樹脂皮膜與金屬板更強固地接著。 在本發明的第2實施形態,係爲一種預塗覆金屬板, 具備金屬板、及藉由形成於其表面的氟系樹脂所構成的樹 脂皮膜之預塗覆金屬板,其特徵爲:前述樹脂皮膜具備氟 系樹脂陣列層、與分散於前述氟系樹脂陣列層中之胺甲酸 乙酯珠,前述胺甲酸乙酯珠之含有率係對於前述氟系樹脂 陣列層’呈5質量%以上50質量%以下,前述胺甲酸乙酯 珠的平均粒徑係前述氟系樹脂陣列層的平均厚度之1 . 1倍 以上5倍以下,當以方程式(1 )計算在前述樹脂皮膜的 最外表面之氟濃度的比例時,前述氟濃度的比例爲1 5 %以 上’並且以方程式(1 )計算在前述樹脂皮膜的皮膜內部 之皮膜厚度大約1 /2的位置之氟濃度的比例時,前述氟濃 度的比例爲15%以下, A(o/〇) = {F/(F + C + O + N)}xl00 …(1)1272135 (1) 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明method. [Prior Art] P is a metal sheet represented by a steel plate, an aluminum plate or an aluminum alloy plate. It has excellent strength and workability, and can be used for various products such as electrical products, automotive vehicle parts, and further construction materials. The processed product of the metal plate for use is subjected to surface treatment for the purpose of improving corrosion resistance and the like. This surface treatment is mainly for processing a metal sheet into a predetermined shape and then applying a coating method. However, in recent years, for the purpose of improving the simplification of the workplace process and reducing the cost, etc., The surface-treated precoated metal sheet is also shaped into a predetermined shape and is gradually being used. Moreover, in recent years, the pre-coated metal sheet products - mechanical diversification and high quality, and to give various functions; fingerprint, damage resistance, ground connection 'heat dissipation, heat shielding · functional pre-function Coated metal sheets have been developed and widely used. In recent years, such pre-coated metal sheets have been given various functions such as fingerprint resistance and grounding resistance, heat dissipation and heat shielding in order to respond to products-mechanical defects and high quality. Functional metal sheets such as antibacterial properties have been developed and widely used. Various materials such as parts are suitable for home use. Appearance or resistance to the past, cover (post environment or metal plate into the pre-coating in order to respond to, for example, resistance, antibacterial, and diversified damage, sexual pre-coating -4- (2) (2) 1272135 The pre-coated metal sheet is subjected to the forming process in the state where the surface coating is applied. Therefore, not only the coating film is required to have excellent moldability, but also the appearance after press forming directly becomes the appearance of the product, so it is also required. Excellent surface appearance and traits, etc. For example, in Japanese Patent No. 3 3 3 8 1 5 6 (paragraph ~0017), it is disclosed that: for an aluminum alloy sheet, an epoxy resin or a urethane resin is used. And the acrylic resin alone or a mixture thereof as a base resin, and comprising 5 to 40% of a particle size of 0.1 μm or less of S i Ο 2, and 5 to 60% of a lubricant coating, to 〇·5~ A coating of a thickness of 10 μπι, and a pre-coated metal sheet having excellent formability and damage resistance, which is controlled to have a coefficient of friction of 〇·15 or less, is disclosed in Japanese Patent No. 3 3 3 8 1 5 6 Bulletin (paragraph 000 8.~ 0 0 1 7 ) The pre-coated metal sheets disclosed are composed of a metal alloy sheet, but pre-coated metal sheets generally made of aluminum are often used for applications requiring light weight, for example, for notebook computers. Cover of optical disc drive (driver), or frame of liquid crystal display, back cover, ECU (Electronic Control Unit) or car audio, car navigation system, disk auto changer, etc. Among these, in the case of a disc drive or an autochanger, a disc such as a CD or a DVD is mounted. Recently, the popularity of the write type driver has been popular, and the music CD has been edited personally. The self-made disc 10 is gradually increased. Further, as shown in FIG. 4(a), such a self-made disc 10 is used in a state in which the surface of the disc D is subsequently identified by the identification label L. -5- (3) (3) 1272135 [Description of the Invention] However, as described above, the optical disk drive or the automatic changer may have a possibility of inserting an adhesive such as the identification tag L into the device. Need to pre- The heat generated by the device is prevented from being peeled off by the device, and a part of the identification label L is peeled off. Then, the adhered portion Ln is likely to adhere to each part in the device. As a method for preventing such danger. For example, in the portion where the adhesive (identification label L) is likely to adhere, a method of performing surface treatment in which the adhesive is not easily adhered is effective. For example, as shown in Fig. 4 (b), in the case of the optical disc drive 20, The upper surface of the tray 21 carrying the self-made disc 10, or the inner surface of the cover 22 covering the self-made disc 10, and the like, adjacent to the member made of the disc 1 and having a larger area, the greater the risk of adhesion of the adhesive . Therefore, in the pre-coated metal sheet used for processing these parts, the surface treatment is performed in advance, so that the adhesive such as the identification label L is not easily attached, which helps to avoid adhesion of the attached matter. Moreover, the nature of such an adhesive which is not easily adhered is actually not only an adhesive but also a property of various substances such as oil or dirt, so that it is used for building materials, automotive parts, and indoor equipment for a long period of time. For the purpose of use, it can be expected to reduce the frequency of maintenance. Further, in addition to the above-described problem, as shown in FIG. 4(b), the conventional optical disk drive 20 is generally provided with the tray 21 itself for mounting the self-made disc 10 from the optical disc drive 20 when the self-made disc 10 is inserted and removed. The drawer is taken out and placed in the drawer drive 20. -6 - (4) 1272135 In contrast, recently, instead of removing the disc inserted into the disc as described above, a suction type (actuator) that emits light to the opening of the disc drive cover has been developed. The inhaled disc drive will be removed from the inner surface of the disc drive cover, and the problem of sliding scratches on the disc surface and the disc drive cover will occur when the disc drive is removed. In the slot-type disc drive, when the disc is loaded It is necessary to prevent the surface of the optical disc from being damaged. In the past, it has to be treated by spray coating or the like. This method must be processed after each press processing. Therefore, the process becomes complicated and the system becomes complicated. The problem is very large. By the pre-scratch prevention treatment, it is expected that the process is simplified and the cost is reduced. Therefore, the inventors of the present invention have combined the specific fluororesin and hard coating in order to achieve the problem. Baking, forming the resin skin on the surface of the metal plate to make the most appropriate baking, so that the film of the resin film becomes thicker, ensuring the non-adhesiveness of the adhesive, and at the same time reducing, well A precoated metal sheet which maintains a non-adhesive property between a metal sheet and a resin film and a manufacturing method thereof. The object of the present invention is to provide a formed metal sheet and a method of manufacturing the same, which not only has a good use of a disc for mounting the disc itself but also is inserted into the setting In the case of the disc-in), the disc is driven, so that the disc is easily placed and removed when the disc is rubbed, and the disc is easily slid and damaged. However, the optical disc drive cover is reduced in productivity, and the aluminum plate before the forming, the productivity is improved, and the above-mentioned requirements, the film of the fluorine-based paint of the test agent, and the fluorine concentration blended into the outermost surface is low. The fluorine inside the film has a strong method of strength. Formability and lubricity of pre-coating for processing (5) 1272135 'Appearance' and the properties of the article are not easily adhered to the use of the adhesive for use, and the dirt or the like are not easily adhered. Another object of the present invention is to provide a coated metal sheet for forming processing and a method for producing the same, which not only have excellent formability slipperiness 'appearance' but also have an adhesive property even for use in adhesives for use. Adhesion, dirt or adhesion is also difficult to adhere to, and it is not easy to cause scratches on the surface of the disc. According to a first embodiment of the present invention, a precoated metal sheet comprising a metal plate and a fluororesin formed on a surface of the precoated metal is characterized in that: (1) When the ratio of the fluorine concentration on the outermost surface of the resin film is calculated, the ratio of the front concentration is 20% or more, and the film thickness inside the film of the resin film is calculated by the equation (1) to be about 1/2. In the case of the ratio of fluorine, the ratio of the fluorine concentration is 15% or less, A (%) = {F / (F + C + 0 + N)} xlOO (1) where, in the above equation (1), A is The ratio of the fluorine concentration is 5% by mass of fluorine, C is % by mass of carbon, 0 is % by mass of oxygen, and N is nitrogen. By making such a structure, since the fluorine of the resin film is thickened at the outermost surface, the resin film can be obtained. The peeling strength of the adhesive is maintained in a state. Further, in the film except the outermost surface, fluorine can be suppressed to be low, so that the resin film and the metal plate are firmly adhered to each other even if the resin-based underlayer or the adhesive layer is not formed. Also, in the precoating of the metal sheet, the aforementioned resin film system Calculate the concentration of fluorine, the amount of F, and the concentration of F. The concentration of ethylamine-8-(6) 1272135 can be combined with guanamine, urea. At least one of the combination has at least one of a hydroxyl group, a carboxyl group and an amine group having two or more isocyanate groups (isocyan acid ester compounds are combined and combined. If the molecules are used as a fluorine-based resin, these chemicals are combined into three times. Further, in the pre-coated metal sheet, the average molecular weight of the fluorine-based tree is 200,000 or less. The fluorine-based resin is obtained, and two or more isocyanates are obtained. The acid-compatibility is improved, and the obtained fluorine-based resin skin is measured at 60° specular gloss, and has a gloss appearance of more than 80. Further, in the pre-coated metal sheet, it is resistant to the metal. a uranium film. If the corrosion resistance of the junction-coated metal sheet is made, the resin can be brought into contact with the metal sheet. Further, the metal sheet is pre-coated with the metal sheet. If the structure is used, it is compared with the use thereof. Further, the precoating according to the first embodiment is characterized in that: the first process of the metal plate is performed; and the baking is performed at 200 ° C or more and 280 ° C or less. a fluorine-based resin which forms a chemical bond of the second type of the fluorine-based resin film, and a molecular weight of the isocyanate of the ate group), which is strongly bonded to the metal plate by a crosslinking reaction. When the structure is heavy, the surface glossiness of the ester-based isocyanate film can be obtained by having an excellent plate and the above-mentioned resin film structure, and the pre-film can be enhanced to be stronger as a metal plate or a metal plate of a metal plate. In the case where the metal plate is produced, the fluorine-based paint is applied to the surface, and the fluorine-based paint is processed. When the -9 - (7) (7) 1272135 structure is formed, the fluorine concentration of the resin film can be made thicker on the outermost surface of the film by the baking treatment at a predetermined temperature, and can be suppressed to be low inside the film. Therefore, the peel strength of the adhesive of the resin film can be further maintained lower, and the resin film and the metal plate can be further firmly adhered. According to a second aspect of the present invention, there is provided a precoated metal sheet comprising a metal sheet and a resin film formed of a fluorine resin formed on a surface thereof, wherein the precoated metal sheet is characterized in that: The resin film has a fluorine-based resin array layer and urethane beads dispersed in the fluorine-based resin array layer, and the content of the urethane beads is 5% by mass or more with respect to the fluorine-based resin array layer '50. In the mass% or less, the average particle diameter of the urethane beads is 1.1 times or more and 5 times or less the average thickness of the fluorine-based resin array layer, and is calculated on the outermost surface of the resin film by the equation (1). In the case of the ratio of the fluorine concentration, the ratio of the fluorine concentration is 15% or more', and when the ratio of the fluorine concentration at the position of the film thickness of the inside of the film of the resin film is about 1 / 2 is calculated by the equation (1), the fluorine concentration is The ratio is below 15%, A(o/〇) = {F/(F + C + O + N)}xl00 ...(1)
其中,在前述方程式(1 ) ,A爲氟濃度的比例%,F 爲氟質量%,C爲碳質量%,〇爲氧質量%,n爲氮質量% 〇 若作成這種結構的話,藉由控制分散於氟系樹脂陣列 層(樹脂皮膜)中之胺甲酸乙酯珠的含有率及平均粒徑, 即使光碟等接觸,也由於胺甲酸乙酯珠可做爲緩衝材來發 揮作用,故能夠防止樹脂皮膜在光碟等的表面造成傷痕。 -10- (8) 1272135 又’由於在樹脂皮膜表面,氟在皮膜 將對於樹脂皮膜之黏著物的剝離強度 ’同時由於在除了皮膜最外表面之皮 抑制成低,故即使未形成樹脂系底層 氟系樹脂皮膜與金屬板強固地接著。 氟系樹脂陣列層之平均厚度更大的胺 樹脂陣列層中,故樹脂皮膜的表面形 面,在黏著物附著到樹脂皮膜之際, 的空氣層,使黏著物與樹脂皮膜的接 ,可將對於樹脂皮膜之黏著物的剝離 又,在於預塗覆金屬板,前述樹 列層係以胺甲酸乙酯結合、醯胺結合 一種的化學結合,來將具有氫氧基、 種類的氟系樹脂;與具有2個以上之 酯化合物予以結合加以構成。 若作成這種結構的話,由於氟系 些化學結合產生交聯反應而形成三次 樹脂皮膜更強固地與金屬板接著。 又,在於預塗覆金屬板,前述胺 徑爲前述氟系樹脂陣列層的平均厚度 下。 若作成這種結構的話,可提升胺 材的作用,可更進一步防止樹脂皮膜 傷痕。 最外表面變濃,故可 維持成低的狀態。又 膜內部,可將氟濃度 或接著劑層,也能使 且,由於平均粒徑較 甲酸乙酯珠含於氟系 成具有細微凹凸之表 在細微凹凸形成微少 觸面積降低。其結果 強度維持成低。 脂皮膜的氟系樹脂陣 、尿素結合中之至少 羧基及胺基中至少一 異氰酸酯基的異氰酸 樹脂的分子利用以這 元網眼構造,故可使 甲酸乙酯珠的平均粒 之1 .5倍以上4倍以 甲酸乙酯珠做爲緩衝 在光碟等的表面造成 -11 - (9) (9)1272135 又,在預塗覆金屬板,前述胺甲酸乙酯珠的含有率係 爲對於前述氟系樹脂陣列層,呈1 0質量%以上4 0質量% 以下。 若作成這種結構的話,可提升胺甲酸乙酯珠做爲緩衝 材的作用,可更進一步防止光碟等的表面受到樹脂皮膜所 造成傷痕。又’爲了形成樹脂皮膜,而在金屬板表面塗佈 分散有胺甲酸乙酯珠之氟系塗料之際,將氟系塗料的黏度 調整成預定範圍,可使塗裝性提昇。 又,在預塗覆金屬板,在前述金屬板與前述樹脂皮膜 之間,具備耐蝕性皮膜。若作成這種結構的話,可提升預 塗覆金屬板之耐蝕性,並且可使得樹脂皮膜更加以強固地 與金屬板接著。 在預塗覆金屬板,前述金屬板爲鋁板或鋁合金板。 若作成這種結構的話,比起使用其他金屬板之情況, 可謀求輕量化。 又,在前述第2實施形態之預塗覆金屬板的製造方法 ,其特徵爲:包含:在前述金屬板的表面,塗佈分散有胺 甲酸乙酯珠之氟系塗料之第1製程;與在200 °C以上280 °C以下,將前述氟系塗料進行烘烤,以形成前述氟系樹脂 皮膜之第2製程。 若作成這種順序的話,藉由預定溫度的烘烤處理,能 夠使樹脂皮膜的氟濃度在皮膜最外表面變濃,並且可在皮 膜內部被抑制成低,因此可進一步將樹脂皮膜的黏著物之 剝離強度維持更低,又,可使樹脂皮膜與金屬板更強固地 -12- (10) 1272135 _ 接著。又’由於胺甲酸乙酯珠固定於樹脂皮膜,做爲緩衝 材來發揮作用,故可防止在光碟等的表面造成傷痕。 ^ (發明效果) 若根據本發明的第1實施形態的話,藉由在金屬板的 表面形成氟系樹脂皮膜,對於成形加工後使用之預塗覆金 屬板’不僅具有優良之成形性、潤滑性、外觀,並且兼具 φ 即使使用於倂用黏著物之用途上,黏著物也不易附著,污 垢或由也不易附著之特性,並且不需經由樹脂系底層或接 著劑層’能將氟系樹脂皮膜強固地接著到金屬板。又,藉 由控制成爲氟系塗料的主劑之氟系樹脂的分子量,可控制 表面光澤。 又’若根據本發明的第1實施形態之預塗覆金屬板的 製造方法的話,可不需形成樹脂系底層或接著劑層,來製 造黏著物剝離強度小之預塗覆金屬板。 • 且’若根據本發明的第2實施形態的話,對於成形加 工後使用之預塗覆金屬板,不僅具有優良之成形性、潤滑 性' 外觀’並且兼具即使使用於倂用黏著物之用途上,黏 著物也不易附著,污垢或由也不易附著,並且不需經由樹 ^ 脂系底層或接著劑層,能將氟系樹脂皮膜強固地接著到金 * 屬板。又,藉由將分散於樹脂皮膜(氟系樹脂陣列層)的 胺甲酸乙酯珠的含有率或平均粒徑加以最適當化,可在兼 具黏著物不易附著到樹脂皮膜表面的特性,即使樹脂皮膜 表面與光碟癟面滑動接觸的情況,也可防止光碟受到損傷 -13- (11) (11)I272l35 又,若根據本發明的第2實施形態之預塗覆金屬板的 製造方法的話,可不需形成樹脂系底層或接著劑層,來製 造黏著物剝離強度小、且具有優良之對於光碟之防止受損 性之預塗覆金屬板。又,藉由預先對於加工成形前的鋁板 實施防止受損處理,比起在成形加工後實施防止受損處理 之情況,能以簡單的製程、高度的生產性、低成本來實施 防止受損處理。 【實施方式】 以下,詳細地說明關於本發明之實施形態。 (第1實施形態) 1 ·預塗覆金屬板 首先,說明關於本發明的第1實施形態之預塗覆金屬 板的結構。 本發明的第1實施形態之預塗覆金屬板1 a係如圖1 a 所示’具備:基礎材料之金屬板2a;與形成於金屬板2a 的表面’且被控制成皮膜最外表面與皮膜內部的氟濃度之 比例成爲預定値之樹脂皮膜3 a。在此,金屬板2 a的表面 係指金屬板2 a之至少其中一方的面,理想係指兩面。其 次’說明關於預塗覆金屬板1 a之各結構。 (1 )金屬板 -14- (12) (12)1272135 在第1貫施形態所使用之金屬板2 a,不被特別限定 ’除了最平常之冷軋鋼板以外,熔融鍍鋅鋼板、電鍍鋅鋼 板、合金化熔融鍍鋅鋼板或鍍銅鋼板、鍍錫鋼板等的各種 鍍裝鋼板,且不銹鋼等的合金鋼板、鋁或鋁合金鋼板、銅 或銅合金板等的非鐵金屬板等均可適用。又,對於筆記型 電腦搭載用的光碟機(驅動器)的蓋、液晶顯示裝置的框 架、車用電裝零件之蓋等,被要求輕量之用途,鋁或鋁合 金爲佳。特別是依據JIS 5052或JIS 5182之Al-Mg系合 金更理想。 (2 )樹脂皮膜 (2 - 1 )氟濃度之比例 在本發明的第1實施形態所使用之預塗覆金屬板1 a 係當以方程式(1 )計算時,樹脂皮膜3 a的在皮膜最外表 面之氟濃度的比例爲2 0 %以上,並且當以同式(1 )計算 時,樹脂皮膜3 a之在皮膜內部的氟濃度之比例爲1 5 %以 下。 A(%) = {F/(F + C + O+N)}xl00 … (1) 在方程式(1 ) ,A爲氟濃度的比例%,F爲氟質量% ,c爲碳質量%,Ο爲氧質量%,N爲氮質量°/〇。 在此情況,氟濃度的比例係使用以ESCA等所測定、 換算之樹脂皮膜3a的皮膜最外表面及皮膜內部之氟質量 %、碳質量%、氧質量%及氮質量%,以方程式(1 )計算 。再者,在此所謂的皮膜最外表面係指黏著物(圖4所示 -15- (13) (13)1272135 的識別標籤L等)所附著之側的表面即預塗覆金屬板1 b 之皮膜最外表面,並非指樹脂皮膜3 a與金屬板2 b之界面 。又,針對皮膜內部之測定,由樹脂皮膜3 a之皮膜最外 表面朝厚度方向測定皮膜厚度之大約1 /2的部分。關於樹 脂皮膜3 a的皮膜最外表面及皮膜內部之氟濃度的比例測 定,因在第2實施形態的(2 -1 )之「氟濃度之比例」有 詳細說明,參照該部分。 如後述的比較例所示,在樹脂皮膜3 a的交聯反應不 充分之情況或產生熱劣化(分解)之情況,會有皮膜最外 表面之氟濃度的比例未滿20%之情況。在此情況,由於存 在於樹脂皮膜3 a的皮膜最外表面之與黏著劑的剝離性相 關聯之氟的比例少,故樹脂皮膜3 a的黏著物剝離強度變 大,並且污垢或油容易附著。另一方面,當皮膜內部的氟 濃度之比例超過1 5 %時,則若不進行形成樹脂底層或接著 劑層等的處置的話,會使皮膜無法強固地接著於金屬板 1 a之表面。 樹脂皮膜3 a係胺甲酸乙酯結合、醯胺結合、尿素結 合中之至少一種的化學結合,來將具有氫氧基、羧基及胺 基中至少一種類的氟系樹脂;與具有2個以上、理想爲3 個以上之異氰酸酯基(isocyanate group )的異氰酸酯化 合物予以結合(交聯)爲佳。藉此,能夠在樹脂皮膜3 a 形成穩定之交聯構造,使得樹脂皮膜3 a可更強固地接著 於金屬板2a。做爲上述的氫氧基,包含醇系氫氧基或酚 基系氫氧基,在廣泛的意思下,亦包含與異氰酸酯基反應 -16- (14) (14)1272135 之介質等。又,做爲上述羧基,包含羧基單體、被無水化 之羧基等’與異氰酸酯基反應之所有的介質。同樣地,做 爲上述胺基’包含與異氰酸酯基反應之所有的介質。再者 ’被交聯的樹脂皮膜3 a之交聯度係以該交聯度之指標的 JIS K6796所規定之膠體含量,80%以上爲佳。 (2 - 2 )氟系樹脂的分子量 成爲氟系塗料之主劑的氟系樹脂的分子量係影響樹脂 皮膜3a之表面光澤,結果決定預塗覆金屬板ia的表面光 澤者。本第1實施形態之預塗覆金屬板1 a的表面光澤, 光澤高者或光澤低(無光澤外觀)中的任一者均可,但考 量家電製品的外板材等之用途,光澤高者爲佳。以下敘述 氟系樹脂的分子量與表面光澤之關係。 氟系樹脂的分子量,在重量平均分子量呈20萬以下 之情況,由於主劑與硬化劑均等地相溶,故形成光澤性高 之樹脂皮膜3 a。又,成爲主劑之氟系樹脂的分子量,在 重量平均分子量超過20萬之情況,由於主劑與硬化劑之 相溶性降低,會成爲無光澤外觀者。自者,主劑之氟系樹 脂的分子量,在重量平均分子量超過20萬之情況,由於 主劑的黏度變得過高,故在將主劑聚合之際,變得不易均 等地反應,進行滾筒塗裝時塗料之拾取(Pickup )性降低 ,表面的光澤度不易變得均等。又’主劑之氟系樹脂的分 子量,在重量平均分子量呈1 〇萬以下之情況’由於主劑 的黏度變得過低,故在藉由例如汆筒塗裝’在金屬板2 a -17- (15) (15)1272135 的表面形成樹脂皮膜3 a之際,會有變得不易保持膜厚之 均等性之情事。 (2-3)樹脂皮膜的厚度:〇.1〜20μηα 在本實施形態之樹脂皮膜3a的厚度係20μιη爲 佳。在厚度未滿0.1 μηι 之情況,無法均等地披覆金屬板2 a全面,造成黏著 物之剝離強度變大。又,在厚度超過2 0 μ m之情況,與金 屬板2 a之緊密接者性降低’造成樹脂皮膜3 a對於金屬板 2a之接著性降低。 (2 - 4 )耐蝕性皮膜 本第1實施形態之預塗覆金屬板la,在金屬板2a與 樹脂皮膜3 a之間進一步具備耐蝕性皮膜爲佳。藉由形成 耐蝕性皮膜,可賦予預塗覆金屬板1 a耐蝕性,並且可提 升金屬板2 a與樹脂皮膜3 a之接著性。耐蝕性皮膜的結構 如下所述。 做爲本第1實施形態之耐飽性皮膜,可適宜地使用包 含以Cr或Zr爲成分之以往習知的耐蝕性皮膜之磷鉻酸( phosphoric chromate)皮膜' 鉻鉻酸(chromic chromate )皮膜、磷酸鉻皮膜、氧化鉻系皮膜、塗佈型鉻酸皮膜或 塗佈型锆皮膜。又,耐蝕性皮膜之附著量,以C r或Z r的 換算値,呈10〜5 Omg/m2爲佳。當耐蝕性皮膜之附著量變 得較10m g/m2少時,則無法均等地披覆金屬板2a全面, -18- (16) (16)1272135 不易確保耐蝕性,無法承受長時間使用。又,當附著量超 過5 0 m g / m 2時,則在沖壓成形時,會在耐蝕性皮膜產生裂 痕(剝離)’變得不易在長期間維持高度的耐蝕性。 2 ·預塗覆金屬板的製造方法 本第1實施形態之預塗覆金屬板1 a的製造方法,係 包含在金屬板2a的表面塗佈氟系塗料之第1製程;與在 2 〇 〇 °C以上2 8 0 °C以下,將氟系塗料進行烘烤處理,以形 成氟系樹脂皮膜3 a之第2製程。以下,說明關於各製程 (1 )第1製程 第1製程係在本第1實施形態之金屬板2a的表面塗 佈氟系塗料之製程。此氟系塗料係做爲主劑,在具有氫氧 基、羧基及胺基中至少一種類的氟系樹脂,混合做爲硬化 劑之具有2個以上、理想爲3個以上之異氰酸酯基異氰酸 酯化合物、更理想爲將異氰酸酯基予以嵌段(block )之 異氰酸酯化合物混合者爲佳。又,亦可在氟系塗料,添加 天然蠟、石油蠟、合成蠟或這些的混合物等之潤滑劑。且 ,在本發明所請求的範圍下,不被特別限定,可添加以著 色爲目的之染料或顏料,用來提高樹脂皮膜3a的硬度或 耐受損性之各種無機塡充劑、導電性添加劑等的添加劑。 所謂嵌段異氰酸酯化合物,係指異氰酸酯化合物的活 性異氰酸酯基藉由活性氫化合物等的嵌段化劑予以穩定化 -19- (17) (17)1272135 者,在常溫下不具有反應性。此嵌段異氰酸酯化合物係藉 由烘烤處理等的加熱,使嵌段化劑解離,使得活性異氰酸 酯基再生,成爲具有反應性。做爲嵌段異氰酸酯化合物的 嵌段化劑,包含甲醇、乙醇、η-丙醇及tert-丁醇等的醇類 ,酉分、m -甲酉分及異辛酉分(Isooctyl phenol)及間苯二酚等 的酚類,ε -己內醯胺,肟(oxime)類,乙基丙酮( Acetylacetone)、甲乙酮(methyl ethyl ketone)及乙基 環已烷(Vinylclohexane )等的活性乙烯化合物類,以及 亞硫酸鈉等。另一方面,做爲具有嵌段異氰酸酯基之異氰 酸酯化合物,包含有甲苯二異氰酸酯、4,4’-二苯基甲烷二 異氰酸酯(MDI )、聚合MDI、異佛爾酮二異氰酸酯( Isophorone diisocyanate )、及己二異氰酸酯( hexamethylene diisocyanate)等。又,多價醇變性型聚合 異氰酸酯及滴定結合或異氰酸酯結合之聚合異氰酸酯等, 亦含於做爲異氰酸酯化合物。 如此使用嵌段化之硬化劑的氟系塗料,由於在常溫下 ,硬化劑的異氰酸酯基被嵌段,故主劑的氫氧基、羧基及 胺基與硬化劑之異氰酸酯基的反應(交聯反應)不會進行 ,而藉由後述的第2製程之烘烤處理首先進行反應(交聯 ),使得氟系塗料硬化。因此,能夠將氟系塗料在混合了 主劑與硬化劑之狀態下長時間保存,並且可將氟系塗料連 續塗佈到長條的金屬板,有利於工業。 氟系塗料之塗佈能使用滾筒塗佈機、淋幕(c u r t a i η flow)式塗佈機、滾幕(roller curtain)式塗佈機、靜電 -20- (18) (18)1272135 塗裝機、刮刀塗佈機、擠壓(d i e )式塗佈機等之任一方 法’特別是使用塗佈量均等,並且作業簡單之滾筒塗佈機 更爲理想。塗佈量係以在金屬板2 a的表面形成厚度〇 · 1〜 2〇 μηι之氟系樹脂皮膜3a的方式,考量金屬板2a的搬送 速度、滾筒塗佈機之旋轉方向與旋轉速度等,適宜設定。 亦可在進行氧系塗料塗佈之前,設置將金屬板2 a的 表面脫脂之脫脂製程。例如,將鹼性水溶液噴灑於金屬板 2a的表面,然後加以水洗,將金屬板2a的表面脫脂。且 ’在如前所述,於金屬板2 a與氟系樹脂皮膜3 a之間具備 耐蝕性皮膜之情況,能夠接續脫脂製程,藉由將包含鉻離 子等之化成處理液噴灑於金屬板2a之表面等,形成耐蝕 性皮膜。 (2 )第2製程 係在本第1實施形態之金屬板2 a的表面形成氟系樹 脂皮膜3 a之製程,其係在2 0 0 °C以上2 8 0 °C以下,將在第 1製程所塗佈之氟系塗料進行烘烤處理,使氟系塗料硬化 (交聯)。然後,藉由氟系塗料硬化(交聯),形成皮膜 最外表面之氟濃度比例爲2 0 %以上且皮膜內部之氟濃度的 比例爲15%以下之氟系樹脂皮膜3a。又,樹脂皮膜3a強 固地接著至金屬板2 a。在此,所謂烘烤溫度係指金屬板 2 a的溫度之峰値溫度。 當供烤溫度未滿2 0 0 C時’則氣系塗料的硬化(交聯 )變得不充分,而當烘烤溫度超過2 8 時,由於氟系塗 -21 - (19)1272135 料會熱劣化(分解),故無法將氟濃度的比例做 値’使得黏著物對於氟系樹脂皮膜3 a的皮膜表 強度變商。供烤處理時間係2 0〜6 0秒爲佳。在 未滿2 0秒之情況’烘烤容易變得不充分,而當走 時,則烘烤處理時間過長,平均時間之生產性容 又’烘烤處理係使用例如熱風爐、誘導加熱爐、 爐、遠紅外線爐、能量線硬化爐來進行。 其次,詳細說明關於第1實施形態之實施例 (實施例1〜5 ) 實施例1〜5係根據上述的製造方法,製作 屬板1 a。預塗覆金屬板1 a之各結構如以下所述 (金屬板) 使用厚度〇.5mm、以JIS 5 05 2 -H34爲基準 板。 (耐蝕性皮膜) 在鋁合金板的兩面形成磷鉻酸皮膜。磷鉻酸 著量,以Cr換算,爲20mg/m2。 (氟系樹脂皮膜) 在磷鉻酸皮膜的最外表面塗佈氟系塗料,以 (金屬板2a之峰値溫度)200、220、250、260、 成期望的 面之剝離 處理時間 i過6 0秒 易降低。 近紅外線 預塗覆金 之鋁合金 皮膜之附 烘烤溫度 2 8 0 〇C 進 -22- (20) 1272135 行烘烤處理,做成皮膜厚度5 μπι之氟系樹脂皮膜。在此 ,做爲氟系塗料,使用混合的以下之2種液體之氟系塗料 〇 (主劑):具有氫氧基之_系樹脂(重量平均分子量 :176000) (硬化劑):具有3個異氰酸酯基之嵌段異氰酸酯化 合物。 (比較例1〜7 ) 在比較例1〜4,除了在烘烤溫度1 2 5、1 5 0、1 7 0、 3 0 0 °C以下進行以外,其餘與實施例1〜5相同之方法,製 作預塗覆金屬板1 a。又,在比較例5、6,使用與第1實 施形態不同之氟系樹脂,製作氟系樹脂披覆鋁板。再者, 做爲披覆膜(樹脂皮膜)所使用之ETFE (乙烯-四氟乙烯 )薄膜,由於無法直接接著到鋁板表面,故選擇經由樹脂 φ 系底層將ETFE薄膜積層之方法。又,在比較例7,除了 使用環氧系樹脂代替氟系樹脂以外,其餘與實施例3相同 之方法,製作預塗覆金屬板1 a。 接著,針對實施例1〜5、比較例1〜7的預塗覆金屬 板1 a之樹脂皮膜3 a,測定樹脂皮膜3 a的最外表面及皮 膜內部之氟濃度的比例、有無胺甲酸乙酯結合,將其結果 顯示於表1。再者,各特性之測定方法如下所述。 (氟濃度的比例) -23- (21) (21)1272135 將樹脂皮膜3a的皮膜最外表面及皮膜內部以ESCA ( 島津製作所製)加以測定’獲得氟、碳、氧、氮及銘的5 種元素之原子%。使用各元素之原子量,將這些原子0/。換 算成質量^)。在這些之中,僅使用構成皮膜的元素即氟質 量% ( F )、碳質量% ( C )、氧質量% ( 〇 )及氮質量% ( N ),以方程式(1 )算出氟濃度之比例(A ( % ))。 A(%)={F/(F + C + O+N)}xl00 …(1) 在此,做爲皮膜最外表面,將如前述所製作之預塗覆 金屬板1 a的表面在該狀態下即氬濺鍍時間爲零之狀態下 進行測定,而針對皮膜內部,在以氬餓刻將樹脂皮膜3 a 朝厚度方向蝕刻至皮膜厚度的1 /2爲止之深度的狀態下加 以測定。在此,皮膜厚度的1 /2係指氬濺鍍時間爲到達樹 脂皮膜3 b與鋁的界面之剛好1 /2的時間之皮膜的深度狀 態之情事,又樹脂皮膜3 a與鋁的界面係指所測定的上述 5種元素(氟質量% ( F )、碳質量% ( C )、氧質量% ( Ο )及氮質量% ( N )以及鋁質量% ( A1 ))中,相當於金屬 板的A1之質量成爲全體質量%的50%之氬濺鍍時間之皮 膜的深度狀態。 (胺甲酸乙酯結合) 以FTIR (塞莫-尼科萊特日本(Thermo Nicolet Japan )社製)來測定樹脂皮膜3 a,確認有無相當於胺甲酸乙 酯結合之吸收峰値。 -24- (22) 1272135 (黏著物剝離性) 測定評價實施例1〜5、比較例1〜7之預塗覆金屬板 1 a的黏著物剝離性。將其結果顯示於表1。再者,黏著物 剝離性的測定、評價方法如下所述。Wherein, in the above equation (1), A is a ratio % of fluorine concentration, F is a fluorine mass %, C is a carbon mass %, 〇 is an oxygen mass %, and n is a nitrogen mass %, and if such a structure is formed, The content and the average particle diameter of the urethane beads dispersed in the fluorine-based resin array layer (resin film) are controlled, and even if the optical disk or the like is in contact, the urethane beads can function as a buffer material, so that Prevents the resin film from causing scratches on the surface of a disc or the like. -10- (8) 1272135 'Because of the peeling strength of fluorine on the surface of the resin film, the adhesion of fluorine to the resin film is also low, so even if the skin is not formed on the outermost surface of the film, the resin-based underlayer is not formed. The fluorine-based resin film is firmly adhered to the metal plate. In the amine resin array layer having a larger average thickness of the fluorine-based resin array layer, the surface layer of the resin film and the air layer at the time of adhesion of the adhesive to the resin film allow the adhesion of the adhesive to the resin film. The peeling of the adhesive on the resin film is in the pre-coating of the metal plate, and the tree-layer layer is a chemical combination of urethane bonding and guanamine bonding to form a fluorine-based resin having a hydroxyl group and a type; It is combined with two or more ester compounds. If such a structure is formed, a three-part resin film is formed to be more strongly adhered to the metal plate due to a chemical reaction of fluorine to form a crosslinking reaction. Further, the metal plate is precoated, and the amine diameter is the average thickness of the fluorine resin array layer. If such a structure is formed, the action of the amine material can be enhanced, and the resin film flaw can be further prevented. The outermost surface becomes thicker and can be maintained in a low state. Further, in the inside of the film, the fluorine concentration or the adhesive layer can be made, and the average particle diameter is smaller than that of the ethyl formate beads contained in the fluorine system, and the fine contact area is reduced. As a result, the strength is kept low. The fluororesin matrix of the lipid film, at least the carboxyl group in the urea bond, and the molecule of the isocyanate resin having at least one of the isocyanate groups in the amine group are formed by the mesh structure, so that the average particle size of the ethyl formate beads can be made 1 . 5 times or more and 4 times with ethyl formate beads as a buffer on the surface of a disc or the like -11 - (9) (9) 1272135 Further, in the precoated metal sheet, the content of the aforementioned urethane beads is The fluorine-based resin array layer is 10% by mass or more and 40% by mass or less. When such a structure is formed, the urethane beads can be used as a buffer material, and the surface of the optical disk or the like can be further prevented from being damaged by the resin film. Further, in order to form a resin film, when the fluorine-based paint in which the urethane beads are dispersed is applied to the surface of the metal plate, the viscosity of the fluorine-based paint is adjusted to a predetermined range, and the paintability can be improved. Further, in the pre-coating of the metal plate, a corrosion-resistant film is provided between the metal plate and the resin film. If such a structure is formed, the corrosion resistance of the precoated metal sheet can be improved, and the resin film can be more strongly adhered to the metal sheet. In the pre-coating of the metal sheet, the aforementioned metal sheet is an aluminum sheet or an aluminum alloy sheet. When such a structure is formed, weight reduction can be achieved compared with the case of using another metal plate. Further, in the method of producing a precoated metal sheet according to the second embodiment, the method includes the first process of applying a fluorine-based paint in which urethane beads are dispersed on a surface of the metal sheet; The fluorine-based paint is baked at 200 ° C or more and 280 ° C or less to form a second process of the fluorine-based resin film. When the order is made, the fluorine concentration of the resin film can be made thicker on the outermost surface of the film by the baking treatment at a predetermined temperature, and can be suppressed to be low inside the film, so that the resin film can be further adhered. The peel strength is kept lower, and the resin film and the metal plate can be made stronger -12-(10) 1272135 _ Next. Further, since the urethane beads are fixed to the resin film and function as a cushioning material, it is possible to prevent scratches on the surface of the optical disk or the like. (Effect of the Invention) According to the first embodiment of the present invention, the fluorine-containing resin film is formed on the surface of the metal plate, and the pre-coated metal sheet used after the forming process has excellent moldability and lubricity. , appearance, and both φ Even in the use of adhesives for adhesives, the adhesive is not easy to adhere, the dirt or the property is not easy to adhere, and it is not necessary to pass the resin base layer or the adhesive layer to enable the fluorine resin. The film is firmly pressed to the metal plate. Further, the surface gloss can be controlled by controlling the molecular weight of the fluorine-based resin which is the main component of the fluorine-based paint. Further, according to the method for producing a precoated metal sheet according to the first embodiment of the present invention, it is possible to produce a precoated metal sheet having a small peel strength of the adhesive without forming a resin base layer or an adhesive layer. In addition, according to the second embodiment of the present invention, the precoated metal sheet used after the forming process has excellent moldability and lubricity 'appearance' and has a use even for use in an adhesive for use. On the other hand, the adhesive is not easily adhered, and the dirt or the like is not easily adhered, and the fluorine-based resin film can be strongly adhered to the gold plate without passing through the resin base layer or the adhesive layer. Moreover, by optimizing the content rate or the average particle diameter of the urethane beads dispersed in the resin film (fluorine-based resin array layer), it is possible to have a property that the adhesive is less likely to adhere to the surface of the resin film, even if When the surface of the resin film is in sliding contact with the surface of the optical disk, the optical disk can be prevented from being damaged. - 13 - (11) (11) I272l35 Further, according to the method for manufacturing a precoated metal plate according to the second embodiment of the present invention, It is not necessary to form a resin-based underlayer or an adhesive layer to produce a pre-coated metal sheet having a small peel strength of the adhesive and excellent damage prevention for the optical disc. In addition, by performing damage prevention treatment on the aluminum plate before the forming, the damage prevention treatment can be performed in a simple process, high productivity, and low cost compared to the case where the damage prevention process is performed after the forming process. . [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. (First Embodiment) 1. Pre-coated metal sheet First, the structure of the pre-coated metal sheet according to the first embodiment of the present invention will be described. The precoated metal sheet 1a according to the first embodiment of the present invention is provided with a metal plate 2a of a base material and a surface formed on the metal plate 2a and controlled to the outermost surface of the film as shown in Fig. 1a. The ratio of the fluorine concentration inside the film becomes a predetermined resin film 3a. Here, the surface of the metal plate 2a refers to at least one of the faces of the metal plate 2a, and ideally refers to both faces. Next, the description will be made regarding the respective structures of the precoated metal sheets 1a. (1) Metal plate-14- (12) (12) 1272135 The metal plate 2 a used in the first embodiment is not particularly limited. In addition to the most common cold-rolled steel sheet, hot-dip galvanized steel sheet and electro-galvanized steel. Various plated steel sheets such as steel sheets, alloyed hot-dip galvanized steel sheets, copper-plated steel sheets, and tin-plated steel sheets, and alloy steel sheets such as stainless steel, aluminum or aluminum alloy steel sheets, non-ferrous metal sheets such as copper or copper alloy sheets, etc. Be applicable. In addition, a cover for an optical disk drive (driver) for mounting a notebook computer, a frame for a liquid crystal display device, and a cover for a vehicle electrical component are required to be lightweight, and aluminum or aluminum alloy is preferred. In particular, an Al-Mg alloy according to JIS 5052 or JIS 5182 is more preferable. (2) Proportion of fluorine film concentration of the resin film (2 - 1) The precoated metal sheet 1 a used in the first embodiment of the present invention is calculated by the equation (1), and the resin film 3 a is the most in the film. The ratio of the fluorine concentration of the outer surface is 20% or more, and when calculated by the same formula (1), the ratio of the fluorine concentration inside the film of the resin film 3a is 15% or less. A(%) = {F/(F + C + O+N)}xl00 (1) In equation (1), A is the ratio of fluorine concentration, F is fluorine mass%, and c is carbon mass%, Ο It is the oxygen mass %, and N is the nitrogen mass ° / 〇. In this case, the ratio of the fluorine concentration is the outermost surface of the film of the resin film 3a measured by ESCA or the like, and the fluorine mass%, carbon mass%, oxygen mass%, and nitrogen mass% in the inner surface of the film, by the equation (1). ) Calculation. Further, the outermost surface of the film referred to herein is the surface on the side to which the adhesive (the identification label L of -15-(13) (13) 1272135 shown in Fig. 4) is attached, that is, the precoated metal sheet 1 b The outermost surface of the film does not refer to the interface between the resin film 3a and the metal plate 2b. Further, for the measurement of the inside of the film, the outermost surface of the film of the resin film 3a was measured in the thickness direction by about 1 / 2 of the thickness of the film. The ratio of the fluorine concentration on the outermost surface of the film of the resin film 3a and the inside of the film is determined by the "ratio of the fluorine concentration" in (2 -1) of the second embodiment. As shown in the comparative example described later, when the crosslinking reaction of the resin film 3a is insufficient or thermal deterioration (decomposition) occurs, the ratio of the fluorine concentration on the outermost surface of the film may be less than 20%. In this case, since the proportion of fluorine associated with the peeling property of the adhesive present on the outermost surface of the film of the resin film 3a is small, the peeling strength of the adhesive of the resin film 3a becomes large, and the dirt or oil is easily attached. . On the other hand, when the ratio of the fluorine concentration in the film exceeds 15%, the treatment of the resin underlayer or the adhesive layer or the like is not performed, so that the film cannot be firmly adhered to the surface of the metal plate 1a. a resin film 3a is a chemical combination of at least one of a urethane bond, a guanamine bond, and a urea bond to form a fluorine-based resin having at least one of a hydroxyl group, a carboxyl group, and an amine group; and having two or more It is preferred that the isocyanate compound having three or more isocyanate groups be bonded (crosslinked). Thereby, a stable crosslinked structure can be formed in the resin film 3a, so that the resin film 3a can be more strongly adhered to the metal plate 2a. The above-mentioned hydroxyl group includes an alcohol-based hydroxyl group or a phenol-based hydroxyl group, and in a broad sense, a medium in which -16-(14)(14) 1272135 is reacted with an isocyanate group. Further, as the carboxyl group, all of the medium which reacts with the isocyanate group, such as a carboxyl group or a carboxyl group which has been anhydrous, is used. Similarly, as the above amine group, all of the mediums which react with the isocyanate groups are contained. Further, the degree of crosslinking of the resin film 3a to be crosslinked is preferably 80% or more of the colloid content specified by JIS K6796 which is an index of the degree of crosslinking. (2 - 2) Molecular weight of the fluorine-based resin The molecular weight of the fluorine-based resin which is the main component of the fluorine-based coating affects the surface gloss of the resin film 3a, and as a result, the surface gloss of the precoated metal plate ia is determined. The surface of the precoated metal sheet 1 a of the first embodiment may be any one of high gloss or low gloss (glossy appearance), but the use of an outer panel of home electric appliances is considered, and the gloss is high. It is better. The relationship between the molecular weight of the fluorine-based resin and the surface gloss will be described below. When the weight average molecular weight of the fluorine-based resin is 200,000 or less, the main component and the curing agent are uniformly dissolved, so that the resin film 3 a having high gloss is formed. In addition, when the weight average molecular weight exceeds 200,000, the molecular weight of the fluorine-based resin which is a main component is lowered, and the compatibility between the main component and the curing agent is lowered to give a matte appearance. In the case where the weight average molecular weight is more than 200,000, the viscosity of the main component is too high. Therefore, when the main component is polymerized, it becomes difficult to uniformly react and roll. The picking property of the paint during painting is lowered, and the gloss of the surface is not easily equalized. Further, the molecular weight of the fluorine-based resin of the main component is such that the weight average molecular weight is less than 1 million. 'Because the viscosity of the main agent is too low, it is coated on the metal plate 2 a -17 by, for example, a cylinder. - (15) When the resin film 3a is formed on the surface of (15) 1272135, it becomes difficult to maintain the uniformity of the film thickness. (2-3) Thickness of the resin film: 〇.1 to 20 μηα The thickness of the resin film 3a of the present embodiment is preferably 20 μm. In the case where the thickness is less than 0.1 μηι, the metal plate 2a cannot be uniformly covered, and the peeling strength of the adhesive becomes large. Further, in the case where the thickness exceeds 20 μm, the adhesion to the metal plate 2a is lowered, and the adhesion of the resin film 3a to the metal plate 2a is lowered. (2 - 4) Corrosion-resistant film The pre-coated metal sheet 1a of the first embodiment is preferably provided with a corrosion-resistant film between the metal plate 2a and the resin film 3a. By forming the corrosion-resistant film, the corrosion resistance of the precoated metal sheet 1a can be imparted, and the adhesion of the metal sheet 2a to the resin film 3a can be improved. The structure of the corrosion resistant film is as follows. As the saturable film of the first embodiment, a phosphoric chromate film containing a conventional corrosion-resistant film containing Cr or Zr as a component can be suitably used. A chromium phosphate film, a chromium oxide film, a coated chromic film or a coated zirconium film. Further, the amount of adhesion of the corrosion-resistant film is preferably 10 to 5 Omg/m2 in terms of C r or Z r . When the adhesion amount of the corrosion-resistant film is less than 10 m g/m2, the metal plate 2a cannot be uniformly coated, and the -18-(16) (16) 1272135 is difficult to ensure corrosion resistance and cannot withstand long-term use. In addition, when the amount of adhesion exceeds 50 m g / m 2 , cracking (peeling) in the corrosion-resistant film during press forming becomes difficult to maintain high corrosion resistance for a long period of time. 2. Method for Producing Precoated Metal Sheet The method for producing a precoated metal sheet 1 a according to the first embodiment includes a first process of applying a fluorine-based paint on the surface of the metal plate 2a; The fluorine-based coating material is baked at a temperature of °C or higher and 280 ° C or lower to form a second process of the fluorine-based resin film 3 a. In the following, each process (1) first process is performed. The first process is a process in which a fluorine-based paint is applied to the surface of the metal plate 2a of the first embodiment. The fluorine-based paint is used as a main component, and a fluorine-based resin having at least one of a hydroxyl group, a carboxyl group, and an amine group is mixed with two or more, and preferably three or more, isocyanate-based isocyanate compounds. More preferably, it is preferred to mix an isocyanate compound in which an isocyanate group is blocked. Further, a lubricant such as a natural wax, a petroleum wax, a synthetic wax or a mixture of these may be added to the fluorine-based paint. Further, in the scope of the present invention, it is not particularly limited, and various inorganic chelating agents and conductive additives for improving the hardness or damage resistance of the resin film 3a may be added by dyes or pigments for coloring purposes. Additives such as. The blocked isocyanate compound means that the active isocyanate group of the isocyanate compound is stabilized by a blocking agent such as an active hydrogen compound. -19-(17) (17) 1272135 It does not have reactivity at normal temperature. This block isocyanate compound is dissociated by heating by a baking treatment or the like to regenerate the active isocyanate group to become reactive. As a blocking agent for a blocked isocyanate compound, it includes alcohols such as methanol, ethanol, η-propanol and tert-butanol, and is divided into m, formazan, and isooctyl phenol. a phenol such as benzenediol, a reactive ethylene compound such as ε-caprolactam, oxime, Acetylacetone, methyl ethyl ketone or Vinylclohexane. And sodium sulfite and the like. On the other hand, as an isocyanate compound having a blocked isocyanate group, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI, isophorone diisocyanate, And hexamethylene diisocyanate and the like. Further, the polyvalent alcohol-denatured polymerized isocyanate and the titrated or isocyanate-bonded polymeric isocyanate are also contained as an isocyanate compound. In the fluorine-based coating material using the block hardener as described above, since the isocyanate group of the curing agent is blocked at normal temperature, the reaction of the hydroxyl group, the carboxyl group and the amine group of the main component with the isocyanate group of the hardener (crosslinking) The reaction does not proceed, and the reaction (crosslinking) is first performed by the baking treatment of the second process described later to cure the fluorine-based paint. Therefore, the fluorine-based paint can be stored for a long period of time in a state in which the main agent and the hardener are mixed, and the fluorine-based paint can be continuously applied to a long metal plate, which is advantageous to the industry. For coating of fluorine-based paint, a roller coater, a curtai η flow coater, a roller curtain coater, and an electrostatic -20- (18) (18) 1272135 coater can be used. Any of the methods such as a knife coater and a die coater is particularly preferable to use a roll coater which is uniform in coating amount and which is simple in operation. In the coating amount, the fluorine-based resin film 3a having a thickness of 〇·1 to 2〇μηι is formed on the surface of the metal plate 2a, and the conveyance speed of the metal plate 2a, the rotation direction and the rotation speed of the roll coater, and the like are considered. Suitable for setting. It is also possible to provide a degreasing process for degreasing the surface of the metal plate 2a before the application of the oxygen coating. For example, an alkaline aqueous solution is sprayed on the surface of the metal plate 2a, and then washed with water to degrease the surface of the metal plate 2a. In the case where the corrosion-resistant film is provided between the metal plate 2a and the fluorine-based resin film 3a as described above, the degreasing process can be continued, and the chemical conversion treatment solution containing chromium ions or the like is sprayed on the metal plate 2a. The surface or the like forms a corrosion-resistant film. (2) The second process is a process of forming a fluorine-based resin film 3a on the surface of the metal plate 2a of the first embodiment, and is in the range of 200 ° C or more and 280 ° C or less. The fluorine-based paint applied by the process is baked to cure (crosslink) the fluorine-based paint. Then, the fluorine-based paint is cured (crosslinked) to form a fluorine-based resin film 3a having a fluorine concentration ratio on the outermost surface of the film of 20% or more and a fluorine concentration in the film of 15% or less. Further, the resin film 3a is firmly adhered to the metal plate 2a. Here, the baking temperature means the peak temperature of the temperature of the metal plate 2a. When the baking temperature is less than 2 0 0 C, the hardening (crosslinking) of the gas-based paint becomes insufficient, and when the baking temperature exceeds 2 8 , the fluorine-based coating - 21 - 1272135 Since the heat is degraded (decomposed), the ratio of the fluorine concentration cannot be made 値, so that the adhesion strength of the adhesive to the fluorine-based resin film 3a is changed. The baking time is preferably 20 to 60 seconds. In the case of less than 20 seconds, the baking tends to be insufficient, and when it is gone, the baking treatment time is too long, and the production time of the average time is 'bake processing using, for example, a hot air furnace, an induction heating furnace. , furnace, far infrared furnace, energy line hardening furnace to carry out. Next, the examples of the first embodiment (Examples 1 to 5) will be described in detail. Examples 1 to 5 are based on the above-described production method, and the base plate 1 a is produced. Each structure of the precoated metal sheet 1a is as follows (metal plate) using a thickness of 55 mm and a JIS 5 05 2 -H34 as a reference plate. (Corrosion resistant film) A phosphochromic film was formed on both surfaces of the aluminum alloy plate. The amount of phosphochromic acid was 20 mg/m2 in terms of Cr. (Fluorine-based resin film) A fluorine-based paint is applied to the outermost surface of the phosphochromic film, and the peeling treatment time of the desired surface is 200 (200, 220, 250, 260). 0 seconds is easy to reduce. Near-infrared pre-coated gold-coated aluminum alloy film Bake temperature 2 8 0 〇C Into -22- (20) 1272135 The baking treatment is carried out to form a fluorine resin film with a film thickness of 5 μm. Here, as a fluorine-based paint, a fluorine-based paint enamel (main agent) of the following two kinds of liquids is used: a resin having a hydroxyl group (weight average molecular weight: 176,000) (hardener): three Isocyanate-based blocked isocyanate compound. (Comparative Examples 1 to 7) In Comparative Examples 1 to 4, the same methods as in Examples 1 to 5 were carried out except that the baking temperatures were 1 25, 150, 170, 300 ° C or lower. , making a pre-coated metal sheet 1 a. Further, in Comparative Examples 5 and 6, a fluorine-based resin-coated aluminum plate was produced by using a fluorine-based resin different from that of the first embodiment. Further, since the ETFE (ethylene-tetrafluoroethylene) film used as the coating film (resin film) cannot directly adhere to the surface of the aluminum plate, a method of laminating the ETFE film via the resin φ-based underlayer is selected. Further, in Comparative Example 7, a precoated metal sheet 1a was produced in the same manner as in Example 3 except that an epoxy resin was used instead of the fluorine resin. Next, with respect to the resin film 3 a of the precoated metal sheet 1 a of Examples 1 to 5 and Comparative Examples 1 to 7, the ratio of the fluorine concentration of the outermost surface of the resin film 3 a and the inside of the film was measured, and the presence or absence of the amine formate B was measured. The esters were combined and the results are shown in Table 1. Furthermore, the measurement method of each characteristic is as follows. (the ratio of the fluorine concentration) -23- (21) (21) 1272135 The outermost surface of the film of the resin film 3a and the inside of the film were measured by ESCA (manufactured by Shimadzu Corporation) to obtain fluorine, carbon, oxygen, nitrogen, and Ming 5 The atomic % of the element. Using the atomic weight of each element, these atoms are 0/. Converted to quality ^). Among these, the ratio of the fluorine concentration is calculated by the equation (1) using only the elements constituting the film, that is, fluorine mass % ( F ), carbon mass % ( C ), oxygen mass % (〇), and nitrogen mass % ( N ). (A ( % )). A (%) = {F / (F + C + O + N)} xl00 (1) Here, as the outermost surface of the film, the surface of the precoated metal sheet 1 a produced as described above is In the state where the argon sputtering time was zero, the measurement was carried out, and the inside of the film was measured while the resin film 3 a was etched in the thickness direction to a depth of 1 /2 of the film thickness. Here, the thickness of the film of 1 /2 means that the argon sputtering time is the depth state of the film which reaches the interface of the resin film 3b and the aluminum of exactly 1 /2, and the interface between the resin film 3a and the aluminum is It means that the above five elements (fluorine mass % ( F ), carbon mass % ( C ), oxygen mass % ( Ο ), and nitrogen mass % ( N ) and aluminum mass % ( A1 ) are equivalent to the metal plate. The mass of A1 is the depth state of the film of argon sputtering time of 50% of the total mass%. (Ethyl urethane bond) The resin film 3 a was measured by FTIR (manufactured by Thermo Nicolet Japan Co., Ltd.) to confirm the presence or absence of an absorption peak corresponding to the combination of the ethyl carbamate. -24- (22) 1272135 (Adhesive peeling property) The adhesive peelability of the precoated metal sheets 1a of Examples 1 to 5 and Comparative Examples 1 to 7 was measured. The results are shown in Table 1. Further, the method for measuring and evaluating the peeling property of the adhesive is as follows.
黏著物剝離強度係根據S K 6 8 5 4 - 2所規定之1 8 0度 剝離試驗進行測定。黏著物使用柯尼卡噴墨紙光標籤(柯 尼卡美能達(Konica Minolta Holdings)(股)製、商品 號QP10A4GMT)。又,做爲測定條件,使用長度1 〇 〇 m m x寬度60mm之預塗覆金屬板la、長度lOOmmx寬度6mm 之標籤,而剝離速度設爲50mm/min。再者,表1之剝離 評價係黏著物剝離強度爲0.1 N/6 mm以下之情況時,使用 “G”,表示「良好(Good )」,在超過 0· IN/6mm之情況 時,使用“B”,表示「不良(Bad )」。The peel strength of the adhesive was measured in accordance with the 180 degree peel test specified in S K 6 8 5 4-2. The adhesive was Konica Minolta Holdings (manufactured by Konica Minolta Holdings Co., Ltd., product number QP10A4GMT). Further, as a measurement condition, a precoated metal plate la having a length of 1 〇 〇 m m x width of 60 mm and a label having a length of 100 mm and a width of 6 mm were used, and the peeling speed was set to 50 mm/min. In the case where the peeling evaluation of Table 1 is a peel strength of 0.1 N/6 mm or less, "G" is used to indicate "Good", and when it exceeds 0·IN/6 mm, "Use" B" means "bad".
-25- 1272135-25- 1272135
〔1谳〕 比較例7 環氧系 塗料 1 250 | ΟΙ Ol CQ I比較例6 ETFE 薄膜 積層 Pll 0.06 〇 V? 脑 m B m ϋ )5¾ g ^ ii 比較例5 [ ETFE 薄膜 積層 朝 0.04 α 比較例4 本發明 塗料 300 21 00 0.13 比較例3 本發明 塗料 SI 21 0.20 CQ 比較例2 本發明 塗料 §1 21 On 0.80 CQ 比較例1 本發明 塗料 51 21 〇 1.50 PQ 實施例5 本發明 塗料 280 v〇 0.03 〇 實施例4 本發明 塗料 260 (N 0.05 〇 實施例3 本發明 塗料 250 〇 0.05 〇 i實施例2 本發明 塗料 220 CN C\ 0.07 〇 實施例1 本發明 塗料 200 QO 0.06 〇 樹脂皮膜 烘烤溫度 (°C) 漱芸~ i 1w | i 皮膜內部的氟濃 度之比例 (%) 胺甲酸乙酯結合 黏著物 剝離強度 (N/6mm) 剝離評價 備註 黏著物 剝離性 -26- (24) (24)1272135 由表1之結果,確認了實施例1〜5之預塗覆金屬板 1 a,其黏著物剝離強度低。另一方面,比較例1〜4及比 較例7之預塗覆金屬板1 a呈黏著物剝離強度高之結果, 比較例5及比較例6之預塗覆金屬板丨a雖黏著物剝離強 度低,但不易將樹脂皮膜3 a接著(披覆)到金屬板2 a。 又,將實施例1〜5的預塗覆金屬板1 a沖壓加工成光 碟機之托盤(承載自作C D之部位)及光碟機的上蓋(覆 蓋自作CD之部位)。此時,也無產生成形不良等,在所 製作之碟片表面也無傷痕寺的外觀不良、或附著污垢或油 等。且,以鮑登滑動試驗測定實施例1〜5之摩擦係數的 結果,摩擦係數爲0 · 04〜0 · 〇 5,確認了在於潤滑性也極爲 良好。再者,摩擦係數係3 / 1 6英吋鋼球、荷重〇 . 5 k g、滑 動速度200mm/min、無塗油,在金屬板2a的壓延方向呈 直角地進行測定。 (實施例6〜1 3 ) 其次,說明關於成爲主劑的氟系樹脂之重量平均分子 量與外觀。做爲實施例6〜1 3,根據前述的製造方法製作 預塗覆金屬板la。預塗覆金屬板la之各結構如下所述。 (金屬板) 使用厚度0.5mm、以JIS 5052-H34爲基準之鋁合金 板。 -27- (25) (25)1272135 (耐蝕性皮膜) 在鋁合金板的兩面形成磷鉻酸皮膜。磷鉻酸皮膜之附 著量,以Cr換算,爲20mg/m2。 (氟系樹脂皮膜) 在磷鉻酸皮膜的最外表面塗佈氟系塗料,以烘烤溫度 (金屬板2a之峰値溫度)2 5 0 °C進行烘烤處理,做成皮膜 厚度5 μηι之氟系樹脂皮膜。在此,做爲氟系塗料,使用 混合的以下之2種液體之氟系塗料。 (主劑):使用8種類之具有氫氧基之氟系樹脂,其 重量平均分子量爲130000〜224000之範圍。 (硬化劑):具有3個異氰酸酯基之嵌段異氰酸酯化 合物。 接著,針對實施例6〜1 3的預塗覆金屬板1 a之樹脂 皮膜3 a,測定表面的光澤度。其結果顯示於表2。再者, 測定方法如下所述。 (光澤度) 使用光澤度計(日本電色工業製),以根據JIS Z 8 74 1之60度鏡面光澤條件,測定預塗覆金屬板ia的樹 脂皮膜3 a之表面的光澤度。測定係以在鋁合金板的壓延 平行方向與與壓延直角方向進行測定,算出平均値。 (目視外觀評價) -28- (26) 1272135 . 請任意選出的1 〇人,以目視觀察預塗覆金屬板1 a之 外觀,在判斷具有光澤性之人數爲9人以上的情況則評價 爲「光澤」,在判斷具有光澤性之人數爲8人以下的情況 ' 則評價爲「無光澤」。 接著,測定評價實施例6〜1 3的預塗覆金屬板1 a之 黏著物剝離性。其結果顯示於表2。再者,黏著物剝離性 之測定、評價方法係以與實施例1相同的方法實施。[1谳] Comparative Example 7 Epoxy coating 1 250 | ΟΙ Ol CQ I Comparative Example 6 ETFE film laminate Pll 0.06 〇V? Brain m B m ϋ ) 53⁄4 g ^ ii Comparative Example 5 [ ETFE film laminate toward 0.04 α comparison Example 4 Coating of the Invention 300 21 00 0.13 Comparative Example 3 Coating of the Invention SI 21 0.20 CQ Comparative Example 2 Coating of the Invention § 1 21 On 0.80 CQ Comparative Example 1 Coating of the Invention 51 21 〇 1.50 PQ Example 5 Coating 280 v of the Invention 〇0.03 〇Example 4 Coating 260 of the invention (N 0.05 〇Example 3 Coating of the invention 250 〇0.05 〇i Example 2 Coating 220 of the invention CN C\ 0.07 〇 Example 1 Coating 200 QO 0.06 〇 resin film baking of the invention Baking temperature (°C) 漱芸~ i 1w | i Ratio of fluorine concentration inside the film (%) Ethyl carbamate combined with adhesive peel strength (N/6mm) Peeling evaluation Remarks Adhesive stripping -26- (24) (24) 1272135 From the results of Table 1, it was confirmed that the precoated metal sheets 1a of Examples 1 to 5 had low peeling strength of the adhesive. On the other hand, the precoating of Comparative Examples 1 to 4 and Comparative Example 7 Metal plate 1 a As a result of the high peeling strength of the article, the precoated metal sheet 比较a of Comparative Example 5 and Comparative Example 6 had a low peeling strength of the adhesive, but it was difficult to coat (coat) the resin film 3 a to the metal sheet 2 a. The precoated metal sheets 1a of Examples 1 to 5 were press-formed into a tray of an optical disk drive (a portion carrying a CD) and an upper cover of the optical disk drive (covering a portion which was used as a CD). At this time, no molding failure occurred. On the surface of the disc to be produced, the appearance of the scratched temple was not good, or dirt or oil was adhered thereto. Moreover, the friction coefficient of Examples 1 to 5 was measured by the Bowden sliding test, and the friction coefficient was 0 · 04 to 0. · 〇5, it is confirmed that the lubricity is also very good. Furthermore, the friction coefficient is 3 / 16 6 inch steel ball, load weight 〇 5 kg, sliding speed 200mm / min, no oil, calendering on the metal plate 2a The measurement was carried out at right angles. (Examples 6 to 13) Next, the weight average molecular weight and appearance of the fluorine-based resin to be the main component will be described. As Examples 6 to 13, the precoating was carried out according to the above-described production method. Laminated metal sheet la. pre-coated metal sheet la The structure is as follows. (Metal plate) having a thickness of 0.5mm, to JIS 5052-H34 aluminum alloy sheet of the reference. -27- (25) (25) 1272135 (Corrosion resistant film) A phosphochromic film is formed on both sides of an aluminum alloy plate. The amount of the phosphochromic film attached was 20 mg/m2 in terms of Cr. (Fluoro resin film) A fluorine-based paint is applied to the outermost surface of the phosphochromic film, and baked at a baking temperature (peak temperature of the metal plate 2a) at 250 ° C to form a film thickness of 5 μηι. A fluorine-based resin film. Here, as the fluorine-based paint, a fluorine-based paint of the following two kinds of liquids is used. (Main component): Eight kinds of fluorine-based resins having a hydroxyl group are used, and the weight average molecular weight thereof is in the range of 130,000 to 224,000. (hardener): a blocked isocyanate compound having 3 isocyanate groups. Next, with respect to the resin film 3 a of the precoated metal sheet 1 a of Examples 6 to 13 , the glossiness of the surface was measured. The results are shown in Table 2. Furthermore, the measurement method is as follows. (Glossiness) Using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.), the glossiness of the surface of the resin film 3a of the precoated metal sheet ia was measured in accordance with the 60-degree specular gloss condition of JIS Z 8 74 1. The measurement was carried out by measuring the parallel direction of the rolling of the aluminum alloy sheet and the direction perpendicular to the rolling, and calculating the average enthalpy. (Evaluation of Visual Appearance) -28- (26) 1272135 . The appearance of the pre-coated metal sheet 1 a was visually observed by one of the selected persons, and the number of people who judged the glossiness was 9 or more. "Gloss" is evaluated as "matte" when it is judged that the number of people having luster is 8 or less. Next, the adhesive peelability of the precoated metal sheets 1a of Examples 6 to 13 was evaluated. The results are shown in Table 2. Further, the measurement and evaluation method of the adhesive peeling property were carried out in the same manner as in Example 1.
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〔i 實施例13 224000 m 無光澤 0.04 〇 實施例12 209000 Ο 無光澤 0.06 〇 實施例11 177000 S ”丨, f—Η ΓΊ (Ν ,ι — 光澤 0.03 〇 實施例10 176000 m cn <Ν ?—Η 光澤 0.05 〇 實施例9 154000 S ......Η (Ν Η 光澤 0.06 〇 實施例8 150000 ON Os 芝 r—H 卜 t—^ 光澤 0.03 〇 實施例7 147000 s 沄 ψ " ^ 光澤 0.04 〇 i實施例6 130000 cn Ov 〇 m f—H <Ν ,丨丨丨丨"Η 光澤 0.05 〇 主劑的重量平均分子量 壓延直角方向 壓延平行方向 平均値 騷 黏著物 剝離強度 (N/6mm) 讎評價 60度鏡面 v r » n mi t m 黏著物 剝離性 -30- (28) (28)1272135 由表2的結果確認了,實施例6〜1 3之預塗覆金屬板 1 a的任一者之黏著物剝離強度均小。 又,做爲成爲主劑之氟系樹脂,使用重量平均分子量 爲200000以者之實施例6〜13的預塗覆金屬板la均爲 8 0以上,即使以目視評價,也呈優良之光澤性。 (第2實施形態) 1.預塗覆金屬板 其次,說明關於本發明的第2實施形態之預塗覆金屬 板的結構。 本發明的第2實施形態之預塗覆金屬板1 b係如圖1 b 所示,具備:基礎材料之金屬板2b ;與形成於金屬板2b 的表面,且被控制成皮膜最外表面與皮膜內部的氟濃度之 比例成爲預定値之樹脂皮膜3b。在這之中,樹脂皮膜3b 係以氟系樹脂陣列層4、與分散於此氟系樹脂陣列層4中 之胺甲酸乙酯珠5所構成,控制成胺甲酸乙酯珠5的含有 率及平均粒徑形成預定値。在此,胺甲酸乙酯珠5之「胺 甲酸乙酯」係以胺甲酸乙酯結合完成交聯反應之聚胺酯樹 脂。又,表面係指金屬板2b的至少其中一方的面。其次 ,說明關於各結構。 (1 )金屬板 在第2實施形態所使用之金屬板2b,不被特別限定 ’除了最平常之冷軋鋼板以外,熔融鍍鋅鋼板、電鍍鋅鋼 -31 - (29) 1272135 • 板、合金化溶融鍍鋅鋼板或鍍銅鋼板、鍍錫鋼板等的各種 鍍裝鋼板’且不銹鋼等的合金鋼板、鋁或鋁合金鋼板、銅 或銅合金板等的非鐵金屬板等均可適用。在此,對於筆記 型笔腦ί合載用的光碟機(驅動器)的蓋、液晶顯示裝置的 框架、車用電裝零件之蓋等,被要求輕量之用途,鋁或鋁 合金爲佳。特別是依據JIS 5052或JIS 5182之Al-Mg系 合金更理想。 (2 )樹脂皮膜 (2-1 )氟濃度之比例 在本發明的第2實施形態所使用之預塗覆金屬板1 b 係當以方程式(1 )計算時,樹脂皮膜3 b的在皮膜最外表 面之氟濃度的比例爲1 5 %以上,並且當以同式(1 )計算 時,樹脂皮膜3b之在皮膜內部的氟濃度之比例爲15%以 下。 • A(%) = {F/(F + C + O + N)}xl00 … (1) 在方程式(1 ) ,A爲氟濃度的比例%,F爲氟質量% ,C爲碳質量%,0爲氧質量%,N爲氮質量%。 在此情況,氟濃度的比例係使用以ESCA等所測定、 ~ 換算之樹脂皮膜3b的皮膜最外表面及皮膜內部之氟質量 - %、碳質量%、氧質量%及氮質量%,以方程式(1 )計算 。再者,在此所謂的皮膜最外表面係指黏著物(圖4所示 的識別標籤L等)所附著之側的表面,即預塗覆金屬板 lb之皮膜最外表面,並非指樹脂皮膜3a與金屬板2b之 -32- (30) (30)1272135 界面。又,所謂皮膜內部係指除了與黏著物附著之表面( 最外表面)與和金屬板2b接著之表面之外的樹脂皮膜3 b 之部分,皮膜內部係指由樹脂皮膜3 b之皮膜最外表面朝 厚度方向測定皮膜厚度之大約1 /2的部分。 更具體而言,皮膜最外表面的氟濃度之比例,係指在 由預塗覆金屬板1 b的表面朝內部,藉由氬濺鍍等加以蝕 刻後以ESCA進行各元素分析之情況,根據當氬濺鍍時間 爲零時所獲得之氟質量%、碳質量%、氧質量%及氮質量% 之各元素質量%所獲得之値。即,由於氬濺鍍時間爲零是 意味著以氬未將表面蝕刻之意,故可定義成皮膜最外表面 之測定。另一方面,當持續進行氬濺鍍時,則由於與氬濺 鍍時間呈比例,表面被深深地蝕刻,故氬濺鍍時間越長, 則顯示更深的內部之元素狀態。在進行某種程度蝕刻後, 因金屬板2 b之成分開始出現,所以將此金屬板2 b之元素 組成的質量%超過全體質量%的50%之時間點的氬濺鍍時 間定義成樹脂皮膜3b與金屬板2b之界面。當將到達此界 面爲止之氬濺鍍時間做爲「T」時,則本第2實施形態之 在皮膜內部的氟濃度之比例,換言之,在由樹脂皮膜3 b 的皮膜最外表面朝厚度方向之皮膜厚度的1 /2部分的氟濃 度之比例,被定義爲:根據在氬濺鍍時間爲上述「T」的 1 /2之時間點所獲得之各元素質量%,所獲得之値。 再者,若根據本第2實施形態的話,由氟系樹脂陣列 層4與胺甲酸乙酯珠5所構成之樹脂皮膜3 b,當看到微 紋時則爲不均等的皮膜。因此,在以ESCA進行分析之際 -33- (31) 1272135 . ,當將分析表面的面積做成過窄時,則會局部地獲得氟系 樹脂陣列層4之濃厚(rich )的部分、或相反地獲得胺甲 酸乙酯珠5之濃厚的部分之資訊,故會有在每個測定的時 β 間點,氟濃度之比例參差不齊之虞。因此,在本第2實施 形態,使用在分析表面的面積爲3 mm 0之測定値,來獲得 樹脂皮膜3 b之平均的資訊。 如後述的比較例所示,在氟系樹脂陣列層4之交聯反 φ 應不均等之情況或產生熱劣化(分解)之情況,會有皮膜 最外表面之氟濃度的比例形成未滿1 5%之情況。在此情況 下,由於影響黏著物的剝離性之樹脂皮膜3b的在皮膜最 外表面的氟之比例少,故使得對於樹脂皮膜3 b之黏著物 的剝離強度變大,並且使得污垢或油變得容易附著。另外 ,當皮膜內部的氟濃度之比例超過1 5 %時,則必須進行形 成樹脂底層或接著劑層等之處置,變得無法將樹脂皮膜 3b強固地接著至金屬板2b表面。 (2 - 2 )氟系樹脂陣列層 氟系樹脂陣列層4係藉由熱使成爲主劑之氟系樹脂與 硬化劑產生反應,在其分子內具有交聯構造者爲佳。且, ^ 做爲主劑與硬化劑之組合,胺甲酸乙酯結合、醯胺結合、 > 尿素結合中之至少一種的化學結合,來將具有氫氧基、殘 基及胺基中至少一種類的氟系樹脂;與具有2個以上、理 想爲3個以上之異氰酸酯基的異氰酸酯化合物予以結合( 交聯)爲佳。藉此,能夠在氟系樹脂陣列層4 (樹脂皮膜 -34- (32) (32)1272135 3 b )形成穩定之交聯構造,使得氟系樹脂陣列層4 (樹脂 皮膜3 b )可更強固地接著於金屬板2b。做爲上述的氫氧 基’當然包含醇系氫氧基或酚基系氫氧基,在廣泛的意思 下’亦包含與異氰酸酯基反應之介質等。又,做爲上述羧 基’當然包含羧基單體、亦包含被無水化之羧基等,與異 氰酸酯基反應之所有的介質。同樣地,做爲上述胺基,包 含與異氰酸酯基反應之所有的介質。再者,被交聯的氟系 樹脂陣列層4之交聯度係以該交聯度之指標的jis K6 796 所規定之膠體含量,80 %以上爲佳。 (2-3 )胺甲酸乙酯珠 — 爲了將預塗覆金屬板lb適用於直接與光碟等滑動之 部分,需要抑制因滑動對於光碟等所造成之傷痕。在此, 爲了防止光碟等受到損傷,將樹脂皮膜3 b做軟爲不可欠 缺的。通常,做爲將樹脂做軟之方法,具有將樹脂的玻璃 移轉溫度降低之方法、或抑制樹脂與硬化劑的交聯反應之 方法等。爲了有效地將樹脂皮膜3 b做軟,而將樹脂皮膜 3 b的主成分之陣列樹脂加以軟質化最爲有效,實際上, 對於陣列樹脂,採用這些方法,能夠將樹脂皮膜3 b予以 軟質化。 但,由於以這些方法隨著樹脂皮膜3 b之軟質化的進 行,會有在樹脂皮膜3b產生增黏(tack)性之副作用’ 故會產生有損對於樹脂皮膜3b之黏著物(識別標籤L、 參照圖4 )之防止附著性的問題。另外,不是將樹脂皮膜 - 35- (33) (33)1272135 j b之陣列树脂加以軟質化,而是將胺甲酸乙酉曰珠5這種 軟質之微粒子添加至樹脂皮膜3 b (氟系樹脂陣列層4 )中 ,則不會有使陣列樹脂的玻璃移轉溫度降低,或抑制交聯 反應,而可將樹脂皮膜3 b全體予以軟質化。因此,不會 產生阻礙對於樹脂皮膜3 b之黏著物(識別標籤L、參照 圖4 )的防止附著性之增黏,可確保對於光碟等之防止受 損性。再者,做爲這種的胺甲酸乙酯珠5,可舉出例如三 洋化成製的梅爾德克斯(MELTEX ;登錄商標)、大曰精 化製大米克珠錄商標)、根上工業製的 阿德帕爾(登錄商標)等。 (胺甲酸乙酯珠的含有率:5質量%以上5 0質量%以下) 爲了提高對於光碟等之防止受損性,胺甲酸乙酯珠5 之含有率係對於氟系樹脂陣列層4較多爲佳。在胺甲酸乙 酯珠5的含有率未滿5質量%,則固定於氟系樹脂陣列層 4中之胺甲酸乙酯珠5的量少,做爲緩衝材之作用降低, 防止受損性不充分。又,胺甲酸乙酯珠5的含有率做得越 高,則由於使胺甲酸乙酯珠5分散之塗料的黏度變得越大 ,故在以滾筒塗裝等將塗料塗裝至金屬板2b之情況,均 等膜厚之塗裝性降低。且’由於佔於樹脂皮膜3b之氟系 樹脂陣列層4的比率降低至需要値以下,故皮膜最外表面 的氟濃度之比例下降至1 5 %以下,造成黏著物(識別標籤 L )的附著防止性也降低。基於上述理由,胺甲酸乙酯珠 5的含有率係做成對於氟系樹脂陣列層4,呈5質量%以 -36 - (34) (34)1272135 上50質量%以下。又,爲了以高的水準維持防止受損性 ’胺甲酸乙酯珠5的含有率係1 〇質量%以上爲佳,爲了 確保穩定之塗裝性,胺甲酸乙酯珠5的含有率係4 0質量 %以下爲佳。 (胺甲酸乙酯珠的平均粒徑:氟系樹脂陣列層的平均厚度 之1 · 1倍以上5倍以下) 爲了以胺甲酸乙酯珠5確保對於光碟等的受損防止性 ’胺甲酸乙酯珠5的平均粒徑較氟系樹脂陣列層4的平均 厚度更大爲重要的。藉此如圖1所示,樹脂皮膜3b之斷 面形狀係由於胺甲酸乙酯珠5所存在的部分凸化,故成爲 細微凹凸形狀。藉此,可大幅減少光碟等與氟系樹脂陣列 層4之接觸面積的同時,在接觸部位,由於柔軟之胺甲酸 乙酯珠5做爲緩衝材來發揮作用,故可確保對於光碟等之 防止受損性。 在此,當胺甲酸乙酯珠5的平均粒徑對於氟系樹脂陣 列層4的平均厚度超過5倍時,則由於大半的胺甲酸乙酯 珠5會變得不易被固定於氟系樹脂陣列層4中,故造成防 止對於光碟等的滑動傷痕的效果降低。又,當胺甲酸乙酯 珠5的平均粒徑對於氟系樹脂陣列層4的平均厚度呈1 . 1 倍以下時,則粒徑小的胺甲酸乙酯珠5容易被埋沒到氟系 樹脂陣列層4中,故造成防止對於光碟等的滑動傷痕的效 果降低。因此,胺甲酸乙酯珠5的平均粒徑理想爲氟系樹 脂陣列層4的平均厚度之1 · 1倍以上5倍以下,更理想爲 -37- (35) (35)1272135 氟系樹脂陣列層4的平均厚度之]· 5倍以上4倍以下。 若胺甲酸乙酯珠5的平均粒徑與氟系樹脂陣列層4的 平均厚度保持成上述關係的話’則能夠防止對於光碟等之 滑動傷痕產生。但,即使保持了上述關係,但使用必要以 上之大的粒徑之胺甲酸乙酯珠5的情況’由於也需要將氟 系樹脂陣列層4的平均厚度增厚,故樹脂皮膜3 b變得需 要以上之厚度,在經濟性上不理想。相反地,在使用必要 以上的小之胺甲酸乙酯珠5的情況’控制胺甲酸乙酯珠5 的平均粒徑與氟系樹脂陣列層4的平均厚度之關係,在工 業性上變得困難。因此,做爲胺甲酸乙酯珠5 ’期望利用 平均粒徑爲5〜30 μιη左右之胺甲酸乙酯珠’而氟系樹脂 陣列層4的平均厚度係3 μιη以上1 〇 μηι以下爲佳。再者, 氟系樹脂陣列層4之平均厚度係測定每單位面積之樹脂皮 膜3 b的重量,將比重做爲1加以換算之値。 在實際的胺甲酸乙酯珠之粒徑’存在有分佈之情況。 例如,若爲積算體積50%粒子徑大約爲8μιη左右之珠的 話,其粒徑分佈係大致分佈在最小左右至最大20 左右之範圍(參照大日精化的日語網頁之大米克珠(夕''彳 S 7;登錄商標)的粒度分佈(與粒徑分佈同義))。 因此,在本第2實施形態,採用平均粒徑做爲胺甲酸乙酯 珠5之粒徑的指標。再者,平均粒徑係指在使胺甲酸乙酯 珠5分散於水之狀態下,以雷射反折式粒度分佈測定器等 所測定到之積算體積50%之粒子徑。 又,如上所述,藉由將胺甲酸乙酯珠5的平均粒徑做 -38- (36) (36)1272135 成較氟系樹脂陣列層4的平均厚度更大’能在樹脂皮膜 3 b的表面形成細微凹凸。藉此,在黏著物附著到樹脂皮 膜3 b之際,在細微凹凸形成微少的空氣層’使得黏著物 與樹脂皮膜3 b之接觸面積減少。因此,能將對於樹脂皮 膜3 b之黏著物的剝離強度維持成低。 其次,本第2實施形態之預塗覆金屬板1 b,亦可在 金屬板2 b、與包含胺甲酸乙酯珠5的氟系樹脂陣列層4 之間具備耐蝕性皮膜(未圖示)。藉由形成耐鈾性皮膜, 可賦予預塗覆金屬板lb耐蝕性,並且提昇金屬板2b與樹 脂皮膜3 b之接著性。耐蝕性皮膜之結構如下所述。 (2-4)耐蝕性皮膜 做爲耐蝕性皮膜,可適宜地使用包含以Cr或Zr爲成 分之以往習知的耐蝕性皮膜之磷鉻酸(phosphoric chromate)皮膜、鉻絡酸(chromic chromate)皮膜、憐 酸锆皮膜、氧化鉻系皮膜、塗佈型鉻酸皮膜或塗佈型锆皮 膜。又,耐蝕性皮膜之附著量,以Cr或Zr的換算値,呈 10〜50mg/m1爲佳。當耐蝕性皮膜之附著量變得較 10mg/m1少時’則無法均等地披覆金屬扳2a全面,不易 確保耐蝕性,無法承受長時間使用。又,當附著量超過 5 Omg/m1時’則在沖壓成形時,會在耐蝕性皮膜產生裂痕 (剝離),變得不易在長期間維持高度的耐蝕性。 -39- 1 .預塗覆金屬板的製造方法 (37) 1272135 本第2實施形態之預塗覆金屬板〗b的製造方 包含在金屬板2 b的表面塗佈分散有胺甲酸乙醋珠 系塗料之第1製程;與在2 0 〇 °C以上2 8 0 °C以下, 塗料進行烘烤處理,以形成氟系樹脂皮膜3 b之第 。以下,說明關於各製程。 (1 )第1製程 第1製程係在金屬板2 b的表面塗佈分散有胺 酯珠5之氧系塗料之製程。此氟系塗料,做爲主劑 有氫氧基、羧基及胺基中至少一種類的氟系樹脂, 爲硬化劑之具有2個以上、理想爲3個以上之異氰 異氰酸酯化合物、更理想爲將異氰酸酯基予以嵌段 酸酯化合物混合者爲佳。又,亦可在氟系塗料,添 蠟、石油蠟、合成蠟或這些的混合物等之潤滑劑。 本發明所請求的範圍下,不被特別限定,可添加以 目的之染料或顏料,用來提高樹脂皮膜3 a的硬度 損性之各種無機塡充劑、導電性添加劑等的添加劑 所謂嵌段異氰酸酯化合物,係指異氰酸酯化合 性異氰酸酯基藉由活性氫化合物等的嵌段化劑予以 者,在常溫下不具有反應性。此嵌段異氰酸酯化合 由烘烤處理等的加熱,使嵌段化劑解離,使得活性 酯基再生,成爲具有反應性。做爲嵌段異氰酸酯化 嵌段化劑,包含甲醇、乙醇、η-丙醇及tert-丁醇等 ,酷、ηα -甲酸及異辛酣(Isooctyl phenol)及間苯 法,係 5之氟 將氟系 2製程 甲酸乙 ,在具 混合做 酸酯基 之異氰 加天然 且,在 著色爲 或耐受 〇 物的活 穩定化 物係藉 異氰酸 合物的 的醇類 二酚等 -40- (38) (38)1272135 的酚類,ε -己內Μ胺,照(oxime )類,乙基丙_ ([i Example 13 224000 m matte 0.04 〇 Example 12 209000 Ο matt 0.06 〇 Example 11 177000 S ”, f—Η ΓΊ (Ν ,ι — gloss 0.03 〇Example 10 176000 m cn <Ν ? —Η Gloss 0.05 〇Example 9 154000 S ......Η (Ν 光泽 Gloss 0.06 〇Example 8 150000 ON Os 芝r r—H 卜t—^ Gloss 0.03 〇Example 7 147000 s 沄ψ " ^ Gloss 0.04 〇i Example 6 130000 cn Ov 〇mf—H <Ν ,丨丨丨丨"Η Gloss 0.05 重量 The weight average molecular weight of the main agent is calendered in the direction perpendicular to the direction of the rolling parallel direction average 値 黏 adhesive peel strength (N / 6mm) 雠 evaluation 60 degree mirror surface vr » n mi tm Adhesive peelability -30- (28) (28) 1272135 It was confirmed from the results of Table 2 that the precoated metal sheets of Examples 6 to 13 were In addition, as for the fluorine-based resin to be the main component, the pre-coated metal sheets la of Examples 6 to 13 having a weight average molecular weight of 200,000 are all 80 or more, even if It is also evaluated by visual inspection and has excellent gloss. 1. Pre-coated metal sheet Next, the structure of the pre-coated metal sheet according to the second embodiment of the present invention will be described. The pre-coated metal sheet 1b according to the second embodiment of the present invention is as shown in Fig. 1b. And a metal plate 2b of a base material; and a resin film 3b formed on the surface of the metal plate 2b and controlled to have a ratio of fluorine concentration at the outermost surface of the film to the inside of the film to be a predetermined thickness. Among them, the resin film 3b is composed of a fluorine-based resin array layer 4 and urethane beads 5 dispersed in the fluorine-based resin array layer 4, and the content ratio and the average particle diameter of the urethane beads 5 are controlled to form a predetermined enthalpy. Here, the "urethane" of the urethane beads 5 is a polyurethane resin which is bonded to the ethyl urethane to complete the crosslinking reaction. Further, the surface means at least one of the faces of the metal plate 2b. Next, the description (1) The metal plate 2b used in the second embodiment is not particularly limited. In addition to the most common cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanized steel-31 - (29) 1272135 • Plate, alloyed molten galvanized steel or Various types of plated steel sheets such as copper steel sheets and tin-plated steel sheets, and alloy steel sheets such as stainless steel, aluminum or aluminum alloy steel sheets, non-ferrous metal sheets such as copper or copper alloy sheets, etc., are applicable. The cover of the optical disk drive (driver), the frame of the liquid crystal display device, and the cover of the vehicle electrical component are required to be lightweight, and aluminum or aluminum alloy is preferred. In particular, an Al-Mg-based alloy according to JIS 5052 or JIS 5182 is more preferable. (2) Ratio of fluorine film concentration of resin film (2-1) In the precoated metal sheet 1b used in the second embodiment of the present invention, when calculated by the equation (1), the resin film 3b is the most in the film. The ratio of the fluorine concentration on the outer surface is 15% or more, and when calculated by the same formula (1), the ratio of the fluorine concentration inside the film of the resin film 3b is 15% or less. • A(%) = {F/(F + C + O + N)}xl00 ... (1) In equation (1), A is the ratio % of fluorine concentration, F is the mass % of fluorine, and C is the mass % of carbon. 0 is oxygen mass %, and N is nitrogen mass %. In this case, the ratio of the fluorine concentration is based on the outermost surface of the film of the resin film 3b measured by ESCA or the like, and the fluorine mass %, carbon mass %, oxygen mass %, and nitrogen mass % in the inner surface of the film. (1) Calculation. In addition, the outermost surface of the film refers to the surface on the side to which the adhesive (the identification label L shown in FIG. 4) is attached, that is, the outermost surface of the film of the precoated metal sheet lb, and does not mean the resin film. 3a and the -32- (30) (30) 1272135 interface of the metal plate 2b. Further, the inside of the film means a portion other than the surface (the outermost surface) to which the adhesive adheres and the surface of the resin film 3b which is adjacent to the surface of the metal plate 2b, and the inside of the film means the outermost surface of the film of the resin film 3b. The portion of the film thickness of about 1 /2 was measured in the thickness direction. More specifically, the ratio of the fluorine concentration on the outermost surface of the film means that the element is analyzed by ESCA after being etched by argon sputtering or the like from the surface of the precoated metal plate 1 b toward the inside, according to The obtained mass % of each of the fluorine mass %, carbon mass %, oxygen mass %, and nitrogen mass % obtained when the argon sputtering time is zero. That is, since the argon sputtering time is zero, it means that the surface is not etched by argon, so it can be defined as the measurement of the outermost surface of the film. On the other hand, when argon sputtering is continued, the surface is deeply etched in proportion to the argon sputtering time, so that the longer the argon sputtering time, the deeper internal element state is exhibited. After a certain degree of etching, since the composition of the metal plate 2b starts to appear, the argon sputtering time at which the mass % of the elemental composition of the metal plate 2b exceeds 50% of the total mass% is defined as a resin film. The interface between 3b and the metal plate 2b. When the argon sputtering time to reach the interface is "T", the ratio of the fluorine concentration in the inside of the film in the second embodiment, in other words, in the thickness direction from the outermost surface of the film of the resin film 3b The ratio of the fluorine concentration in the 1 / 2 portion of the film thickness is defined as the enthalpy obtained from the mass % of each element obtained at the time point of the argon sputtering time of 1 /2 of the above "T". According to the second embodiment, the resin film 3b composed of the fluororesin array layer 4 and the urethane beads 5 is an uneven film when micro-grain is observed. Therefore, when analyzing the area by the ESCA-33-(31) 1272135., when the area of the analysis surface is made too narrow, the rich portion of the fluorine-based resin array layer 4 is partially obtained, or On the contrary, information on the thick portion of the urethane beads 5 is obtained, so that there is a difference in the ratio of the fluorine concentration at the β-point between each measurement. Therefore, in the second embodiment, the average of the resin film 3b is obtained by using a measurement enthalpy having an area of the analysis surface of 3 mm 0 . As shown in the comparative example described later, in the case where the crosslinking inverse φ of the fluorine-based resin array layer 4 is not uniform or the thermal deterioration (decomposition) occurs, the ratio of the fluorine concentration on the outermost surface of the film may be less than 1 5% of the situation. In this case, since the proportion of fluorine on the outermost surface of the film of the resin film 3b which affects the peeling property of the adhesive is small, the peeling strength of the adhesive to the resin film 3b is made large, and the dirt or oil is changed. It is easy to attach. Further, when the ratio of the fluorine concentration in the film exceeds 15%, it is necessary to perform treatment such as formation of a resin underlayer or an adhesive layer, and it is impossible to firmly adhere the resin film 3b to the surface of the metal plate 2b. (2 - 2) Fluorine-based resin array layer The fluorine-based resin array layer 4 is preferably a reaction between a fluorine-based resin which is a main component and a curing agent by heat, and has a cross-linking structure in its molecule. And, as a combination of a main agent and a hardener, at least one of a hydroxyl group, a guanamine bond, a urea bond, and a urea bond, at least one of a hydroxyl group, a residue and an amine group A fluorine-based resin of a type is preferably bonded (crosslinked) to an isocyanate compound having two or more, and preferably three or more, isocyanate groups. Thereby, a stable crosslinked structure can be formed in the fluorine-based resin array layer 4 (resin film-34-(32) (32) 1272135 3 b ), so that the fluorine-based resin array layer 4 (resin film 3 b ) can be made stronger The ground is next to the metal plate 2b. The above-mentioned hydrogen oxy group is of course an alcohol-based hydroxy group or a phenol group-based hydroxy group, and in a broad sense, a medium which reacts with an isocyanate group is also included. Further, all of the above-mentioned carboxy group's include a carboxyl group monomer and a carboxyl group which is anhydrousated, and reacts with an isocyanate group. Similarly, as the above amine group, all of the mediums which react with the isocyanate groups are contained. Further, the degree of crosslinking of the crosslinked fluorine-based resin array layer 4 is preferably 80% or more of the colloid content specified by jis K6 796 which is an index of the degree of crosslinking. (2-3) Ethyl urethane beads - In order to apply the precoated metal sheet lb to a portion directly sliding with a disc or the like, it is necessary to suppress scratches caused by sliding on a disc or the like. Here, in order to prevent damage to the optical disk or the like, it is indispensable to soften the resin film 3b. In general, as a method of softening the resin, there is a method of lowering the glass transition temperature of the resin or a method of inhibiting the crosslinking reaction between the resin and the curing agent. In order to effectively soften the resin film 3b, it is most effective to soften the array resin of the main component of the resin film 3b. In fact, for the array resin, the resin film 3b can be softened by these methods. . However, since the softening of the resin film 3b is carried out by these methods, there is a side effect of tacking the resin film 3b, so that the adhesive to the resin film 3b is damaged (identification label L) Refer to Figure 4) for the problem of preventing adhesion. Further, instead of softening the array resin of the resin film - 35-(33) (33) 1272135 jb, the soft fine particles of the urethane bead bead 5 are added to the resin film 3 b (fluoro resin array layer). In 4), the glass transition temperature of the array resin is not lowered, or the crosslinking reaction is inhibited, and the entire resin film 3b can be softened. Therefore, the adhesion to the adhesive of the resin film 3b (identification label L, see Fig. 4) is prevented from increasing, and the damage resistance to the optical disk or the like can be ensured. In addition, as such a urethane bead 5, for example, Merdecy (MELTEX; registered trademark) manufactured by Sanyo Chemical Co., Ltd., Otsuka Seiki Co., Ltd. Adepar (registered trademark) and so on. (Content of urethane beads: 5% by mass or more and 50% by mass or less) In order to improve damage prevention for optical disks and the like, the content of the urethane beads 5 is more than that of the fluororesin array layer 4 It is better. When the content of the urethane beads 5 is less than 5% by mass, the amount of the urethane beads 5 fixed in the fluororesin array layer 4 is small, and the effect as a cushioning material is lowered to prevent damage. full. Further, the higher the content of the urethane beads 5 is, the higher the viscosity of the coating material dispersing the urethane beads 5 is. Therefore, the coating material is applied to the metal plate 2b by roller coating or the like. In the case, the coating property of the uniform film thickness is lowered. In addition, since the ratio of the fluorine-based resin array layer 4 which accounts for the resin film 3b is reduced to less than 値, the ratio of the fluorine concentration on the outermost surface of the film is reduced to 15% or less, resulting in adhesion of the adhesive (identification label L). Preventiveness is also reduced. For the reason described above, the content of the urethane beads 5 is 5% by mass to 5% by mass of -36 - (34) (34) 1272135 for the fluororesin array layer 4. In addition, in order to maintain the damage resistance at a high level, the content of the urethane beads 5 is preferably 1% by mass or more, and the content of the urethane beads 5 is 4 in order to ensure stable coating properties. 0% by mass or less is preferred. (Average particle diameter of the urethane-based bead beads: 1 to 1 time or more and 5 times or less of the average thickness of the fluororesin array layer) To prevent damage to the optical disk or the like by the urethane beads 5 It is important that the average particle diameter of the ester beads 5 is larger than the average thickness of the fluorine-based resin array layer 4. As a result, as shown in Fig. 1, the cross-sectional shape of the resin film 3b is partially convex due to the presence of the urethane beads 5, so that it has a fine uneven shape. In this way, the contact area between the optical disk and the like and the fluorine-based resin array layer 4 can be greatly reduced, and the soft urethane beads 5 act as a cushioning material at the contact portion, thereby ensuring prevention of the optical disk and the like. Impaired. Here, when the average particle diameter of the urethane beads 5 is more than 5 times the average thickness of the fluororesin array layer 4, most of the urethane beads 5 become difficult to be fixed to the fluororesin array. In the layer 4, the effect of preventing sliding scratches on a disc or the like is lowered. When the average particle diameter of the urethane beads 5 is at most 1.1 times the average thickness of the fluororesin array layer 4, the urethane beads 5 having a small particle diameter are easily buried in the fluororesin array. In the layer 4, the effect of preventing sliding scratches on a disc or the like is lowered. Therefore, the average particle diameter of the urethane beads 5 is preferably from 1. 1 time to 5 times the average thickness of the fluororesin array layer 4, and more preferably -37-(35) (35) 1272135 fluorine-based resin array. The average thickness of the layer 4 is 5 times or more and 4 times or less. When the average particle diameter of the urethane beads 5 is maintained in the above relationship with the average thickness of the fluororesin array layer 4, it is possible to prevent the occurrence of sliding scratches on the optical disk or the like. However, even if the above relationship is maintained, in the case where the urethane beads 5 having a large particle diameter or more are used, the average thickness of the fluororesin array layer 4 needs to be increased, so that the resin film 3b becomes The above thickness is required, which is not economically desirable. On the contrary, in the case where the small urethane beads 5 or more are used, the relationship between the average particle diameter of the urethane beads 5 and the average thickness of the fluororesin array layer 4 is difficult to industrially. . Therefore, it is preferable to use the urethane beads having an average particle diameter of about 5 to 30 μm as the urethane beads 5', and the average thickness of the fluorine-based resin array layer 4 is preferably 3 μm or more and 1 μm or less. In addition, the average thickness of the fluororesin array layer 4 is measured by measuring the weight of the resin film 3 b per unit area, and converting the specific gravity to 1. There is a distribution in the particle size ' of the actual urethane beads. For example, if the volume is 50% of the particles with a particle diameter of about 8 μm, the particle size distribution is roughly distributed from a minimum of about 20 to a maximum of about 20 (refer to the Japanese version of the Japanese-made Japanese page of the Dayi Refinery)彳S 7; registered trademark) particle size distribution (synonymous with particle size distribution)). Therefore, in the second embodiment, the average particle diameter is used as an index of the particle diameter of the urethane beads 5. In addition, the average particle diameter refers to a particle diameter of 50% of the integrated volume measured by a laser reflex type particle size distribution analyzer or the like in a state in which the urethane beads 5 are dispersed in water. Further, as described above, by making the average particle diameter of the urethane beads 5 -38-(36) (36) 1272135 into a larger average thickness than the fluorine-based resin array layer 4, the resin film 3b can be formed in the resin film 3b. The surface forms fine irregularities. Thereby, when the adhesive adheres to the resin film 3b, a slight air layer is formed in the fine unevenness, so that the contact area between the adhesive and the resin film 3b is reduced. Therefore, the peeling strength of the adhesive to the resin film 3b can be kept low. In the precoated metal sheet 1 b of the second embodiment, a corrosion-resistant film (not shown) may be provided between the metal sheet 2 b and the fluororesin array layer 4 including the urethane beads 5 . . By forming the uranium-resistant film, the corrosion resistance of the precoated metal sheet lb can be imparted, and the adhesion of the metal sheet 2b to the resin film 3b can be improved. The structure of the corrosion resistant film is as follows. (2-4) The corrosion-resistant film is used as a corrosion-resistant film, and a phosphoric chromate film containing a conventional corrosion-resistant film containing Cr or Zr as a component, or a chroma chromate can be suitably used. A film, a zirconium acid film, a chromium oxide film, a coated chromic film or a coated zirconium film. Further, the amount of adhesion of the corrosion-resistant film is preferably 10 to 50 mg/m1 in terms of Cr or Zr. When the adhesion amount of the corrosion-resistant film is less than 10 mg/m1, the metal plate 2a cannot be uniformly coated, and it is difficult to ensure corrosion resistance and cannot withstand long-term use. In addition, when the amount of adhesion exceeds 5 Omg/m1, cracking (peeling) occurs in the corrosion-resistant film during press forming, and it is difficult to maintain high corrosion resistance for a long period of time. -39- 1 . Method for producing precoated metal sheet (37) 1272135 The prepreg metal sheet b of the second embodiment is produced by coating and dispersing urethane acetate beads on the surface of the metal sheet 2 b. The first process of the coating is performed; and the coating is baked at a temperature of 20 ° C or more and 280 ° C or less to form a fluorine-based resin film 3 b. Hereinafter, each process will be described. (1) First Process The first process is a process in which an oxygen-based paint in which the amine ester beads 5 are dispersed is applied to the surface of the metal plate 2b. The fluorine-based coating material is a fluorine-based resin having at least one of a hydroxyl group, a carboxyl group and an amine group as a main component, and is preferably a curing agent having two or more, preferably three or more isocyanate compounds, more preferably It is preferred to mix the isocyanate group with the block ester compound. Further, a lubricant such as a fluorine-based paint, a wax, a petroleum wax, a synthetic wax or a mixture thereof may be used. In the scope of the present invention, it is not particularly limited, and an additive such as a dye or a pigment for the purpose of improving the hardness of the resin film 3 a, an additive such as a conductive additive, or the like, a block isocyanate may be added. The compound means that the isocyanate compound isocyanate group is a blocking agent such as an active hydrogen compound, and does not have reactivity at normal temperature. This block isocyanate compound is heated by a baking treatment or the like to dissociate the blocking agent, and the active ester group is regenerated to become reactive. As a block isocyanate blocker, including methanol, ethanol, η-propanol and tert-butanol, etc., cool, ηα-carboxylic acid and Isooctyl phenol and meta-benzene method, the fluorine of 5 Fluorine 2 process formic acid B, in the case of isocyanine with a mixture of ester groups, and in the case of a live-stable compound that is colored or tolerant to sputum, an alcoholic diphenol such as an isocyanate. (38) (38) 1272135 phenols, ε-caprolactam, oxime, ethyl propyl _ (
Acetylacetone )、甲乙酮(methyl ethyl ketone )及乙基 環已院(V i n y 1 c 1 o h e x a n e )等的活性乙烧化合物類,以及 亞硫酸鈉等。另一方面,做爲具有嵌段異氰酸酯基之異氰 酸酯化合物,包含有甲苯二異氰酸酯、4,4’-二苯基甲烷二 異氰酸酯(MDI)、聚合MDI、異佛爾酮二異氰酸酯( Isophorone diisocyanate )、及己二異氰酸醋( hexamethylene diisocyanate)等。又,多價醇變性型聚合 異氰酸酯及滴定結合或異氰酸酯結合之聚合異氰酸酯等’ 亦含於做爲異氰酸酯化合物。 如此使用嵌段化之硬化劑的氟系塗料,由於在常溫下 ,硬化劑的異氰酸酯基被嵌段’故主劑的氫氧基、羧基及 胺基與硬化劑之異氰酸酯基的反應(交聯反應)不會進行 ,而藉由後述的第2製程之烘烤處理首先進行反應(交聯 ),使得氟系塗料硬化。因此’能夠將氟系塗料在混合了 主劑與硬化劑之狀態下長時間保存’並且可將氟系塗料連 續塗佈到長條的金屬板’有利於工業。 做爲對於氟系塗料之胺甲酸乙酯珠5的分散處理方法 ,包含有超音波處理’利用磁鐵攪拌器或葉輪攪拌機等之 攪拌處理,使用均質機 '球磨機、珠磨機等之攪拌處理等 〇 氧系塗料之塗佈’能使用滾筒塗佈機、淋幕(curtain flow)式塗佈機、滾幕(roller curtain)式塗佈機、靜電 塗裝機、刮刀塗佈機、擠壓(die )式塗佈機等之任一方 -41 - (39) (39)1272135 法,特別是使用塗佈量均等,並且作業簡單之滾筒塗佈機 更爲理想。塗佈量係以在金屬板2 b的表面形成厚度3〜 10 μπι之氟系樹脂陣列層4的方式,考量金屬板2b的搬送 速度、滾筒塗佈機之旋轉方向與旋轉速度等,適宜設定。 亦可在進行氟系塗料塗佈之前,設置將金屬板2 b的 表面脫脂之脫脂製程。例如,將鹼性水溶液噴灑於金屬板 2 b的表面,然後加以水洗,將金屬板2 b的表面脫脂。且 ,在如前所述,於金屬板2b與氟系樹脂皮膜3 b之間具備 耐蝕性皮膜之情況,能夠接續脫脂製程,藉由將包含鉻離 子等之化成處理液噴灑於金屬板2b之表面等,形成耐蝕 性皮膜。 (2 )第2製程 係在金屬板2b的表面形成氟系樹脂皮膜3b (包含胺 甲酸乙酯珠5之氟系樹脂陣列層4 )之製程,其係在200 °C以上2 8 0 °C以下,將在第1製程所塗佈之氟系塗料進行 烘烤處理’使氟系塗料硬化(交聯)。然後,藉由系塗 料硬化(交聯),形成皮膜最外表面之氟濃度比例爲1 5 % 以上且皮膜內部之氟濃度的比例爲1 5 %以下之氟系樹脂皮 膜3b。又,樹脂皮膜3b強固地接著至金屬板2b。在此, 所§胃烘烤溫度係指金屬板2b的溫度之峰値溫度。與此同 時,胺甲酸乙酯珠5被固定於氟系樹脂陣列層4。 當烘烤溫度未滿2 0 0 °C時,則氟系塗料的硬化(交聯 )變得不充分,而當烘烤溫度超過280 °C時,由於氟系塗 -42- (40) 1272135 料會熱劣化(分解),故無法將氟濃度的比例做成期望的 値,使得黏著物對於氟系樹脂皮膜3 a的皮膜表面之剝離 強度變高。烘烤處理時間係2 0〜6 0秒爲佳。在處理時間 未滿2 0秒之情況,烘烤容易變得不充分,而當超過6 0秒 時,則烘烤處理時間過長,平均時間之生產性容易降低。 又,烘烤處理係使用例如熱風爐、誘導加熱爐、近紅外線 爐、遠紅外線爐、能量線硬化爐來進行。 其次,詳細說明關於第2實施形態之實施例。 在本實施例,實施關於針對在於第2實施形態之預塗 覆金屬板1 b,在變更分散於樹脂皮膜3 b (氟系樹脂陣列 層4 )之胺甲酸乙酯珠5的含有率、平均粒徑之對於光碟 等的防止受損性與黏著物剝離性之變化的試驗,加以確認 (實施例1〜9 ) φ 做爲實施例1〜9,根據前述的製造方法,製作預塗 覆金屬板lb。預塗覆金屬板lb之各結構如以下所述。 (金屬板) 使用厚度〇.5mm、以JIS 5 0 5 2-H34爲基準之鋁合金 ’板。 (耐蝕性皮膜) 在鋁合金板的兩面形成磷鉻酸皮膜。磷鉻酸皮膜之附 -43- (41) 1272135 . 著量,以Cr換算,爲20mg/m2。 ^ (氟系樹脂皮膜) '在磷鉻酸皮膜的最外表面塗佈氟系塗料,以烘烤溫度 (金屬板2b之峰値溫度)2 5 0 t進行烘烤處理,形成樹脂 皮膜3 b (氟系樹脂陣列層4 )。 在此,做爲氟系塗料,使用混合的以下之2種液體之 φ 氟系塗料。又,爲了進行胺甲酸乙酯珠5對於氟系塗料之 分散,而使用利用磁鐵攪拌器之攪拌處理。且,關於氟系 樹脂陣列層4之平均厚度(A)、所使用之胺甲酸乙酯珠 5的平均粒徑(B ) 、( B/A )及含有率,記載於表3。 (主劑):具有氫氧基之氟系樹脂,使用重量平均分 子量爲1 8 2 000者。 (硬化劑):具有3個異氰酸酯基之嵌段異氰酸酯化 合物。 (比較例1〜9 ) 與前述實施例1〜9對應地,在比較例1〜9,製作預 塗覆金屬板1 b。在比較例1,製作使用未含胺甲酸乙酯珠 " 5的氟系塗料之預塗覆金屬板1 b,在比較例2〜7,使用 > :除了胺甲酸乙酯珠5在平均粒徑與氟系樹脂陣列層4的 平均厚度之關係、或胺甲酸乙酯珠5的含有率之其中一條 件未能符合本發明的請求範圍以外,其餘在與實施例1〜 9相同之條件下所製作的預塗覆金屬板1 b。又,比較例8 -44- (42) 1272135 . 、9,在未符合本發明的請求範圍之烘烤溫度下進行烘烤 處理。 接著,針對實施例1〜9、比較例1〜9的預塗覆金屬 β 板1 b之樹脂皮膜3 b,測定樹脂皮膜3 b的最外表面及皮 膜內部之氟濃度的比例,並且測定有無表現氟系樹脂陣列 層4的交聯構造之胺甲酸乙酯結合,將其結果顯示於表3 。再者,各特性之測定方法如下所述。 (氟濃度的比例) 將樹脂皮膜3b的皮膜最外表面及皮膜內部以ESCA (島津製作所製)加以測定,獲得氟、碳、氧、氮及銘的 5種元素之原子%。使用各元素之原子量,將這些原子% 換算成質量%。在這些之中,僅使用構成皮膜的元素即氟 質量% ( F )、碳質量% ( C )、氧質量% ( 0 )及氮質量% (N),以方程式(1 )算出氟濃度之比例(A ( % ))。 • A(%)={F/(F + C + 0 + N)}xlOO … (1) 在此,做爲皮膜最外表面,將如前述所製作之預塗覆 金屬板1 b的表面在該狀態下即氬濺鍍時間爲零之狀態下 進行測定,而針對皮膜內部,在以氬蝕刻將樹脂皮膜3 b 朝厚度方向蝕刻至皮膜厚度的1 /2爲止之深度的狀態下加 ^ 以測定。在此,皮膜厚度的1 /2係指氬濺鍍時間爲到達樹 脂皮膜3 b與鋁的界面之剛好1 /2的時間之皮膜的深度狀 態之情事,又樹脂皮膜3b與鋁的界面係指所測定的上述 5種兀素(氟質量%(?)、碳質量。/〇(C)、氧質量%(0 -45- (43) 1272135 )及氮質量% ( N )以及鋁質量% ( A1 ))中,相當於金屬 板的 A1之質量成爲全體質量%的50%之氬濺鍍時間之皮 膜的深度狀態係如前所述。 且,爲了使得樹脂皮膜3 b之微紋不均等性不會影響 分析,而將分析表面的面積作成3 m m 0。對於皮膜最外表 面及皮膜內部,均選擇不會受到油類污染的部位進行測定 (胺甲酸乙酯結合) 以FTIR (塞莫-尼科萊特日本(Thermo Nicolet Japan )社製)來測定樹脂皮膜3 b,確認有無相當於胺甲酸乙 酯結合之吸收峰値。 其次,測定評價實施例1〜9、比較例1〜9之預塗覆 金屬板1 b的之對於光碟等的防止受損性及黏著物剝離性 。將其結果顯示於表3。再者,防止受損性及黏著物剝離 φ 性的測定、評價方法如下所述。 (對於光碟之防止受損性) 使市面販售的光碟之記錄面的全面接觸於預塗覆金屬 板1 b的樹脂皮膜3 b之表面,在以手指輕微按壓之狀態下 朝左右往復摩擦1〇次後,以目視評價光碟表面的傷痕 。此時’參照圖2〜圖3的光碟傷痕樣本,選定受損狀態 相近之傷痕樣本’將該所選定的傷痕樣本做爲預塗覆金屬 板1 b之防止受損性的判定結果。 -46- (44) (44)1272135 再者,在光碟傷痕樣本,在圖2(a)使用“E”表示「 優良(Excellent)」,在圖2(b)使用“G”,表示「良好 (Good )」,在圖3 ( a)使用“NG”表示「稍稍不良(Not So Good)」,在圖3(b)使用“B”表示「不良(Bad)」 。又,使用“£”、“G”、“NG”、“B”的任一個文字,來將防 止受損性的判定結果顯示於表3。 但,關於光碟的邊緣受到摩擦所產生之傷痕,不在判 定對象內,僅嚴密地判定樹脂皮膜..3 b的表面與碟片記錄 面的滑動傷痕。 (黏著物剝離性) 黏著物剝離強度係根據JIS K6 8 5 4-2所規定之180度 剝離試驗進行測定。黏著物使用柯尼卡噴墨紙光標籤(柯 尼卡美能達(Konica Minolta Holdings)(股)製、商品 號QP10A4GMT)。又,做爲測定條件,使用長度100mm X寬度60mm之預塗覆金屬板、長度i〇〇mmx寬度6mm之 標籤’而剝離速度設爲50mm/min。再者,表3之剝離評 價係黏著物剝離強度爲0· lN/6mm以下之情況時,使用 “G”’表示「良好(Good)」,在超過0.1N/6mm之情況 時,使用“B”,表示「不良(Bad)」。 -47- 1272135Acetylacetone), methyl ethyl ketone, and active ethyl-alkali compounds such as acetazone (V i n y 1 c 1 o h e x a n e ), and sodium sulfite. On the other hand, as an isocyanate compound having a blocked isocyanate group, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI, isophorone diisocyanate, And hexamethylene diisocyanate and the like. Further, the polyvalent alcohol-denatured polymerizable isocyanate and the titrated or isocyanate-bonded polymeric isocyanate or the like are also contained as an isocyanate compound. In the fluorine-based coating material using the blocked hardener as described above, since the isocyanate group of the curing agent is blocked at normal temperature, the reaction of the hydroxyl group, the carboxyl group and the amine group of the main component with the isocyanate group of the curing agent (crosslinking) The reaction does not proceed, and the reaction (crosslinking) is first performed by the baking treatment of the second process described later to cure the fluorine-based paint. Therefore, it is advantageous for the industry to be able to store the fluorine-based paint in a state in which the main agent and the hardener are mixed for a long period of time and to continuously apply the fluorine-based paint to the long metal plate. As a method of dispersing the urethane beads 5 of the fluorine-based paint, the ultrasonic treatment includes a stirring treatment using a magnet agitator or an impeller mixer, and a homogenizer, a ball mill, a bead mill, or the like. The coating of the neodymium coating can use a roller coater, a curtain flow coater, a roller curtain coater, an electrostatic coater, a knife coater, and extrusion ( A die coater or the like - 41 - (39) (39) 1272135, in particular, a roll coater which is uniform in application amount and which is simple in operation, is more preferable. In the coating amount, the fluorine-based resin array layer 4 having a thickness of 3 to 10 μm is formed on the surface of the metal plate 2b, and the conveyance speed of the metal plate 2b, the rotation direction and the rotation speed of the roll coater, and the like are appropriately determined. . It is also possible to provide a degreasing process for degreasing the surface of the metal plate 2b before applying the fluorine-based paint. For example, an alkaline aqueous solution is sprayed on the surface of the metal plate 2b, and then washed with water to degrease the surface of the metal plate 2b. In addition, as described above, a corrosion-resistant film is provided between the metal plate 2b and the fluororesin film 3b, and the degreasing process can be continued, and the chemical conversion treatment solution containing chromium ions or the like is sprayed on the metal plate 2b. A surface or the like forms a corrosion-resistant film. (2) The second process is a process of forming a fluorine-based resin film 3b (a fluorine-based resin array layer 4 containing urethane beads 5) on the surface of the metal plate 2b, which is 200 ° C or higher and 200 ° C Hereinafter, the fluorine-based paint applied in the first process is subjected to a baking treatment to cure (crosslink) the fluorine-based paint. Then, the fluorine-based resin film 3b having a fluorine concentration ratio of the outermost surface of the film of 15% or more and a fluorine concentration inside the film of 15% or less is formed by the coating material being hardened (crosslinked). Further, the resin film 3b is firmly adhered to the metal plate 2b. Here, the "stomach baking temperature" means the peak temperature of the temperature of the metal plate 2b. At the same time, the urethane beads 5 are fixed to the fluororesin array layer 4. When the baking temperature is less than 200 °C, the hardening (crosslinking) of the fluorine-based coating becomes insufficient, and when the baking temperature exceeds 280 °C, the fluorine-based coating-42-(40) 1272135 Since the material is thermally deteriorated (decomposed), the ratio of the fluorine concentration cannot be made into a desired enthalpy, and the peeling strength of the adhesive on the surface of the film of the fluororesin film 3 a becomes high. The baking treatment time is preferably 20 to 60 seconds. When the treatment time is less than 20 seconds, the baking tends to be insufficient, and when it exceeds 60 seconds, the baking treatment time is too long, and the productivity of the average time is liable to lower. Further, the baking treatment is carried out using, for example, a hot air furnace, an induction heating furnace, a near infrared ray furnace, a far infrared ray furnace, and an energy ray hardening furnace. Next, an embodiment of the second embodiment will be described in detail. In the present embodiment, the content and average of the urethane beads 5 dispersed in the resin film 3b (the fluorine-based resin array layer 4) are changed for the precoated metal sheet 1b according to the second embodiment. The test for the change in the damage prevention property of the optical disk or the like and the peeling property of the adhesive was confirmed (Examples 1 to 9) φ As Examples 1 to 9, the precoated metal was produced according to the above-described production method. Board lb. The structures of the precoated metal sheets lb are as follows. (Metal plate) An aluminum alloy plate having a thickness of 55 mm and based on JIS 5 0 5 2-H34 was used. (Corrosion resistant film) A phosphochromic film was formed on both surfaces of the aluminum alloy plate. Attached to the phosphochromic film -43- (41) 1272135 . The amount of the sample is 20 mg/m2 in terms of Cr. ^ (Fluororesin film) 'The fluorine-based paint is applied to the outermost surface of the phosphochromic film, and baked at a baking temperature (peak temperature of the metal plate 2b) 250 k to form a resin film 3 b (Fluororesin array layer 4). Here, as the fluorine-based paint, a φ fluorine-based paint of the following two kinds of liquids is used. Further, in order to disperse the urethane beads 5 for the fluorine-based paint, a stirring treatment using a magnet stirrer is used. Further, the average thickness (A) of the fluororesin array layer 4, the average particle diameter (B), (B/A) and the content ratio of the urethane beads 5 used are described in Table 3. (main agent): a fluorine-based resin having a hydroxyl group, and a weight average molecular weight of 1 8 2 000 is used. (hardener): a blocked isocyanate compound having 3 isocyanate groups. (Comparative Examples 1 to 9) Corresponding to the above Examples 1 to 9, the precoated metal sheets 1b were produced in Comparative Examples 1 to 9. In Comparative Example 1, a precoated metal plate 1 b using a fluorine-based paint containing no urethane beads " 5 was prepared, and in Comparative Examples 2 to 7, use > except for the urethane beads 5 in average The conditions of the relationship between the particle diameter and the average thickness of the fluororesin array layer 4 or the content of the urethane bead 5 are not in accordance with the scope of the present invention, and the same conditions as in the examples 1 to 9 are satisfied. The precoated metal sheet 1 b produced below. Further, Comparative Examples 8-44-(42) 1272135., 9, were subjected to a baking treatment at a baking temperature which did not satisfy the scope of the present invention. Next, with respect to the resin film 3 b of the precoated metal β plate 1 b of Examples 1 to 9 and Comparative Examples 1 to 9, the ratio of the fluorine concentration of the outermost surface of the resin film 3 b and the inside of the film was measured, and the presence or absence of the measurement was measured. The urethane bond showing the crosslinked structure of the fluororesin array layer 4 was shown, and the results are shown in Table 3. Furthermore, the measurement method of each characteristic is as follows. (Proportion of Fluorine Concentration) The outermost surface of the film of the resin film 3b and the inside of the film were measured by ESCA (manufactured by Shimadzu Corporation) to obtain atomic percentages of five elements of fluorine, carbon, oxygen, nitrogen and Ming. These atomic % are converted into mass % using the atomic weight of each element. Among these, the ratio of the fluorine concentration is calculated by the equation (1) using only the elements constituting the film, that is, fluorine mass % ( F ), carbon mass % ( C ), oxygen mass % ( 0 ), and nitrogen mass % (N). (A ( % )). • A(%)={F/(F + C + 0 + N)}xlOO (1) Here, as the outermost surface of the film, the surface of the precoated metal sheet 1 b produced as described above is In this state, the argon sputtering time is measured in a state where the argon sputtering time is zero, and the inside of the film is etched in a state where the resin film 3b is etched in the thickness direction to a depth of 1 /2 of the film thickness by argon etching. Determination. Here, the thickness of the film of 1 /2 means that the argon sputtering time is the depth state of the film which reaches the interface of the resin film 3 b and the aluminum at exactly 1 /2, and the interface between the resin film 3b and the aluminum means The above five kinds of halogens (fluorine mass % (?), carbon mass % / 〇 (C), oxygen mass % (0 - 45 - (43) 1272135 ) and nitrogen mass % (N ) and aluminum mass % ( In A1)), the depth state of the film corresponding to the argon sputtering time at which the mass of the metal plate A1 is 50% of the total mass% is as described above. Further, in order to make the unevenness of the grain of the resin film 3b not affect the analysis, the area of the analysis surface was made 3 m m 0 . The outermost surface of the film and the inside of the film were selected for measurement without oil contamination (ethyl urethane bonding). The resin film was measured by FTIR (manufactured by Thermo Nicolet Japan Co., Ltd.). 3 b, confirm whether there is an absorption peak corresponding to the combination of urethane. Next, the damage prevention property and the peeling property of the optical disk and the like of the precoated metal sheets 1b of Examples 1 to 9 and Comparative Examples 1 to 9 were evaluated. The results are shown in Table 3. In addition, the measurement and evaluation methods for preventing damage and adhesion peeling φ are as follows. (For the damage prevention of the optical disk) The surface of the recording surface of the optical disk sold in the market is completely contacted with the surface of the resin film 3b of the precoated metal plate 1b, and rubbed back and forth toward the right and left with a slight finger pressing. After the squatting, the scratches on the surface of the disc were visually evaluated. At this time, with reference to the disc scratch samples of Figs. 2 to 3, the scar samples having the same damaged state were selected as the result of the damage prevention of the pre-coated metal sheets 1b. -46- (44) (44) 1272135 Furthermore, in the case of disc scratches, "E" is used to indicate "Excellent" in Figure 2(a), and "G" is used in Figure 2(b) to indicate "Good". (Good), in Fig. 3 (a), "NG" is used to indicate "Not So Good", and in Fig. 3 (b), "B" is used to indicate "Bad". Further, the results of the determination of the damage prevention are shown in Table 3 using any of the characters "£", "G", "NG", and "B". However, the flaws caused by the friction of the edge of the optical disc are not determined in the object, and only the surface of the resin film. 3b and the sliding scratch of the recording surface of the disc are strictly determined. (Adhesive peeling property) The peeling strength of the adhesive was measured in accordance with a 180-degree peeling test prescribed in JIS K6 8 5 4-2. The adhesive was Konica Minolta Holdings (manufactured by Konica Minolta Holdings Co., Ltd., product number QP10A4GMT). Further, as a measurement condition, a precoated metal plate having a length of 100 mm X and a width of 60 mm and a label of a length i 〇〇 mm x width of 6 mm were used, and the peeling speed was set to 50 mm/min. In the case where the peeling evaluation of Table 3 is when the peel strength of the adhesive is 0·lN/6 mm or less, "G" is used to indicate "Good", and when it is more than 0.1 N/6 mm, "B" is used. "," means "bad". -47- 1272135
〔i 比較例 9 寸 00 oi (N 1 Cs ω QQ 比較例 1 8 tn 寸 OO (N 〇 m rH 卜 LU 〇 OQ 比較例 7 S 沄 ΓΜ (N οο a 7: g 〇 a !比較例 ..6 . 寸 dl 〇 (N οο CQ S 〇 a 比_父例 1 1 5 21 泛 (N un (Ν οο OQ d a 比較例 4 〇 Ό SI 〇 (N (Ν 00 CQ g ο a 比較例 3 寸 00 CN SI 沄 (N 21 tn ω CN Ο CQ 魏湖 細 比較例 2 OO <N ml (N οο (Ν οο a 7: s d a 比較例 1 蕻 朝 〇 (Ν as <Ν ο CQ s o a 實施例 9 泛 (Ν ΓΛ (Ν r- a O o a 實施例 8 ο o m· 沄 (Ν ^Τ) (Ν οο ta o o a 實施例 I 7 ο 〇 w-i (N 卜 tu s o a 實施例 6 ο 寸· 〇 wn (Ν ^Τ) (Ν a o o a 實施例 5 wn 寸 OO (N Ο *Τ) CN 卜 ω g o o 塗裝性 稍差 實施例 4 in 寸 OO (N 〇 泛 (Ν r- ω 名 o a 實施例 3 to 寸 00 CN 泛 (Ν CN 00 ω g o a 實施例 2 OO <N 〇 沄 (Ν 00 (Ν os ω s o o 實施例 1 寸 00 (N in 沄 (Ν as (Ν On a g d a 嚷言 ft < gg m Ift 味ST 械14· # I 题ώ S ® £ ^ 經1 < 餵_ N] » E" & 烘烤溫度(°c) 胺甲酸乙酯結合 m 1¾ ^ ^ m μ ^ ^ IK g ss ^ s Μ ®Ε ^ M G' ^ ϋ ^ ^ ^ ^ §5 g gg e s M •Ν #i 搂® 剝離強度 (N/6mm) 剝離評價 備註 黏著物 剝離性 -48- (46) (46)1272135 由表3之結果’確認了實施例1〜9之預塗覆金屬板 1 b ’其黏著物剝離強度低,並且針對對於光碟之防止受損 性也良好。又,確認了胺甲酸乙酯珠5的含有率越多,則 防止受損性越提昇之傾向,若含有率爲5質量。以上的話 ’大致良好,而含有率爲1 0質量%以上的話,顯示了優 良之防止受損性。且,實施例5,由於胺甲酸乙酯珠5的 含有率爲5 0質量%之多量的含有率,故氟系塗料的黏度 增加’在塗裝性上稍有難點,但在實用上未形成任何問題 〇 另一方面,比較例1〜2、比較例4〜7之預塗覆金屬 板1 b ’黏著物剝離強度均低於〇· 1N/6mm,具有優良之黏 著物剝離性,但對於光碟之防止受損性差。又,比較例3 、8、9 ’均顯示優良之對於光碟之防止受損性,但,黏著 物剝離強度均超過〇· IN/6mm,黏著物剝離性差。且,比 較例3之胺甲酸乙酯珠5的含有率爲60質量%,超過本 發明之請求範圍,故氟系塗料之黏度顯著增加,塗裝性極 差。 又,將實施例1〜9的預塗覆金屬板lb沖壓加工成光 碟機之托盤(承載自作光碟之部位)及與光碟機的上蓋之 自作光碟對應的部位。此時,也無產生成形不良等,在所 製作之托盤、上蓋表面,也無確認到傷痕等的外觀不良、 污垢或油之附著。 【圖式簡單說明】 -49- (47) 1272135 圖1 ( a )係示意地顯示本發明的第1實施形態之預 塗覆金屬板的結構之斷面圖,(b )爲示意地顯示本發明 的第2實施形態之預塗覆金屬板的結構之斷面圖。 圖2係判定對於光碟的防止受損性之光碟受損樣子的 照片,(a )爲防止受損性優良之傷痕樣子,(b )爲防止 受損性良好之傷痕樣子。 圖3係判定對於光碟的防止受損性之光碟受損樣子的 φ 照片,(a )爲防止受損性稍稍不良之傷痕樣子,(b )爲 防止受損性不良之傷痕樣子。 圖4 ( a )係示意地顯示自作碟片的結構、及識別標 籤的一部分剝落之狀態的斜視圖,(b )爲示意地顯示光 碟驅動器的結構之斜視圖。 【主要元件符號說明】 1 a :預塗覆金屬板 _ 2 a :金屬板 3 a :樹脂皮膜 1 b :預塗覆金屬板 2b :金屬板 • 3b :樹脂皮膜 ~ 4 :氟系樹脂陣列層 5 :胺甲酸乙酯珠 -50-[i Comparative Example 9 inch 00 oi (N 1 Cs ω QQ Comparative Example 1 8 tn inch OO (N 〇m rH 卜 LU 〇 OQ Comparative Example 7 S 沄ΓΜ (N οο a 7: g 〇a ! Comparative Example: 6. Inch dl 〇 (N οο CQ S 〇a ratio _ parent example 1 1 5 21 ubi (N un (Ν οο OQ da Comparative Example 4 〇Ό SI 〇 (N (Ν 00 CQ g ο a Comparative Example 3 inch 00 CN SI 沄(N 21 tn ω CN Ο CQ Wei Hu fine comparison example 2 OO <N ml (N οο (Ν οο a 7: sda Comparative Example 1 蕻朝〇(Ν as <Ν ο CQ soa Example 9泛(Ν ΓΛ (Ν r- a O oa Example 8 ο om· 沄 (Ν ^Τ) (Ν οο ta ooa Example I 7 ο 〇wi (N 卜 tu soa Example 6 ο inch·〇wn (Ν ^Τ) (Ν aooa Example 5 wn inch OO (N Ο *Τ) CN 卜 goo Paintability is slightly poor Example 4 in inch OO (N 〇 Ν (Ν r- ω name oa Example 3 to inch 00 CN泛(Ν CN 00 ω goa Example 2 OO <N 〇沄(Ν 00 (Ν os ω soo Example 1 inch 00 (N in 沄(Ν as (Ν On agda ftft < Gg m Ift 味ST械14·# I ώ S ® £ ^ by 1 < _ _ N] » E"& baking temperature (°c) urethane combination m 13⁄4 ^ ^ m μ ^ ^ IK g ss ^ s Μ ®Ε ^ MG' ^ ϋ ^ ^ ^ ^ §5 g gg es M •Ν #i 搂® Peel Strength (N/6mm) Peel Evaluation Remarks Adhesive Peelability -48- (46) (46 1272135 From the results of Table 3, it was confirmed that the precoated metal sheets 1b' of Examples 1 to 9 had low peel strength of the adhesive, and were also excellent in preventing damage to the optical disc. Further, it was confirmed that the more the content of the urethane beads 5 is, the more the damage is prevented from increasing, and the content is 5 mass. In the above case, 'beautiful is good, and when the content is 10% by mass or more, excellent damage prevention is exhibited. Further, in Example 5, since the content ratio of the urethane beads 5 is 50% by mass, the viscosity of the fluorine-based paint increases. 'The coating property is slightly difficult, but it is not practically formed. Any problem, on the other hand, the pre-coated metal sheets 1 b of Comparative Examples 1 to 2 and Comparative Examples 4 to 7 have adhesive peeling strengths lower than 〇·1N/6 mm, and have excellent adhesive peelability, but The disc is poorly protected from damage. Further, Comparative Examples 3, 8, and 9' all showed excellent damage prevention properties to the optical disk, but the adhesive peeling strength exceeded 〇·IN/6 mm, and the adhesive peelability was poor. Further, the content of the urethane beads 5 of Comparative Example 3 was 60% by mass, which exceeded the range of the present invention. Therefore, the viscosity of the fluorine-based coating material was remarkably increased, and the coating property was extremely poor. Further, the precoated metal sheets 1b of the first to ninth embodiments were press-formed into a tray (a portion carrying the self-made optical disc) of the optical disk drive and a portion corresponding to the self-made optical disk of the upper cover of the optical disk drive. At this time, no molding failure or the like occurred, and no appearance defects such as scratches or adhesion of dirt or oil were observed on the surface of the prepared tray or the upper cover. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1( a ) is a cross-sectional view schematically showing a structure of a precoated metal sheet according to a first embodiment of the present invention, and (b) is a schematic view showing the present invention. A cross-sectional view showing the structure of a precoated metal sheet according to a second embodiment of the invention. Fig. 2 is a photograph for judging the damage of the optical disc against the damage of the optical disc, (a) for preventing the damage from being damaged, and (b) for preventing the damage from being damaged. Fig. 3 is a photograph of φ which determines the damage of the optical disc against the damage of the optical disc, (a) to prevent the damage from being slightly damaged, and (b) to prevent the damage from being damaged. Fig. 4 (a) is a perspective view schematically showing the structure of the self-made disc and a state in which a part of the identification label is peeled off, and (b) is a perspective view schematically showing the structure of the optical disc drive. [Description of main component symbols] 1 a : Precoated metal plate _ 2 a : Metal plate 3 a : Resin film 1 b : Precoated metal plate 2b : Metal plate • 3b : Resin film ~ 4 : Fluorine resin array layer 5: urethane beads -50-
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JP2005294109A JP3846807B1 (en) | 2005-10-06 | 2005-10-06 | Pre-coated metal plate and manufacturing method thereof |
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JP4831552B1 (en) * | 2011-03-28 | 2011-12-07 | Jx日鉱日石金属株式会社 | Co-Si copper alloy sheet |
JP5914169B2 (en) * | 2012-05-28 | 2016-05-11 | 株式会社有沢製作所 | Resin composition for flexible printed wiring board |
JP7016862B2 (en) * | 2017-03-29 | 2022-02-07 | 関東電化工業株式会社 | Paint composition |
JP6271062B1 (en) * | 2017-04-26 | 2018-01-31 | 日新製鋼株式会社 | Water-based treatment liquid, chemical conversion treatment method, and chemical conversion treatment steel plate |
JP6962215B2 (en) * | 2018-01-24 | 2021-11-05 | 日本製鉄株式会社 | End face rust preventive treatment liquid for plated steel sheet, chemical conversion treatment method for end face of plated steel sheet, chemical conversion treated steel sheet and molded products |
JP6962216B2 (en) * | 2018-01-24 | 2021-11-05 | 日本製鉄株式会社 | Anti-rust treatment liquid for welded steel pipes, chemical conversion treatment methods for welded steel pipes, molded products of welded steel pipes and welded steel pipes |
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JPH04249507A (en) * | 1991-01-07 | 1992-09-04 | Daikin Ind Ltd | Fluorocopolymer and hardenable composition |
EP0509494B1 (en) * | 1991-04-16 | 1997-02-05 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Process for the production of polyurethane, and true spherical, fine polyurethane particles |
JP2845024B2 (en) * | 1991-04-16 | 1999-01-13 | 大日精化工業株式会社 | Method for producing uncrosslinked polyurethane and spherical uncrosslinked polyurethane fine particles |
JPH08176477A (en) * | 1994-12-26 | 1996-07-09 | Nippon Paint Co Ltd | Electrodeposition coating composition and method for forming electrodeposition coating film of high weatherability |
JP4686831B2 (en) * | 2000-08-30 | 2011-05-25 | 住友金属工業株式会社 | Coating film and coated metal plate with excellent weather resistance |
JP2003293169A (en) * | 2002-04-04 | 2003-10-15 | Furukawa Electric Co Ltd:The | FLUORORESIN-COATED Al MATERIAL |
JP2004074606A (en) * | 2002-08-20 | 2004-03-11 | Mitsubishi Kagaku Sanshi Corp | Composite metallic resin sheet with low staining properties and its manufacturing method |
JP4067368B2 (en) * | 2002-09-12 | 2008-03-26 | 住友軽金属工業株式会社 | Pre-coated aluminum alloy plate with excellent scratch resistance for electrical and electronic equipment casings |
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