200944372 六、發明說明 【發明所屬之技術領域】 本發明是關於汽車、家電製品、建材等 裝鋼板，詳而言之，是關於樹脂塗裝鋼板製 加工步驟、加工後的組裝步驟、成爲製品後 任一步驟中都不容易產生傷痕的樹脂塗裝鋼 〇 【先前技術】 以往，爲了提高美觀性和耐蝕性而在金 樹脂皮膜的方法是已知的。樹脂皮膜要求良 耐蝕性、耐刮傷性等，爲了改良這些特性而 0 例如，在日本特開2007-168273號揭示 異的塗裝鋼板，其具有在玻璃轉化溫度（Ιί 10〜50°C的樹脂中含有Tg爲70〜12CTC的樹 〇 膜。另外，在日本特開2001-9366號揭示一 ，利用以Tg爲20〜80°C的聚酯樹脂爲主成 ，而能承受引縮加工等的嚴格的成形加工。 特開平9-1 1 1 183號揭示，藉由以Tg爲-25-脂爲主成分的樹脂塗膜來提高加工性的技術 然而，這些習知技術無法滿足最近的嚴 傷性。例如，作爲在金屬板的端緣等的樹脂 的評價方法，鉛筆硬度試驗是已知的，但 2007-1 68273號並未進行鉛筆硬度的評價。 使用的樹脂塗 造步驟、衝壓 的移送步驟等 板。 屬板表面形成 好的加工性、 有各種的硏究 一種加工性優 >下稱爲Tg) 脂粒子的頂塗 種預塗布鋼板 分的1層塗膜 另外，在曰本 -35°C的聚酯樹 〇 格標準的耐刮 皮膜的刮傷性 是在日本特開 另外，在曰本 200944372 特開2001-9366號和日本特開平9-111183號，雖然進行了 鉛筆硬度的評價，但頂多只到Η，並沒有形成能夠承受更 硬的鉛筆硬度的樹脂皮膜構造。亦即，若選擇能夠隨著引 縮或彎曲等加工時的柔軟的樹脂時，耐刮傷性會變差。 若金屬板的端緣等受到碰觸而在樹脂皮膜上形成裂痕 等傷痕，其品質外觀明顯變差而成爲不良品，因此直接關 係到成本。因此，要求改善耐刮傷性，其標準越來越嚴格 Θ 關於著眼於耐刮傷性的技術，例如在日本特開2007-23 00 99號所記載的技術，認識到加工性和耐刮傷性爲相反 的性質（〔0009〕），爲了謀求兼具兩特性，在柔軟的基 底塗膜上形成硬質的島狀頂塗膜。但是，未形成硬質頂塗 膜的部分的耐刮傷性差，而且用來形成上述構造的塗膜的 步驟複雜，導致成本變高。 【發明內容】 © 於是，本發明是考慮到上述各情況，其課題在於提供 :在樹脂塗裝鋼板製造步驟、衝壓加工步驟、加工後的組 裝步驟、成爲製品後的輸送步驟等的任一步驟都不容易產 生傷痕而適於嚴格標準的耐刮傷性之樹脂塗裝鋼板。 本發明之樹脂塗裝鋼板，是在冷軋鋼板或合金化熔融 鍍鋅鋼板的表面形成厚度12 μιη以下的樹脂皮膜，該皮膜 的玻璃轉化溫度（Tg)爲-10°C〜32°C。 樹脂皮膜是由含有有機溶劑可溶型聚酯樹脂的原料組 -6 - 200944372 成物所得出的’以及在原料組成物含有三聚氰胺系交聯劑 ，都是本發明的較佳實施方式。 本發明的樹脂塗裝鋼板，是在高硬度的冷軋鋼板或合 金化熔融鍍鋅鋼板的表面設置具有特定Tg的薄的樹脂皮 膜’因此能夠提供具有3H以上的鉛筆硬度的耐刮傷性優 異的樹脂塗裝鋼板。另外，由於本發明的樹脂塗裝鋼板在 各種步驟中不易產生傷痕，因此可減少不良品的產生，有 0 助於降低成本。因此，本發明的樹脂塗裝鋼板適用在汽車 、家電製品、建材等方面。 【實施方式】 在本發明的樹脂塗裝鋼板，原板材（形成樹脂皮膜前 的板材）必須是冷軋鋼板或合金化熔融鏟鋅鋼板（以下， 可將兩者一倂稱爲原板材）。這是因爲其等的維氏硬度大 ，且本發明人等發現該原板材的硬度會影響耐刮傷性。以 G 往經常使用的熔融鍍鋅鋼板，由於鍍鋅層軟，即使與本發 明鋼板相同地在鍍鋅層上方形成樹脂皮膜，也無法獲得充 分的耐刮傷性。如此，考慮到耐刮傷性和原板材的硬度， 使樹脂皮膜的Tg和膜厚適於原板材的硬度，是本發明獨 特的技術思想，根據該技術思想，能夠實現3H以上的極 高標準的耐刮傷性。再者，本發明的合金化熔融鍍鋅鋼板 ，是具有將鋅和鐵合金化的鍍層的鋼板（GA鋼板）。 冷軋鋼板或合金化熔融鏟鋅鋼板的硬度’較佳爲維氏 硬度ΙΟΟΗν以上。冷軋鋼板的硬度至少比Fe的維氏硬度 200944372 大，因此爲ΙΟΟΗν以上。合金化熔融鑛鋅鋼板的硬度，由 於鍍層通常以<51相爲主體，因此是和<51相的維氏硬度 大致相同爲284〜3 00Hv。合金化熔融鍍鋅層的附著量沒有 特別限定，但爲了防止彎曲加工時鍍層的剝離，較佳爲 50g/m2以下，更佳爲40g/m2以下。原板材的厚度根據用 途適當決定即可。還有，若在原板材的表面設置凹凸則傷 痕變得不明顯，因此屬於本發明較佳的實施態樣。 樹脂皮膜的厚度爲12μιη以下。超過12μηι時，原板 材的硬度無法反映於皮膜特性，鉛筆硬度降低。更佳爲 10 μιη以下，特佳爲8μιη以下。膜厚的下限沒有特別限定 ，若考慮耐蝕性和潤滑性，膜厚宜爲0.3 μιη以上。 另外，樹脂皮膜當中，在原板材側和/或皮膜表面側 ，也可以形成厚度2 μιη以下的不符合本發明的Tg規定範 圍的樹脂皮膜（其他的樹脂皮膜）。例如，如果是1 2μιη 的樹脂皮膜，其中ΙΟμηι是符合本發明的規定範圍的樹脂 皮膜即可。其理由在於，即使是在符合本發明規定範圍的 Q 樹脂皮膜的下側和/或上側形成2μιη以下的其他樹脂皮膜 ，也可以發揮本發明的效果而表現良好的耐刮傷性。 在本發明將上述樹脂皮膜的Tg設定爲- l〇°C〜+ 32°C。 在本發明，原板材具有即使負載應力也不會產生塑性變形 的硬度，樹脂皮膜具有能夠使應力分散緩和程度的柔軟度 ，將Tg設定在此範圍能有效地讓原板材的硬度反映到耐 刮傷性。以往的想法認爲，使樹脂皮膜變硬能有效改良耐 刮傷性，因此是利用Tg高的樹脂，但若樹脂的Tg升高， -8- 200944372 形成塗裝鋼板所需的加工性變差，而且即使提高Tg， 刮傷性也無法大幅提昇。在本發明，基於上述想法而推 ，將樹脂皮膜的Tg設定爲較低而防止局部應力集中（ 生傷痕的程度）會使耐刮傷性大幅提昇。 但是，若樹脂皮膜的Tg低於-lot，在通常的使用 境下過於柔軟，反而使傷痕容易產生，因此是不適合的 樹脂皮膜的Tg更佳爲0°c以上，特佳爲5°c以上。若 〇 超過32 °C，有鉛筆硬度降低的傾向，因此，Tg爲32 °C 下。Tg較佳爲25°C以下，更佳爲19°C以下。 爲了測定樹脂皮膜的Tg，例如從鋼板削下樹脂皮 ，用示差掃描熱量計（DSC)在氮環境氣氛、溫度範圍 -100°C〜180°C、升溫速度20°C/min下進行。在樹脂皮 ，除樹脂成分（有時也是樹脂+交聯劑）外，雖可能含 防銹劑、消光劑、塡充劑、顏料等公知的添加劑，由 Tg不受分散的固體添加物的影響，因此能夠藉由上述 Ο 法測定樹脂皮膜的Tg。 作爲能夠用於形成樹脂皮膜的樹脂，只要樹脂皮膜 Tg能符合上述範圍即可，沒有特別的限定，可使用汎 的樹脂。例如可例舉：聚酯系樹脂、丙烯酸系樹脂、聚 酯系樹脂、聚烯烴系樹脂、氟系樹脂、矽酮系樹脂以及 等樹脂的混合物或變性樹脂等。若將環氧樹脂或不飽和 酯樹脂等的熱固性樹脂作爲基質樹脂的原料來使用，所 到的硬化塗膜變得過硬，變形性差，因此對本發明是不 合的。考慮到樹脂塗裝鋼板所要求的彎曲加工性、皮膜 耐 測 產 環 〇 Tg 以 膜 膜 有 於 方 的 用 胺 該 聚 得 適 密 -9- 200944372 合性、耐蝕性等的特性，較佳爲有機溶劑可溶型（非晶性 )的聚酯樹脂》 作爲有機溶劑可溶型的聚酯樹脂，基於可取得豐富且 齊全的種類的觀點，宜使用東洋紡績公司製的「VYLON ( 註冊商標）」系列。聚酯樹脂，可用三聚氰胺等來進行交 聯。作爲三聚氰胺樹脂包括：住友化學公司製的「 SUMIMAL (註冊商標）」系列、三井氰特公司（MITSUI CYTEC Co.)製的「CYMEL (註冊商標）」系列。關於樹 脂和交聯劑的比例，基於加工性等和耐久性的均衡的觀點 ，在乾燥後的樹脂皮膜中，交聯劑（反應後）的含量宜爲 5〜30質量％。 前述東洋紡績公司製的「VYLON (註冊商標）」系列 產品的 Tg 如下所示。VYLON 1 03 ( 4 7 〇C ) 、VYLON 200 (6 7〇C ) 、VYLON 22 0 ( 5 3 °C ) ' VYLON 226 ( 65 °C )、 VYLON 240 ( 60°C ) ' VYLON 245 ( 60°C ) 、VYLON 270 (6 7〇C ) 、VYLON 280 ( 6 8 °C ) 、VYLON 2 90 ( 7 2〇C )、 VYLON 2 9 6 ( 7 1 °C ) 、VYLON 3 00 ( 7 °C ) 、VYLON 500 (4°C ) 、VYLON 5 16 ( -17 °C ) 、VYLON 5 5 0 ( - 1 5 °C )。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Resin coated steel sheet which is less likely to cause scratches in one step [Prior Art] Conventionally, a method of coating a gold resin film in order to improve the appearance and corrosion resistance is known. The resin film is required to have good corrosion resistance, scratch resistance, etc., in order to improve these characteristics. For example, Japanese Laid-Open Patent Publication No. 2007-168273 discloses a coated steel sheet having a glass transition temperature (Ιί 10 to 50 ° C). In the resin, a sapphire film having a Tg of 70 to 12 CTC is contained. In addition, Japanese Laid-Open Patent Publication No. 2001-9366 discloses that a polyester resin having a Tg of 20 to 80 ° C is used as a main component, and can be subjected to a shrinking process or the like. A technique for improving the workability by a resin coating film having a Tg of -25-lip as a main component is disclosed in Japanese Patent Laid-Open No. Hei 9-1 1 1 183. However, these conventional techniques cannot satisfy the recent strictness. For example, as a method for evaluating a resin such as an edge of a metal plate, a pencil hardness test is known, but the pencil hardness is not evaluated in 2007-1 68273. The resin coating step used, stamped Plates such as transfer steps. The surface of the plate is formed into a good processability, and various types of coatings are excellent in processing properties. The first coating film of the top coating type of the precoated steel sheet is referred to as Tg). -35 ° C polyester tree 标准 standard scratch resistance The scratch resistance of the film is in Japan. In addition, in the case of Sakamoto 200944372, JP-A-2001-9366 and JP-A-H09-111183, although the pencil hardness was evaluated, at most, it was only Η, and it was not formed. A resin film structure that withstands a harder pencil hardness. In other words, when a soft resin which can be processed by shrinkage or bending is selected, the scratch resistance is deteriorated. When the edge of the metal plate is touched and a flaw such as a crack is formed on the resin film, the quality appearance thereof is remarkably deteriorated and becomes a defective product, so that the cost is directly related. Therefore, it is required to improve the scratch resistance, and the standard thereof is becoming more and more strict. Regarding the technique of scratch resistance, for example, the technique described in Japanese Laid-Open Patent Publication No. 2007-23 0099 recognizes workability and scratch resistance. The property is the opposite property ([0009]), and in order to achieve both characteristics, a hard island-shaped top coat film is formed on the soft base coating film. However, the portion where the hard top coat film is not formed is inferior in scratch resistance, and the steps for forming the coating film of the above configuration are complicated, resulting in high cost. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide any step of a resin-coated steel sheet manufacturing step, a press working step, an assembly step after processing, and a transport step after the product is formed. It is not easy to produce scratches and is suitable for a strict standard scratch-resistant resin coated steel sheet. In the resin-coated steel sheet of the present invention, a resin film having a thickness of 12 μm or less is formed on the surface of the cold-rolled steel sheet or the alloyed molten galvanized steel sheet, and the glass transition temperature (Tg) of the film is -10 ° C to 32 ° C. The resin film is obtained from a raw material group -6 - 200944372 containing an organic solvent-soluble polyester resin, and the raw material composition contains a melamine-based crosslinking agent, which is a preferred embodiment of the present invention. The resin-coated steel sheet of the present invention is provided with a thin resin film having a specific Tg on the surface of a high-hardness cold-rolled steel sheet or an alloyed hot-dip galvanized steel sheet. Therefore, it is excellent in scratch resistance with a pencil hardness of 3H or more. Resin coated steel plate. Further, since the resin-coated steel sheet of the present invention is less likely to cause scratches in various steps, the occurrence of defective products can be reduced, and the cost can be reduced. Therefore, the resin-coated steel sheet of the present invention is suitably used in automobiles, home electric appliances, building materials and the like. [Embodiment] In the resin-coated steel sheet of the present invention, the original sheet (the sheet before the resin film is formed) must be a cold-rolled steel sheet or an alloyed molten shovel-zinc steel sheet (hereinafter, both of them may be referred to as original sheets). This is because the Vickers hardness of the same is large, and the inventors have found that the hardness of the original sheet affects the scratch resistance. In the hot-dip galvanized steel sheet which is frequently used for G, since the galvanized layer is soft, even if a resin film is formed on the galvanized layer in the same manner as the steel sheet of the present invention, sufficient scratch resistance cannot be obtained. Thus, considering the scratch resistance and the hardness of the original sheet, the Tg and the film thickness of the resin film are suitable for the hardness of the original sheet, which is a unique technical idea of the present invention, and according to the technical idea, a very high standard of 3H or higher can be achieved. Scratch resistant. Further, the alloyed hot-dip galvanized steel sheet according to the present invention is a steel sheet (GA steel sheet) having a plating layer in which zinc and iron are alloyed. The hardness ' of the cold-rolled steel sheet or the alloyed molten shovel zinc steel sheet is preferably a Vickers hardness ΙΟΟΗν or more. The hardness of the cold-rolled steel sheet is at least larger than the Vickers hardness of 200944372, so it is ΙΟΟΗν or more. The hardness of the alloyed molten ore zinc steel sheet is mainly composed of the <51 phase, and therefore the Vickers hardness of the <51 phase is approximately 284 to 30,000 Hv. The amount of adhesion of the alloyed hot-dip galvanized layer is not particularly limited. However, in order to prevent peeling of the plating layer during bending, it is preferably 50 g/m2 or less, more preferably 40 g/m2 or less. The thickness of the original sheet can be appropriately determined depending on the application. Further, if unevenness is provided on the surface of the original sheet material, the flaw becomes inconspicuous, and therefore it is a preferred embodiment of the present invention. The thickness of the resin film is 12 μm or less. When it exceeds 12 μm, the hardness of the original sheet cannot be reflected in the film properties, and the pencil hardness is lowered. More preferably, it is 10 μm or less, and particularly preferably 8 μm or less. The lower limit of the film thickness is not particularly limited, and in consideration of corrosion resistance and lubricity, the film thickness is preferably 0.3 μm or more. Further, among the resin films, a resin film (other resin film) having a thickness of 2 μm or less and not conforming to the Tg prescribed range of the present invention may be formed on the original plate side and/or the film surface side. For example, in the case of a resin film of 1 2 μm, wherein ΙΟμηι is a resin film in accordance with the range specified in the present invention. The reason for this is that even if another resin film of 2 μm or less is formed on the lower side and/or the upper side of the Q resin film in accordance with the range of the present invention, the effect of the present invention can be exhibited and the scratch resistance can be improved. In the present invention, the Tg of the above resin film is set to -10 ° C to + 32 ° C. In the present invention, the original sheet material has a hardness which does not undergo plastic deformation even under load stress, and the resin film has a softness which can relax the stress dispersion, and setting the Tg in this range can effectively reflect the hardness of the original sheet to the scratch resistance. Injurious. In the past, it has been thought that hardening the resin film can effectively improve the scratch resistance. Therefore, a resin having a high Tg is used. However, if the Tg of the resin is increased, the workability required for forming a coated steel sheet is deteriorated from -8 to 200944372. And even if the Tg is increased, the scratch resistance cannot be greatly improved. In the present invention, based on the above idea, the Tg of the resin film is set to be low to prevent local stress concentration (to the extent of scratches), and the scratch resistance is greatly improved. However, if the Tg of the resin film is lower than -lot, it is too soft in normal use, and the scar is easily generated. Therefore, the Tg of the resin film which is not suitable is more preferably 0 ° C or more, and particularly preferably 5 ° C or more. . If 〇 exceeds 32 °C, there is a tendency for the pencil hardness to decrease, so the Tg is 32 °C. The Tg is preferably 25 ° C or lower, more preferably 19 ° C or lower. In order to measure the Tg of the resin film, for example, the resin skin is peeled off from the steel sheet, and it is carried out by a differential scanning calorimeter (DSC) in a nitrogen atmosphere, a temperature range of -100 ° C to 180 ° C, and a temperature increase rate of 20 ° C / min. In addition to the resin component (sometimes also a resin + cross-linking agent), the resin skin may contain a known additive such as a rust preventive, a matting agent, a chelating agent, or a pigment, and is affected by the solid additive in which Tg is not dispersed. Therefore, the Tg of the resin film can be measured by the above Ο method. The resin which can be used for the formation of the resin film is not particularly limited as long as the resin film Tg can satisfy the above range, and a versatile resin can be used. For example, a polyester resin, an acrylic resin, a polyester resin, a polyolefin resin, a fluorine resin, an anthrone resin, a mixture of resins such as a resin, or a denatured resin may, for example, be mentioned. When a thermosetting resin such as an epoxy resin or an unsaturated ester resin is used as a raw material of the matrix resin, the cured coating film becomes too hard and has poor deformability, which is not preferable to the present invention. In view of the bending workability required for the resin-coated steel sheet and the resistance of the film to the production of the ring Tg, it is preferable that the film has a property such as an amine which is densely mixed with an amine, and has corrosion resistance and the like. Organic solvent-soluble (amorphous) polyester resin. As an organic solvent-soluble polyester resin, it is preferable to use "VYLON (registered trademark) by Toyobo Co., Ltd. based on the viewpoint that a wide variety of products can be obtained. "series. The polyester resin can be crosslinked by melamine or the like. The melamine resin includes the "SUMIMAL (registered trademark)" series manufactured by Sumitomo Chemical Co., Ltd. and the "CYMEL (registered trademark)" series manufactured by Mitsui Cypress Co., Ltd. The ratio of the resin to the crosslinking agent is preferably from 5 to 30% by mass based on the balance between the workability and the durability, and the content of the crosslinking agent (after the reaction) in the resin film after drying. The Tg of the "VYLON (registered trademark)" series manufactured by Toyobo Co., Ltd. is as follows. VYLON 1 03 ( 4 7 〇C ) , VYLON 200 (6 7〇C ) , VYLON 22 0 ( 5 3 °C ) ' VYLON 226 ( 65 ° C ), VYLON 240 ( 60 ° C ) ' VYLON 245 ( 60 ° C), VYLON 270 (6 7〇C), VYLON 280 (6 8 °C), VYLON 2 90 (7 2〇C), VYLON 2 9 6 (7 1 °C), VYLON 3 00 ( 7 °C) , VYLON 500 (4°C), VYLON 5 16 ( -17 °C), VYLON 5 5 0 ( - 1 5 °C)
、VYLON 5 6 0 ( 7 °C ) 、VYLON 6 0 0 ( 47 °C ) 、VYLON 63 0 ( 7°C ) 、VYLON 65 0 ( 1 0 °C ) 、VYLON GK 110 ( 50, VYLON 5 6 0 ( 7 °C ) , VYLON 6 0 0 ( 47 ° C ) , VYLON 63 0 ( 7 ° C ) , VYLON 65 0 ( 1 0 ° C ) , VYLON GK 110 ( 50
°C ) 、VYLON GK 13 0 ( 1 5 °C ) ' VYLON GK 140 ( 2 0°C )> VYLON GK 1 50 ( 20°C ) ' VYLON GK 180 ( 0°C )、 VYLON GK 19 0 ( 1 1 °C ) 、VYLON GK 2 5 0 ( 60 °C )、 VYLON GK 3 3 0 ( 1 6 °C ) 、VYLON GK 3 6 0 ( 5 6 °C )、 200944372 VYLON GK 590 ( 1 5。。） 、VYLON GK 6 4 0 ( 7 9 °C )、 VYLON GK 680 ( 10 t： ) 、VYLON GK 7 8 0 ( 3 6 °C )、 VYLON GK 8 10 ( 46 °C ) 、VYLON GK 8 8 0 ( 84 °C )、 VYLON GK 890 ( 1 7°C ) 、V Y L ON B X 1 0 0 1 ( -1 8 °C )等等 。其等的Tg是記載於網頁中的溫度。又其等的分子量（ Μη)是在 3x103~30x103 的範圍。 在本發明的樹脂皮膜，亦可含有用於賦予導電性的導 〇 電性粒子。作爲導電性粒子，可例舉金屬粒子、或者在無 機或有機聚合物粒子表面設置金屬等導電性層的粒子等。 作爲金屬粒子，基於導電性、耐蝕性的觀點，可使用磁性 粉、鎳、磷化鐵等。對樹脂塗裝鋼板必須進一步賦予電磁 波遮蔽性能的情況，可將具有良好的導電性且兼具電磁波 吸收性的磁性金屬粉末作爲導電性粒子來使用。這種磁性 金屬粉末，較佳爲坡莫合金（Ni-Fe系合金，Ni含量爲35 質量％以上）或三斯達特合金（Si-Al-Fe系合金）、羰基 〇 鐵等。導電性粒子的平均粒徑較佳爲大致3〜30μιη左右。 還有，該平均粒徑r，是藉由雷射繞射法（散射法）測定 的50%體積平均粒子徑。 爲了製造本發明的樹脂塗裝鋼板的較佳方法，是調製 出樹脂皮膜的原料組成物，將其塗裝於前述原板材後進行 乾燥。所使用的原料組成物，是用有機溶劑等將樹脂、按 照需要來添加的交聯劑等稀釋成爲適於塗布的黏度的組成 物。作爲有機溶劑沒有特別限定，可例舉出：甲苯、二甲 苯等芳香族系烴；醋酸乙酯、醋酸丁酯等脂肪族酯類；環 -11 - 200944372 己烷等的脂環族烴類；己烷、戊烷等的脂肪族烴類等；甲 基乙基酮、環己酮等的酮類等。原料組成物的固體成分濃 度較佳爲5~60質量％左右。 在上述原料組成物中，在不妨礙本發明目的的範圍內 ，亦可添加消光劑、體質顏料、防銹劑、防沉澱劑、蠟等 在樹脂塗裝鋼板領域中所使用的各種公知的添加劑。另外 ，也可以添加碳黑等的用於賦予散熱性的添加劑。 在原板材上塗布上述原料組成物的方法沒有特別限定 ，可以採用棒塗法、輥塗法、噴塗法、簾塗法等。塗布後 進行乾燥，在交聯劑添加系中，宜在交聯劑能產生反應的 溫度進行加熱乾燥。具體而言，可在100~2 5 0°C進行1〜5 分鐘左右的加熱乾燥。此外，冷軋鋼板和合金化熔融鎮鋅 鋼板，基於提高耐蝕性、和樹脂皮膜的密合性等的目的， 也可以預先實施鉻酸鹽處理、非鉻酸鹽處理、磷酸鹽處理 等公知的表面處理（基底處理）。 〔實施例〕 以下，根據實施例詳細說明本發明。下述實施例並非 用來限定本發明，在不超出本發明主旨的範圍內的變更實 施，都包含於本發明中。還有，以下沒有特別說明時，“ %”表示“質量％” ， “份”表示“質量份”。 (原板材） 下面顯示所使用的原板材及其簡稱。還有，鍍敷是在 -12- 200944372 金屬板的兩面進行。另外，這些原板材是日本帕卡拉精（ PARKERIZING )公司製「CTE-2 1 3」，並進行基底處理。 乾燥溫度爲到達板溫loot，進行1分鐘乾燥。附着量爲 1 00mg/m2 ° GA :合金化熔融鍍鋅鋼板…板厚：0.5mm、鍍敷附著量 :每個單面40g/m2、鍍敷中的Fe量：8.6% CR:冷軋鋼板…板厚：0.5mm φ EG :電鍍鋅鋼板…板厚：0.5mm、鍍敷附著量：每個 單面20g/m2 GI :溶融鍍鋅鋼板...板厚：0.5mm、鍍敷附著量：每 個單面40g/m2 (樹脂） 使用東洋紡績公司製的有機溶劑可溶型聚酯樹脂之「 VYLON (註冊商標）」系列。表示使用的種類和Tg。 ❹ VYLON BX1001 ( T g ： -1 8 °C ) 、VYLON GK180 ( Tg ：0°C ) > VYLON 5 00 ( Tg ： 4 °C ) 、VYLON GK680 ( Tg ：10°C ) ' VYLON GK590 ( Tg ： 1 5 °C ) ' VYLON GK140 (Tg : 2 0 °C ) 、VYLON GK780 ( Tg : 3 6 °C ) 、VYLON GK840 ( Tg : 4 6 °C ) 、VYLON GK3 60 ( Tg : 5 6 °C )、 VYLON GK250 ( Tg ： 6 0°C ) 、VYLON 200 ( Tg ： 6 7〇C ) ' VYLON 296 ( Tg ： 71 °C ) 爲了形成既定的Tg，是混合2種以上的聚醋來使用 。此外，爲了形成既定的Tg，即以下述的要領進行混合 -13- 200944372 。2種原料的混合物的Tg大致由下式決定。°C ) , VYLON GK 13 0 ( 1 5 ° C ) ' VYLON GK 140 ( 2 0 ° C )> VYLON GK 1 50 ( 20 ° C ) ' VYLON GK 180 ( 0 ° C ), VYLON GK 19 0 ( 1 1 °C), VYLON GK 2 5 0 (60 °C), VYLON GK 3 3 0 (16 °C), VYLON GK 3 6 0 (5 6 °C), 200944372 VYLON GK 590 (1 5... ), VYLON GK 6 4 0 ( 7 9 °C ), VYLON GK 680 ( 10 t: ), VYLON GK 7 8 0 ( 3 6 °C ), VYLON GK 8 10 ( 46 °C ), VYLON GK 8 8 0 ( 84 ° C ), VYLON GK 890 ( 1 7 ° C ), VYL ON BX 1 0 0 1 ( -1 8 ° C ) and so on. The Tg of these is the temperature described in the web page. The molecular weight (??) of the other is in the range of 3x103 to 30x103. The resin film of the present invention may further contain conductive particles for imparting conductivity. The conductive particles may, for example, be metal particles or particles in which a conductive layer such as a metal is provided on the surface of the inorganic or organic polymer particles. As the metal particles, magnetic powder, nickel, iron phosphide or the like can be used from the viewpoint of conductivity and corrosion resistance. Further, it is necessary to impart electromagnetic shielding properties to the resin-coated steel sheet, and a magnetic metal powder having excellent conductivity and electromagnetic wave absorbing properties can be used as the conductive particles. The magnetic metal powder is preferably a permalloy (a Ni-Fe alloy, a Ni content of 35 mass% or more) or a three-star alloy (Si-Al-Fe alloy) or carbonyl ruthenium iron. The average particle diameter of the conductive particles is preferably about 3 to 30 μm. Further, the average particle diameter r is a 50% by volume average particle diameter measured by a laser diffraction method (scattering method). In order to produce a resin-coated steel sheet according to the present invention, a raw material composition of a resin film is prepared, which is applied to the original sheet and dried. The raw material composition to be used is a composition which is diluted with a resin or a crosslinking agent which is added as needed with an organic solvent or the like to have a viscosity suitable for coating. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene; aliphatic esters such as ethyl acetate and butyl acetate; and alicyclic hydrocarbons such as cyclo-11 - 200944372 hexane; An aliphatic hydrocarbon such as hexane or pentane; or a ketone such as methyl ethyl ketone or cyclohexanone. The solid content of the raw material composition is preferably about 5 to 60% by mass. In the above-mentioned raw material composition, various known additives used in the field of resin coated steel sheets, such as a matting agent, an extender pigment, a rust preventive, an anti-precipitating agent, and a wax, may be added to the extent that the object of the present invention is not impaired. . Further, an additive for imparting heat dissipation properties such as carbon black may be added. The method of applying the raw material composition to the original plate material is not particularly limited, and a bar coating method, a roll coating method, a spray coating method, a curtain coating method, or the like can be employed. After the application, the drying is carried out, and in the crosslinking agent addition system, it is preferred to carry out heat drying at a temperature at which the crosslinking agent can react. Specifically, it can be heated and dried at 100 to 250 ° C for about 1 to 5 minutes. In addition, the cold-rolled steel sheet and the alloyed molten zinc-plated steel sheet may be previously known to have chromate treatment, non-chromate treatment, phosphate treatment, etc., for the purpose of improving corrosion resistance and adhesion of the resin film. Surface treatment (substrate treatment). [Examples] Hereinafter, the present invention will be described in detail based on examples. The following examples are not intended to limit the invention, and modifications are intended to be included within the scope of the invention. Further, when not specifically described below, "%" means "% by mass", and "part" means "parts by mass". (Original sheet) The original sheet used and its abbreviation are shown below. Also, the plating is performed on both sides of the -12-200944372 metal plate. In addition, these original sheets were "CTE-2 1 3" manufactured by PARKERIZING Co., Ltd., and were subjected to substrate treatment. The drying temperature was reached to the plate temperature loot and dried for 1 minute. The amount of adhesion is 100 mg/m2 ° GA: alloyed hot-dip galvanized steel sheet... thickness: 0.5 mm, plating adhesion: 40 g/m2 per one side, Fe amount in plating: 8.6% CR: cold rolled steel sheet ... plate thickness: 0.5mm φ EG : galvanized steel plate... plate thickness: 0.5mm, plating adhesion: 20g/m2 per one side GI: molten galvanized steel sheet... thickness: 0.5mm, plating adhesion : "VYLON (registered trademark)" series of organic solvent-soluble polyester resins manufactured by Toyobo Co., Ltd., each 40g/m2 (resin). Indicates the type and Tg used. ❹ VYLON BX1001 ( T g : -1 8 °C ) , VYLON GK180 ( Tg : 0 ° C ) > VYLON 5 00 ( Tg : 4 ° C ) , VYLON GK680 ( Tg : 10 ° C ) ' VYLON GK590 ( Tg : 1 5 °C ) ' VYLON GK140 (Tg : 2 0 °C ) , VYLON GK780 ( Tg : 3 6 ° C ) , VYLON GK840 ( Tg : 4 6 ° C ) , VYLON GK3 60 ( Tg : 5 6 ° C ), VYLON GK250 (Tg: 60 °C), VYLON 200 (Tg: 6 7〇C) 'VYLON 296 (Tg: 71 °C) In order to form a predetermined Tg, two or more types of polyester are mixed and used. In addition, in order to form a predetermined Tg, it is mixed in the following manner -13- 200944372. The Tg of the mixture of the two raw materials is roughly determined by the following formula.
Tg(b)= Tg(cl)xwl/l〇〇 + Tg(c2)x( 1 00-wl )/1 00 在此，Tg(b):混合物的Tg，Tg(cl):第1原料 的Tg ’ wl :第1原料的重量分率（％ ) . Tg ( c2 ):第2 原料的Tg。 因此，爲了能夠得到既定的Tg(b)，只要調整w 1 即可。原料爲3種以上時，同樣調整各原料的重量分率即 可。例如，爲了得到實驗No. 7~ 1 2的T g = 5 t的混合物， 是取等重量的Tg=〇°C的VYLON GK180和Tg=l(TC的 VYLON GK680，溶解於溶劑之環己烷，混合交聯劑而調 整成組成物。 〔交聯劑〕 使用三聚氰胺樹脂（「SUMIMAL (註冊商標）M-4〇ST」，住友化學公司製）。 〔導電性粒子〕 使用鎳粉（日興力高公司製「CNS-10」，平均粒徑 6·3μιη，表中的Ni) 、Ni-Fe合金磁性粉（三菱製鋼公司 製鈹莫合金：78Ni-lMo-FP，平均粒徑7.6μηι，表中的Fe-Ni)。其等的平均粒徑，是使用Leeds & Northrup公司製 的 MICROTRACK FRA9220，藉由雷射繞射法（散射法） 測定出的50%體積平均粒徑》 -14- 200944372 〔散熱性賦予劑〕 使用碳黑（三菱化學公司製的“三菱碳黑MA100” ， 平均粒徑24nm )。表中的CB。 〔樹脂皮膜用原料組成物的調製〕 混合聚酯樹脂和上述交聯劑（固體成分8 0% )兩者， 使塗膜固體成分1 00%中，聚酯樹脂爲80%，交聯劑（乾 Φ 燥）爲20%。用二甲苯/環己酮混合溶劑（二甲苯：環己 酮=1: 1)稀釋，使原料組成物的固體成分濃度成爲 10〜30%，用手持式均質機以10000rpm攪拌10分鐘，調 製成原料組成物。另外，在實驗4，使用添加導電性粒子 及/或碳黑的原料組成物。表中的添加量（％ )，是相對於 上述聚酯樹脂和交聯劑（乾燥）和添加劑合計1 〇 〇質量％ 的百分率。 〇 〔樹脂塗裝鋼板的製作〕 將樹脂皮膜用原料組成物用棒塗法塗布於各種原板材 上’形成表中所示的膜厚，在熱風乾燥爐內以到達板溫 23 0°C加熱2分鐘，製作成樹脂塗裝鋼板。附著量，是藉 由改變棒塗器的編號來進行調整。表中的樹脂皮膜的厚度 ，是根據附著量和樹脂的比重算出的値。 〔Tg的测定〕 依據JIS K 7121，使用示差掃描熱量計（商品名·· -15- 200944372Tg(b)= Tg(cl)xwl/l〇〇+ Tg(c2)x( 1 00-wl )/1 00 Here, Tg(b): Tg of the mixture, Tg(cl): the first raw material Tg ' wl : weight fraction (%) of the first raw material. Tg ( c2 ): Tg of the second raw material. Therefore, in order to obtain a predetermined Tg(b), it is only necessary to adjust w 1 . When the amount of the raw materials is three or more, the weight fraction of each raw material may be adjusted in the same manner. For example, in order to obtain a mixture of T g = 5 t of Experiment No. 7 to 12, VYLON GK180 and Tg = 1 of Tg = 〇 ° C of equal weight (VYLON GK680 of TC, cyclohexane dissolved in a solvent) The mixture is adjusted to a composition by mixing a crosslinking agent. [Crosslinking agent] A melamine resin ("SUMIMAL (registered trademark) M-4〇ST", manufactured by Sumitomo Chemical Co., Ltd.) is used. [Electroconductive particles] Nickel powder is used. High company "CNS-10", average particle size of 6.3μm, Ni) in the table, Ni-Fe alloy magnetic powder (Melmo alloy made by Mitsubishi Steel Corporation: 78Ni-lMo-FP, average particle size 7.6μηι, table In the case of Fe-Ni), the average particle size of the particles is 50% by volume average particle diameter determined by laser diffraction (scattering method) using MICROTRACK FRA9220 manufactured by Leeds & Northrup. 200944372 [The heat-dissipating agent] Carbon black (Mitsubishi carbon black MA100, manufactured by Mitsubishi Chemical Corporation, average particle diameter: 24 nm) is used. CB in the table. [Preparation of raw material composition for resin film] Mixed polyester resin and the above Both the crosslinking agent (solid content 80%), the solid content of the coating film is 100%, The ester resin was 80%, and the crosslinking agent (dry Φ) was 20%. It was diluted with a mixed solvent of xylene/cyclohexanone (xylene: cyclohexanone = 1 : 1) to make the solid content concentration of the raw material composition 10 to 30%, and a raw material composition was prepared by stirring at 10000 rpm for 10 minutes using a hand-held homogenizer. In addition, in the experiment 4, a raw material composition containing conductive particles and/or carbon black was used. The percentage of the polyester resin and the crosslinking agent (drying) and the total amount of the additive is 1% by mass. 〇 [Production of resin-coated steel sheet] The raw material composition for the resin film is applied to various materials by bar coating. On the original sheet, the film thickness shown in the table was formed and heated in a hot air drying oven at a plate temperature of 23 ° C for 2 minutes to prepare a resin-coated steel sheet. The amount of adhesion was changed by changing the number of the bar coater. The thickness of the resin film in the table is calculated based on the amount of adhesion and the specific gravity of the resin. [Measurement of Tg] According to JIS K 7121, a differential scanning calorimeter (product name·· -15- 200944372) is used.
Thermo Plus DSC823 0，理學公司製）來進行測定。具體 而言，是從上述般製作出的樹脂塗裝鋼板用切刀削取樹脂 皮膜而取得樣品。將該樣品裝設於示差掃描熱量計，冷卻 至-100°C，在穩定後，以20°C/分鐘的昇溫速度昇溫至180 °C，根據所得到的DSC曲線來求出玻璃轉化溫度（Tg ) 〔耐刮傷性（鉛筆硬度）〕 _ 進行根據JIS K5600-5-4的鉛筆硬度實驗。判定基準 如下所述。 ◎:用4H以上的鉛筆沒有傷痕 〇：用4H的鉛筆有傷痕，用3H的沒有傷痕 △:用3H的鉛筆有傷痕，用2H的沒有傷痕 x:用Η以下的鉛筆有傷痕 實驗1 〇 探討樹脂皮膜的Tg和耐刮傷性。原板材，在表1爲 合金化熔融鍍鋅鋼板，在表2爲冷軋鋼板。在表1和2中 顯示結果。可知，只要樹脂皮膜的Tg在-10 °C〜+ 32 °C的 範圍，即可獲得優異的耐刮傷性。 % 200944372 〔表1〕 實驗No. 原板材 TgCC) 膜厚(μιη) 耐刮傷性(鉛筆硬度） 判定 備註 1 GA -5 7 3Η 〇 實施例 2 0 1 511以上 ◎ 實施例 3 3 511以上 ◎ 實施例 4 5 5Η以上 ◎ 實施例 5 7 4Η ◎ 實施例 6 9 3Η 〇 實施例 7 5 1 511以上 ◎ 實施例 8 3 5Η以上 ◎ 實施例 9 5 5只以上 ◎ 實施例 10 7 5Η以上 ◎ 實施例 11 9 3Η 〇 實施例 12 11 3Η 〇 實施例 13 10 1 5Η以上 ◎ 實施例 14 3 5Η以上 ◎ 實施例 15 5 5Η以上 ◎ 實施例 16 7 5Η以上 ◎ 實施例 17 9 3Η 〇 實施例 18 11 3Η ◦ 實施例 19 15 1 5Η以上 ◎ 實施例 20 3 5Η以上 ◎ 實施例 21 5 5Η以上 ◎ 實施例 22 7 5Η以上 ◎ 實施例 23 9 3Η 〇 實施例 24 11 3Η 〇 實施例 25 19 1 511以上 ◎ 實施例 26 3 5Η以上 ◎ 實施例 27 5 5Η以上 ◎ 實施例 28 7 5峨上 ◎ 實施例 29 9 3Η ◦ 實施例 30 11 3Η 〇 實施例 31 25 1 5Η以上 ◎ 實施例 32 3 5Η以上 ◎ 實施例 33 5 5Η以上 ◎ 實施例 34 7 4Η ◎ 實施例 35 9 3Η 〇 實施例 36 30 1 5Η以上 ◎ 實施例 37 3 5Η以上 ◎ 實施例 38 5 4Η ◎ 實施例 39 7 4Η ◎ 實施例 40 9 3Η 〇 實施例 41 40 9 Η X 比較例 42 60 9 F X 比較例 43 -15 9 Η X 比較例 -17- 200944372 〔表2〕 實驗No. 原板材 Tg(°C) 膜厚(μιη) 耐刮傷性(鉛筆硬度） 判定 備註 44 CR -5 7 3Η 〇 實施例 45 0 1 511以上 ◎ 實施例 46 3 5Η以上 ◎ 實施例 47 5 5Η以上 ◎ 實施例 48 7 4Η ◎ 實施例 49 9 3Η 〇 實施例 50 5 1 5Η以上 ◎ 實施例 51 3 5Η以上 ◎ 實施例 52 5 511以上 ◎ 實施例 53 7 5Η以上 ◎ 實施例 54 9 3Η 〇 實施例 55 11 3Η 〇 實施例 56 10 1 5Η以上 ◎ 實施例 57 3 5Η以上 ◎ 實施例 58 5 5聪上 ◎ 實施例 59 7 5Η以上 ◎ 實施例 60 9 3Η 〇 實施例 61 11 3Η 〇 實施例 62 15 1 5Η以上 ◎ 實施例 63 3 5Η以上 ◎ 實施例 64 5 5聪上 ◎ 實施例 65 7 5Η以上 ◎ 實施例 66 9 3Η 〇 實施例 67 11 3Η 〇 實施例 68 19 1 5Η以上 ◎ 實施例 69 3 5Η以上 ◎ 實施例 70 5 5Η以上 ◎ 實施例 71 7 4Η ◎ 實施例 72 9 3Η 〇 實施例 73 25 1 511以上 ◎ 實施例 74 3 5Η以上 ◎ 實施例 75 5 5Η以上 ◎ 實施例 76 7 4Η ◎ 實施例 77 9 3Η 〇 實施例 78 30 1 5Η以上 ◎ 實施例 79 3 5Η以上 ◎ 實施例 80 5 4Η ◎ 實施例 81 7 4Η ◎ 實施例 82 9 3Η 〇 實施例 83 40 9 Η X 比較例 84 60 9 F X 比較例 85 -15 9 F X 比較例 200944372 實驗2 探討樹脂皮膜的厚度超過本發明規定範圍的例子（表 3)。即使Tg在本發明規定範圍內，若膜厚爲13 μπι時’ 耐刮傷性變差。 C表3〕 實驗No· 原板材 Tg(°C) 膜厚(μΐη) 耐刮傷性(鉛筆硬度） 判定 備註 86 GA 0 13 2Η Δ 比較例 87 5 13 2Η Δ 比較例 88 10 13 2Η Δ 比較例 89 15 13 2Η Δ 比較例 90 19 13 2Η Δ 比較例 91 25 13 2Η Δ 比較例 92 30 13 Η X 比較例 93 CR 0 13 Η X 比較例 94 5 13 2Η Δ 比較例 95 10 13 2Η Δ 比較例 96 15 13 2Η Δ 比較例 97 19 13 2Η Δ 比較例 98 25 13 2Η Δ 比較例 99 30 13 Η X 比較例 ❾Thermo Plus DSC823 0 (manufactured by Rigaku Corporation) was used for the measurement. Specifically, the resin coated steel sheet produced as described above was obtained by cutting a resin film with a cutter to obtain a sample. The sample was placed in a differential scanning calorimeter, cooled to -100 ° C, and after stabilization, the temperature was raised to 180 ° C at a temperature increase rate of 20 ° C / min, and the glass transition temperature was determined from the obtained DSC curve ( Tg) [Scratch resistance (pencil hardness)] _ A pencil hardness test according to JIS K5600-5-4 was performed. The criteria for judgment are as follows. ◎: There is no scar with a pencil of 4H or more. There is a scar with a pencil of 4H, no scar with 3H. △: There is a scar with a pencil of 3H, and no scar with a 2H. x: A pencil with a flaw of the following is a test. The Tg and scratch resistance of the resin film. The original sheets are shown in Table 1 as alloyed hot-dip galvanized steel sheets and in Table 2 as cold-rolled steel sheets. The results are shown in Tables 1 and 2. It is understood that excellent scratch resistance can be obtained as long as the Tg of the resin film is in the range of -10 °C to + 32 °C. % 200944372 [Table 1] Test No. Original sheet TgCC) Film thickness (μιη) Scratch resistance (pencil hardness) Judgment remark 1 GA -5 7 3Η 〇 Example 2 0 1 511 or more ◎ Example 3 3 511 or more ◎ Example 4 5 5 Η or more ◎ Example 5 7 4 Η ◎ Example 6 9 3 Η 〇 Example 7 5 1 511 or more ◎ Example 8 3 5 Η or more ◎ Example 9 5 5 or more ◎ Example 10 7 5 Η or more ◎ Implementation Example 11 9 3 Η 〇 Example 12 11 3 Η Example 13 10 1 5 Η or more ◎ Example 14 3 5 Η or more ◎ Example 15 5 5 Η or more ◎ Example 16 7 5 Η or more ◎ Example 17 9 3 Η 〇 Example 18 11 3Η 实施 Example 19 15 1 5Η or more ◎ Example 20 3 5Η or more ◎ Example 21 5 5Η or more ◎ Example 22 7 5Η or more ◎ Example 23 9 3Η 〇 Example 24 11 3Η 〇 Example 25 19 1 511 or more ◎ Example 26 3 5Η or more ◎ Example 27 5 5Η or more ◎ Example 28 7 5峨上◎ Example 29 9 3Η 实施 Example 30 11 3Η 〇 Example 31 25 1 5Η ◎ Example 32 3 5 Η or more ◎ Example 33 5 5 Η or more ◎ Example 34 7 4 Η ◎ Example 35 9 3 Η 〇 Example 36 30 1 5 Η or more ◎ Example 37 3 5 Η or more ◎ Example 38 5 4 Η ◎ Example 39 7 4Η ◎ Example 40 9 3Η 〇 Example 41 40 9 Η X Comparative Example 42 60 9 FX Comparative Example 43 -15 9 Η X Comparative Example -17- 200944372 [Table 2] Experimental No. Original plate Tg (°C Film thickness (μιη) Scratch resistance (pencil hardness) Judgment remark 44 CR -5 7 3 Η 〇 Example 45 0 1 511 or more ◎ Example 46 3 5Η or more ◎ Example 47 5 5Η or more ◎ Example 48 7 4Η ◎ Example 49 9 3 Η 〇 Example 50 5 1 5 Η or more ◎ Example 51 3 5 Η or more ◎ Example 52 5 511 or more ◎ Example 53 7 5 Η or more ◎ Example 54 9 3 Η 〇 Example 55 11 3 Η Example 56 10 1 5Η or more ◎ Example 57 3 5 Η or more ◎ Example 58 5 5 聪上 ◎ Example 59 7 5 Η or more ◎ Example 60 9 3 Η 〇 Example 61 11 3 Η 〇 Example 62 15 1 5 Η上实施例 63 3 5Η or more ◎ Example 64 5 5 Cong ◎ Example 65 7 5 Η or more ◎ Example 66 9 3 Η 〇 Example 67 11 3 Η 〇 Example 68 19 1 5 Η or more ◎ Example 69 3 5 Η or more ◎ Example 70 5 5 Η or more ◎ Example 71 7 4 Η ◎ Example 72 9 3 Η 〇 Example 73 25 1 511 or more ◎ Example 74 3 5 Η or more ◎ Example 75 5 5 Η or more ◎ Example 76 7 4 Η ◎ Example 77 9 3 Η 〇 Example 78 30 1 5 Η or more ◎ Example 79 3 5 Η or more ◎ Example 80 5 4 Η ◎ Example 81 7 4 Η ◎ Example 82 9 3 Η 〇 Example 83 40 9 Η X Comparative Example 84 60 9 FX Comparative Example 85 -15 9 FX Comparative Example 200944372 Experiment 2 An example in which the thickness of the resin film exceeded the range specified in the present invention was examined (Table 3). Even if the Tg is within the range specified by the present invention, the scratch resistance is deteriorated when the film thickness is 13 μm. C Table 3] Experimental No. Original sheet Tg (°C) Film thickness (μΐη) Scratch resistance (pencil hardness) Judgment Remarks 86 GA 0 13 2Η Δ Comparative Example 87 5 13 2Η Δ Comparative Example 88 10 13 2Η Δ Comparison Example 89 15 13 2Η Δ Comparative Example 90 19 13 2Η Δ Comparative Example 91 25 13 2Η Δ Comparative Example 92 30 13 Η X Comparative Example 93 CR 0 13 Η X Comparative Example 94 5 13 2 Η Δ Comparative Example 95 10 13 2 Η Δ Comparison Example 96 15 13 2Η Δ Comparative Example 97 19 13 2Η Δ Comparative Example 98 25 13 2Η Δ Comparative Example 99 30 13 Η X Comparative Example❾
實驗3 對添加了導電性粒子和/或碳黑的情況的耐刮傷性進 行探討。其結果在表4中顯不°樹脂皮膜的Tg在本發明 範圍外的情況，耐刮傷性變差。 200944372Experiment 3 The scratch resistance of the case where conductive particles and/or carbon black were added was examined. As a result, in Table 4, when the Tg of the resin film was outside the range of the present invention, the scratch resistance was deteriorated. 200944372
〔表4〕 實驗No. 原板材 Tg (°C) 添加劑種類 添加量 (%) 膜厚 (μιη) 耐刮傷性 (鉛筆硬度） 判定 備註 100 GA 15 Ni 30 7 5Η以上 ◎ 實施例 101 50 7 5Η以上 ◎ 實施例 102 Fe-Ni 50 5 5Η以上 ◎ 實施例 103 50 7 5Η以上 ◎ 實施例 104 60 Ni 50 7 2Η Δ 比較例 105 CR 15 Ni 30 7 511以上 ◎ 實施例 106 50 7 5Η以上 ◎ 實施例 107 Fe-Ni 50 5 5Η以上 ◎ 實施例 108 50 7 5Η以上 ◎ 實施例 109 60 Ni 50 7 2Η Δ 比較例 110 GA 15 Ni 30 7 4Η ◎ 實施例 CB 10 111 Ni 50 7 4Η ◎ 實施例 CB 10 112 5 Fe-Ni 50 5 4Η ◎ 實施例 CB 10 113 Fe-Ni 50 7 4Η ◎ 實施例 CB 10 實驗4 對原板材使用本發明的規定範圍以外的電鍍鋅鋼板（ EG )和熔融鍍鋅鋼板（GI )的情況的耐刮傷性進行探討。 結果顯示於表5。由於原板材的硬度不足，故耐刮傷性差 -20- 200944372 ❿ 〔表5〕 實驗No. 原板材 Tg(°C) 膜厚㈣ 耐刮傷性(鉛筆硬度） 判定 備註 114 EG 5 5 Η X 比較例 115 10 5 Η X 比較例 116 15 5 Η X 比較例 117 GI 5 5 Η X 比較例 118 10 5 Η X 比較例 119 15 5 Η X 比較例 本發明的樹脂塗裝鋼板能夠用於汽車、家電製品、傢 倶、建材等。也適用於這些領域之外的要求高標準耐刮傷 性的用途。 -21 -[Table 4] Test No. Original sheet Tg (°C) Additive amount of additive type (%) Film thickness (μιη) Scratch resistance (pencil hardness) Judgment remark 100 GA 15 Ni 30 7 5Η or more ◎ Example 101 50 7 5Η or more ◎ Example 102 Fe-Ni 50 5 5Η or more ◎ Example 103 50 7 5Η or more ◎ Example 104 60 Ni 50 7 2Η Δ Comparative Example 105 CR 15 Ni 30 7 511 or more ◎ Example 106 50 7 5Η or more ◎ Example 107 Fe-Ni 50 5 5 Η or more ◎ Example 108 50 7 5 Η or more ◎ Example 109 60 Ni 50 7 2 Η Δ Comparative Example 110 GA 15 Ni 30 7 4 Η ◎ Example CB 10 111 Ni 50 7 4 Η ◎ Examples CB 10 112 5 Fe-Ni 50 5 4 Η ◎ Example CB 10 113 Fe-Ni 50 7 4 Η ◎ Example CB 10 Experiment 4 For the original sheet, an electrogalvanized steel sheet (EG) and hot-dip galvanizing were used outside the specified range of the present invention. The scratch resistance of the steel sheet (GI) is discussed. The results are shown in Table 5. Since the hardness of the original sheet is insufficient, the scratch resistance is poor -20- 200944372 〔 [Table 5] Experiment No. Original sheet Tg (°C) Film thickness (4) Scratch resistance (pencil hardness) Judgment remarks 114 EG 5 5 Η X Comparative Example 115 10 5 Η X Comparative Example 116 15 5 Η X Comparative Example 117 GI 5 5 Η X Comparative Example 118 10 5 Η X Comparative Example 119 15 5 Η X Comparative Example The resin-coated steel sheet of the present invention can be used for automobiles, Home appliances, furniture, building materials, etc. It is also suitable for applications requiring high standards of scratch resistance outside these fields. -twenty one -