1277640 表面電阻值。依此，於家電製品用PCM中，以表面電阻 值作為塗膜帶電性之指標則不具意義。 第二項是前述藉由奥尼斯特靜電測試儀測定之初期帶 電壓與半衰期（JIS L 1094)，此係測定強制地於塗膜施加電 壓而使其帶電時之初期帶電壓，與解除施加電壓後直到降 低至初期帶電壓之1/2電壓為止之時間（半衰期），且初期 f電壓愈局則愈容易帶電，半衰期愈長則愈不易放電。依 此’初期帶電壓愈低且半衰期愈短之PCM，則愈不容易 引起沾覆灰塵等靜電問題，然而，若測定各種PCM之初 期帶電壓及半衰期並比較於實際冰箱組裝線上之灰塵沾覆 之實際情況，則完全不沾覆灰塵之PCM塗膜之初期帶電 壓較南而半衰期長，即，在目前之初期帶電壓與半衰期理 論下無法說明實際上沾覆灰塵之現象，且無法以這些值來 作為塗膜帶電性之指標。 因此，發明人所應用的是使塗膜與適當對象物接觸· 剝離而使其帶電時之帶電電壓（以下簡稱為剝離帶電後之 帶電電壓）。該剝離帶電後之帶電電壓與藉由奥尼斯特靜 電測5式儀測定之初期帶電壓不同之處係，初期帶電麼為非 接觸且猎由施加一定電壓而帶電’因此，初期帶電壓為僅 依據該塗膜固有之物理性質之電壓，相對於此，剝離帶電 後之帶電電壓係藉由與對象物之接觸·剝離而帶電，因此 ，剝離帶電後之帶電電壓成為不僅包含塗膜固有之物理性 質也包含塗膜形狀或黏著性之與對象物間親和性有關之因 11 1277640 子之電壓。結果，剝離帶電後之帶電電壓宜作為整體地評 價該塗膜帶電性之指標，又，帶電電壓可藉由市售之非接 觸式場強計而輕易地測定。 再者，帶電電壓與沾覆灰塵之程度大致上只有一種含 意地相對應，此係發明人藉由如下述之方法所確認者，即 :將使實際情況中容易沾覆灰塵之PCM、不易沾覆灰塵 之PCM、塗膜厚度較厚之PCM、塗膜厚度較薄之pcM、 藉由溶劑系塗料之PCM、藉由粉體塗料之pCM、具有裏 面塗膜之PCM、未具有裏面塗膜之PCM等各種PCM切 斷為A4尺寸者垂直地放置於非導電性之平台上，於該狀 態下使其與氯丁二烯橡膠摩擦而使塗膜強制帶電，以使帶 電電壓為0·1、0.2、0.3、〇·4、〇·5、〇.6kV。為了使帶電電 壓調和為預定，採取藉由摩擦使其帶電至成為稱微提 尚之電壓為止，並且一面觀察場強計一面以導電性棒輕觸 PCM而放電至成為預定電壓為止之方法。一旦成為預定 帶電電壓’使以切斷為lem方塊之瞻用薄膜來作為灰 塵替代品者附著於已帶電之PCM塗膜表面，並確認是否 因本身重量而掉落。進行該試驗時，與前述pCM種類完 全無關，若帶電電壓小於0.4kv則〇Hp薄膜掉落，若為 〇.5kV以上則不會掉^而吸附。當然，使氣丁二稀橡膠摩 擦時之帶電電壓上昇之方法雖然依照簡種類而有所不 同，不過，若即使是帶電電壓不易上昇者亦強制地使其帶 電至〇.5kV，貝ij 0HP薄膜仍會附著。由該情形來看，可以 12 1277640 說與塗膜之種類無關，只要決定塗膜之帶電電壓，則可大 致只有一種含意地決定灰塵沾覆之程度，換言之，不易沾 覆灰塵之PCM塗膜係（同一條件下之）剝離帶電後之帶電電 壓低’且絕對不是即使帶電電壓高亦不會沾覆灰塵者。再 者，一旦沾覆灰塵之OHP薄膜，即使後來使其放電而使 帶電電壓構成0亦仍會沾覆灰塵，這是因為在OHP薄膜 與塗膜表面黏合之部分電荷已中和而為〇，即使由該狀態 下放電，黏合部分之電荷平衡亦不會改變之故。依此，在 沾覆有灰塵之瞬間之塗膜帶電電壓決定灰塵沾覆之程度， 即使臨時使用放電性佳之材料而在沾覆灰塵後迅速地將電 荷變為0，亦與降低灰塵沾覆無關。由前述議論看來，所 謂剝離帶電後之帶電電壓低與由靜電引起之灰塵沾覆少兩 者可以等效地來處理。 於本發明中之方法1及方法2皆為測定前述剝離帶電 後之帶電電壓之條件。方法1係於2YC、5〇% RH之室内 ，將在業經切斷為15cm之平滑預鍍敷金屬板之對象塗 裝面之中央疊合有業經切斷為5>< i〇cin、硬度50、含碳黑 里為31質量％ 、厚度5mm之氣丁二烯橡膠片者，放置在 水平之陶究製平台上使預鍍敷金屬板位於下側，且將lkg 之砝碼放置於上部1〇秒鐘並壓接，於慢慢地移除砝碼後 ’朝垂直方向剝下氣丁二烯橡膠片，然後迅速地以非接觸 式場強計測定預鍍敷金屬板之塗裝面中央部之帶電電壓者 ’若為藉由方法1所得之帶電電壓小於〇.15kv之PCM， 13 1277640 則於室溫下不會產生由靜電引起之灰塵沾覆。另一方面， 方法2係於70°C之烘爐中預先將預鍍敷金屬板、氯丁二 烯橡膠片、陶瓷製平台及砝碼加熱1〇分鐘，取出後於3〇 秒内完成方法1中之程序者，若為藉由方法2所得之帶電 電壓小於0.25kV之PCM，則即使於50〜100°C之高溫亦 不會產生由靜電引起之灰塵沾覆。於高溫之抗灰塵沾覆性 係例如於冰箱加工程序中所要求，雖然於冰箱加工後會注 入作為隔熱材之發泡胺基甲酸酯，但是胺基甲酸酯之反應 熱會使溫度上昇至80°C，而即使於該狀態下，亦要求不 έ產生由靜電引起之灰塵沾覆。一般而言，若塗膜之溫度 咼，則因接觸·剝離而產生之靜電會增加，一般認為這是 因為高溫時塗膜軟化且與對象物接觸時黏著而有效接觸面 積增加之故。 若PCM用塗料中含有異氰酸酯衍生物時，則對於抑 制剝離帶電後之帶電電壓極為有效，其理由雖不明確，然 而，可以理解由於藉由含有異氰酸酯衍生物而使塗膜之帶 電列上之位置降低且與氣丁二烯橡膠之相對位置變近，因 此可抑制所產生之靜電量。 所謂異氰酸酯衍生物係指藉由甲醇、乙醇、丁醇、丙 醇、苯酚、曱苯酚、氯酚、硝苯酚、羥苯酚、乙醯丙鲷、 乙醯乙酸乙酯、丙二酸乙酯、己内醯胺、碳醯氯、1_氯 基一2 —丙醇、ΜΕΚ肟類等所代表之阻斷劑，阻斷IpDl( 異佛爾酮二異氰酸酯）、TDI(甲苯二異氰酸酯）、MDI(4,4, 14 1277640 一二苯曱烷二異氰酸酯）、HMDI(六亞甲二異氰酸酯）、氫 化MDI、氫化XDI(二曱苯二異氰酸酯）、氫化TDI等所代 表之各種異氰酸酯之單聚物、二聚物、三聚物及骨架中具 有前述異氰酸酯之預聚合物者，然而，異氰酸酯之種類或 阻斷劑之種類並不限於前述。 若使用異佛爾酮二異氰酸酯（IPDI)衍生物作為異氰酸 酯衍生物，則可抑制PCM塗膜燒固時黃化或經過長時間 κ化，因此較為理想。又，若IPDI衍生物相對於全固體 成分之比例為5質量％以上，則靜電抑制效果顯著。關於 靜電抑制效果，雖然在IPDI衍生物之添加量上並未設定 上限，然而若過量添加則不僅其效果飽和且不經濟，亦有 加工性等其他性能降低之情形，因此宜依照適當必要量來 添加。 若於PCM用塗料中同時含有異氰酸酯衍生物與燒氧 基胺鹽，則對於加倍地抑制剝離帶電後之帶電電壓是有效 的，其理由雖不明確，但一般認為可能是藉由含有烷氧基 胺鹽使塗膜之介電常數上昇且塗膜之靜電電容（蓄電效果） 提高，因此塗膜表層之電位降低且帶電電壓下降。若烧氧 基胺鹽相對於全固體成分之比例為1質量％以上，則靜電 抑制效果特別地顯著。烷氧基胺鹽可列舉如共榮社化學（ 股）製之佛羅倫（7口一b^)AE—2、日本諾普科 〕）(股）製之SN司達特（只夕y卜）824、楠本化成（股）製之 帝斯巴隆（亍彳只八口 ^)1121等，然而並不限於此。 15 1277640 關於靜電抑制效果，雖然在燒氧基胺鹽之添加量上並 未汉疋上限，然而若過量添加則不僅其效果飽和且不經濟 ’亦有加工性等其他性能降低之情形，因此宜依照適當必 要量來添加。 本發明之塗料所使用之樹脂可為高分子聚S旨樹脂系、 日树月曰系、3衣氧樹脂系、丙烯酸樹脂系、胺基甲酸酯樹 脂系、含氟樹脂系、氣乙烯樹脂系、烯烴樹脂系、酮樹脂 系等有機樹脂、石夕氧燒系、I系、财氧烧系等無機系樹 脂與將碎減、卿氧燒等無機《導人有機樹脂中之有 機無機複合型樹脂之任一者，硬化劑可使用三聚氰胺樹脂 系、苯I系、異氰酸g旨系與前述三者之併用系等任一者。 作為本發明基材之金屬板可使用冷乳鋼板、熱軋鋼板 、各種鍍敷鋼板（例如鍍鋅、鍍鋅合金、鍍錫、鍍鉛、鍍 銘、鑛鉻鋼板等）、不鏽鋼板、鈦板、lg㈣任意金屬板 ，且可直接使用或施行通常之轉化處理再使用。又，為了 使金屬板肖塗膜之黏合性冑高，金屬板之塗底塗料亦可使 用塗布有如尼龍、聚丙烯酸、聚乙烯、聚丙烯、聚酯、聚 胺基甲酸酯、環氧樹脂、聚醯胺、苯酚、聚烯烴等者。 製造本發明PCM之方法可於製造一般PCM之線上藉 由與通常相同之方法來製造。將塗料塗裝於金屬板表面之 方法可使用浸潰法、簾塗法、輥塗法、棒塗法、靜電法、 刷塗法、T型塑模法、層合法等任一種方法。 燒固方法可列舉如藉由熱風、常溫、近紅外線、遠紅 16 1277640 外線、高頻感應加熱或綜合前述方法之加熱法。 例 以下以實施例及比較例說明本發明。 所製作之PCM原板係使用厚度〇 6mm之溶融鑛辞鋼 板（YP · 19kg/mm2、TS : 34kg/mm2、EL : 45% )(以下簡稱 GI)、厚度0.6mm之電鍍鍍鋅鋼板（機械特性與QI同等： 簡稱為EG)及厚度〇.6mm之冷軋壓延鋼板（機械特性與⑴ 同等：簡稱為冷軋）。前處理係藉由表裏同一方法而以標 準條件施行塗布型鉻酸鹽處理及磷酸鋅處理（磷酸鹽覆膜 處理）。 塗膜構造係表面構成為下層塗膜、上層塗膜之雙面塗 布雙面燒固，上層塗膜相當於最表層塗膜，底漆係使用聚 酉曰系塗料A及環氧系塗料b，且藉由輥塗來塗布，以使乾 燥膜厚為5μηι，並於熱風烘爐中以pMT(最高到達板溫度） 為215 C來燒固。於底漆上方，最表層塗膜係將表丨所示 之各種塗料藉由輥塗來塗布，使乾燥膜厚為15μιη，且於 熱風烘爐中以ΡΜΤ為23(rc來燒固。襄面係將所有三聚氰 胺醇酸系裏面用塗料藉由輥塗來塗布，使乾燥膜厚為5μπι ，且於熱風烘爐中以ΡΜΤ為215°C及230°C來進行2次燒 固。 表1所示之最表層塗膜用之各塗料皆為日本塗料（股） 製造，且為藉由鈦顏料著色之白色塗料。所使用之樹脂係 C(高分子聚酯/三聚氰胺硬化系）、D(高分子聚酯/苯酚硬化 17 1277640 系）及E(丙烯酸/三聚氰胺硬化系）。所添加之異氰酸酯衍生 物係業經己内醯胺阻斷IPDI(異佛爾酮二異氰酸酯）、 MDI(4,4’一二苯甲烷二異氰酸酯）及HMDI(六亞甲二異氰 酸酯）之各單聚物者。又，烷氧基胺鹽係使用F(3級銨鹽 :楠本化成（股）製之帝斯巴隆1121)。再者，亦準備相對 於樹脂C而添加有10質量％之G(將前述氣丁二烯橡膠冷 凍粉碎並分級者：最大粒徑200μπι)及H(PTFE(聚四氟乙 烯）樹脂粉末）來作為其他添加物。 藉由方法1及方法2之帶電電壓係如下述來測定。 方法1係於23°C、50% RH之室内，將業經切斷為7 X 15cm之平滑PCM放置在絕緣物之陶器製紗管上，使測 定對象之塗裝面位於上方，暫時地接地使pCM之電荷構 成〇 ’接著，於PCM之中央放置業經切斷為5>< i〇cm、硬 度50、合碳黑量為31質量％ 、厚度5mm之氣丁二烯橡膠 片（i號·黑35〇、加貫滚輪製作所製造），且於上部放置 1kg之荷重均等地作用於該氯丁二烯橡膠片全面之底面平 坦之砝碼10秒鐘並壓接，於慢慢地移除砝碼後，在3秒 以内朝垂直方向剝下氣丁二烯橡膠片，然後在3秒以内以 希姆克〇^厶η)公司製之場強計FMX—〇〇2測定預鍍敷金 屬板之塗震面中央部之帶電電壓，以同—條件進行5次之 測定並取其平均值。 〜方去2係準備5組PCM、氯丁二烯橡膠片、陶器製 紗管及砝碼，並於70<t之烘爐中將該等加熱ι〇分鐘後i 18 1277640 組1組地取出，取出後於30秒内完成方法1之帶電電壓 測定作業’平均依此得到之η == 5之值。 將各PCM帶入實際冰箱組裝線上來調查抗灰塵沾覆 性及耐電擊性。抗灰塵沾覆性係評價在發泡胺基甲酸酯注 入前之程序（常溫）及發泡胺基甲酸酯注入後之程序（pCM 塗膜表面溫度上昇至約70°C為止）中，藉由氣丁二烯製吸 附夾具來搬送框體後之灰塵沾覆程度，並分別將明顯沾覆 灰塵者評價為X ，沾覆些許灰塵者評價為△，未沾覆灰塵 者評價為〇。耐電擊性係於電擊最頻繁之PCM塗膜與皮 帶運輸機之皮素材激烈地摩擦之程序後，以金屬製之棒子 觸碰PCM端面時是否產生電弧放電來評價，產生電弧放 電者為X ，產生若干電弧放電者為△，未產生者為〇。燒 固時之黃化性係以未添加異氰酸酯衍生物而沒有黃化之比 較例1為基準，藉由目測將燒固後之塗膜上有明顯黃化者 砰價為X，將有些許黃化者評價為△，將與比較例丨同樣 地完全未黃化者評價為〇。 19 1277640 ί1277640 Surface resistance value. Accordingly, in the PCM for household electrical appliances, it is meaningless to use the surface resistance value as an indicator of the chargeability of the coating film. The second term is the initial band voltage and half-life (JIS L 1094) measured by the Onist electrostatic tester, which measures the initial band voltage when the voltage is applied to the coating film to electrify it, and the applied voltage is released. After that, it is reduced to the time (half-life) of the initial voltage of 1/2 of the initial voltage, and the initial f voltage is more likely to be charged, and the longer the half-life is, the more difficult it is to discharge. According to this, the PCM with lower voltage and shorter half-life is less likely to cause electrostatic problems such as dusting. However, if the initial voltage and half-life of various PCMs are measured and compared with dust on the actual refrigerator assembly line, In the actual situation, the initial voltage of the PCM coating film which is completely free of dust is relatively long in the south and has a long half-life. That is, in the current initial band voltage and half-life theory, it is impossible to explain the actual dusting phenomenon, and it is impossible to use these. The value is used as an indicator of the chargeability of the coating film. Therefore, the inventors applied a charging voltage (hereinafter simply referred to as a charging voltage after stripping electrification) when the coating film is brought into contact with and peeled off from an appropriate object and charged. The charging voltage after the stripping is different from the initial band voltage measured by the Onist electrostatic meter 5 is that the initial charging is non-contact and the hunting is charged by applying a certain voltage. Therefore, the initial band voltage is only Depending on the voltage of the physical properties of the coating film, the charging voltage after stripping and charging is charged by contact and peeling with the object. Therefore, the charging voltage after stripping and charging is not only the physical property inherent to the coating film. The nature also includes the voltage of the 11 1277640 sub-related to the affinity of the coating or the adhesion of the object. As a result, the charged voltage after stripping electrification is preferably used as an integral measure of the chargeability of the coating film, and the charged voltage can be easily measured by a commercially available non-contact field strength meter. Furthermore, the charged voltage and the degree of dusting are substantially corresponding to one meaning, and the inventors confirmed by the method described below that the PCM which is easy to be dusted in the actual situation is not easily stained. PCM with dust coating, PCM with thick coating film, pcM with thin coating film, PCM with solvent coating, pCM with powder coating, PCM with inner coating, no inner coating Various PCMs such as PCM are cut into A4 size and placed vertically on a non-conductive platform. In this state, the CMP is rubbed to force the coating film to be charged, so that the charging voltage is 0.1. 0.2, 0.3, 〇·4, 〇·5, 〇.6kV. In order to adjust the charging voltage to a predetermined value, a method of charging the battery to a voltage which is called a micro-lift is performed, and the field strength meter is used to touch the PCM with a conductive bar and discharge to a predetermined voltage. Once it becomes a predetermined charging voltage, the film which is cut into lem squares is attached as a dust substitute to the surface of the charged PCM coating film, and it is confirmed whether it is dropped by its own weight. When this test is carried out, it is completely irrelevant to the above-mentioned pCM type. If the charged voltage is less than 0.4 kV, the 〇Hp film falls, and if it is 〇.5 kV or more, it does not fall and is adsorbed. Of course, the method of increasing the charging voltage when the gas is rubbed by the rubber is different depending on the type, but if the charging voltage is not easily risen, it is forcibly charged to 〇.5 kV. Still attached. From this point of view, it can be said that 12 1277640 is irrelevant to the type of coating film. As long as the charging voltage of the coating film is determined, there is roughly only one degree of intentionally determining the degree of dust coating, in other words, the PCM coating system which is not easy to be dusted. (Under the same condition) The charged voltage after stripping electrification is low' and it is definitely not that the dust will not be contaminated even if the charging voltage is high. Furthermore, once the OHP film is covered with dust, even if it is discharged later, the charged voltage is 0, and the dust is still contaminated because the partial charge adhered to the surface of the OHP film and the coating film is neutralized. Even if discharged by this state, the charge balance of the bonded portion does not change. Accordingly, the charged voltage of the coating film at the moment of dusting determines the degree of dusting, and even if the material with good discharge property is temporarily used, the electric charge is quickly changed to 0 after dusting, which is not related to reducing dust adhesion. . From the foregoing discussion, it is said that the low charging voltage after stripping electrification and the less dusting caused by static electricity can be handled equivalently. Both the method 1 and the method 2 in the present invention are conditions for measuring the charging voltage after the stripping electrification. Method 1 is in a room of 2YC, 5〇% RH, and the center of the coated surface of the smooth pre-plated metal sheet cut into 15cm is cut into 5><i〇cin, hardness 50. For the butadiene rubber sheet containing 31% by mass and 5 mm thick in carbon black, place it on the horizontal ceramic substrate so that the pre-plated metal plate is on the lower side, and place the weight of lkg on the upper part. After 1 second and crimping, after slowly removing the weight, 'strip the gas butadiene rubber sheet vertically, and then quickly measure the center of the coated surface of the pre-plated metal sheet with a non-contact field strength meter. If the charging voltage obtained by Method 1 is less than 〇.15kv PCM, 13 1277640 will not cause dusting caused by static electricity at room temperature. On the other hand, the method 2 is to preheat the pre-plated metal plate, the chloroprene rubber sheet, the ceramic platform and the weight for 1 minute in an oven at 70 ° C, and take out the method in 3 seconds. In the case of the program of 1, if the PCM having a charged voltage of less than 0.25 kV obtained by the method 2 is used, dusting due to static electricity does not occur even at a high temperature of 50 to 100 °C. The anti-dust adhesion at high temperatures is required, for example, in the processing of a refrigerator. Although the foamed urethane as a heat insulating material is injected after processing in the refrigerator, the heat of reaction of the urethane causes the temperature. It rises to 80 ° C, and even in this state, it is required to cause dust adhesion caused by static electricity. In general, when the temperature of the coating film is 咼, the static electricity generated by contact and peeling increases, and it is considered that this is because the coating film is softened at a high temperature and adheres to the object, and the effective contact area increases. When the PCM coating material contains an isocyanate derivative, it is extremely effective for suppressing the charging voltage after peeling and charging, and the reason is not clear. However, it can be understood that the position on the charging column of the coating film by containing the isocyanate derivative is understood. It is lowered and brought closer to the relative position of the butadiene rubber, so that the amount of static electricity generated can be suppressed. By isocyanate derivative is meant by methanol, ethanol, butanol, propanol, phenol, nonanol, chlorophenol, nitrophenol, hydroxyphenol, acetophenone, ethyl acetate, ethyl malonate, A blocking agent represented by indoleamine, carbon chlorochloride, 1-chloro-2-propanol, anthracene, etc., blocking IpDl (isophorone diisocyanate), TDI (toluene diisocyanate), MDI ( Monomers of various isocyanates represented by 4,4, 14 1277640 diphenylnonane diisocyanate), HMDI (hexamethylene diisocyanate), hydrogenated MDI, hydrogenated XDI (diphenylene diisocyanate), hydrogenated TDI, etc. The dimer, the trimer, and the prepolymer having the aforementioned isocyanate in the skeleton, however, the kind of the isocyanate or the kind of the blocking agent is not limited to the above. When an isophorone diisocyanate (IPDI) derivative is used as the isocyanate derivative, it is preferable to suppress yellowing during SiC coating film baking or to undergo kination for a long period of time. Further, when the ratio of the IPDI derivative to the total solid content is 5% by mass or more, the static electricity suppressing effect is remarkable. Regarding the effect of suppressing static electricity, although the upper limit is not set in the amount of addition of the IPDI derivative, if it is excessively added, not only the effect is saturated but also uneconomical, and other properties such as workability are lowered, so it is preferable to use an appropriate amount. Add to. When the PCM coating material contains both an isocyanate derivative and an alkoxyamine salt, it is effective to double the charging voltage after peeling and charging, and the reason is not clear, but it is generally considered to be by containing an alkoxy group. The amine salt increases the dielectric constant of the coating film and increases the electrostatic capacitance (storage effect) of the coating film, so that the potential of the surface layer of the coating film is lowered and the charging voltage is lowered. When the ratio of the oxygenated amine salt to the total solid content is 1% by mass or more, the static electricity suppressing effect is particularly remarkable. The alkoxyamine salt may, for example, be a sylvester of florin (7-port-b^) AE-2, 2 nopko] (shared) manufactured by Kyoeisha Chemical Co., Ltd. Bu) 824, Nanben Huacheng (share) system of Spartan (亍彳 only eight mouth ^) 1121, etc., however, is not limited to this. 15 1277640 Regarding the static suppression effect, although the upper limit of the amount of the alkoxyamine salt added is not exceeded, if it is excessively added, not only the effect is saturated and uneconomical, but also other properties such as processability are lowered. Add according to the appropriate amount. The resin used in the coating material of the present invention may be a polymer poly-resin resin, a Japanese resin, a 3 epoxy resin, an acrylic resin, a urethane resin, a fluorine resin, or a vinyl resin. An inorganic resin such as an organic resin such as an olefin resin or a ketone resin, or an inorganic resin such as a sulphur oxide system, an I system, or a sulphuric acid system, and an organic-inorganic composite in an inorganic organic resin such as a crushed or oxidized or burned inorganic resin. As the curing agent, any of the melamine resin type, the benzene I type, the isocyanic acid g, and the combination of the above three may be used as the curing agent. As the metal sheet of the substrate of the present invention, cold milk steel sheets, hot rolled steel sheets, various plated steel sheets (for example, galvanized, galvanized alloy, tin-plated, lead-plated, plated, ore-plated steel sheets, etc.), stainless steel sheets, and titanium can be used. Plate, lg (four) any metal plate, and can be used directly or subjected to the usual conversion treatment. Moreover, in order to improve the adhesion of the metal plate, the primer of the metal plate may also be coated with a coating such as nylon, polyacrylic acid, polyethylene, polypropylene, polyester, polyurethane, epoxy resin. , polyamine, phenol, polyolefin, etc. The method of manufacturing the PCM of the present invention can be manufactured by the same method as usual in the manufacture of a general PCM line. The method of applying the coating material to the surface of the metal plate may be any one of a dipping method, a curtain coating method, a roll coating method, a bar coating method, an electrostatic method, a brush coating method, a T-die molding method, and a layering method. The baking method may, for example, be a heating method by hot air, normal temperature, near-infrared rays, far-red 16 1277640 external line, high-frequency induction heating, or a combination of the foregoing methods. EXAMPLES Hereinafter, the present invention will be described by way of examples and comparative examples. The PCM original plate produced is a galvanized steel plate with a thickness of 〇6 mm (YP · 19kg/mm2, TS: 34kg/mm2, EL: 45%) (hereinafter referred to as GI) and a thickness of 0.6mm (mechanical characteristics) The same as QI: EG) and 〇.6mm thick rolled rolled steel sheet (mechanical characteristics are equivalent to (1): cold rolling for short). The pretreatment was carried out by a coating type chromate treatment and a zinc phosphate treatment (phosphate coating treatment) under standard conditions by the same method in the table. The surface of the coating film structure is formed by double-sided coating of the lower coating film and the upper coating film, and the upper coating film is equivalent to the outermost coating film, and the primer is a polyanthracene coating A and an epoxy coating b. Further, it was applied by roll coating to have a dry film thickness of 5 μm, and was baked in a hot air oven at pMT (maximum plate temperature) of 215 C. Above the primer, the outermost coating film is coated with various coatings shown in the surface by roll coating to a dry film thickness of 15 μm, and is baked in a hot air oven at 23 (rc). All the melamine alkyd-based coatings were applied by roll coating to a dry film thickness of 5 μm, and were baked twice in a hot air oven at 215 ° C and 230 ° C. Table 1 Each of the coatings for the outermost coating film is made of Japanese paint (stock) and is a white paint colored by titanium pigment. The resin used is C (polymer polyester/melamine hardening), D (high) Molecular polyester / phenol hardened 17 1277640 series) and E (acrylic acid / melamine hardening system). The added isocyanate derivative is blocked by caprolactam IPDI (isophorone diisocyanate), MDI (4, 4' Each of the monomers of diphenylmethane diisocyanate and HMDI (hexamethylene diisocyanate). Further, the alkoxyamine salt system uses F (grade 3 ammonium salt: Diane Barron made from Nanben Chemical Co., Ltd.) 1121). Further, it is also prepared to add 10% by mass of G to the resin C. The diene rubber was freeze-pulverized and classified by a maximum particle diameter of 200 μm and H (PTFE (polytetrafluoroethylene) resin powder) as other additives. The charged voltages of the methods 1 and 2 were measured as follows. 1 is placed in a chamber of 23 ° C, 50% RH, and a smooth PCM cut into 7 × 15 cm is placed on the ceramic tube of the insulator, so that the coating surface of the measurement object is located above, temporarily grounded to make pCM The electric charge constitutes 〇'. Next, a butadiene rubber sheet (i, black) which is cut into 5<i〇cm, hardness 50, carbon black content of 31% by mass, and thickness 5 mm is placed in the center of the PCM. 35〇, manufactured by the Roller Manufacturing Co., Ltd.), and the load of 1kg placed on the upper part is equally applied to the flat bottom of the chloroprene rubber sheet for 10 seconds and crimped, and the weight is slowly removed. After that, the gas-butadiene rubber sheet was peeled off in a vertical direction within 3 seconds, and then the pre-plated metal sheet was measured by a field strength meter FMX-〇〇2 manufactured by Shimke®® within 3 seconds. The charged voltage in the central part of the tempering surface is measured and measured in the same condition for 5 times. Value. ~Part 2 to prepare 5 sets of PCM, chloroprene rubber sheets, pottery tubes and weights, and take them in a 70 ° t oven for 1 minute after the i 18 1277640 group After the removal, the charged voltage measurement operation of the method 1 is completed within 30 seconds, and the average value of η == 5 obtained therefrom is obtained. Each PCM was brought into an actual refrigerator assembly line to investigate dust resistance and electric shock resistance. The dust-resistant coating was evaluated in the procedure before the foaming urethane injection (normal temperature) and the procedure after the foaming urethane injection (the surface temperature of the pCM coating film was raised to about 70 ° C). The degree of dust adhesion after the frame was conveyed by the gas-butadiene-made adsorption jig was evaluated as X in the case of obvious dusting, △ in the case of dusting, and 〇 in the case of non-sticking. The electric shock resistance is evaluated by the process of intensely rubbing the PCM coating film of the electric shock with the leather material of the belt conveyor, and whether the arcing is generated when the metal rod touches the PCM end face, and the arc discharge is X, which is generated. Some arc dischargers are △, and those not produced are 〇. The yellowing property at the time of baking is based on Comparative Example 1 in which no isocyanate derivative is added without yellowing, and the apparent yellowing on the coating film after burning is visually determined to be X, which is somewhat yellow. The evaluator was evaluated as Δ, and the same as the comparative example 完全 was evaluated as 〇. 19 1277640 ί
表面電阻値 /kY ο — /\ 彆 /\ tr o iH /\ z o 八 贊 Ο η A c A , b 八 Ο /\ ο — A 〇 — A V rH b r-t /\ tr O H A b A 酽 ο 八 ψ b A ψ s 八 彎 b /\ 罾 O — A 罾 Ο 一 r\ ο — /Ν w o rH /\ 6 y^n 八 〇 /\ b T-l /\ O ㈣ /N fit 姹孱δ e贓鹏 威趣1 1 1 1 1 280 o iii CSJ 230 370 300 260 1 1 1 I 1 1 1 1 ί i 1 1 i _ | 1 l 1 1 1 1 ! 1 1 燒固 黃化性 〇 ! 〇 〇 0 0 0 0 0 0 1 i 0 1 0 0 <d X X X X 1 0 0 <1 <; < 0 1 〇 0 耐電 擊性 <3 <3 0 0 0 0 0 0 0 0 0 0 X <1 〇 0 0 X 0 0 0 0 <1 X < <3 t is tnfli 磡 70*0 X X X X X X <3 < 0 0 0 0 X < 0 〇 0 X < 0 0 〇 X X < < 常溫 0 0 〇 0 〇 s 0 0 s 0 J 3 0 0 0 0 "Π 0 」 0 0 0 0 0 0 0 0 0 0 溢 rtirr] ιρ 方法2 /kV 0, 46 0.40 0. 37 5 6 S i m I _ i ε ι Μ I i i I i a g 〇 0. 30 0.23 ! ·« d s ο U) U) o 0. 30 I 0.22 1 φ 6 6 I g πιι<·ί«^ϋΐ limj _ δ 方法1 > Ο wn d CJ d 1 0.10 00 o d I 0. 10 1 0.07 〇· 1 0.07 1 0.07 1 0.06 g d 〇 0-14 o Q ο s o d ·»« 〇· 0. 08 j 0.08 1 § ο 若 d tn r~* C KO H d i 剡 _ Μ 酿 其他添 加物 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 • I 1 1 I 1 1 α s 1 1 烷氧基胺鹽 含有量 (註2) 1 1 1 — I H C4 1. N 1 CSI 1 1 ca 1 内 ea I 1 C3 I 種類 1 ! k i |l 1 k 1 Ck fie. I CS-. tt. 1 bu 1 to. 1 匕 Cc. 1 1 b· I Cm. fa. I 1 It. 1 IS irlnj] Ss en 1 e*9 ΙΛ u> Φ <x> CO S3 s C4 iO IA CM 丨" 1 I L. C9 2 [ CO οι Μ 04 1 1 <0 2 wc， t Μ itfrtl 聰 1 1PDI ΠΡΟ! 1 IPDI 1 IPDI »« eu — o a* mm 1 IPDI Γΐροι g 1 IPDI M 0. 2 5: ICDI »-· 9 mi MDI HMDI HMDI 丨 HKDI 1 — a s a 1 1 o 0u Ml a Q. 叫 樹脂系 u o 1 U o o 〇 o o o 〇 O O o ο ο o 0 a mm < < < *< < << < < < < < < -< < < < < < -< < < < < < < 前處理 1 翻 s 逾 i 趙 溁 i I 芻 i 潘 芻 i 麴 I i 你 i 遨 潘 弟 i 麄 雄 i £ 编 i 翻 镟 i 趣 i i i i i i 结 i £ 頦 i i 頦 s 趙 i 趣 练 § i 頦 i i 葙 i 1 墟 I i 练 i 琮 m 编 趙 18 趣 镟 21 Γ 一 mm 功 G mm u 9m u μ Μ 3 Μ ο M 5 Ο 5 5 Ξ Μ ««Μ mm O rH M § 镯 u cn 每 _ 寸 § 握 _ ΙΛ 辑 u v〇 匡 辑 u ί 00 § i _ Ο % i c i 择 ι 1 « i cs i 辑 w cn i _ i « wn i 摈 _ VC i 駟 i 握 00 i i ms i 握 φΕ i l 莩 握 駟 CO S _ _ _ i 瑋 _ v〇 CN {K ^_®φ链 11 画w^lgil 画湘¾¾¾¾¾鬆^腾縮张>_擗邻^任谳(csii) #ssffi魅ΕΓΐ], % 联f*Kss^i4Hi&igiic3l<T-la)- w f B 次 OOCNSTSKIK)鬆抵 ^ltstuh减：o ArHCNIIiiHJEt&iils^件®)® 镞褰ε:fc 避憩减MnfrM 忆·· ΚΠΑΙΗ ,魍趙««nigfr^n-寸> :i ,避趙caKnlMtsl: 3041 味«嵌⑴/趙ί?Μ : 3 ,味翠酲溢擗、避踩^φ岖：α ,味^酿狴_^川/避联屮余«:3 條祕f : η ,味避鞔：v , ®1^ί·ί^: ιίίΕ,堪lt敏鐳绞：10,赵1^敏顧«: 03 20 1277640 21 1277640 若觀察實施例1〜42及比較例則可得知剝離 帶電後之帶電電壓與抗灰塵沾覆性具有高度相關，若藉由 方法1之帶電電壓大於〇.15kV，又，藉由方法2之帶電電 壓大於0.25kV,則分別在常溫及70t之抗灰塵沾覆性降 低，由於實施例1〜42在方法1中之帶電電壓小於〇 15kv ，因此於常溫之抗灰塵沾覆性良好。藉由增加異氰酸酯衍 生物之添加量、增加烷氧基胺鹽之添加量而有剝離帶電後 之帶電電壓降低之傾向，又，若併用異氰酸酯衍生物與烷 氧基胺鹽，則特別是在方法2 _可加倍地降低剝離帶電後 之帶電電壓，若充分發揮前述效果，則如實施例9〜12、 15 〜17、20〜22、27、32、33、35、36、38、39、41 及 42 ’於70 C之抗灰塵沾覆性亦良好。實施例23及24係 分別於比較例1中添加氯丁二烯橡膠之粉碎物及pTFE, 且剝離帶電後之帶電電壓降低，一般認為此係藉由添加氣 丁二烯橡膠或PTFE ,使測定帶電電壓時之對象物之氣丁 二烯橡膠片與塗膜間之帶電列上之位置關係相對地變近所 致。如該例所示，只要將剝離帶電後之帶電電壓納入預定 範圍内’則可提昇抗灰塵沾覆性，且並不限於添加異氰酸 醋衍生物或烷氧基胺鹽之方法，即使將原板種類由GI變 更為EG或冷軋（實施例37〜42、比較例9、10)，即使將 前處理由鉻酸鹽處理變更為磷酸鋅處理（實施例34〜36、 比較例8)，又，即使將下層塗膜由聚酯系變更為環氧系（ 實施例31〜33、比較例7)，PCM之剝離帶電後之帶電電 22 1277640 壓亦沒有值得注意之改變，且抗灰塵沾覆性亦沒有改變， 由此可知，最表層塗膜之性質對於剝離帶電後之帶電電壓 八有支配丨生之響’若將最表層塗膜之樹脂系由高分子聚 酉曰/-聚氰胺硬化系變更為高分子聚酯/苯紛硬化系或丙婦 酸/三聚氰胺硬化系（實施例25〜3G、比較例5、6卜則整 體而言有剝離帶電後之帶電電壓提高之傾向，而帶電電壓 與抗灰塵沾覆性之相關性係位於同一線上。 耐電擊性與PCM剝離帶電後之帶電電a亦大致相關 ，耐電擊性良好之大致標準可說是方法i中之帶電電壓小 於O.lkV者。 異氰酸酯之種類為使用IPDI、Mm及HMm時，雖 然同樣地具有降低剝離帶電後之帶電電壓之效果，不過， 由於在燒固時之抗黃化性以IPDI最好，HMm(實施例Μ 〜22)之抗黃化性則有些許降低，而Mm(實施例i3〜i7) 之抗黃化性則大幅地降低，因此若要求具有抗黃化性時宜 使用IPDI。 由於比較例1〜10之剝離帶電後之帶電電壓皆超過本 發明之範圍，因此抗灰塵沾覆性差。 另，表中顯示自以往起即作為抗灰塵沾覆性指標之奥 尼斯特靜電測試儀之半衰期及表面電阻值之測定值以作為 參考，半衰期方面僅顯示部分實施例及比較例，於測定各 值時，奥尼斯特靜電測試儀係使用戶商會製造之S 一 4104,且施加電壓設為8kv，表面電阻計則使用希姆克公 23 1277640 司製造之ST—3型。 右镜察半衰期，則可看出藉由添加ipm而半衰期變 長，且藉由添加烷氧基胺鹽而半衰期反而縮短之傾向，雖 然對於抗灰塵沾覆性皆為有效之處理方法，然而針對半衰 期方面則顯示相反之傾向，又，抗灰塵沾覆性差之比較例 1〜4之半衰期亦較短。依此，以往所謂半衰期愈短則抗 灰塵沾覆性愈佳之想法在此則不成立，半衰期與抗灰塵沾 覆性也沒有任何相關性，可知半衰期並無法構成抗灰塵沾 覆性之指標。另一方面，若觀察表面電阻值，則所有 PCM顯示出1〇14歐姆以上之值，可知此亦無法成為抗灰 塵沾覆性之指標。 產業上之可利用性 如前所示，藉由本發明，可提供一種不會大幅提高成 本而可確實地抑制由塗膜之靜電所引起之帶電之PCM。 【圖式簡單說明】 (無） 24Surface resistance 値/kY ο — /\ 别/\ tr o iH /\ zo 八赞Ο η A c A , b Ο Ο /\ ο — A 〇 — AV rH b rt /\ tr OHA b A 酽ο ψ b A ψ s Eight bends b /\ 罾O — A 罾Ο a r\ ο — /Ν wo rH /\ 6 y^n 八〇/\ b Tl /\ O (4) /N fit 姹孱δ e赃鹏威Interest 1 1 1 1 1 280 o iii CSJ 230 370 300 260 1 1 1 I 1 1 1 1 ί i 1 1 i _ | 1 l 1 1 1 1 ! 1 1 Burnt yellowing 〇! 〇〇0 0 0 0 0 0 1 i 0 1 0 0 <d XXXX 1 0 0 <1 <;< 0 1 〇0 Resistance to electric shock <3 <3 <3 0 0 0 0 0 0 0 0 0 0 X < 1 〇0 0 X 0 0 0 0 <1 X <<3 t is tnfli 磡70*0 XXXXXX <3 < 0 0 0 0 X < 0 〇0 X < 0 0 〇XX << Normal temperature 0 0 〇0 〇s 0 0 s 0 J 3 0 0 0 0 "Π 0 ” 0 0 0 0 0 0 0 0 0 0 overflow rtirr] ιρ Method 2 /kV 0, 46 0.40 0. 37 5 6 S im I _ i ε ι Μ I ii I iag 〇0. 30 0.23 ! ·« ds ο U) U) o 0. 30 I 0.22 1 φ 6 6 I g πιι<·ί«^ϋΐ limj _ δ method 1 > Ο wn d CJ d 1 0.10 00 od I 0. 10 1 0.07 〇· 1 0.07 1 0.07 1 0.06 gd 〇0-14 o Q ο sod ·»« 〇· 0. 08 j 0.08 1 § ο If d tn r~* C KO H di 剡_ Μ Brewing other additives 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 • I 1 1 I 1 1 α s 1 1 Alkoxyamine salt content (Note 2) 1 1 1 — IH C4 1. N 1 CSI 1 1 ca 1 Internal ea I 1 C3 I 1 ! ki |l 1 k 1 Ck fie. I CS-. tt. 1 bu 1 to. 1 匕Cc. 1 1 b· I Cm. fa. I 1 It. 1 IS irlnj] Ss en 1 e*9 ΙΛ u> Φ <x> CO S3 s C4 iO IA CM 丨" 1 I L. C9 2 [ CO οι Μ 04 1 1 <0 2 wc, t Μ itfrtl Satoshi 1 1PDI ΠΡΟ! 1 IPDI 1 IPDI »« Eu — oa* mm 1 IPDI Γΐροι g 1 IPDI M 0. 2 5: ICDI »-· 9 mi MDI HMDI HMDI 丨HKDI 1 — asa 1 1 o 0u Ml a Q. Called resin uo 1 U oo 〇ooo 〇OO o ο ο o 0 a mm <<<*<<<<<<<<<<&<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<£ 颏 ii 颏 s Zhao i 趣 § i 颏 ii 葙i 1 I I i 练 i i 琮 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 ««Μ mm O rH M § Bracelet u cn Every _ inch § Grip _ ΙΛ Collection uv〇匡u ί 00 § i _ Ο % ici Select 1 1 i cs i series w cn i _ i « wn i 摈_ VC i 驷i grip 00 ii ms i grip φΕ il 莩 grip 驷 CO S _ _ _ i 玮 _ v〇CN {K ^_® φ chain 11 draw w^lgil draw 湘 3⁄43⁄43⁄43⁄43⁄4 loose ^ 腾 shrink Zhang > _ 擗邻^任谳(csii)#ssffiΕΓΐ], % 联 f*Kss^i4Hi&igiic3l<T-la)- wf B times OOCNSTSKIK) loose ^ltstuh minus: o ArHCNIIiiHJEt&iils^®®) ε:fc 憩 憩 Mn Mn Mn Mn Mn Mn Mn Mn Mn Mn Mn « « « « « « « « « « « « « « « « « « « ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca Stepping on ^φ岖:α,味^狴狴_^川/避联屮余«:3 secret f: η ,味避鞔:v , ®1^ ί· ί^: ιίίΕ, 堪特敏镭绞: 10, Zhao 1^敏顾«: 03 20 1277640 21 1277640 If we observe the examples 1 to 42 and the comparative example, we can know the charged voltage and anti-ash after stripping electrification. The adhesion is highly correlated. If the charged voltage of the method 1 is greater than 1515 kV, and the charged voltage of the method 2 is greater than 0.25 kV, the dust resistance at room temperature and 70t is reduced, respectively. The charging voltage in the method 1 to 42 is less than 〇15 kv, so that the dust resistance at normal temperature is good. By increasing the amount of the isocyanate derivative added and increasing the amount of the alkoxyamine salt added, the charging voltage after peeling electrification tends to decrease, and when the isocyanate derivative and the alkoxyamine salt are used in combination, the method is particularly 2 _ can reduce the charging voltage after stripping electrification twice, and if the above effects are fully exerted, as in Examples 9 to 12, 15 to 17, 20 to 22, 27, 32, 33, 35, 36, 38, 39, 41 And 42' is also good at dust resistance at 70 C. In Examples 23 and 24, the pulverized material of chloroprene rubber and pTFE were added to Comparative Example 1, respectively, and the charging voltage after stripping electrification was lowered. It is generally considered that this is determined by adding gas butadiene rubber or PTFE. When the charged voltage is applied, the positional relationship between the gas butadiene rubber sheet of the object and the coating film is relatively close. As shown in this example, as long as the charged voltage after stripping electrification is included in the predetermined range, the dust-resistant property can be improved, and it is not limited to the method of adding an isocyanate derivative or an alkoxyamine salt, even if The original plate type was changed from GI to EG or cold rolling (Examples 37 to 42 and Comparative Examples 9 and 10), and the pretreatment was changed from chromate treatment to zinc phosphate treatment (Examples 34 to 36 and Comparative Example 8). Further, even if the undercoat film was changed from a polyester type to an epoxy type (Examples 31 to 33 and Comparative Example 7), the voltage of the charged electric power 22 1277640 after peeling off of the PCM was not noticeably changed, and it was resistant to dust. The coverage has not changed. It can be seen that the properties of the outermost coating film have a dominant effect on the electrification voltage after stripping electrification. 'If the resin of the outermost coating film is made of polymer poly-/polycyanide The amine hardening system is changed to a polymer polyester/benzoic acid-based or a propylene-glycolic acid/melamine-curing system (Examples 25 to 3G and Comparative Examples 5 and 6 have a tendency to increase the charging voltage after peeling electrification as a whole, The correlation between charged voltage and dust resistance It is located on the same line. The electric shock resistance is also roughly related to the charged electric power a after the PCM stripping and charging. The general standard of good electric shock resistance can be said that the charging voltage in method i is less than O.lkV. The type of isocyanate is IPDI, Mm. In the case of HMm, although the effect of reducing the charging voltage after stripping electrification is similarly applied, the anti-yellowing property at the time of baking is preferably IPDI, and the anti-yellowing property of HMm (Examples 〜 22) is somewhat The yellowing resistance of Mm (Examples i3 to i7) is greatly reduced, so IPDI should be used if it is required to have anti-yellowing properties. Since the charging voltages of the comparative examples 1 to 10 after stripping are more than this The scope of the invention is therefore poor in dust-resistant adhesion. In addition, the table shows the measured values of the half-life and surface resistance of the Onisert electrostatic tester as an indicator of dust-resistant adhesion from the past as a reference, and only the half-life is only used. Some embodiments and comparative examples are shown. When measuring each value, the Onister electrostatic tester makes the S-4104 manufactured by the user's chamber, and the applied voltage is set to 8kv, and the surface resistance meter is used by Himke 23 1277640 ST-3 type manufactured by the company. Right half-life of the mirror, it can be seen that the half-life is lengthened by the addition of ipm, and the half-life is shortened by the addition of the alkoxyamine salt, although it is resistant to dust. Sexuality is an effective treatment method. However, in terms of half-life, the opposite tendency is shown, and in Comparative Examples 1 to 4, which have poor anti-dust adhesion, the half-life is also short. Accordingly, the shorter the half-life is, the dust-resistant coating is used. The idea of better sex is not established here, and there is no correlation between half-life and anti-dust adhesion. It is known that half-life does not constitute an indicator of dust-resistant adhesion. On the other hand, if the surface resistance value is observed, all PCMs are displayed. A value of 1 〇 14 ohm or more indicates that this cannot be an indicator of dust repellency. Industrial Applicability As described above, according to the present invention, it is possible to provide a PCM capable of reliably suppressing charging due to static electricity of a coating film without greatly increasing the cost. [Simple description of the diagram] (none) 24