TW200414940A - Method for coating metal materials and coated materials - Google Patents
Method for coating metal materials and coated materials Download PDFInfo
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- TW200414940A TW200414940A TW92121653A TW92121653A TW200414940A TW 200414940 A TW200414940 A TW 200414940A TW 92121653 A TW92121653 A TW 92121653A TW 92121653 A TW92121653 A TW 92121653A TW 200414940 A TW200414940 A TW 200414940A
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200414940 玖、發明說明： 【發明所屬之技術領域】 本务明有關一種對鎂合金材料等金屬材料進行塗裝的塗 裝方法，而且又有關利用該系統塗裝的家電製品、〇A設 備、行動設備等電子設備、汽車部件等之塗裝物。 【先前技術】 在鎂合金材料等表面缺陷（皺紋、凹痕、穴坑）較多的金屬 材料上，係依據例如曰本特開20^4 1672號公報、特開 2002-177878號公報所揭示般’塗裝作爲底塗層塗料的溶劑 型或粉末型的熱固性環氧樹脂塗料，另外，根據需要在其 表面塗層塗裝含有紹薄片、雲母薄片等光澤性材料的溶劑 型熱固性丙烯酸酯樹脂塗料。但是，該方法，存在著如下 問題。 ⑴底塗層中使用的溶劑型熱固性環氧樹脂塗料隱蔽金屬 材料的表面缺陷的功能I古八 、， 、 天丨曰的力月b不充分，亚且粉末型熱固性環氧樹 脂塗料表面的平滑性冰々# < 人佺，（2)因爲表面塗層使用的溶劑 型熱固性丙烯酸醋樹脂塗料難以將塗膜表面光澤調整在寬 廣範圍，所以限制了色相外觀；(3)另一方面，行動電話所 用框體利用规樹脂、聚碳酸酉旨樹脂等塑膠原材料和㈣ 材：組合製造，因爲塑膠原材料部分耐熱性差所以底塗層 不能用熱固性塗斜。田+ 上 曰 因此，在塑膠原材料部分和鎂原材料 邛为中存在著塗膜的構成 題。 U 巳相外硯也完全不同等問 另外， 又考慮到在溶劑型熱 固性環氧樹脂塗膜上形成熱200414940 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a coating method for coating metal materials such as magnesium alloy materials, and also relates to home appliance products, 0A equipment, and actions that are painted using this system. Coatings for electronic equipment such as equipment and automobile parts. [Prior art] Metal materials with many surface defects (wrinkles, dents, pits) such as magnesium alloy materials are disclosed based on, for example, Japanese Patent Publication No. 20 ^ 4 1672 and Japanese Patent Publication No. 2002-177878. Generally, a solvent-based or powder-type thermosetting epoxy resin coating is used as an undercoating coating, and a solvent-based thermosetting acrylate resin containing a glossy material such as a thin sheet and a mica sheet is coated on the surface as required. coating. However, this method has the following problems.溶剂 The function of the solvent-based thermosetting epoxy resin coating used in the undercoating to hide the surface defects of metal materials. The ancient force b is insufficient, and the surface of the powder-type thermosetting epoxy coating is smooth.性 冰 々 # < Human 佺, (2) because the solvent-based thermosetting acrylic resin coating used in the surface coating is difficult to adjust the surface gloss of the coating film in a wide range, so the hue appearance is limited; (3) on the other hand, action The frame used for the phone is made of plastic raw materials such as gauge resin, polycarbonate resin, etc .: The combination is manufactured. Because the plastic raw materials are poor in heat resistance, the undercoat layer cannot be coated with thermosetting. Tian + Previously, there is a problem of coating film formation in plastic raw materials and magnesium raw materials. The U phase is also completely different. In addition, considering the formation of heat on the solvent-based thermosetting epoxy resin coating film,
O:\87\87171.DOC 200414940 塑性丙烯酸酷樹脂塗膜的基礎上，又形成活性能量線固化 型透明塗膜的積層方法，該塗裝方法中也存在著問題。即， 口爲如上所述的環氧樹脂塗料的底塗層的缺陷隱蔽性不充 分，所以需要在活性能量線固化型透明塗膜形成後對殘存 的缺fe邛刀進行修補。但是，因爲活性能量線固化型塗膜 的重塗引起密著性不良，所以實際上修補是不可能的。因 此’不能採用該塗裝方法。 【發明内容】 本發明的目的是提供一種在鎂合金材料等金屬材料表面 上形成具充分硬物之塗膜且耐磨耗性優異而且能展現寬範 圍的色相外觀的塗膜、而且即使是行動電話用的框體等使 塑膠原材料和金屬原材料組合的塗裝物、色相外觀也均一 的塗膜之方法及使用該方法之塗裝物。 、本I月的第-發明係金屬材料之塗裝方法，係在金屬材 料表面上，利用粉末塗料形成膜厚爲2〇〜4〇 的固化塗 膜，在该固化塗膜上利用有機溶劑型的熱塑性丙烯酸酯樹 脂塗料形成著色塗膜，接著在該著色塗膜上利用活性能量 線固化型透明塗料形成透明塗膜，其特徵在於該粉末塗料 的烘烤固化條件下之熔融最低黏度在10〜2〇pa.s之範圍。 。上述粉末塗料的烘烤固化條件較佳為溫度在14〇〜2〇〇 C、時間爲1分鐘〜3〇分鐘。而且，作爲金屬材料的例子能 列舉鎂合金、紹合金、辞合金。另外，上述透明塗膜中還 包含消光塗膜般半透明塗膜。 上述熱塑性丙烯酸酯樹脂塗料所形成的上述著色塗膜可O: \ 87 \ 87171.DOC 200414940 On the basis of plastic acrylic cool resin coating film, an active energy ray-curable transparent coating film is also laminated. There are also problems in this coating method. That is, the defect concealment of the undercoat layer of the epoxy resin coating as described above is insufficient, so it is necessary to repair the remaining missing trowel after the formation of the active energy ray-curable transparent coating film. However, since re-coating of the active energy ray-curable coating film causes poor adhesion, repair is not practically possible. Therefore, this coating method cannot be used. [Summary of the Invention] The object of the present invention is to provide a coating film having a sufficiently hard object on the surface of a metal material such as a magnesium alloy material, a coating film excellent in abrasion resistance, and exhibiting a wide range of hue appearance, and even in action A method for making a coating material for a combination of plastic raw materials and metal raw materials and a coating film having a uniform hue appearance, such as a housing for a telephone, and a coating material using the same. The coating method of the first-invention-based metal material in this month is to form a cured coating film with a thickness of 20 to 40 by powder coating on the surface of the metal material, and use an organic solvent type on the cured coating film. A thermoplastic acrylate resin coating is used to form a colored coating film, and then on the colored coating film, an active energy ray-curable transparent coating is used to form a transparent coating film, which is characterized in that the powder coating has a minimum melt viscosity of 10 to 10 under baking and curing conditions. 2〇pa.s range. . The baking and curing conditions of the powder coating are preferably a temperature of 14 to 200 ° C and a time of 1 minute to 30 minutes. Examples of the metal material include magnesium alloys, alloys, and alloys. The transparent coating film also includes a translucent coating film such as a matte coating film. The colored coating film formed by the thermoplastic acrylate resin coating may be
O:\87\87171.DOC 200414940 以幵> 成爲一層、兩層或二層。另外，上述熱塑性丙稀酸酯 树脂塗料中也可以含光亮材料。上述熱塑性丙烯酸酯樹脂 塗料塗裝後，可以在30〜80°C、10秒鐘〜1〇分鐘的條件下 進行強制乾燥，形成上述著色塗膜。 上述活性能量線固化型透明塗料為UV固化型透明塗 料，塗裝該透明塗料後，可以照射200〜1500 mJ/cm2範圍 的紫外線，形成上述透明塗膜。 猎由本發明第一發明之塗裝方法之塗裝物是利用上述各 塗裝方法在上述金屬材料上形成塗裝膜所形成的，亦可由 形成有上述塗裝膜的金屬材料舆依次形成上述溶劑型熱塑 性丙烯酸酯樹脂塗料的著色塗膜及上述活性能量線固化型 透明塗料的透明塗膜的塑膠材料組合形成。 本發明之第二發明係有關複合材料之塗裝方法，其特徵 在於：在上述金屬材料上形成上述粉末塗料的固化塗膜 後，使形成有該粉末塗膜的金屬材料和塑膠材料組合，製 造金屬-塑膠複合材料’可以在該複合材料表面上依次形成 上述溶劑型熱塑性丙烯酸酯樹脂塗料的著色塗膜及上述活 性能量線固化型透明塗料的透明塗膜。而且藉由該複合材 料之塗裝方法所得之塗裝物亦為第二發明目的之一。口 电製品、〇A設 另外，作爲上述塗裝物的例子可列舉家 備、行動設備等電子設備、汽車部件。 【實施方式】 以下，具體地敍述本發明。 首先在金屬材料 在作爲本發明第一發明之塗裝方法中O: \ 87 \ 87171.DOC 200414940 becomes 一层 > one, two, or two. The thermoplastic acrylic resin coating material may contain a bright material. After the thermoplastic acrylate resin coating is applied, it can be forcedly dried at 30 to 80 ° C for 10 seconds to 10 minutes to form the colored coating film. The above-mentioned active energy ray-curable transparent coating is a UV-curable transparent coating. After coating the transparent coating, it can be irradiated with ultraviolet rays in the range of 200 to 1500 mJ / cm2 to form the transparent coating film. The coating material according to the coating method of the first invention of the present invention is formed by forming a coating film on the above-mentioned metal material by using each of the above-mentioned coating methods, or the above-mentioned solvent may be sequentially formed from the metal material on which the above-mentioned coating film is formed. The coloring coating film of the thermoplastic thermoplastic acrylate resin coating and the plastic material of the transparent coating film of the above-mentioned active energy ray-curable transparent coating are combined. The second invention of the present invention relates to a coating method for a composite material, which is characterized in that: after forming the cured coating film of the powder coating on the metal material, the metal material and the plastic material on which the powder coating film is formed are combined and manufactured The metal-plastic composite material can sequentially form the colored coating film of the solvent-based thermoplastic acrylate resin coating and the transparent coating film of the active energy ray-curable transparent coating on the surface of the composite material. In addition, the coating material obtained by the coating method of the composite material is also one of the objects of the second invention. Electronic products, OA equipment, etc. Examples of the coating materials include electronic equipment such as home appliances and mobile equipment, and automobile parts. [Embodiment] Hereinafter, the present invention will be specifically described. First, in a metal material, in the coating method as the first invention of the present invention,
O:\87\87171.DOC 200414940 上塗粉末塗料並進行烘烤固化。在粉末塗料的烘烤固化條 件下的上述粉末塗料的熔融最低黏度在1〇〜2 圍内。 · 在^ °兒明溶融最低黏度。在被塗物上塗佈之粉末塗料 由於烘烤、被塗物溫度上升而慢慢熔融，而且由於溫度上 升黏度逐漸降低。但是，之後，由於固化催化劑的作用， 開始膠凝且最終固&。本發明所謂之炼融最低黏度是指從 由於上述溫度上升而黏度降低到由於膠凝開始而黏度上升 之間出現的最低黏度的值。 因爲熔融最低黏度低KLOh.s時黏度不夠，所以熔融塗 料完全沈在表面缺陷的穴底無法覆蓋缺陷部表面，結果産 生凹面。另外，因爲熔融最低黏度超過2〇 Pa.s時流動性差， 斤乂 "、、法/σ著至屬表面缺陷形狀形成塗膜，結果殘留有凹 面。溶融最低黏度上限值較佳爲L8 · S，下限值較佳爲 1 ·5 Pa · s。決疋上述炼融最低黏度係例如使用社製造 的y y牛7卜〆一夕—MR300般的黏度測定機，可連續地 測定在烘烤固化條件下的黏度變化。熔融最低黏度的具體 測定方法如下所述。 對測定物件的各粉末塗料加壓並球狀化，將該球狀化的 物質夾在測定部，加溫到100。〇。接著，一邊以1(rc/min 的升溫速度上升溫度一邊測定黏度。在丨6〇。〇下使升溫固定 化’測定塗料從增黏到固化的黏度，此時的最低黏度作爲 溶融最低黏度。 作爲上述金屬材料列舉鎂合金、鋁合金、鋅合金等。上 O:\87\87171.DOC -9- 述金屬材料即使有表面缺陷也可以。這 如多以電氣— ~件，例 模鑄件可列舉镇文：了 態使用。作爲上述 杈_件、觸變模成型鎂合金、鋁模鑄件等。 二3粉末塗料的塗佈方式並無特別限定，具體可列 牛 衣法、靜電粉末塗裝法、流動浸潰法等本領域技 術人員衆所周知的方法。但是，纖效率方面考慮= ^使用利用粉末塗裝搶的靜電粉末塗裝法。且，至於上述 粉末塗裝搶，較好使用電暈帶電型塗裝搶或摩擦帶電型塗 裝搶等。 i 猎由上述塗裝在金屬材料上形成的塗膜塗裝爲在供烤後 的膜厚成爲20〜40 _。上述膜厚不足2〇 _時，在有表面 夹的if況下’不此完全隱蔽表面缺陷，另外，超過_ 塗裝則浪費。 上述烘肖固化條件較好為使上述金屬材料的表面溫度在 140〜200 C下保持1〜3〇分鐘。更好下限值爲15〇。〇、上限 值爲170°C。該表面溫度不足14〇。〇日寺，上述炫融最低黏度 難以下降到先前規定的範圍；超過2〇〇。〇時，引起空氣從金 屬表面缺陷部分逸出，有損塗膜的平滑性。另外，上述表 面溫度的保持時間更好下限值爲4分鐘、上限值爲2〇分鐘。 該保持時間不足1分鐘時，上述熔融最低黏度難以下降到先 鈾規疋的範圍，因爲通常熔融的粉末塗料的固化在3 〇分鐘 時結束，所以即使保持溫度比這時間還長，也是能量的浪 費。 本發明之塗裝方法使用的粉末塗料如果滿足在上述烘烤 O:\87\87I71.DOC -10- 200414940 u化條件下的熔融最低黏度的必 ^ _ 文俅仟即可，亚無特別限 定。目前’藉由測定衆所周知的—般粉末塗料在烘烤固化 條件下的諸最低黏度可選定上述粉末塗料。另外，在粉 末塗料的設計中，#由考慮樹脂的玻璃化轉變溫度、或選 擇各成份㈣是固化劑種類或增㈣、及在烘烤固化條件 下組合並分別改變它們的配合量可控制上述熔融最低黏 度0 ^於適於本發明塗裝方法之粉末塗料，可列舉出將含有 環氧基的樹脂和含有羧酸基或羧酸酐的固化劑（以下稱爲 |含有羧酸（酐）基的固化劑，）作爲主成份的物質: 至於上述含有環氧基的樹脂可列舉一分子内含有兩個以 上的環氧基的化合物，具體地說’使用酚醛清漆型苯酚樹 脂和環氧氯丙烷的反應生成物、雙酚樹脂（A型、B型、？型 等）和％氧氣丙烷的反應生成物、酚醛清漆型苯酚樹脂和雙 酚树知（A型、B型、F型等）和環氧氯丙烧的反應生成物、酚 醛清漆型苯酚樹脂和雙酚樹脂（A型、B型、F型等）的反應生 成物、曱酚酚醛等的甲酚化合物和環氧氯丙烷的反應生成 物、乙二醇、丙二醇、丨，4-丁二醇、聚乙二醇、聚丙二醇、 新戊一醇、甘油等醇類化合物和環氧氣丙烧反應而得到的 縮水甘油醚、琥珀酸、己二酸、癸二酸、鄰苯二甲酸、對 苯二曱酸、六氫化鄰苯二甲酸、偏苯三酸等羧酸化合物和 %氧氯丙烷反應而得到的縮水甘油酯、卜氧基苯甲酸、万_ 奈盼酸等經基羧酸和環氧氯丙烷的反應生成物、異氰脲酸 二縮水甘油酯及其衍生物。O: \ 87 \ 87171.DOC 200414940 Apply powder coating and bake and cure. The minimum melting viscosity of the above powder coating under the baking curing conditions of the powder coating is in the range of 10 ~ 2. · Melt the lowest viscosity at ^ °. The powder coating applied to the coated object slowly melts due to baking and the temperature of the coated object, and the viscosity gradually decreases as the temperature increases. However, after that, due to the effect of the curing catalyst, gelation started and eventually solidified. The so-called smelting minimum viscosity in the present invention refers to the value of the lowest viscosity that occurs between the decrease in viscosity due to the above temperature rise and the increase in viscosity due to the start of gelation. Because the viscosity is not enough when the minimum melt viscosity is low KLOh.s, the molten coating completely sinks to the bottom of the surface defect and cannot cover the surface of the defect, resulting in a concave surface. In addition, since the fluidity is poor when the minimum melt viscosity exceeds 20 Pa.s, a coating film is formed due to the shape of the surface defect, resulting in a concave surface. The upper limit of the melting minimum viscosity is preferably L8 · S, and the lower limit is preferably 1 · 5 Pa · s. Decided that the above-mentioned minimum viscosity for melting and melting is, for example, a viscosity measuring machine such as y y yiu 7 yue yue MR300 manufactured by the company, which can continuously measure the viscosity change under baking curing conditions. The specific method for measuring the minimum melt viscosity is as follows. Each powder coating material of the measurement object was pressurized and spheroidized, and the spheroidized substance was sandwiched between the measurement sections and heated to 100 ° C. 〇. Next, the viscosity was measured while increasing the temperature at a temperature increase rate of 1 (rc / min. The temperature was fixed at 60.0 ° C to measure the viscosity of the coating from thickening to curing. The lowest viscosity at this time was taken as the minimum viscosity for melting. Examples of the above-mentioned metal materials include magnesium alloys, aluminum alloys, zinc alloys, etc. The above O: \ 87 \ 87171.DOC -9- metal materials can be used even if there are surface defects. This is mostly the case with electrical components, such as mold castings. List the town text: use it as the state. As the above-mentioned parts, thixotropic mold forming magnesium alloy, aluminum mold casting, etc. The coating method of the powder coating is not particularly limited, and it can be listed in the cow coat method and electrostatic powder coating. Methods, flow dipping methods, and other methods well known to those skilled in the art. However, fiber efficiency considerations = ^ use of electrostatic powder coating method using powder coating. And, as for the powder coating method, it is better to use Corona charged coating or friction charged coating, etc. i The coating film coating formed on the metal material by the above coating is coated to a thickness of 20 to 40 mm after baking. The above film thickness is insufficient 2〇_ at the surface In the case of “if”, the surface defects are not completely hidden, and coating is more than _. The above curing conditions are preferably such that the surface temperature of the metal material is maintained at 140 to 200 C for 1 to 30 minutes. A better lower limit is 15.0, and an upper limit is 170 ° C. The surface temperature is less than 14.0, and the minimum viscosity of the above-mentioned Hyun Rong is difficult to fall to the previously specified range; when it exceeds 20.00 It causes air to escape from the defective part of the metal surface, which impairs the smoothness of the coating film. In addition, the lower limit of the surface temperature holding time is 4 minutes and the upper limit is 20 minutes. The holding time is less than 1 minute. At this time, the above-mentioned melting minimum viscosity is difficult to fall to the range of the pre-uranium gauge plutonium, because the curing of the molten powder coating usually ends at 30 minutes, so even if the temperature is kept longer than this time, it is a waste of energy. If the powder coating used in the packaging method satisfies the minimum melting viscosity required under the above baking conditions of O: \ 87 \ 87I71.DOC -10- 200414940 u ^ 俅 仟 亚, it is not particularly limited. Currently 'borrowed' By test It is well known that the minimum viscosity of the general powder coating under baking curing conditions can be selected from the above powder coatings. In addition, in the design of powder coatings, #by considering the glass transition temperature of the resin, or by selecting each component, it is cured The types of additives or additives, and their combination under baking and curing conditions and changing their blending amounts can control the above-mentioned minimum melt viscosity. 0 ^ Suitable for powder coatings suitable for the coating method of the present invention. Resin and a curing agent containing a carboxylic acid group or a carboxylic acid anhydride (hereinafter referred to as | curing agent containing a carboxylic acid (anhydride) group,) as a main component: As for the above epoxy resin-containing resin, two molecules in one molecule may be listed. More than one epoxy-based compound, specifically using a reaction product of a novolac-type phenol resin and epichlorohydrin, a bisphenol resin (type A, type B,? Type, etc.) and reaction products with% oxygen propane, novolac type phenol resin and bisphenol tree (type A, B, F, etc.) and epichlorohydrin reaction products, novolac type phenol resin and Reaction products of bisphenol resins (types A, B, F, etc.), reaction products of cresol compounds such as resorcinol and epichlorohydrin, ethylene glycol, propylene glycol, and 1,4-butanediol , Glyceryl ether, succinic acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, etc. Glycidyl esters, glycidyl benzoic acid, manganese carboxylic acid and cyclic compounds such as dicarboxylic acid, hexahydrophthalic acid, trimellitic acid and other carboxylic acid compounds reacted with% oxychloropropane A reaction product of oxychloropropane, diglycidyl isocyanurate, and derivatives thereof.
O:\87\87171 DOC -11 - 200414940 另外’也可使用含有環氧基的丙烯酸酯樹脂，例如藉由 常法使丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油能、甲義 丙烯酸2-曱基縮水甘油酯等含有環氧基的單體作爲必需成 份和（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸孓羥丙酯、（甲基） 丙烯酸4-羥丁酯、（甲基）丙烯酸2_羥乙酯和聚己内§旨的加成 物、單（甲基）丙烯酸聚（亞烷基）二醇酯類等含有羥基的單 體、及（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯 酸正-丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸第三-丁酯、 苯乙烯、乙烯基甲苯、p-氯苯乙烯等自由基聚合性單體聚 合的物質。 上述含有環氧基的樹脂也可以兩種以上併用。另外，作 爲上述含有環氧基的樹脂的環氧當量沒有特別限制，較好 爲200〜3000、更好爲300〜2800。當上述環氧當量比2〇〇 小’則貯藏穩定性降低；比3〇〇〇大時，固化性降低。另一 方面，作爲上述含有環氧基的樹脂的數均分子量沒有特別 限制，較好爲200〜10000、更好爲5〇〇〜5〇〇〇。上述數均分 子量比200小時得到的塗膜性能降低，熔融最低黏度也變得 比1 Pa· s小；另一方面，比1〇〇⑼大時，得到的塗膜的平滑 性降低，熔融最低黏度變得比2 Pa.s大。而且，上述含有 環氧基的樹脂的軟化點沒有特別限制，通常較佳爲2〇〜ι〇〇 C、更佳爲50〜lOOt：。上述軟化點比2(rc低時，抗黏連性 降低，另一方面，比1 00°C高時，得到的塗膜平滑性降低。 作爲上述含有幾酸（酐）基的固化劑，可列舉一分子内含有 兩個或兩個以上的羧酸（酐）基化合物及樹脂。具體地能列舉O: \ 87 \ 87171 DOC -11-200414940 In addition, epoxy-based acrylate resins can also be used, for example, glycidyl acrylate, glycidyl methacrylate, 2-fluorenyl methacrylate, etc. Glycidyl ester-containing monomers as essential components, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (methyl ) Adducts of 2-hydroxyethyl acrylate and polycaprolactone, monomers containing hydroxyl groups such as poly (alkyl) glycol mono (meth) acrylates, and methyl (meth) acrylates, Ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, styrene, vinyltoluene, p-chlorostyrene Substances such as radical polymerizable monomers. The said epoxy group containing resin may be used together 2 or more types. The epoxy equivalent of the epoxy-group-containing resin is not particularly limited, but is preferably 200 to 3000, more preferably 300 to 2800. When the above epoxy equivalent is smaller than 2000 ', the storage stability is lowered; when larger than 3000, the curability is lowered. On the other hand, the number-average molecular weight of the epoxy-group-containing resin is not particularly limited, but it is preferably 200 to 10,000, more preferably 500 to 50,000. The performance of the coating film obtained by the above number average molecular weight ratio is lower than 200 hours, and the minimum melt viscosity also becomes smaller than 1 Pa · s. On the other hand, when it is larger than 100⑼, the smoothness of the coating film obtained is reduced and the melting is lowest. The viscosity becomes larger than 2 Pa.s. The softening point of the epoxy group-containing resin is not particularly limited, but it is usually preferably from 20 to 100 ° C, more preferably from 50 to 100 t: When the softening point is lower than 2 (rc), the blocking resistance is lowered. On the other hand, when it is higher than 100 ° C, the smoothness of the obtained coating film is lowered. As the curing agent containing a few acid (anhydride) groups, the List two or more carboxylic acid (anhydride) -based compounds and resins in one molecule. Specific examples include
O:\87\87171.DOC > 12- 200414940 如下：多元竣酸（酐）化合物、含有羧酸（酐）基的丙烯酸g旨樹 脂、含有羧酸（酐）的聚酯樹脂等。可組合多種使用。 另外，作爲上述多元竣酸（酐）化合物可列舉如下：偏苯二 酸、鄰苯二曱酸等芳香族多元羧酸（酐）、咪唑啉二致酸等多 環式多元羧酸（酐）、癸烷二羧酸、癸二酸等脂肪族多元绩 酸。另外，作爲含有竣酸（酐）基的丙烯酸酯樹脂，一分子内 含有兩個或兩個以上的羧酸（酐）基的丙烯酸酯樹脂，例如藉 由常法使丙烯酸、甲基丙烯酸等的含有羧酸（酐）基的單體作 爲必需單體，和（甲基）丙烯酸2-羥乙酯、（甲基）丙稀酸2_經 丙酿、（甲基）丙烯酸4-羥丁酯、（甲基）丙烯酸2_羥乙酯和聚 己内醋的'加成物、單（甲基）丙烯酸聚（亞烷基）二醇酯類等含 有經基的單體、及（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、 (甲基）丙烯酸正-丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸 第二-丁酯、苯乙烯、乙烯基甲苯、p_氯苯乙烯等自由基聚 合性單體聚合的物質。 而且，作爲上述含有緩酸（酐）基的聚酯樹脂可列舉一分子 内含有兩個或兩個以上的羧酸（酐）基的多元羧酸作爲主成 份的酸成份和多元醇作爲主成份的醇成份作爲原料藉由縮 聚反應而得到的物質。作爲上述酸成份可列舉如下：對苯 二甲酸、間苯二甲酸、鄰笨二甲酸及其酸酐、2,6_萘二羧酸、 2,7-萘二羧酸等芳香族二羧酸類及其酸酐、琥珀酸、己二 酸、壬一酸、癸二酸、十二烷二羧酸、丨，4_環己烷二羧酸等 飽和月曰肪知一竣酸及其酸酐、T _ 丁内酯、e ·己内酯等内酯 類、P-氧基乙氧基笨甲酸等芳香族氧基單羧酸類、與其對O: \ 87 \ 87171.DOC > 12- 200414940 are as follows: polybasic acid (anhydride) compounds, acrylic acid g resins containing carboxylic acid (anhydride) groups, polyester resins containing carboxylic acid (anhydride), and the like. Can be used in combination. Examples of the polybasic acid (anhydride) compounds include aromatic polycarboxylic acids (anhydrides) such as trimellitic acid and phthalic acid, and polycyclic polycarboxylic acids (anhydrides) such as imidazoline diacid. , Decanedicarboxylic acid, Sebacic acid and other aliphatic polybasic acids. In addition, as an acrylate resin containing an acid (anhydride) group, an acrylate resin containing two or more carboxylic acid (anhydride) groups in one molecule, for example, the acrylic resin, methacrylic acid, etc. A monomer containing a carboxylic acid (anhydride) group is an essential monomer, and 2-hydroxyethyl (meth) acrylate, 2-methyl (meth) acrylic acid, 2-propanol, 4-hydroxybutyl (meth) acrylate , Adducts of 2-hydroxyethyl (meth) acrylate and polycaprolactone, monomers containing a radical such as poly (alkyl) glycol mono (meth) acrylate, and (meth) ) Methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second-butyl (meth) acrylate, styrene, vinyl toluene, A substance that polymerizes a radical polymerizable monomer such as p-chlorostyrene. In addition, as the polyester resin containing a slow acid (anhydride) group, a polycarboxylic acid containing two or more carboxylic acid (anhydride) groups in one molecule as an acid component and a polyhydric alcohol as a main component can be cited. The alcohol component is obtained by polycondensation reaction as a raw material. Examples of the acid component include the following: aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and its anhydride, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and Its anhydrides, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 4-cyclohexanedicarboxylic acid are saturated saturated fatty acids, their anhydrides, and T_ Lactones such as butyrolactone and e-caprolactone; aromatic oxymonocarboxylic acids such as P-oxyethoxybenzylcarboxylic acid;
O:\87\8717i.DOC -13 - 200414940 應的羥基羧酸等。亦可組合兩種以上使用。 至於上述醇成份可列舉如下：乙二醇、二乙二醇、三乙 二醇、1，2-丙二醇、1，3-丙二醇、1，2-丁 二醇、1，3_丁 二醇、 1，4-丁二醇、it戊二醇、2,3-戊二醇、1，4-戊二醇、匕：戊 二醇、1,4-己二醇、1，5-己二醇、2,5-己二醇、1，4-環己二醇、 1，‘環己二曱醇、雙酚A的亞烷基氧化物加成物、雙盼3的 亞烧基氧化物加成物、新戊二醇、3 -甲基-1，5-戊二醇、2 2 十二烷二醇、1，入十八烷二醇等具有側鏈的脂肪族醇類、三 經甲基丙烷、甘油、季戊四醇等三元以上的多元醇類等。 亦可組合兩種以上。 至於上述含有羧酸（酐）基的固化劑的數均分子量沒有特 別限制，較佳爲100〜10000、更好爲200〜5000。上述數均 分子量比100小時，得到的塗膜性能降低；另一方面，比 1 0000大時，得到的塗膜平滑性降低。 至於上述含有羧酸（酐）基的固化劑的玻璃化轉變溫度從 抗黏連性及所得到的塗膜的平滑性的觀點考慮，較佳爲川 〜100C、更佳爲5G〜1GG°C。另外，本發明的玻璃化轉變 溫度可以根據差示掃描熱量計（DSC)求得，在上述含有魏酸 (酐）基=固化劑4含有竣酸（針）基丙烯酸酯樹脂的情況 下紹之具有構成共聚合物❺已知的玻璃化轉變溫度的單 體比求得。 具有3有上述每氧基的樹脂的環氧基的總量和具有含有 上料酸（酐）基的固化劑的酸基的總量的摩耳比可用和熔 融取低黏度的關係來適當設定，通常爲^O: \ 87 \ 8717i.DOC -13-200414940 corresponding hydroxycarboxylic acids. It is also possible to use a combination of two or more. As for the above-mentioned alcohol components, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, it pentanediol, 2,3-pentanediol, 1,4-pentanediol, dagger: pentanediol, 1,4-hexanediol, 1,5-hexanediol , 2,5-hexanediol, 1,4-cyclohexanediol, 1, 'cyclohexanediol, bisphenol A alkylene oxide adduct, bispan 3 oxyalkylene oxide addition Products, neopentyl glycol, 3-methyl-1,5-pentanediol, 2 2 dodecanediol, 1, octadecanediol, and other aliphatic alcohols with side chains, trimethoprim Trihydric or higher polyhydric alcohols such as propane, glycerin, pentaerythritol and the like. It is also possible to combine two or more kinds. The number average molecular weight of the curing agent containing a carboxylic acid (anhydride) group is not particularly limited, but is preferably 100 to 10,000, more preferably 200 to 5,000. When the number average molecular weight ratio is more than 100 hours, the performance of the obtained coating film is reduced. On the other hand, when it is larger than 10,000, the smoothness of the obtained coating film is reduced. As for the glass transition temperature of the carboxylic acid (anhydride) group-containing curing agent, from the viewpoints of blocking resistance and smoothness of the obtained coating film, it is preferably from Chuan to 100C, more preferably from 5G to 1GG ° C. . In addition, the glass transition temperature of the present invention can be obtained by a differential scanning calorimeter (DSC), and is described in the case where the above-mentioned wei acid (anhydride) group = curing agent 4 contains a citric acid (acid) -based acrylate resin. The ratio of the monomers having a known glass transition temperature constituting the copolymer ❺ was obtained. The molar ratio of the total epoxy group of the resin having 3 per-oxyl group and the total amount of the acid group of the curing agent containing a feeding acid (anhydride) group can be appropriately set by the relationship between melting and low viscosity. , Usually ^
O:\87\87i71.DOC -14- 200414940 佳马。上述環氧基比…小日寺，得到的塗料 ㈣融最士低黏度可能低於……。另外，上述環氧基比丨 〇.5大時’得到的塗料的熔融最低黏度可能高於2 〇p"。 除上述成份以外，根據需要，本發明使用的粉末塗料中 也可以含有表面調整劑、消光劑、增黏劑、著色顏料、防 銹顏料、體質顏料、固化催化劑、可塑劑、顏料分散劑等 添加劑。 ⑪至：上述表面調整劑可列舉··二f基聚矽氧烷、甲苯基 聚石夕氧院等聚石夕氧烧、丙烯酸醋寡聚物等。另外，作爲消 光劑可列舉··各種犧類、下述的各種體質顏 黏劑可列舉:物石、膨潤土等，作爲著色顏料可二曰 —錢鈦、印度紅、氧化鐵、碳黑、酞菁藍、敝菁綠、芝 7監類顏料、喧°丫綱類顏料、偶氮類顏料，作爲防錄顏 诉可列舉：三聚魏_，作爲體質顏料可列舉氧化銘、 滑石、黏土、碳酸鈣、硫酸鋇、二氧化矽等。 而且作爲固化催化劑可使用咪唑類固化催化劑、咪唑啉 等’作爲可塑劑可使用環氧化大豆油等。另外，上述各種 Γ加劑f含量除顏料外、在上述粉末塗料_質量份中較好 :貝里伤α 了。超過i 0質量份時得到的塗膜的平滑性降 低。另外，顏料總含量在上述粉末塗料⑽質量份_較 質量份以下。超過50質量份時塗膜的平滑性降低。，·-、 日本發明使用的粉末塗料的製造方法並無特別限制，可以 是在粉末塗料領域衆所周知的製造方法。示出其中的—例 方法是’將上述原料在亨舍_拌機等中乾式混合後、^O: \ 87 \ 87i71.DOC -14- 200414940 Jiama. The above epoxy group ratio ... Xiaori Temple, the coating viscosity obtained may be lower than ... In addition, when the above epoxy group is larger than 丨 0.5, the obtained coating may have a minimum melting viscosity higher than 200 p ". In addition to the above components, the powder coating used in the present invention may also contain additives such as surface modifiers, matting agents, tackifiers, coloring pigments, rust preventive pigments, extender pigments, curing catalysts, plasticizers, pigment dispersants, etc. . ⑪ to: Examples of the surface conditioner include: bis-based polysiloxanes, tolyl-based polysiloxanes, etc., polyacrylamide, acrylic oligomers, and the like. In addition, examples of matting agents include various sacrifices, and the following constitutional adhesives include minerals, bentonite, and the like. As a coloring pigment, titanium oxide, Indian red, iron oxide, carbon black, and phthalate can be mentioned. Cyan blue, cyanine green, Zhizhi 7 kinds of pigments, noisy pigments, and azo pigments can be listed as anti-recording appeals: Trimeric Wei_, as physical pigments can be oxidized Ming, talc, clay, Calcium carbonate, barium sulfate, silicon dioxide, etc. As the curing catalyst, an imidazole curing catalyst, imidazoline, etc. can be used. As the plasticizer, an epoxidized soybean oil or the like can be used. In addition, the content of the various Γ adjuvants f, in addition to pigments, is better in the above powder coatings_mass parts: Bailey α. When the content exceeds i 0 parts by mass, the smoothness of the coating film decreases. In addition, the total pigment content is less than or equal to the mass fraction of the powder coating. When it exceeds 50 mass parts, the smoothness of a coating film will fall. The production method of the powder coating used in the Japanese invention is not particularly limited, and may be a manufacturing method well-known in the field of powder coating. An example is shown. The method is to ‘dry mix the above ingredients in a hensher_mixer, etc. ^
0\87\87i7l.DOC -15- 捏和擠壓機等中、含右f 化射u虛 脂和含有㈣（軒）基的固 以不反應的溫度下㈣混煉、冷卻後粉碎分級的方、去。 本發明❹的粉末塗料㈣積平均粒㈣無制， 從塗裝操作性及得到的塗膜平滑性等觀點考慮，較佳^〜 5一。特別是在具有表面缺陷的金屬材料中，粉料 體積平均粒徑較佳爲5〜25陴。藉由成爲這樣小的粒徑，粉 末：融流動化，該熔融物進入上述缺陷部，結果更進—步 提门了塗膜的平滑性。更佳粒徑爲5 _以下的顆粒的含量 爲25重量％以下。因爲更進—步提高了平滑性。 _本U中’因爲和樹脂框體用行動電話的外觀設計吻 5所以使用有機溶劑型的熱塑性丙稀酸酉旨樹脂塗料。 本發明使用的有機溶劑型熱塑性丙烯酸S旨樹脂中含有的 熱塑性丙烯酸類樹脂，是使用偶氮類或過氧化物類的聚合 引Ιχ Θ]並利用衆所周知的方法使（甲基）丙烯酸酯類單體和 苯乙烯類單體、含有經基的單體、含有缓基的單體及其它 單體藉由水合所得到的物質。此熱塑性丙烯酸類樹脂也可 以兩種以上併用。 在此，苯乙烯類單體可列舉如苯乙烯' 0：_甲基苯乙烯、 乙烯基、第三·丁基苯乙烯、對氯苯乙稀及乙烯基蔡。 (甲基）丙烯酸酯類單體可列舉··丙烯酸甲酯、甲基丙烯酸 甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正-丁酯、甲 基丙烯酸正-丁酯、丙烯酸異丁酯、丙烯酸第三-丁酯、丙烯 酸2-乙基己g旨、甲基丙烯酸2_乙基己酯、τ基丙烯酸月桂 S旨、丙烯酸苯酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、0 \ 87 \ 87i7l.DOC -15- Kneading and extruding machines, including right and left, and acetic acid, and fluorene (xanthyl) group are mixed at a non-reactive temperature, mixed, cooled and crushed and classified. Party, go. The powder average particle size of the powder coating of the present invention is not prepared. From the viewpoints of coating operability and smoothness of the obtained coating film, it is preferably ^ ~ 51. Especially in a metal material having surface defects, the volume average particle diameter of the powder is preferably 5 to 25 陴. By having such a small particle diameter, the powder melts and flows, and the molten material enters the above-mentioned defective portion, and as a result, the smoothness of the coating film is further improved. A more preferable content of particles having a particle size of 5 mm or less is 25% by weight or less. Because it goes a step further-it improves smoothness. _In this U ’, because it is compatible with the appearance design of the mobile phone for the resin frame, an organic solvent-based thermoplastic acrylic resin coating is used. The thermoplastic acrylic resin contained in the organic solvent-based thermoplastic acrylic S resin used in the present invention is an azo or peroxide-based polymer (1 × Θ), and a (meth) acrylate is made by a well-known method. Monomers and styrenic monomers, monomers containing warp groups, monomers containing retarder groups, and other monomers are obtained by hydration. These thermoplastic acrylic resins may be used in combination of two or more. Here, examples of the styrene-based monomer include styrene '0: -methylstyrene, vinyl, tertiary-butylstyrene, p-chlorostyrene, and vinylene. Examples of (meth) acrylic monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and isobutyl acrylate. Ester, tertiary-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl succinate tau, phenyl acrylate, isobornyl acrylate, isobornyl methacrylate ,
O:\87\87171.DOC -16- 200414940 甲基丙烯酸環己酯、丙烯酸第三-丁基環己酯、甲基丙烯酸 第二-丁基1衣己酯、丙烯酸二環戊二烯酯、甲基丙烯酸二環 戊二烯酯、丙烯酸二氫化二環戊二烯酯及甲基丙烯酸二氫 化二環戊二浠酯。 含有羥基的單體可列舉··丙烯酸2-羥基乙酯、甲基丙烯 酸2-羥基乙酯、丙烯酸孓羥基丙酯、甲基丙烯酸2_羥基丙 酯、丙烯酸4-羥基丁酯。 作爲含有羧基的單體可列舉：丙烯酸、甲基丙烯酸、巴 五酸、異巴丑酸、丙烯酸二聚物。作爲其他的單體可列舉： 聚合性醯胺（例如丙烯醯胺、甲基丙烯醯胺、N_羥甲基曱基 丙烯醯胺及N-曱氧基甲基丙烯醯胺等）、聚合性腈（例如丙 浠腈、甲基丙烯腈專）、乙烯鹵化物（例如氯化乙烯、溴化乙 烯、氟化乙烯等）、α _烯烴（例如乙烯、丙烯等）、乙烯酯（例 如乙酸乙烯酯、丙酸乙烯酯等）及二烯（例如丁二烯、異戊二 烯等）。 另一方面，作爲偶氮類的聚合引發劑列舉如下··偶氮雙 異丁腈、2,2’-偶氮雙（2-曱基丁腈）及2,2，-偶氮雙（2,4-二曱基 戊腈）。另外，作爲過氧化物類的聚合引發劑列舉如下：苯 曱fe過氧化物、雙氣苯曱醯過氧化物、月桂基過氧化物及 第三-丁基過苯甲酸酯。 熱塑性丙烯酸類樹脂的重量平均分子量爲5〇,〇〇〇以上， 特佳爲50,000〜100,000。重量平均分子量不足5〇,〇〇〇時， 得到的塗膜耐水性降低。具體地說，該塗膜浸入水中時， 該塗膜容易從底塗膜或舊塗膜上剝離下來，另外，塗膜白 O:\87\87171.DOC -17- 200414940 化或谷易、纟但小或膨服。另一方面，击b 垔：s平均分子|却 1〇〇,〇〇〇時，黏度變高，該塗料的塗裝操作性降低。1 熱塑性丙烯酸類樹脂的玻璃化轉變溫度較佳爲60。^、 下。玻璃化轉變溫度超過60t:時， 以 丁 土肤的彷者性變得不 为，具體地說，該塗膜容易從該底泠 ^ 4辰塗層的粉末塗膜上剝離 下來。另夕卜，此處的玻璃化轉變溫度由製造熱塑性 樹脂時使料單體的时玻璃化轉變師 I、 權平均求得。 此糟由加 本發明使用的溶劑型熱塑性丙烯_樹脂塗料除上述必 需成份以外，含有顏料，也可以含有其他有機溶劑類樹脂、 各種添加劑、溶劑等。至於顏料可使用在塗料領域内通常 使用的物質’例如使用紹膏、珍珠雲母粉、石墨、雲母狀 氧化鐵溱青片、碳黑、鈦白、溱菁藍等鋁顏料或著色顏 .料等。 〜 另外，作爲有機溶劑類樹脂可列舉醇酸樹脂、聚酯樹脂、 %氧树月曰、蜜胺樹脂、含有甲矽烷基的樹脂、纖維素乙酸 、-曰文〖生丙稀酸醋樹脂、石肖基纖維素改性丙烯酸酯樹脂 、 疋此有機〉谷劑類樹脂較好使用和上述的熱塑性丙 烯酸類樹脂具有相溶性的物質。使用沒有相溶性的有機溶 ^犬員树脂時’熱塑性丙烯酸酯樹脂塗料的穩定性降低，其 、、。果唯，忍该塗料發生返粗，該塗料所形成的塗膜中引起變 色等’有損於塗膜外觀。O: \ 87 \ 87171.DOC -16- 200414940 cyclohexyl methacrylate, third-butyl cyclohexyl acrylate, second-butyl 1-hexyl methacrylate, dicyclopentadiene acrylate, Dicyclopentadiene methacrylate, dicyclopentadiene acrylate and dicyclopentadienyl methacrylate. Examples of the hydroxyl-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl acrylate. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, pentaconic acid, isoparic acid, and acrylic acid dimer. Examples of other monomers include polymerizable amidines (for example, acrylamide, methacrylamide, N-methylol amidyl acrylamide, and N-acetoxymethacrylamide), and polymerizability. Nitriles (such as propionitrile, methacrylonitrile), ethylene halides (such as ethylene chloride, ethylene bromide, fluorinated ethylene, etc.), alpha olefins (such as ethylene, propylene, etc.), vinyl esters (such as vinyl acetate Esters, vinyl propionate, etc.) and dienes (such as butadiene, isoprene, etc.). On the other hand, examples of the azo-based polymerization initiator include azobisisobutyronitrile, 2,2'-azobis (2-fluorenylbutyronitrile), and 2,2, -azobis (2 , 4-Difluorenylvaleronitrile). Examples of the peroxide-based polymerization initiator include benzenefluorene peroxide, digas benzenefluorene peroxide, lauryl peroxide, and tert-butylperbenzoate. The thermoplastic acrylic resin has a weight average molecular weight of 50,000 or more, and particularly preferably 50,000 to 100,000. When the weight average molecular weight is less than 50,000, the water resistance of the obtained coating film is reduced. Specifically, when the coating film is immersed in water, the coating film is easily peeled off from the base coating film or the old coating film. In addition, the coating film is white O: \ 87 \ 87171.DOC -17- 200414940 But small or inflated. On the other hand, when b 垔: s average molecular | is 100, 000, the viscosity becomes high, and the coating workability of the coating material decreases. 1 The glass transition temperature of the thermoplastic acrylic resin is preferably 60. ^, Next. When the glass transition temperature exceeds 60 t :, the imitative nature of butyl clay becomes ineffective. Specifically, the coating film is easily peeled from the powder coating film of the base coating. In addition, the glass transition temperature here is obtained from the glass transition division I and the weight average of the monomers used in the manufacture of the thermoplastic resin. The problem is that the solvent-borne thermoplastic propylene-resin coating used in the present invention contains pigments in addition to the above-mentioned essential components, and may also contain other organic solvent-based resins, various additives, solvents, and the like. As for the pigment, substances commonly used in the field of coatings can be used, such as using aluminum pastes such as paste, pearl mica powder, graphite, mica-like iron oxide cyanine flakes, carbon black, titanium white, and cyanine blue, or colored pigments. . ~ In addition, examples of the organic solvent-based resin include alkyd resin, polyester resin,% oxo resin, melamine resin, silyl-containing resin, cellulose acetic acid, It is preferable to use a substance having a compatibility with the above-mentioned thermoplastic acrylic resin. When using organic solvents that are not compatible, the stability of the thermoplastic acrylate resin coating is reduced, which is. As a matter of course, the paint is tolerant to coarsening, and the discoloration or the like caused in the coating film formed by the coating is detrimental to the appearance of the coating film.
σ » I 作爲各種添加劑可列舉表面調整劑、紫外線吸收 ^4呂顏料防沈降劑、流體控制劑等。另外，溶劑可使用σ »I Examples of the various additives include surface modifiers, ultraviolet absorbers, pigment anti-settling agents, and fluid control agents. Alternatively, solvents can be used
O:\87\8717l DOC -18- 200414940 甲苯、二甲苯、乙酸乙、 醇等 乙馱丁酉曰、甲基異丁基酮、丁 、乍A k料用通常使用的物質。 笨 '上述顏料、有機溶劑類樹脂、各種添加劑及溶劑 可以兩種類或兩種類以上併用。 有機溶劑型的熱塑性丙烯酸醋樹脂塗料在上述粉末塗料 处上較好塗裝乾燥膜厚3〜2〇μιη。塗裝方法沒有特別限制， :用衆所周知的喷塗塗敷、浸潰塗敷等塗裝方法。另外， :裝後的乾燥較好在3〇〜8(rc、更好在％〜赃、及帅 鐘〜1〇分鐘、更好3〇秒鐘〜3分鐘的條件下進行強制乾燥。 ^燥膜厚比3幽’會受底層色相影響。另外，乾燥膜 厚比20 μηα厚時’被塗物的微小圖案（凹凸）變得不顯著或完 全消失。 本發明使用的活性能量線固化劑透明塗料，用活性能量 線固化以規定的針入度而得到的塗膜，樹脂成份沒有特別 的限制’能使用無溶劑型、水性或有機溶劑型的自由基固 化型反應性組合物、陽離子固化劑型反應組合物及併用固 化型反應性組合物。 在此，作爲活性能量線列舉紫外線、電子線等，其中， 因紫外線具有照射的方便性而較佳。 在此，所謂針入度是指用鑽石針以一定的負荷、一定的 速度刺入固化塗膜，塗膜被破壞時刻的數值。通常，該數 值可以爲200〜400。 作爲上述自由基固化型反應性組合物，列舉具有（甲基） 丙烯酸酯基、烯丙基等自由基聚合性反應基的含有自由基 O:\87\8717l.DOC -19- 200414940 聚合性化合物的物質μ乍爲自由基聚合性化合物的具體 例，列舉下述一或一種以上的混合物。 ⑴3皂基或％氧基之聚酯樹脂、聚碳酸酯、環氧樹脂、 胺基甲酸㈣脂 '丙稀酸酉旨樹脂等以之含（甲基）丙稀酸等酸 的單體改性之含有自由基聚合性不飽和基之樹脂。 (2) 用（甲基）丙烯酸縮纟甘油、（甲基）丙稀基縮水甘油鍵 等3有細水甘油基的單體使含有羧基的聚酯樹脂、聚碳酸 醋樹脂、環氧樹脂、胺基甲酸酯樹脂、丙烯酸酯樹脂等改 i*生之§有自由基聚合性不飽和基之樹脂。 (3) 由（曱基）丙烯酸2-羥酯、（曱基）丙烯酸縮水甘油酯、二 丙烯酸二甲基丙酯、三丙烯酸季戊四醇酯等含有羥基的丙 烯酸酯單體與六甲撐二異氰酸酯、苯二甲基二異氰酸g旨、 甲苯一異氰酸酯等異氰酸酯單體以及視需要之乙二醇、丙 二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇等多元 醇、或含有兩個以上羥基的聚酯樹脂、聚碳酸酯樹脂、環 氧树月曰、胺基曱酸酯樹脂、丙烯酸酯樹脂等多元醇樹脂所 得到的胺基曱酸酯丙稀酸酯樹脂。 (4) (甲基）丙烯酸乙二醇酯、二（曱基）丙烯酸乙二醇酯、單 (甲基）丙烯酸1，6-己二醇酯、二（甲基）丙烯酸it己二醇 醋、二（曱基）丙烯酸三曱基丙酯、三（曱基）丙烯酸三曱基丙 酯、三（曱基）丙烯酸季戊四醇酯、四（曱基）丙烯酸季戊四醇 酯、五（曱基）丙烯酸季戊四醇酯、五（曱基）丙烯酸二季戊四 醇酯、六（曱基）丙烯酸二季戊四醇酯等自由基聚合性單體 類0 O:\87\87171.DOC -20- 200414940 其中，胺基甲酸酯丙烯酸酯樹脂，因爲具有高的紫外線 固化性並可以得到規定的塗膜進入度而特佳。 至於上述陽離子固化型反應性組合物，列舉包含具有環 氧基、氧雜環丁烷基、乙烯基等之陽離子聚合性反應基的 陽離子聚合性化合物。至於陽離子聚合性化合物的具體 例’列舉如下一種或一種以上的混合物。 (1)使雙酚A、B、F或聚亞烷基二醇和環氧氯丙烷反應而 得到的含有縮水甘油基的環氧樹脂。 ⑺將苯乙烯·丁二烯共聚樹脂、苯乙烯·異戊二稀共聚 树月曰、聚丁二烯樹脂、不飽和聚酯樹脂等含有不飽和基的 樹脂進行環氧化而得到的環氧化樹脂。 (3) 使用衆所周知的聚合引發劑使（甲基）丙烯酸（甲基乂缩 水甘油酯、賽克羅馬M100(Daicel化學公司製、具有脂環式 環氧基的甲基丙烯酸酯）、賽克羅馬A2〇〇(DaiceHt學公司 製、具有脂環式環氧基的丙烯酸酯）等和（甲基）丙烯酸甲 酉旨甲基）丙烯酸乙酉旨、（甲基）丙_丙酉旨等（甲基）丙稀酸 酯皁體、苯乙烯、乙烯基甲苯等芳香族單體、乙酸乙烯酯、 丙酸乙烯S旨等乙稀基單體等進行聚合而得到的含有環氧基 的丙烯酸醋樹脂。 (4) 魏酸3,4-環氧基環己基曱基-3,‘環氧基環己酯、雙 气3,4-環己基）己二酸酯等脂環式環氧化合物。 (5) 3-乙基-3-羥曱基氧雜環丁烷、仏雙〔(3_乙基_3_氧雜 環丁烧基甲氧基）曱基〕笨等含有氧雜環丁烧基的化合物。 ⑹正-丁基乙烯醚、環己烷二甲醇二乙烯醚、三羥甲基丙 O:\87\87171.DOC -21 · 200414940 烷三乙烯醚等含有乙烯基的化合物。 至於併用固化型反應性組合物，可列舉上述自由基聚人 性化合物、推混有陽離子聚合性化合物者、或者分子中同 時具有（甲基）丙婦酸酯基、稀丙基等自由基聚合性反應基與 環氧基、氧雜環丁烷基等陽離子聚合性反應基的剛敍述的 赛克羅馬Ml 〇〇、賽克羅馬A2〇〇、烯丙基縮水甘油醚等。在 併用固化型反應組合物的情況下，因爲配合含有氮原子的 胺基甲酸酯丙烯酸酯樹脂等時使固化性降低而不佳。 在利用活性能量線照射使之固化的情況下，自由基固化 型反應性組合物、併用固化型反應性組合物中可配合苯偶 姻甲基醚、苯偶姻丙基醚、苯偶醯、苄基二甲基酮縮醇、 苯甲酸基環己醇等光自由基聚合引發劑的一種或一種以 上。陽離子固化型反應性組合物、併用固化型反應組合物 中可配合三苯基銃六氟磷酸鹽、三苯基銃六氟銻酸鹽、 2,4,6-二甲基苯基二苯基錡甲基苯磺酸鹽等光陽離子聚 合引發劑的一種或一種以上。 本發明使用的活性能量線固化型透明塗料中，亦可配合 熱塑性樹脂、有機溶劑、碳、氧化鈦、珍珠顏料等著色劑、 用於防止塗料起泡、改良塗裝操作、防止靜電、防止破壞 的聚石夕氧類、氟類、丙烯酸醋樹脂類的各種添力口劑。但是， 因爲會使紫外線固化性降低之陽離子固化型反應性組合 物’併用固化型反應性組合物中較好不配合顯示驗性的材 料。 活性能量線固化型透明塗膜是藉由衆所周知的喷塗O: \ 87 \ 8717l DOC -18- 200414940 Toluene, xylene, ethyl acetate, alcohol, etc. Acetylbutadiene, methyl isobutyl ketone, butyl, and zinc are commonly used materials. The above pigments, organic solvent-based resins, various additives and solvents may be used in combination of two or more types. The organic solvent type thermoplastic acrylic resin coating is preferably coated with a dry film thickness of 3 to 20 μm on the powder coating. The coating method is not particularly limited, and a coating method such as well-known spray coating, dip coating, or the like is used. In addition, it is preferable to perform forced drying under the conditions of 30 ~ 8 (rc, more preferably% ~~, and handsome bell ~ 10 minutes, more preferably 30 seconds ~ 3 minutes). The film thickness ratio of 3 'is affected by the underlying hue. In addition, when the dry film thickness is greater than 20 μηα, the minute pattern (concavity and convexity) of the object to be coated becomes inconspicuous or completely disappears. The active energy ray curing agent used in the present invention is transparent Coatings, coatings obtained by curing with active energy ray at a predetermined penetration, and resin components are not particularly limited. 'Free-agent, water-based, or organic solvent-based radical-curable reactive compositions and cationic curing agents can be used. Reaction composition and combined curing type reactive composition. Here, examples of active energy rays include ultraviolet rays, electron rays, and the like. Among them, ultraviolet rays are convenient because of the convenience of irradiation. Here, the penetration refers to the use of diamonds. The value at which the needle penetrates the cured coating film at a constant load and speed, and the coating film is broken. Usually, this value can be 200 to 400. Examples of the above-mentioned radical-curable reactive composition include Radical-containing O: \ 87 \ 8717l.DOC with free-radically polymerizable reactive groups such as (meth) acrylate, allyl, etc. Substances of polymerizable compounds μ are specific examples of radical polymerizable compounds Examples include one or more of the following mixtures: 皂 3 soap-based or% oxy-based polyester resins, polycarbonates, epoxy resins, urethane resins, acrylic resins, etc. (a A radically polymerizable unsaturated resin containing a monomer modified with an acid such as acrylic acid. (2) Glycidyl (meth) acrylate, (glycidyl) glycidyl bond, etc. Glycerol-based monomers make carboxyl-containing polyester resins, polycarbonate resins, epoxy resins, urethane resins, acrylate resins, etc. free radical polymerizable unsaturated groups. (3) It consists of hydroxy-containing acrylate monomers such as 2-hydroxy (meth) acrylate, glycidyl (meth) acrylate, dimethylpropyl diacrylate, pentaerythritol triacrylate, and hexamethylene diisocyanate. , Xylylene diisocyanate g, toluene one Isocyanate monomers such as cyanate esters, as well as polyols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol, or polyester resins and polycarbonates containing two or more hydroxyl groups Polyurethane resins such as resins, epoxy resins, amino resins, and acrylate resins. (4) Glycol (meth) acrylate, two (Fluorenyl) ethylene glycol acrylate, 1,6-hexanediol mono (meth) acrylate, hexanediol di (meth) acrylate, trimethylpropyl propyl (fluorenyl) acrylate, (Fluorenyl) trimethylpropyl acrylate, pentaerythritol tri (fluorenyl) acrylate, pentaerythritol tetrakis (pentyl) acrylate, pentaerythritol penta (pentyl) acrylate, dipentaerythritol penta (fluorenyl) acrylate, hexa ( (Fluorenyl) radically polymerizable monomers such as dipentaerythritol acrylate 0 O: \ 87 \ 87171.DOC -20- 200414940 Among them, the urethane acrylate resin has high ultraviolet curability and can be regulated Excellent film penetrationExamples of the cation-curable reactive composition include a cationically polymerizable compound containing a cationically polymerizable reactive group having an epoxy group, an oxetanyl group, a vinyl group, or the like. Specific examples of the cationically polymerizable compound include one or more of the following mixtures. (1) A glycidyl group-containing epoxy resin obtained by reacting bisphenol A, B, F or polyalkylene glycol with epichlorohydrin.的 An epoxidized resin obtained by epoxidizing a resin containing unsaturated groups such as styrene-butadiene copolymer resin, styrene-isoprene copolymer tree, polybutadiene resin, unsaturated polyester resin, etc. . (3) Using a well-known polymerization initiator, (meth) acrylic acid (methyglycidyl glycidyl ester, Sycromax M100 (a methacrylic acid ester having an alicyclic epoxy group manufactured by Daicel Chemical Co., Ltd.), Croma A200 (DaiceHt Scientific Co., acrylate having alicyclic epoxy group), etc. and (meth) acrylic acid methyl ester) acrylic acid ethyl ester, (meth) propane-propyl alcohol ester, etc. ( Epoxy group-containing acrylic vinegar obtained by polymerization of methyl) acrylic acid soap body, aromatic monomers such as styrene and vinyltoluene, vinyl monomers, and vinyl monomers such as vinyl propionate. Resin. (4) Alicyclic epoxy compounds such as 3,4-epoxycyclohexylfluorenyl-3, 'epoxycyclohexyl, digas 3,4-cyclohexyl) adipate. (5) 3-ethyl-3-hydroxyfluorenyloxetane, bis ([3-ethyl_3_oxetanylmethoxy) fluorenyl] oxetane, etc. Burnt-based compounds. ⑹N-butyl vinyl ether, cyclohexanedimethanol divinyl ether, trimethylol propane O: \ 87 \ 87171.DOC -21 · 200414940 alkyl trivinyl ether and other compounds containing vinyl groups. Examples of the curable reactive composition used in combination include the above-mentioned radically polymerizable human compounds, those mixed with a cationic polymerizable compound, or those having both (meth) propanoate groups and dilute propyl groups in the molecule. The reactive groups and cationically polymerizable reactive groups such as epoxy groups and oxetanyl groups have been described with Sycromone M100, Sycromone A200, allyl glycidyl ether, and the like. When a curable reaction composition is used in combination, the curing properties are lowered when a urethane acrylate resin containing a nitrogen atom is blended. In the case of curing by active energy ray irradiation, benzoin methyl ether, benzoin propyl ether, benzoin, One or more photoradical polymerization initiators such as benzyl dimethyl ketal and benzoate cyclohexanol. A cation-curable reactive composition and a combined curing-type reaction composition may contain triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-dimethylphenyldiphenyl. One or more photocationic polymerization initiators such as fluorene methylbenzenesulfonate. In the active energy ray-curable transparent paint used in the present invention, colorants such as thermoplastic resins, organic solvents, carbon, titanium oxide, and pearl pigments can also be added to prevent paint foaming, improve coating operations, prevent static electricity, and prevent damage Polysilicone Oxygen, Fluorine, Acrylic Resin-based additives. However, it is preferable not to mix a material exhibiting a test property with a combination of the cation-curable reactive composition ' and the curable reactive composition that reduce ultraviolet curability. Active energy ray-curable transparent coating film
O:\87\8717l.DOC -22- 200414940 敷、次潰塗敷等在上述熱塑性丙烯酸酯樹脂塗膜上形成 的σ亥塗膜的熱軟化溫度較好爲45〜65 °C。熱軟化溫度比 45 C低時，塗膜的機械強度降低且耐擦傷性出現障礙，另 一方面，超過65 °C時，塗膜沒有可撓性且耐衝擊性降低。 另外，此處所說的熱軟化溫度是藉由以下測定法（熱機械分 析，Thermal Mechanical Anaiysis)測定者。亦即，測定設備 可使用精工儀器公司製的TMA12〇cu、依據i 的石英 探針用針入法測定。石英探針的負荷爲1〇〇克，一邊以5它 /min的升溫速度使被測定體（活性能量線固化型透明塗膜） 升溫至-25°C〜125t： —邊實施測定。 另外，膜厚較好爲3〜20 μχη。膜厚比3 μχη薄時，造膜性 變得不充分，不能完全覆蓋從上述熱塑性丙烯酸酯塗膜面 突出的光亮性顏料，無法出現良好的外觀效果。另外，超 過20 μιη時，對例如行動電話的按鈕孔尺寸有影響等，被塗 物的微小圖案變得不明顯或完全消失。 在活性能量線固化型透明塗膜的固化中，特別是使用υν 固化型透明塗料時’作爲該紫外線源，可以使用低壓水銀 燈、咼壓水銀燈、i化金屬燈、無電極放電燈、氙氣燈' 激悲原子燈等。1外線的照射量較好爲200〜丨5⑼mj/ cm2。UV固化型透明塗料中配合有機溶劑或水時，希望塗 佈後在30〜8〇°C、較好在30〜6(rc的溫風下乾燥1〇秒鐘 1 0分鐘，使有機溶劑或水蒸發後照射紫外線。 本發明的第二發明係有關金屬-塑膠複合材料的塗裝方 法。即，依據此複合材料的塗裝方法，可使用“與 O:\87\87171.DOC >23 - 200414940 ABS樹脂或聚碳酸醋草 、土勝材料組合的金屬-塑膠複合材 1 :即，在上述金屬材料上，以上述粉末塗料形成固化 』後’使形成有該粉末塗膜的金屬材料和未塗裝的塑膠 材料組合’製造行動雷每+轉 ^ . σ 肢、α車車身等金屬-塑膠複合 在該複合材料的表面上’依次形成上述溶劑型埶塑 性丙婦酸酯樹脂塗料的乾燥膜厚及上述活性能量線固化型 2塗膜’進行本發明的第二發明的塗裝方法，藉由該方 法也可以製造塗裝物。 八另外’作爲本發明第一發明的塗裝方法的變形，有完全 分開塗裝金屬材料和塑膠材料、之後使之組合形成的方 法。即，利用本發明的塗裝方法、以粉末塗料、溶劑型熱 塑性丙烯酸酉旨樹脂塗料及活性能量線透明塗料的順序對金 屬=料進行塗裝、另外利用和上述金屬材料令使用的同樣 的&劑型熱塑性丙烯酸s旨樹脂塗料及活性能量線透明塗 料、以該順序對塑勝進行塗裝、使依此分別得到的經塗裝 金屬材料及塑膠材料組合而得到複合材料的塗裝物之二 法0 如果用上述兩種方法製造本發明的金屬-塑膠複合材料 構成的塗裝物，就能將金屬部分的塗裝膜和 裝膜製成爲近乎相同色相外觀。 “的- 〔實施例〕 以下，藉由實施例及比較例詳細敍述本發明。另外，各 例的配合中，‘份，或‘％，分別表示‘質量份，、‘質量。/。，。 〔粉末塗料的合成〕O: \ 87 \ 8717l.DOC -22- 200414940 The thermal softening temperature of the σ-sea coating film formed on the above thermoplastic acrylate resin coating film such as coating, sub-coating, etc. is preferably 45 to 65 ° C. When the heat softening temperature is lower than 45 C, the mechanical strength of the coating film is reduced and scratch resistance is impaired. On the other hand, when it exceeds 65 ° C, the coating film is not flexible and the impact resistance is reduced. The thermal softening temperature referred to here is measured by the following measurement method (Thermal Mechanical Anaiysis). In other words, the measurement device can be measured by a needle-in method using a TMA12〇cu manufactured by Seiko Instruments Inc. and a quartz probe according to i. The load of the quartz probe was 100 g, and the temperature of the test object (active energy ray-curable transparent coating film) was raised to -25 ° C to 125t at a temperature increase rate of 5 it / min:-The measurement was performed. The film thickness is preferably 3 to 20 μχη. When the film thickness is thinner than 3 μχη, the film-forming property becomes insufficient, and the bright pigment protruding from the surface of the thermoplastic acrylate coating film cannot be completely covered, and a good appearance effect cannot be obtained. In addition, if it exceeds 20 μm, for example, the size of the button hole of a mobile phone is affected, and the minute pattern of the coating becomes inconspicuous or completely disappears. In the curing of the active energy ray-curable transparent coating film, especially when the νν-curable transparent coating is used, as the ultraviolet source, a low-pressure mercury lamp, a high-pressure mercury lamp, a metallized metal lamp, an electrodeless discharge lamp, and a xenon lamp can be used. Agitated atomic lamp and so on. 1 The irradiation amount of the outside line is preferably 200 to 5⑼mj / cm2. When an organic solvent or water is added to the UV-curable transparent coating material, it is desirable to dry the organic solvent or water at 30 to 80 ° C, preferably 30 to 6 (rc) for 10 seconds and 10 minutes after coating. After the evaporation, it is irradiated with ultraviolet rays. The second invention of the present invention relates to a coating method of a metal-plastic composite material. That is, according to the coating method of the composite material, "and O: \ 87 \ 87171.DOC > 23- 200414940 Metal-plastic composite material 1 combining ABS resin or polycarbonate grass and soil win material: That is, on the above-mentioned metal material, the above-mentioned powder coating is formed and cured, and the metal material and the metal material on which the powder coating film is formed are formed. The coated plastic material combination 'manufactured action thunder + turn ^. Σ metal-plastic composites such as limbs and α car bodies on the surface of the composite material' in order to form a dry film of the above-mentioned solvent-based plastic plastic methacrylate resin coating The above-mentioned active energy ray-curable type 2 coating film is used to perform the coating method of the second invention of the present invention, and by this method, it is also possible to produce a coating object. In addition, as a modification of the coating method of the first invention of the present invention , Have full points A method of coating a metal material and a plastic material, and then combining them. That is, using the coating method of the present invention, powder coating, solvent-based thermoplastic acrylic resin coating, and active energy ray transparent coating are sequentially applied to the metal material. Painting, using the same & dosage form of thermoplastic acrylic resin resin coating and active energy ray transparent coating as those used for the above-mentioned metal materials, coating plastic coatings in this order, and applying the resulting coatings separately The second method to obtain a composite coating material by combining a metal material and a plastic material. 0 If the coating material composed of the metal-plastic composite material of the present invention is manufactured by the above two methods, the coating film and coating of the metal portion can be applied. The films were made to have nearly the same hue appearance. "-[Examples] Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples. In addition, in the blending of each example," parts "or"% "means" parts by mass, " "'Quality.' [Synthesis of Powder Coatings]
0A87\87171.DOC -24- 200414940 <合成例>0A87 \ 87171.DOC -24- 200414940 < Synthesis example >
由艾坡脫特NTm(環氧當量475的環氧樹月旨、東都化成公 司製）33份、艾坡脫特NT112(環氧當量MO的環氧樹脂、東 都化成公司製）33份、固化催化劑（咪唑）〇〇5份、表面調整 劑2.5份、消光齊⑴分、白色顏料（二氧化鈦）2q份、體質㈣ (氧化鋁及二氧化矽)10份及作爲固化劑的味唑啉的酸酐化 合物4」份構成的原料在㈣機（日本思賓達_製造公司製） 内混合約3分鐘，藉由捏和擠壓機（布斯社製），在約i〇〇〇c的 條件下進行溶融混煉。 將所得到的溶融混煉物冷卻到室溫，粗粉碎後，用微却 粉碎機（”噴射細S_2型"、日本紐馬奇克社製）粉碎後，^ 300目的篩分級，得到體積平均粒徑爲18㈣的粉末塗料 另外體積平均粒控的測定是使用微跡hra χ·⑽（日機裝 社製）。 〔對鎂合金的塗裝〕 <實施例1 >33 parts of Epotere NTm (epoxy equivalent of 475 epoxy equivalent, manufactured by Totsu Kasei Co., Ltd.), 33 parts of Epotete NT112 (epoxy equivalent of epoxy equivalent MO, manufactured by Todo Chemical Co., Ltd.), cured 005 parts of catalyst (imidazole), 2.5 parts of surface conditioner, extinction content, 2q parts of white pigment (titanium dioxide), 10 parts of physique (alumina and silica), and acid anhydride of oxazoline as a curing agent The raw material consisting of 4 "parts of the compound was mixed for about 3 minutes in a kiln (manufactured by Japan Spinner Co., Ltd.), and was kneaded by an extruder (manufactured by Booth Co., Ltd.) under the condition of about 1000 c. Melt and knead. The obtained melt-kneaded product was cooled to room temperature, coarsely pulverized, and then pulverized with a micro-crusher ("jet fine S_2 type", manufactured by Newmark Co., Ltd.), classified by a sieve of 300 mesh to obtain a volume The powder volume coating with an average particle size of 18 另外 was measured using a microtrace hra χ · ⑽ (manufactured by Nikkiso Co., Ltd.). [Coating of magnesium alloys] < Example 1 >
50 mmx200 mmx2 mm)的表面 Mm的藍寶石針的鉛筆硬度測 、深3〇 μηι的人工傷痕。 在試樣（鎂合金製壓鑄件、 上，藉由前端裝著有直徑爲5 定機’荷重4.9N，造成寬50 Μ成Μ傷痕的試樣上’以供烤後的塗膜厚爲 μπι的方式，靜電塗裝上述合成例中製造的粉末塗料，在 烤爐中，試樣的溫度在約彳〇 长、々10分鐘内從20°C升溫到160°C， 持該溫度5分鐘，烘烤塗膜 π 土胰。故期間，用黏度測定機（丨丨黏 計MR300"、UBM钍制、、日丨—， 版）測疋粉末塗料的黏度隨時間的50 mmx200 mmx2 mm) surface Mm sapphire needle pencil hardness test, 30 μm deep artificial scars. A sample (magnesium alloy die-casting piece) was mounted on the front end with a diameter of 5 sets, a load of 4.9N, and a sample with a width of 50 μM and a flaw of 50 μm. The thickness of the coating film after baking was μπι. The method is to electrostatically apply the powder coating produced in the above synthesis example. In an oven, the temperature of the sample is raised from 20 ° C to 160 ° C in about 10 minutes and 10 minutes, and the temperature is held for 5 minutes. Bake the coating film π soil pancreas. Therefore, the viscosity of the powder coating over time is measured with a viscosity measuring machine (丨 丨 Viscometer MR300 ", UBM ,, Japan 丨 ,, edition).
O:\87\87171.DOC -25- 200414940 化，炫融最低黏度爲1.7 Pa · s。 式在該粉末塗料形成的塗膜上，以乾燥膜厚爲7-的方 月:利用工虱贺塗塗裝含有鋁薄片顏料〗5%的丙烯酸酯樹 =溶劑型塗料（馬可達因PL_B、日本油漆社製），在帆 乾舞3分鐘，完成底層塗膜。 介接著’在底層塗膜上，以乾燥膜厚爲δ _的方式，利用 塗塗裝UV固化型透明塗料（„馬可達因PL_C”、日本油 二社製），在800 mJ/cm2的條件下照射紫外線使之固化， :到具有粉末塗料膜、熱塑性丙烯酸g旨塗料膜及w固化劑 壯明塗膜的三層的塗膜構造的塗裝物。各塗料的性狀、塗 :物的塗膜構造如表i所示。另外，製造的塗I物的評價以 如下的方式進行，結果如表2所示。 〔評價〕 <塗膜完成> 、犯否從表層塗膜上看到人工傷痕，以目視用以下的標準 進行判斷。 ◎:完全不能看到人工傷痕存在。 〇：仔細看能看到人工傷痕的存在，使用上沒有問題。 X ·人工傷隱藏得不充分，並能容易地看到。 <塗膜的色相外觀〉 《鏡面光澤度》 ，通過JISK 5600-4-7’使用數位變角光澤計（斯嘉試驗機社 製）測定表層塗膜的6〇度鏡面光澤度。數值越高表 越高。 又O: \ 87 \ 87171.DOC -25- 200414940, and the minimum viscosity is 1.7 Pa · s. On the coating film formed by this powder coating, a dry film with a thickness of 7-square month is used: Use the industrial louse coating to paint containing aluminum flake pigments 5% acrylic resin = solvent-based coating (Marcoin PL_B (Manufactured by Japan Paint Co.), dry dancing for 3 minutes to complete the bottom coating film. Intermediately, the UV-curable transparent coating ("Marcoin PL_C", manufactured by Nippon Oil Co., Ltd.) was applied on the underlying coating film with a dry film thickness of δ _ at 800 mJ / cm2. It is cured by irradiating ultraviolet rays under conditions, to a coating article having a three-layer coating film structure having a powder coating film, a thermoplastic acrylic coating film, and a curing agent coating. The coating film structure and coating properties of each coating are shown in Table i. The evaluation of the manufactured coating material I was performed as follows. The results are shown in Table 2. [Evaluation] < Completion of coating film >, whether artificial flaws were seen from the surface coating film, and the following criteria were used to judge visually. ◎: Artificial scars cannot be seen at all. 〇: If you look closely, you can see the existence of artificial scars, and there is no problem in use. X · Artificial injuries are not sufficiently concealed and can be easily seen. < Hue appearance of the coating film> "Mirror Gloss", 60 ° specular gloss of the surface coating film was measured by JISK 5600-4-7 'using a digital variable angle gloss meter (manufactured by Scarlett Test Co., Ltd.). The higher the value, the higher the table. also
°A87\87171 DOC -26- 200414940 《FF、SV及IV》 使用變角色差計（ALCOPELMRIOO、關西油漆社製），檢 查表層塗膜的FF(觸發性（fllp-flop))、SV(光的散射）及Iv(明 亮度）。 FF值越大表示光亮性顏料越定向，色相外觀就越高。 值越小表示色相外觀上越沒有斑點。另外，IV值越小表示 金屬光澤感越高。 <鉛筆劃痕值> 通過JIS K 5600-5-4的（b)，判斷表層塗膜的鉛筆硬度。較 佳硬度爲Η以上。 <複合化> 在複合鎂合金材料和ABS樹脂材料的塗裝方法中，檢杳 色相外觀能否均勻。表中，”同時塗裝”表示對“^合金材料 進行粉末塗裝後和ABS樹脂材料組合並複合化，之後的熱 塑性丙稀酸g旨樹脂塗裝、UV固化型透明塗裝一起進行· ”分別塗裝’’表示Mg合金材料的塗裝和ABS樹脂材料的塗裝 完全分別進行（但是，使用同種類的熱塑性丙烯酸酯樹脂塗 料和UV固化型透明塗料）、完成各自塗裝後再組合。此處的 "〇”表示即使複合化因爲沒有色相不同所以也有統一感； ” X ”表示色相不同且不統一。結果如表i及表2所示。 O:\87\87171 DOC -27- 200414940 表1 \ 粉末塗料 丙稀酸S旨塗料 UV塗料 粒徑 (μιη) 熔融最低 黏度(Pa-s) 膜厚 (μπι) 膜最 (μπι) 光亮材料 含量(％) 膜厚 (μιη) 實施例1 18 1.7 25 7 15 8 實施例2 18 1.0 25 7 15 8 實施例3 18 1.4 25 7 15 8 實施例4 18 2.0 25 7 15 8 實施例5 18 1.7 35 7 15 8 實施例6 18 1.7 25 4 15 8 實施例7 18 1.7 25 18 15 8 實施例8 18 1.7 25 7 15 4 實施例9 18 1.7 25 7 15 18 實施例10 25 1.7 25 7 15 8 比較例1 18 0.8 20 7 15 8 比較例2 18 2.3 25 7 15 8 比較例3 使用現有的溶劑型塗 料代替粉末塗料 20 25 3 - 比較例4 . 同上 20 7 5 8 比較例5 同上 20 7 7 8° A87 \ 87171 DOC -26- 200414940 《FF, SV, and IV》 Using variable character difference meter (ALCOPELMRIOO, manufactured by Kansai Paint Co., Ltd.), check the FF (fllp-flop), SV (light Scattering) and Iv (brightness). The larger the FF value, the more oriented the bright pigment, and the higher the hue appearance. The smaller the value, the less mottled the appearance of the hue. The smaller the IV value, the higher the metallic luster. < Pencil scratch value > The pencil hardness of the surface coating film was judged by (b) of JIS K 5600-5-4. The better hardness is more than Η. < Compositing > In a coating method of a composite magnesium alloy material and an ABS resin material, it is checked whether the hue appearance is uniform. In the table, "simultaneous coating" means "combining and compounding the powder of the alloy material with the ABS resin material and then compounding, and then the thermoplastic acrylic acid resin coating and UV-curing transparent coating are performed together." `` Separate painting '' means that the painting of the Mg alloy material and the painting of the ABS resin material are performed completely separately (however, the same kind of thermoplastic acrylate resin coating and UV-curable transparent coating are used), and the respective coatings are completed and then combined. "&Quot; 〇" here means that even if the composite is not different in hue, there is a sense of unity; "X" means that the hue is different and not uniform. The results are shown in Table i and Table 2. O: \ 87 \ 87171 DOC -27- 200414940 Table 1 \ Powder coating Acrylic acid S coating UV coating particle size (μιη) Lowest melting viscosity (Pa-s) Film thickness (μπι) Film maximum (μπι) Bright material content (%) Film thickness (μιη) Example 1 18 1.7 25 7 15 8 Example 2 18 1.0 25 7 15 8 Example 3 18 1.4 25 7 15 8 Example 4 18 2.0 25 7 15 8 Example 5 18 1.7 35 7 15 8 Example 6 18 1.7 25 4 15 8 Example 7 18 1.7 25 18 15 8 Example 8 18 1.7 25 7 15 4 Example 9 18 1.7 25 7 15 18 Example 10 25 1.7 25 7 15 8 Comparative Example 1 18 0.8 20 7 15 8 Comparative Example 2 18 2.3 25 7 15 8 Comparative Example 3 Uses existing solvent-based coatings instead of powder coatings 20 25 3-Comparative Example 4. Ibid. 20 7 5 8 Comparative Example 5 Ibid. 20 7 7 8
表2 \ 塗膜 完成 塗膜色相外觀 鉛筆 硬度 複合化 鏡面 光澤度 FF SV IV 同時 塗裝 分別 塗裝 實施例1 ◎ 100% 1.9 66 400 2Η 〇 〇 實施例2 〇 100% 1.9 71 400 2Η 〇 〇 實施例3 ◎ 100% 1.9 68 400 2Η 〇 〇 實施例4 〇 100% 1.7 83 218 2Η 〇 〇 實施例5 ◎ 100% 1.9 63 400 2Η 〇 〇 實施例6 ◎ 100% 1.6 88 163 2Η 〇 〇 實施例7 ◎ 100% 1.9 65 400 2Η 〇 〇 實施例8 ◎ 90% 1.6 80 142 Η 〇 〇 實施例9 ◎ 100% 1.9 64 400 2Η 〇 〇 實施例10 ◎ 100% 1.7 86 220 2Η 〇 〇 比較例1 X 100% 1.9 69 400 2Η 〇 〇 比較例2 X 100% 1.5 97 135 2Η 〇 〇 比較例3 X 90% 1.5 24 31 Η X X 比較例4 X 70% 1.3 105 90 Η X X 比較例5 X 30% 1.0 179 104 Η X X 註)IV值400表示是超過測定界限400的值、400以上。 O:\87\87171.DOC -28- 200414940 〔實施例2〜1 〇，比較例1、2〕 除了籾末塗料的粒徑、熔融最低黏度、乾燥膜厚、溶劑 型熱塑性丙烯酸酯塗料的乾燥膜厚及UV固化型塗料的乾 知膜厚予以麦化以外，製造與實施例丨同樣的塗裝物，進行 與實施例1同樣的評價。各塗料的性狀、塗裝物的塗膜構造 如表1所示，另外，塗裝物的評價如表2所示。在此，熔融 最低黏度藉由環氧樹脂的分子量和添加犧來調整。 〔比較例3〕 代替實施例1的粉末塗料，空氣喷塗塗裝溶劑型塗料（"歐 爾嘉分選30NC底漆Ρ-2”、日本油漆社製），在16〇t下烘烤 20分鐘，形成乾燥膜厚爲2〇μιη的底層塗膜，而且，在其上 面二氣噴塗塗裝含有3%鋁薄片顏料的丙烯酸酯樹脂類溶 剤型塗料（超雷克1〇〇”、曰本油漆社製），在16〇。〇下烘烤汕 分鐘，形成乾燥膜厚爲25 μιη的表層塗膜。塗裝物的塗膜構 造如表1所示，另外，塗裝物的評價如表2所示。 〔比較例4、5〕 除了使丙烯酸酯樹脂溶劑型塗料的鋁薄片顏料含量變化 爲5%及7%以外，製造與比較例3同樣的塗裝物，塗裝物的 塗膜構造如表1所示，另外，塗裝物的評價如表2所示。 以上，從各例的結果可知：本發明的塗裝物隱藏了鎮合 金的傷痕並沒有對表層塗膜産生影響，另外，表層塗膜具 有充分光澤而且觸發性等其他的色相外觀也優秀。而且， 鉛筆硬度充分、耐摩耗性也優異。即使與塑膠材料進行複 合化，對於含有光亮性顏料的溶劑型熱塑性丙烯酸酉旨樹脂 O:\87\87171.DOC -29- 200414940 塗料所形成的塗膜和UV固化型透明塗料 丁寸所形成的塗膜來 說，因爲與使用於鎂合金的塗料相同的4Table 2 Finished coating film Hue appearance Pencil hardness composite mirror gloss FF SV IV Simultaneous coating Example 1 ◎ 100% 1.9 66 400 2Η 〇 Example 2 〇 100% 1.9 71 400 2Η 〇〇 Example 3 ◎ 100% 1.9 68 400 2Η 〇〇 Example 4 〇 100% 1.7 83 218 2Η 〇〇 Example 5 ◎ 100% 1.9 63 400 2Η 〇 Example 6 ◎ 100% 1.6 88 163 2Η 〇 Example 7 ◎ 100% 1.9 65 400 2 Η〇〇 Example 8 ◎ 90% 1.6 80 142 Η 〇〇 Example 9 ◎ 100% 1.9 64 400 2 Η 〇 Example 10 ◎ 100% 1.7 86 220 2 Η 〇 Comparative Example 1 X 100% 1.9 69 400 2Η〇〇Comparative Example 2 X 100% 1.5 97 135 2Η〇〇Comparative Example 3 X 90% 1.5 24 31 Η XX Comparative Example 4 X 70% 1.3 105 90 Η XX Comparative Example 5 X 30% 1.0 179 104 Η XX Note) An IV value of 400 indicates a value that exceeds the measurement limit 400 and is 400 or more. O: \ 87 \ 87171.DOC -28- 200414940 [Examples 2 to 10, Comparative Examples 1 and 2] Except the particle size of the final coating, the minimum melt viscosity, the dry film thickness, and the drying of the solvent-based thermoplastic acrylate coating The film thickness and the dry film thickness of the UV-curable coating material were changed to wheat, and the same coating material as in Example 丨 was produced, and the same evaluation as in Example 1 was performed. The properties of each coating and the coating film structure of the coating are shown in Table 1, and the evaluation of the coating is shown in Table 2. Here, the minimum melt viscosity is adjusted by the molecular weight of the epoxy resin and the sacrifice of addition. [Comparative Example 3] Instead of the powder coating of Example 1, air-coating a solvent-based coating (" Orga Sorting 30NC Primer P-2 ", manufactured by Nippon Paint Co., Ltd.), and baked at 160 ° t. An undercoat film having a dry film thickness of 20 μm was formed in 20 minutes, and an acrylic resin-based solvent-based coating (Super Rake 100 ”, (Made by this paint company), at 160. Bake at 0 ° C for 15 minutes to form a surface coating film with a dry film thickness of 25 μm. The coating film structure of the coating is shown in Table 1, and the evaluation of the coating is shown in Table 2. [Comparative Examples 4 and 5] Except that the aluminum flake pigment content of the acrylic resin solvent-based coating was changed to 5% and 7%, the same coating material as in Comparative Example 3 was manufactured. The coating film structure of the coating material is shown in Table 1. The evaluations are shown in Table 2 below. From the results of the above examples, it can be seen that the coating of the present invention hides the flaws of the alloying agent and does not affect the surface coating film. In addition, the surface coating film has sufficient gloss and other hue appearance such as triggering properties. In addition, the pencil has sufficient hardness and excellent wear resistance. Even if it is compounded with plastic materials, the solvent-based thermoplastic acrylic resin containing bright pigments O: \ 87 \ 87171.DOC -29- 200414940 is a coating film formed by a coating and a UV-curable transparent coating. The coating film is the same as the coating used for magnesium alloys. 4
W貝也適用於ABS 樹脂材料，所以沒有色相的不同，並有統—感 發明效果 本發明的塗裝方法，因爲在金屬材料表面上塗裝規定了 熔融最低黏度和塗膜厚的粉末塗料、在其上面再塗裝規定 ， 了塗膜厚的熱塑性丙烯酸酯樹脂塗料和活性能量線型固化 型透明塗料，所以能隱藏金屬材料的表面缺陷、能形成塗 膜硬度充分且耐摩耗性優異、色相外觀優異的塗膜。土 〇 另外，本發明的塗裝方法t，因爲使用光亮性塗膜用熱 塑性丙烯酸酯樹脂塗料、透明塗膜用活性能量線固化型塗 料，所以在塑膠材料上也能塗裝這些塗料所形成的塗膜^ 因此，即使相對於使金屬材料和塑膠組合的複合材料也能 形成色彩外觀統^—的塗膜。 如上所述，藉由本發明的塗裝方法所製造的本發明塗裝 物因爲具有上述特徵，所以適用於電視機、錄影機等家電 製品、行動電話、PHS、筆記型個人電腦、而、數碼相機、 投影機、MD、CD、DVD等〇A設備·行動設備或汽車車身、， ί飞車輪胎用車輪、發動機套、方向盤、自動二輪車汽油桶 . 套、擋風等汽車零件。W shell is also suitable for ABS resin materials, so there is no difference in hue, and there is a unified-sense of the invention. The coating method of the present invention, because the powder coating on the surface of the metal material has a minimum melting viscosity and coating film thickness, Coating rules are applied on top of it. The thickness of the thermoplastic acrylate resin coating and active energy ray-curable transparent coating can be hidden, so that the surface defects of metal materials can be hidden, the coating film can be formed with sufficient hardness, excellent abrasion resistance, and hue appearance. Excellent coating film. In addition, since the coating method t of the present invention uses a thermoplastic acrylate resin coating for a bright coating film and an active energy ray-curable coating for a transparent coating film, the coating formed by these coatings can also be applied to plastic materials. Coating film ^ Therefore, a coating film with a uniform color appearance can be formed even with a composite material in which a metal material and a plastic are combined. As described above, the coated article of the present invention produced by the coating method of the present invention has the above-mentioned characteristics, and is therefore suitable for use in home appliances such as televisions, video recorders, mobile phones, PHS, notebook personal computers, and digital cameras. OA equipment such as projectors, MDs, CDs, DVDs, mobile devices, or car bodies, automotive wheels, wheels, engine covers, steering wheels, gasoline tanks for motorcycles, windshields, etc.
O:\87\87171.DOC -30-O: \ 87 \ 87171.DOC -30-
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| JP4382389B2 (en) * | 2003-05-15 | 2009-12-09 | 三菱製鋼株式会社 | Manufacturing method of magnesium or magnesium alloy product |
| JP4616573B2 (en) * | 2004-04-05 | 2011-01-19 | アーク岡山株式会社 | Manufacturing method of product made of magnesium or magnesium alloy |
| WO2006051877A1 (en) * | 2004-11-10 | 2006-05-18 | Dai Nippon Printing Co., Ltd. | Process for forming metal oxide films |
| JP2006150261A (en) * | 2004-11-30 | 2006-06-15 | Fukuda Corporation:Kk | How to paint magnesium alloy moldings |
| JP5083148B2 (en) * | 2008-09-29 | 2012-11-28 | 住友電気工業株式会社 | Magnesium alloy parts |
| CN101463220A (en) * | 2009-01-06 | 2009-06-24 | 深圳桑菲消费通信有限公司 | UV coating for spraying magnesium aluminum alloy surface |
| JP5671240B2 (en) * | 2010-02-18 | 2015-02-18 | 日鉄住金鋼板株式会社 | Painted metal plate |
| CN101934265A (en) * | 2010-08-04 | 2011-01-05 | 六和轻合金（昆山）有限公司 | Coating method of aluminum alloy wheel rim |
| JP2014221575A (en) * | 2013-05-13 | 2014-11-27 | 株式会社レイズ | Vehicular wheel |
| CN103725143B (en) * | 2013-12-13 | 2016-01-13 | 中昊北方涂料工业研究设计院有限公司 | A kind of moisture-proof coating |
| KR101825474B1 (en) * | 2016-09-28 | 2018-02-06 | (주)탑아이엔디 | Manufacturing method for Vehicle's High Loop and thereby Vehicle's High Loop |
| CN106827764A (en) * | 2017-01-18 | 2017-06-13 | 北京钢研新冶工程设计有限公司 | A kind of continuous P VD UV color coatings Unit errigers and production technology |
| KR102934807B1 (en) * | 2022-10-28 | 2026-03-06 | 주식회사 명주 | Fluorescent powder coating composition and fluorescent powder coating method using same |
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| TWI633205B (en) * | 2014-05-29 | 2018-08-21 | 日商日新製鋼股份有限公司 | Method for manufacturing coated metal sheets and exterior building materials |
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