201004792 六、發明說明： 【聲明所屬之技彳椅領域】 發明領域 . 本發明係有關於一種業經著色之彩色透明漆塗裝不鏽 鋼板及其製造方法。 本發明主張2008年2月8曰申請之曰本專利第 2008-029712號之優先權，且在此援用其内容。 【^tr 冬奸】 ^ 背景技術 藉由壓縮成形等使不鏽鋼板成形之成形品經常使用於 電氣製品、電子機械製品等之框體，且該使用於電氣製品、 _ 電子機械製品等之框體成形材料的不鏽鋼板，會為了提高 框體之設計性，在不損及不鏽鋼板原板之辨識性的程度 下，預先形成彩色透明漆塗膜以著色(請參照專利文獻1〜3 )。 近年來，電氣製品、電子機械製品等逐漸要求較高之201004792 VI. Description of the invention: [Technical field of the technical field to which the invention belongs] Field of the invention The present invention relates to a stainless steel plate coated with a colored transparent paint which is colored and a method for producing the same. The present invention claims priority to Japanese Patent Application No. 2008-029712, filed on Jan. 28, 2008, the content of which is incorporated herein. [^tr 冬奸] ^ Background Art A molded article obtained by molding a stainless steel sheet by compression molding or the like is often used for a frame of an electric product, an electromechanical product, or the like, and is used for a frame of an electric product, an electromechanical product, or the like. In order to improve the design of the frame, the stainless steel plate of the molding material is colored in advance to form a color clear paint film without damaging the visibility of the original plate of the stainless steel plate (see Patent Documents 1 to 3). In recent years, electrical products, electronic mechanical products, etc. are gradually demanding higher
設計性，並要求使用於該等框體之成形材料的彩色透明漆 W 塗裝不鏽鋼板須為著色較濃者。 但是，若將專利文獻1〜3所揭示之彩色透明漆塗裝不鏽 鋼板以較濃色調著色，彩色透明漆塗膜之透明性會降低， 因而降低不鏽鋼板原板之辨識性，因此，會無法達到活用 不鏽鋼板原板之光輝性以提高設計性之目的。有鑑於此， 為了活有不鏽鋼板原板本身原有的光輝性，以達到提高彩 色透明漆塗裝不鏽鋼板之設計性的目的，故要求一種會提 高彩色透明漆塗膜之透明性及鮮豔性，並且可以使用較濃 3 201004792 色調著色者。 【專利文獻1】特開2004-58273號公報 【專利文獻2】特開2004-202988號公報 【專利文獻3】特開2005-7586號公報 【發明内容】 發明之揭示 發明欲解決之課題 有鑑於前述原因，本發明之目的在於提供一種彩色透 明漆塗膜之透明性及鮮豔性優異外，又可以使用較濃色調 參 著色，並且具有高度設計性之彩色透明漆塗裝不鏽鋼板及 其製造方法。 用以解決課題之手段 本發明包含有下列態樣。 本發明之彩色透明漆塗裝不鏽鋼板，係包含有不鏽鋼 _ 板原板，以及於前述不鏽鋼板原板之至少一面側成膜的彩 色透明漆塗膜，又，前述彩色透明漆塗膜係含有平均一次 粒子徑為10〜llOOnm之顏料，且該顏料容積濃度為0.5〜5.0% 者。 本發明之彩色透明漆塗裝不鏽鋼板中，前述彩色透明 漆塗膜之顏料分散粒度亦可為25μιη以下。 本發明之彩色透明漆塗裝不錄鋼板之製造方法係在不 鏽鋼板原板上，塗裝含有平均一次粒子徑為丨〇-llOOnm之顏 料的於色透明漆塗料，使所得之彩色透明漆塗膜的顏料容 積濃度為0.5〜5.0%者。 4 201004792 本發明之彩色透明漆塗裝不鏽鋼板之製造方法中，前 述彩色透明漆塗料之塗裝亦可使彩色透明漆塗膜之顏料分 散粒度為25μηι以下。 發明效果 本發明之彩色透明漆塗裝不鏽鋼板，係一種彩色透明 漆塗膜之透明性及鮮豔性優異，且可以使用較濃色調著 色’並且具有高度設計性者。 根據本發明之彩色透明漆塗裝不鏽鋼板之製造方法， 可製造出一種彩色透明漆塗膜之透明性及鮮豔性優異，且 可以使用較濃色調著色，並且具有高度設計性之彩色透明 漆塗裝不鏽鋼板。 圖式簡單說明 第1圖係顯示本發明之彩色透明漆塗裝不鏽鋼板的一 個實施形態例之截面圖。 第2圖係顯示實驗例1〜6之顏料容積濃度與相對透光率 之間的關係圖表。 第3圖係顯示實驗例7〜12之顏料容積農度與相對透光 率之間的關係圖表。 第4圖係顯示實驗例13〜18之顏料容積濃度與相對透光 率之間的關係圖表。 第5圖係顯示實驗例25〜28之顏料分散粒度與20度光澤 度之間的關係圖表。 第6圖係顯示實驗例29〜32之顏料分散粒度與2〇度光澤 度之間的關係圖表。 5 201004792 第7圖係顯示實驗例33〜36之顏料分散粒度與20度光澤 度之間的關係圖表。 第8圖係顯示實驗例1〜3拉伸變形後之20度光澤度的圖 表。 符號說明 10.. .彩色透明漆塗裝不鏽鋼板 11.. .不鏽鋼板原板 12.. .化成處理塗膜 13.. .彩色透明漆塗膜 【實施方式3 用以實施發明之最佳形態 就本發明之彩色透明漆塗裝不鏽鋼板的一個實施形態 例加以說明。 第1圖係本實施形態例之彩色透明漆塗裝不鏽鋼板的 示意圖。本實施形態例之彩色透明漆塗裝不鏽鋼板10包含 有不鏽鋼板原板11、成膜於不鏽鋼板原板11單面上之化成 處理塗膜12、以及成膜於化成處理塗膜12表面之彩色透明 漆塗膜13。 前述彩色透明漆塗裝不鏽鋼板10之不鏽鋼板原板11係 使用習知者。 [化成處理塗膜] 化成處理塗膜12最好使用含有胺基矽烷系矽烷耦合 劑、環氧矽烷系矽烷耦合劑之1種或2種之塗膜。若在不鏽 鋼板原板11以及彩色透明漆塗膜13之間，形成有含該等矽 201004792 烷耦合劑之化成處理塗膜12，就是一種不會造成公害之非 鉻品，並可提高不鏽鋼板原板11與彩色透明漆塗膜13之間 的密著性。 在此，胺基矽烷系耦合劑可舉例如：N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、N-2-(胺乙基)-3-胺丙基三乙氧 基碎烧、3-胺丙基三曱氧基砍烧等。 環氧系矽烷耦合劑可舉例如：2-(3,4-環氧基環己基）乙 基三甲氧基矽烷、3-甘油醚氧丙基三甲氧基矽烷、3-甘油醚 氧丙基甲基二乙氧基矽烷等。 化成處理塗膜12之附著量最好在2至50 mg/m2之間，若 化成處理塗膜12之附著量低於2mg/m2時，會容易降低光澤 以及防蝕性；若附著量超過50mg/m2時，經沸騰水實驗後， 塗膜表面會產生水泡。化成處理塗膜12之附著量上限以 30mg/m2為佳，又以10mg/m2更佳。 前述化成處理塗膜12之附著量係根據螢光X光分析所 測得之Si02量求得者。 [彩色透明漆塗膜] 本實施形態例之彩色透明漆塗膜13係一種含有顏料之 塗膜。此處之顏料可使用無機顏料、碳顏料、有機顏料其 中之任一者。 無機顏料可舉例如：氧化鐵等。 碳顏料可舉例如：碳黑等。 有機顏料可舉例如：偶氮系顏料、多環系顏料、金屬 配位系顏料等。 7 201004792 偶氮系顏料可舉例如：溶性偶氮、縮合偶氮、單偶氮、 重氮等。 多環系顏料可舉例如：狄菁(phthalocyanine)、蔥酿i、 散藍、茈系（perylene)、紫環酮（perinone)、二噚畊（di〇xazine)、 0奎0丫咬（quinacridone)、異 η弓卜朵（is〇ind〇iinone)、各并吼〇各 二 _ (DPP)、黃蔥酮（flavanthr〇ne)、蒽素喷咬 (anthrapyrimidine)、醯胺、喳吖酞酮、吲呻(pyrr〇c〇line)、佛 爾羅濱（7瓜才口匕°>)等。 金屬配位系顏料可舉例如：鎳偶氮等。 顏料之平均一次粒子徑為1〇〜11〇〇ηπι，以1〇〜8〇〇nm較 佳，又以10〜500nm更佳。 特別是，若該顏料為無機顏料，平均一次粒子徑以 100〜200nm為佳，以100〜I80nm更佳，又以100〜I50nm特佳。 若該顏料為碳顏料’平均一次粒子徑以丨〇〜8〇nm為 佳，又以10〜50nm更佳。 右该顏料為有機顏料’平均一次粒子徑以〜ll〇〇nm 為佳，以50〜800nm更佳，又以50〜500nm特佳。 若顏料之平均一次粒子徑未達前述底限值，會不容易 使用較濃色調著色，且難以取得粒子低於前述底限值之顏 料；另一方面，若顏料之平均一次粒子徑超過前述上限值， 會造成彩色透明漆塗膜13之透明性及鮮豔性降低，因而降 低彩色透明漆塗裝不鑛鋼板10之設計性。 又，本發明所述之平均一次粒子徑係藉由電子顯微 鏡、動態光散射法、雷射繞射散射法等方法所測得之數值。 201004792 再者’就更加提高彩色透明漆塗膜13之鮮豔性而言， 顏料之顏料分散粒度以25μιη以下為佳，又以20μιη以下更 佳另，就實用性而言，最好是5 μιη以上。 顏料分散粒度係使用具有傾斜成習知傾度之溝槽的分 散粒度測量器來測量，具體而言，係在分散粒度測量器之 傾斜溝槽充填顏料，並觀察顏料由形成有溝槽之表面的最 先突出處者，然而，顏料最先突出處之溝槽深度即為分散 粒度。 彩色透明漆塗膜13之顏料容積濃度為〇.5〜5.〇%，以 0.8〜4.0%為佳，又以〇8〜25%更佳。在此，顏料容積濃度 係藉由下列公式求得之值，且顏料容積濃度亦稱為pvc。 顏料容積濃度=[(顏料容積)/(顏料容積+樹脂容積)]χ 100(%) 若顏料容積濃度低於前述底限值，不管使用何種顏 料，都會不容易以較濃色調著色；另一方面，若超過前述 上限值，不管使用何種顏料，彩色透明漆塗膜13之透明性 及鮮豔性都會降低，此外，還會難以形成平均塗膜，因而 降低彩色透明漆塗裝不鏽鋼板1〇之設計性。 又，由於對色彩看法係憑感覺，故藉由顏料而成之設 計性優異之彩色透明漆塗膜13的可見紐射率範圍也有差 異’舉例來說’紅色顏料(絲紅)之相對透光率為5〇〜6冰， 藍色顏料(瓶菁藍)之相對透光率為3〇〜55%，掠色顏。 品名：C〇L〇RFINE BR0WN)之相對透光率為55〜7〇%時两 就設計性而言相#優異，又，當相對透光率低於前述底限 9 201004792 值會有透明性不足之傾向；若超過前述上限值則會有彩色 透明漆塗膜顏色變淡的傾向° 前述相對透光率要求之顏料容積濃度，茈系紅為 0.8〜2.4%，銅酞菁藍為0.8〜2.1°/。，COLORFINE BROWN為 1.5-5.0% ° 由於顏料分散性高會更加提高透明性及鮮豔性，故彩 色透明漆塗膜13中最好含有分散劑。 此處之分散劑可舉例如：驗性分散劑、酸性分散劑、 兩性分散劑等，可依所使用的顏料適當選擇，例如，若彥貝 料為酸性顏料(如喳吖啶紅、碳黑等）則使用鹼性分散劑；若 顏料為兩性顏料（如偶氮紅、異吲哚黃等）則使用兩性分散 劑；若顏料為鹼性顏料(如狄菁藍/綠、氧化鐵、豬石等）則 使用酸性分散劑。 彩色透明漆塗膜13所含之熱硬化性樹脂組成物最好含 有藉由封端異氰酸酯化合物所交聯之具交聯性官能基的 丙烯酸樹脂（以下略稱為丙烯酸樹脂）。 此處之交聯性官能基係選自於經基，基、烧氧石夕燒 基等1種或2種以上之官能基，且丙烯酸樹脂以每！分子^ 有2個以上之交聯性官能基者為佳。 丙稀酸樹脂係至少1種非官能性丙烯酸單體以及至少i 種官能性單體之共聚物。 非官能性丙締酸單體可舉例如：丙歸酸甲醋、丙_ 乙醋、丙稀酸異丙醋、丙稀酸正丁醋、丙稀酸2乙、 甲基丙稀酸甲醋、甲基丙埽酸乙醋、甲基丙稀酸異丙S旨、 201004792 ^基丙烯酸正己酯、丙埽酸環己醋、 甲基丙細月桂酯等脂㈣丙稀酸醋 吕月b I王早篮f舉例如.丹有美 單體、具有烷氧矽烷基之單體等。 具有經基之單體可舉例如：㈣酸^乙酉旨、甲基丙Designed and required for the use of colored clear lacquers for the forming materials of such frames. W Painted stainless steel sheets shall be thicker. However, if the colored clear lacquer coated stainless steel sheets disclosed in Patent Documents 1 to 3 are colored in a rich color tone, the transparency of the colored clear lacquer coating film is lowered, thereby reducing the visibility of the original sheet of the stainless steel sheet, and thus, it is impossible to achieve Use the brightness of the original plate of stainless steel to improve the design. In view of this, in order to live the original brightness of the original stainless steel plate, in order to improve the design of the color transparent paint coated stainless steel plate, it is required to improve the transparency and vividness of the color transparent paint film. And you can use the thicker 3 201004792 shader. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-58988 (Patent Document No. 2004-202988) [Patent Document 3] JP-A-2005-7586 SUMMARY OF INVENTION In view of the foregoing, it is an object of the present invention to provide a color clear lacquer coated stainless steel sheet which is excellent in transparency and vividness of a color clear varnish coating film, and which can be colored with a thick color ginseng, and which has high design and a manufacturing method thereof. . Means for Solving the Problems The present invention encompasses the following aspects. The color transparent paint-coated stainless steel plate of the present invention comprises a stainless steel plate original plate and a color transparent paint film formed on at least one side of the original plate of the stainless steel plate, and the color transparent paint film system has an average of one time. A pigment having a particle diameter of 10 to 10 nm and having a volume concentration of 0.5 to 5.0%. In the color clear paint-coated stainless steel sheet of the present invention, the color clear paint coating film may have a pigment dispersion particle size of 25 μm or less. The method for manufacturing a color transparent varnish coated non-recorded steel sheet of the present invention is applied to a stainless steel plate original plate, and a color clear lacquer coating containing a pigment having an average primary particle diameter of 丨〇-llOOnm is applied to obtain a colored transparent varnish coating film. The pigment has a volume concentration of 0.5 to 5.0%. 4 201004792 In the method for producing a color transparent paint-coated stainless steel sheet according to the present invention, the color clear paint coating may be applied to a color clear paint film having a pigment dispersion particle size of 25 μm or less. EFFECTS OF THE INVENTION The colored clear varnish coated stainless steel sheet of the present invention is a color clear lacquer coating film which is excellent in transparency and vividness, and can be colored with a rich color tone and has a high degree of design. According to the method for producing a color transparent varnish coated stainless steel sheet of the present invention, it is possible to produce a color transparent lacquer coating film which is excellent in transparency and vividness, and can be colored with a rich color tone, and has a highly designed color transparent lacquer coating. Install stainless steel plate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a color clear paint-coated stainless steel sheet of the present invention. Fig. 2 is a graph showing the relationship between the pigment volume concentration and the relative light transmittance of Experimental Examples 1 to 6. Fig. 3 is a graph showing the relationship between the pigment volume degree of the experimental examples 7 to 12 and the relative light transmittance. Fig. 4 is a graph showing the relationship between the pigment volume concentration and the relative light transmittance of Experimental Examples 13 to 18. Fig. 5 is a graph showing the relationship between the pigment dispersion particle size and the 20 degree gloss of Experimental Examples 25 to 28. Fig. 6 is a graph showing the relationship between the pigment dispersion particle size of Experimental Examples 29 to 32 and the 2 degree gloss. 5 201004792 Fig. 7 is a graph showing the relationship between the pigment dispersion particle size and the 20 degree gloss of Experimental Examples 33 to 36. Fig. 8 is a graph showing the gloss of 20 degrees after tensile deformation of Experimental Examples 1 to 3. DESCRIPTION OF SYMBOLS 10.. Color transparent varnish coated stainless steel plate 11.. Stainless steel plate original plate 12.. Chemical treatment coating film 13.. Color transparent varnish coating film [Embodiment 3 is used to implement the best form of the invention An embodiment of the colored clear varnish coated stainless steel sheet of the present invention will be described. Fig. 1 is a schematic view showing a color clear paint-coated stainless steel plate of this embodiment. The color clear paint-coated stainless steel sheet 10 of the present embodiment includes a stainless steel plate original plate 11, a chemical conversion coating film 12 formed on one surface of the original stainless steel plate 11, and a color transparent film formed on the surface of the chemical conversion coating film 12. Paint film 13. The stainless steel plate original plate 11 of the above-mentioned colored transparent paint-coated stainless steel plate 10 is used by a known person. [Chemical Treatment Coating Film] It is preferable to use a coating film containing one or two kinds of an amine-based decane-based decane coupling agent or an epoxy decane-based decane coupling agent. If a chemical conversion coating film 12 containing the 矽201004792 alkane coupling agent is formed between the original stainless steel plate 11 and the colored transparent lacquer coating film 13, it is a non-chromium product which does not cause pollution, and the original plate of the stainless steel plate can be improved. The adhesion between 11 and the color clear lacquer coating film 13. Here, the amino decane-based coupling agent may, for example, be N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane or N-2-(aminoethyl)-3-aminepropane The base is triethoxy pulverized, 3-aminopropyl tridecyloxy chopped, and the like. Examples of the epoxy decane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 3-glyceryloxypropyltrimethoxydecane, and 3-glyceryloxypropylpropyl group. Diethoxy decane and the like. The adhesion amount of the chemical conversion coating film 12 is preferably between 2 and 50 mg/m2, and if the adhesion amount of the chemical conversion coating film 12 is less than 2 mg/m2, the gloss and the corrosion resistance are easily lowered; if the adhesion amount exceeds 50 mg/ At m2, after the boiling water test, blisters are formed on the surface of the coating film. The upper limit of the adhesion amount of the chemical conversion coating film 12 is preferably 30 mg/m2, more preferably 10 mg/m2. The amount of adhesion of the chemical conversion coating film 12 was determined based on the amount of SiO 2 measured by fluorescent X-ray analysis. [Color Clear Paint Coating Film] The color clear paint coating film 13 of the present embodiment is a coating film containing a pigment. The pigment herein may be any of an inorganic pigment, a carbon pigment, and an organic pigment. The inorganic pigment may, for example, be iron oxide or the like. The carbon pigment may, for example, be carbon black or the like. The organic pigment may, for example, be an azo pigment, a polycyclic pigment or a metal complex pigment. 7 201004792 The azo-based pigment may, for example, be a soluble azo, a condensed azo, a monoazo or a diazo. The polycyclic pigments may, for example, be phthalocyanine, scallions, sapphire, perylene, perinone, di〇xazine, quinacridone. ), η 弓 卜 朵 (is〇ind〇iinone), each 吼〇 _ _ (DPP), flavon ketone (flavanthr〇ne), anthrapyrimidine, anthraquinone, fluorenone , 吲呻 (pyrr〇c〇line), Florabin (7 melons 匕 ° °) and so on. The metal coordination pigment may, for example, be nickel azo or the like. The average primary particle diameter of the pigment is from 1 〇 to 11 〇〇ηπι, preferably from 1 〇 to 8 〇〇 nm, and more preferably from 10 to 500 nm. In particular, if the pigment is an inorganic pigment, the average primary particle diameter is preferably 100 to 200 nm, more preferably 100 to I80 nm, and particularly preferably 100 to 150 nm. If the pigment is a carbon pigment, the average primary particle diameter is preferably 丨〇8 〇 nm, and more preferably 10 to 50 nm. The pigment on the right is an organic pigment. The average primary particle diameter is preferably ll 〇〇 nm, more preferably 50 to 800 nm, and particularly preferably 50 to 500 nm. If the average primary particle diameter of the pigment does not reach the above-mentioned lower limit value, it is not easy to use a thicker color tone, and it is difficult to obtain a pigment having a particle lower than the above-mentioned lower limit value; on the other hand, if the average primary particle diameter of the pigment exceeds the above The limit value causes a decrease in transparency and vividness of the color clear paint coating film 13, thereby reducing the design of the color transparent paint coated non-mineral steel sheet 10. Further, the average primary particle diameter of the present invention is a value measured by an electron microscope, a dynamic light scattering method, a laser diffraction scattering method or the like. 201004792 In addition, in order to further improve the vividness of the color transparent paint film 13, the pigment dispersion particle size of the pigment is preferably 25 μm or less, more preferably 20 μm or less, and practically, it is preferably 5 μm or more. . The pigment dispersion particle size is measured using a dispersion particle size measuring device having a groove inclined to a known inclination, specifically, a tilt groove in a dispersion particle size measuring device is filled with a pigment, and the pigment is observed from a grooved surface. The first to stand out, however, the depth of the groove where the pigment first protrudes is the dispersed particle size. The color clear paint coating film 13 has a pigment volume concentration of 〇.5~5.〇%, preferably 0.8 to 4.0%, and more preferably 〇8 to 25%. Here, the pigment volume concentration is a value obtained by the following formula, and the pigment volume concentration is also referred to as pvc. Pigment volume concentration = [(pigment volume) / (pigment volume + resin volume)] χ 100 (%) If the pigment volume concentration is lower than the above-mentioned lower limit value, it will not easily be colored in a richer color regardless of the pigment used; On the other hand, if the above upper limit value is exceeded, the transparency and vividness of the color clear lacquer coating film 13 are lowered regardless of the pigment used, and in addition, it is difficult to form an average coating film, thereby reducing the color transparent varnish coated stainless steel plate. 1〇 design. Moreover, since the color perception is based on the feeling, the visible ray-injection rate of the color transparent lacquer film 13 which is excellent in design by the pigment is also different, for example, the relative light transmission of the red pigment (silk red) The rate is 5〇~6 ice, and the relative light transmittance of the blue pigment (cyanine blue) is 3〇~55%. Product name: C〇L〇RFINE BR0WN) When the relative light transmittance is 55~7〇%, the two are excellent in terms of design, and when the relative light transmittance is lower than the above-mentioned bottom limit 9 201004792, there will be transparency. If it exceeds the above upper limit, the color of the color clear paint film may become lighter. The pigment volume concentration required for the relative light transmittance is 0.8 to 2.4% for lanthan red and 0.8 for copper phthalocyanine blue. ~2.1°/. COLORFINE BROWN is 1.5-5.0%. Since the high dispersibility of the pigment increases the transparency and vividness, the color clear coating film 13 preferably contains a dispersing agent. The dispersing agent herein may, for example, be an indispensable dispersing agent, an acidic dispersing agent, an amphoteric dispersing agent or the like, and may be appropriately selected depending on the pigment to be used, for example, if the beetle is an acidic pigment (such as acridine red or carbon black). Or alkaline dispersing agent; if the pigment is an amphoteric pigment (such as azo red, isophthalocyanine, etc.), use an amphoteric dispersant; if the pigment is a basic pigment (such as delphinium blue / green, iron oxide, pig Stone, etc.) use an acidic dispersant. The thermosetting resin composition contained in the color clear varnish coating film 13 preferably contains an acrylic resin (hereinafter abbreviated as an acrylic resin) having a crosslinkable functional group crosslinked by a blocked isocyanate compound. Here, the crosslinkable functional group is one or more functional groups selected from the group consisting of a transradical group, a base, and an aerobic oxide base, and an acrylic resin is used per! Molecular^ It is preferred that there are two or more crosslinkable functional groups. The acrylic resin is a copolymer of at least one non-functional acrylic monomer and at least one functional monomer. The non-functional propionic acid monomer may, for example, be methyl acetoacetate, propyl ketone, isopropyl acetonate, n-butyl acrylate, 2 propyl acrylate or methyl acetonate. , methyl propyl acetate, isopropyl isopropyl acrylate, 201004792 ^ hexyl methacrylate, propylene hexanoic acid, methyl propyl fine lauryl ester and other lipids (four) acrylate vinegar Lu Yi b I The Wang early basket f, for example, Dan has a monomer, a monomer having an alkoxyalkyl group, and the like. The monomer having a transradical group may, for example, be: (iv) acid, ethyl, methyl, methyl
稀酸2細、丙稀酸㈣旨、甲基丙稀酸經丙醋等經基 燒基醋，含有㈣改f經基之_基單體(D—i Ιη—ω.(以^化学工業）製，商品名： PLACCELCTV夕七少则〜5、ρΑι〜5)。 具有縣之單體可舉例如：㈣酸、曱基_酸、衣 康酸、馬來酸、富馬酸等。 具有燒氧魏基之單體可舉例如：乙稀基三甲氧基石夕 烷、乙烯基三乙氧基矽烷、曱基丙醯氧基丙基三甲氧基矽 烷等。Dilute acid 2 fine, acrylic acid (4), methyl acrylate acid via propyl vinegar and other base-based vinegar, containing (four) modified f-based monomer (D-i Ι η - ω. (to chemical industry ), the product name: PLACCELCTV eve seven less ~ 5, ρ Α ι ~ 5). The monomer having a county may, for example, be (iv) acid, mercapto-acid, itaconic acid, maleic acid, fumaric acid or the like. The monomer having a calcined weigen group may, for example, be ethylene trimethoxy oxalate, vinyl triethoxy decane, decyl propyl methoxy propyl trimethoxy decane or the like.
甲基丙稀酸正丁酯、 甲基丙烯酸環己酯、 或是環式丙烯酸酯。 稀酸樹&亦可與非官能性丙稀酸單體及官能性單體 以外之其他單體絲，财他單财舉例如：曱基乙稀基 醚乙基乙稀基喊、正丙基乙稀基喊、正丁基乙稀基崎、 等乙稀基咖·，笨乙稀、α•曱基笨乙稀等乙丙稀酿 胺Ν I甲基丙烯酿胺、二丙酮丙歸酿胺等丙稀酿胺系單 體等。 丙烯酸樹脂之玻璃轉移點以3〇〜9〇<t為佳，又以5〇〜9〇 °C更佳。前述彩色透明漆塗裝不鏽鋼板10在連續加壓時會 摩擦並加工產熱，錢表面溫度上升·〜刚。c，因此， 11 201004792 若丙稀酸樹脂之玻螭轉移點低於30。匸，彩色透明漆塗媒13 會軟化並附著於模具上；又，若丙烯酸樹脂之玻璃轉移點 超過90°C，則會容易出現氣孔、不夠平坦等。 可適當選用丙烯酸樹脂之構成，以使丙烯酸樹脂之破 璃轉移溫度維持在前述範圍。 丙烯酸樹脂之數平均分子量以3〇〇〇〜5〇〇〇〇為佳，又以 4000〜10000更佳。若丙烯酸樹脂之數平均分子量低於 3000，會降低與封端異氰酸酯化合物之反應性，不易形成 彩色透明漆塗膜13 ;若丙稀酸樹脂之數平均分子量超過 參 50000，會降低溶劑溶解性，因而難以得到彩色透明漆塗料。 丙稀酸樹脂之數平均分子量可依據製造丙烯酸樹脂時 - 的條件（如聚合溫度、聚合引個之賴及量等）來加以調 整。 ' 一作為用以交聯丙烯酸樹脂之交聯劑的封端異氰酸酯化 - 合物係在1分子中具有2個以上異氰酸之化合物，具體 而言’可舉例如伸甲笨基二異氣酸s|、二苯基二異氰酸？ 醋、苯二甲二異氰酸_ U氛酸S旨等芳香族二異_ ® 酯，六曱基二異氰酸酯、二聚物酸二異氰酸酯等脂肪族二 錢酸醋；異佛爾酮二異氰酸醋、環己统二異氛酸醋等脂 ί哀族二異氰酸酿；前述聚異氣酸醋之縮二服型加成物、三 聚異氰酸環型加成物等，還有_、㈣、活性甲稀類、 卜己内酿胺類、三唾基類、一類等封端劑所封端者，又， 使用-月桂酸二丁基锡等有機錫催化劑來作為封端劑之解 離促進劑使用。 12 201004792 封端異氰酸酯化合物之市售品可舉例如：歹7β二 '—(Desmodule)BLl 100 ' BL1265MPA/X ' VPLS2253 ' BL3475BS/SN、BL3272MPA、BL3370MPA、BL4265SN、 X 只 ΐ 一 f Λ (Desmotherm)2170、只 S ^ 二一 /V (Sumidule)3175(上述產品皆為 Sumika Bayer Urethane Co.， Ltd.(住化八彳工/V々卜夕>^株式会社)製），歹'二歹本一卜 (Duranate)17B-60PX、TPA-B80X、MF-B60X、MF-K60X(上 述產品皆為 Asahi Kasei Chemicals Corporation(旭化成">* S 力少 乂株式会社）製），/ 一 / V 夕（Burn〇ck)DB-980K、 D-550、B3-867、B7-887-60(上述產品皆為 Dainippon Ink and Chemicals(大日本彳化学工業株式会社)製），口氺一 卜（Coronate)2515、2507、2513(上述產品皆為 Nippon Polyurethane Industry Co.，Ltd.(日本术口 夕卜夕：/工業株 式会社)製）等’且該等封端異氰酸酯化合物可單獨使用，亦 可併用2種以上。 由於彩色透明漆塗膜13愈硬，丙烯酸樹脂之抗磨刮性 愈咼，故不只可以使用上述封端異氰酸酯化合物，又以使 用胺基樹脂（三聚氰胺樹脂）交聯者為佳。 胺基樹脂係指使胺基化合物（三聚氰胺、胍胺、尿素） 以及甲醛（福馬林）產生加成反應並以醇加以改質的樹脂總 稱。具體而言，可舉例有三聚氰胺樹脂、苯并胍胺樹脂、 尿素樹脂、丁基化尿素樹脂、丁基化尿素三聚氰胺樹脂、 甘脲樹脂、乙醯胍胺樹脂、環己基胍胺樹脂等，其中就耐 指紋污染性、耐磨到性、耐藥性而言又以三聚氰胺樹脂為 13 201004792 佳。 依照用以改質之醇種類，三聚氰胺樹脂又可分類成甲 基化三聚氰胺樹脂、正丁基化三聚氰胺樹脂、異丁基化三 聚氰胺樹脂、混合烷基化三聚氰胺樹脂等。 具體而言，曱基化三聚氰胺樹脂可舉例如寸彳〆少 (Cymel)300、301、303、350、370、771、325、327、703、 712、715、701、267、285、232、235、236、238、211、 254、204、212、202、207(上述產品皆為Mitsui Cytec Ltd.(三 井廿彳亍V夕株式会社）製）、LUWIPAL 063、066、068、 069、072、073(上述產品皆為BASF製）、只一八一-^少力S ^(SuperBeckamine)L-105(上述產品皆為Dainippon Ink and Chemicals(大日本彳^年化学工業株式会社）製）、〆7 (Melan)522、523、620、622、623(上述產品皆為 Hitachi Chemical Co.，Ltd·(日立化成工業株式会社)製）等。 正丁基化三聚氰胺樹脂可舉例如7彳；π — (Mycoat)506、508(上述產品皆為Mitsui Cytec Ltd.(三井f 彳亍 y 夕株式会社)製）、二一，>(Uvan)20SB、20SE、21R、 22R、122、125、128、220、225、228、28-60、20HS、2020、 2021 ' 2028、120(上述產品皆為Mitsui Chemical，Inc.(三井 化学株式会社)製）、PLASTOPALEBS 100A、100B、400B、 600B、CB(上述產品皆為BASF製）、只一八一/^;/力S y (SuperBeckamine)J-820 ' L-109、L-117、L-127、L-164(上 述產品皆為Dainippon Ink and Chemicals(大日本彳>^年化 学工業株式会社)製）、^ 歹 ^(Melan)21A、22、220、2000、 201004792 8000(上述產品皆為Hitachi Chemical Co.，Ltd.(日立化成工 業株式会社）製）、于只 7 ^^(Tesazine)3020、3021、3036(上 述產品皆為Hitachi Kasei Polymer Co.，Ltd.(日立化成求y 7—株式会社)製）等。 異丁基化三聚氰胺樹脂可舉例如rL — A^(Uvan)60R、 62、62E、360、361、165、166-60、169、2061(上述產品 皆為Mitsui Chemical, Inc.(三井化学株式会社)製）、7—八 一^< y 力 S ；y(SuperBeckamine)G-821、L-145、L-110、 L-125(上述產品皆為Dainippon Ink and Chemicals(大日本 彳化学工業株式会社)製）、PLASTOPAL EBS 4001、 FIB、H731B、LR8824(上述產品皆為BASF製）' 夕 y ^ (Melan)27、28、28D、245、265、269、289(上述產品皆為 Hitachi Chemical Co.，Ltd.(日立化成工業株式会社)製）、亍 只 7 e^(Tesazine)3027、3028、3029、3030、3037(上述產 品皆為Hitachi Kasei Polymer Co.，Ltd.(日立化成求 P 71— 株式会社)製）等。 混合烷基化三聚氰胺樹脂可舉例如廿彳 > 少 (Cymel)267、285、232、235、236、238、211、254、204、 212、202、207(上述產品皆為Mitsui Cytec Ltd.(三井廿彳亍 V夕株式会社)製）等。 胺基樹脂可單獨使用，亦可併用2種以上。 彩色透明漆塗膜13最好含有聚烯烴系蠟，若彩色透明 漆塗膜13含有聚烯烴系蠟，該彩色透明漆塗裝不鏽鋼板1〇 之潤滑性會比塗布油性潤滑劑等要來的高，且加工性更為 15 201004792 優異。 聚烯烴系蠟可舉例如石蠟、微晶蠟、聚乙烯、聚乙烯_ 氟等之烴系蠟等。 在加工彩色透明漆塗裝不鏽鋼板10時，由於會因加工 發熱及摩擦熱而讓塗膜溫度上升，故聚烯烴系蠛之融點以 70〜160°C為佳’若聚烯烴系蠛之融點低於7〇〇c，會在加工 時軟化溶融而無法發揮作為固形潤滑添加物之優異特性； 若聚烯烴系蠛之融點高於160°C，由於表面上會有硬粒子而 降低摩擦特性，故無法得到高度加工性。 參 聚烯烴系蠟之酸值最好是0〜30，若聚烯烴系織之酸值 高於30，由於會提高與熱硬化性樹脂組成物之互溶性而 使聚烯烴系蠟難以平均地浮至塗膜表面，故彩色透明漆塗 裝不鏽鋼板10之加工性會不夠充分。 · 彩色透明漆塗膜13中之聚烯烴系蠟含量相對於熱硬化 - 性樹脂組成物之固形物含量1〇〇質量份，以含有〇25〜1〇質 量份者為佳。若聚烯烴系蠟含量低於〇.25質量份，加工性 會不夠充分，若高於10質量份，塗膜表面會產生深淺不均， 〇 因而損及彩色透明漆塗裝不鏽鋼板10之外觀。 又’彩色透明漆塗膜13可含有矽溶膠，此處之石夕溶膠 意指奈米（nm)等級之二氧化矽粒子。若彩色透明漆塗骐13 含有矽溶膠，可提高塗膜硬度、耐磨刮性、耐指紋污染性。 矽溶膠含量最好是每一熱硬化性樹脂組成物1〇〇質量 份，固形物含量為2_0〜10質量份，又以3.〇〜8.0質量份更佳。 若矽溶膠含量低於2.0質量份，耐磨刮性、硬度等會不足； 16 201004792 若超過ίο質量份則會有降低加工性之傾向。 更甚者’彩色透明漆塗膜13中亦可含有作為添加劑之 平坦劑、消泡劑、抗氧化劑、紫外線吸收劑、去光劑、石夕 烷耦合劑等，又，亦可含有環氧樹脂、矽氧樹脂、敦樹脂、 聚酯等。 彩色透明漆塗膜13之膜厚度以1〜ιομη!為佳。若彩色透 明漆塗膜13之膜厚度低於Ιμηι，會無法充分發揮彩色透明 漆塗膜13之潤滑功能，且除了會有彩色透明漆塗裝不鏽鋼 板10加工性降低之傾向外，彩色透明漆塗膜13構成之著色 效果亦會不夠充分，無法提高彩色透明漆塗裝不鏽鋼板1〇 之設計性；又，若彩色透明漆塗膜13之膜厚度超過1〇μιη， 彩色透明漆塗膜13之潤滑功能會飽和且難以形成彩色透明 漆塗膜13，更甚者，彩色透明漆塗膜13之透明性會降低而 無法看到不鏽鋼板原板11之原有材質，因而降低設計性。 [製造方法] 再者，就前述彩色透明漆塗裝不鏽鋼板之製造方法的 一例加以說明。 又’彩色透明漆塗裝不鏽鋼板1〇之製造方法並不受限 於下列例子。 在該例之製造方法中’首先，先對不鏽鋼板原板11施 加以熱驗脫脂、酸/驗等進行餘刻等習知前處理。 接著’在不鏽鋼板原板u上塗布含有胺基矽烷系耦合 劑及環氧矽烷系耦合劑其中一種或兩種之化成處理液，乾 燥並形成化成處理塗膜12。 17 201004792 前述化成處理液可使用市售品，該市售之化成處理液 可舉例如：一卜（pal-C〇at)E305、3750、375卜 3753、 3756、3757、3970(Nihon Parkerizing Co” Ltd.(日本〆一力 7 彳夕:/夂株式会社）製），7々f* — 7(Alsur〇44〇(Nipp〇n Paint Co·，Ltd.(日本八彳 > 卜株式会社）製）等。 化成處理液之塗布方法可採用如噴塗法、輥塗法、棒 塗法、簾流動塗布法、靜電塗布法等方法。 化成處理液之乾燥溫度（表面溫度）以6〇〜14〇〇c為佳。 再者，在化成處理塗膜12之表面上塗布彩色透明漆塗 料並加以乾燥（燒固），形成彩色透明漆塗膜丨3，藉此得到彩 色透明漆塗裝不鏽鋼板1〇。 衫色透明漆塗料中之丙稀酸樹脂以及封端異氛酸醋之 比例以相對於丙稀_脂之交雛官能基i莫耳，含有異氛 曰基0.1 2.0莫耳之比例者為佳；以相對於丙稀酸樹脂之 父聯性官能基1莫耳，含有異氰酸g旨基gi〜iq莫耳之比例者 φ 更佳；又以相對於__脂之㈣性官能基以耳，含有 異氰_基0.2〜0.8莫耳之比例者特佳。。 塗料々色透明'黍塗膜13之形成相，彩色透明漆 塗枓可含有封端異氰酸醋化合物之固化催化劑。 =異氛_化合物之固化催化劑可舉例如：氧化二 正丁基錫、氣化二正丁基錫 m , χ . 、一月桂酸二正丁基錫、二醋 酸一正丁基錫、氧化二正辛 四正丁基錫等。 基錫、二月桂酸二正辛基錫、 除了封端異氰酸酿化合物以外，若彩色透明漆塗料含 18 201004792 有胺基樹脂來作為交聯劍，彩色透明漆塗料中之胺基樹脂 含量相對於丙烯酸樹脂固形物含量100質量份，以10〜40質 量份者為佳，又以15〜30質量份者更佳。若彩色透明漆塗料 中之胺基樹脂含量低於10質量份’會無法充分提高耐磨刮 性；若超過40質量份，則會難以形成彩色透明漆塗膜13。 又，若彩色透明漆塗料含有胺基樹脂，丙烯酸樹脂之 固化時間（燒固時間）會加長，因此，可含有胺基樹脂之固化 催化劑，若彩色透明漆塗料含有胺基樹脂之固化催化劑， 可縮短固化時間。 作為胺基樹脂之固化催化劑可舉例如：磺酸系催化 劑、胺系催化劑等，但由於P-甲苯磺酸系催化劑可特別發 揮縮短燒固時間之效果，又以該者為佳。 設丙烯酸樹脂、封端異氰酸酯化合物以及胺基樹脂合 計量為100質量份，胺基樹脂之固化催化劑量以0.5〜5質量 份為佳，又以1〜2質量份更佳。 設丙烯酸樹脂、封端異氰酸酯化合物以及胺基樹脂合 計量為100質量份，若胺基樹脂之固化催化劑量低於0.5質 量份，會無法縮短固化時間；若超過5質量份，所得之彩色 透明漆塗裝不鑛鋼板10的加工性會降低。 若彩色透明漆塗料含有聚烯烴系蠟，該聚烯烴系蠟之 平均粒徑以0·1~7.0μηι為佳。若聚烯烴系蠟之平均粒徑超過 7.0μιη，會降低彩色透明漆塗膜13中之聚烯烴系蠟的分散 性；若低於〇·1μπι，所得之彩色透明漆塗裝不鏽鋼板10之加 工性會降低。 19 201004792 若要使彩色透明漆塗料含有矽溶膠，亦可藉由添加有 機矽溶膠來調製彩色透明漆塗料。 有機矽溶膠意指在有機溶劑中穩定地分散有奈米尺寸 膠態矽之膠態溶液。 有機矽溶膝可舉例如：MA-ST-M、IPA-ST、EG_ST、 EG-ZL、NPC-ST、DMAC-ST、DMAC-ST-ZL、XBA-ST、 MIBK-ST(上述產品皆為Nissan Chemical Industries, Ltd.(日 産化学工業株式会社)製）等。該有機矽溶膠可單獨使用，亦 可併用2種以上。 可使用與用以塗布化成處理液之相同方法來作為彩色 透明漆塗料之塗布方法。 在前述所說明之彩色透明漆塗裝不鏽鋼板1〇中，由於 於色透明漆塗膜13含有平均一次粒子徑為1 〇〜11 〇〇nrn之顏 料，且顏料容積濃度為〇_5〜5 〇質量％，故具有優異之透明 性及鮮豔性外且可著色較濃，因此，會因為不鏽鋼板原板 之辨識性優異，且可維持住不鏽鋼質感而以較濃色調著 色，故該彩色透明漆塗裝不鏽鋼板1〇具有高度設計性。 前述彩色透明漆塗裝不鏽鋼板10最適合使用於家庭用 或商業用之電氣製品、電子機械製品之框體。 又，本發明並不受限於前述實施形態例，例如，前述 實施形態例係僅在不鏽鋼板原板單面上形成彩色透明漆塗 膜者’但是亦可在不鏽鋼板原板雙面上皆形成彩色透明漆 塗膜；又’前述實施形態例在不鏽鋼板原板以及彩色透明 漆塗膜之間具有化成處理塗膜，但若不具有化成處理塗膜 201004792 也無妨。 [實施例] (實驗例1) 在具有溫度計、回流冷凝器、攪拌器、滴液漏斗、氮 氣導管之四口燒瓶中，依第1表所示之調配量放入甲苯、乙 酸丁酯，昇溫至no°c並一面灌入氮氣一面攪拌，並將甲基 丙烯酸甲酯、苯乙烯、曱基丙烯酸正丁酯、曱基丙烯酸2_ 羥乙酯、丙烯酸曱酯、偶氮異丁腈（AIBN)之混合物經滴液3 個小時’在滴液結束後，追加AIBN並以相同溫度再反應3 個小時’而得到不揮發成分為50%之丙烯酸樹脂溶液。 接著’調入作為固化劑之封端異氰酸酯「浐只千夕二 一/^(Desmodule)VPLS2253 j (Sumika Bayer Urethane Co., Ltd.(住化’彳工卜夕^株式会社)製，nc〇含有率為 1〇.5質量％)，以得到彩色透明漆塗料。 再者’在該彩色透明漆塗料中，以顏料容積濃度0.8〇/〇 之比例來調合作為紅色顏料之茈系紅（平均一次粒子徑： 40〜100nm，分散粒度：ΙΟμπι以下），再調合聚烯烴系蠟(融 點為120°C、粒徑為2μιη之聚乙烯蠟)2.〇質量份，以得到彩 色透明漆塗料。 接著’在厚度為1.3mm之玻璃板(MatsunamiGlassInd·， S力只）製）單面上塗布前述彩色透明漆塗料， 並以180。(：、20分鐘之條件燒固，以成膜出厚度為3μιη之彩 色透明漆塗膜。 [第1表] 21 201004792 (實驗例2〜18) 除了顏料容積濃度及顏料種類變更成第2表所示者 外，其餘皆以實驗例1相同條件於玻璃板上成膜出彩色透明 漆塗膜。 測量實驗例1〜18之彩色透明漆塗膜的相對透光率，第2 圖係顯示實驗例卜6之結果，第3圖係顯示實驗例7〜12之結 果，第4圖係顯示實驗例13〜18之結果。 此處之彩色透明漆塗膜的相對透光率係以下列方法測 量。 ❹ 首先，調製出除了不含顏料以外，其餘條件皆相同之 透明漆塗料，並塗布於厚度1.3mm之玻璃板上以成膜出透 明漆塗膜。 接著’測量用以塗布彩色透明漆塗料之玻璃板本身的 可見光透射率（測定器：Shimadzu Corporation(島津製作所） 製分光光度計UV2500PC)，並製成基線，接著，測量將彩 色透明漆塗膜成膜於玻璃板上之彩色透明漆塗裝玻璃板的 可見光透射率’或是測量將透明漆塗膜成膜於玻璃板上之 ® 透明漆塗裝玻璃板的可見光透射率。 再者’設透明漆塗裝玻璃板之可見光透射率為100〇/〇， 以求出彩色透明漆塗裝玻璃板之可見光透射率的比例，此 即相對透光率。 該相對透光率為彩色透明漆塗膜透明性之指標，若相 對透光率愈尚，則表示透明性愈高。 [第2表] 22 201004792 依據第2圖〜第4圖之結果，可知顏料容積濃度愈高，透 明性愈低’然而’藉由目視所得之評價而言，含有平均— 次粒子徑為10〜11〇〇nm之顏料，且顏料容積濃度為〇 5〜5 〇% 之實驗例2〜5、8〜11及14〜π的彩色透明漆塗膜，透明性高 且顏色較濃。 特別是’若紅色顏料（茈系紅）之相對透光率為 5〇〜65/〇 ’藍色顏料(銅狄菁藍）之相對透光率為30〜55%，棕 骞 色顏料（商品名：COLORFINE BROWN)之相對透光率為 5·5〜7〇%時，彩色透明漆塗膜之_性會更高，且顏色會更 濃(如第2圖〜第4圖之空心記號數值(◊)範圍）。又，若各個 顏料之相對透光率低於底限值，著色力會降低 :若超過上 限值透明性則會降低而不適合使用（如帛2圖〜第4圖之實 心記號數值。 因此，在不鏽鋼板原板上形成有含有平均一次粒子徑 為11 〇〇nm之顏料，且該顏料容積濃度為〇 5〜5 0%之彩色 • 透明漆塗膜’所得到之彩色透明漆塗裝不繡鋼板中，不鏽 鋼板原板之辨識性高，且可活用該原板之不鏽鋼 質感並著 色較濃。 (實驗例19〜24) •除了顏料變更成第3表所示者外，其餘皆以實驗例】相 肖條件於麵板上形成彩色透明漆塗膜，並且藉由實驗例 4同方去來测1相對透光率，其顯示於第3表。 [第3表] 第表所示，含有平均一次教子徑為〇誰之顏 23 201004792 料的彩色透明漆塗骐，透明性優異，然而，藉由目視所得 之評價而言，所得之彩色透明漆塗膜係著色較濃者。 因此，在不鏽鋼板原板上形成有含有平均一次粒子徑 為10〜llOOnm之顏料的彩色透明漆塗膜，所得到之彩色透明 漆塗裝不鏽鋼板中，不鏽鋼板原板之辨識性高，且可活用 該原板之不鏽鋼質感並著色較濃。 (實驗例25〜36) 除了顏料分散粒度及顏料容積濃度變更成第4表所示 者外，其餘皆以實驗例丨相同條件於玻璃板上形成彩色透明 參 漆塗膜，且以JIS K 5600-4-7為準則使用光澤測定儀 (BYK-Gardner GmbH製，型號micro_TRI_gl〇ss)對各個彩色 透明漆塗膜測量20度光澤度，其結果如第5圖〜第7圖所示， 又，20度光澤度為鮮豔性之指標，2〇度光澤度愈高，鮮豔 性愈優異。 - 若顏料分散粒度為25μιη以下，紅色、藍色 '棕色任— 色之20度光澤度皆很高，且鮮豔性優異（如第5圖〜第7圖之 空心記號數值（◊)範圍）；相對地，若顏料分散粒度超過 魯 25μηι，20度光澤度則會低於8〇% ,有鮮豔性降低之傾向（如 第5圖〜第7圖之實心記號數值(♦))。 [第4表] (實施例1) 本發明之彩色透明漆塗膜不鏽鋼板，即為用以預敷、 壓縮成形等之成形用材料，因此，最重要的是必須具有高 度成形後之設計性。在此，為了調查彩色透明漆塗膜不鏽 24 201004792 鋼板成形後之设計性，測量拉伸實驗後之2〇度光澤度。又， 由於壓縮成形會產生拉伸變形，故拉伸實驗後之光澤度可 視為壓縮成开>後之光澤度，特別是在拉伸率❶時相關性最 高。 以下s兒明彩色透明漆塗膜不鏽鋼板之製造方法及拉伸 «實驗方法。 藉由塗布輥在不鏽鋼板原板（SUS3〇42N〇.4精加工研 φ 磨品）之單面上，塗布含有胺基矽烷系耦合劑之化成處理 劑，並以表面溫度為l〇〇°C進行乾燥，並成膜出附著量為 l〇mg/m2之化成處理塗膜。 接著，藉由塗布棒在化成處理塗膜表面上塗布與實驗 • 例2相同之彩色透明漆塗料，並以表面溫度224。(：進行燒 、 固，成膜出厚度為3〜5μιη之彩色透明漆塗膜，以得到彩色 透明漆塗裝不鏽鋼板。 (實驗例2、3) ® 除了彩色透明漆塗料變更成如實驗例8、14者外，其餘 白以實驗例1相同條件得到彩色透明漆塗裝不鏽鋼板。 藉由下列條件進行實驗例1〜3之彩色透明漆塗裝不鏽 板的拉伸實驗’並測量實驗後之20度光澤度，其測量結果 如第8圖所示。 [拉伸實驗] 測量機械：島津製作所製AUTOGRAFH(才一卜夕'歹7) 抵伸迷度：50mm/分鐘 扳伸率：2% 25 201004792 測量溫度：23°C [光澤度測量] 以JIS K 5600-4-7為準則使用光澤測定儀 (BYK-Gardner GmbH製，型號micr〇_TRI_gi〇ss)測量作為鮮 豔性指標之20度光澤度。 如第8圖所示，即使以拉伸率2%使實施例丨〜3之彩色透 明漆塗裝不鏽鋼板拉伸變形後，可確認2〇度光澤度不會出 現大幅降低，仍為80%以上，而可抑制設計性降低。 [產業上之可利用性] Φ 根據本發明，可提供一種不鏽鋼板原板之辨識性優 異，且可維持住不鏽鋼質感而以較濃色調著色，以藉此具 有高度設計性之彩色透明漆塗裝不鏽鋼板，又，由於該彩 色透明漆塗裝不鏽鋼板在壓縮成形之後光澤度不會大幅降 低可抑制設計性降低，因此，最適合使用於家庭用或商 - 業用之電氣製品、電子機械製品之框體。 26 201004792N-butyl methacrylate, cyclohexyl methacrylate, or a cyclic acrylate. Dilute acid tree & can also be combined with non-functional acrylic acid monomers and other monomeric filaments of functional monomers, such as: mercapto ethyl ether ethyl ethyl ketone shout, positive Ethyl propyl sulfonate, n-butyl ethene keisaki, etc. Ethyl kiwi, stupid ethylene, α• 曱 笨 笨 乙 等 等 等 Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Acrylic amine and other monomers such as amine. The glass transition point of the acrylic resin is preferably 3 〇 to 9 〇 < t, and more preferably 5 〇 to 9 〇 ° C. The above-mentioned color clear paint-coated stainless steel sheet 10 rubs and processes heat during continuous pressurization, and the surface temperature of the money rises. c, therefore, 11 201004792 If the glass transition point of the acrylic resin is below 30.匸, the color clear lacquer medium 13 softens and adheres to the mold; and if the glass transition point of the acrylic resin exceeds 90 ° C, pores and flatness are likely to occur. The constitution of the acrylic resin can be suitably selected so that the glass transition temperature of the acrylic resin is maintained within the above range. The number average molecular weight of the acrylic resin is preferably 3 Å to 5 Å, and more preferably 4,000 to 10,000. If the number average molecular weight of the acrylic resin is less than 3,000, the reactivity with the blocked isocyanate compound is lowered, and the color clear paint coating film 13 is not easily formed; if the number average molecular weight of the acrylic resin exceeds the reference of 50000, the solvent solubility is lowered. It is therefore difficult to obtain a color clear lacquer coating. The number average molecular weight of the acrylic resin can be adjusted depending on the conditions at which the acrylic resin is produced (e.g., polymerization temperature, polymerization amount, etc.). A blocked isocyanate compound which is a crosslinking agent for crosslinking an acrylic resin is a compound having two or more isocyanic acid in one molecule, and specifically, for example, Acid s|, diphenyl diisocyanate? Vinegar, phthalic acid diisocyanate _ U acyl acid S is an aromatic diiso _ ethyl ester, hexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic dinic acid vinegar; isophorone diiso Cyanic acid vinegar, cycloheximide diiso-acid vinegar and other fat 哀 族 二 diisocyanate brewing; the above polyisogas vinegar condensed two-type adduct, trimeric isocyanate ring-type adduct, etc. There are also _, (4), reactive urethanes, chlorhexidine, trisal, and other types of blocking agents, and an organotin catalyst such as dibutyltin laurate is used as a blocking agent. Dissociation accelerator is used. 12 201004792 Commercially available blocked isocyanate compounds include, for example, 歹7β二'-(Desmodule) BLl 100 'BL1265MPA/X ' VPLS2253 'BL3475BS/SN, BL3272MPA, BL3370MPA, BL4265SN, X only ΐ one f Λ (Desmotherm) 2170, only S ^ 2 / V (Sumidule) 3175 (the above products are all made by Sumika Bayer Urethane Co., Ltd.), 歹 '二歹Duranate 17B-60PX, TPA-B80X, MF-B60X, MF-K60X (all of the above products are manufactured by Asahi Kasei Chemicals Corporation (Asahi Kasei Chemicals Corporation), / / / V ( (Burn 〇 )) DB-980K, D-550, B3-867, B7-887-60 (all of the above products are manufactured by Dainippon Ink and Chemicals (Dainippon Chemical Industry Co., Ltd.)) Coronate) 2515, 2507, 2513 (all of the above products are manufactured by Nippon Polyurethane Industry Co., Ltd.) and the blocked isocyanate compounds may be used alone or in combination. Use two or more types. Since the color clear coating film 13 is harder and the acrylic resin has a higher scratch resistance, it is preferable to use not only the blocked isocyanate compound but also an amine resin (melamine resin). The amine-based resin is a general term for a resin which causes an addition reaction of an amine compound (melamine, guanamine, urea) and formaldehyde (formalin) and is modified with an alcohol. Specifically, examples thereof include a melamine resin, a benzoguanamine resin, a urea resin, a butylated urea resin, a butylated urea melamine resin, a glycoluril resin, an acetamide resin, a cyclohexyl decylamine resin, and the like. In terms of fingerprint resistance, abrasion resistance, and chemical resistance, melamine resin is preferred as 13 201004792. The melamine resin can be classified into a methylated melamine resin, a n-butylated melamine resin, an isobutylated melamine resin, a mixed alkylated melamine resin, etc., depending on the type of alcohol to be modified. Specifically, the thiolated melamine resin may, for example, be Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, 715, 701, 267, 285, 232, 235. , 236, 238, 211, 254, 204, 212, 202, 207 (all of the above products are manufactured by Mitsui Cytec Ltd.), LUWIPAL 063, 066, 068, 069, 072, 073 (The above products are all made by BASF), and only Super 8 -8 S (SuperBeckamine) L-105 (all of the above products are made by Dainippon Ink and Chemicals), 〆7 (Melan) 522, 523, 620, 622, and 623 (all of the above products are manufactured by Hitachi Chemical Co., Ltd., manufactured by Hitachi Chemical Co., Ltd.). The n-butylated melamine resin may, for example, be 7 彳; π — (Mycoat) 506 and 508 (all of the above products are manufactured by Mitsui Cytec Ltd.), 2, > (Uvan) 20SB, 20SE, 21R, 22R, 122, 125, 128, 220, 225, 228, 28-60, 20HS, 2020, 2021 '2028, 120 (all of the above products are manufactured by Mitsui Chemical, Inc.) ), PLASTOPALEBS 100A, 100B, 400B, 600B, CB (all of the above products are made of BASF), only one eight one / ^; / force S y (SuperBeckamine) J-820 'L-109, L-117, L-127 L-164 (all of the above products are manufactured by Dainippon Ink and Chemicals), ^ 歹^(Melan) 21A, 22, 220, 2000, 201004792 8000 (all of the above products are Hitachi Chemical Co., Ltd. (made by Hitachi Chemical Co., Ltd.), only 7 ^^ (Tesazine) 3020, 3021, 3036 (all of the above products are Hitachi Kasei Polymer Co., Ltd. (Hitachi Kasei Polymer Co., Ltd.) Co., Ltd.)). The isobutylated melamine resin may, for example, be rL-A^(Uvan)60R, 62, 62E, 360, 361, 165, 166-60, 169, 2061 (the above products are Mitsui Chemical, Inc. (Mitsui Chemical Co., Ltd.) )), 7-81^< y force S; y (SuperBeckamine) G-821, L-145, L-110, L-125 (all of the above products are Dainippon Ink and Chemicals) Club)), PLASTOPAL EBS 4001, FIB, H731B, LR8824 (all of the above products are made by BASF) ' 夕 y ^ (Melan) 27, 28, 28D, 245, 265, 269, 289 (all of the above products are Hitachi Chemical Co ., Ltd. (made by Hitachi Chemical Co., Ltd.), 亍 7 e^(Tesazine) 3027, 3028, 3029, 3030, 3037 (all of the above products are Hitachi Kasei Polymer Co., Ltd. (Hitachi Kasei Polymer Co., Ltd.) — Co., Ltd.)). The mixed alkylated melamine resin may, for example, be 廿彳>Cymel 267, 285, 232, 235, 236, 238, 211, 254, 204, 212, 202, 207 (all of the above products are Mitsui Cytec Ltd. Mitsui 廿彳亍V Xi Co., Ltd.)). The amine-based resin may be used singly or in combination of two or more. The color clear varnish coating film 13 preferably contains a polyolefin-based wax, and if the color clear varnish coating film 13 contains a polyolefin-based wax, the color transparent lacquer-coated stainless steel sheet has a lubricity which is higher than that of an oil-based lubricant. High, and more processing 15 201004792 excellent. Examples of the polyolefin-based wax include hydrocarbon waxes such as paraffin wax, microcrystalline wax, polyethylene, and polyethylene-fluorine. When the color transparent lacquer is applied to the stainless steel plate 10, since the temperature of the coating film rises due to processing heat and frictional heat, the melting point of the polyolefin system is preferably 70 to 160 ° C. If the melting point is lower than 7〇〇c, it will soften and melt during processing and will not exhibit the excellent properties as a solid lubricating additive. If the melting point of the polyolefin system is higher than 160 °C, it will be lowered due to the presence of hard particles on the surface. Due to the friction characteristics, high workability cannot be obtained. The acid value of the polyolefin-based wax is preferably from 0 to 30. If the acid value of the polyolefin-based wax is higher than 30, the polyolefin-based wax is difficult to float evenly because it improves the mutual solubility with the thermosetting resin composition. As far as the surface of the coating film is concerned, the processability of the colored transparent varnish coated stainless steel sheet 10 may be insufficient. The content of the polyolefin-based wax in the color clear varnish coating film 13 is preferably 1 part by mass based on the solid content of the thermosetting resin composition, and preferably contains 〇25 to 1 〇 by mass. If the content of the polyolefin-based wax is less than 0.25 parts by mass, the processability may be insufficient. If it is more than 10 parts by mass, the surface of the coating film may be uneven in depth, thereby damaging the appearance of the colored transparent varnish coated stainless steel sheet 10. . Further, the color clear paint film 13 may contain a cerium sol, and the cerium sol herein means a nanometer (nm) cerium oxide particle. If the color transparent paint 骐13 contains bismuth sol, it can improve the hardness, scratch resistance and fingerprint contamination of the film. The cerium sol content is preferably 1 part by mass per thermosetting resin composition, and the solid content is 2_0 to 10 parts by mass, more preferably 3. 〇 to 8.0 parts by mass. If the sol content is less than 2.0 parts by mass, abrasion resistance, hardness, and the like may be insufficient; 16 201004792 If it exceeds ί mass parts, there is a tendency to reduce workability. Moreover, the color transparent paint film 13 may also contain a flattening agent as an additive, an antifoaming agent, an antioxidant, an ultraviolet absorber, a delustering agent, a stone coupling agent, etc., and may also contain an epoxy resin. , enamel resin, Dun resin, polyester, etc. The film thickness of the color clear lacquer coating film 13 is preferably 1 to ιομη! If the film thickness of the color clear paint film 13 is lower than Ιμηι, the lubricating function of the color clear paint film 13 may not be fully exerted, and in addition to the tendency of the color transparent paint-coated stainless steel plate 10 to have reduced workability, the color clear paint The coloring effect of the coating film 13 may not be sufficient, and the design of the color transparent paint-coated stainless steel plate may not be improved; and if the film thickness of the color transparent paint film 13 exceeds 1 μm, the color transparent paint film 13 The lubricating function is saturated and it is difficult to form the color clear paint film 13, and moreover, the transparency of the color clear paint film 13 is lowered, and the original material of the original plate 11 of the stainless steel plate cannot be seen, thereby degrading the design. [Manufacturing Method] An example of a method for producing the above-described colored clear varnish-coated stainless steel sheet will be described. Further, the manufacturing method of the color transparent paint-coated stainless steel sheet is not limited to the following examples. In the manufacturing method of this example, first, the stainless steel plate original plate 11 is subjected to a conventional pretreatment such as thermal degreasing, acid/test, and the like. Then, a chemical conversion treatment liquid containing one or both of an amino decane-based coupling agent and an epoxy decane-based coupling agent is applied onto the original stainless steel plate u, and dried to form a chemical conversion coating film 12. 17 201004792 A commercially available product can be used as the chemical conversion treatment liquid, and the commercially available chemical conversion treatment liquid can be, for example, pal-C〇at E305, 3750, 375, 3,753, 3,756, 3,757, 3,970 (Nihon Parkerizing Co). Ltd. (made by Nippon Shoji 7: 夂: 夂), 7々f* — 7(Alsur〇44〇(Nipp〇n Paint Co·, Ltd.) The coating method for the chemical conversion treatment liquid may be, for example, a spray coating method, a roll coating method, a bar coating method, a curtain flow coating method, an electrostatic coating method, etc. The drying temperature (surface temperature) of the chemical conversion treatment liquid is 6 〇 14 Further, 彩色c is preferred. Further, a color clear lacquer coating is applied on the surface of the chemical conversion coating film 12 and dried (burned) to form a color transparent varnish coating film ,3, thereby obtaining a color transparent varnish coated stainless steel plate. 1〇. The proportion of acrylic resin and blocked isocyanic acid vinegar in the transparent paint of the shirt is relative to the propylene-based fat-based functional group i mole, containing a ratio of 0.1 2.0 moles of different thiol groups. It is preferred; it contains isocyanate g relative to the parental functional group of the acrylic resin. The ratio of the base gi~iq Moer is better; it is especially good in terms of the ratio of the isocyanine-based 0.2 to 0.8 molar relative to the __ lipid (four) functional group. 'The formation phase of the ruthenium coating film 13, the color transparent varnish coating 枓 can contain a curing catalyst for the blocked isocyanate compound. The curing catalyst of the heterogeneous compound can be, for example, di-n-butyltin oxide or di-n-butyltin oxide. , χ . , di-n-butyltin laurate, n-butyltin diacetate, di-n-octyl butyltin oxide, etc. base tin, di-n-octyltin dilaurate, in addition to blocked isocyanate compound, if color Clear lacquer coating containing 18 201004792 Amine-based resin as cross-linking sword, the content of amine-based resin in color clear lacquer coating is 100 parts by mass relative to the solid content of acrylic resin, preferably 10 to 40 parts by mass, and 15 More preferably, it is difficult to form a color clear paint film 13 if it exceeds 40 parts by mass. Also, if the color is transparent The coating contains an amine-based resin, and the curing time (burning time) of the acrylic resin is lengthened. Therefore, the curing catalyst of the amine-based resin may be contained, and if the color clear lacquer coating contains a curing catalyst of an amine-based resin, the curing time can be shortened. The curing catalyst of the base resin may, for example, be a sulfonic acid catalyst or an amine catalyst. However, since the P-toluenesulfonic acid catalyst can particularly exhibit the effect of shortening the baking time, it is preferable to use an acrylic resin or a seal. The total amount of the terminal isocyanate compound and the amine-based resin is 100 parts by mass, and the amount of the curing catalyst of the amine-based resin is preferably 0.5 to 5 parts by mass, more preferably 1 to 2 parts by mass. The total amount of the acrylic resin, the blocked isocyanate compound, and the amine-based resin is 100 parts by mass. If the amount of the curing catalyst of the amine-based resin is less than 0.5 parts by mass, the curing time cannot be shortened; if it exceeds 5 parts by mass, the resulting colored transparent paint The workability of the coated non-mineral steel sheet 10 is lowered. If the color clear lacquer coating contains a polyolefin-based wax, the average particle diameter of the polyolefin-based wax is preferably from 0.1 to 7.0 μm. If the average particle diameter of the polyolefin-based wax exceeds 7.0 μm, the dispersibility of the polyolefin-based wax in the color clear paint coating film 13 is lowered; if it is less than 〇·1 μm, the obtained color transparent paint-coated stainless steel sheet 10 is processed. Sex will decrease. 19 201004792 In order to make the color clear lacquer coating contain cerium sol, the color clear lacquer coating can also be prepared by adding a cerium sol. The organic cerium sol means a colloidal solution in which a nano-sized colloidal cerium is stably dispersed in an organic solvent. For example, MA-ST-M, IPA-ST, EG_ST, EG-ZL, NPC-ST, DMAC-ST, DMAC-ST-ZL, XBA-ST, MIBK-ST (all of the above products are Nissan Chemical Industries, Ltd., manufactured by Nissan Chemical Industries, Ltd.). The organic cerium sol may be used singly or in combination of two or more. The same method as that for coating the chemical conversion treatment liquid can be used as the coating method of the color clear lacquer paint. In the color clear paint-coated stainless steel sheet 1 ー described above, since the color clear paint coating film 13 contains a pigment having an average primary particle diameter of 1 〇 to 11 〇〇nrn, and the pigment volume concentration is 〇_5 to 5 〇% by mass, so it has excellent transparency and vividness, and can be colored more. Therefore, it is because the original plate of stainless steel plate has excellent visibility and can maintain the texture of stainless steel and is colored in a rich color. Therefore, the color transparent paint The coated stainless steel plate is highly designed. The above-mentioned color clear varnish coated stainless steel sheet 10 is most suitable for use in a housing for electrical or electronic mechanical products for domestic or commercial use. Further, the present invention is not limited to the above-described embodiment. For example, in the above-described embodiment, the color clear paint coating film is formed only on one surface of the original stainless steel plate, but the color may be formed on both sides of the original plate of the stainless steel plate. The transparent paint coating film; in the above embodiment, the chemical conversion coating film is provided between the original stainless steel plate and the color clear paint coating film, but it is not necessary to have the chemical conversion coating film 201004792. [Examples] (Experimental Example 1) In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel, and a nitrogen gas line, toluene and butyl acetate were placed in the amount shown in Table 1, and the temperature was raised. Stir to no °c while filling with nitrogen, and methyl methacrylate, styrene, n-butyl methacrylate, 2-hydroxyethyl methacrylate, decyl acrylate, azoisobutyronitrile (AIBN) The mixture was dripped for 3 hours 'after the completion of the dropping, AIBN was added and reacted for another 3 hours at the same temperature' to obtain an acrylic resin solution having a nonvolatile content of 50%. Then, 'the blocked isocyanate as a curing agent' was added to the VPLS2253 j (Sumika Bayer Urethane Co., Ltd.), nc〇 The content is 1〇.5 mass%) to obtain a color clear lacquer coating. In addition, in the color clear lacquer coating, the red pigment is blended with a pigment volume concentration of 0.8 〇 / 〇 (average Primary particle diameter: 40 to 100 nm, dispersion particle size: ΙΟμπι or less), and then blended with polyolefin wax (polyethylene wax having a melting point of 120 ° C and a particle size of 2 μηη) 2. 〇 by mass to obtain a color transparent lacquer coating Then, the above-mentioned color clear lacquer coating was applied on one side of a glass plate (Matsunami Glass Ind, S-only) having a thickness of 1.3 mm, and baked at 180° (for 20 minutes) to form a film thickness. The film was coated with a color transparent paint of 3 μm. [Table 1] 21 201004792 (Experimental Examples 2 to 18) In the same manner as in Experimental Example 1, except that the pigment volume concentration and the type of the pigment were changed to those shown in the second table. A color transparent paint film is formed on the board. The relative light transmittance of the color clear paint film of Test Examples 1 to 18, the second figure shows the results of Experimental Example 6, the third figure shows the results of Experimental Examples 7 to 12, and the fourth figure shows Experimental Example 13. The result of ~18. The relative light transmittance of the color clear paint film here is measured by the following method. ❹ First, a clear paint coating having the same conditions except for the absence of the pigment is prepared and coated to a thickness of 1.3 mm. The transparent lacquer coating film was formed on the glass plate. Next, the visible light transmittance of the glass plate itself for coating the color clear varnish coating (measuring device: Shimadzu Corporation, Shimadzu Corporation, spectrophotometer UV 2500 PC) was measured and made. Baseline, then, measure the visible light transmittance of a color clear lacquer coated glass plate that is coated with a colored clear lacquer film on a glass plate or measure the clear lacquer coating of a clear varnish film formed on a glass plate The visible light transmittance of the glass plate. In addition, the visible light transmittance of the transparent varnish coated glass plate is 100 〇 / 〇 to determine the ratio of the visible light transmittance of the colored transparent lacquer coated glass plate. The light transmittance is an index of the transparency of the color clear paint coating film. If the relative light transmittance is higher, the transparency is higher. [Table 2] 22 201004792 According to Fig. 2 to 4 As a result of the graph, it is found that the higher the volume concentration of the pigment, the lower the transparency. However, by visual evaluation, the pigment having an average-order particle diameter of 10 to 11 Å is contained, and the pigment volume concentration is 〇5. ～5 〇% of the color transparent lacquer coatings of Experimental Examples 2 to 5, 8 to 11, and 14 to π, which have high transparency and a strong color. In particular, if the red light pigment (lanthanide red) has a relative light transmittance of 5 〇 to 65 / 〇 'blue pigment (copper phthalocyanine blue), the relative light transmittance is 30 to 55%, and the brown ochre pigment (commercial product) Name: COLORFINE BROWN) When the relative light transmittance is 5·5~7〇%, the color transparent paint film will be more sturdy and the color will be more concentrated (such as the hollow mark values in Figures 2 to 4). (◊) range). Moreover, if the relative light transmittance of each pigment is lower than the lower limit value, the coloring power is lowered: if the transparency exceeds the upper limit value, the transparency is lowered and it is not suitable for use (for example, the solid mark values of 帛2 to 4). A pigment having an average primary particle diameter of 11 〇〇nm is formed on the original plate of the stainless steel plate, and the color concentration of the pigment is 〇5 to 50% of the color. • The transparent lacquer coating obtained by the transparent lacquer coating is not embroidered. Among the steel sheets, the original sheet of the stainless steel sheet has high visibility, and the stainless steel texture of the original sheet can be utilized and the color is thicker. (Experimental Examples 19 to 24) • Except that the pigment is changed to the one shown in Table 3, the rest are experimental examples. The color transparent paint coating film was formed on the panel, and the relative light transmittance was measured by the same method as in Experimental Example 4, which is shown in Table 3. [Table 3] The table shows that the average value is included once. The color of the transparent transparent paint is excellent, and the transparency is excellent. However, the color transparent paint film obtained by the visual evaluation is more colored. Therefore, in the stainless steel plate Contained on the original plate The color clear lacquer coating film of the pigment having a primary particle diameter of 10 to 10 nm is obtained, and the obtained transparent lacquer coated stainless steel plate has high visibility of the original plate of the stainless steel plate, and can utilize the stainless steel texture of the original plate and is colored more. (Experimental Examples 25 to 36) A color transparent varnish coating film was formed on a glass plate under the same conditions as in Experimental Example 除了 except that the pigment dispersion particle size and the pigment volume concentration were changed to those shown in Table 4, and JIS K 5600 was used. -4-7 is a standard measuring gloss of 20 degrees for each color clear paint film using a gloss meter (manufactured by BYK-Gardner GmbH, model micro_TRI_gl〇ss), and the results are shown in Fig. 5 to Fig. 7, and The 20-degree gloss is an indicator of vividness, and the higher the gloss of 2〇, the better the vividness. - If the pigment dispersion particle size is 25 μm or less, the red and blue 'brown color-color 20-degree gloss is high. And the vividness is excellent (such as the range of the hollow mark value (◊) in Fig. 5 to Fig. 7); relatively, if the pigment dispersion particle size exceeds Lu 25μηι, the 20 degree gloss degree is lower than 8〇%, and the vividness is lowered. Tendency (Figure 5) The solid symbol value (♦) of Fig. 7 [Table 4] (Example 1) The color clear paint coated stainless steel sheet of the present invention is a molding material for pre-application, compression molding, or the like. The most important thing is that it must have a highly formed design. Here, in order to investigate the design of the color transparent paint film stainless steel 24 201004792 steel sheet after forming, measure the 2 degree gloss after the tensile test. Compression forming will produce tensile deformation, so the gloss after the tensile test can be regarded as the gloss after compression into the opening, especially in the case of the stretching rate 。. The following s children bright color transparent paint film stainless steel Plate manufacturing method and stretching «experimental method. By applying a coating roll to a single side of a stainless steel plate original plate (SUS3〇42N〇.4 finishing φ grinding product), a chemical conversion treatment agent containing an amino decane-based coupling agent is applied, and the surface temperature is l〇〇°C. The film was dried, and a coating film having a deposition amount of 10 mg/m 2 was formed. Next, the same color clear lacquer paint as in Experimental Example 2 was applied onto the surface of the chemical conversion treatment coating film by a coating bar, and the surface temperature was 224. (: Burning and solidifying, forming a color transparent paint film having a thickness of 3 to 5 μm to obtain a color transparent paint coated stainless steel plate. (Experimental Examples 2, 3) ® In addition to the color clear paint coating, as in the experimental example Except for the others of 8, and 14, the colored transparent paint-coated stainless steel plate was obtained under the same conditions as in Experimental Example 1. The tensile test of the color transparent paint-coated stainless steel plate of Experimental Examples 1 to 3 was carried out and the measurement experiment was carried out by the following conditions. After the 20 degree gloss, the measurement results are shown in Fig. 8. [Tensile experiment] Measuring machine: AUTOGRAFH manufactured by Shimadzu Corporation (Jinyi 夕 '歹7) Tension: 50mm/min. 2% 25 201004792 Measurement temperature: 23 ° C [Gloss measurement] Using a gloss meter (manufactured by BYK-Gardner GmbH, model micr〇_TRI_gi〇ss) as a criterion for vividness, using JIS K 5600-4-7 as a guideline 20 degree gloss. As shown in Fig. 8, even if the color clear paint-coated stainless steel plate of Example 丨~3 was stretched and deformed at an elongation ratio of 2%, it was confirmed that the 2 degree gloss did not significantly decrease. , still more than 80%, and can inhibit the design decline. UTILITY] Φ According to the present invention, it is possible to provide an original plate of a stainless steel plate which is excellent in visibility and can maintain a stainless steel texture and is colored in a rich color tone, thereby coating a stainless steel plate with a highly designed color transparent paint. Since the colored transparent varnish-coated stainless steel sheet is not greatly reduced in gloss after compression molding and the design is suppressed from being lowered, it is most suitable for use in a housing for electrical or electronic mechanical products for household or commercial use. 201004792
[第1表] 丙烯酸樹脂 曱苯 25.0質量份 乙酸丁酯 24.0質量份 甲基丙烯酸甲酯 16.0質量份 苯乙烯 5.0質量份 曱基丙烯酸正丁酯 19.5質量份 甲基丙烯酸2-羥乙酯 9.0質量份 丙烯酸甲酯 0.5質量份 偶氮異丁腈（AIBN) 1.0質量份 數平均分子量 5000 玻璃轉移點 60°C 交聯劑 封端異氰酸酯 (Desmodule VPLS2253) 20.0質量份 [第2表] 實驗例編號 顏料種類 顏料容積濃度 (%) 相對透光率 (%) 1 茈系紅 0.3 75 2 0.8 65 3 1.7 56 4 2.0 53 5 2.4 50 6 4.0 40 7 銅酜菁藍 0.3 75 8 0.8 52 9 1.4 38 10 1.8 33 11 2.1 31 12 3.0 20 13 透明性氧化鐵 (標色） 0.3 75 14 0.5 70 15 3.0 65 16 3.8 59 17 4.7 57 18 6.0 45 27 201004792 [第4表] 實驗例編號 顏料種類 顏料容積濃度 (%) 顏料分散粒度 (μιη) 25 A系紅 2.0 10 26 15 27 25 28 40 29 銅酜菁藍 2.0 10 30 15 31 20 32 30 33 透明性氧化鐵 (棕色） 4.0 10 34 15 35 20 36 35[Table 1] Acrylic resin phthalic acid 25.0 parts by mass butyl acetate 24.0 parts by mass methyl methacrylate 16.0 parts by mass styrene 5.0 parts by mass n-butyl decyl acrylate 19.5 parts by mass 2-hydroxyethyl methacrylate 9.0 mass Methyl acrylate 0.5 parts by mass azoisobutyronitrile (AIBN) 1.0 parts by mass average molecular weight 5000 glass transfer point 60 ° C crosslinker blocked isocyanate (Desmodule VPLS 2253) 20.0 parts by mass [Table 2] Experimental example number pigment Volumetric concentration of pigments (%) Relative transmittance (%) 1 Lanthanum red 0.3 75 2 0.8 65 3 1.7 56 4 2.0 53 5 2.4 50 6 4.0 40 7 Copper phthalocyanine blue 0.3 75 8 0.8 52 9 1.4 38 10 1.8 33 11 2.1 31 12 3.0 20 13 Translucent iron oxide (standard color) 0.3 75 14 0.5 70 15 3.0 65 16 3.8 59 17 4.7 57 18 6.0 45 27 201004792 [Table 4] Experimental example No. Pigment type Pigment volume concentration (%) ) Pigment Dispersion Particle Size (μιη) 25 A Series Red 2.0 10 26 15 27 25 28 40 29 Copper Phthalocyanine Blue 2.0 10 30 15 31 20 32 30 33 Transparent Iron Oxide (Brown) 4.0 10 34 15 35 20 36 35
[第3表] 實驗例編號 顏料種類 顏料之平均一次粒子徑 (nm) 19 茈系紅 40〜150 20 銅酜菁藍 50-120 21 氧化鐵 100〜200 22 嗜D丫咬 40〜150 23 二噚畊紫 40〜150 24 碳黑 10 〜80 I：圖式簡單說明3 第1圖係顯示本發明之彩色透明漆塗裝不鏽鋼板的一 個實施形態例之截面圖。 第2圖係顯示實驗例1〜6之顏料容積濃度與相對透光率 之間的關係圖表。 第3圖係顯示實驗例7〜12之顏料容積濃度與相對透光 率之間的關係圖表。 28 201004792 第4圖係顯示實驗例13〜18之顏料容積濃度與相對透光 率之間的關係圖表。 第5圖係顯示實驗例2 5〜2 8之顏料分散粒度與2 0度光澤 度之間的關係圖表。 第6圖係顯示實驗例29〜32之顏料分散粒度與20度光澤 度之間的關係圖表。 第7圖係顯示實驗例33〜36之顏料分散粒度與20度光澤 度之間的關係圖表。 第8圖係顯示實驗例1〜3拉伸變形後之2 0度光澤度的圖 表。 【主要元件符號說明】 10.. .彩色透明漆塗裝不鏽鋼板 12...化成處理塗膜 11.. .不鏽鋼板原板 13...彩色透明漆塗膜 ❹ 29[Table 3] Experimental example No. Pigment type Pigment Average primary particle diameter (nm) 19 Tannin red 40~150 20 Copper phthalocyanine blue 50-120 21 Iron oxide 100~200 22 Azure bite 40~150 23 II噚耕紫40~150 24 Carbon black 10 〜80 I: BRIEF DESCRIPTION OF THE DRAWINGS 3 Fig. 1 is a cross-sectional view showing an embodiment of a color clear varnish coated stainless steel sheet of the present invention. Fig. 2 is a graph showing the relationship between the pigment volume concentration and the relative light transmittance of Experimental Examples 1 to 6. Fig. 3 is a graph showing the relationship between the pigment volume concentration and the relative light transmittance of Experimental Examples 7 to 12. 28 201004792 Fig. 4 is a graph showing the relationship between the pigment volume concentration and the relative light transmittance of Experimental Examples 13 to 18. Fig. 5 is a graph showing the relationship between the pigment dispersion particle size of Experimental Example 2 5 to 28 and the gloss of 20 degrees. Fig. 6 is a graph showing the relationship between the pigment dispersion particle size and the 20 degree gloss of Experimental Examples 29 to 32. Fig. 7 is a graph showing the relationship between the pigment dispersion particle size and the 20 degree gloss of Experimental Examples 33 to 36. Fig. 8 is a graph showing the gloss of 20 degrees after the tensile deformation of Experimental Examples 1 to 3. [Description of main component symbols] 10.. Color transparent paint coated stainless steel plate 12...Chemical processing coating film 11.. Stainless steel plate original plate 13...Color transparent paint film ❹ 29