201239049 六、發明說明： 【發明所屬之技術領域】 本發明關於一種紫外線（uv)固化型處理劑，尤其關於— 種應用於塗裝工業之紫外線固化型處理劑。 【先前技術】 塗料的應用範圍非常廣泛，從日常生活用品到高科技的 電子產品，例如從家具、汽車零組件、化妝品外殼到各種 3C電子或電器產品（如數位相機、筆記型電腦及手機等）之 外殼都會使用塗料塗佈在基材上，以提供保護性或裝飾性 塗裝效果。然而，由於基材及塗料種類之變化，可能對塗 層性質造成影響，因此，如何提供外觀優美且密著性良好 之塗層一直是技術領域中研究人員努力的重要課題。 常用之基材，如木材、玻璃、金屬或塑膠基材，在製 la加工、搬運及保存期間會有油酯、氧化物鏽皮、氫氧 化物、灰塵等汙物附著於基材表面上，為了確保良好的塗 裝效果’基材表面必須清潔（即無油污、無錄潰）及無缺 陷（即無刮花），否則會影向塗層的附著力。 2胳基材般係藉由模鑄成形、擠壓成形、射出成形等 方法製備。基於成形方法之限制，此類基材易於表面產生 細溝、小孔等成形缺陷，此外，$留在基材表面之脫膜劑 油巧可能在塗佈時浮出，影響後續之塗層之密著性及外 觀。 另外，技術領域中已知可添加纖維，例如玻璃纖維、碳 纖維、賴維或金屬纖維，至塑膠基材中以改良其強度。 152050.doc 201239049 然而，由於纖維與塑膠材質不同，兩者質量密度及流動性 皆存在差異，在流動充填時，纖維易與塑料分離，造成浮 纖。此外，射出時的摩擦剪力會造成局部黏度差異，黏度 小的地方抓不住纖維，纖維便會向製品表面㈣，此亦造 成浮纖之原因之一。 為解決基材之成形缺陷並去除表面污物，提供外觀優美 且达者性良好之塗層，技術領域中一般係在塗佈前對基材 進行前處理。習知之前處理方法包括砂磨、除油、除錢水 洗及塗佈底漆(⑽叫等。這些程序㈣繁複且費時。 【發明内容】 本案發明人經廣泛研究發現—種新穎紫外線固化型處理 組合物，可有效解決基材表㈣缺陷和汙物4需再經由 其他基材前處理的方法，即可賦予塗膜與基材所需的附著 性’可符合業界的需求。 本發明之主要目的為提供一種紫外線固化型處理劑 包含以下組分： 、 ⑷3至V 一個雙鍵之單體、至少一個雙鍵之寡聚 混合物； 升 (b) 光起始劑；及201239049 VI. Description of the Invention: [Technical Field] The present invention relates to an ultraviolet (uv) curing type treating agent, and more particularly to an ultraviolet curing type treating agent applied to the coating industry. [Prior Art] Coatings are used in a wide range of applications, from everyday products to high-tech electronic products, such as furniture, automotive components, cosmetic casings, to various 3C electronic or electrical products (such as digital cameras, notebook computers, and mobile phones). The outer shell is coated with a coating on the substrate to provide a protective or decorative finish. However, variations in the type of substrate and coating may affect the properties of the coating. Therefore, how to provide a coating with good appearance and good adhesion has been an important task for researchers in the technical field. Commonly used substrates, such as wood, glass, metal or plastic substrates, may adhere to the surface of the substrate during the processing, handling and storage of oil, ester, hydroxide, dust, etc. In order to ensure a good coating effect, the surface of the substrate must be clean (ie no oil, no cracking) and no defects (ie no scratches), otherwise it will affect the adhesion of the coating. The two substrates are prepared by die casting, extrusion molding, injection molding, and the like. Due to the limitation of the forming method, such a substrate is liable to cause surface defects such as fine grooves and small holes, and in addition, the release agent oil remaining on the surface of the substrate may float during coating, which affects the subsequent coating. Adhesion and appearance. Additionally, it is known in the art to add fibers, such as glass fibers, carbon fibers, riviers or metal fibers, to plastic substrates to improve their strength. 152050.doc 201239049 However, due to the difference in fiber and plastic materials, there are differences in mass density and fluidity. When flowing, the fibers are easily separated from the plastic and cause floating fibers. In addition, the frictional shear force at the time of injection causes a difference in local viscosity. Where the viscosity is small, the fiber cannot be caught, and the fiber will be directed to the surface of the product (4), which is one of the reasons for the floating fiber. In order to solve the formation defects of the substrate and remove the surface dirt, a coating having a beautiful appearance and a good appearance is provided, and in the technical field, the substrate is generally pretreated before coating. Conventional treatment methods include sanding, degreasing, degreasing, and coating of primers ((10), etc. These procedures (4) are complicated and time consuming. [Inventive content] The inventors of the present invention have extensively discovered that a novel ultraviolet curing treatment The composition can effectively solve the defects of the substrate table (4) and the method that the dirt 4 needs to be pre-treated through other substrates, so as to impart the desired adhesion to the coating film and the substrate, which can meet the needs of the industry. The object is to provide an ultraviolet curable treatment agent comprising the following components: (4) 3 to V a double bond monomer, at least one double bond oligomer mixture; liter (b) photoinitiator;
(c) 熱塑性樹脂， 其中以1〇〇重量份4 L ^組刀⑷计，所述組分（b)之含量為0·5_20 里伤且組分（c)之含量為30-1,〇〇〇重量份。 本發明的有益效果是：本發明的紫外線固 劑，藉由添加特定tl + 處理 特疋比例的熱塑性樹脂，改善基材與塗料樹 152050.doc 201239049 脂的附著性，能有效地流平及潤濕，可克服基材成形缺 陷。其乾燥速度快，可在纖維浮出乾燥固化，改善浮纖現 象，並可將基材表面的汙物或油污與塗層隔絕。因此，可 簡化習知前處理方法的施工程式，改善後續塗層的附著力 及外觀，有效解決先前技術的問題。 【實施方式】 本發明所使用之組分（a)係含至少一個雙鍵之單體、至少 一個雙鍵之寡聚物或其混合物，較佳為丙烯酸酯單體、丙 烯酸酯寡聚物或其混合物》 可用於本發明之丙烯酸酯單體具有至少一個官能基，其 例如但不限於選自2-苯氧基乙基丙烯酸酯（PHEA)、乙氧基 乙氧基乙基丙烯酸酯（EOEOEA)、異癸基丙烯酸酯 (ISODA)、異冰片基丙烯酸酯（IBOA)、丙烯酸2-羥基乙酯 (HEA)、曱基丙烯睃2-羥基乙酯（HEMA)、二丙烯酸二丙二 醇酯（DPGDA)、二丙烯酸三丙二醇酯（TPGDA)、二丙烯酸 1,6-己二醇酯（HDDA)、二曱基丙烯酸二乙二醇酯 (DEGDMA)、二丙烯酸聚乙二醇（400)酯（PEG(400)DA)、二 丙烯酸聚乙二醇（600)酯（PEG(600)DA)、二曱基丙烯酸二 乙二醇酯（EGDMA)、二丙烯酸乙氧基化（10)雙酚酯 (BPA10EODA)、二曱基丙烯酸乙氧基化（10)雙酚酯 (BPA10EODMA)、二丙烯酸三環癸烷二曱醇酯 (TCDMDA)、二丙烯酸丙氧化（2)新戊二醇酯 (NPG2PODA) ' Nanocryl 0396(含 50% 奈米氧化石夕之 DPGDA)、Nanocryl 0768(含 50%奈米氧化石夕之 HDDA)、三 152050.doc 201239049 丙烯酸三羥甲基丙烷酯（TMPTA)、三丙烯酸乙氧化（3)三羥 曱基丙烷酯（TMP3EOTA)、三丙烯酸乙氧化（6)三羥曱基丙 烷酯（TMP6EOTA)、三丙烯酸乙氧化（9)三羥曱基丙烷酯 (TMP9EOTA)、三丙浠酸乙氧化（15)三羥甲基丙烷酯 (TMP15EOTA)、三丙烯酸乙氧化（20)三羥甲基丙烷酯 (TMP20EOTA)、三丙烯酸丙氧化（6)三羥曱基丙烷酯 (TMP6POTA)、三丙烯酸丙氧化（3)丙三醇酯（G3POTA)、 四丙烯酸二-(三羥曱基丙烷）酯（DI-TMPTA)、季戊四醇三 丙烯酸酯（PET3A)及六丙烯酸二季戊四醇酯（DPHA)及彼等 之混合物所組成之群組。 可用於本發明之丙烯酸酯單體較佳係選自異癸基丙烯酸 酯（ISODA)、異冰片基丙烯酸酯（IBOA)、丙烯酸2-羥基乙 酯（HEA)、曱基丙烯酸2-羥基乙酯（HEMA)、三丙烯酸三羥 曱基丙烷酯（TMPTA)、三丙烯酸乙氧化（3)三羥曱基丙烷酯 (TMP3EOTA)、三丙烯酸乙氧化（6)三羥甲基丙烷酯 (TMP6EOTA)、三丙烯酸乙氧化（9)三羥甲基丙烷酯 (TMP9EOTA)、三丙烯酸乙氧化（15)三羥曱基丙烷酯 (TMP15EOTA)、三丙烯酸乙氧化（20)三羥曱基丙烷酯 (TMP20EOTA)、三丙烯酸丙氧化（6)三羥曱基丙烷酯 (TMP6POTA)、三丙烯酸丙氧化（3)丙三醇酯（G3POTA)、 四丙烯酸二-(三羥曱基丙烷）酯（DI-TMPTA)、季戊四醇三 丙烯酸酯（PET3 A)及六丙烯酸二季戊四醇酯（DPHA)及彼等 之混合物所組成之群組。 可用於本發明之市售丙烯酸酯單體包括：EM210、 152050.doc 201239049 EM211、EM219、EM70、EM223、EM328、EM2308、 EM231 、EM235 、EM2381 、EM2382 、EM2383 、 EM2384、EM2385 、EM2386、EM2387 、EM331 、 EM3380、EM241 、EM2411 ' EM242 、EM2421 及 EM265(長興化工製）；EBECRYL-160、EBECRYL-853、 EBECRYL-2047、EBECRYL-40 及 EBECRYL-140(優喜碧 (UCB)股份有限公司製）；CD501、SR351、SR368、 SR415、SR444、SR454、SR454HP、SR492、SR499、 SR9008、SR9035、CD9051 ' SR350 ' SR9009、SR9011、 SR295 、 SR9020 、 SR9021 ' SR355 、 SR399 、 SR494 、 SR9041、Ricacryl3500 及 Ricacryl3801(SARTOMER 公司 製）；MIRAMER M5 00及 MIRAMER M600(Miwon公司製）》 可用於本發明之丙烯酸酯募聚物含有至少1個雙鍵，較 佳含有至少2個雙鍵，更佳含有3至15個雙鍵，其分子量並 無特殊限制，一般係介於400至5,000間，較佳係介於500 至3，000間。上述丙烯酸酯寡聚物之種類例如但不限於係 選自由環氧丙稀酸酿（epoxy acrylate)，如雙酌·Α環氧二丙 稀酸醋（bisphenol-A epoxy diacrylate)、2-經基-3-苯氧丙基 丙稀酸酯、酌酸環氧丙稀酸酯（novolac epoxy acrylate); 聚胺基曱酸醋丙浠酸酯（polyurethane acrylate)，如脂肪族 胺基曱酸酯丙稀酸醋（aliphatic urethane acrylate)或芳香族 胺基甲酸醋丙稀酸醋（aromatic urethane acrylate);聚醋丙 稀酸醋（polyester acrylate)，如聚醋二丙烯酸醋（polyester diacrylate)、脂肪族聚醋丙稀酸醋（aliphatic polyester 152050.doc -8- 201239049 acrylate) 或芳香族聚醋丙烯酸g旨（aromatic polyester acrylate);聚丙烯酸酯（Polyacrylate);胺基丙烯酸酯 (amine acrylate)及其混合物所組成之群組，較佳係聚胺基 曱酸酯丙稀酸酯、聚酯丙稀酸酯或其混合物。上述聚胺基 甲酸酯丙烯酸酯以脂肪族聚胺基甲酸酯丙烯酸酯不易有黃 變問題，為更佳選擇。 可用於本發明之市售丙烯酸酯寡聚物例子包括：環氧丙 烯酸酯寡聚物：AgiSyn™ 2901A50、AgiSyn™ 1010、 AgiSyn™ 1010A80 > AgiSyn™ 1010B80 ' AgiSyn™ 1010C80、AgiSyn™ 2010 及 AgiSyn™ 2500(新力美科技股 份有限公司製）；621、621-100、622 ' 623、6210G、 624 ' 6231 、 6241 、 6213-100 ' 6215-100 ' 625 ' 625C-60 、 625C-40、6261 及 620-100(長興化工製）；EBECRYL-600、 EBECRYL-605 、 EBECRYL-648 、 EBECRYL-1608 、 EBECRYL-3105 、EBECRYL-3213 、EBECRYL-3416、 EBECRYL-3700、EBECRYL-3701 、EBECRYL-3703 、 EBECRYL-3708、EBECRYL-3740 及 EBECRYL-6040(優喜 碧（UCB)股份有限公司製）。 脂肪族胺基甲酸酯丙烯酸酯寡聚物：6101-100、 611A-85、611B-85、6112-100、6113、6114、6115J-80、 6130B-80、6131-1、6134B-80、6141H-80、6143A-80、 6143C-60、6144-100、6145-100、6145-100H、6148J-75、 6148T-85 、 6149-100 ' 615-100 、 6150-100 、 6151 、 6152B-80 、 6153-1 、 6154B-80 、 6157B-80 、 6158B-80 、 152050.doc •9- 201239049 6160B-70、6161-100、6181 及 6196-100(長興化工製）； AgiSyn™ 230S1-15HD ' AgiSyn™ 230S2-30TP ' AgiSyn™ 230SM-20TP 、 AgiSyn™ 230SN-20TP 、 AgiSyn™ 230SR-20TP、AgiSyn™ 230T1 及 AgiSyn™ 230A2(新力美 科技股份有限公司製）；EBECRYL-264、EBECRYL-294/25 HD 、 EBECRYL-4820 、 EBECRYL-4858 、 EBECRYL-5129 、EBECRYL-8210、EBECRYL-8402、 EBECRYL-8405 、EBECRYL-8406、EBECRYL-8407、 EBECRYL-270 、 EBECRYL-230 、 EBECRYL-284 及 EBECRYL-1290(優喜碧（UCB)股份有限公司製）；HENKEL 6010 (COGNIS 公司製）；CN9001、CN9002、CN9004 及 CN9006(沙多瑪（Sartomer)公司製）；Desmolux® U100、 Desmolux® VP LS 2265、Desmolux® VP LS 2308、 Desmolux® U375H、Desmolux® VP LS 2220、Desmolux® XP 2491、Desmolux® XP 2513、Desmolux® U200 及 Desmolux® XP 2609(拜耳（Bayer)公司製）。 芳香族胺基曱酸酯丙烯酸酯寡聚物：6120F-80、 6121F-80、6122F-80及 6146-100(長興化工製）；AgiSyn™ 670TH-20TP ' AgiSyn™ 670S1-20TP ' AgiSyn™ 670T1、 AgiSyn™ 670A2(新力美科技股份有限公司製）； EBECRYL-204 、 EBECRYL-205 、 EBECRYL-210 、 EBECRYL-215、EBECRYL-220 及 EBECRYL-6202(優喜碧 (UCB)股份有限公司製）。 聚酯丙烯酸酯寡聚物：EBECRYL-830、EBECRYL-810 152050.doc -10- 201239049 及EBECRYL-524(優喜碧（UCB)股份有限公司製）；6315、 6320 、 6323-100 、 6325-100 、 6327-100 、 6336-100 及 6361-100(長興化工製）；BE-101、BE112DP10、BE-211、 JL-103M、JL-106E 及 JL-126(Bomar Specialties Company 製）。 聚丙烯酸酯寡聚物：AgiSyn™ 2266(新力美科技股份有 限公司製）；EBECRYL-745(優喜碧（UCB)股份有限公司 製）；DOUBLEMER3778 、 DOUBLEMER1701 、 DOUBLEMER345、DOUBLEMER1703、DOUBLEMER530、 DOUBLEMER570、DOUBLEMER236 及 DOUBLEMER584 (雙鍵化工有限公司製）；6530B-40、6531B-40、6532B-40 及6533B-40(長興化工製）。 本發明所使用之組份（b)光起始劑，並無特殊限制，係 經光照射後會產生自由基，而透過自由基之傳遞引發聚合 反應者。其例如但不限於選自以下組成之組群：二笨甲 酮-胺共軛體系；苯偶姻醚類；苯偶醯及其縮酮類；及苯 乙酮衍生物類。此外，可視需要使用兩種或兩種以上之光 起始劑。 根據本發明，組分（b)光起始劑之用量並無特殊限制， 可視需要依處理劑所含組分（a)之單體和寡聚物之種類及其 用量進行調整。一般而言，以100重量份組分（a)計，組分 (b)之含量為0.5至20重量份，較佳為1.0至14.0重量份。 可用於本發明之市售光起始劑的例子包括： CHIVACURE 115、CHIVACURE ITX(異丙基硫雜蒽酮）、 152050.doc 201239049 CHIVACURE EPD (對-(二曱胺基）苯曱酸乙酯）、 CHIVACURE OMB(鄰-苯甲醯基苯甲酸曱酯）、 CHIVACURE EMK (N，N，N'，N·-四乙基-4,4，-二胺基二苯曱 酮）、CHIVACURE BDK (2,2’_二曱基-1，2-二苯基乙烷-1-酮）、CHIVACURE BMS (4-苯甲醯基-4'-甲基二苯基硫 醚）、CHIVACURE 184 (1 -羥基環己基苯基酮）、 CHIVACURE 173 (2-羥基-2-曱基-1 -苯基-丙-1 -酮）、 CHIVACURE TPO (2,4,6-三曱基苯曱醯基二苯基膦氧化物） 及CHIVACURE 200(苯基乙醇酸甲酯）（雙鍵化工（DBC)有限 公司製）；AgiSyn™_i8i2(i-羥基環己基苯基酮）、 AgiSynTM-1810(2-羥基-2-曱基-1-苯基丙-1-酮）、 AgiSyn™-1801及AgiSyn™-003(新力美科技股份有限公司 製）；IRGACURE 369 (2-苄基-2-N，N-二曱基胺基-1-(4-嗎 啉基苯基-1-丁酮）及IRGACURE 2959 (4-(2-羥基乙氧基）-苯基-(2_羥基-2-曱基丙基）酮）(BASF公司製）。 本發明於處理劑中添加組份（c)熱塑性樹脂，可調整處理 劑之黏度，對於有表面缺陷之基材，能有效地流平及潤 濕，達到修飾外觀之效果；且可加快塗膜的乾燥速度，有 利於減少浮纖現象或隔絕殘留於基材上之油污。再者，一 般處理劑塗膜經UV固化後會產生高收縮應力，易造成翹 曲、龜裂等現象，對密著性也有不良影響，於處理劑中添 加熱塑性樹脂，可增加塗膜與基材的密著性並防止塗膜龜 裂，較佳為使用具有較高玻璃化轉變溫度的熱塑性樹脂可 加快塗膜的乾燥速度。 152050.doc -12- 201239049 本發明之熱塑性樹脂與募聚物及/或單體的相容性佳， 可直接掺雜（blending)在處理劑中，不會與寡聚物及/或單 體產生反應，因此可作為一緩衝的介質，以釋放1;乂固化 過程中，因快速固化而產生的應力。另一方面’由於此類 樹脂的表乾能力強，所以在乾燥過程中，可促進溶劑由塗 膜中移除，可避免垂流現象。 本發明所使用之組份（c)熱塑性樹脂係選自由丙烯酸樹 脂、氣醋樹脂、氯化聚烯烴樹脂、聚酯樹脂、松香樹脂及 其混合物所組成之群組。上述熱塑性樹脂可為均聚物或共 聚物，其分子量一般介於5,〇〇〇至25〇,〇〇〇間較佳介於 10,000至200,000間，更佳介於25，_至1〇〇 〇〇〇間。根據本 發明，以組分（a)為100重量份計，組份（c)熱塑性樹脂之用 量為30-1，〇〇〇重量份，更佳為4〇 4〇〇重量份。 上述氯醋樹脂，可為均聚物或共聚物，其例如但不限 於：氯乙烯和醋酸乙烯之共聚物或氯乙烯和醋酸乙烯和二 羧酸之三元共聚物。 可用於本發明之市售熱塑性氯醋樹脂例子包含·· ％抓 E15/45、Vinnol Hl4/36、Vinn〇1 Hi5/42、心―(c) a thermoplastic resin in which the content of the component (b) is 0·5_20 and the content of the component (c) is 30-1, based on 1 part by weight of the 4 L^ group of knives (4). 〇〇 by weight. The invention has the beneficial effects that the ultraviolet solid agent of the invention can improve the adhesion between the substrate and the paint tree 152050.doc 201239049 by adding a specific tl + treatment special ratio thermoplastic resin, and can effectively level and moisten. Wet to overcome substrate forming defects. The drying speed is fast, the fiber can be dried and solidified, the floating fiber phenomenon can be improved, and the dirt or oil on the surface of the substrate can be isolated from the coating. Therefore, the construction procedure of the conventional pretreatment method can be simplified, the adhesion and appearance of the subsequent coating can be improved, and the problems of the prior art can be effectively solved. [Embodiment] The component (a) used in the present invention is a monomer having at least one double bond, an oligomer of at least one double bond, or a mixture thereof, preferably an acrylate monomer, an acrylate oligomer or The mixture of the acrylate monomers useful in the present invention has at least one functional group such as, but not limited to, selected from the group consisting of 2-phenoxyethyl acrylate (PHEA), ethoxyethoxyethyl acrylate (EOEOEA). ), isodecyl acrylate (ISODA), isobornyl acrylate (IBOA), 2-hydroxyethyl acrylate (HEA), nonyl propylene 2-hydroxyethyl ester (HEMA), dipropylene glycol diacrylate (DPGDA) ), tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), diethylene glycol dimethacrylate (DEGDMA), polyethylene glycol (400) diacrylate (PEG) (400)DA), polyethylene glycol (600) diacrylate (PEG (600) DA), diethylene glycol dimethacrylate (EGDMA), ethoxylated (10) bisphenol ester of diacrylate ( BPA10EODA), dimercaptoacrylic acid ethoxylated (10) bisphenol ester (BPA10EODMA), tricyclodecane didecyl diacrylate (T CDMDA), propionic acid diacrylate (2) neopentyl glycol ester (NPG2PODA) ' Nanocryl 0396 (containing 50% nano-oxidized stone DPGDA), Nanocryl 0768 (including 50% nano-oxidized stone HDDA), three 152050.doc 201239049 Trimethylolpropane acrylate (TMPTA), ethoxylated (3) trishydroxypropyl propane ester (TMP3EOTA), ethoxylated (6) trihydroxymercaptopropane ester (TMP6EOTA), three Acetate ethoxylated (9) trihydroxymercaptopropane ester (TMP9EOTA), tripropionate ethoxylated (15) trimethylolpropane ester (TMP15EOTA), ethoxylated (20) trimethylolpropane triacrylate (TMP20EOTA) ), propane trioxide oxidized (6) trihydroxymercapto propane ester (TMP6POTA), propane trioxide oxidized (3) glycerol ester (G3POTA), di-(trihydroxydecylpropane) tetraacrylate (DI-TMPTA) a group consisting of pentaerythritol triacrylate (PET3A) and dipentaerythritol hexaacrylate (DPHA) and mixtures thereof. The acrylate monomer usable in the present invention is preferably selected from the group consisting of isodecyl acrylate (ISODA), isobornyl acrylate (IBOA), 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate. (HEMA), trihydroxymercaptopropane triacrylate (TMPTA), ethoxylated (3) trihydroxymercaptopropane triacrylate (TMP3EOTA), ethoxylated (6) trimethylolpropane triacrylate (TMP6EOTA), Ethylene oxide acrylate (9) trimethylolpropane ester (TMP9EOTA), ethoxylated (15) trihydrocarbyl propane ester (TMP15EOTA), ethoxylated (20) trihydroxymercapto propane ester (TMP20EOTA) , (3) trihydroxymercaptopropane ester (TMP6POTA), propane trioxide (3) glycerol triacrylate (G3POTA), di-(trihydroxydecylpropane) tetraacrylate (DI-TMPTA) a group consisting of pentaerythritol triacrylate (PET3 A) and dipentaerythritol hexaacrylate (DPHA) and mixtures thereof. Commercially available acrylate monomers useful in the present invention include: EM210, 152050.doc 201239049 EM211, EM219, EM70, EM223, EM328, EM2308, EM231, EM235, EM2381, EM2382, EM2383, EM2384, EM2385, EM2386, EM2387, EM331 , EM3380, EM241, EM2411 'EM242, EM2421 and EM265 (manufactured by Changxing Chemical); EBECRYL-160, EBECRYL-853, EBECRYL-2047, EBECRYL-40 and EBECRYL-140 (made by UBC Co., Ltd.); CD501 , SR351, SR368, SR415, SR444, SR454, SR454HP, SR492, SR499, SR9008, SR9035, CD9051 'SR350 'SR9009, SR9011, SR295, SR9020, SR9021 'SR355, SR399, SR494, SR9041, Ricacryl3500 and Ricacryl3801 (Manufactured by SARTOMER MIRAMER M5 00 and MIRAMER M600 (manufactured by Miwon Co., Ltd.) The acrylate polymer which can be used in the present invention contains at least one double bond, preferably at least 2 double bonds, more preferably 3 to 15 double bonds. The molecular weight is not particularly limited and is generally between 400 and 5,000, preferably between 500 and 3,000. The type of the above acrylate oligomer is, for example but not limited to, selected from epoxy acrylate, such as bisphenol-A epoxy diacrylate, 2-base. -3-phenoxypropyl acrylate, novolac epoxy acrylate; polyurethane acrylate, such as aliphatic amine phthalate acrylate Aliphatic urethane acrylate or aromatic urethane acrylate; polyester acrylate, such as polyester diacrylate, aliphatic poly Acetylene acrylate (aliphatic polyester 152050.doc -8- 201239049 acrylate) or aromatic polyester acrylate; polyacrylate; amine acrylate and mixtures thereof The group of compositions is preferably a polyamine phthalate acrylate, a polyester acrylate or a mixture thereof. The above-mentioned polyurethane acrylate is more preferable because it is less susceptible to yellowing of the aliphatic urethane acrylate. Examples of commercially available acrylate oligomers useful in the present invention include: epoxy acrylate oligomers: AgiSynTM 2901A50, AgiSynTM 1010, AgiSynTM 1010A80 > AgiSynTM 1010B80 'AgiSynTM 1010C80, AgiSynTM 2010 and AgiSynTM 2500 (made by Xinlimei Technology Co., Ltd.); 621, 621-100, 622 '623, 6210G, 624 '6231, 6241, 6213-100 '6215-100 ' 625 ' 625C-60 , 625C-40 , 6261 and 620 -100(Changxing Chemical);EBECRYL-600, EBECRYL-605, EBECRYL-648, EBECRYL-1608, EBECRYL-3105, EBECRYL-3213, EBECRYL-3416, EBECRYL-3700, EBECRYL-3701, EBECRYL-3703, EBECRYL- 3708, EBECRYL-3740 and EBECRYL-6040 (made by UBC Co., Ltd.). Aliphatic urethane acrylate oligomers: 6101-100, 611A-85, 611B-85, 6112-100, 6113, 6114, 6115J-80, 6130B-80, 6131-1, 6134B-80, 6141H -80, 6143A-80, 6143C-60, 6144-100, 6145-100, 6145-100H, 6148J-75, 6148T-85, 6149-100 '615-100, 6150-100, 6151, 6152B-80, 6153 -1, 6154B-80, 6157B-80, 6158B-80, 152050.doc •9- 201239049 6160B-70, 6161-100, 6181 and 6196-100 (made by Changxing Chemical); AgiSynTM 230S1-15HD ' AgiSynTM 230S2 -30TP 'AgiSynTM 230SM-20TP, AgiSynTM 230SN-20TP, AgiSynTM 230SR-20TP, AgiSynTM 230T1 and AgiSynTM 230A2 (made by Xinlimei Technology Co., Ltd.); EBECRYL-264, EBECRYL-294/25 HD, EBECRYL -4820, EBECRYL-4858, EBECRYL-5129, EBECRYL-8210, EBECRYL-8402, EBECRYL-8405, EBECRYL-8406, EBECRYL-8407, EBECRYL-270, EBECRYL-230, EBECRYL-284 and EBECRYL-1290 (Youxibi UCB) Co., Ltd.); HENKEL 6010 (manufactured by COGNIS); CN9001, CN9002, CN9004 and CN9006 (Sartomer) Desmolux® U100, Desmolux® VP LS 2265, Desmolux® VP LS 2308, Desmolux® U375H, Desmolux® VP LS 2220, Desmolux® XP 2491, Desmolux® XP 2513, Desmolux® U200 and Desmolux® XP 2609 (Bayer ( Bayer) company system). Aromatic amine phthalate acrylate oligomers: 6120F-80, 6121F-80, 6122F-80 and 6146-100 (made by Changxing Chemical); AgiSynTM 670TH-20TP 'AgiSynTM 670S1-20TP ' AgiSynTM 670T1 AgiSynTM 670A2 (made by Xinlimei Technology Co., Ltd.); EBECRYL-204, EBECRYL-205, EBECRYL-210, EBECRYL-215, EBECRYL-220 and EBECRYL-6202 (made by UBC Co., Ltd.). Polyester acrylate oligomer: EBECRYL-830, EBECRYL-810 152050.doc -10- 201239049 and EBECRYL-524 (made by UBS), 6315, 6320, 6323-100, 6325-100, 6327-100, 6336-100 and 6361-100 (manufactured by Changxing Chemical Industry Co., Ltd.); BE-101, BE112DP10, BE-211, JL-103M, JL-106E and JL-126 (manufactured by Bomar Specialties Company). Polyacrylate oligomer: AgiSynTM 2266 (manufactured by Xinlimei Technology Co., Ltd.); EBECRYL-745 (made by UBC Co., Ltd.); DOUBLEMER3778, DOUBLEMER1701, DOUBLEMER345, DOUBLEMER1703, DOUBLEMER530, DOUBLEMER570, DOUBLEMER236 and DOUBLEMER584 (made by Double Key Chemical Co., Ltd.); 6530B-40, 6531B-40, 6532B-40 and 6533B-40 (made by Changxing Chemical Industry Co., Ltd.). The component (b) photoinitiator used in the present invention is not particularly limited, and a radical is generated by light irradiation, and a polymerization reaction is initiated by radical transfer. It is, for example but not limited to, a group selected from the group consisting of a dimercapto-ketone-amine conjugated system; a benzoin ether; a benzoin and a ketal thereof; and a acetophenone derivative. Further, two or more kinds of photoinitiators may be used as needed. According to the present invention, the amount of the component (b) photoinitiator to be used is not particularly limited, and may be adjusted depending on the kind of the monomer and oligomer of the component (a) contained in the treating agent and the amount thereof. In general, the component (b) is contained in an amount of from 0.5 to 20 parts by weight, preferably from 1.0 to 14.0 parts by weight, based on 100 parts by weight of the component (a). Examples of commercially available photoinitiators which can be used in the present invention include: CHIVACURE 115, CHIVACURE ITX (isopropyl thioxanthone), 152050.doc 201239049 CHIVACURE EPD (p-(diamido) benzoic acid ethyl ester ), CHIVACURE OMB (ortho-benzylidene benzoate), CHIVACURE EMK (N,N,N',N·-tetraethyl-4,4,-diaminodibenzophenone), CHIVACURE BDK (2,2'-dimercapto-1,2-diphenylethane-1-one), CHIVACURE BMS (4-benzylidene-4'-methyldiphenyl sulfide), CHIVACURE 184 ( 1-hydroxycyclohexyl phenyl ketone), CHIVACURE 173 (2-hydroxy-2-mercapto-1 -phenyl-propan-1-one), CHIVACURE TPO (2,4,6-trimercaptophenyl fluorenyl) Diphenylphosphine oxide) and CHIVACURE 200 (methyl phenylglycolate) (manufactured by Double Bond Chemicals (DBC) Co., Ltd.); AgiSynTM_i8i2 (i-hydroxycyclohexyl phenyl ketone), AgiSynTM-1810 (2- Hydroxy-2-mercapto-1-phenylpropan-1-one), AgiSynTM-1801 and AgiSynTM-003 (manufactured by Xinlimei Technology Co., Ltd.); IRGACURE 369 (2-benzyl-2-N, N -didecylamino-1-(4-morpholinylphenyl-1-butanone) and IRGACURE 2959 (4-(2-hydroxyethyl) Oxyphenyl)-phenyl-(2-hydroxy-2-mercaptopropyl)one (manufactured by BASF Corporation). The present invention adds a component (c) thermoplastic resin to the treating agent, and the viscosity of the treating agent can be adjusted. The substrate with surface defects can effectively level and wet, and achieve the effect of modifying the appearance; and can accelerate the drying speed of the coating film, which is beneficial to reduce the floating fiber phenomenon or isolate the oil residue remaining on the substrate. Generally, the coating film of the treating agent will have high shrinkage stress after UV curing, which is easy to cause warpage and cracking, and has adverse effects on the adhesion. The thermoplastic resin is added to the treating agent to increase the density of the coating film and the substrate. To prevent the coating film from cracking, it is preferred to use a thermoplastic resin having a higher glass transition temperature to accelerate the drying speed of the coating film. 152050.doc -12- 201239049 The thermoplastic resin of the present invention and the polymer and/or the polymer and/or The monomer has good compatibility, can be directly blended in the treating agent, does not react with the oligomer and/or monomer, and therefore can be used as a buffering medium to release 1; , stress caused by rapid curing. Terms' dry due to the strong ability of such resins, it is during the drying process, the solvent can be removed from the promotion of the coating film, the vertical flow phenomena can be avoided. The component (c) thermoplastic resin used in the present invention is selected from the group consisting of acrylic resins, vinegar resins, chlorinated polyolefin resins, polyester resins, rosin resins, and mixtures thereof. The above thermoplastic resin may be a homopolymer or a copolymer, and its molecular weight is generally from 5, 〇〇〇 to 25 〇, preferably between 10,000 and 200,000, more preferably between 25 and _ to 1 〇〇〇. In the daytime. According to the present invention, the component (c) is used in an amount of 30-1, 〇〇〇 by weight, more preferably 4 〇 4 parts by weight, based on 100 parts by weight of the component (a). The above chloroacetic resin may be a homopolymer or a copolymer such as, but not limited to, a copolymer of vinyl chloride and vinyl acetate or a terpolymer of vinyl chloride and vinyl acetate and dicarboxylic acid. Examples of commercially available thermoplastic chloroacetic resins that can be used in the present invention include ··% catching E15/45, Vinnol Hl4/36, Vinn〇1 Hi5/42, heart-
Hll/59、Vinn〇l H40/43、vinn〇I H4〇/5〇、ν—〇ι H40/55、Vinnol H4〇/6〇(威凱化學公司製）、 VYHD、VMCH、VMCC、VAGH、VAGF(陶氏化學公司 製）。 可用於本發明之市售熱塑性氯化聚烯烴樹脂例子包含··Hll/59, Vinn〇l H40/43, vinn〇I H4〇/5〇, ν—〇ι H40/55, Vinnol H4〇/6〇 (made by Weikai Chemical Co., Ltd.), VYHD, VMCH, VMCC, VAGH, VAGF (manufactured by The Dow Chemical Company). Examples of commercially available thermoplastic chlorinated polyolefin resins useful in the present invention include
Eastman CP-7in 1、c * “卜】、Eastman AP550-1、Eastman CP-343- I52050.doc -13· 201239049 1 ' Eastman CP-343-3 ' Eastman CP-515-2 ' Eastman CP-153-2 及 Eastman CP164-1(伊士 曼化學（EASTMAN)公司 製）；PPB、13-LP、16-LP、14LWP、B-13MLJ、P-555 1、 CY-9122P、CY-9124P、HM-21P、14CE、CY-9124MB、 DX-526P、DX-530P、F-2P、F-6P、F-2MB、EH-801、 EW-5303、EW53-3、EY-4052、EY-4075、NA-3002、NZ-1004、MD-15B及HD-15(東洋紡織株式會社（TOYOBO) 製）；Superchlon 822S(曰本立邦制紙株式會社製）。 可用於本發明之市售熱塑性聚酯樹脂例子包含： DYNAPOL®L206、DYNAPOL®L205、DYNAPOL®L411、 DYNAPOL®LTW、DYNAPOL®LTW-B 及 DYNAPOL®LTH (Evonik Degussa 製）；VYLON®200、VYLON®270、 VYLON®600 、 VYLON®300 、 VYLON®500 、 VYLON®560 、VYLON®PCR-925 、VYLON®GK100 及 VYLON®GK780 (東洋紡織株式會社（TOYOBO)製）； SKYBON ES100、SKYBON ES110、SKYBON ES910、 SKYBON ES160、SKYBON ES402、SKYBON ES500 及 SKYBON ES300(SK Chemicals 製）；ETERKYD 5011-X-50、 ETERKYD 5058-R-40、ETERKYD 5021-R-40、ETERKYD 5〇54_R_4〇、ETERKYD 5022-TK-40、ETERKYD 5015-X-50、 ETERKYD 5016-X-50 及 ETERKYD 5014-X-50 (長興化工 製）。 可用於本發明之市售熱塑性松香樹脂例子包含：Eastman CP-7in 1, c * "Bu", Eastman AP550-1, Eastman CP-343- I52050.doc -13· 201239049 1 ' Eastman CP-343-3 ' Eastman CP-515-2 ' Eastman CP-153- 2 and Eastman CP164-1 (manufactured by Eastman Chemical Co., Ltd.); PPB, 13-LP, 16-LP, 14LWP, B-13MLJ, P-555 1, CY-9122P, CY-9124P, HM-21P , 14CE, CY-9124MB, DX-526P, DX-530P, F-2P, F-6P, F-2MB, EH-801, EW-5303, EW53-3, EY-4052, EY-4075, NA-3002 NZ-1004, MD-15B, and HD-15 (manufactured by Toyobo Co., Ltd.); Superchlon 822S (manufactured by Nippon Nippon Paper Co., Ltd.) Examples of commercially available thermoplastic polyester resins which can be used in the present invention include: DYNAPOL®L206, DYNAPOL®L205, DYNAPOL®L411, DYNAPOL®LTW, DYNAPOL®LTW-B and DYNAPOL®LTH (made by Evonik Degussa); VYLON®200, VYLON®270, VYLON®600, VYLON®300, VYLON®500 , VYLON®560, VYLON® PCR-925, VYLON®GK100 and VYLON®GK780 (manufactured by Toyobo Co., Ltd.); SKYBON ES100, SKYBON ES110, SKYBON ES910, SKYBON ES160, SKYBON ES402, SKYBON ES500 SKYBON ES300 (manufactured by SK Chemicals); ETERKYD 5011-X-50, ETERKYD 5058-R-40, ETERKYD 5021-R-40, ETERKYD 5〇54_R_4〇, ETERKYD 5022-TK-40, ETERKYD 5015-X-50, ETERKYD 5016-X-50 and ETERKYD 5014-X-50 (manufactured by Changxing Chemical Industry Co., Ltd.) Examples of commercially available thermoplastic rosin resins which can be used in the present invention include:
SYLVA1ITE®RE 88、SYLVA1ITE®RE 100、SYLVA1ITE®RE 152050.doc -14- 201239049 115&SYLVATAC®RE95(ArizonaChemica^);TAMANOL 145、TAMANOL 340、TAMANOL 350、TAMANOL 353、 TAMANOL 359、TAMANOL 361、TAMANOL 366、 TAMANOL 392 (荒川化學工業株式會社）。 根據本發明之一實施態樣’選用之熱塑性樹脂係熱塑性 丙烯酸樹脂。上述熱塑性丙烯酸樹脂包含一或多種具有大 於20°C ’較佳大於60°C，更佳介於70。(：至150°C間的玻璃 化轉變溫度（Tg)之丙浠酸樹脂，一般而言，當Tg小於2〇。〇 時會造成耐溶劑性不優’且塗膜耐熱性不佳，保護力不 足；當Tg大於1 50°C時，會造成流平性不優，衍生出加工 不易的問題。 根據本發明之另一實施態樣’除了使用具有大於2〇。〇之 玻璃化轉變溫度的熱塑性丙稀酸樹脂之外，可視需要另添 加具有較南玻璃化轉變溫度’例如，大於6 〇 ，較佳介於 70°C至150°C間之玻璃化轉變溫度的熱塑性丙烯酸樹脂。 上述熱塑性丙烯酸樹脂’可為均聚物或共聚物，其係衍 生自至少一種選自以下單體的高分子：丙烯酸、甲基丙稀 酸、丙烯酸烷基酯以及曱基丙烯酸烷基酯。 上述丙烯酸烷基酯及曱基丙烯酸烷基酯單體之實例包括 丙稀酸曱酯、曱基丙烯酸甲酯、丙烯酸乙酯、甲基丙炜酸 乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙 酯、曱基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙稀酸正丁 酯' 丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸異辛酯、 曱基丙烯酸異辛酯、丙烯酸環己酯、甲基丙烯酸環己酯、 152050.doc •15· 201239049 丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、丙烯酸羥乙 酯、丙烯酸羥丙酯' 丙烯酸_2·羥基乙酯.、曱基丙烯酸_2_ 羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2羥基丙酯； 曱基丙烯酸羥丙酯、丙烯酸異冰片酯及甲基丙烯酸異冰片 酯及其混合物》 根據本發明之一具體實施例，選用的熱塑性丙烯酸樹脂 係以一或多種下列單體作為聚合單元：丙烯酸、曱基丙烯 酉文、丙烯酸曱醋、曱基丙婦酸曱g旨、丙稀酸正丁醋、甲基 丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯 酸羥乙酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯 酸-2-羥基乙酯、曱基丙烯酸羥基乙酯、丙烯酸2_羥基 丙S曰及甲基丙稀酸2 -經基丙醋，較佳為以一或多種下列單 體作為聚合單元：丙烯酸_2_羥基乙酯、曱基丙烯酸_2_羥 基乙醋、丙稀酸甲酿 '甲基丙烯酸曱酯、丙烯酸正丁酯、 曱基丙烯酸正丁酯、丙烯酸異冰片酯及甲基丙烯酸異冰片 酉旨。 可用於本發明之市售熱塑性丙烯酸樹脂例子包含： 7119-TB-50、7626-1、7128-TB-50、7305-2-XS-50、 7329-XP-45 、 7329-TS-45 、 7117-TS-50 、 7352-TS-50 及 7630(長興化工製）；BR113、BR116、BR-115、BR 106、 BR-85、BR-73、MB2952、MB3015及MB 2660(日本三菱 公司製）；B-725、B-735、B-736及B-805(荷蘭捷利康公司 製）；AR-1042 及 AR-1090F(長春公司製）。A-646、A-14、 A-ll、A-21、B-60、B-66、B-64、B-82 及 B-72(R&H製）； 152050.doc -16· 201239049 及FS-2970A(德謙企業股份有限公司製）；LF-1113、 LF-1115及LF-1117(立驊公司製）。 本發明之紫外線固化型處理劑可視需要包含一或多種本 發明所屬技術領域具有通常知識者所知之添加劑作為組分 (d)。可用於本發明之添加劑並無特殊限制，例如但不限 於，選自由潤濕劑、平坦劑、消泡劑、分散劑及其組合所 組成之群組。上述添加劑的種類係本發明所屬技術領域中 具有通常知識者所習知者，而其用量亦為本發明所屬技術 領域中具有通常知識者依不同需求而可輕易決定者。一般 而言，以組分（a)與（c)合計100重量份計，組分（d)添加劑之 含量為0.05-1重量份。 本發明視需要使用的潤濕劑來降低處理劑表面張力，使 處理劑更易於展布於基材表面上，潤濕劑可以選自由聚酯 改性有機矽、聚醚改性有機矽、含氟丙烯酸樹酯、氟碳樹 脂及其混合物所組成的群組。本發明也可選的使用平坦 劑，有利於基材的潤濕和塗膜的流平。市售潤濕劑或平坦 劑例子包括：EFKA3777、EFKA3886、EFKA3883 及 EFKA3600(荷蘭埃夫卡公司製）；BYK366、BYK300、 BYK333、BYK307、BYK340、BYK341、BYK344、 BYK3500、BYK3510、BYK3530及 BYK3570(畢克化學公 司（BYK)製）；TEGO Twin 4000、TEGO Wet270、TEGO 410及 TEGO 450(德國迪高公司（TEGO)製）；CARBOWET® 13-40 SURFACTANT(美商亞普有限公司（Air Products) 製）；Modaflow resin、Modaflow 2100、Modaflow 9200、 152050.doc •17- 201239049SYLVA1ITE® RE 88, SYLVA1ITE® RE 100, SYLVA1ITE® RE 152050.doc -14- 201239049 115&SYLVATAC® RE95 (ArizonaChemica^); TAMANOL 145, TAMANOL 340, TAMANOL 350, TAMANOL 353, TAMANOL 359, TAMANOL 361, TAMANOL 366 TAMANOL 392 (Arakawa Chemical Industry Co., Ltd.). According to an embodiment of the present invention, a thermoplastic resin-based thermoplastic acrylic resin is selected. The above thermoplastic acrylic resin comprises one or more having more than 20 ° C', preferably more than 60 ° C, more preferably 70. (: a propionate resin having a glass transition temperature (Tg) to 150 ° C. Generally, when the Tg is less than 2 Å, the solvent resistance is not good, and the heat resistance of the coating film is poor, and protection The force is insufficient; when the Tg is greater than 150 ° C, the leveling property is not good, and the problem of processing is difficult to be derived. According to another embodiment of the present invention, 'the glass transition temperature is greater than 2 〇. In addition to the thermoplastic acrylic resin, a thermoplastic acrylic resin having a glass transition temperature of more than 6 Å, preferably between 70 ° C and 150 ° C, may be additionally added as needed. The acrylic resin' may be a homopolymer or a copolymer derived from at least one polymer selected from the group consisting of acrylic acid, methyl acrylic acid, alkyl acrylate, and alkyl methacrylate. Examples of the base ester and the alkyl methacrylate monomer include decyl acrylate, methyl methacrylate, ethyl acrylate, ethyl propyl acrylate, n-propyl acrylate, n-propyl methacrylate, Isopropyl acrylate Ester, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate 'isobutyl acrylate, isobutyl methacrylate, isooctyl acrylate, isooctyl methacrylate, acrylonitrile Ester, cyclohexyl methacrylate, 152050.doc •15· 201239049 Glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate 'Acrylic acid · hydroxyethyl ester., methacrylic acid _2_ hydroxyethyl ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; hydroxypropyl methacrylate, isobornyl acrylate and isobornyl methacrylate and mixtures thereof according to one embodiment of the invention For example, the selected thermoplastic acrylic resin is composed of one or more of the following monomers as a polymer unit: acrylic acid, decyl propylene sulfonate, acrylic acid vinegar, thioglycolate, butyl acrylate, methacrylic acid N-butyl ester, isobutyl acrylate, isobutyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, isobornyl methacrylate, 2-hydroxyethyl acrylate, hydroxyl methacrylate Ethyl ester, 2-hydroxypropyl sulfonium acrylate and 2-methyl propyl acrylate, preferably one or more of the following monomers as polymerized units: 2-hydroxyethyl acrylate, methacrylic acid _2 _Hydroxyethyl vinegar, acrylic acid, yttrium methacrylate, n-butyl acrylate, n-butyl methacrylate, isobornyl acrylate and isobornyl methacrylate. Commercially available thermoplastics useful in the present invention. Examples of acrylic resins include: 7119-TB-50, 7626-1, 7128-TB-50, 7305-2-XS-50, 7329-XP-45, 7329-TS-45, 7117-TS-50, 7352-TS -50 and 7630 (manufactured by Changxing Chemical Industry Co., Ltd.); BR113, BR116, BR-115, BR 106, BR-85, BR-73, MB2952, MB3015 and MB 2660 (manufactured by Mitsubishi Corporation, Japan); B-725, B-735, B-736 and B-805 (made by Zeolite Co., Ltd.); AR-1042 and AR-1090F (manufactured by Changchun Co., Ltd.). A-646, A-14, A-ll, A-21, B-60, B-66, B-64, B-82 and B-72 (R&H); 152050.doc -16· 201239049 and FS-2970A (made by Deqian Enterprise Co., Ltd.); LF-1113, LF-1115 and LF-1117 (manufactured by Licensing Co., Ltd.). The ultraviolet curable treating agent of the present invention may optionally contain, as component (d), one or more additives known to those skilled in the art to which the present invention pertains. The additive which can be used in the present invention is not particularly limited, and is, for example, but not limited to, selected from the group consisting of a wetting agent, a flat agent, an antifoaming agent, a dispersing agent, and a combination thereof. The types of the above-mentioned additives are well known to those of ordinary skill in the art to which the present invention pertains, and the amounts thereof are also easily determined by those having ordinary knowledge in the technical field to which the present invention pertains according to different needs. In general, the component (d) additive is contained in an amount of from 0.05 to 1 part by weight based on 100 parts by weight of the total of the components (a) and (c). The present invention optionally uses a wetting agent to reduce the surface tension of the treating agent, so that the treating agent can be more easily spread on the surface of the substrate, and the wetting agent can be selected from the group consisting of polyester modified organic germanium, polyether modified organic germanium, and A group consisting of fluoroacrylic acid resins, fluorocarbon resins, and mixtures thereof. The present invention also optionally employs a flattening agent to facilitate wetting of the substrate and leveling of the coating film. Examples of commercially available wetting agents or flattening agents include: EFKA3777, EFKA3886, EFKA3883 and EFKA3600 (made by Evka, the Netherlands); BYK366, BYK300, BYK333, BYK307, BYK340, BYK341, BYK344, BYK3500, BYK3510, BYK3530 and BYK3570 Chemicals Company (BYK); TEGO Twin 4000, TEGO Wet270, TEGO 410 and TEGO 450 (made by TEGO); CARBOWET® 13-40 SURFACTANT (Air Products) ); Modaflow resin, Modaflow 2100, Modaflow 9200, 152050.doc •17- 201239049
Modaflow AQ-3000、Modaflow AQ-3025 、Multiflow resin、XL 480、XL 490、VXL 6230、VXL 6236、XW 390、XW 395、VXW 6508、VXW 4971、VXW 6214及 VXW 6502(CYTEC公司製）。 本發明視需要使用的消泡劑可抑制塗料塗佈過程中產生 氣泡而造成塗膜缺陷，消泡劑可以選自由聚醚-矽氧烷共 聚物乳液、二曱基聚矽氧烷類、有機改質聚矽氧烷類、高 分子型化合物、改質聚矽氧烷類及其混合物所組成之組 群。市售消泡劑例子包括：BYK-052、BYK-053、 BYK-056、BYK-057、BYK-065、BYK-066、BYK-067、 BYK-070、BYK-077、BYK-088、BYK-141、BYK-354、 BYK-392、BYK-A530、BYKbyketol-OK、BYK byketol-specia卜 BYK-020、BYK-051 及 Airex-980(畢克化學公司（BYK) 製）；Airex_986、Airex-900、Airex-920、TEGO-Foamex N 及TEGO-Foamex 840(香港高施米特太平洋公司（TEGO) 製）；DEUCHEM5300、DEUCHEM6500、DEUCHEM2700、 DEUCHEM3600 、DEUCHEM2700 、DEUCHEM3100 及 DEUCHEM5700(德謙企業股份有限公司製）。 本發明視需要使用的分散劑可提供穩定分散效果，將處 理劑成分均勻化。分散劑可以選自不飽和聚胺酸與胺類、 高分子量不飽和聚羧酸類、非離子型有機表面活性劑及其 混合物所組成的組群。市售分散劑例子包括：Anti-Terra-U、 Anti-Terra-203 、 Anti-Terra-204 、 disperbyklOl 、 disperbykl 03 、 disperbykl 10 、 disperbykl 15 、 152050.doc •18- 201239049 disperbykl 16 disperbykl 62 disperbykl68 disperbyk2000 disperbyk142 、 disperbyk163 、 disperbyk181 、 disperbyk2001 、 disperbykl61 、 disperbykl 64 、 disperbykl83 、 disperbyk2150 、Modaflow AQ-3000, Modaflow AQ-3025, Multiflow resin, XL 480, XL 490, VXL 6230, VXL 6236, XW 390, XW 395, VXW 6508, VXW 4971, VXW 6214, and VXW 6502 (manufactured by CYTEC). The antifoaming agent used in the invention can inhibit the generation of bubbles in the coating process to cause coating film defects, and the antifoaming agent can be selected from the group consisting of polyether-methoxane copolymer emulsion, dimercapto polyoxyalkylene, organic A group consisting of modified polyoxyalkylenes, polymeric compounds, modified polyoxyalkylenes, and mixtures thereof. Examples of commercially available defoamers include: BYK-052, BYK-053, BYK-056, BYK-057, BYK-065, BYK-066, BYK-067, BYK-070, BYK-077, BYK-088, BYK- 141, BYK-354, BYK-392, BYK-A530, BYKbyketol-OK, BYK byketol-specia, BYK-020, BYK-051 and Airex-980 (by BYK); Airex_986, Airex-900 , Airex-920, TEGO-Foamex N and TEGO-Foamex 840 (manufactured by Hong Kong High Tech Pacific (TEGO)); DEUCHEM 5300, DEUCHEM 6500, DEUCHEM 2700, DEUCHEM 3600, DEUCHEM 2700, DEUCHEM 3100 and DEUCHEM 5700 (manufactured by Deqian Enterprise Co., Ltd.) . The dispersant used in the present invention as needed provides a stable dispersion effect and homogenizes the components of the treatment agent. The dispersing agent may be selected from the group consisting of unsaturated polyamines and amines, high molecular weight unsaturated polycarboxylic acids, nonionic organic surfactants, and mixtures thereof. Examples of commercially available dispersants include: Anti-Terra-U, Anti-Terra-203, Anti-Terra-204, disperbyklOl, disperbykl 03, disperbykl 10, disperbykl 15, 152050.doc • 18- 201239049 disperbykl 16 disperbykl 62 disperbykl68 disperbyk2000 disperbyk142 , disperbyk163, disperbyk181, disperbyk2001, disperbykl61, disperbykl 64, disperbykl83, disperbyk2150,
disperbykl07、BYK-bykumen、BYK P104、BYK 220S、 BYK Lactimon、BYK W-975、BYK W-995、dispers-610、 dispers-610S、dispers-630、dispers-700及 dispers-710(畢克 化學公司（BYK)製）；DEUCHEM 929、DEUCHEM 901F、 DEUCHEM-VP DP9220、DEUCHEM-VP 556、DEUCHEM 912、DEUCHEM 904、DEUCHEM 910 及 DEUCHEM 9US(德謙企業股份有限公司製）；TEGO Wet 500及 TEGO-Foamex 840(香港高施米特太平洋公司（TEGO)製）、 伊士肯EC-8715/A及伊士肯EC-8000/A(伊士肯化學股份有 限公司製）；EFKA-5054、EFKA-5065 及 EFKA-5066(荷蘭 埃夫卡助劑公司（EFKA)製）。 本發明可視需要添加組分（e)溶劑，以調整處理劑黏度在 適合操作的範圍。溶劑可在調配各成分時添加，亦可在最 終欲進行喷塗時添加。根據本發明之一實施態樣，溶劑宜 在調配各成分時適當添加，並在最終欲進行噴塗時，進一 步調整到喷塗的黏度，例如，使固成份在約15〜40%之範 圍。溶劑之含量並無任何限制，可依實際之條件及需求而 進行調整，獲得所需的塗料黏度即可。 本發明所使用的溶劑，並無特殊限制，可為任何本發明 所屬技術領域具有通常知識者所已知者，可選自但不限於 152050.doc •19· 201239049 烷烴類、芳烴類、酮類、酯類、醇類、醚醇類及其混合物 所組成之組群。 適用於本發明之烷烴類溶劑可選自但不限於正己烷、正 庚烷及異庚烷及其混合物所組成的群組。適用於本發明之 芳族烴類溶劑可選自但不限於苯、曱笨及二甲笨及其混合 物所組成的群組。適用於本發明之酮類溶劑可選自但不限 於曱基乙基酮（MEK)、丙嗣、甲基異丁基酮、環己酮及4_ 毯基4-曱基-2-戊酮及其混合物所組成的群組。適用於本 發明之酯類溶劑可選自但不限於乙酸異丁酯（IBAC)、乙酸 乙酯（EAC)、乙酸丁酯（BAC)、曱酸乙酯、乙酸甲酯、乙 酸乙氧基乙酯、乙酸乙氧基丙酯、異丁酸乙酯、單曱基醚 丙一醇乙酸酯及乙酸戊酯及其混合物所組成的群組。適用 於本發明之醇類溶劑可選自但不限於乙醇、異丙醇、正丁 醇及異戊醇及其混合物；適用於本發明的醚醇類溶劑例如 但不限於乙二醇單丁醚（BCS)、乙二醇單乙醚乙酸酯 (CAC)、乙二醇單乙醚（Ecs)、丙二醇單甲喊、丙二醇單曱 醚乙酸酯（PMA)及丙二醇單曱醚丙酸酯（PMP)及其混合物 所组成的群組。 本發明之紫外線固化型處理劑可視需要包含組分⑴密著 促進劑’以進一步提高處理劑與基材表面之密著性，尤其 係選用金屬基材或含纖維之複合基.材時。選擇極性與基材 相近之單體作為密著促進劑，可增加塗料與基材之接觸面 積，提高潤濕效果及降低表面張力，有助於塗料樹脂與基 材之間的密著性。適用於本發明之密著促進劑例如但不限 152050.doc •20· 201239049 於磷酸醋或有機矽烷偶合劑’其含量以組分（a)與（c)合計 為100重量份計，為0.1-5重量份，較佳為0.2-2重量份。 適用於UV塗料或UV油墨的麟酸S旨較佳為填酸醋丙稀酸 酯，可選自但不限於曱基丙烯酸2-羥基乙基酯磷酸酯 (2-Hydroxyethyl Methacrylate Phosphate)、三官能基丙稀 酸酉旨構酸醋（Trifunctional Acid Ester Phosphate)及其混合 物所組成的組群。 適用於本發明的有機矽烷偶合劑例如但不限於乙烯基三 甲氧基石夕院（vinyltrimethoxysilane)、2-(3，4環氧基環己基） 乙基三 曱 氧基石夕院 (2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane)、3-縮水甘油丙基三曱氧基石夕院（3-glycidoxypropyltrimethoxysilane)、3 _(曱基丙浠酿氧）丙基 三甲氧基石夕烧（3-methacryloxypropyltrimethoxysilane)或 Ν'-苯基-3-胺丙基二曱氧基碎烧（N-phenyl-3· aminopropyltrimethoxysilane)或其混合物。 市售密著促進劑的例子包括·· CD9050、CD9051、 CD9053 及 CD9054(沙多瑪（SARTOMER)公司製）；EM39(長 興化工製）；KBM-303、KBM-403、KBM-503、 KBM-573、KBM-803、KBM-9103 及 KBM-1003(信越 ShinEtsu 製）。 本發明之UV型處理劑具有填補基材表面之缺陷、隔絕 表面之污物或油污、及改善基材與塗料樹脂之密著性等功 效。適用於各種需要表面前處理之基材或者經初步前處理 之基材，改善外觀及增加塗料與基材之黏著性，尤其適用 152050.doc -21- 201239049 於對外觀及表面性質要求較高之3C電子產品、化妝品、家 電及金屬之表面塗裝及處理。 本發明之紫外線固化型處理劑所適用之基材並無特殊限 制，例如可為瓷磚、木材、皮革、石材、玻璃、金屬、合 金、紙張、塑膠、纖維、棉織品等，較佳為玻璃、金屬、 塑膠或複合基材》上述金屬基材，例如但不限於不鏽鋼、 鋅合金、鋁、鋁合金、鎂合金及鉻。上述塑膠基材例如但 不限於 ABS、PC、PP、PMMA、PS、PC/ABS 或其混合。 上述複合基材係指含纖維之塑膠基材，其例如但不限於含 玻璃纖維之尼龍或PC。 本發明之處理劑可藉由任何本發明所屬技術領域中具有 通常知識者所習知之方式塗覆至基材的表面上。舉例言 之’可經由包含以下步驟之方法加以施用： (1) 選擇所需之（a)不飽和雙鍵之單體或募聚物或其混合物 及（c)熱塑性樹脂’視需要加入溶劑，授拌混合； (2) 加入（b)光起始劑，再加入視需要之（d)添加劑、（e)溶 劑與（f)密著促進劑’搜拌均句，調整至適當黏度 (800〜2500 cps)以形成一液態可聚合組合物； (3) 將步驟（2)所得之液態可聚合組合物以適當溶劑稀釋（黏 度50 cps以下），並以適當之方式塗佈於一基材上作表 面處理，形成一塗層； (4) 視需要加熱以揮發溶劑，溫度控制於約5〇。〇〜7〇它，於 固定溫度下反應約1〜5分鐘； (5) 視需要將底漆塗佈於由上述步驟而得之塗層上，形成 152050.doc -22· 201239049 另一塗層；及·. (6)照射能量射線以使該等塗層固化。 上述步驟（3)中所使用之塗佈方式，可採用線杆塗布（bar coating)、狹縫式模壓塗布（slot die coating)、凸版印刷塗 布（gravure coating)、斜板式塗布（slide coating)、淋幕式 塗布（curtain coating)或喷霧式塗布（Spray coating)，較佳 為喷霧式塗佈（噴塗）。 較佳地’步驟（6)之塗層固化步驟係藉由照射能量射線 產生光聚合反應而進行，該能量射線係指一定範圍波長之 光源’較佳為紫外光（波長為200-400 nm)。照射強度可為 自5 00至1，200毫焦耳/平方公分（mj/cm2)，較佳係自6〇〇至 1,000 mJ/cm2。 以下實施例係用於對本發明作進一步說明，唯非用以限 制本發明之範圍。任何熟悉此項技藝之人士可輕易達成之 修飾及改變均包括於本案說明書揭示内容及所附申請專利 範圍之範圍内。 製備例1 -10 依據表1所列成分及比例’調配本發明之紫外線固化型 處理劑。 表1 製備例 1 2 3 4 5 6 7 al(克） 4.1 4.1 4.1 .......; · 1 呦克） 4.1 4.1 4.1 ：!\ . . - »3(克） r::: 7.8 5.4 152050.doc •23· 201239049 a4(克） 5.3 a5(克） 8.0 2.5 a6(克） 15.0 bl(克） 0.5 0.5 0.5 0.1 1.1 0.5 0.5 cl(克） 15.4 15.4 15.4 c2(克） 9.2 9.2 9.2 c3(克） 24.2 c4(克） 21.3 c5(克） 20.8 35.0 dl(克） 0.1 0.1 0.1 0.1 d2(克） 0.1 d3(克） 0.1 el(克） 20.5 20.5 20.5 22.3 15.9 8.3 e2(克） 15.3 15.3 15.3 24.2 31.9 12.5 20.0 e3(克） 5.1 5.1 5.1 e4(克） 15.3 15.3 15.3 15.3 15.9 24.9 e5(克） 10.2 10.2 10.2 e6(克） 4.8 e7(克） 8.3 e8(克） 16.6 e9(克） 10.0 elO(克） 20.0 η(克） 0.2 0.2 0.2 β(克） 0.2 0.1 β(克） 0.5 總重(克） 100 99.8 99.9 99.9 100 100.1 100.1 表1-續 製備例 8 9 10 a3(克） 4.0 a5(克） 16.0 8.5 3.2 152050.doc •24- 201239049 a7(克） 4.0 ------1 3.2 a8(克） 4.0 .·-，..···_··. - ·.·>"··· a9(克） 2.0 alO(克） 7.5 8.0 J ...π all(克） .V；.；· - 3.5 ... τ*7· — b2(克） 1.6 1.2 0.8 c4(克） 18.0 '.v. T-*· .. . .:.:、 c6(克） 12.0 c7(克） ： ：,/： ·|·:- :-- 6.4 d3(克） — 0.1 0.1 0.1 el(克） — 9.5 e2(克） 23.0 23.0 〜----- 9.5 e3(克） 4.4 --- 〉.. · 一.^f -... e4(克） • ·· ·' .:· ..d'::.. -—·— 22.3 e6(克） 23.0 -· - ———^ 35.0 ...二Πr-•- - —；--------- e7(克） '7 .匕 --L 12.7 ----- e8(克） ---—. 31.8 fl(克） 0.4 β(克） 0.4 0.4 ----- 0.1 總重(克） 100.0 ----- 100.0 100.1 ------ al: a2: a3 : a4: a5: a6: a7: 六丙稀酸一季戊四醇醋單體（長興化工，EM265) 脂肪族聚胺基曱酸酯六丙烯酸酯寡聚物（長興化工 6145-100) 季戊四醇三丙烯酸酯單體（長興化工，eM235) 異癸基丙烯酸酯單體（長興化工，EM219) 脂肪族聚胺基f駿醋三丙稀酸醋寡聚物（長興化工 611B-85) 氧丙烯酸酗暴聚物（長興化工，621-100) 基丙心旨單體（長興化工，EM231) 152050.doc •25· 201239049 a8:甲基丙烯酸2-羥基乙酯單體（日本觸媒，HEMA) a9:聚醋丙烯酸酯寡聚物（B〇inar Specialties，JL_1〇6E) alO:聚醋丙烯酸酯寡聚物（B〇niar Speciahies，be-112DP10) all:異冰片基丙稀酸酯單體（長興化工，em7〇) bl: 1-羥基環己基笨基酮（雙鍵化工，CHIVAcuRE 184) b2: 2,2·-二曱基_1}2_二苯基乙烷-j酮（雙鍵化工， CHIVACURE BDK) cl.熱塑性丙稀酸樹脂（長興化工，7ii7_ts_50) c2.熱塑性丙稀酸樹脂（長興化工，7329-TS-45) c3:熱塑性丙烯酸樹脂（長興化工，7128 Tb_5〇) c4.熱塑性丙稀酸樹脂（長興化工，7329_χρ_45) c5.熱塑性丙稀酸樹脂（長興化工，7119_τβ·5〇) c6:熱塑性丙烯酸樹脂（長興化工，763〇) c7:氯醋樹脂（威凱化學公司，Vinn〇iH14/36) dl.潤濕劑（德國迪高公司，TEg〇 Wet27〇) d2.平坦劑（荷蘭埃夫卡公司，EFKA3777) d3 .含氟丙烯酸樹脂潤濕劑（畢克化學公司， el:二曱苯 e2:乙酸丁酯 e3:乙二醇單丁醚 科：甲基異丁基酮 e5:單甲基醚丙二醇乙酸酯 e6:曱苯 152050.doc -26 - 201239049 e 7:環己酮 曱基乙基酮 e9:異丙醇 e 10:乙酸乙酯 fl: 3-(曱基丙烯醯氧）丙基三甲氧基矽烷（信越公司生產， KBM-503) f2: 2-羥基乙基曱基丙烯酸酯磷酸酯（長興化工，EM 39) f3:三官能基丙烯酸酯磷酸酯（沙多瑪化學公司，CD9〇5l) 實施例1 使用製備例1之紫外線固化型處理劑，視需要以溶劑調整 黏度至岩田杯9秒左右，以空氣喷搶喷塗於PMMA塑膠基 板上’接著於6(TC的烘箱内進行3〜5分鐘的預烤，塗膜厚 度1〜3微米，然後，經中壓水銀燈（4〇〇 mJ/cm2)進行曝光。 而後’喷塗uv電鍍底漆（長興化工製，eTERCURE8250U-9A)，接著於60°C的烘箱内進行5〜1〇分鐘的預烤，經中壓 水銀燈（800 mJ/cm2)進行曝光，底漆厚度1〇〜15微米，製備 具塗膜之基板。 實施例2 紫外線固化型處理劑之組成及製造方式同實施例t，改變 基板為PS塑膠基板。 實施例3 紫外線固化型處理劑之組成及製造方式同實施例丄，改變 基板為PC塑膠基板。 實施例4 152050.doc -27- 201239049 紫外線固化型處理劑之組成及製造方式同實施例1 ’改變 基板為ABS塑膠基板。 實施例5 使用製備例2之紫外線固化型處理劑，製造方式及基板選 擇同實施例1。 實施例6 使用製備例3之紫外線固化型處理劑，製造方式及基板選 擇同實施例1 » 實施例7 使用製備例4之紫外線固化型處理劑，視需要以溶劑調整 黏度至岩田杯9秒左右，以空氣喷搶喷塗於PMMA塑膠基 板上’塗膜厚度1〜3微米，再噴塗UV電鍍底漆（長興化工 製’ ETERCURE8250U-9A)，接著於60°C的烘箱内進行 5〜10分鐘的預烤，經中壓水銀燈（8〇〇 mj/Cm2)進行曝光， 底漆厚度10〜15微米，製備具塗膜之基板。 實施例8 使用製備例5之紫外線固化型處理劑，視需要以溶劑調整 黏度至石田杯10秒左右’以空氣喷搶喷塗於含玻璃纖維之 尼龍複合基板上，塗膜厚度1〜3微米，接著於6(rc的烘箱 内進行3〜5分鐘的預烤，然後喷塗UV電鍍底漆（長興化工 製，ETERCURE8250U-9A) ’接著於60X：的烘箱内進行 5〜分鐘的預烤，經中壓水銀燈（800 mJ/cm2)進行曝光， 底漆厚度10〜15微米，製備具塗膜之基板。 實施例9 152050.doc -28 201239049 使用製備例6之紫外線固化型處理劑，視需要以溶劑調整 黏度至岩田杯9秒左右，以空氣噴搶喷塗於pc塑膠基板 上，接著於6(TC的烘箱内進行3〜5分鐘的預烤缺後\ 中壓水銀燈（400 mJ/cm2)進行曝光，塗膜厚度卜3微米。而 後喷塗uv電鐘底漆（長興化工製，etercure8^〇u_ 9A)’接著於6(TC的烘箱内進行5〜1〇分鐘的預烤，經中壓 . 水銀燈_議瓜2)進行曝光，底漆厚度10〜15微米，製 • 具塗膜之基板。 實施例10 &用製備例7之紫外線固化型處理劑，視需要以溶劑調整 黏度至岩田杯9秒左右，以空氣喷搶喷塗於pc/玻纖複合基 板上，塗膜厚度6〜8微米，接著於⑽的烘箱内進行5分鐘 的預烤，然後，經中塵水銀燈（8〇〇 mJ/cm2)進行曝光。而 後喷塗uv電鍍底漆（長興化工製，etercure825〇u_ 9A)’接著於6(rc的烘箱内進行5分鐘的預烤，經中壓水銀 燈（800 mj/cm2)進行曝光，底漆厚度1〇~15微米，製備具塗 • 膜之基板。 . 實施例11 使用製備例8之紫外線固化型處理劑，視需要以溶劑調整 黏度至岩田杯9秒左右，以空氣喷搶喷塗於玻璃基板上， 塗膜厚度1〜3微米，接著於6〇t的烘箱内進行5分鐘的預 烤’然後，經中壓水銀燈_ mJ/cm2)進行曝光。而後喷 塗UVt鍍底漆（長興化工製，ETERCURE8250U-9A)，接著 ； 的大、箱内進行5分鐘的預烤，經中壓水銀燈（800 152050.doc •29- 201239049 mJ/cm2)進行曝光，底漆厚度1〇〜15微米，製備具塗膜之基 板。 實施例12 使用製備例9之紫外線固化型處理劑，視需要以溶劑調整 黏度岩田杯9秒左右，以空氣喷搶喷塗於不鏽鋼基板上， 接著於60 C的烘箱内進行5分鐘的預烤，然後，經中壓水 銀燈（800 mJ/cm2)進行曝光，塗膜厚度卜3微米。而後喷塗 UV電鍍底漆（長興化工製，etERcURE8250U-9A)，接著 於60 C的烘箱内進行5分鐘的預烤，經中壓水銀燈（8〇〇 mJ/cm2)進行曝光，底漆厚度1〇〜15微米，製備具塗膜之基 板。 實施例13 紫外線固化型處理劑、製造方式及基板選擇同實施例 12 ’改變喷塗濟罩光漆（長興化工製，ETERCURE6763M-4) ’接著於60°C的烘箱内進行5分鐘的預烤，經中壓水銀燈 (800 mJ/cm2)進行曝光，底漆厚度1〇〜15微米，製備具塗膜 之基板。 實施例14 紫外線固化型處理劑及製造方式同實施例12，改變基板 為PC塑膠基板’改變喷塗uv硬罩層（長興化工製， ETERCURE6776-3B) ’接著於60°C的烘箱内進行5分鐘的預 烤，經中壓水銀燈（800 mJ/cm2)進行曝光，底漆厚度1〇〜15 微米，製備具塗膜之基板。 實施例15 J52050.doc •30- 201239049 使用製備例ίο之紫外線固化型處理劑，視需要以溶劑調 整黏度至岩田杯9秒左右，以空氣喷槍喷塗於PC塑膠基板 上，接著於60°C的烘箱内進行3〜5分鐘的預烤，然後，經 中壓水銀燈（400 mJ/cm2)進行曝光，塗膜厚度1〜3微米。而 後噴塗UV電鍍底漆（長興化工製，ETERCURE8250U-9A)， 接著於60°C的烘箱内進行5〜10分鐘的預烤，經中壓水銀燈 (800 mJ/cm2)進行曝光，底漆厚度10〜15微米，製備具塗膜 之基板。 實施例16 紫外線固化型處理劑及製造方式同實施例15，改變基板 為ABS塑膠基板。 測試方法 塗膜與基板的附著性：根據ASTM D3359-93檢驗方法， 以百格刮刀刮於塗膜表面，後以膠帶黏緊後，90°撕起， 判定剝落格數。 外觀：利用肉眼檢視塗膜外觀。 塗膜耐熱性：將上述實施例所製得之樣品放置80°C烘箱 96小時後，利用肉眼檢視塗膜表面有無裂痕、脫落等缺 陷0 表2 附著性 外觀 耐熱性 實施例1 100/100 平整、無缺陷 無裂痕、無脫落 實施例2 80/100 平整、無缺陷 無裂痕、無脫落 實施例3 100/100 平整、無缺陷 無裂痕、無脫落 152050.doc -31 - 201239049 ^ y«.l C 1 Λ A / 1 ΛΑ 、Ti av · ----- 實施例7 100/100Disperbykl07, BYK-bykumen, BYK P104, BYK 220S, BYK Lactimon, BYK W-975, BYK W-995, dispers-610, dispers-610S, dispers-630, dispers-700 and dispers-710 (BYK Chemicals, Inc. ( BYK)); DEUCHEM 929, DEUCHEM 901F, DEUCHEM-VP DP9220, DEUCHEM-VP 556, DEUCHEM 912, DEUCHEM 904, DEUCHEM 910 and DEUCHEM 9US (made by Deqian Enterprise Co., Ltd.); TEGO Wet 500 and TEGO-Foamex 840 (Hong Kong High-Smith Pacific (TEGO)), Easton EC-8715/A and Easton EC-8000/A (made by Eastken Chemical Co., Ltd.); EFKA-5054, EFKA-5065 and EFKA-5066 (made by EFKA, Netherlands). The present invention may optionally add component (e) solvent to adjust the viscosity of the treatment agent to suit the range of operation. The solvent can be added during the preparation of the ingredients, or it can be added at the end of the spraying process. According to one embodiment of the present invention, the solvent is suitably added when the ingredients are formulated, and further adjusted to the viscosity of the spray when the final application is to be carried out, for example, to have a solid content of about 15 to 40%. There is no limit to the solvent content, which can be adjusted according to the actual conditions and requirements to obtain the desired coating viscosity. The solvent to be used in the present invention is not particularly limited and may be any one known to those skilled in the art to which the present invention pertains, and may be selected from, but not limited to, 152050.doc • 19·201239049 Alkanes, aromatic hydrocarbons, ketones a group consisting of esters, alcohols, ether alcohols, and mixtures thereof. Alkane solvents suitable for use in the present invention may be selected from the group consisting of, but not limited to, n-hexane, n-heptane, and isoheptane, and mixtures thereof. The aromatic hydrocarbon solvent suitable for use in the present invention may be selected from the group consisting of, but not limited to, benzene, hydrazine, and dimethyl stannous and mixtures thereof. The ketone solvent suitable for use in the present invention may be selected from, but not limited to, mercaptoethyl ketone (MEK), propyl hydrazine, methyl isobutyl ketone, cyclohexanone, and 4-based 4-mercapto-2-pentanone. a group of its mixtures. The ester solvent suitable for use in the present invention may be selected from, but not limited to, isobutyl acetate (IBAC), ethyl acetate (EAC), butyl acetate (BAC), ethyl decanoate, methyl acetate, ethoxy acetate. A group consisting of esters, ethoxypropyl acetate, ethyl isobutyrate, monodecyl ether propanol acetate, and amyl acetate, and mixtures thereof. Alcohol solvents suitable for use in the present invention may be selected from, but not limited to, ethanol, isopropanol, n-butanol, and isoamyl alcohol, and mixtures thereof; ether alcohol solvents suitable for use in the present invention such as, but not limited to, ethylene glycol monobutyl ether (BCS), ethylene glycol monoethyl ether acetate (CAC), ethylene glycol monoethyl ether (Ecs), propylene glycol monomethyl sulfonate, propylene glycol monoterpene ether acetate (PMA) and propylene glycol monoterpene ether propionate (PMP) And a group of mixtures thereof. The ultraviolet curable treating agent of the present invention may optionally contain the component (1) adhesion promoter ' to further improve the adhesion of the treating agent to the surface of the substrate, especially when a metal substrate or a composite substrate containing fibers is used. Selecting a monomer with a polarity similar to that of the substrate as a adhesion promoter increases the contact area between the coating and the substrate, improves the wetting effect and lowers the surface tension, and contributes to the adhesion between the coating resin and the substrate. The adhesion promoter suitable for use in the present invention is, for example but not limited to, 152050.doc •20·201239049 in a phosphate vinegar or an organic decane coupling agent, and its content is 0.1 parts by weight based on 100 parts by weight of the total of components (a) and (c). - 5 parts by weight, preferably 0.2 to 2 parts by weight. The linonic acid S suitable for UV coating or UV ink is preferably filled with acid acrylate acrylate, which may be selected from, but not limited to, 2-Hydroxyethyl Methacrylate Phosphate, trifunctional A group consisting of Trifunctional Acid Ester Phosphate and mixtures thereof. Organic decane coupling agents suitable for use in the present invention are, for example but not limited to, vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyxanthine (2-(3, 4-epoxycyclohexyl) ethyltrimethoxysilane), 3-glycidoxypropyltrimethoxysilane, 3- methacryloxypropyltrimethoxysilane or Ν -Phenyl-3-aminopropylaminopropyltrimethoxysilane or a mixture thereof. Examples of commercially available adhesion promoters include: CD9050, CD9051, CD9053, and CD9054 (made by SARTOMER); EM39 (made by Changxing Chemical); KBM-303, KBM-403, KBM-503, KBM- 573, KBM-803, KBM-9103, and KBM-1003 (manufactured by Shin-Etsu ShinEtsu). The UV-type treating agent of the present invention has the effects of filling defects on the surface of the substrate, insulating dirt or oil stain on the surface, and improving the adhesion between the substrate and the coating resin. It is suitable for all kinds of substrates that require surface pretreatment or substrates that have been pretreated, to improve the appearance and increase the adhesion of the coating to the substrate. Especially for 152050.doc -21- 201239049, which requires high appearance and surface properties. 3C electronic products, cosmetics, home appliances and metal surface coating and processing. The substrate to which the ultraviolet curable treatment agent of the present invention is applied is not particularly limited, and may be, for example, ceramic tile, wood, leather, stone, glass, metal, alloy, paper, plastic, fiber, cotton, etc., preferably glass or metal. , plastic or composite substrate. The above metal substrate, such as but not limited to stainless steel, zinc alloy, aluminum, aluminum alloy, magnesium alloy and chromium. The above plastic substrate is, for example but not limited to, ABS, PC, PP, PMMA, PS, PC/ABS or a mixture thereof. The above composite substrate refers to a fiber-containing plastic substrate such as, but not limited to, nylon or PC containing glass fibers. The treating agent of the present invention can be applied to the surface of the substrate by any means known to those skilled in the art to which the present invention pertains. For example, it can be applied by a method comprising the steps of: (1) selecting a desired monomer or a polymer or a mixture thereof of (a) an unsaturated double bond and (c) a thermoplastic resin, optionally adding a solvent, Mixing and mixing; (2) Adding (b) photoinitiator, adding optional (d) additive, (e) solvent and (f) adhesion promoter, and adjusting to appropriate viscosity (800) ~2500 cps) to form a liquid polymerizable composition; (3) The liquid polymerizable composition obtained in the step (2) is diluted with a suitable solvent (viscosity of 50 cps or less) and applied to a substrate in an appropriate manner. The surface is treated to form a coating; (4) heated as needed to volatilize the solvent, and the temperature is controlled to about 5 Torr. 〇~7〇, react at a fixed temperature for about 1~5 minutes; (5) Apply the primer to the coating obtained by the above steps as needed to form 152050.doc -22· 201239049 Another coating And (6) illuminating the energy rays to cure the coatings. The coating method used in the above step (3) may be a bar coating, a slot die coating, a gravure coating, a slide coating, or the like. A curtain coating or a spray coating is preferred by spray coating (spray coating). Preferably, the step of curing the coating of step (6) is carried out by photopolymerization by irradiation of an energy ray, which refers to a source of light of a certain range of wavelengths, preferably ultraviolet light (wavelength of 200-400 nm). . The irradiation intensity may be from 500 to 1,200 mJ/cm 2 (mj/cm 2 ), preferably from 6 to 1,000 mJ/cm 2 . The following examples are intended to be illustrative of the invention and are not intended to limit the scope of the invention. Modifications and variations that may be readily made by those skilled in the art are included within the scope of the disclosure of the present disclosure and the scope of the appended claims. Preparation Example 1 - 10 The ultraviolet curable treatment agent of the present invention was formulated in accordance with the components and ratios listed in Table 1. Table 1 Preparation Example 1 2 3 4 5 6 7 al (g) 4.1 4.1 4.1 .......; 1 gram) 4.1 4.1 4.1 :!\ . . - »3 (g) r::: 7.8 5.4 152050.doc •23· 201239049 a4(g) 5.3 a5(g) 8.0 2.5 a6(g) 15.0 bl(g) 0.5 0.5 0.5 0.1 1.1 0.5 0.5 cl(g) 15.4 15.4 15.4 c2(g) 9.2 9.2 9.2 c3 (g) 24.2 c4 (g) 21.3 c5 (g) 20.8 35.0 dl (g) 0.1 0.1 0.1 0.1 d2 (g) 0.1 d3 (g) 0.1 el (g) 20.5 20.5 20.5 22.3 15.9 8.3 e2 (g) 15.3 15.3 15.3 24.2 31.9 12.5 20.0 e3 (g) 5.1 5.1 5.1 e4 (g) 15.3 15.3 15.3 15.3 15.9 24.9 e5 (g) 10.2 10.2 10.2 e6 (g) 4.8 e7 (g) 8.3 e8 (g) 16.6 e9 (g) 10.0 elO ( g) 20.0 η (g) 0.2 0.2 0.2 β (g) 0.2 0.1 β (g) 0.5 total weight (g) 100 99.8 99.9 99.9 100 100.1 100.1 Table 1 - continued Preparation 8 9 10 a3 (g) 4.0 a5 (g ) 16.0 8.5 3.2 152050.doc •24- 201239049 a7(g) 4.0 - -----1 3.2 a8 (g) 4.0 ..-,..···_··. - ···>"··· a9 (g) 2.0 alO (g) 7.5 8.0 J .. .π all(克) .V;.;· - 3.5 ... τ*7· — b2(g) 1.6 1.2 0.8 c4(g) 18.0 '.v. T-*· .. . .:.:, C6 (g) 12.0 c7 (g) : :, /: ·|·:- :-- 6.4 d3 (g) — 0.1 0.1 0.1 el (g) — 9.5 e2 (g) 23.0 23.0 ~----- 9.5 E3 (g) 4.4 --- 〉.. · one.^f -... e4 (g) • ·· ·' .:· ..d'::.. -—·— 22.3 e6 (g) 23.0 -· - ———^ 35.0 ... 二Πr-•- -_;--------- e7(g) '7 .匕--L 12.7 ----- e8(g) - ---. 31.8 fl (g) 0.4 β (g) 0.4 0.4 ----- 0.1 total weight (g) 100.0 ----- 100.0 100.1 ------ al: a2: a3 : a4: a5 : a6: a7: Hexaacrylic acid-pentaerythritol vinegar monomer (Changxing Chemical, EM265) Aliphatic polyamine phthalate hexaacrylate oligomer (Changxing Chemical 6145-100) Pentaerythritol triacrylate monomer (Changxing Chemical) ,eM235) isodecyl acrylate monomer (Changxing Chemical, EM219) aliphatic polyamine based f vinegar tripropylene Vinegar oligomer (Changxing Chemical 611B-85) Oxygen acrylate cesium polymer (Changxing Chemical, 621-100) propyl propyl monomer (Changxing Chemical, EM231) 152050.doc •25· 201239049 a8: methacrylic acid 2 -Hydroxyethyl ester monomer (Japanese catalyst, HEMA) a9: Polyacetate acrylate oligomer (B〇inar Specialties, JL_1〇6E) alO: Polyacetate acrylate oligomer (B〇niar Speciahies, be-112DP10) All: isobornyl acrylate monomer (Changxing Chemical, em7〇) bl: 1-hydroxycyclohexyl phenyl ketone (double bond chemical, CHIVAcuRE 184) b2: 2,2·-dimercapto_1} 2_Diphenylethane-j ketone (double bond chemical, CHIVACURE BDK) cl. Thermoplastic acrylic resin (Changxing Chemical, 7ii7_ts_50) c2. Thermoplastic acrylic resin (Changxing Chemical, 7329-TS-45) c3: Thermoplastic Acrylic Resin (Changxing Chemical, 7128 Tb_5〇) c4. Thermoplastic Acrylic Resin (Changxing Chemical, 7329_χρ_45) c5. Thermoplastic Acrylic Resin (Changxing Chemical, 7119_τβ·5〇) c6: Thermoplastic Acrylic Resin (Changxing Chemical, 763) 〇) c7: chloroacetate resin (Weikai Chemical Company, Vinn〇iH14/36) dl. Wetting agent (Germany Digo, Teg 〇Wet27〇) d2. Flattening agent (Efka, EFKA3777, Netherlands) d3. Fluorinated acrylic resin wetting agent (Bick Chemical Company, el: diphenyl benzene e2: butyl acetate e3: ethylene glycol monobutyl ether Section: methyl isobutyl ketone e5: monomethyl ether propylene glycol acetate e6: toluene benzene 152050.doc -26 - 201239049 e 7: cyclohexanone decyl ethyl ketone e9: isopropanol e 10: acetic acid Ester fl: 3-(decyl propylene oxime) propyl trimethoxy decane (manufactured by Shin-Etsu Company, KBM-503) f2: 2-hydroxyethyl decyl acrylate phosphate (Changxing Chemical, EM 39) f3: three Functional acrylate phosphate (Shadosulfon Chemical Co., Ltd., CD9 〇 5l) Example 1 Using the ultraviolet curable treatment agent of Preparation Example 1, if necessary, adjust the viscosity to the Iwata Cup with a solvent for about 9 seconds, spray with air. On the PMMA plastic substrate, 'pre-bake for 3 to 5 minutes in a TC oven, the film thickness was 1 to 3 μm, and then exposed to a medium pressure mercury lamp (4 μm/cm 2 ). Then, the spray uv plating primer (eTERCURE 8250U-9A, manufactured by Changxing Chemical Co., Ltd.) was pre-baked in an oven at 60 ° C for 5 to 1 minute, and exposed to a medium pressure mercury lamp (800 mJ/cm 2 ). A lacquer thickness of 1 〇 15 μm is used to prepare a substrate with a coating film. Example 2 The composition and manufacturing method of the ultraviolet curable treatment agent were the same as those in the example t, and the substrate was changed to a PS plastic substrate. Example 3 The composition and manufacturing method of the ultraviolet curable treatment agent were the same as those in the examples, and the substrate was changed to a PC plastic substrate. Example 4 152050.doc -27- 201239049 The composition and manufacturing method of the ultraviolet curing type treating agent are the same as those in the embodiment 1'. The substrate is an ABS plastic substrate. Example 5 Using the ultraviolet curable treatment agent of Preparation Example 2, the production method and substrate were selected in the same manner as in Example 1. Example 6 The ultraviolet curable treatment agent of Preparation Example 3 was used, and the production method and substrate selection were the same as in Example 1 » Example 7 Using the ultraviolet curable treatment agent of Preparation Example 4, the viscosity was adjusted to the Iwata Cup by the solvent as needed for about 9 seconds. Sprayed on the PMMA plastic substrate with air spray. The coating film thickness is 1~3 microns, and then sprayed with UV plating primer (ETERCURE8250U-9A made by Changxing Chemical), followed by 5~10 minutes in an oven at 60 °C. Pre-baked, exposed by medium pressure mercury lamp (8〇〇mj/Cm2), primer thickness 10~15 microns, to prepare a substrate with a coating film. Example 8 The ultraviolet curable treatment agent of Preparation Example 5 was used, and the viscosity was adjusted to the Ishida Cup for about 10 seconds with the solvent as needed. The air was sprayed onto the nylon composite substrate containing the glass fiber, and the thickness of the coating film was 1 to 3 μm. Then, pre-bake for 3 to 5 minutes in an oven of 6 (rc), and then spray a UV plating primer (made by Changxing Chemical Co., Ltd., ETERCURE 8250U-9A). Then, pre-bake for 5 minutes in a 60X: oven. The substrate with a coating film was prepared by exposure to a medium pressure mercury lamp (800 mJ/cm 2 ), and the thickness of the primer was 10 to 15 μm. Example 9 152050.doc -28 201239049 The ultraviolet curing treatment agent of Preparation Example 6 was used, as needed. Adjust the viscosity to the Iwata Cup with solvent for about 9 seconds, spray it on the pc plastic substrate with air spray, and then carry out 3~5 minutes of pre-baked in the oven of 6 (TC oven). Medium pressure mercury lamp (400 mJ/cm2) ) Exposure, film thickness of 3 micron. Then spray uv electric clock primer (made by Changxing Chemical, etercure8^〇u_ 9A)' followed by 6 (TC oven) for 5~1〇 minutes of pre-baking, Medium pressure. Mercury lamp _ melon 2) exposure, primer thickness 10~15 M., system: substrate with coating film. Example 10 & UV-curing treatment agent of Preparation Example 7, if necessary, adjust the viscosity to the Iwata Cup with solvent for about 9 seconds, spray air on PC/glass fiber On the composite substrate, the coating film has a thickness of 6 to 8 μm, and then pre-baked in an oven of (10) for 5 minutes, and then exposed to a dust mercury lamp (8 μm/cm 2 ), and then sprayed with a uv plating primer ( Changxing Chemical, etercure825〇u_ 9A)' is then pre-baked in a 6 (rc oven) for 5 minutes, exposed to a medium pressure mercury lamp (800 mj/cm2), and the primer thickness is 1〇15 microns. • Substrate of the film. Example 11 The ultraviolet curable treatment agent of Preparation Example 8 was used, and the viscosity was adjusted to a Iwatian cup with a solvent as needed for about 9 seconds, and sprayed on a glass substrate by air jet coating at a thickness of 1 to 3 Micron, followed by 5 minutes of pre-baking in a 6 〇 oven, then exposed to a medium pressure mercury lamp _ mJ / cm 2 . Then spray UVt primer (ETERCURE 8250U-9A), followed by; Large, pre-baked for 5 minutes in the box, medium pressure mercury (800 152050.doc • 29-201239049 mJ/cm2) The exposure was carried out, and the thickness of the primer was 1 〇 15 μm to prepare a substrate having a coating film. Example 12 The ultraviolet curing treatment agent of Preparation Example 9 was used, and a solvent was used as needed. Adjust the viscosity Iwata Cup for about 9 seconds, spray it on the stainless steel substrate with air spray, then pre-bake in a 60 C oven for 5 minutes, then expose it by medium pressure mercury lamp (800 mJ/cm2). The thickness is 3 microns. Then spray UV plating primer (Changxing Chemical, etERcURE8250U-9A), then pre-bake in a 60 C oven for 5 minutes, exposure by medium pressure mercury lamp (8〇〇mJ/cm2), primer thickness 1 〇~15 μm, a substrate with a coating film was prepared. Example 13 UV-curable treatment agent, manufacturing method and substrate selection were the same as in Example 12 'Change spray varnish (manufactured by Changxing Chemical Co., Ltd., ETERCURE6763M-4)' followed by pre-baking in an oven at 60 ° C for 5 minutes. The substrate was coated with a film by exposure to a medium pressure mercury lamp (800 mJ/cm2) and a primer thickness of 1 〇 to 15 μm. Example 14 The ultraviolet curable treatment agent and the manufacturing method were the same as those in the example 12, and the substrate was changed to a PC plastic substrate. The modified UV hard cover layer (made by Changxing Chemical Co., Ltd., ETERCURE 6776-3B) was then carried out in an oven at 60 ° C. The pre-baked for a minute, exposed by a medium pressure mercury lamp (800 mJ/cm2), and the thickness of the primer is 1 〇 15 15 μm to prepare a substrate with a coating film. Example 15 J52050.doc •30- 201239049 Using the UV-curing treatment agent of the preparation example, the viscosity was adjusted to the Iwata Cup by solvent for about 9 seconds, and sprayed on the PC plastic substrate with an air spray gun, followed by 60°. The oven was dried in C for 3 to 5 minutes, and then exposed to a medium pressure mercury lamp (400 mJ/cm2) with a film thickness of 1 to 3 μm. Then spray UV plating primer (Changxing Chemical, ETERCURE 8250U-9A), then pre-bake in 5 ° 10 minutes in an oven at 60 ° C, exposure by medium pressure mercury lamp (800 mJ / cm2), primer thickness 10 ~15 micron to prepare a substrate with a coating film. Example 16 An ultraviolet curable treatment agent and a manufacturing method were the same as those in Example 15, and the substrate was changed to an ABS plastic substrate. Test method Adhesion between the coating film and the substrate: According to the inspection method of ASTM D3359-93, the surface of the coating film was scraped with a hundred-bar blade, and then the tape was adhered and then torn at 90° to determine the number of peeling cells. Appearance: Use the naked eye to check the appearance of the film. Coating film heat resistance: After the sample prepared in the above examples was placed in an oven at 80 ° C for 96 hours, the surface of the coating film was visually inspected for defects such as cracks and peeling off. Table 2 Adhesive appearance heat resistance Example 1 100/100 leveling No defect, no crack, no shedding Example 2 80/100 flat, no defects, no cracks, no shedding Example 3 100/100 flat, no defects, no cracks, no shedding 152050.doc -31 - 201239049 ^ y«.l C 1 Λ A / 1 ΛΑ , Ti av · ----- Example 7 100/100
^•”、·τ*ν /uc j™- mw 實施例8 100/100平整、無缺陷 〇 mn/m. ~ΓΙΓ~---~~~~廈、無脫洛 實施例9 100/100 實施例10 100/100 實施例11 100/100 平整、無缺陷 平整、無缺陷 實施例12 100/100 實施例 13 100/100 | 實施例 14 100/100 實施例 15 100/100 實施例16 100/100 痕、無脫落 無脫落 無脫落 無脫落 無脫落 無脫落 --- __—-歸4/〇你 根據上述實驗結果可知，傕用士找 田一 1更用本發明之紫外線固化型處 理劑處理後之基材，不需再經由其扎 、他則處理之方法，即可 賦予塗膜與基材所需之附著性， 且所得塗膜外觀平整、無 缺陷且耐熱性佳，可符合業界之需求。 152050.doc 32-^•”,·τ*ν /uc jTM- mw Example 8 100/100 flat, defect-free 〇mn/m. ~ΓΙΓ~---~~~~Ha, no detachment Example 9 100/100 Example 10 100/100 Example 11 100/100 flat, defect free flat, defect free Example 12 100/100 Example 13 100/100 | Example 14 100/100 Example 15 100/100 Example 16 100/ 100 marks, no shedding, no shedding, no shedding, no shedding, no shedding, no shedding, no peeling--- __--returning to 4/〇. According to the above experimental results, it can be seen that the use of the UV curable treatment agent of the present invention is further treated by the use of the invention. After the substrate, the desired adhesion of the coating film to the substrate can be imparted without the need of the method of treatment, and the obtained coating film has a flat appearance, no defects and good heat resistance, and can conform to the industry. Demand. 152050.doc 32-