TW201102412A - UV curable color coating composition - Google Patents

UV curable color coating composition Download PDF

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TW201102412A
TW201102412A TW98123772A TW98123772A TW201102412A TW 201102412 A TW201102412 A TW 201102412A TW 98123772 A TW98123772 A TW 98123772A TW 98123772 A TW98123772 A TW 98123772A TW 201102412 A TW201102412 A TW 201102412A
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Taiwan
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component
coating composition
acrylate
coating
pigmented coating
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TW98123772A
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Chinese (zh)
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TWI393753B (en
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Hung-Wen Huang
Chun-Chieh Tseng
ai-chun Zhang
wei-li Wang
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Eternal Chemical Co Ltd
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Publication of TWI393753B publication Critical patent/TWI393753B/en

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Abstract

The present invention pertains to a UV curable color coating composition comprising: (a) an oligomer containing at least one double bond; (b) a diluent monomer; (c) a photoinitiator; (d) a thermoplastic acrylate resin; and (e) a colorant. The inventive coating composition can be used in one-step applications to form a colorful coating exhibiting high performance. Compared to conventional two-layer or three-layer coating methods, the coating method using the coating composition of the invention can provide a high production efficiency, low energy consumption, low process cost, and low waste production.

Description

201102412 六、發明說明： 【發明所屬之技術領域】 本發明關於一種uv可固化有色塗料組合物，尤其關於 一種一次喷塗用UV可固化有色塗料組合物。 【先前技術】 目前各種電子或電器產品，如數位相機、筆記型電腦、 手機、化妝品、汽車零組件等，已廣泛應用於人們生活。 這類產品的外殼大多由塑膠製成，塑膠具有易成型、成本 低、重量輕、不易腐蝕等優點，但卻有不美觀、易老化、 機械性能差、耐熱差、吸水率高等缺點，因此外殼在加工 成型後，往往需在表面上塗佈保護性和裝飾性塗料。 過去塑膠基材之塗佈方法，大多需要經過二塗二烤或三 塗三烤程序，即，先喷底漆以提供顏色、封固基底、增強 面漆與基底的附著力等；及再噴透明漆，其與底漆搭配使 整體塗層顯出光澤及色彩感，並使塗層具有高耐磨等特 性。如此工序造成塗料產量及工時之浪費。 舉例言之，美國專利第6,514,568 B1號揭示一種包括先 在基材上分兩次塗佈第一次塗層組成物及第二次塗層組成 物，令該兩種塗層組成物固化後，再塗佈透明塗層組成物 之方沬。台灣專利第1390903號揭示一種製造多層、保護 及/或裝飾性塗料之方法，該方法包括： Ο)將含有顏料之底漆塗佈於素材表面； (2) 由步驟（1)塗佈之底漆形成聚合物膜； (3) 將透明面漆塗佈於由此而得之底漆；及 139499.doc 201102412 (4) 一起固化底漆與面漆，其中該面漆係以溶於一或多 種有機冷劑中之聚丙稀酸酯樹脂$主成&，該有機溶劑含 -或多種亞磷酸酯，其特徵在於以丙稀酸酯樹脂溶液之固 體3量為基準，該聚丙烯酸酯樹脂溶液含有〇·〇5至1〇重量 %之一或多種有機亞磷酸酯。 上述一塗或二塗型的塗覆方法，不僅耗能、費時、需較 大生產空間且具有成本高等缺點。因此，業界S希開發能 • 藉由一次塗裝即達到美觀與性能兼具之塗層的塗料組合 物例如，σ灣專利第1290566號揭示一種一次喷塗用珍 珠漆糸外線塗料組成物，其雖然可利用一次施工的方式即 可獲得美觀的外表，但卻僅限於使用半透明的珠光漆，若 改以非透明性的實色顏料，由於顏料的遮光性質，使得 UV光線無法穿透塗層，故其固化過程，容易產生塗膜不 乾或半乾的問題。 塗料組合物如果要應用於一次施工，往往因為色漆樹脂 φ 系，”充和UV樹脂相容性不佳，因此，顏色不易控制，易造 成密著性不好，且色料有屏蔽光的性質，導致UV光線無 法順利穿透，使得UV樹脂不易固化。 本案發明人經廣泛研究發現，添加具有高玻璃轉換溫度 的熱可塑性丙烯酸樹脂於塗料組合物中，可使塗料中的 UV樹脂具有良好的相容性，因此使得塗料具有良好的密 著性。再者，藉由使用二種或二種以上的光起始劑，可吸 收不同波長的光，因而可克服υν樹脂不易固化的問題， 能有效解決上述的缺點。 139499.doc 201102412 【發明内容】 本毛明之主要目的為提供—種―可固化有色塗料組合 物，其包含以下組分： (a) 3有至少1個不飽和雙鍵之寡聚物； (b) 稀釋單體； (C)光起始劑； (d) 熱可塑性丙稀酸樹脂；及 (e) 色料》 其中組分⑷與、组分（b)之重量比為1:4至4:1 组分⑷以 組分⑷與組分（b)合計100重量份計，其含量為52〇重量 份，組分（d)以組分（a)與組分（b)合計1〇〇重量份計其含量 為20-100重量f刀，組分（e)以組分⑷⑻與⑷合計⑽重量 份計，其含量為2-50重量份。 【實施方式】 本發明之UV可固化有色塗料組合物中所包含之含有至 1個不飽和雙鍵之寡聚物（a)，較佳為含有至少2個不飽和 雙鍵之养聚物，尤佳係為具3至15個不飽和雙鍵之寡聚 物。上述寡聚物係選自由環氧丙浠酸酿（EpOXy Acrylate)寡 聚物、聚胺基甲酸醋丙稀酸醋（p〇lyUrethane Acrylate)、聚 酯丙烯酸酯（Polyester Acrylate)、聚丙烯酸酯（p〇iyacrylate)、 胺基丙烯酸酯（Amine Acrylate)寡聚物及矽基丙稀酸酿 (Silicon Acrylate)寡聚物及其混合物所構成群組，較佳係 選自由環氧丙烯酸酯寡聚物、聚胺基曱酸酯丙烯酸酯募聚 物、聚酯丙烯酸酯寡聚物及聚丙烯酸酯寡聚物及其混合物 139499.doc 201102412 所構成群組，其中聚胺基甲酸酯丙烯酸酯可為脂肪族聚胺 基曱酸酯丙烯酸酯或芳香族聚胺基曱酸酯丙烯酸酯，其中 以脂肪族聚胺基曱酸酯丙烯酸酯不易有黃變問題，為更佳 選擇。 市售此類含有至少1個不飽和雙鍵之募聚物例子包含：201102412 VI. Description of the Invention: [Technical Field] The present invention relates to a uv curable pigmented coating composition, and more particularly to a UV curable pigmented coating composition for primary spraying. [Prior Art] At present, various electronic or electrical products, such as digital cameras, notebook computers, mobile phones, cosmetics, automobile components, etc., have been widely used in people's lives. The outer casing of these products is mostly made of plastic. The plastic has the advantages of easy molding, low cost, light weight and corrosion resistance, but it has the disadvantages of unsightly, easy aging, poor mechanical properties, poor heat resistance and high water absorption. After processing, it is often necessary to apply a protective and decorative coating to the surface. In the past, most of the coating methods of plastic substrates required two-coating or three-coating three-bake procedures, that is, first applying primer to provide color, sealing the substrate, enhancing the adhesion of the topcoat and the substrate, and the like. The clear lacquer, which is combined with the primer, gives the overall coating a luster and a sense of color and gives the coating a high abrasion resistance. This process causes waste of paint production and man-hours. For example, U.S. Patent No. 6,514,568 B1 discloses a method of coating a first coating composition and a second coating composition twice on a substrate to cure the two coating compositions. The square of the clear coating composition is then coated. Taiwan Patent No. 1,390,903 discloses a method of producing a multilayer, protective and/or decorative coating comprising: Ο applying a pigment-containing primer to a surface of a material; (2) coating the bottom of the step (1) Varnishing a polymer film; (3) applying a clear topcoat to the resulting primer; and 139499.doc 201102412 (4) curing the primer and topcoat together, wherein the topcoat is soluble in one or A polyacrylate resin of a plurality of organic refrigerants, comprising: - or a plurality of phosphites, characterized by a solid amount of the acrylate resin solution, the polyacrylate resin The solution contains 〇·〇 5 to 1% by weight of one or more organic phosphites. The above-mentioned one-coating or two-coating coating method is not only energy-consuming, time-consuming, requires a large production space, and has high cost and the like. Therefore, the industry has developed a coating composition capable of achieving a combination of aesthetics and performance by one coating, for example, Sigma Bay Patent No. 1290566 discloses a pearl paint enamel outer coating composition for one-time spraying, which Although a beautiful appearance can be obtained by one-time construction, it is limited to the use of translucent pearlescent paint. If it is changed to a non-transparent solid pigment, the UV light cannot penetrate the coating due to the light-shielding property of the pigment. Therefore, the curing process is prone to the problem that the coating film is not dry or semi-dry. If the coating composition is to be applied to a single construction, it is often because of the varnish resin φ system, "the compatibility between the filling and the UV resin is not good, therefore, the color is not easy to control, and the adhesion is not good, and the coloring material has a shielding light. The nature of the UV light can not penetrate smoothly, making the UV resin difficult to cure. The inventors of the present invention have extensively found that adding a thermoplastic acrylic resin with a high glass transition temperature in the coating composition can make the UV resin in the coating good. The compatibility of the coating makes the coating have good adhesion. Furthermore, by using two or more kinds of photoinitiators, light of different wavelengths can be absorbed, thereby overcoming the problem that the υν resin is not easily cured. The above disadvantages can be effectively solved. 139499.doc 201102412 [Summary of the Invention] The main purpose of the present invention is to provide a curable pigmented coating composition comprising the following components: (a) 3 having at least one unsaturated double bond (b) dilute monomer; (C) photoinitiator; (d) thermoplastic acrylate resin; and (e) pigment" wherein component (4) and component (b) It is 1:4 to 4:1. The component (4) is contained in an amount of 52 parts by weight based on 100 parts by weight of the component (4) and the component (b), and the component (d) is composed of the component (a) and the component ( b) The total content is 20-100 parts by weight of the knives, and the component (e) is 2-50 parts by weight based on the total (10) parts by weight of the components (4) (8) and (4). The oligomer (a) containing one unsaturated double bond contained in the UV curable pigmented coating composition of the invention is preferably an oligomer containing at least 2 unsaturated double bonds, and particularly preferably An oligomer of 3 to 15 unsaturated double bonds. The above oligomer is selected from the group consisting of EpOXy Acrylate oligomer, p〇lyUrethane Acrylate, a group of polyester acrylate (polyester Acrylate), polyacrylate (P〇iyacrylate), amide acrylate (Amine Acrylate) oligomer, and thiopropyl acrylate oligomer (Silicon Acrylate) oligomer and mixtures thereof Preferably, it is selected from the group consisting of epoxy acrylate oligomers, polyamino phthalate acrylate polymers, polyester acrylate oligomers, and polypropylene. And a mixture of ester oligomers and mixtures thereof 139499.doc 201102412, wherein the polyurethane acrylate may be an aliphatic polyamino phthalate acrylate or an aromatic polyamine phthalate acrylate, wherein It is more preferable to use an aliphatic polyamino phthalate acrylate which is less susceptible to yellowing. Commercial examples of such a polymer having at least one unsaturated double bond include:

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） 公司製）；621、622、623、6210G、624、6231、6241、 6213-100 、 6215-100 、 625 、 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）。 脂肪族聚胺基曱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 ' 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、 139499.doc 201102412Epoxy acrylate oligomers: AgiSynTM 2901A50, AgiSynTM 1010 'AgiSynTM 1010A80, AgiSynTM 1010B80 ' AgiSynTM 1010C80, AgiSynTM 2010 and AgiSynTM 2500 (made by Xinlimei Technology Co., Ltd.); 621, 622, 623, 6210G, 624, 6231, 6241, 6213-100, 6215-100, 625, 6261 and 620-100 (manufactured by Changxing Chemical Industry Co., Ltd.); 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 polyamino phthalate 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 ' 6160B-70 , 6161-100 , 6181 and 6196-100 (made by Changxing Chemical Industry Co., Ltd.); AgiSynTM 230S1-15HD, AgiSynTM 230S2-30TP, AgiSynTM 230SM -20TP, AgiSynTM 230SN-20TP, AgiSynTM 230SR-20TP, 139499.doc 201102412

AgiSyn™ 230T1及AgiSyn™ 230A2(新力美科技（股）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(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(Bayer公司製）。 芳香族聚胺基曱酸酯丙烯酸酯寡聚物：6120F-80、 6 121F-80、6122F-80 及 6146-100(長興化工製）；AgiSynTM 670TH-20TP ' AgiSyn™ 670S1-20TP、AgiSynTM 670T1、 AgiSyn™ 670A2(新力美科技（股）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 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-[〇〇(長興化工製）。 聚丙烯酸酯寡聚物：AgiSyn™ 2266(新力美科技（股）公 139499.doc 201102412 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、653 1B-40、6532B-40 及 6533B-40(長興化 工製）。 本發明UV可固化有色塗料組合物中所使用之稀釋單體 (b)，為具有至少2個官能基的丙烯酸酯類單體，較佳係為 具3至6個官能基者。組分（a)之總重量與組分（b)之總重量 比為1:4至4:1，較佳為1:1至2:1。根據本發明，UV可固化 有色塗料組合物的調製過程中，若稀釋單體的含量太低， 則塗料組合物的黏度太大，導致操作性變差，有流平性不 良等缺點。反之，若稀釋單體之含量太高，則塗料經固化 後會降低塗膜性能，例如導致塗膜柔韌性不足，而易龜 裂。 可用於本發明中的稀釋單體，例如但不限於選自二丙烯 酸二丙二醇酯（DPGDA)、二丙烯酸三丙二醇酯（TPGDA)、 二丙烯酸1，6-己二醇醋（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 I39499.doc 201102412 0396(含 50%奈米氧化石夕之DPGDA)、Nanocryl 0768(含 50% 奈米氧化矽之HDDA)、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)三羥曱基丙烷酯 (TMP6EOTA)、三丙烯酸乙氧化（9)三羥曱基丙烷酯 (TMP9EOTA)、三丙烯酸乙氧化（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)、 三丙烯酸季戊四醇酯（PETIA)、四丙烯酸二-(三羥甲基丙 烷）酯（DI-TMPTA)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。 可用於本發明中的稀釋單體，較佳為選自三丙烯酸三羥 曱基丙烷酯（TMPTA)、三丙烯酸乙氧化（3)三羥甲基丙烷酯 (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)、三丙烯酸乙氧化（15)三羥甲基丙烷酯 (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)三羥甲基丙烷酯 (TMP6POTA)、三丙烯酸丙氧化（3)丙三醇酯（G3POTA)、 三丙烯酸季戊四醇酯（PETIA)、四丙烯酸二-(三羥曱基丙 烷）酯（DI-TMPTA)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。 市售此類單體的例子包括：EM223、EM328、EM2308、 139499.doc -10- 201102412 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 M500及 MIRAMER M600(Miwon公司製）。 本發明所使用之組份（c)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。其例如選自以下組成之組群：二苯曱酮-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。 根據本發明，組分（c)光起始劑之用量並無特殊限制，可 視需要依UV可固化有色塗料組合物所包含之寡聚物和稀 釋單體之種類及其用量進行調整。一般而言，以組分（a)與 組分（b)合計100重量份計，組分（c)之含量為5至20重量 份。由於不同的光起始劑對不同波段的光具有不同程度的 吸收，因此不同顏色的色料選用的光起始劑亦不相同，通 常會使用至少2種以上之光起始劑。 市售光起始劑的例子包括：CHIVACURE 115、 139499.doc -11 - 201102412 CHIVACURE ITX(異丙基硫雜蒽酮）、CHIVACURE EPD (對-(二曱胺基）苯甲酸乙酯）、CHIVACURE OMB(鄰-苯曱 醯基苯甲酸曱酯）、CHIVACURE ΕΜΚ (Ν，Ν，Ν'，Ν·-四乙基-4,4匕二胺基二苯曱酮）、CHIVACURE BDK (2,2’_ 二甲基-1，2-二苯基乙烷-1-酮）、（：111¥入(：1；1^3]\^(4-苯甲醯基-4、 曱基二苯基硫醚）、CHIVACURE 184 (1-羥基環己基苯基 酮）、CHIVACURE 173 (2-經基-2-甲基-1-苯基-丙-1-酮）、 CHIVACURE TPO (2,4,6-三甲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）；AgiSynTM-1812(l-羥基環己基苯基酮）、AgiSyn™-1810(2-羥基-2-曱基-1-苯基-丙-1-酮）、八呂13丫111^-1801及 AgiSyn™-003(新力美科技股份有限公司製）；IRGACURE 369 (2-苄基-2-N，N-二甲基胺基-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）（CIBA公司製），為克服色料有屏蔽光的性質， 上述之光始起劑的選用，可視需要選用兩種或兩種以上混 合使用皆可。 本發明所使用之組份（d)熱可塑性丙烯酸樹脂，主要作 用是增加塗膜與基材的密著與防止塗膜龜裂，由於塗膜經 UV固化後會產生高收縮應力，易造成翹曲、龜裂等現 象，對密著也有不良影響，於塗料中添加較高玻璃化溫度 (Tg)的熱可塑性丙烯酸樹脂，可以調整塗料的黏度，同時 提供塗膜更佳的密著力，加快塗膜的乾燥速度。本發明所 使用之熱可塑性丙烯酸樹脂與寡聚物及/或單體的相容性 139499.doc -12- 201102412 佳，可直接摻雜（blending)在塗料組合物中，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UV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，所以在乾燥過程令，可 促進溶劑由塗膜中移除，可避免垂流現象。 本發明所選用之熱可塑性丙烯酸樹脂，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、曱基丙烯酸、丙烯酸烷基酯以及曱基丙烯酸烷基醋。 上述丙稀酸烧基醋及甲基丙稀酸烧基醋單體之實例包括 丙烯酸甲酯、曱基丙烯酸甲酯、丙烯酸乙酯、曱基丙稀酸 乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸異丁醋、曱 基丙烯酸異丁酯、丙烯酸異辛酯、曱基丙烯酸異辛酯、丙 稀酸％己S旨、甲基丙稀酸環己醋、丙烯酸縮水甘油酿、甲 基丙烯酸縮水甘油酯、丙烯酸羥乙酯、丙烯酸經丙醋、甲 基丙稀酸-2-沒基乙S旨、丙烯酸2-經基丙醋、甲基丙烯酸2_ 羥基丙酯、曱基丙烯酸羥丙酯、丙烯酸異冰片醋及甲基丙 烯酸異冰片酯及其混合物。 根據本發明之一較佳具體實施例，選用的熱可塑性丙烯 酸樹脂係以一或多種下列單體作為聚合單元：丙烯酸、曱 基丙烯酸、丙烯酸甲酯、甲基丙烯酸曱酯、丙烯酸丁酯、 甲基丙烯酸丁酯、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、曱基丙烯酸異冰片酯、丙 烯酸-2-羥基乙酯、甲基丙烯酸_2_羥基乙酯、丙烯酸2_羥 基丙酯及曱基丙烯酸2-羥基丙酯，較佳為以一或多種下列 139499.doc •13· 201102412 單體作為聚合單元：丙稀酸-2-經基乙酯、甲基丙稀酸_2_ 羥基乙酯、丙烯酸甲酯、f基丙烯酸曱酯、丙烯酸丁酯、 曱基丙烯酸丁酯、丙烯酸異冰片酯及曱基丙烯酸異冰片 酯。此外，本發明所使用之熱可塑性丙烯酸樹脂須具有大 於60C之玻璃轉換溫度’較佳為具有75 °C至11〇 °C之玻璃 轉換溫度。若熱可塑性丙烯酸樹脂的玻璃轉換溫度太低， 塗膜对熱性不佳’保s蔓力不足。反之，玻璃轉換溫度過 高，卻又衍生出加工不易的問題。 市售熱可塑性丙烯酸樹脂例子包含：71 19_TB 5〇、 7626-1 、 7128-TB-50 、 7305-2-XS-50 、 7329-XP-45 、 7329- TS-45、7117-TS-50 及 7352-TS-50(長興化工製）；BR113、 BR116、BR-115、BR 106、BR-85、BR-73、MB2952、MB 3015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_1〇42及AR1〇9〇F(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）；及FS_2970A(德謙企業股份有 限公司製）。 本發明所使用之色料組份（e)可為透明、半透明或不透明 之材料，係可給予本發明之組合物及由該等組合物形成之 塗層實質顏色或修飾素材表面缺陷之顏料、染料或填料。 根據本發明之一實施態樣，本發明所使用之組份（e)係為 顏料，塗佈於基材，可覆蓋基材之原色。可賦予顏色之顏 料係為熟悉此項技術者所知，其可為有機顏料或無機顏 料。無機顏料一般是礦物性物質，包括：鈦白粉顏料、氧 139499.doc 201102412 化鐵顏料、鉻系顏料、黑鈦、碳黑、銀漿笙。士 m眾等。有機顏料主 要包括：偶氮顏料、菁類顏料等，有機顏料的具體例子包 括C.I.顏料黃83、C.I.顏料黃150、C.I.顏料黃138、 、 、C · I.顏 料黃128、C.I.顏料橙43、C.I.顏料紅177、c • A ·顧料紅 202、C.I.顏料紅209、C.I.顏料紅254、C.I.顏料紅255 C.I.顏料綠7、C.I.顏料綠36、C.]：，顏料藍15、c丄顏料藍 15:3、C_I·顏料藍 15:4、C.I.顏料藍 15:6、C.I·顏料紫 23、 Φ C.I.顏料黑1、C.I·顏料黑7等。為了符合各種顏色需求，可 以使用一或多種的色料。市售色料的例子包括：AlkaliAgiSynTM 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 (made by UBC Co., Ltd.); HENKEL 6010 (manufactured by COGNIS); CN9001, CN9002 CN9004 and CN9006 (manufactured by 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 (manufactured by Bayer). Aromatic polyamine phthalate acrylate oligomers: 6120F-80, 6 121F-80, 6122F-80 and 6146-100 (manufactured by Changxing Chemical Industry Co., Ltd.); AgiSynTM 670TH-20TP 'AgiSynTM 670S1-20TP, AgiSynTM 670T1 AgiSynTM 670A2 (manufactured by Sony Biotech Co., Ltd.); EBECRYL-204, EBECRYL-205, EBECRYL-210, EBECRYL-215, EBECRYL-220, and EBECRYL-6202 (manufactured by UBC Co., Ltd.). Polyester acrylate oligomers: EBECRYL-830, EBECRYL-810 and EBECRYL-524 (made by UBS); 6315, 6320, 6323-100, 6325-100, 6327-100, 6336-100 And 6361-[〇〇 (Changxing Chemical Industry). Polyacrylate oligomer: AgiSynTM 2266 (Xinlimei Technology Co., Ltd. 139499.doc 201102412 system); EBECRYL-745 (UCB) Co., Ltd.; DOUBLEMER3778, DOUBLEMER1701, DOUBLEMER345, DOUBLEMER1703, DOUBLEMER530 , DOUBLEMER 570, DOUBLEMER 236 and DOUBLEMER 584 (manufactured by Double Bond Chemical Co., Ltd.); 6530B-40, 653 1B-40, 6532B-40 and 6533B-40 (manufactured by Changxing Chemical Industry Co., Ltd.). The diluted monomer (b) used in the UV curable pigmented coating composition of the present invention is an acrylate monomer having at least 2 functional groups, preferably having 3 to 6 functional groups. The total weight ratio of component (a) to component (b) is from 1:4 to 4:1, preferably from 1:1 to 2:1. According to the present invention, in the preparation process of the UV curable pigmented coating composition, if the content of the diluted monomer is too low, the viscosity of the coating composition is too large, resulting in poor workability and poor leveling property. On the other hand, if the content of the diluted monomer is too high, the coating will be cured to lower the film properties, for example, the coating film is insufficient in flexibility and is easily cracked. Diluted monomers useful in the present invention, such as, but not limited to, selected from the group consisting of dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), diterpenes Diethylene glycol acrylate (DEGDMA), polyethylene glycol (400) diacrylate (PEG (400) DA), polyethylene glycol (600) diacrylate (PEG (600) DA), dimercapto Diethylene glycol acrylate (EGDMA), ethoxylated (10) bisphenol ester (BPA10EODA), ethoxylated (10) bisphenol ester (BPA10EODMA), tricyclodecane diacrylate Disterol ester (TCDMDA), propionic acid propionate (2) neopentyl glycol ester (NPG2PODA), Nanocryl I39499.doc 201102412 0396 (including 50% nano-oxidized stone DPGDA), Nanocryl 0768 (including 50% Nai HDDA of rice cerium oxide, trihydroxymercaptopropane triacrylate (TMPTA), ethoxylated (3) trishydroxypropyl propane ester (TMP3EOTA), ethoxylated (6) trihydroxymercaptopropane triacrylate ( TMP6EOTA), ethoxylated (9) trihydroxymercaptopropane ester (TMP9EOTA), ethoxylated (15) trimethylolpropane triacrylate (TM) P15EOTA), ethoxylated (20) trimethylolpropane triacrylate (TMP20EOTA), propionic acid triacrylate (6) trihydroxymercaptopropane ester (TMP6POTA), propionic acid triacrylate (3) glycerol ester (G3POTA And a group consisting of pentaerythritol triacrylate (PETIA), di-(trimethylolpropane) tetraacrylate (DI-TMPTA) and dipentaerythritol hexaacrylate (DPHA) and mixtures thereof. The diluent monomer which can be used in the present invention is preferably selected from the group consisting of trihydroxymercaptopropane triacrylate (TMPTA), ethoxylated (3) trimethylolpropane triacrylate (TMP3EOTA), and ethoxylated triacrylate (6). Trihydroxymercaptopropane ester (TMP6EOTA), ethoxylated (9) trihydroxymercaptopropane triacrylate (TMP9EOTA), ethoxylated (15) trimethylolpropane triacrylate (TMP15EOTA), ethoxylated triacrylate ( 20) Trihydroxydecylpropane ester (TMP20EOTA), propionic acid trioxide (6) trimethylolpropane ester (TMP6POTA), propionic acid triacrylate (3) glycerol ester (G3POTA), pentaerythritol triacrylate (PETIA) a group consisting of di-(trihydroxydecylpropane) tetraacrylate (DI-TMPTA) and dipentaerythritol hexaacrylate (DPHA) and mixtures thereof. Examples of such commercially available monomers include: EM223, EM328, EM2308, 139499.doc -10- 201102412 EM231, EM235, EM2381, EM2382, EM2383, EM2384, EM2385, EM2386, EM2387, EM331, EM3380, EM241, EM2411, EM242 , EM2421 and EM265 (manufactured by Changxing Chemical Industry Co., Ltd.); EBECRYL-160, EBECRYL-853, EBECRYL-2047, EBECRYL-40 and EBECRYL-140 (made by UBS), 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 M500 and MIRAMER M600 ( Miwon company). The component (c) 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 the transfer of a radical. It is, for example, selected from the group consisting of a benzophenone-amine conjugate system; a benzoin ether; a benzoin and a ketal thereof; and an acetophenone derivative. According to the present invention, the amount of the component (c) photoinitiator is not particularly limited, and may be adjusted depending on the kind of the oligomer and the diluent monomer contained in the UV curable pigment coating composition and the amount thereof. In general, the component (c) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the total of the component (a) and the component (b). Since different photoinitiators have different degrees of absorption of light in different wavelength bands, the photoinitiators used in the different colorants are also different, and at least two or more photoinitiators are usually used. Examples of commercially available photoinitiators include: CHIVACURE 115, 139499.doc -11 - 201102412 CHIVACURE ITX (isopropyl thioxanthone), CHIVACURE EPD (p-(diamido) benzoate ethyl ester), CHIVACURE OMB (decyl-phenyl-benzoylbenzoate), CHIVACURE® (Ν,Ν,Ν',Ν·-tetraethyl-4,4匕diaminodibenzophenone), CHIVACURE BDK (2,2 '_Dimethyl-1,2-diphenylethane-1-one), (: 111 ¥ into (:1; 1^3)\^(4-benzylidene-4, decyldiphenyl Thioether), CHIVACURE 184 (1-hydroxycyclohexyl phenyl ketone), CHIVACURE 173 (2-carbo-2-methyl-1-phenyl-propan-1-one), CHIVACURE TPO (2,4, 6-trimethylphenylnonyldiphenylphosphine oxide) and CHIVACURE 200 (methyl phenylglycolate) (manufactured by Double Bond Chemicals (DBC) Co., Ltd.); AgiSynTM-1812 (1-hydroxycyclohexylphenyl) Ketone), AgiSynTM-1810 (2-hydroxy-2-mercapto-1-phenyl-propan-1-one), Balu 13丫111^-1801 and AgiSynTM-003 (made by Xinlimei Technology Co., Ltd.) ); IRGACURE 369 (2-benzyl-2-N,N-dimethylamino-1-(4-morpholinylphenyl-1-butanone) and IRGACURE 2959 (4-(2-hydroxyl) Ethyl ethoxy)-phenyl-(2-hydroxy-2-mercaptopropyl) ketone (manufactured by CIBA Co., Ltd.), in order to overcome the light-shielding property of the coloring material, the above-mentioned light initiator can be selected as needed It is preferred to use two or more kinds of the mixture. The component (d) of the thermoplastic resin used in the invention mainly serves to increase the adhesion between the coating film and the substrate and prevent cracking of the coating film due to the coating film. After UV curing, high shrinkage stress will occur, which will easily cause warping, cracking, etc., and also have adverse effects on the adhesion. Adding a higher glass transition temperature (Tg) of thermoplastic acrylic resin to the coating can adjust the viscosity of the coating. At the same time, it provides better adhesion of the coating film and accelerates the drying speed of the coating film. The compatibility of the thermoplastic acrylic resin used in the invention with the oligomer and/or monomer is preferably 139499.doc -12-201102412 Blending in the coating composition does not react with oligomers and/or monomers, and therefore acts as a buffering medium to release stress due to rapid curing during UV curing. Aspect 'because of this type of resin The surface drying ability is strong, so the drying process can promote the solvent to be removed from the coating film, and the vertical flow phenomenon can be avoided. The thermoplastic acrylic resin selected for use in the present invention can be a homopolymer or a copolymer, which is derived from At least one polymer selected from the group consisting of acrylic acid, methacrylic acid, alkyl acrylate, and alkyl methacrylate. Examples of the above-mentioned acrylic acid-based vinegar and methyl acrylate acid-based vinegar monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl thioglycolate, butyl acrylate, methacrylic acid. Butyl ester, isobutyl acrylate, isobutyl methacrylate, isooctyl acrylate, isooctyl methacrylate, acrylic acid, methacrylate, propylene glycol, acrylic glycidol, A Glycidyl acrylate, hydroxyethyl acrylate, acrylic acid propylene vinegar, methyl acrylate-2-mercaptoethyl s, acrylic acid 2- propyl acetonate, 2-hydroxypropyl methacrylate, hydroxy hydroxy acrylate Propyl ester, isobornyl acrylate vinegar and isobornyl methacrylate and mixtures thereof. According to a preferred embodiment of the present invention, the thermoplastic acrylic resin selected is one or more of the following monomers as polymerized units: acrylic acid, mercaptoacrylic acid, methyl acrylate, methacrylate methacrylate, butyl acrylate, nail Butyl acrylate, isobutyl acrylate, isobutyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, isobornyl methacrylate, 2-hydroxyethyl acrylate, _2 hydroxy methacrylate The ester, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate are preferably one or more of the following 139499.doc •13·201102412 monomers as polymerized units: 2-ethylidene ethyl acrylate, Methyl acrylate 2-hydroxyethyl ester, methyl acrylate, decyl acrylate, butyl acrylate, butyl methacrylate, isobornyl acrylate and isobornyl methacrylate. Further, the thermoplastic acrylic resin used in the present invention must have a glass transition temperature of more than 60 C', preferably a glass transition temperature of from 75 °C to 11 °C. If the glass transition temperature of the thermoplastic acrylic resin is too low, the coating film is not good for heat. On the contrary, the glass transition temperature is too high, but the problem of processing is not easy. Examples of commercially available thermoplastic acrylic resins include: 71 19_TB 5〇, 7626-1, 7128-TB-50, 7305-2-XS-50, 7329-XP-45, 7329-TS-45, 7117-TS-50 and 7352-TS-50 (manufactured by Changxing Chemical Industry Co., Ltd.); BR113, BR116, BR-115, BR 106, BR-85, BR-73, MB2952, MB 3015 and MB 2660 (manufactured by Mitsubishi Corporation, Japan); b-725, B- 735, B-736 and B-805 (made by Zeolite Co., Ltd.); aR_1〇42 and AR1〇9〇F (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); and FS_2970A (Deqian Enterprise Limited) Company system). The color component (e) used in the present invention may be a transparent, translucent or opaque material, and may be used to impart the composition of the present invention and the pigment which is formed by the composition to form a substantial color or to modify the surface defects of the material. , dye or filler. According to an embodiment of the present invention, the component (e) used in the present invention is a pigment which is applied to a substrate and covers the primary color of the substrate. The pigments that can be imparted to the color are known to those skilled in the art and can be organic pigments or inorganic pigments. Inorganic pigments are generally mineral substances, including: titanium white pigment, oxygen 139499.doc 201102412 iron pigment, chromium pigment, black titanium, carbon black, silver pulp.士 m public. The organic pigment mainly includes: an azo pigment, a cyanine pigment, etc., and specific examples of the organic pigment include CI Pigment Yellow 83, CI Pigment Yellow 150, CI Pigment Yellow 138, , C·I. Pigment Yellow 128, CI Pigment Orange 43, CI Pigment Red 177, c • A · Guhonghong 202, CI Pigment Red 209, CI Pigment Red 254, CI Pigment Red 255 CI Pigment Green 7, CI Pigment Green 36, C.]:, Pigment Blue 15, c丄 Pigment Blue 15:3, C_I·Pigment Blue 15:4, CI Pigment Blue 15:6, CI·Pigment Violet 23, Φ CI Pigment Black 1, CI·Pigment Black 7, etc. To meet a variety of color requirements, one or more colorants can be used. Examples of commercially available pigments include: Alkali

Blue D6100LD、Alkali Blue D6101 及 Alkali Blue D6200 (BASF製）；CHROMACON-K 及 CHROMACON-A(美商公利 洋行提供）；Y14、Y17、Y110、013、016、R53、R48、 V19、B15、SB-746 及 G7(曰本 DIC 製）；PY12 YeUow DHG、DHG02、Red F5RK、Red F4RK、Red F7RK、Red F3RK70、PB15:3 Blue B2G、Blue B4G、Blue R56、PV23 φ Violet RL02 及 Violet P-RL(Clariant 公司製）；Black 6 (DEGUSSA公司製）；l〇9S、900S、111、T60-10、100、R-901D、R-900M及R-900S(優克化工有限公司製）；A-HG(默 克化學製）。 本發明除可利用組份（b)稀釋單體來調整塗料黏度外， . 視需要，也可添加有機溶劑於塗料中以調整塗料黏度在適 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，以控制固成份（solid content)在約 139499.doc -15- 201102412 3〇〜观之範圍，並在最終欲調整黏度時，進—步調整到 喷塗的黏度，使固成份在約20〜4〇%之範圍。有機溶劑之 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。 本發明所使用的有機溶劑，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，其例如但不 限於烧烴類、芳烴類、_類、醇類及料類所組成之組 群。 適用於本發明之烷烴類溶劑可選自但不限於正己烷、正 庚烧及異歧及其混合物所組成的群組。適用於本=明之 芳族烴類溶劑可選自但不限於苯、甲苯及二f苯及其混合 物所組成的群組m本發明之酮類溶劑可選自作 於甲基乙基酮(臟)、丙，、甲基異丁基綱、冑己酮及4_ 麵基-4-甲基·2_戊酮及其混合物所組成的群組。適用於本 發明之醋類溶劑可選自但不限於乙酸異丁醋（ibac)、乙酸 乙酯(EAC)、乙酸丁酯(BAC)、甲酸乙酯、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 丙二醇乙酸醋&乙酸戊酉旨及其混合物戶斤組成的群組。=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)、丙二醇單甲醚、丙二醇單曱 醚乙酸醋（PMA)及丙二醇單甲醚丙酸醋（pMp)及其混合物 所組成的群組。 139499.doc -16· 201102412 依照所需成品塗膜的用途，本發明塗料組成物可進一步 包含一或多種本發明所屬技術領域中慣用的助劑。可視需 要採用的助劑例如包括分散劑、消光劑、消泡劑、抗氧化 劑，搖變助劑、安定劑、流平劑、潤濕劑、密著促進劑及 防浮色劑及其組合，這些助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。Blue D6100LD, Alkali Blue D6101 and Alkali Blue D6200 (manufactured by BASF); CHROMACON-K and CHROMACON-A (provided by Meishang Gongli); Y14, Y17, Y110, 013, 016, R53, R48, V19, B15, SB- 746 and G7 (Sakamoto DIC system); PY12 YeUow DHG, DHG02, Red F5RK, Red F4RK, Red F7RK, Red F3RK70, PB15: 3 Blue B2G, Blue B4G, Blue R56, PV23 φ Violet RL02 and Violet P-RL ( Clariant company); Black 6 (made by DEGUSSA); l〇9S, 900S, 111, T60-10, 100, R-901D, R-900M and R-900S (made by Yuke Chemical Co., Ltd.); A-HG (Merck Chemical). In addition to the use of component (b) to dilute the monomer to adjust the viscosity of the coating, the present invention may also add an organic solvent to the coating to adjust the viscosity of the coating in a suitable range of operation. The solvent can be added when the ingredients are formulated, or it can be added when the final coating is desired. According to an embodiment of the present invention, the solvent should be appropriately added in the formulation of the components to control the solid content in the range of about 139499.doc -15-201102412 3 〇 观 观 , , , , , , , , , , , , , , , , , , , , , , , The step is adjusted to the viscosity of the spray to make the solid content in the range of about 20 to 4%. The content of the organic solvent is not limited, and it can be adjusted according to actual conditions and requirements to obtain the desired coating viscosity. The organic solvent 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, for example, but not limited to, hydrocarbons, aromatic hydrocarbons, ketones, alcohols, and materials. The group formed. 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 heterogeneous, 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, toluene, and difbenzene, and mixtures thereof. The ketone solvent of the present invention may be selected from methyl ethyl ketone (dirty). a group consisting of C, C, methyl isobutyl, hexanone, and 4-formyl-4-methyl-2-pentanone, and mixtures thereof. The vinegar solvent suitable for use in the present invention may be selected from, but not limited to, isobacin acetate (ibac), ethyl acetate (EAC), butyl acetate (BAC), ethyl formate, methyl acetate, ethoxyethyl acetate. A group consisting of ethoxypropyl acetate, ethyl isobutyrate, monodecyl ether propylene glycol acetate vinegar & The alcohol solvent used 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 ether, propylene glycol monoterpene ether acetate (PMA) and propylene glycol monomethyl ether propionic acid vinegar (pMp And a group of mixtures thereof. 139499.doc -16· 201102412 The coating composition of the present invention may further comprise one or more auxiliaries conventionally used in the art to which the present invention pertains, depending on the intended use of the finished film. The auxiliary agent which may be used as needed includes, for example, a dispersing agent, a matting agent, an antifoaming agent, an antioxidant, a shaking aid, a stabilizer, a leveling agent, a wetting agent, a adhesion promoter, an anti-floating agent, and a combination thereof. The types of these auxiliaries are well known to those of ordinary skill in the art to which the present invention pertains, and the amounts thereof are also readily determinable by those of ordinary skill in the art to which the present invention pertains.

本發明視需要使用的分散劑主要作為顏料分散解絮凝 劑，分散劑可以選自含顏料親和基團之高分子共聚體成 份、.不飽和聚胺酸與胺類、高分子量不飽和聚羧酸類及非 離子型有機表面活性劑。市售分散劑例子包括：八!^-Terra-U、Anti-Terra-203、Anti-Terra-204、disperbyklOl、 disperbykl03、disperbykllO、disperbykll5、disperbykll6、 disperbykl42、disperbykl61、disperbykl62 ' disperbykl63、 disperbykl64、disperbykl68、disperbykl81、disperbykl83、 disperbyk2000、disperbyk2001、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 923S(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 139499.doc •17· 201102412 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）。 本發明視需要使用的流平劑可增加塗膜平坦性，流平劑 可以選自EFKA3883、EFKA3886及EFKA3600(荷蘭埃夫卡 公司製）；BYK366、BYK300、BYK333、BYK307、 BYK3500、BYK3510 ' BYK3530 及 BYK3570(畢克化學公 司（BYK)製）；TEGO 410及TEGO 450(德國迪高公司 (TEGO)製）。 本發明視需要使用的消光劑可使塗膜達到低光澤和消光 效果，消光劑可以選自S-363及S-381 N1 (Shamrock公司 製）；ED-2、ED-3、ED-30、ED-40、ED-44、ED-50及 ED-80 (GRACE 公司製）；OK412、OK500、OK520 及 OK607 (DEGUSSA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、二甲基聚矽氧烷類、有機改質聚矽氧烷類、高 分子型化合物及改質聚矽氧烷類所組成之組群。市售消泡 劑例子包括：6丫反-052、8丫1(：-053、8丫1!：-056、：8丫反-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-special 、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 139499.doc •18· 201102412 TEGO-Foamex 840(香港高施米特太平洋公司（TEGO)製）； DEUCHEM5300、DEUCHEM6500、DEUCHEM2700、 DEUCHEM3600、DEUCHEM2700、DEUCHEM3100 及 DEUCHEM5 700(德謙企業股份有限公司製）。 本發明視需要使用的搖變助劑（rheology additive)可讓塗 料具有穩定結構，保護已分散的顏料顆粒，保持優良的流 平性，防止色料的沉降。搖變助劑可為有機膨潤土系列、 • 蓖麻油類及其衍生物、聚醯胺類、聚長鏈烯烴類及改性脲 溶液。市售搖變助劑例子包括：BYK-410、BYK-411及 BYK-605(畢克化學公司（BYK)製）；DEUCHEM VP-2810、 DEUCHEM 219、DEUCHEM 201 ' DEUCHEM-202SP ' DEUCHEM-209、DEUCHEM-211 及 DEUCHEM-212(德謙企 業股份有限公司製）；伊士肯EC-8037(伊士肯化學股份有 限公司製）；BENTONE®、BENGEL®、THIXATROL® ST、MPA®、RHEOLATE® 及 BENAQUA® (海名斯公司 φ 製）。 本發明視需要使用的抗氧化劑（antioxidant)可使塗料不 變色，不變黃。抗氧化劑為二苯甲酮類化合物或芳香酯類 化合物或其混合物。市售抗氧化劑例子包括：Chinox 1010 ' Chinox 1330、Chinox 1076、Chinoxl68、Chisorb 292、Chinox 626及Chinox PEPQ(雙鍵化工有限公司製）。 本發明之塗料組合物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： 139499.doc •19· 201102412 (1) 添加（a)寡聚物、（b)稀釋單體及（e)色料高速攪拌均 勻混合，視需要添加溶劑與助劑，經球磨機（ball miller)分 散； (2) 添加（d)熱可塑性丙稀酸樹脂及（c)光起始劑及視需要 之溶劑與其它添加劑，攪拌均勻，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°c〜70°C， 於固定溫度下反應約3〜12分鐘；及 (5) 對所得塗層照射能量射線以使該塗層固化。 上述步驟（3)中所使用之塗佈方式，可採用線杆塗布（bar C〇ating)、狹縫式模壓塗布（slot die coating)、凸版印刷塗 布（gravure coating)、斜板式塗布（snde⑺…％)、淋幕式 塗布（CUrtain coating)或喷霧式塗布（spray coating)，較佳 為喷霧式塗佈（喷塗）。所述之基材並無特殊限制，例如可 為竟碑、木材、皮革、石材、玻璃、金屬、合金、紙張、 塑膠、纖維、棉織品等’較佳為金屬或塑膠。所述塑膠基 材尤才曰3C電子產品、家電及化妝品用之塑膠基材，例如 為ABS、pc、pp、PMMA或其混合。 較佳地，步驟（5)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 光源例如可為紫外光或熱線（放射或輻射）等，較佳為紫 139499.doc -20· 201102412 外光（波長為200〜400 nm)。照射強度可為自500至1200毫 焦耳/平方公分（mJ/cm2)，較佳係自600至1000 mJ/cm2。 本發明之UV可固化有色塗料組合物，當以一次喷塗施 工即可獲得美觀與高性能兼具的塗膜，相較於傳統二次或 三次的塗裝方式，本發明具有高生產效率、低耗能與低成 本等優點。 實施例 [組合物的調製]依據下表1至5所列成分及比例，調配 本發明之塗料組合物。表中所列各成分之後以括弧表示之 英文字母，即對應於本發明說明書中所列之各成分。 實施例1 表1 成分 重量(公克） Eternal 6145-100 (a) 25.0 Eternal EM265 (b) 16.0 CHIVACURE BDK 2,2，·二曱基-1，2-二苯基乙烷-1 -酮(c) 3.0 CfflVACURE TPO 2,4,6-三曱基苯曱醢基二苯基膦氧化物(c) 3.0 Eternal 7329-TS-45 (d) 38.0 DEGUSSA Black 6(e) 2.0 溶劑 醋酸丁酯(BAC)/乙二醇單丁醚(BCS)=1/1 7.2 助劑 BYK disperbykl64 (分散劑） 1.0 BYK Anti-Terra-U (分散劑） 0.5 BYK 3510 (流平劑） 0.3 BYK-088 (消泡劑） 0.05 Shamrock S-3 63 (消光劑） 4.0The dispersant used in the present invention is mainly used as a pigment dispersion deflocculant, and the dispersant may be selected from a polymer copolymer component containing a pigment affinity group, an unsaturated polyamine and an amine, and a high molecular weight unsaturated polycarboxylic acid. And nonionic organic surfactants. Examples of commercially available dispersants include: eight!^-Terra-U, Anti-Terra-203, Anti-Terra-204, disperbyklOl, disperbykl03, disperbykllO, disperbykll5, disperbykll6, disperbykl42, disperbykl61, disperbykl62 'disperbykl63, disperbykl64, disperbykl68, disperbykl81 , disperbykl83, disperbyk2000, disperbyk2001, disperbyk2150, disperbykl07, 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 (made by BYK); DEUCHEM 929, DEUCHEM 901F, DEUCHEM-VP DP9220, DEUCHEM-VP 556, DEUCHEM 912, DEUCHEM 904, DEUCHEM 910 and DEUCHEM 923S (made by Deqian Enterprise Co., Ltd.) ;TEGO Wet 500 and TEGO-Foamex 840 (Hong Kong High Simmet Pacific (TEGO)), Ishiken 139499.doc •17· 201102412 EC-8715/A and Easton EC-8000/A (East Ken Chemical Co., Ltd.); EFKA-5054, EFKA-5065 and EFKA-5066 (made by EFKA). The leveling agent can be used according to the invention to increase the flatness of the coating film. The leveling agent can be selected from the group consisting of EFKA3883, EFKA3886 and EFKA3600 (made by Evka, Netherlands); BYK366, BYK300, BYK333, BYK307, BYK3500, BYK3510 'BYK3530 and BYK3570 (made by BYK); TEGO 410 and TEGO 450 (made by TEGO). The matting agent used in the present invention can achieve a low gloss and matting effect on the coating film, and the matting agent can be selected from the group consisting of S-363 and S-381 N1 (manufactured by Shamrock Co., Ltd.); ED-2, ED-3, ED-30, ED-40, ED-44, ED-50, and ED-80 (manufactured by GRACE); OK412, OK500, OK520, and OK607 (manufactured by DEGUSSA). 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, dimethyl polyoxane, organic A group consisting of modified polyoxyalkylenes, polymeric compounds, and modified polyoxyalkylenes. Examples of commercially available defoamers include: 6丫反-052, 8丫1 (:-053, 8丫1!:-056,:8丫反-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-special, BYK-020, BYK-051 and Airex-980 (Bick Chemical Company (BYK); Airex-986, Airex-900, Airex-920, TEGO, Foamex N and 139499.doc •18· 201102412 TEGO-Foamex 840 (Hong Kong High Simmet Pacific (TEGO)); DEUCHEM 5300, DEUCHEM 6500, DEUCHEM 2700, DEUCHEM 3600, DEUCHEM 2700, DEUCHEM 3100 and DEUCHEM 5 700 (manufactured by Deqian Enterprise Co., Ltd.) The rherology additive used in the present invention allows the coating to have a stable structure and protect the dispersed pigment. The granules maintain excellent leveling and prevent sedimentation of the pigments. The rocking aids can be organic bentonite series, • castor oil and its derivatives, polyamines, poly-long-chain olefins and modified urea solutions. Examples of commercially available shake additives include: BYK-410, BYK-411, and BYK-605 (by BYK) DEUCHEM VP-2810, DEUCHEM 219, DEUCHEM 201 ' DEUCHEM-202SP ' DEUCHEM-209, DEUCHEM-211 and DEUCHEM-212 (made by Deqian Enterprise Co., Ltd.); ISKKEN EC-8037 (Isken Chemical Co., Ltd.) BENTONE®, BENGEL®, THIXATROL® ST, MPA®, RHEOLATE® and BENAQUA® (Hammins φ). The anti-oxidant used in the present invention allows the coating to not discolor and does not change yellow. Antioxidants are benzophenones or aromatic esters or mixtures thereof. Examples of commercially available antioxidants include: Chinox 1010 ' Chinox 1330, Chinox 1076, Chinoxl 68, Chisorb 292, Chinox 626 and Chinox PEPQ (Double Bond Chemicals Limited) The coating composition of the present invention can be applied to the surface of a substrate by any means known to those skilled in the art to which the present invention pertains. For example, it can be applied by the method comprising the following steps: 139499.doc •19· 201102412 (1) Adding (a) oligomer, (b) diluting monomer and (e) coloring agent, mixing at high speed, uniform mixing, It is necessary to add solvent and auxiliary agent and disperse through ball miller; (2) Add (d) thermoplastic acrylic resin and (c) photoinitiator and optional solvent and other additives, stir evenly, adjust 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 below 50 cps) and coated in an appropriate manner Surface treatment on a substrate to form a coating; (4) heating as needed to volatilize the solvent, the temperature is controlled at about 5 ° C ~ 70 ° C, at a fixed temperature for about 3 to 12 minutes; and 5) The resulting coating is irradiated with energy rays to cure the coating. The coating method used in the above step (3) can be bar coating, slot die coating, gravure coating, slant coating (snde(7)... %), CUrtain coating or spray coating, preferably spray coating (spraying). The substrate is not particularly limited, and may be, for example, metal, plastic, stone, glass, metal, alloy, paper, plastic, fiber, cotton, etc., preferably metal or plastic. The plastic substrate is particularly suitable for plastic substrates for 3C electronic products, home appliances and cosmetics, such as ABS, pc, pp, PMMA or a mixture thereof. Preferably, the coating curing step of the step (5) is carried out by photopolymerization by irradiating the energy ray. The energy ray refers to a light source of a certain range of wavelengths, for example, ultraviolet light or hot line (radiation or radiation). Preferably, it is purple 139499.doc -20· 201102412 external light (wavelength is 200~400 nm). The irradiation intensity may be from 500 to 1200 mJ/cm 2 (mJ/cm 2 ), preferably from 600 to 1000 mJ/cm 2 . The UV curable pigmented coating composition of the invention can obtain a coating film with both aesthetic appearance and high performance by one spray coating construction, and has high production efficiency compared with the conventional secondary or tertiary coating method. Low energy consumption and low cost. EXAMPLES [Preparation of Composition] The coating composition of the present invention was formulated in accordance with the ingredients and ratios listed in Tables 1 to 5 below. The ingredients listed in the table are followed by the English letters in parentheses, corresponding to the ingredients listed in the description of the present invention. Example 1 Table 1 Component Weight (g) Eternal 6145-100 (a) 25.0 Eternal EM265 (b) 16.0 CHIVACURE BDK 2,2, · Dimercapto-1,2-diphenylethane-1-one (c 3.0 CfflVACURE TPO 2,4,6-trimercaptobenzoyldiphenylphosphine oxide (c) 3.0 Eternal 7329-TS-45 (d) 38.0 DEGUSSA Black 6(e) 2.0 Solvent butyl acetate (BAC) )/Ethylene glycol monobutyl ether (BCS)=1/1 7.2 Additive BYK disperbykl64 (dispersant) 1.0 BYK Anti-Terra-U (dispersant) 0.5 BYK 3510 (leveling agent) 0.3 BYK-088 (Defoaming) Agent) 0.05 Shamrock S-3 63 (matting agent) 4.0

將上述所獲得之組合物添加稀釋劑（醋酸丁酯/甲苯/乙二 醇單丁醚=2/2/1)至岩田杯10秒左右，以空氣喷槍噴塗於塑 139499.doc •21 - 201102412 膠基板上，接著於60°C之烘箱内進行5〜10分鐘的預烤，然 後，經中壓水銀燈（800 mJ/cm2)進行曝光。而後，將完成 曝光後之具有塗膜之基板進行物性測試。 物性測試結果如下： 塗膜形成12-20 μιη的塗膜 塗膜與基板之附著性（根據ASTM D3359-93檢驗方法）： 100/100 塗膜硬度（根據ASTMD3363-74檢驗方法）：2Η 塗膜光澤度（利用光澤計以60°進行測試）：65 塗膜耐熱性（80°C烘箱放置96小時）：通過（外觀無裂痕、 脫落） 外觀：平整，具有黑色半消光效果。 實施例2 表2 成分 重量(公克） Sartomer CN9006 (a) 27.0 Miwon MIRAMER M500 (b) 16.0 二苯曱酮(c) 1.0 CfflVACURE 184(1-羥基環己基苯基酮)(c) 2.0 R&H B-60 (d) 13.05 優克化工R-900S(e) 10.0 溶劑 醋酸丁酯(B AC)/曱苯=45/10 15.95 醋酸丁酯/曱苯=1/1 8.0 助劑 DEUCHEM 910 (分散劑） 2.0 DEUCHEM 923S (分散劑） 1.0 TEGO 450(流平劑） 0.2 Shamrock S-363 (消光劑） 4.0 139499.doc -22- 201102412 將上述所獲得之組合物添加稀釋劑（醋酸丁酯/甲苯/乙二 醇單丁醚=2/2/1)至岩田杯10秒左右，以空氣噴槍噴塗於塑 膠基板上，接著於60°C之烘箱内進行5〜10分鐘的預烤，然 後，經中壓水銀燈（800 mJ/cm2)進行曝光。而後，將完成 曝光後之具有塗膜之基板進行物性測試。 物性測試所得結果如下： 塗膜形成10-15 μιη的塗膜 φ 塗膜與基板之附著性（根據ASTM D3359-93檢驗方法）： 100/100 塗膜硬度（根據ASTMD3363_74檢驗方法）： 塗膜光澤度（利用光澤計以60°進行測試）：85 塗膜耐熱性（80°C烘箱放置96小時）：通過（外觀無裂痕、 脫落） 外觀：平整，具有珍珠半光效果。 實施例3 癱 表3 成分 重量(公克） Eternal 611B-85(a) 7.5 Eternal 6145-100(a) 10.0 Eternal 6143C-60 (a) 5.0 Eternal EM235 (b) 15.0 Eternal EM231 (b) 4.5 二苯曱酮(c) 1.0 CfflVACURE 184 (1-羥基環己基苯基酮)(c) 2.0 CHIVACURE TPO (2,4,6-三曱基苯曱醯基二苯基膦氧化物)(c) 2.0 DEUCHEM FS-2970A (d) 15.0 139499.doc •23- 201102412 DIC SB-746 (e) 3.0 溶劑 醋酸丁酯(BAC)/乙二醇單丁醚(BCS)=1/1 5.0 甲苯 12.0 異丁醇/異丁酸乙酯=1/1 10.0 乙二醇單丁醚(BCS) 6.2 助劑 BYK disperbykl64 (分散劑） 0.5 DEUCHEM 923S (分散劑） 0.5 TfflXATROL ST (搖變助劑） 0.5 BYK 300 (流平劑） 0.3 BYK-065 (消泡劑） 0.05 將上述所獲得之組合物添加稀釋劑（醋酸丁酯/甲苯/乙二 醇單丁醚=2/2/1)至岩田杯10秒左右，以空氣喷槍喷塗於塑 膠基板上，接著於60°C之烘箱内進行5〜10分鐘的預烤，然 後，經中壓水銀燈（800 mJ/cm2)進行曝光。而後，將完成 曝光後之具有塗膜之基板進行物性測試。 物性測試所得結果如下： 塗膜形成20-25 μηι的塗膜 塗膜與基板之附著性（根據ASTM D3359-93檢驗方法）： 100/100 塗膜硬度（根據ASTM D3363-74檢驗方法）：2ΗΒ 塗膜光澤度（利用光澤計以60°進行測試）：90 塗膜耐熱性（80°C烘箱放置96小時）：通過（外觀無裂痕、 脫落） 外觀：平整，具有藍色全光效果。 實施例4 139499.doc -24- 201102412The above obtained composition was added with a diluent (butyl acetate / toluene / ethylene glycol monobutyl ether = 2 / 2 / 1) to the Iwata Cup for about 10 seconds, and sprayed with an air spray gun on the plastic 139499.doc • 21 - 201102412 On the rubber substrate, pre-baking was carried out in an oven at 60 ° C for 5 to 10 minutes, and then exposed to a medium pressure mercury lamp (800 mJ/cm 2 ). Then, the substrate having the coating film after the exposure is completed is subjected to physical property test. The physical property test results are as follows: Coating film forming 12-20 μηη coating film adhesion to the substrate (according to ASTM D3359-93 inspection method): 100/100 coating film hardness (according to ASTM D3363-74 inspection method): 2Η coating film Gloss (tested at 60° using a gloss meter): 65 Heat resistance of the film (96 hours in an oven at 80 ° C): Pass (no cracks, peeling off) Appearance: Flat, with a black semi-dull effect. Example 2 Table 2 Component Weight (g) Sartomer CN9006 (a) 27.0 Miwon MIRAMER M500 (b) 16.0 Dibenzophenone (c) 1.0 CfflVACURE 184 (1-hydroxycyclohexyl phenyl ketone) (c) 2.0 R&H B-60 (d) 13.05 Yoke Chemical R-900S(e) 10.0 Solvent butyl acetate (B AC) / benzene = 45/10 15.95 Butyl acetate / benzene = 1 / 1 8.0 Auxiliary DEUCHEM 910 (dispersed 2.0) DEUCHEM 923S (dispersant) 1.0 TEGO 450 (leveling agent) 0.2 Shamrock S-363 (matting agent) 4.0 139499.doc -22- 201102412 Adding the above-obtained composition to the diluent (butyl acetate / toluene) /Ethylene glycol monobutyl ether = 2/2/1) to the Iwata Cup for about 10 seconds, sprayed on a plastic substrate with an air spray gun, and then pre-baked in an oven at 60 ° C for 5 to 10 minutes, then Medium pressure mercury lamp (800 mJ/cm2) for exposure. Then, the substrate having the coating film after the exposure is completed is subjected to physical property test. The results obtained by the physical property test are as follows: Coating film to form 10-15 μηη coating film φ Coating film adhesion to substrate (according to ASTM D3359-93 inspection method): 100/100 coating film hardness (according to ASTM D3363_74 inspection method): coating film gloss Degree (tested by 60° with gloss meter): 85 Heat resistance of coating film (96 hours in oven at 80 ° C): Pass (no crack, peeling off) Appearance: Flat, with pearl semi-gloss effect. Example 3 瘫 Table 3 Component Weight (g) Eternal 611B-85(a) 7.5 Eternal 6145-100(a) 10.0 Eternal 6143C-60 (a) 5.0 Eternal EM235 (b) 15.0 Eternal EM231 (b) 4.5 Diphenylene Ketone (c) 1.0 CfflVACURE 184 (1-hydroxycyclohexyl phenyl ketone) (c) 2.0 CHIVACURE TPO (2,4,6-trimercaptobenzoyldiphenylphosphine oxide) (c) 2.0 DEUCHEM FS -2970A (d) 15.0 139499.doc •23- 201102412 DIC SB-746 (e) 3.0 Solvent butyl acetate (BAC) / ethylene glycol monobutyl ether (BCS) = 1 / 1 5.0 Toluene 12.0 isobutanol / different Ethyl butyrate = 1/1 10.0 Ethylene glycol monobutyl ether (BCS) 6.2 Auxiliary BYK disperbykl64 (dispersant) 0.5 DEUCHEM 923S (dispersant) 0.5 TfflXATROL ST (shake aid) 0.5 BYK 300 (leveling agent) 0.3 BYK-065 (antifoaming agent) 0.05 Add the above-mentioned composition to the diluent (butyl acetate / toluene / ethylene glycol monobutyl ether = 2 / 2 / 1) to the Iwata Cup for about 10 seconds, with air The spray gun was sprayed on a plastic substrate, and then pre-baked in an oven at 60 ° C for 5 to 10 minutes, and then exposed to a medium pressure mercury lamp (800 mJ/cm 2 ). Then, the substrate having the coating film after the exposure is completed is subjected to physical property test. The results obtained by the physical property test are as follows: The coating film forms a coating film of 20-25 μηι and the adhesion of the substrate (according to ASTM D3359-93 test method): 100/100 film hardness (according to ASTM D3363-74 test method): 2ΗΒ Coating gloss (tested at 60° using a gloss meter): 90 Heat resistance of the film (96 hours in an oven at 80 ° C): Pass (no cracks, peeling off) Appearance: Flat, with a blue all-optical effect. Example 4 139499.doc -24- 201102412

表4 成分Table 4 Composition

Eternal 6145-100(a)Eternal 6145-100(a)

Eternal EM265 (b) CHIVACURE 184 (1-羥基環己基苯基酮)⑷ CHIVACURE TPO (2,4,6-三曱基苯甲醯基二苯^^ 物)(c) 溶劑 助劑 甲苯Eternal EM265 (b) CHIVACURE 184 (1-hydroxycyclohexyl phenyl ketone) (4) CHIVACURE TPO (2,4,6-trimercaptobenzamide diphenyl) (c) Solvent Additive Toluene

Eternal 7329-XP-45 (d) Clariant Red F5RK (e) 異丁酸乙酯 乙二醇單丁醚(BCS) BYK disperbykl64 (分散劑) BYKAnti-Terra-U (分散劑) TEGO 450(流平劑）Eternal 7329-XP-45 (d) Clariant Red F5RK (e) Ethyl isobutyrate ethylene glycol monobutyl ether (BCS) BYK disperbykl64 (dispersant) BYKAnti-Terra-U (dispersant) TEGO 450 (leveling agent) )

將上述所獲得之組合物添加稀釋劑（醋酸丁 g旨/ f苯/ & 二The above-obtained composition is added with a diluent (acetate butyl g / f benzene / &

醇單丁醚=2/2/1)至岩田杯10秒左右，以空氣喷搶喷塗於塑 膠基板上，接著於60°C之烘箱内進行5〜10分鐘的預烤，然 後，經中壓水銀燈（800 mJ/cm2)進行曝光。而後，將完成 曝光後之具有塗膜之基板進行物性測試。 物性測試所得結果如下： 塗膜形成15-20 μιη的塗膜 塗膜與基板之附著性（根據ASTM D3359-93檢驗方法）： 100/100 塗膜硬度（根據ASTMD3363-74檢驗方法）：2Η 塗膜光澤度（利用光澤計以60°進行測試）：65 塗膜耐熱性（80°C烘箱放置96小時）：通過（外觀無裂痕、 139499.doc -25- 201102412 脫落） 外觀：平整，具有紅色全光效果。 實施例5 表5 成分 重量(公克） BAYER Desmolux® U100 (a) 25.0 Eternal EM265 (b) 10.0 Eternal EM235 (b) 8.0 CHIVACURE BDK (2,2，-二曱基-1，2-二苯基乙烷-1-酮)(c) 3.0 CHIVACURE TPO (2,4,6-三曱基苯曱醯基二苯基膦氧化 物)(c) 3.0 Eternal 7352-TS-50 (d) 35.0 DIC Green G7 (e) 5.0 溶劑 甲苯 3 醋酸丁酯 3 乙二醇單丁醚 3.2 助劑 BYK disperbykl64 (分散劑） 1.5 BYK3510 (流平劑） 0.3 BYK-088(消泡劑） 0.05 將上述所獲得之組合物添加稀釋劑（醋酸丁酯/曱苯/乙二 醇單丁醚=2/2/1)至岩田杯10秒左右，以空氣喷搶喷塗於塑 膠基板上，接著於60°C之烘箱内進行5〜10分鐘的預烤，然 後，經中壓水銀燈（800 mJ/cm2)進行曝光。而後，將完成 曝光後之具有塗膜之基板進行物性測試。 物性測試所得結果如下： 塗膜形成12-20 μηι的塗膜 塗膜與基板之附著性（根據ASTM D3359-93檢驗方法）： 139499.doc -26- 201102412 100/100 塗膜硬度（根據ASTMD3363-74檢驗方法）： 塗膜光澤度（利用光澤計以60°進行測試）：65 塗膜耐熱性（80°C烘箱放置96小時）：通過（外觀無裂痕、 脫落） 外觀：平整，具有綠色全光效果。Alcohol monobutyl ether = 2/2 / 1) to the Iwata Cup for about 10 seconds, sprayed on the plastic substrate with air spray, and then pre-baked in an oven at 60 ° C for 5 to 10 minutes, then, in the middle The mercury lamp (800 mJ/cm2) was pressed for exposure. Then, the substrate having the coating film after the exposure is completed is subjected to physical property test. The results obtained by the physical property test are as follows: Coating film to form 15-20 μηη coating film adhesion to the substrate (according to ASTM D3359-93 inspection method): 100/100 coating film hardness (according to ASTM D3363-74 inspection method): 2Η coating Film gloss (tested at 60° using a gloss meter): 65 Heat resistance of the film (96 hours in an oven at 80 ° C): Pass (no crack on the appearance, 139499.doc -25-201102412) Appearance: flat, with red Full light effect. Example 5 Table 5 Component Weight (g) BAYER Desmolux® U100 (a) 25.0 Eternal EM265 (b) 10.0 Eternal EM235 (b) 8.0 CHIVACURE BDK (2,2,-dimercapto-1,2-diphenyl Alkan-1-one) (c) 3.0 CHIVACURE TPO (2,4,6-trimercaptophenylene diphenylphosphine oxide) (c) 3.0 Eternal 7352-TS-50 (d) 35.0 DIC Green G7 (e) 5.0 Solvent toluene 3 Butyl acetate 3 Ethylene glycol monobutyl ether 3.2 Additive BYK disperbykl64 (dispersant) 1.5 BYK3510 (leveling agent) 0.3 BYK-088 (antifoaming agent) 0.05 The composition obtained above Add diluent (butyl acetate / benzene / ethylene glycol monobutyl ether = 2 / 2 / 1) to the Iwata Cup for about 10 seconds, spray on the plastic substrate with air spray, and then in an oven at 60 ° C Prebaking was carried out for 5 to 10 minutes, and then exposed to a medium pressure mercury lamp (800 mJ/cm2). Then, the substrate having the coating film after the exposure is completed is subjected to physical property test. The results obtained by the physical property test are as follows: The adhesion of the coating film to the substrate formed by the coating film of 12-20 μη (according to the inspection method according to ASTM D3359-93): 139499.doc -26- 201102412 100/100 The hardness of the coating film (according to ASTM D3363- 74 test method): Coating gloss (tested by 60° with gloss meter): 65 Heat resistance of film (96 hours in oven at 80 °C): Pass (no cracks, peeling off) Appearance: flat, green Light effect.

139499.doc -27-139499.doc -27-

Claims (1)

201102412 七、申請專利範圍： 1. 一種UV可固化有色塗料組合物，其包含： (a) 3有至少1個不飽和雙鍵之寡聚物； (b) 稀釋單體； (c) 光起始劑； (d) 熱可塑性丙浠酸樹脂；及 (e) 色料； • 其中組分⑷與組分(b)之重量比為Η至4:1 ;組分⑷以組 :⑷與組分⑻合計1〇〇重量份計，其含量為5】重量 份，組分（d)以組分（a)與組分合計1〇〇重量份計其含 里為20-1〇〇重里份，組分⑷以組分⑷、⑻與⑷合計⑽ 重量份計’其含量為2-5〇重量份。 2. 如請求項1之1；乂可固化有色塗料組合物，其中組分（^與 組分（b)之重量比為ι:ι至2:1。 3. 如請求項1之UV可固化有色塗料組合物，其中組份（&)之 鲁含有至少1個不飽和雙鍵之寡聚物係為具至少2個不飽和雙 鍵之寡聚物。 4. 如請求項1之UV可固化有色塗料組合物，其中組份（a)之 含有至少1個不飽和雙鍵之寡聚物係為具3至15個不飽和雙 鍵之寡聚物。 5 ·如請求項1之UV可固化有色塗料組合物，其中組份（a)之 含有至少1個不飽和雙鍵之寡聚物係選自由環氧丙烯酸 酯、聚胺基曱酸酯丙烯酸酯、聚酯丙烯酸酯、聚丙烯酸 酯、胺基丙烯酸酯、矽基丙烯酸酯及其混合物所構成群 139499.doc 201102412 組。 6. 如請求項1之UV可固化有色塗料組合物，其中組份之 含有至少1個不飽和雙鍵之寡聚物為聚胺基甲酸酯丙烯 酸醋® 7. 如請求項1之UV可固化有色塗料組合物，其中組份⑷之 含有至少1個不飽和雙鍵之寡聚物為脂肪族聚胺基曱酸 酯丙烯酸酯。 8·如請求項1之11乂可固化有色塗料組合物，其中組份化）之 稀釋單體為具有至少2個官能基的丙烯酸酯類單體。 9.如請求項1之UV可固化有色塗料組合物，其中組份之 稀釋單體為具有3至6個官能基之丙烯酸酯類單體。 ίο.如請求項1之uv可固化有色塗料組合物，其中組份（d)之 熱可塑十生丙烯酸樹脂係為均聚物或共聚物，其係衍生自 至少一種選自以下單體的高分子：丙烯酸、甲基丙烯 酸、丙烯酸烷基酯以及甲基丙烯酸烷基酯。 η·如請求項1谓可固化有色塗料組合物，其中組份⑷之 .、，、可塑f生丙烯^ Μ脂具有大於之玻璃轉換溫度。 12. 如請求項RUV可固化有色塗料組合物其中組份⑷之 熱可塑性丙婦酸樹脂具有75〇C至11〇〇C之玻璃轉換溫 度。 、'皿 13. 如請求項1之u V可田儿‘ A〜 固化有色塗料組合物，其中組份（e)之 色料係選自由顏粗 貝14、染料或填料及其混合物所構成群 組。 14. 如請求項1之UV可m儿本 J固化有色塗料組合物，其中組份（e)之 139499.doc 201102412 色料為顏料。 15.如請求項1之UV可固化有色塗料組合物，進一步包含有 機溶劑。201102412 VII. Patent Application Range: 1. A UV curable pigmented coating composition comprising: (a) 3 oligomers having at least one unsaturated double bond; (b) diluting monomers; (c) light-emitting (d) thermoplastic propionic acid resin; and (e) colorant; • wherein the weight ratio of component (4) to component (b) is Η to 4:1; component (4) is group: (4) and group The content of (8) is 5 parts by weight in total, and the component (d) is 20-1 〇〇 in parts by weight of the component (a) and the total of 1 part by weight of the component. The component (4) is contained in an amount of 2 to 5 parts by weight based on the total of (10) parts by weight of the components (4), (8) and (4). 2. According to claim 1 of the present invention; a curable pigmented coating composition wherein the weight ratio of the component (^ to component (b) is from ι:ι to 2:1. 3. UV curable according to claim 1 A pigmented coating composition wherein the oligomer of the component (&) containing at least one unsaturated double bond is an oligomer having at least 2 unsaturated double bonds. 4. The UV of claim 1 A colored coating composition is cured, wherein the oligomer of the component (a) containing at least one unsaturated double bond is an oligomer having 3 to 15 unsaturated double bonds. 5 · The UV of claim 1 Curing a pigmented coating composition wherein the oligomer of component (a) containing at least one unsaturated double bond is selected from the group consisting of epoxy acrylate, polyamino phthalate acrylate, polyester acrylate, polyacrylate A group of 139499.doc 201102412. A UV curable pigmented coating composition according to claim 1 wherein the component contains at least one unsaturated double bond. The oligomer is a polyurethane acrylate vinegar® 7. The UV curable pigmented coating composition of claim 1 The oligomer of the middle component (4) containing at least one unsaturated double bond is an aliphatic polyamino phthalate acrylate. 8. The curable pigmented coating composition of claim 1 is as shown in claim 1 The dilute monomer is an acrylate monomer having at least two functional groups. 9. The UV curable pigmented coating composition of claim 1 wherein the diluent monomer of the component is an acrylate monomer having from 3 to 6 functional groups. Ίο. The uv curable pigmented coating composition of claim 1, wherein the thermoplastic acryl resin of component (d) is a homopolymer or a copolymer derived from at least one selected from the group consisting of Molecules: acrylic acid, methacrylic acid, alkyl acrylates and alkyl methacrylates. η·If the claim 1 is a curable pigmented coating composition, wherein the component (4), the plasticized propylene resin has a glass transition temperature greater than that. 12. The heat transferable composition of the RUV curable pigmented coating composition of claim (4) has a glass transition temperature of from 75 ° C to 11 ° C. , 'Dish 13. as claimed in claim 1 u V 可田儿' A~ cured colored coating composition, wherein the component (e) is selected from the group consisting of Yanbeibei 14, dyes or fillers and mixtures thereof group. 14. The UV-curable coating composition of claim 1 wherein the component (e) 139499.doc 201102412 colorant is a pigment. 15. The UV curable pigmented coating composition of claim 1 further comprising an organic solvent. 139499.doc 201102412 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： • 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 139499.doc139499.doc 201102412 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: • 5. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: (none) 139499.doc
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CN102825887A (en) * 2011-06-16 2012-12-19 房士君 Processing technology of transparent UV wear-resistant coating
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TWI487758B (en) * 2011-03-24 2015-06-11 Eternal Materials Co Ltd Uv curable-type treating agent
CN102825888A (en) * 2011-06-16 2012-12-19 房士君 Printed UV wear-resistant coating processing technology
CN102825887A (en) * 2011-06-16 2012-12-19 房士君 Processing technology of transparent UV wear-resistant coating
TWI713936B (en) * 2017-11-28 2020-12-21 南韓商Ｌｇ化學股份有限公司 A composition for light-shielding a waveguide edge with excellent adhesion
US10895678B2 (en) 2017-11-28 2021-01-19 Lg Chem, Ltd. Waveguide edge light shielding composition having excellent adhesive strength

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