TWI487758B - Uv curable-type treating agent - Google Patents

Uv curable-type treating agent Download PDF

Info

Publication number
TWI487758B
TWI487758B TW100110262A TW100110262A TWI487758B TW I487758 B TWI487758 B TW I487758B TW 100110262 A TW100110262 A TW 100110262A TW 100110262 A TW100110262 A TW 100110262A TW I487758 B TWI487758 B TW I487758B
Authority
TW
Taiwan
Prior art keywords
component
ultraviolet curable
treatment agent
acrylate
agent
Prior art date
Application number
TW100110262A
Other languages
Chinese (zh)
Other versions
TW201239049A (en
Inventor
Shih Kung Tseng
Hung Wen Huang
Yu-Tao Zhang
chun-yang Li
Original Assignee
Eternal Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eternal Materials Co Ltd filed Critical Eternal Materials Co Ltd
Priority to TW100110262A priority Critical patent/TWI487758B/en
Publication of TW201239049A publication Critical patent/TW201239049A/en
Application granted granted Critical
Publication of TWI487758B publication Critical patent/TWI487758B/en

Links

Landscapes

  • Paints Or Removers (AREA)

Description

紫外線固化型處理劑UV curing treatment agent

本發明關於一種紫外線(UV)固化型處理劑，尤其關於一種應用於塗裝工業之紫外線固化型處理劑。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.

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。Coatings are used in a wide range of applications, from everyday items to high-tech electronics, such as furniture, automotive components, cosmetic enclosures, and various 3C electronics or electrical products (such as digital cameras, notebooks, and mobile phones). A coating is applied to the substrate to provide a protective or decorative coating effect. However, changes 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.

常用之基材，如木材、玻璃、金屬或塑膠基材，在製造、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、無鏽漬)及無缺陷(即無刮花)，否則會影向塗層的附著力。Commonly used substrates, such as wood, glass, metal or plastic substrates, may have oil, oxide scale, hydroxide, dust and other contaminants attached to the surface of the substrate during manufacturing, processing, handling and storage. In order to ensure a good coating effect, the surface of the substrate must be clean (ie no oil, no rust) and no defects (ie no scratches), otherwise it will affect the adhesion of the coating.

塑膠基材一般係藉由模鑄成形、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，殘留在基材表面之脫膜劑油污可能在塗佈時浮出，影響後續之塗層之密著性及外觀。The plastic substrate is generally prepared by die casting, extrusion molding, injection molding, and the like. Due to the limitation of the forming method, such a substrate is prone to surface defects such as fine grooves and small holes, and in addition, the oil of the release agent remaining on the surface of the substrate may float during coating, which affects the adhesion of the subsequent coating. Sex and appearance.

另外，技術領域中已知可添加纖維，例如玻璃纖維、碳纖維、硼纖維或金屬纖維，至塑膠基材中以改良其強度。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累積，此亦造成浮纖之原因之一。Additionally, it is known in the art to add fibers, such as glass fibers, carbon fibers, boron fibers or metal fibers, to a plastic substrate to improve its strength. 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, resulting in floating fibers. In addition, the frictional shear force at the time of injection causes a difference in local viscosity, and the fiber can be caught in the place where the viscosity is small, and the fiber accumulates on the surface of the product, which also causes one of the reasons for the floating fiber.

為解決基材之成形缺陷並去除表面污物，提供外觀優美且密著性良好之塗層，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、除銹水洗及塗佈底漆(primer)等。這些程序不但繁複且費時。In order to solve the formation defects of the substrate and remove the surface dirt, a coating having a beautiful appearance and good adhesion is provided, and in the technical field, the substrate is generally pretreated before coating. Prior art treatments include sanding, degreasing, descaling, and coating primers. These procedures are complicated and time consuming.

本案發明人經廣泛研究發現一種新穎紫外線固化型處理組合物，可有效解決基材表面的缺陷和汙物，不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。The inventors of the present invention have found through extensive research that a novel ultraviolet curable treatment composition can effectively solve defects and dirt on the surface of the substrate, and can be applied to the coating film and the substrate without the need of pretreatment by other substrates. Adhesion can meet the needs of the industry.

本發明之主要目的為提供一種紫外線固化型處理劑，其包含以下組分：The main object of the present invention is to provide an ultraviolet curable treatment agent comprising the following components:

(a)　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；(a) a monomer comprising at least one double bond, an oligomer of at least one double bond, or a mixture thereof;

(b)　光起始劑；及(b) a photoinitiator; and

(c)　熱塑性樹脂，(c) thermoplastic resin,

其中以100重量份組分(a)計，所述組分(b)之含量為0.5-20重量份，且組分(c)之含量為30-1,000重量份。Wherein the component (b) is contained in an amount of from 0.5 to 20 parts by weight based on 100 parts by weight of the component (a), and the component (c) is contained in an amount of from 30 to 1,000 parts by weight.

本發明的有益效果是：本發明的紫外線固化型處理劑，藉由添加特定比例的熱塑性樹脂，改善基材與塗料樹脂的附著性，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。The invention has the beneficial effects that the ultraviolet curable treatment agent of the invention can improve the adhesion between the substrate and the coating resin by adding a specific proportion of the thermoplastic resin, can effectively level and wet, and can overcome the defects of substrate formation. . The drying speed is fast, the fiber can be dried and solidified, the floating fiber phenomenon is 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.

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。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 a mixture thereof.

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)、甲基丙烯酸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)、二甲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)、二甲基丙烯酸二乙二醇酯(EGDMA)、二丙烯酸乙氧基化(10)雙酚酯(BPA10EODA)、二甲基丙烯酸乙氧基化(10)雙酚酯(BPA10EODMA)、二丙烯酸三環癸烷二甲醇酯(TCDMDA)、二丙烯酸丙氧化(2)新戊二醇酯(NPG2PODA)、Nanocryl 0396(含50%奈米氧化矽之DPGDA)、Nanocryl 0768(含50%奈米氧化矽之HDDA)、三丙烯酸三羥甲基丙烷酯(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)三羥甲基丙烷酯(TMP6POTA)、三丙烯酸丙氧化(3)丙三醇酯(G3POTA)、四丙烯酸二-(三羥甲基丙烷)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。The acrylate monomer 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), and different Mercaptoacrylate (ISODA), isobornyl acrylate (IBOA), 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), dipropylene glycol diacrylate (DPGDA), diacrylic acid Tripropylene glycol ester (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 (BPA10EODA), two Ethoxylated methacrylic acid (10) bisphenol ester (BPA10EODMA), tricyclodecane dimethanol diacrylate (TCDMDA), propionic acid diacrylate (2) neopentyl glycol ester (NPG2PODA), Nanocryl 0396 (including 50% nano cerium oxide DPGDA), Nanocryl 0768 (HDDA containing 50% nano cerium oxide), trimethylolpropane triacrylate (TMPTA), ethoxylated (3) trimethylolpropane triacrylate ( TMP3 EOTA), ethoxylated (6) trimethylolpropane triacrylate (TMP6EOTA), ethoxylated (9) trimethylolpropane triacrylate (TMP9EOTA), ethoxylated (15) trimethylolpropane triacrylate (TMP15EOTA), ethoxylated (20) trimethylolpropane triacrylate (TMP20EOTA), propoxylated (6) trimethylolpropane triacrylate (TMP6POTA), propane oxidized (3) glycerol triacrylate ( G3POTA), a group consisting of di-(trimethylolpropane) tetraacrylate (DI-TMPTA), pentaerythritol triacrylate (PET3A), and dipentaerythritol hexaacrylate (DPHA) and mixtures thereof.

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)、甲基丙烯酸2-羥基乙酯(HEMA)、三丙烯酸三羥甲基丙烷酯(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)三羥甲基丙烷酯(TMP6POTA)、三丙烯酸丙氧化(3)丙三醇酯(G3POTA)、四丙烯酸二-(三羥甲基丙烷)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。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), trimethylolpropane triacrylate (TMPTA), ethoxylated (3) trimethylolpropane triacrylate (TMP3EOTA), ethoxylated (6) trimethylolpropane triacrylate (TMP6EOTA), Ethylene oxide acrylate (9) trimethylolpropane ester (TMP9EOTA), ethoxylated (15) trimethylolpropane triacrylate (TMP15EOTA), ethoxylated (20) trimethylolpropane triacrylate (TMP20EOTA) , (3) trimethylolpropane triacrylate (TMP6POTA), propane trioxide (3) glycerol triacrylate (G3POTA), di-(trimethylolpropane) tetraacrylate (DI-TMPTA) a group consisting of pentaerythritol triacrylate (PET3A) and dipentaerythritol hexaacrylate (DPHA) and mixtures thereof.

可用於本發明之市售丙烯酸酯單體包括：EM210、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 M500及MIRAMER M600(Miwon公司製)。Commercially available acrylate monomers useful in the present invention include: EM210, 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 Industry Co., Ltd.); 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 M500 And MIRAMER M600 (made by Miwon Corporation).

可用於本發明之丙烯酸酯寡聚物含有至少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烯酸酯(epoxy acrylate)，如雙酚A環氧二丙烯酸酯(bisphenol-A epoxy diacrylate)、2-羥基-3-苯氧丙基丙烯酸酯、酚醛環氧丙烯酸酯(novolac epoxy acrylate)；聚胺基甲酸酯丙烯酸酯(polyurethane acrylate)，如脂肪族胺基甲酸酯丙烯酸酯(aliphatic urethane acrylate)或芳香族胺基甲酸酯丙烯酸酯(aromatic urethane acrylate)；聚酯丙烯酸酯(polyester acrylate)，如聚酯二丙烯酸酯(polyester diacrylate)、脂肪族聚酯丙烯酸酯(aliphatic polyester acrylate)或芳香族聚酯丙烯酸酯(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，較佳係聚胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯或其混合物。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。The acrylate oligomer which can be used in the present invention contains at least one double bond, preferably contains at least 2 double bonds, more preferably 3 to 15 double bonds, and the molecular weight thereof is not particularly limited, and is generally from 400 to 5,000. Preferably, the range is between 500 and 3,000. The types of the above acrylate oligomers are, for example but not limited to, selected from epoxy acrylates such as bisphenol-A epoxy diacrylate, 2-hydroxy-3-phenoxypropyl acrylate. Alkyl acrylate, novolac epoxy acrylate; polyurethane acrylate, such as aliphatic urethane acrylate or aromatic urethane Aromatic urethane acrylate; polyester acrylate, such as polyester diacrylate, aliphatic polyester acrylate or aromatic polyester acrylate (aromatic polyester) Acrylate; a group of polyacrylates; amine acrylates and mixtures thereof, preferably polyurethane acrylates, polyester acrylates or mixtures thereof. The above-mentioned polyurethane acrylate is more preferable in that the aliphatic polyurethane acrylate is less susceptible to yellowing.

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：AgiSynTM 2901A50、AgiSynTM 1010、AgiSynTM 1010A80、AgiSynTM 1010B80、AgiSynTM 1010C80、AgiSynTM 2010及AgiSynTM 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)。The present invention Commercially available acrylate oligomer examples thereof include: epoxy acrylate oligomer: AgiSyn TM 2901A50, AgiSyn TM 1010 , AgiSyn TM 1010A80, AgiSyn TM 1010B80, AgiSyn TM 1010C80, AgiSyn TM 2010 and AgiSyn TM 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 (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.).

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、6160B-70、6161-100、6181及6196-100(長興化工製)；AgiSynTM 230S1-15HD、AgiSynTM 230S2-30TP、AgiSynTM 230SM-20TP、AgiSynTM 230SN-20TP、AgiSynTM 230SR-20TP、AgiSynTM 230T1及AgiSynTM 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)；DesmoluxU100、DesmoluxVP LS 2265、DesmoluxVP LS 2308、DesmoluxU375H、DesmoluxVP LS 2220、DesmoluxXP 2491、DesmoluxXP 2513、DesmoluxU200及DesmoluxXP 2609(拜耳(Bayer)公司製)。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, 6160B-70, 6161-100, 6181, and 6196-100 (manufactured by Changxing Chemical Industry Co., Ltd.); AgiSyn TM 230S1-15HD, AgiSyn TM 230S2-30TP, AgiSyn TM 230SM- 20TP, AgiSyn TM 230SN-20TP, AgiSyn TM 230SR-20TP, AgiSyn TM 230T1 and AgiSyn TM 230A2 (manufactured by Sony Biotech 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 (UCB) ; 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).

芳香族胺基甲酸酯丙烯酸酯寡聚物：6120F-80、6121F-80、6122F-80及6146-100(長興化工製)；AgiSynTM 670TH-20TP、AgiSynTM 670S1-20TP、AgiSynTM 670T1、AgiSynTM 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)。Aromatic urethane acrylate oligomers: 6120F-80, 6121F-80, 6122F-80, and 6146-100 (manufactured by Changxing Chemical Industry Co., Ltd.); AgiSyn TM 670TH-20TP, AgiSyn TM 670S1-20TP, AgiSyn TM 670T1 AgiSyn TM 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.).

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6361-100(長興化工製)；BE-101、BE112DP10、BE-211、JL-103M、JL-106E及JL-126(Bomar Specialties Company製)。Polyester acrylate oligomers: EBECRYL-830, EBECRYL-810, and EBECRYL-524 (made by UBC Co., Ltd.); 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).

聚丙烯酸酯寡聚物：AgiSynTM 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)。Polyacrylate oligomer: AgiSyn TM 2266 (manufactured by Xinlimei Technology Co., Ltd.); EBECRYL-745 (made by UBC Co., Ltd.); DOUBLEMER 3778, DOUBLEMER 1701, DOUBLEMER 345, DOUBLEMER 1703, DOUBLEMER 530, DOUBLEMER 570, DOUBLEMER 236, and DOUBLEMER 584 (made by Double Key Chemical Co., Ltd.); 6530B-40, 6531B-40, 6532B-40 and 6533B-40 (made by Changxing Chemical Industry Co., Ltd.).

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：二苯甲酮-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。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 the transfer of a radical. It is, for example but not limited to, a group selected from the group consisting of benzophenone-amine conjugated systems; benzoin ethers; benzoin and its ketals; and acetophenone derivatives. In addition, two or more photoinitiators may be used as needed.

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。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 the 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).

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)、CHIVACURE EPD(對-(二甲胺基)苯甲酸乙酯)、CHIVACURE OMB(鄰-苯甲醯基苯甲酸甲酯)、CHIVACURE EMK(N,N,N',N'-四乙基-4,4'-二胺基二苯甲酮)、CHIVACURE BDK(2,2'-二甲基-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-甲基-1-苯基-丙-1-酮)、CHIVACURE TPO(2,4,6-三甲基苯甲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(1-羥基環己基苯基酮)、AgiSynTM -1810(2-羥基-2-甲基-1-苯基-丙-1-酮)、AgiSynTM -1801及AgiSynTM -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-甲基丙基)酮)(BASF公司製)。Examples of commercially available photoinitiators which can be used in the present invention include: CHIVACURE 115, CHIVACURE ITX (isopropyl thioxanthone), CHIVACURE EPD (p-(dimethylamino) benzoate), CHIVACURE OMB ( Benzyl-benzylidene benzoate), CHIVACURE EMK (N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone), CHIVACURE BDK (2,2' - dimethyl-1,2-diphenylethane-1-one), CHIVACURE BMS (4-benzylidene-4'-methyldiphenyl sulfide), CHIVACURE 184 (1-hydroxycyclohexyl) Phenyl ketone), CHIVACURE 173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one), CHIVACURE TPO (2,4,6-trimethylbenzhydryldiphenylphosphine oxide And CHIVACURE 200 (methyl phenylglycolate) (manufactured by Double Bond Chemicals (DBC) Co., Ltd.); AgiSyn TM -1812 (1-hydroxycyclohexyl phenyl ketone), AgiSyn TM -1810 (2-hydroxy-2) -Methyl-1-phenyl-propan-1-one), AgiSyn TM -1801 and AgiSyn TM -003 (manufactured by Xinlimei Technology Co., Ltd.); IRGACURE 369 (2-benzyl-2-N, N-di Methylamino-1-(4-morpholinylphenyl-1-butanone) and IRGACURE 2959 (4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-methylpropyl) ) Ketone) (manufactured by BASF Corporation).

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。The invention adds component (c) thermoplastic resin to the treating agent, can adjust the viscosity of the treating agent, can effectively level and wet the substrate with surface defects, achieve the effect of modifying the appearance; and accelerate the coating film The drying speed is beneficial to reduce the phenomenon of floating fiber or to isolate the oil residue remaining on the substrate. In addition, the general treatment agent coating film will produce high shrinkage stress after UV curing, which may cause warping, cracking, etc., and also adversely affect the adhesion. Adding a thermoplastic resin to the treatment agent may increase the coating film and the base. The adhesion of the material and the cracking of the coating film are prevented. It is preferred to use a thermoplastic resin having a higher glass transition temperature to accelerate the drying speed of the coating film.

本發明之熱塑性樹脂與寡聚物及/或單體的相容性佳，可直接摻雜(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，由於此類樹脂的表亁能力強，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。The thermoplastic resin of the present invention has good compatibility with oligomers and/or monomers, can be directly blended in the treating agent, does not react with oligomers and/or monomers, and thus can be used as a Buffered media to release stress due to rapid cure during UV curing. On the other hand, since such a resin has a strong surface entanglement, it is possible to promote the removal of the solvent from the coating film during the drying process, thereby avoiding the phenomenon of sag.

本發明所使用之組份(c)熱塑性樹脂係選自由丙烯酸樹脂、氯醋樹脂、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5,000至250,000間，較佳介於10,000至200,000間，更佳介於25,000至100,000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30-1,000重量份，更佳為40-400重量份。The component (c) thermoplastic resin used in the present invention is selected from the group consisting of acrylic resins, chloroacetic 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 5,000 to 250,000, preferably from 10,000 to 200,000, more preferably from 25,000 to 100,000. According to the invention, the component (c) thermoplastic resin is used in an amount of from 30 to 1,000 parts by weight, more preferably from 40 to 400 parts by weight, based on 100 parts by weight of the component (a).

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。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.

可用於本發明之市售熱塑性氯醋樹脂例子包含：Vinnol E15/45、Vinnol H14/36、Vinnol H15/42、Vinnol H11/59、Vinnol H40/43、Vinnol H40/50、Vinnol H40/55、Vinnol H40/60(威凱化學公司製)；VYHH、VYHD、VMCH、VMCC、VAGH、VAGF(陶氏化學公司製)。Examples of commercially available thermoplastic chloroacetic resins useful in the present invention include: Vinnol E15/45, Vinnol H14/36, Vinnol H15/42, Vinnol H11/59, Vinnol H40/43, Vinnol H40/50, Vinnol H40/55, Vinnol H40/60 (manufactured by Weikai Chemical Co., Ltd.); VYHH, VYHD, VMCH, VMCC, VAGH, VAGF (manufactured by The Dow Chemical Company).

可用於本發明之市售熱塑性氯化聚烯烴樹脂例子包含：Eastman CP-730-1、Eastman AP550-1、Eastman CP-343-1、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-5551、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(日本立邦制紙株式會社製)。Examples of commercially available thermoplastic chlorinated polyolefin resins useful in the present invention include: Eastman CP-730-1, Eastman AP550-1, Eastman CP-343-1, 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-5551, 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.).

可用於本發明之市售熱塑性聚酯樹脂例子包含：DYNAPOLL206、DYNAPOLL205、DYNAPOLL411、DYNAPOLLTW、DYNAPOLLTW-B及DYNAPOLLTH(Evonik Degussa製)；VYLON200、VYLON270、VYLON600、VYLON300、VYLON500、VYLON560、VYLONPCR-925、VYLONGK100及VYLONGK780(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 5054-R-40、ETERKYD 5022-TK-40、ETERKYD 5015-X-50、ETERKYD 5016-X-50及ETERKYD 5014-X-50(長興化工製)。Examples of commercially available thermoplastic polyester resins useful 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 (made by TOYOBO); SKYBON ES100, SKYBON ES110, SKYBON ES910, SKYBON ES160, SKYBON ES402, SKYBON ES500 and SKYBON ES300 (made by SK Chemicals); ETERKYD 5011-X-50, ETERKYD 5058-R- 40, ETERKYD 5021-R-40, ETERKYD 5054-R-40, ETERKYD 5022-TK-40, ETERKYD 5015-X-50, ETERKYD 5016-X-50 and ETERKYD 5014-X-50 (manufactured by Changxing Chemical Industry Co., Ltd.).

可用於本發明之市售熱塑性松香樹脂例子包含：SYLVAlITERE 88、SYLVAlITERE 100、SYLVAlITERE 115及SYLVATACRE 95(Arizona Chemical製)；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)。Examples of commercially available thermoplastic rosin resins useful in the present invention include: SYLVAlITE RE 88, SYLVAlITE RE 100, SYLVAlITE RE 115 and SYLVATAC RE 95 (manufactured by Arizona Chemical Co., Ltd.); TAMANOL 145, TAMANOL 340, TAMANOL 350, TAMANOL 353, TAMANOL 359, TAMANOL 361, TAMANOL 366, TAMANOL 392 (Arakawa Chemical Co., Ltd.).

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℃，較佳大於60℃，更佳介於70℃至150℃間的玻璃化轉變溫度(Tg)之丙烯酸樹脂，一般而言，當Tg小於20℃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150℃時，會造成流平性不優，衍生出加工不易的問題。According to an embodiment of the present invention, the thermoplastic resin selected is a thermoplastic acrylic resin. The above thermoplastic acrylic resin comprises one or more acrylic resins having a glass transition temperature (Tg) of more than 20 ° C, preferably more than 60 ° C, more preferably between 70 ° C and 150 ° C, in general, when the Tg is less than 20 ° C The solvent resistance is not good, and the heat resistance of the coating film is not good, and the protective force is insufficient; when the Tg is more than 150 ° C, the leveling property is not excellent, and the problem of difficulty in processing is derived.

根據本發明之另一實施態樣，除了使用具有大於20℃之玻璃化轉變溫度的熱塑性丙烯酸樹脂之外，可視需要另添加具有較高玻璃化轉變溫度，例如，大於60℃，較佳介於70℃至150℃間之玻璃化轉變溫度的熱塑性丙烯酸樹脂。According to another embodiment of the present invention, in addition to using a thermoplastic acrylic resin having a glass transition temperature of greater than 20 ° C, it may be additionally added to have a higher glass transition temperature, for example, greater than 60 ° C, preferably 70 A thermoplastic acrylic resin having a glass transition temperature between ° C and 150 ° C.

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、甲基丙烯酸、丙烯酸烷基酯以及甲基丙烯酸烷基酯。The above thermoplastic acrylic resin may be a homopolymer or a copolymer derived from at least one polymer selected from the group consisting of acrylic acid, methacrylic acid, alkyl acrylate, and alkyl methacrylate.

上述丙烯酸烷基酯及甲基丙烯酸烷基酯單體之實例包括丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸異辛酯、甲基丙烯酸異辛酯、丙烯酸環己酯、甲基丙烯酸環己酯、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、甲基丙烯酸-2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、甲基丙烯酸羥丙酯、丙烯酸異冰片酯及甲基丙烯酸異冰片酯及其混合物。Examples of the above alkyl acrylate and alkyl methacrylate monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, acrylic acid. Isopropyl ester, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isooctyl acrylate, isooctyl methacrylate, cyclohexyl acrylate Ester, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxypropyl ester, 2-hydroxypropyl methacrylate, hydroxypropyl methacrylate, isobornyl acrylate and isobornyl methacrylate, and mixtures thereof.

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、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、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、甲基丙烯酸-2-羥基乙酯、丙烯酸2-羥基丙酯及甲基丙烯酸2-羥基丙酯，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、甲基丙烯酸-2-羥基乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸異冰片酯及甲基丙烯酸異冰片酯。According to a specific embodiment of the present invention, the selected thermoplastic acrylic resin is composed of one or more of the following monomers as polymerized units: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, n-butyl acrylate, methacrylic acid. N-butyl ester, isobutyl acrylate, isobutyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, isobornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, preferably having one or more of the following monomers as polymerized units: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid Methyl ester, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobornyl acrylate and isobornyl methacrylate.

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、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-1042及AR-1090F(長春公司製)。A-646、A-14、A-11、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)；LF-1113、LF-1115及LF-1117(立驊公司製)。Examples of commercially available thermoplastic acrylic resins useful in the present invention include: 7119-TB-50, 7626-1, 7128-TB-50, 7305-2-XS-50, 7329-XP-45, 7329-TS-45, 7117 -TS-50, 7752-TS-50 and 7630 (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-1042 and AR-1090F (manufactured by Changchun Co., Ltd.). A-646, A-14, A-11, A-21, B-60, B-66, B-64, B-82 and B-72 (made by R&H); and FS-2970A (Deqian Enterprise Limited) Company system); LF-1113, LF-1115 and LF-1117 (manufactured by Licensing Co., Ltd.).

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。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 skilled 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 of the present invention 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).

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)；CARBOWET13-40 SURFACTANT(美商亞普有限公司(Air Products)製)；Modaflow resin、Modaflow 2100、Modaflow 9200、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)。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 uses 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 Chemical company (BYK); TEGO Twin 4000, TEGO Wet270, TEGO 410 and TEGO 450 (made by TEGO); CARBOWET 13-40 SURFACTANT (manufactured by Air Products); Modaflow resin, Modaflow 2100, Modaflow 9200, 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 Co., Ltd.).

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、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-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)。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, 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-special, 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 Simmet Pacific (TEGO)); DEUCHEM 5300, DEUCHEM 6500, DEUCHEM 2700, DEUCHEM 3600, DEUCHEM 2700, DEUCHEM 3100 and DEUCHEM 5700 (Deqian Enterprise Co., Ltd.) system).

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、disperbyk101、disperbyk103、disperbyk110、disperbyk115、disperbyk116、disperbyk142、disperbyk161、disperbyk162、disperbyk163、disperbyk164、disperbyk168、disperbyk181、disperbyk183、disperbyk2000、disperbyk2001、disperbyk2150、disperbyk107、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)。The dispersant used in the present invention as needed provides a stable dispersion effect and homogenizes the treatment agent component. The dispersant 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, disperbyk 101, disperbyk 103, disperbyk 110, disperbyk 115, disperbyk 116, disperbyk 142, disperbyk 161, disperbyk 162, disperbyk 163, disperbyk 164, disperbyk 168, disperbyk 181, disperbyk 183 , disperbyk2000, disperbyk2001, disperbyk2150, disperbyk107, 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)), Easton EC-8715/A and Easton EC-8000/A (made by Ashkin Chemical Co., Ltd.); EFKA -5054, EFKA-5065 and EFKA-5066 (made by EFKA, Netherlands).

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，亦可在最終欲進行噴塗時添加。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，進一步調整到噴塗的黏度，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。The present invention may optionally add component (e) solvent to adjust the viscosity of the treatment agent in a range suitable for operation. The solvent can be added during the preparation of the ingredients, or it can be added at the end of the spraying. According to an embodiment of the present invention, the solvent is suitably added when the components are formulated, and further adjusted to the viscosity of the spray when the final coating is desired, for example, the solid content is in the range 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.

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。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, alkanes, aromatic hydrocarbons, ketones, esters, alcohols, a group consisting of ether alcohols and mixtures thereof.

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、甲苯及二甲苯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甲基乙基酮(MEK)、丙酮、甲基異丁基酮、環己酮及4-羥基-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)、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、單甲基醚丙二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***乙酸酯(CAC)、乙二醇單***(ECS)、丙二醇單甲醚、丙二醇單甲醚乙酸酯(PMA)及丙二醇單甲醚丙酸酯(PMP)及其混合物所組成的群組。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, toluene, and xylene, and mixtures thereof. The ketone solvent suitable for use in the present invention may be selected from, but not limited to, methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-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 formate, methyl acetate, ethoxyethyl acetate a group consisting of ethoxypropyl acetate, ethyl isobutyrate, monomethyl ether propylene glycol 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 ether, propylene glycol monomethyl ether acetate (PMA), and propylene glycol monomethyl ether propionate (PMP) And a group of mixtures thereof.

本發明之紫外線固化型處理劑可視需要包含組分(f)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於磷酸酯或有機矽烷偶合劑，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。The ultraviolet curable treatment agent of the present invention may optionally contain a component (f) adhesion promoter to further improve the adhesion of the treatment 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 can increase the contact area between the coating and the substrate, improve the wetting effect and lower the surface tension, and contribute 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, a phosphate ester or an organic decane coupling agent in an amount of from 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the components (a) and (c), preferably 0.2-2 parts by weight.

適用於UV塗料或UV油墨的磷酸酯較佳為磷酸酯丙烯酸酯，可選自但不限於甲基丙烯酸2-羥基乙基酯磷酸酯(2-Hydroxyethyl Methacrylate Phosphate)、三官能基丙烯酸酯磷酸酯(Trifunctional Acid Ester Phosphate)及其混合物所組成的組群。Phosphate esters suitable for use in UV coatings or UV inks are preferably phosphate ester acrylates, which may be selected from, but not limited to, 2-Hydroxyethyl Methacrylate Phosphate, trifunctional acrylate phosphates. (Trifunctional Acid Ester Phosphate) and a mixture of its mixtures.

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矽烷(vinyltrimethoxysilane)、2-(3,4環氧基環己基)乙基三甲氧基矽烷(2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane)、3-縮水甘油丙基三甲氧基矽烷(3-glycidoxypropyltrimethoxysilane)、3-(甲基丙烯醯氧)丙基三甲氧基矽烷(3-methacryloxypropyltrimethoxysilane)或N-苯基-3-胺丙基三甲氧基矽烷(N-phenyl-3-aminopropyltrimethoxysilane)或其混合物。Organic decane coupling agents suitable for use in the present invention such as, but not limited to, vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (2-(3,4-epoxycyclohexyl) )ethyltrimethoxysilane), 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane or N-phenyl-3-aminopropane N-phenyl-3-aminopropyltrimethoxysilane or a mixture thereof.

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)。Examples of commercially available adhesion promoters include: CD9050, CD9051, CD9053, and CD9054 (manufactured by SARTOMER); EM39 (manufactured by Changxing Chemical Co., Ltd.); KBM-303, KBM-403, KBM-503, KBM-573 , KBM-803, KBM-9103, and KBM-1003 (made by Shin-Etsu ShinEtsu).

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。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 between the coating and the substrate. It is especially suitable for 3C electronic products, cosmetics and home appliances that require high appearance and surface properties. And the surface coating and treatment of metal.

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。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 is, for example 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.

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：The treatment 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 administered via a method comprising the following steps:

(1)　選擇所需之(a)不飽和雙鍵之單體或寡聚物或其混合物及(c)熱塑性樹脂，視需要加入溶劑，攪拌混合；(1) selecting a desired monomer or oligomer of (a) unsaturated double bond or a mixture thereof and (c) a thermoplastic resin, optionally adding a solvent, and stirring and mixing;

(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，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；(2) Add (b) photoinitiator, add optional (d) additive, (e) solvent and (f) adhesion promoter, stir evenly, adjust to appropriate viscosity (800~2500 cps) to form a liquid polymerizable composition;

(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；(3) The liquid polymerizable composition obtained in the step (2) is diluted with a suitable solvent (viscosity of 50 cps or less), and is applied to a substrate in a suitable manner for surface treatment to form a coating;

(4)　視需要加熱以揮發溶劑，溫度控制於約50℃~70℃，於固定溫度下反應約1~5分鐘；(4) heating as needed to volatilize the solvent, the temperature is controlled at about 50 ° C ~ 70 ° C, the reaction at a fixed temperature for about 1 ~ 5 minutes;

(5)　視需要將底漆塗佈於由上述步驟而得之塗層上，形成另一塗層；及(5) applying a primer to the coating obtained by the above steps as needed to form another coating;

(6)　照射能量射線以使該等塗層固化。(6) Irradiating energy rays to cure the coatings.

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)或噴霧式塗布(spray coating)，較佳為噴霧式塗佈(噴塗)。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).

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500至1,200毫焦耳/平方公分(mJ/cm2 )，較佳係自600至1,000 mJ/cm2 。Preferably, the coating curing step of the step (6) is carried out by photopolymerization by irradiation of an energy ray, which refers to a light source of a certain range of wavelengths, preferably ultraviolet light (wavelength of 200 to 400 nm). . The irradiation intensity may be from 500 to 1,200 mJ/cm 2 (mJ/cm 2 ), preferably from 600 to 1,000 mJ/cm 2 .

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內容及所附申請專利範圍之範圍內。The following examples are intended to illustrate 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.

製system 備例1-10Preparation 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。The ultraviolet curable treatment agent of the present invention was formulated in accordance with the components and ratios listed in Table 1.

a1：六丙烯酸二季戊四醇酯單體(長興化工，EM265)A1: Dipentaerythritol hexaacrylate monomer (Changxing Chemical, EM265)

a2：脂肪族聚胺基甲酸酯六丙烯酸酯寡聚物(長興化工，6145-100)A2: Aliphatic polyurethane hexaacrylate oligomer (Changxing Chemical, 6145-100)

a3：季戊四醇三丙烯酸酯單體(長興化工，EM235)A3: pentaerythritol triacrylate monomer (Changxing Chemical, EM235)

a4：異癸基丙烯酸酯單體(長興化工，EM219)A4: isodecyl acrylate monomer (Changxing Chemical, EM219)

a5：脂肪族聚胺基甲酸酯二丙烯酸酯寡聚物(長興化工，611B-85)A5: Aliphatic polyurethane acrylate oligomer (Changxing Chemical, 611B-85)

a6：環氧丙烯酸酯寡聚物(長興化工，621-100)A6: epoxy acrylate oligomer (Changxing Chemical, 621-100)

a7：三丙烯酸三羥甲基丙烷酯單體(長興化工，EM231)A7: Trimethylolpropane triacrylate monomer (Changxing Chemical, EM231)

a8：甲基丙烯酸2-羥基乙酯單體(日本觸媒，HEMA)A8: 2-hydroxyethyl methacrylate monomer (Japanese catalyst, HEMA)

a9：聚酯丙烯酸酯寡聚物(Bomar Specialties，JL-106E)A9: Polyester acrylate oligomer (Bomar Specialties, JL-106E)

a10：聚酯丙烯酸酯寡聚物(Bomar Specialties，BE-112DP10)A10: Polyester acrylate oligomer (Bomar Specialties, BE-112DP10)

a11：異冰片基丙烯酸酯單體(長興化工，EM70)A11: isobornyl acrylate monomer (Changxing Chemical, EM70)

b1: 1-羥基環己基苯基酮(雙鍵化工，CHIVACURE 184)B1: 1-hydroxycyclohexyl phenyl ketone (double bond chemical, CHIVACURE 184)

b2: 2,2'-二甲基-1,2-二苯基乙烷-1-酮(雙鍵化工，CHIVACURE BDK)B2: 2,2'-dimethyl-1,2-diphenylethane-1-one (double bond chemical, CHIVACURE BDK)

c1：熱塑性丙烯酸樹脂(長興化工，7117-TS-50)C1: thermoplastic acrylic resin (Changxing Chemical, 7117-TS-50)

c2：熱塑性丙烯酸樹脂(長興化工，7329-TS-45)C2: thermoplastic acrylic resin (Changxing Chemical, 7329-TS-45)

c3：熱塑性丙烯酸樹脂(長興化工，7128-TB-50)C3: thermoplastic acrylic resin (Changxing Chemical, 7128-TB-50)

c4：熱塑性丙烯酸樹脂(長興化工，7329-XP-45)C4: Thermoplastic acrylic resin (Changxing Chemical, 7329-XP-45)

c5：熱塑性丙烯酸樹脂(長興化工，7119-TB-50)C5: thermoplastic acrylic resin (Changxing Chemical, 7119-TB-50)

c6：熱塑性丙烯酸樹脂(長興化工，7630)C6: Thermoplastic Acrylic Resin (Changxing Chemical, 7630)

c7：氯醋樹脂(威凱化學公司，Vinnol H14/36)C7: Chloroacetate resin (Weikai Chemical Company, Vinnol H14/36)

d1：潤濕劑(德國迪高公司，TEGO Wet270)D1: wetting agent (TEGO Wet270, Germany)

d2：平坦劑(荷蘭埃夫卡公司，EFKA3777)D2: Flat agent (Evka, EFKA3777, the Netherlands)

d3：含氟丙烯酸樹脂潤濕劑(畢克化學公司，BYK340)D3: Fluorinated acrylic resin wetting agent (BYK 340, BYK Chemical Company)

e1：二甲苯E1: xylene

e2：乙酸丁酯E2: butyl acetate

e3：乙二醇單丁醚E3: ethylene glycol monobutyl ether

e4：甲基異丁基酮E4: methyl isobutyl ketone

e5：單甲基醚丙二醇乙酸酯E5: monomethyl ether propylene glycol acetate

e6：甲苯E6: toluene

e7：環己酮E7: cyclohexanone

e8：甲基乙基酮E8: methyl ethyl ketone

e9：異丙醇E9: isopropanol

e10：乙酸乙酯E10: ethyl acetate

f1：3-(甲基丙烯醯氧)丙基三甲氧基矽烷(信越公司生產，KBM-503)F1: 3-(methacryloxy)propyltrimethoxydecane (manufactured by Shin-Etsu Company, KBM-503)

f2：2-羥基乙基甲基丙烯酸酯磷酸酯(長興化工，EM-39)F2: 2-hydroxyethyl methacrylate phosphate (Changxing Chemical, EM-39)

f3：三官能基丙烯酸酯磷酸酯(沙多瑪化學公司，CD9051)F3: trifunctional acrylate phosphate (Shado Chemical Co., CD9051)

實施例1Example 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，以空氣噴槍噴塗於PMMA塑膠基板上，接著於60℃的烘箱內進行3~5分鐘的預烤，塗膜厚度1~3微米，然後，經中壓水銀燈(400 mJ/cm2 )進行曝光。而後，噴塗UV電鍍底漆(長興化工製，ETERCURE8250U-9A)，接著於60℃的烘箱內進行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。Using the ultraviolet curable treatment agent of Preparation Example 1, if necessary, adjust the viscosity to the Iwata Cup for about 9 seconds, spray it on the PMMA plastic substrate with an air spray gun, and then pre-bake it in an oven at 60 ° C for 3 to 5 minutes. The film thickness was 1 to 3 μm, and then exposed to a medium pressure mercury lamp (400 mJ/cm 2 ). Then, spray UV plating primer (ETERCURE 8250U-9A, manufactured by Changxing Chemical Co., Ltd.), then pre-bake in an oven at 60 ° C for 5 to 10 minutes, and expose by medium pressure mercury lamp (800 mJ/cm 2 ). A substrate having a coating film is prepared at 10 to 15 μm.

實施例2Example 2

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PS塑膠基板。The composition and manufacturing method of the ultraviolet curable treatment agent are the same as those in the first embodiment, and the substrate is changed to a PS plastic substrate.

實施例3Example 3

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PC塑膠基板。The composition and manufacturing method of the ultraviolet curable treatment agent were the same as those in the first embodiment, and the substrate was changed to a PC plastic substrate.

實施例4Example 4

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。The composition and manufacturing method of the ultraviolet curable treatment agent were the same as those in the first embodiment, and the substrate was changed to an ABS plastic substrate.

實施例5Example 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。The ultraviolet curable treatment agent of Preparation Example 2 was used, and the production method and substrate selection were the same as in Example 1.

實施例6Example 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。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.

實施例7Example 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，以空氣噴槍噴塗於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℃的烘箱內進行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。Using the UV-curing treatment agent of Preparation Example 4, if necessary, adjust the viscosity to the Iwatani Cup with solvent for about 9 seconds, spray it on the PMMA plastic substrate with an air spray gun, apply a film thickness of 1 to 3 μm, and then spray a UV plating primer (Changxing Chemical system, ETERCURE 8250U-9A), followed by pre-baking in an oven at 60 ° C for 5 to 10 minutes, exposure by medium pressure mercury lamp (800 mJ/cm 2 ), primer thickness 10-15 μm, preparation of coating film The substrate.

實施例8Example 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岩田杯10秒左右，以空氣噴槍噴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60℃的烘箱內進行3~5分鐘的預烤，然後噴塗UV電鍍底漆(長興化工製，ETERCURE8250U-9A)，接著於60℃的烘箱內進行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。Using the ultraviolet curable treatment agent of Preparation Example 5, if necessary, adjust the viscosity to the Iwatani Cup with a solvent for about 10 seconds, and spray it on a nylon fiber composite substrate containing glass fibers with an air spray gun, and the thickness of the coating film is 1 to 3 μm, followed by 60 ° C. The oven is pre-baked for 3 to 5 minutes, then sprayed with UV plating primer (ETERCURE 8250U-9A, manufactured by Changxing Chemical Co., Ltd.), and then pre-baked in an oven at 60 ° C for 5 to 10 minutes. Medium pressure mercury lamp (800 mJ/cm 2 ) Exposure was carried out, and the thickness of the primer was 10 to 15 μm to prepare a substrate with a coating film.

實施例9Example 9

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，以空氣噴槍噴塗於PC塑膠基板上，接著於60℃的烘箱內進行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℃的烘箱內進行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。The ultraviolet curable treatment agent of Preparation Example 6 was used, and the viscosity was adjusted to the Iwata Cup by a solvent for about 9 seconds as needed, and sprayed on a PC plastic substrate with an air spray gun, followed by prebaking in an oven at 60 ° C for 3 to 5 minutes. Then, the film was exposed to a medium pressure mercury lamp (400 mJ/cm 2 ) to a 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 / cm 2 ), primer thickness 10 ~15 microns to prepare a substrate with a coating film.

實施例10Example 10

使用製備例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，以空氣噴槍噴塗於PC/玻纖複合基板上，塗膜厚度6~8微米，接著於60℃的烘箱內進行5分鐘的預烤，然後，經中壓水銀燈(800 mJ/cm2 )進行曝光。而後噴塗UV電鍍底漆(長興化工製，ETERCURE8250U-9A)，接著於60℃的烘箱內進行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。The ultraviolet curable treatment agent of Preparation Example 7 was used, and the viscosity was adjusted to a Iwatian cup for about 9 seconds with a solvent, and sprayed on a PC/glass composite substrate with an air spray gun at a coating thickness of 6 to 8 μm, followed by a temperature of 60 ° C. The oven was prebaked for 5 minutes in an oven, and then exposed to a medium pressure mercury lamp (800 mJ/cm 2 ). Then spray UV plating primer (Changxing Chemical, ETERCURE 8250U-9A), then pre-bake in a 60 ° C oven for 5 minutes, exposure by medium pressure mercury lamp (800 mJ / cm 2 ), primer thickness 10 ~ 15 Micron, a substrate with a coating film is prepared.

實施例11Example 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，以空氣噴槍噴塗於玻璃基板上，塗膜厚度1~3微米，接著於60℃的烘箱內進行5分鐘的預烤，然後，經中壓水銀燈(800 mJ/cm2 )進行曝光。而後噴塗UV電鍍底漆(長興化工製，ETERCURE8250U-9A)，接著於60℃的烘箱內進行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。The ultraviolet curable treatment agent of Preparation Example 8 was used, and the viscosity was adjusted to the Iwata Cup by a solvent for about 9 seconds as needed, and sprayed on a glass substrate with an air spray gun at a thickness of 1 to 3 μm, followed by an oven at 60 ° C. Pre-baked for a minute, then exposed to a medium pressure mercury lamp (800 mJ/cm 2 ). Then spray UV plating primer (Changxing Chemical, ETERCURE 8250U-9A), then pre-bake in a 60 ° C oven for 5 minutes, exposure by medium pressure mercury lamp (800 mJ / cm 2 ), primer thickness 10 ~ 15 Micron, a substrate with a coating film is prepared.

實施例12Example 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，以空氣噴槍噴塗於不鏽鋼基板上，接著於60℃的烘箱內進行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1~3微米。而後噴塗UV電鍍底漆(長興化工製，ETERCURE8250U-9A)，接著於60℃的烘箱內進行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。Using the ultraviolet curable treatment agent of Preparation Example 9, if necessary, the viscosity of the Iwata Cup was adjusted with a solvent for about 9 seconds, and sprayed on a stainless steel substrate with an air spray gun, followed by prebaking in an oven at 60 ° C for 5 minutes, and then, in the middle. The mercury lamp (800 mJ/cm 2 ) was exposed to light and the film thickness was 1 to 3 μm. Then spray UV plating primer (Changxing Chemical, ETERCURE 8250U-9A), then pre-bake in a 60 ° C oven for 5 minutes, exposure by medium pressure mercury lamp (800 mJ / cm 2 ), primer thickness 10 ~ 15 Micron, a substrate with a coating film is prepared.

實施例13Example 13

紫外線固化型處理劑、製造方式及基板選擇同實施例12，改變噴塗UV罩光漆(長興化工製，ETERCURE6763M-4)，接著於60℃的烘箱內進行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。The ultraviolet curable treatment agent, the manufacturing method and the substrate were selected in the same manner as in Example 12, and the UV-varnish varnish (manufactured by Changxing Chemical Co., Ltd., ETERCURE6763M-4) was changed, followed by pre-baking in an oven at 60 ° C for 5 minutes, and the medium-pressure mercury lamp. (800 mJ/cm 2 ) was exposed, and the thickness of the primer was 10 to 15 μm to prepare a substrate with a coating film.

實施例14Example 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，改變噴塗UV硬罩層(長興化工製，ETERCURE6776-3B)，接著於60℃的烘箱內進行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。The ultraviolet curable treatment agent and the manufacturing method are the same as those in the embodiment 12, the substrate is changed to a PC plastic substrate, and the UV hard cover layer (ETERCURE 6776-3B, manufactured by Changxing Chemical Co., Ltd.) is changed, and then pre-baked 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/cm 2 ) and a primer thickness of 10 to 15 μm.

實施例15Example 15

使用製備例10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，以空氣噴槍噴塗於PC塑膠基板上，接著於60℃的烘箱內進行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℃的烘箱內進行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。Using the ultraviolet curable treatment agent of Preparation Example 10, if necessary, the viscosity was adjusted to the Iwata Cup by a solvent for about 9 seconds, and sprayed on a PC plastic substrate with an air spray gun, followed by prebaking in an oven at 60 ° C for 3 to 5 minutes. Then, the film was exposed to a medium pressure mercury lamp (400 mJ/cm 2 ) to a 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 / cm 2 ), primer thickness 10 ~15 microns to prepare a substrate with a coating film.

實施例16Example 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。The ultraviolet curable treatment agent and the manufacturing method were the same as those in the fifteenth embodiment, and the substrate was changed to an ABS plastic substrate.

測試方法testing method

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。 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 100-mesh scraper, and then the tape was adhered and then torn at 90° to determine the peeling number.

外觀 ：利用肉眼檢視塗膜外觀。 Appearance : Use the naked eye to check the appearance of the film.

塗膜耐熱性 ：將上述實施例所製得之樣品放置80℃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。 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 observed for defects such as cracks and peeling.

根據上述實驗結果可知，使用本發明之紫外線固化型處理劑處理後之基材，不需再經由其他前處理之方法，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。According to the above experimental results, it is understood that the substrate treated with the ultraviolet curable treating agent of the present invention can impart desired adhesion to the coating film and the substrate without further pretreatment, and the resulting coating film appearance It is flat, flawless and heat resistant, which meets the needs of the industry.

Claims (15)

一種基材前處理紫外線固化型處理劑，其包含：(a)含至少一個雙鍵之丙烯酸酯單體、至少一個雙鍵之丙烯酸酯寡聚物或其混合物；(b)光起始劑；及(c)熱塑性樹脂，其選自由丙烯酸樹脂、氯醋樹脂、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；其中以100重量份組分(a)計，所述組分(b)之含量為0.5-20重量份，且組分(c)之含量為100-1,000重量份；其中該基材前處理紫外線固化型處理劑具有14.3-32.6%之固成份。 A substrate pretreatment ultraviolet curing type treating agent comprising: (a) an acrylate monomer containing at least one double bond, an acrylate oligomer of at least one double bond, or a mixture thereof; (b) a photoinitiator; And (c) a thermoplastic resin selected from the group consisting of acrylic resins, chloroacetic resins, chlorinated polyolefin resins, polyester resins, rosin resins, and mixtures thereof; wherein 100 parts by weight of component (a), The component (b) is contained in an amount of 0.5 to 20 parts by weight, and the component (c) is contained in an amount of 100 to 1,000 parts by weight; wherein the substrate pretreatment ultraviolet curing type treating agent has a solid content of 14.3 to 3.6%. . 如請求項1之紫外線固化型處理劑，其中以100重量份組分(a)計，組分(c)之含量為100-400重量份。 The ultraviolet curable treatment agent of claim 1, wherein the component (c) is contained in an amount of from 100 to 400 parts by weight based on 100 parts by weight of the component (a). 如請求項1之紫外線固化型處理劑，其中丙烯酸酯寡聚物選自由環氧丙烯酸酯、聚胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、聚丙烯酸酯、胺基丙烯酸酯及其混合物所組成之群組。 The ultraviolet curable treatment agent of claim 1, wherein the acrylate oligomer is selected from the group consisting of epoxy acrylate, polyurethane acrylate, polyester acrylate, polyacrylate, urethane, and mixtures thereof The group that makes up. 如請求項3之紫外線固化型處理劑，其中丙烯酸酯寡聚物選自由聚胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯及其混合物所組成之群組。 The ultraviolet curable treatment agent of claim 3, wherein the acrylate oligomer is selected from the group consisting of polyurethane acrylates, polyester acrylates, and mixtures thereof. 如請求項1之紫外線固化型處理劑，其中丙烯酸酯單體為具有至少1個官能團的丙烯酸酯單體。 The ultraviolet curable treatment agent of claim 1, wherein the acrylate monomer is an acrylate monomer having at least one functional group. 如請求項1之紫外線固化型處理劑，其中組份(c)熱塑性 樹脂是熱塑性丙烯酸樹脂。 The ultraviolet curable treatment agent of claim 1, wherein the component (c) is thermoplastic The resin is a thermoplastic acrylic resin. 如請求項6之紫外線固化型處理劑，其中組份(c)熱塑性丙烯酸樹脂包含一或多種具有大於20℃的玻璃化轉變溫度的丙烯酸樹脂。 The ultraviolet curable treatment agent of claim 6, wherein the component (c) the thermoplastic acrylic resin comprises one or more acrylic resins having a glass transition temperature of more than 20 °C. 如請求項6之紫外線固化型處理劑，其中組份(c)熱塑性丙烯酸樹脂包含一或多種具有大於60℃的玻璃化轉變溫度的丙烯酸樹脂。 The ultraviolet curable treatment agent of claim 6, wherein the component (c) the thermoplastic acrylic resin comprises one or more acrylic resins having a glass transition temperature of more than 60 °C. 如請求項6之紫外線固化型處理劑，其中組份(c)熱塑性樹脂包含一或多種具有70℃至150℃的玻璃化轉變溫度的丙烯酸樹脂。 The ultraviolet curable treatment agent of claim 6, wherein the component (c) thermoplastic resin comprises one or more acrylic resins having a glass transition temperature of 70 ° C to 150 ° C. 如請求項1之紫外線固化型處理劑，進一步包含組分(d)添加劑，以組分(a)與(c)合計100重量份計，組分(d)含量為0.05-1重量份。 The ultraviolet curable treatment agent of claim 1, further comprising the component (d) additive, wherein the component (d) 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). 如請求項10之紫外線固化型處理劑，其中組份(d)添加劑選自由潤濕劑、平坦劑、消泡劑、分散劑及其混合物所組成之群組。 The ultraviolet curable treatment agent of claim 10, wherein the component (d) additive is selected from the group consisting of a wetting agent, a flat agent, an antifoaming agent, a dispersing agent, and a mixture thereof. 如請求項1之紫外線固化型處理劑，進一步包含組份(e)溶劑。 The ultraviolet curable treatment agent of claim 1, further comprising a component (e) solvent. 如請求項1至12中任一項之紫外線固化型處理劑，進一步包含組份(f)密著促進劑，以組分(a)與(c)合計為100重量份計，其含量為0.1-5重量份。 The ultraviolet curable treatment agent according to any one of claims 1 to 12, further comprising a component (f) adhesion promoter, in an amount of 0.1 part by weight based on 100 parts by weight of the total of the components (a) and (c) - 5 parts by weight. 如請求項13之紫外線固化型處理劑，其中組份(f)密著促進劑選自由磷酸酯、有機矽烷偶合劑及其混合物所組成的群組。 The ultraviolet curable treatment agent of claim 13, wherein the component (f) adhesion promoter is selected from the group consisting of a phosphate ester, an organic decane coupling agent, and a mixture thereof. 如請求項1之紫外線固化型處理劑，其係用於前處理金屬、玻璃、塑膠或複合基材。 The ultraviolet curable treatment agent of claim 1, which is used for pretreatment of a metal, glass, plastic or composite substrate.
TW100110262A 2011-03-24 2011-03-24 Uv curable-type treating agent TWI487758B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW100110262A TWI487758B (en) 2011-03-24 2011-03-24 Uv curable-type treating agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW100110262A TWI487758B (en) 2011-03-24 2011-03-24 Uv curable-type treating agent

Publications (2)

Publication Number Publication Date
TW201239049A TW201239049A (en) 2012-10-01
TWI487758B true TWI487758B (en) 2015-06-11

Family

ID=47599403

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100110262A TWI487758B (en) 2011-03-24 2011-03-24 Uv curable-type treating agent

Country Status (1)

Country Link
TW (1) TWI487758B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI454548B (en) * 2012-08-01 2014-10-01 Eternal Materials Co Ltd Dual curable adhesive composition
TWI567144B (en) * 2015-01-16 2017-01-21 住華科技股份有限公司 Coating composition, and method of manufacturing coating layer of the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201102412A (en) * 2009-07-14 2011-01-16 Eternal Chemical Co Ltd UV curable color coating composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201102412A (en) * 2009-07-14 2011-01-16 Eternal Chemical Co Ltd UV curable color coating composition

Also Published As

Publication number Publication date
TW201239049A (en) 2012-10-01

Similar Documents

Publication Publication Date Title
CN102199377B (en) Ultraviolet curing processing agent
CN1206288C (en) UV curable paint compositions and method of making and applying same
KR101664735B1 (en) Anti-fingerprint hardcoating composition and anti-fingerprint hardcoating film using the same
TWI393753B (en) Uv curable color coating composition
TW201840750A (en) Active energy ray-curable hard coating agent, hard coating film, and laminate capable of forming a high surface tension coating film and creating a tight adhesion
CN111154383A (en) Radiation curing coating for household appliance metal plate and application thereof
JP3377301B2 (en) Thermoplastic norbornene-based resin molded article having hard coat layer and method for producing the same
TWI487758B (en) Uv curable-type treating agent
KR101403986B1 (en) Ultraviolet-curable coating composition and steel sheet using the same
CN102585579B (en) metal powder oriented resin composition
JP6353888B2 (en) Manufacturing method of substrate with printed layer
US7067462B2 (en) UV curable lubricant compositions
JP2008248084A (en) Ultraviolet ray hardenable topcoat composition, and article coated with the same
JP2020503419A (en) Photocurable adhesive compositions, cured products and uses thereof
CN101069883A (en) Hard resin-layer forming method
JP2004107653A (en) Coating material composition and article obtained by using the composition
JPH1192690A (en) Hard coat material composition and synthetic resin product treated therewith
JP2004107653A6 (en) Coating composition, and article obtained using the composition
JP5930261B2 (en) Metal surface coating composition and laminated molded product
JP2011026409A (en) Fingerprint-resistant curable resin composition and method for forming fingerprint-resistant coating film using the same
CN115820065B (en) High-brightness wear-resistant electrochemical aluminum coating and preparation method and application thereof
JP4078138B2 (en) Photocurable resin coating composition having antifouling property and easy cleaning property, and cured coating film
TWI782170B (en) Photocurable coating formulation and joint sealant comprising the same
CN115558401B (en) High-strength SPC floor UV (ultraviolet) curing coating and preparation method thereof
JP2004051749A (en) Photocurable resin coating composition and cured coated film