CN101275054A - Ultraviolet cured paint composition and preparation thereof - Google Patents

Ultraviolet cured paint composition and preparation thereof Download PDF

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CN101275054A
CN101275054A CN 200710073972 CN200710073972A CN101275054A CN 101275054 A CN101275054 A CN 101275054A CN 200710073972 CN200710073972 CN 200710073972 CN 200710073972 A CN200710073972 A CN 200710073972A CN 101275054 A CN101275054 A CN 101275054A
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uv
coating composition
urethane acrylate
curable coating
composition according
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CN 200710073972
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CN101275054B (en )
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萌 刘
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比亚迪股份有限公司
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The present invention provides an uv curing coating compound and its preparing method, wherein, the weight percentage of the uv curing coating compound is: polyurethane acrylate 35-60%, reactive diluents 10-20%, uv photoinitiator 3-5%, promoter 0-1.5%, fluoride-containing modified polyurethane acrylic 10-20%, organic solvent 10-40%. The protective layer formed by the uv curing coating compound has high rigidity and excellent wear resistance, especially fit for mobile phone keyboard.

Description

一种紫外光固化涂料组合物及其制备方法技术领域本发明属于紫外光固化涂料领域,特别涉及聚碳酸酯塑料表面涂层用的紫外光固化涂料。 One kind of UV-curable coatings and compositions TECHNICAL FIELD The present invention pertains to UV-curable coatings, more particularly to UV curable coatings with a surface coating of polycarbonate plastic. 背景技术制造手机键盘的涂漆包括色漆层和表面透明漆。 BACKGROUND paint comprising a paint manufacturing a phone keypad and a surface layer of lacquer. 目前手机键盘大多用聚碳酸酯塑料为底材,喷涂时一般以热塑性丙烯酸树脂作为色漆层,再喷涂一层紫外光固化的聚氨酯丙烯酸酯涂料作为保护涂层。 Currently most mobile phone keypad with polycarbonate plastic substrate is generally used as a thermoplastic acrylic resin paint coating layer, and then coating a layer of UV cured polyurethane acrylate coating as a protective coating. 色漆层是指所有带有颜色的漆层,比如,底漆是白色,中层漆是黑色,镭雕除去部分黑色的中层漆, 露出数字形状的白色底漆,这种手机按键的数字部分是白色,其余地方是黑色,最后再喷涂一层紫外光固化的聚氨酯丙烯酸酯涂料作为保护涂层。 Refers to all the color lacquer layer is colored lacquer, such as, primers are white, middle black paint, black middle portion of laser engraving paint removed, a white primer digital form, the digital part of the phone keys which are white, the rest is black, and finally to spray a layer of UV-curable urethane acrylate coating as a protective coating. 其中, 底漆和中层漆都是色漆。 Among them, middle primer and paint all paint. 在这种体系中,由于色漆需要喷涂两层或者两层以上,膜厚通常在15〜20um,是只喷一层色漆的手机机壳的2〜3倍,膜层过厚造成保护膜硬度下降;由于手机键盘与人手接触摩擦频繁,因此手机厂商对键盘上涂料的RCA纸带耐磨测试的要求是1000次,是手机机壳的耐磨测试要求的3倍。 In this system, since the need to spray paint over two or more layers, the thickness is usually 15~20um, only one layer of sprayed paint phone casing 2 to 3 times, the film is excessively thick protective film caused by hardness decreases; as a phone keypad frictional contact with the hands frequently, and therefore the requirements of paint manufacturers phone keyboard RCA tapes wear test 1000 times, a wear test requirements phone cases three times. 目前用于手机键盘表面喷涂的紫外光固化涂料大都采用聚氨酯丙烯酸酯作为主体树脂,再加入活性稀释单体调整体系黏度及交联密度,然后加入光引发剂、流平剂、防尘剂、哑光粉等调整表面效果,最后加入有机溶剂组合而成。 Phone keypad surface coating currently used UV-curable urethane acrylate coating mostly used as main resin, reactive diluent monomer added to adjust the crosslink density and viscosity of the system, then adding photoinitiator, leveling agents, anti dusting agents, dumb light adjustment powder surface effects, and finally adding an organic solvent combination. 这种涂料作为一般塑胶件表面保护层涂料时,其硬度和耐磨性能可达到要求,但其用在手机键盘上时,硬度与耐磨达不到要求。 When this coating as the surface protective layer coating of plastic parts in general, which can meet the requirements of hardness and wear resistance, but when it is used on a phone keypad, mainly the hardness and wear resistance. 一般解决的办法有提高配方体系中高官能团的聚氨酯丙烯酸酯的比例和添加无机粉末填料等方法来改善耐磨,例如CN1569992A中公开了一种聚酯涂料,在聚酯涂料中加入一定量的经有机表面处理剂处理后的纳米级功能粉体,该纳米级功能粉体包括纳米氧化钛、氧化硅、氧化锌、氧化镍、氧化铝、氧化铬、氧化锰中的一种或二种的组合来提高耐磨。 The solution is generally proportional urethane acrylate systems to improve the formulation of highly functional group and the addition of inorganic powder filler or the like to improve wear resistance, for example, CN1569992A discloses a polyester coating, the polyester is added in the amount of the organic coating over nano-functional powder after the surface treating agent, nanoscale powders comprising nano-function titanium oxide, silicon oxide, zinc oxide, nickel oxide, aluminum oxide, chromium oxide, manganese oxide, or a combination of two kinds to improve the wear. 虽然在一定程度上提高了产品的耐磨性能。 While increasing the wear resistance of the product to a certain extent. 但是由于高官能团的聚氨酯丙烯酸酯在紫外光作用下聚合时,固化收縮率比较大,在配方中的比例提高后,容易引起涂膜表面开裂及温度冲击试验不通过测试,而且无机粉末密度较大,容易引起涂料沉降结块,降低了涂料的存储性能。 However, due to highly functional urethane acrylate polymerizable group under UV irradiation, curing shrinkage ratio is relatively large, the ratio in the formulation is increased, the coating film surface prone to crack and temperature shock test does not pass the test, and greater density of the inorganic powder , prone to sedimentation blocking coating, reduces the storage properties of the coating. CN1777656A公开了一种水基耐磨涂料, 一种用硅酮树脂作为主体树脂的热固化水基涂料,其用来提高耐磨的发明点是添加氮化硼这种无机填料; 通过添加丙烯酸酯类,聚氨酯树脂(PU),氟聚合物是用来改善涂膜的柔韧性,无法在紫外光照射下固化,同时硅酮树脂为主体树脂的热固化一般烘烤温度在80摄氏度以上,而手机键盘一般都是丙烯腈-丁二烯-苯乙烯共聚物(ABS),超过80摄氏度的温度会引起尺寸形变;其次,手机键盘最外层喷涂膜厚在8〜10um,对漆膜表观要求高,加入氮化硼这种无机颗粒,容易使表面出现麻点,导致外观不良。 CN1777656A discloses a water-based abrasion resistant coating a body with a silicone resin as the thermosetting resin, water-based paints, which is used to improve the wear point of this invention is to add boron inorganic filler; by the addition of an acrylate , polyurethane resin (PU), fluoropolymer is used to improve the flexibility of the coating film can not be cured under ultraviolet radiation, while thermosetting silicone resin as a main resin is typically baked at a temperature above 80 degrees Celsius, while the phone keyboard generally acrylonitrile - butadiene - styrene copolymer (ABS), more than 80 degrees Celsius may cause the size of deformation; secondly, the film thickness of the outermost coating phone keypad 8~10um, the apparent requirement for the film high, the inorganic particles are boron nitride was added, pitting the surface easily, leading to poor appearance. 发明内容本发明的目的是提供一种紫外光固化涂料组合物,该涂料所形成的保护层具有较高的硬度和优异的耐磨性,尤其适用于手机键盘。 Object of the present invention is to provide a UV curable coating composition, the protective coating layer formed has high hardness and excellent wear resistance, especially for mobile phone keypad. 一种紫外光固化涂料组合物,该紫外光固化涂料组合物的重量百分含聚氨酯丙烯酸酯35%〜60% 活性稀释单体10%〜20% 紫外光引发剂3%〜5%助剂0%〜1.5% 氟素改性聚氨酯丙烯酸酯10%〜20% 有机溶剂10%〜40°/。 One kind of UV-curable coating composition, the coating weight of the UV-curable composition containing a urethane acrylate percentage of 35% ~ 60% reactive diluent monomer 10% ~ 20% UV photoinitiator 3% ~ 5% additive 0 % ~ 1.5% fluorine-modified urethane acrylate, 10% ~ 20% organic solvent 10% ~40 ° /. . 所述氟素改性聚氨酯丙烯酸酯为二官能度的脂肪族聚氨酯丙烯酸酯, 该聚氨酯丙烯酸酯的脂肪链的端基为氟原子。 The fluorine-modified urethane acrylate is an aliphatic difunctional urethane acrylate end groups of the aliphatic urethane acrylate chain is a fluorine atom. 氟素改性聚氨酯丙烯酸酯的分子结构式为:QCH?CF其中,两端为对称的氨酯丙烯酸酯单体,n=10~25,优选为11=20。 Molecular structure fluorine-modified urethane acrylate is: QCH CF wherein both ends of the urethane acrylate monomers symmetrical, n = 10 ~ 25, preferably 11 = 20?. 所述聚氨酯丙烯酸酯的分子量为6000~10000。 Molecular weight of the urethane acrylate of 6,000 to 10,000. 光引发剂为分子结构式中的羰基与碳原子相连的光引发剂。 Light photoinitiator agent in the molecular structure a carbonyl group attached to a carbon atom of the initiator. 所述活性稀释单体为己二醇二丙烯酸酯、三丙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二季戊四醇六丙烯酸酯中的一种或几种的混合。 The reactive diluent monomer is hexanediol diacrylate, trimethylol propane triacrylate, dipentaerythritol hexaacrylate mixture of tripropylene glycol diacrylate of one or more. 所述有机溶剂为甲苯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、正丁醇、环已酮、二甲苯、甲基异丁基甲酮、丙酮、乙二醇丁醚、乙二醇乙醚醋酸酯中的一种或者几种的混合。 The organic solvent is toluene, ethyl acetate, butyl acetate, isobutyl acetate, n-butanol, cyclohexanone, xylene, methyl isobutyl ketone, acetone, ethylene glycol butyl ether, ethylene glycol ethyl ether acetate mixing one or several of the ester. 所述助剂选自流平剂、防沉剂、分散剂、消泡剂中的一种或几种。 The additives selected from leveling agents, anti-settling agents, dispersing agents, one or more anti-foaming agent. 一种上述的紫外光固化涂料组合物的制备方法,包括将聚氨酯丙烯酸酯、氟素改性聚氨酯丙烯酸酯、活性稀释单体和有机溶剂相混合,搅拌均匀、静置,形成混合物,过滤得到紫外光固化涂料组合物。 A method for preparing the above UV-curable coating composition comprising a urethane acrylate, fluorine-modified urethane acrylate, reactive diluent monomer, and an organic solvent are mixed, stir and let stand, to form a mixture, and filtered to give an ultraviolet The photocurable coating composition. 优选地,混合物中还包括助剂。 Preferably, the mixture also includes additives. 所述聚氨酯丙烯酸酯是由分子结构中含有氨基甲酸酯链段和丙烯酸酯碳-碳长链的氨酯丙烯酸酯单体发生聚合反应制备得到的,氨酯丙烯酸酯单体的分子结构为:本发明制得的紫外光固化涂料组合物中含有部分氟素改性聚氨酯丙烯酸酯,在固化成膜时由于端基氟原子的存在,降低了涂层的表面张力,从而提高了耐磨性能;而且本发明无需加入无机填料,不会影响存储性。 The urethane acrylate containing a molecular structure of the urethane acrylate segments and carbon - carbon long chain monomer in the preparation of urethane acrylate obtained by polymerization reaction, the molecular structure of urethane acrylate monomers: prepared by the invention is UV-curable coating composition containing a fluorine-modified urethane acrylate portion, the end groups due to the presence of fluorine atoms in the film formation upon curing, lower the surface tension of the coating, thereby improving the wear resistance; Further according to the present invention without the addition of an inorganic filler, it will not affect the storability. 助剂中的紫外光引发剂用于引发聚合反应,微量流平剂和润湿分散剂用于调整涂膜表面效果。 Auxiliaries UV initiator used to initiate polymerization reactions, trace leveling agents and wetting agents dispersing effect for adjusting the coating surface. 理论上交联密度越大,耐磨性越好,但是交联密度的增加,会导致漆膜的内应力增加,使漆膜变脆,导致附着力不稳定,以及在高低温冲击下开裂。 Theory turned-link density greater, better wear resistance, but an increase in the crosslinking density, leads to an increase in film stress, so that the film becomes brittle, leading to unstable adhesion, and cracking at a temperature shock. 本发明制得的紫外光固化涂料组合物可作为手机键盘塑胶件多层喷涂体系的最外透明保护涂层。 Prepared by the invention is UV-curable coating composition can be used as a phone keypad outermost transparent plastic member multilayer coating system for the protection coating. 本发明制得的紫外光固化涂料组合物具有如下优点:在不提高配方固化时的交联密度和收縮率的前提下,使固化后涂层拥有超高的耐磨性及高硬度,同时不影响涂层的附着力,耐温度冲击性能和存储稳定性。 Prepared by the invention is UV-curable coating composition has the following advantages: no increase in the crosslinking density and the shrinkage upon curing of the formulation premise that the cured coating has a high wear resistance and high hardness, while not affect the coating adhesion, thermal shock resistance properties and storage stability. 具体实施方式下面对本发明作出进一步的说明。 DETAILED DESCRIPTION The following description is further made of the present invention. 本发明对稀释剂的种类没有特别的限定,可以为现有的紫外光固化涂料中使用的各种稀释剂。 The present invention is not particularly limited in the type of diluent, it may be various conventional diluents used in UV-curable coatings. 例如,所述稀释剂可以选自甲苯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、正丁醇、环已酮、二甲苯、甲基异丁基甲酮、丙酮、乙二醇丁醚、乙二醇乙醚醋酸酯中的一种或者几种的混合。 For example, the diluent may be selected from toluene, ethyl acetate, butyl acetate, isobutyl acetate, n-butanol, cyclohexanone, xylene, methyl isobutyl ketone, acetone, ethylene glycol butyl ether, ethylene or a mixture of several of glycol ether acetate. 本发明对光引发剂的种类没有特别的限定,可以为现有的紫外光固化涂料中使用的各种光引发剂。 The present invention is the kind of the optical initiator is not particularly limited, and may be used for a variety of conventional UV curable coatings photoinitiator. 例如,所述光引发剂可以选自Irgacure651, Irgacure184, Irgacure369, Irgacure2022, darocur1173中的一种或几种。 For example, the photoinitiator can be selected from Irgacure651, Irgacure184, Irgacure369, Irgacure2022, darocur1173 of one or more. 其中IHT-PI系列是中国国内商品,Irgacure, darocur系列是瑞士汽巴公司产品, 其牌号为本领域技术人员所公知。 IHT-PI series which is Chinese domestic goods, Irgacure, darocur series is the Swiss company Ciba products, the grade is known to those skilled in the art. 上述紫外光固化涂料组合物中所述的氟素改性聚氨酯丙烯酸酯为美国OMNOVA公司的PF-6320, PF-3320, PF-656, PF-6520中的至少一种。 The above-described UV-curable coating composition of the fluorine-modified urethane acrylate U.S. OMNOVA's PF-6320, PF-3320, PF-656, PF-6520 at least one of. 本发明对所述助剂的种类没有特别的限定,可以为现有的紫外光固化涂料中使用的各种助剂。 The present invention is not particularly limited in the kind of the adjuvant, various additives may be cured coatings used for conventional ultraviolet light. 例如,所述助剂为流平剂、防沉剂和分散剂中的一种或几种。 For example, the adjuvant is a leveling agent, one or more anti-settling agents and dispersing agents. 这些助剂的种类已为本领域技术人员所公知。 These types of adjuvants are known to those skilled in the art. 所述流平剂的种类和用量已为本领域技术人员所公知,例如所述流平剂可以选自EFKA3883、 EFKA3886、 EFKA3600、 BYK366, BYK333, BYK307、 DEG0410,德国Cognis的F41中一种或几种。 The leveling agent types and amounts known to those skilled in well-known, for example, the leveling agent may be selected EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, BYK307, DEG0410, Cognis Germany F41 one or several of the species. 其中EFKA系列是荷兰爱夫卡公司产品,BYK系列是BYK公司产品,DEGO系列是德国迪高公司产品, 以上其牌号为本领域技术人员所公知。 EFKA series which is 荷兰爱夫卡 the company's products, BYK BYK series is the company's products, DEGO series is the company's products in Germany Di high above the grade is known to those skilled in the art. 以紫外光固化涂料组合物总重量为基准,所述流平剂的含量为0-1.5重量%。 UV light to cure the coating on the total weight of the composition, the content of the leveling agent is 0 to 1.5 wt%. 所述消泡剂的种类和用量为本领域技术人员所公知,例如,所述消泡剂可以选自荷兰EFKA2527、 EFKA2040、德国Foamex 8050,815N中一种或几种。 The type and amount of defoamer known to those skilled in well-known, for example, antifoaming agents may be selected from the Netherlands EFKA2527, EFKA2040, Germany Foamex 8050,815N one or several. 以紫外光固化涂料组合物总重量为基准,所述防沉剂的含量为0-1.5重所述防沉剂的种类和用量为本领域技术人员所公知,例如,所述防沉剂可以选自德谦的Rheo229、 201p; 日本帝司巴隆6900-20X、 6900-HV中一种或几种。 UV light to cure the coating on the total weight of the composition, the anti-settling agent in an amount of 0 to 1.5 weight of the anti-settling agent types and amounts known to those skilled in the art, e.g., anti-settling agents may be selected from the since Deuchem of Rheo229, 201p; Teijin Division Barron 6900-20X, 6900-HV one or several. 以紫外光固化涂料组合物总重量为基准,所述防沉剂的含量为0-1.5重量%。 UV light to cure the coating on the total weight of the composition, the anti-settling agent in an amount of 0 to 1.5 wt%. 所述分散剂指任何能改善所述主体树脂在溶剂中分散状态的物质,如Kerper-602、 Kerper誦605、 Kerper630、 CFC-500HP、 CFC-510、 CFC-637和CFC-604S, Dispers 710中的一种或几种。 The dispersing agent refers to any substance capable of improving the resin body in a state dispersed in a solvent, such as 710 Kerper-602, Kerper recite 605, Kerper630, CFC-500HP, CFC-510, CFC-637 and CFC-604S, Dispers one or several. 其中Kerper系列为美国Kerper公司产品,CFC系列为法国CFC公司产品,Dispers系列为德国TEGO(迪高) 公司产品。 Which Kerper series for the US Kerper the company's products, CFC CFC series for the French company's products, Dispers series Germany TEGO (Tego) the company's products. 以紫外光固化涂料组合物总重量为基准,所述分散剂的含量为0-1.5重量%。 UV light to cure the coating on the total weight of the composition, the content of the dispersant is from 0 to 1.5 wt%. 所述活性稀释单体为本领域技术人员所公知,如己二醇二丙烯酸酯(HDDA)、三丙二醇二丙烯酸酯(TPGDA)、三羟甲基丙垸三丙烯酸酯(TMPTA)、 二季戊四醇六丙烯酸酯(DPHA)中的一种或几种的混合。 The reactive diluent monomers known to those skilled in the art, such as hexanediol diacrylate (of HDDA), tripropylene glycol diacrylate (of TPGDA), trimethylolpropane triacrylate embankment (of TMPTA), dipentaerythritol hexa mixing one or more acrylate (DPHA) in. 本发明用于手机键盘透明塑料件的紫外光固化涂料组合物的制备方法步骤为本领域的常规添加步骤:将占总体系35%〜60%的聚氨酯丙烯酸酯与占总体系10%〜20%的氟素改性聚氨酯丙烯酸酯以及占总体系10%〜40%的稀释溶剂混合,搅拌至充分溶解,得到第一混合物。 Conventional addition step preparation process steps of the present invention for a phone keypad of a transparent plastic member of UV curable coating compositions are known in the art: the total system of 35% ~ 60% urethane acrylate and 10% ~ 20% of the total system diluting solvent mixture of 10% ~ 40% of the fluorine-modified urethane acrylate and the total system, and stirred until fully dissolved, to obtain a first mixture. 将占总体系10〜20%的活性稀释单体加入上述第一混合物中,搅拌均匀后,密闭放置5〜8小时,形成第二混合物。 10-20% of the total system of the reactive diluent monomer added to the first mixture, after stirring uniformly, placed in a sealed 5 ~ 8 hours to form a second mixture. 再向第二混合物中加0.5%〜1.5%的该领域公知助齐1」,德国BYK公司的流平剂,荷兰EFKA公司的润湿分散剂,德国Cognis公司的消泡剂和3。 Was added into the second mixture of 0.5% ~ 1.5% of the known art together help 1 ", the German company BYK leveling agents, wetting Dutch company EFKA dispersants, defoamers and the German company Cognis 3. /。 /. 〜 5%的紫外光引发剂,高速搅拌至均匀,形成均一的胶体体系。 To 5% of the UV photoinitiator, a high speed stirred until homogeneous, to form a uniform colloidal systems. 降温,过滤静置得到用于手机键盘透明塑胶件的紫外光固化涂料组合物。 Cooling, filtration was allowed to stand to obtain UV-curable coating composition for a transparent plastic member of a phone keypad. 可以采用滤芯为lum的过滤机过滤。 Lum filter may be employed as the filtration filter. 将上述步骤得到的紫外光固化涂料组合物和稀释剂按1:0.8稀释,喷涂于已喷过三层色漆的手机键盘塑胶件上,采用45〜55t:下烘烤5〜8分钟, 然后经紫外光固化机固化,光照能量为800〜1200mj/cr^得到干膜厚度为8〜10pm的漆膜。 Obtained in the above step UV-curable coating composition and a diluent 1: 0.8 diluted to spray paint has been sprayed on the three pieces of plastic phone keypad, using 45~55t: 5 ~ 8 minutes baking, and then curing by UV curing machine, light energy 800~1200mj / cr ^ 8~10pm to give a dry film thickness of the film. 【实施例1】按如下步骤配制紫外光固化涂料组合物:(1) 聚氨酯丙烯酸酯树脂(日本合成化学产品,UV7605B),氟素改性聚氨酯丙烯酸酯(美国OMNONA产品PF-3320),与有机溶剂混合,分散均匀,形成第一混合物;有机溶剂为:甲苯、乙酸乙酯、乙酸丁酯、正丁醇、环己酮的混合物, 其中,甲苯:乙酸乙酯:乙酸丁酯:正丁醇:环己酮=6: 2: 3: 2: 1。 [Example 1] as follows formulated UV-curable coating composition comprising: (1) urethane acrylate resin (Nippon Synthetic Chemical Products, UV7605B), fluorine-modified urethane acrylate (U.S. OMNONA product PF-3320), and the organic solvent was mixed and dispersed uniformly to form a first mixture; organic solvent: toluene, ethyl acetate, butyl acetate, n-butanol, cyclohexanone mixture, wherein toluene: ethyl acetate: butyl acetate: n-butanol : cyclohexanone = 6: 2: 3: 2: 1. (2) 将活性稀释单体(国产的己二醇二丙烯酸酯HDDA)加入到第一混合物中,搅拌、静置,形成第二混合物;(3) 第二混合物中加入助剂,分散均匀后,过滤,滤液为紫外光固化涂料组合物。 (3) a second adjuvant was added, uniformly dispersed; (2) a reactive diluent monomer (made hexanediol diacrylate HDDA) was added to the first mixture, stirred, allowed to stand, form a second mixture The filtrate is an ultraviolet light curable coating composition. 其中,助剂为:光引发剂Irgacure369,流平剂德国Cognis的F41 ,润湿分散剂Dispers 710;各成分的重量百分含量如表1所示。 Wherein the adjuvant is: Irgacure 369 a photoinitiator, leveling agents F41 Cognis, Germany, wetting and dispersing agent Dispers 710; weight percent of the components shown in Table 1. 【实施例2】制备步骤同实施例1。 [Example 2] The same procedure as in Example 1. 其中,氟素改性聚氨酯丙烯酸酯为美国OMNOVA 公司的PF-6320;活性稀释单体为国产的二季戊四醇六丙烯酸酯DPHA;助剂为:光引发剂Irgacure184,流平剂德国DEGO410,润湿分散剂CFC-510;有机溶剂为:乙酸乙酯:正丁醇:环己酮:乙二醇乙醚醋酸酯的混合物, 其中,乙酸乙酯:正丁醇:环己酮:乙二醇乙醚醋酸酯=3: 1: 1: 2。 Wherein the fluorine-modified urethane acrylate U.S. OMNOVA's PF-6320; made reactive diluent monomer is dipentaerythritol hexaacrylate DPHA; auxiliaries: Irgacure 184 a photoinitiator, leveling agents Germany DEGO410, wetting and dispersing agent CFC-510; organic solvent: ethyl acetate: n-butanol: cyclohexanone: ethylene glycol ethyl ether acetate mixture, wherein the ethyl acetate: n-butanol: cyclohexanone: ethylene glycol ethyl ether acetate = 3: 1: 1: 2. 各成分的重量百分含量如表1所示。 Percentage by weight of each component shown in Table 1. 【实施例3】制备步骤同实施例1。 [Example 3] The same procedure as in Example 1. 其中,氟素改性聚氨酯丙烯酸酯为美国OMNOVA 公司的PF-6520;活性稀释单体为国产的三丙二醇二丙烯酸酯TPGDA;助剂为:光引发剂Irgacure184,流平剂德国DEGO410,润湿分散剂Kerper630; 其它同实施例1。 Wherein the fluorine-modified urethane acrylate U.S. OMNOVA's PF-6520; made reactive diluent monomer is tripropylene glycol diacrylate of TPGDA; auxiliaries: Irgacure 184 a photoinitiator, leveling agents Germany DEGO410, wetting and dispersing agents Kerper630; further in Example 1. 各成分的重量百分含量如表1所示。 Percentage by weight of each component shown in Table 1. 【实施例4】同实施例l,其中,各成分的重量百分含量如表1所示。 [Example 4] Example l with the embodiment, wherein the weight percentage of each component is shown in Table 1. 【比较例1】除将氟素改性聚氨酯丙烯酸酯PF-3320改为普通二官能团树脂德国拜耳的2258外,其余和实施例1相同。 [Comparative Example 1] except that the fluorine-modified urethane acrylate PF-3320 resin to the difunctional ordinary Bayer 2258, the remaining same manner as Example 1. 【比较例2】除将氟素改性聚氨酯丙烯酸酯PF-3320替换成主题树脂聚氨酯丙烯酸酯,其余同实施例1。 [Comparative Example 2] except that the fluorine-modified urethane acrylate Alternatively PF-3320 relating to the urethane acrylate resin, remaining the same as in Example 1. 实施例及比较例的各成分的紫外光固化涂料组合物的重量百分含量如表1所示。 Weight percentage of UV-curable coating composition of the respective components of Examples and Comparative Examples are shown in Table 1. 表1<table>table see original document page 13</column></row> <table>【性能测试】漆膜的测试方法如下。 Table 1 <table> table see original document page 13 </ column> </ row> <table> [Film performance tests] Test Method below. 铅笔硬度测试:使用铅笔硬度测试仪,三菱(UNI)硬度铅笔,硬度为2H,负载1千克,笔芯圆柱形,外露约3mm,尖端平整,铅笔与被测表面成45度,匀速移动10mm,分别在5个不同的部位进行测试。 Pencil hardness test: using a pencil hardness tester, Mitsubishi (UNI) hardness pencil hardness of 2H, 1 kg load, a cylindrical cartridge, exposed about 3mm, flat tip, and the measured surface pencil 45 degrees, uniform speed 10mm, It was tested at five different sites. 测试仪器:上海普申化工机械有限公司BY型铅笔硬度计。 Tester: Shanghai Pu Shen Chemical Machinery Co., BY type pencil hardness. 接受标准:2H铅笔测试时表面允许有轻微划痕,但未损伤涂层。 Acceptance criteria: when the surface to allow a slight 2H pencil scratch test, but did not damage the coating. RCA耐磨测试:使用RCA磨损测试仪,摩擦用纸带为11/16inchn800mm(纸带按照ASTM F2357-04的制造标准制造的),负载175 克,转速33圈/分钟;测试仪器:美国NTI公司7-1BB RCA磨耗试验机接受标准:摩擦1000圈后不可露出部品基材。 RCA abrasion tests: RCA wearing tester using the friction of the paper strip 11 / 16inchn800mm (tape manufactured according to the ASTM standard F2357-04 manufactured), 175 g load, speed 33 cycles / min; test equipment: NTI Company USA 7-1BB RCA abrasion tester acceptance criteria: friction ring 1000 is not exposed parts of the substrate. 温度冲击测试:将被测部品放置在温度冲击试验机中,〜40。 Thermal shock test: the parts to be tested is placed in a thermal shock tester, ~ 40. C环境中放置2小时,85°C环境中放置2小时,温度变化时间小于5分钟,共进行72 小时(18个循环),取出后常温下放置4小时。 Placing C environment for 2 hours, and 85 ° C for 2 hours ambient temperature variation less than 5 minutes, for a total of 72 hours (18 cycles), taken after 4 hours at room temperature. 测试仪器:上海宏凌H-TS-603温度冲击试验机接受标准:喷涂表面变色、褪色、涂层凸起、涂层脱落不可接受。 Tester: Shanghai HONGLING H-TS-603 temperature impact testing machine acceptance criteria: spraying the surface discoloration, fading, the coating projection, coating off unacceptable. 实施例及比较例所制成紫外光固化涂料组合物经紫外光固化后的漆膜的性能如下表2。 Examples and Comparative Examples are made by the UV curing properties after film UV curable coating composition in Table 2 below. 表2<table>table see original document page 14</column></row> <table>从表2中可以看出,本发明的紫外光固化涂料组合物实施例1~4的硬度和耐磨性能明显优于比较例1~2,同时并没有导致耐温度冲击性能的下降。 Table 2 <table> table see original document page 14 </ column> </ row> <table> As can be seen from Table 2, Examples 1 to 4, hardness and wear resistance of UV-curable coating composition of the present invention significantly better than Comparative Examples 1 and 2, while the thermal shock resistance did not lead to performance degradation.

Claims (12)

  1. 1. 一种紫外光固化涂料组合物,该紫外光固化涂料组合物的重量百分含量为: 聚氨酯丙烯酸酯35%~60% 活性稀释单体10%~20% 紫外光引发剂3%~5% 助剂0%~1.5% 氟素改性聚氨酯丙烯酸酯10%~20% 有机溶剂10%~40%。 A UV-curable coating compositions, the weight percentage of the UV-curable coating composition: Polyurethane acrylate 35% to 60% of reactive diluent monomer is 10% to 20% UV photoinitiator 3% to 5 % additive 0% to 1.5% fluorine-modified urethane acrylate, 10% to 20% organic solvent 10% to 40%.
  2. 2. 根据权利要求1所述的紫外光固化涂料组合物,其特征在于:所述氟素改性聚氨酯丙烯酸酯为二官能度的脂肪族聚氨酯丙烯酸酯,该聚氨酯丙烯酸酯的脂肪链的端基为氟原子。 The UV-curable coating composition according to claim 1, wherein: said fluorine-modified urethane acrylate is an aliphatic difunctional urethane acrylate end groups of the aliphatic chains of the urethane acrylate is a fluorine atom.
  3. 3. 根据权利要求2所述的紫外光固化涂料组合物,其特征在于:所述氟素改性聚氨酯丙烯酸酯的分子结构式为:<formula>formula see original document page 2</formula>其中,n=10~25。 3. The UV-curable coating composition according to claim 2, wherein: the molecular structure of the fluorine-modified urethane acrylate is: <formula> formula see original document page 2 </ formula> wherein, n- = 10 to 25.
  4. 4.根据权利要求1所述的紫外光固化涂料组合物,其特征在于:所述 The UV-curable coating composition according to claim 1, characterized in that: said
  5. 5. 根据权利要求1所述的紫外光固化涂料组合物,其特征在于:所述光引发剂为分子结构式中的羰基与碳原子相连的光引发剂。 The UV-curable coating composition according to claim 1, wherein: said light photoinitiator agent in the molecular structure a carbonyl group attached to a carbon atom of the initiator.
  6. 6. 根据权利要求1所述的紫外光固化涂料组合物,其特征在于:所述活性稀释单体为己二醇二丙烯酸酯、三丙二醇二丙烯酸酯、三羟甲基丙垸三丙烯酸酯、二季戊四醇六丙烯酸酯中的一种或几种的混合。 6. The UV-curable coating composition according to claim 1, wherein: said reactive diluent monomer is hexanediol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate embankment, mixing one or more of dipentaerythritol hexaacrylate in.
  7. 7. 根据权利要求1所述的紫外光固化涂料组合物,其特征在于:所述有机溶剂为甲苯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、正丁醇、环已酮、 二甲苯、甲基异丁基甲酮、丙酮、乙二醇丁醚、乙二醇乙醚醋酸酯中的一种或者几种的混合。 7. The UV-curable coating composition according to claim 1, wherein: the organic solvent is toluene, ethyl acetate, butyl acetate, isobutyl acetate, n-butanol, cyclohexanone, xylenes , methyl isobutyl ketone, acetone, glycol ether, glycol ether acetate or as a mixture of several of the ester.
  8. 8. 根据权利要求1所述的紫外光固化涂料组合物,其中,所述助剂选自流平剂、消泡剂、分散剂、防沉剂中的一种或几种。 8. The UV-curable coating composition according to claim 1, wherein said adjuvant is selected from leveling agents, defoaming agents, dispersants, anti-settling agent in one or more of.
  9. 9. 一种权利要求1所述的紫外光固化涂料组合物的制备方法,包括将聚氨酯丙烯酸酯、氟素改性聚氨酯丙烯酸酯、活性稀释单体和有机溶剂相混合,搅拌均匀、静置,形成混合物,过滤得到紫外光固化涂料组合物。 Preparation of UV-curable coatings 9. A composition according to claim 1, comprising a urethane acrylate, fluorine-modified urethane acrylate, reactive diluent monomer, and an organic solvent are mixed and uniformly stirred, allowed to stand, The mixture formed was filtered to obtain UV-curable coating composition.
  10. 10. 根据权利要求9所述的紫外光固化涂料组合物的制备方法,其特征在于:混合物中还包括助剂。 10. The UV light according to claim 9, said method for preparing a cured coating composition, wherein: the mixture comprises further additives.
  11. 11. 根据权利要求9所述的紫外光固化涂料组合物的制备方法,其特征在于:所述聚氨酯丙烯酸酯是由分子结构中含有氨基甲酸酯链段和丙烯酸酯碳-碳长链的氨酯丙烯酸酯单体发生聚合反应制备得到的。 11. A method of preparing a UV curable coating composition according to claim 9, wherein: said urethane acrylate and urethane acrylate segments by a molecular structure containing carbon - carbon long chain amino preparation of acrylate monomer in the polymerization reaction obtained.
  12. 12.根据权利要求ll所述的紫外光固化涂料组合物的制备方法,其特征在于:所述氨酯丙烯酸酯单体的分子结构为: 12. A method of preparing a UV curable coating composition according to claim ll, wherein: the molecular structure of the urethane acrylate monomers:
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CN102533067A (en) * 2011-07-01 2012-07-04 深圳市美丽华油墨涂料有限公司 Ultraviolet (UV) cured plastic coating
CN102020881B (en) 2009-09-16 2012-11-07 正美企业股份有限公司 Ultraviolet hardened coating composition and coating method thereof
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