CN104910756A - Modified nanometer titanium dioxide ultraviolet-curable coating - Google Patents

Modified nanometer titanium dioxide ultraviolet-curable coating Download PDF

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CN104910756A
CN104910756A CN201510236986.7A CN201510236986A CN104910756A CN 104910756 A CN104910756 A CN 104910756A CN 201510236986 A CN201510236986 A CN 201510236986A CN 104910756 A CN104910756 A CN 104910756A
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titanium dioxide
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郑端飞
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广德美涂士化工有限公司
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a modified nanometer titanium dioxide ultraviolet-curable coating. Raw materials for preparing the coating comprise polyurethane acrylate elastic prepolymer, epoxy acrylate, organosilicon modified acrylic resin, trimethylolpropane trimethacrylate, triethylene glycol dimethylacrylate, modified nanometer titanium dioxide, nanometer alumina, nanometer zinc oxide, nanometer silica, silicon nitride whisker, 1-hydroxy cyclohexyl phenyl ketone, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, a solvent, a leveling agent and a corrosion inhibitor. The modified nanometer titanium dioxide ultraviolet-curable coating has the advantages of high strength and good antibacterial property.

Description

一种改性纳米二氧化钛紫外光固化涂料 A modified titanium dioxide UV-curable coatings

技术领域 FIELD

[0001] 本发明涉及涂料技术领域,尤其涉及一种改性纳米二氧化钛紫外光固化涂料。 [0001] The present invention relates to coating technology, and in particular relates to a modified titanium dioxide UV-curable coatings.

背景技术 Background technique

[0002] 紫外光固化涂料是一种受光纤照射后,能在较短的时间内迅速发生物理和化学变化的高分子物质,与传统的自然干燥或热固化涂料相比,能量利用率高、适用热敏基材、无污染、成膜速度快、涂膜质量高和适合连续化大生产的涂料品质,符合当前世界各国日益重视环保的要求,被誉为环境友好型涂料。 [0002] UV-curable coating is irradiated with the latter by an optical fiber, high-molecular substance capable of physical and chemical changes occur in a short time rapidly, as compared to conventional natural drying or heat-curable coatings, high energy efficiency, suitable for heat-sensitive substrates, non-polluting, film speed, high coating quality and suitable for continuous mass production of paint quality, in line with the current world growing importance of environmental protection requirements, known as environment-friendly paint.

[0003] 随着人们环境意识日益增强,喜爱环保产品,紫外光固化涂料发展迅速,现已从最初的木材涂料发展到塑料装饰、金属部件涂装、医疗器械、电子元件、信息记录介质、感光印刷和光纤灯工业生产领域。 [0003] With growing environmental awareness, like environmental protection products, the rapid development of UV-curable coatings, has been developed from the initial to the plastic decorative wood coating, metal coating member, medical device, electronic component, the information recording medium, the photosensitive fiber optic lights and printing industrial production. 随着社会的发展,人们对涂料的性能提出了更高的要求,现有的涂料其强度和抗菌性不是很理想,在长期使用的过程中,容易受环境等多种因素的影响而失去其性能,因此制备一种强度高、抗菌性好的涂料是目前亟待解决的问题。 With the development of society, people on the properties of the coating put forward higher requirements, the existing paint and antibacterial strength is not very satisfactory, in the course of long-term use, it is easy affected by many factors of the environment and lose its performance, thus preparing a high strength, good antimicrobial coating is a serious problem.

发明内容 SUMMARY

[0004] 基于背景技术存在的技术问题,本发明提出了一种改性纳米二氧化钛紫外光固化涂料,其强度高,抗菌性好。 [0004] The technical problem is based on the background art, the present invention provides a titanium dioxide modified UV-curable coatings, high strength, good antibacterial properties.

[0005] 本发明提出的一种改性纳米二氧化钛紫外光固化涂料,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体35-65份、环氧丙烯酸酯10-25份、有机硅改性丙烯酸树脂5-15份、三羟甲基丙烷三甲基丙烯酸酯2-7份、二缩三乙二醇二甲基丙烯酸酯5-10份、改性纳米二氧化钛3-8份、纳米氧化铝2-8份、纳米氧化锌1-3份、纳米二氧化硅2-6份、氮化硅晶须2-5份、1-羟基环己基苯基甲酮0.3-1份、安息香双甲醚1-3份、2-羟基-2-甲基-1-苯基-1-丙酮2-5份、2,4,6-三甲基苯甲酰基-二苯基氧化膦0.5-2份、溶剂5_20份、流平剂0.8-1.8份、缓蚀剂1-1.8份。 [0005] The present invention proposes a modified titanium dioxide UV-curable coating material which comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 35-65 parts, 10-25 parts of an epoxy acrylate, an organic 5-15 parts of silicon-modified acrylic resin, 2-7 parts of trimethylol propane trimethacrylate, 5-10 parts of triethylene glycol dimethacrylate, modified titanium dioxide 3-8 parts, 2-8 parts by nano alumina, nano zinc oxide parts 1-3, 2-6 parts by nano silica, 2-5 parts of silicon nitride whiskers, 1-hydroxy cyclohexyl phenyl ketone 0.3-1 parts, benzoin 1-3 parts of bis ether, 2-methyl-1-phenyl-2-5 parts of 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 0.5 2 parts of 5_20 parts solvent, 0.8 to 1.8 parts of a leveling agent, corrosion inhibitor 1-1.8 parts.

[0006] 优选地,其原料中,聚氨酯丙烯酸酯弹性预聚体、环氧丙烯酸酯、有机硅改性丙烯酸树脂、三羟甲基丙烷三甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯的重量比为40-60:13-22:8-15:3-6:7_10ο [0006] Preferably, the raw material, the elastomeric polyurethane acrylate prepolymer, epoxy acrylate, silicone-modified acrylic resin, trimethylol propane trimethacrylate, triethylene glycol dimethacrylate acrylate weight ratio of 40-60: 13-22: 8-15: 3-6: 7_10ο

[0007] 优选地,其原料中,改性纳米二氧化钛、纳米氧化铝、纳米氧化锌、纳米二氧化硅、氮化硅晶须的重量比为4-7:3-6:1.8-2.8:4-6:3_5。 [0007] Preferably, the raw material, the modified titanium dioxide, nano alumina, nano zinc oxide, nano-silicon dioxide, silicon nitride whiskers weight ratio of 4-7: 3-6: 1.8-2.8: 4 -6: 3_5.

[0008] 优选地,其原料中,1-羟基环己基苯基甲酮、安息香双甲醚、2-羟基-2-甲基-1-苯基-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦的重量比为0.5-0.9: [0008] Preferably, the raw material, 1-hydroxy cyclohexyl phenyl ketone, benzoin methyl ether bis, 2-methyl-1-phenyl-1-propanone, 2,4,6-tris methylbenzoyl - diphenyl phosphine oxide weight ratio of 0.5 to 0.9:

1.3-2.7:2.9-4.5:1-2。 1.3-2.7: 2.9-4.5: 1-2.

[0009] 优选地,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体48-53份、环氧丙烯酸酯18-21份、有机硅改性丙烯酸树脂10-13份、三羟甲基丙烷三甲基丙烯酸酯4-5份、二缩三乙二醇二甲基丙烯酸酯8-9份、改性纳米二氧化钛5-6.3份、纳米氧化铝4-5.6份、纳米氧化锌2-2.5份、纳米二氧化娃4.7-5.6份、氮化娃晶须3.6-4.5份、1-轻基环己基苯基甲酮0.6-0.8份、安息香双甲醚1.8-2.3份、2-羟基-2-甲基-1-苯基-1-丙酮3.6-4.2份、2,4,6-三甲基苯甲酰基-二苯基氧化膦1.3-1.7份、溶剂10-17份、流平剂1-1.5份、缓蚀剂1.3-1.7份。 [0009] Preferably, the raw material comprising the following components in parts by weight: Flexible polyurethane acrylate prepolymer 48-53 parts, 18-21 parts epoxy acrylate, 10-13 parts of a silicone-modified acrylic resin, bayerite methyl propane trimethacrylate parts 4-5, 8-9 parts of triethylene glycol dimethacrylate, modified parts titanium dioxide 5-6.3, 4-5.6 parts by nano alumina, nano zinc oxide 2 -2.5 parts, baby dioxide nano 4.7-5.6 parts 3.6-4.5 parts baby nitride whiskers, 1- light cyclohexyl phenyl ketone 0.6 to 0.8 parts, 1.8 to 2.3 parts of benzoin methyl ether bis, 2-hydroxy 2-methyl-1-phenyl-3.6-4.2 parts of 2,4,6-trimethyl benzoyl - 1.3-1.7 parts of diphenyl phosphine oxide, 10-17 parts of a solvent, a leveling 1-1.5 parts agent, 1.3-1.7 parts of a corrosion inhibitor.

[0010] 优选地,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体50份、环氧丙烯酸酯20份、有机硅改性丙烯酸树脂12份、三羟甲基丙烷三甲基丙烯酸酯4.6份、二缩三乙二醇二甲基丙烯酸酯8.7份、改性纳米二氧化钛5.8份、纳米氧化铝5份、纳米氧化锌 [0010] Preferably, the raw material comprising the following components in parts by weight: Flexible polyurethane acrylate prepolymer 50 parts, 20 parts epoxy acrylate, 12 parts of silicone-modified acrylic resin, trimethylol propane trimethacrylate acrylate, 4.6 parts, 8.7 parts of triethylene glycol dimethacrylate, 5.8 parts of modified titanium dioxide, 5 parts of nano alumina, nano zinc oxide

2.2份、纳米二氧化硅5份、氮化硅晶须4份、1-羟基环己基苯基甲酮0.65份、安息香双甲醚2.1份、2-羟基-2-甲基-1-苯基-1-丙酮4份、2,4,6-三甲基苯甲酰基-二苯基氧化膦1.5份、溶剂13份、流平剂1.2份、缓蚀剂1.5份。 2.2 parts, 5 parts of nano-silica, silicon nitride whiskers, 4 parts of 1-hydroxy cyclohexyl phenyl ketone 0.65 parts, 2.1 parts of benzoin methyl ether bis, 2-hydroxy-2-methyl 4 parts of 1-propanone, 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 1.5 parts, 13 parts solvent, 1.2 parts of a leveling agent, 1.5 parts of a corrosion inhibitor.

[0011] 优选地,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯-2,4- 二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,升温至80-95°C,反应6-8h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2-丁基-2-乙基-1,3-丙二醇,升温至80-95°C,反应2-5h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应10-15h,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 [0011] Preferably, the modified titanium dioxide prepared according to the following process: under the protection of nitrogen gas, toluene-2,4-diisocyanate dilaurate and di-n-xylene into Dingjixijia mixed, then added titanium dioxide dispersion uniformly heated to 80-95 ° C, 6-8h the reaction, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; and a modified titanium dioxide was added xylene, 2-butyl-2- ethyl-1,3-propanediol, warmed to 80-95 ° C, the reaction 2 to 5h, and then p-toluenesulfonic acid and vinyltriethoxysilane, 10-15h reaction, after the reaction was filtered, washed, and dried to obtain the modified titanium dioxide.

[0012] 优选地,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯-2,4- 二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,升温至90°C,反应7.5h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2-丁基-2-乙基-1,3-丙二醇,升温至85°C,反应3h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应12h,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 [0012] Preferably, the modified titanium dioxide prepared according to the following process: under the protection of nitrogen gas, toluene-2,4-diisocyanate dilaurate and di-n-xylene into Dingjixijia mixed, then added titanium dioxide dispersion uniformly heated to 90 ° C, 7.5h the reaction, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; titanium dioxide primary modification of xylene was added, was added 2-butyl-2-ethyl - 1,3-propanediol, warmed to 85 ° C, the reaction 3h, then p-toluenesulfonic acid and vinyl triethoxysilane, reaction 12h, after the reaction was filtered, washed, and dried to obtain the modified titanium dioxide.

[0013] 优选地,在改性纳米二氧化钛的制备过程中,甲苯_2,4-二异氰酸酯和纳米二氧化钛的摩尔比为4-5:1 ;优选地,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为 [0013] Preferably, during the preparation of the modified titania nanoparticles, the molar ratio of toluene diisocyanate and _2,4- titanium dioxide is 4-5: 1; preferably, toluene diisocyanate and _2,4- nano the molar ratio of titanium dioxide is

4.3-4.8:1 ;优选地,甲苯-2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为4.6:1。 4.3-4.8: 1; molar ratio is preferably, toluene-2,4-diisocyanate, and titanium dioxide of 4.6: 1.

[0014] 优选地,加入到二甲苯中的一次改性纳米二氧化钛、2-丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5-6:6-8 ;优选地,加入到二甲苯中的一次改性纳米二氧化钦、2_ 丁基-2-乙基_1,3-丙二醇、乙稀基二乙氧基娃烧的摩尔比为1:5.4-5.8:6.6-7.5 ;优选地,加入到二甲苯中的一次改性纳米二氧化钛、2- 丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5.5: 7。 [0014] Preferably, the primary was added to the xylene-modified titanium dioxide, 2-butyl-2-ethyl-1,3-propanediol, vinyltriethoxysilane molar ratio of 1: 5-6 : 6-8; molar ratio is preferably added to a modified nano-silica in xylene Chin, 2_ _1,3- butyl-propanediol, ethylene group diethoxy baby is burned 1: 5.4-5.8: 6.6-7.5; preferably, added to a modified titanium dioxide in xylene, 2-butyl-2-ethyl-1,3-propanediol, vinyltriethoxysilane molar ratio of 1: 5.5: 7.

[0015] 优选地,所述溶剂为异丁醇、醋酸乙酯、甲苯、醋酸丁酯、丙二醇甲醚、甲基异丁基酮中的一种或者多种的组合。 [0015] Preferably, the solvent is isobutanol, ethyl acetate, toluene, butyl acetate, propylene glycol methyl ether, a solution of methyl isobutyl ketone, or any combination thereof.

[0016] 本发明中,所述改性纳米二氧化钛紫外光固化涂料,可以按照常规的紫外光固化涂料制备工艺,将各原料混合均匀后得到。 [0016] In the present invention, the titanium dioxide-modified UV-curable coatings, can be prepared according to a conventional UV-curable coating process, the respective raw materials obtained by mixing uniformly.

[0017] 本发明中,选择了聚氨酯丙烯酸酯弹性预聚体、环氧丙烯酸酯、有机硅改性丙烯酸树脂作为主要物质,并添加了三羟甲基丙烷三甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯作为活性稀释剂,调整了各组分的用量比,使涂料结合了各物质的优势,赋予涂料优异的附着力、柔韧性、耐磨性、耐热性和耐药性;改性纳米二氧化钛、纳米氧化铝、纳米氧化锌、纳米二氧化硅、氮化硅晶须配合作为填料,并控制了各填料的含量,使其在体系中分散均匀,提高了涂料的强度的同时并赋予涂料优异的抗菌性,并且能阻隔紫外线和红外线,提高了涂料的耐候性和耐热性;优选方式中,改性纳米二氧化钛通过有机改性,改变了其表面的亲水性,变为了亲油性,提高了与涂料中有机物的相容性,使其在涂料中分散更加均匀,提高了纳米二氧化钛的补强作用,且将 [0017] In the present invention, the selected elastic polyurethane acrylate prepolymer, epoxy acrylate, silicone-modified acrylic resin as a main material, and adding trimethylol propane trimethacrylate, dipropylene triacetate hexanediol dimethacrylate as a reactive diluent, by adjusting the ratio of the components, the coating combines the advantages of each substance, gives excellent paint adhesion, flexibility, abrasion resistance, heat resistance and sex; modified nano titanium dioxide, nano alumina, nano zinc oxide, nano-silicon dioxide, silicon nitride with whiskers as a filler and to control the content of each filler dispersed uniformly in the system, the strength of the coating simultaneously coating and impart excellent antibacterial properties, and can block ultraviolet and infrared, to improve the heat resistance and weather resistance of the coating; preferred embodiment, the titanium dioxide modified by organic modification, change hydrophilicity of its surface, becomes lipophilicity, improved compatibility with organic coating, the more uniformly dispersed in the coating material to improve the reinforcing effect of the titanium dioxide, and the 双键引入到了改性纳米二氧化钛分子中,其作为一种活性单体,能参与体系的光聚合作用,形成有机-无机杂化结构,提高了在涂料中的强度、硬度、耐磨性、抗菌性和稳定性。 Double bond into the molecules modified titanium dioxide, which is used as a reactive monomer, can participate in the photopolymerization system, forming an organic - inorganic hybrid structure, the strength in the coating, the hardness, wear resistance, antibacterial and stability.

具体实施方式 Detailed ways

[0018] 下面,通过具体实施例对本发明的技术方案进行详细说明。 [0018] Next, a detailed description of the technical solution of the present invention through specific embodiments.

[0019] 在具体实施例中,本发明提出的一种改性纳米二氧化钛紫外光固化涂料,其原料中,聚氨酯丙烯酸酯弹性预聚体的重量份可以为35、36、38、39、42、43、46、48、49、49.3、52、53、56、58、59、59.3、61、62、63、64.5、65 份;环氧丙烯酸酯的重量份可以为10、12、13、15、18,19,19.3、21、23、23.4,24,24.6、25份;有机硅改性丙烯酸树脂的重量份可以为5、6、7、8,8.6、9、9.3、10、10.3、11、11.3、12、12.6、13、13.4、14、14.6、15 份;三羟甲基丙烷三甲基丙烯酸酯的重量份可以为2,2.3,2.8、3、3.4、4、4.6、5、5.3、6、6.7、7份;二缩三乙二醇二甲基丙烯酸酯的重量份可以为5、6、7、8、8.6、9、9.3,9.8、10份;改性纳米二氧化钛的重量份可以为3、4、5、6、6.3、7、7.5、8份;纳米氧化铝的重量份可以为2、2.3,2.6,2.8、3、3.4、4、4.6、5、5.3、6、6.7、7、7.6、8 份;纳米氧化锌的重量份可以为Ul.2,1 [0019] In a particular embodiment, the present invention proposes a modified titanium dioxide UV-curable coatings, in which the raw material, parts by weight of elastomeric polyurethane acrylate prepolymer may be 35,36,38,39,42, 43,46,48,49,49.3,52,53,56,58,59,59.3,61,62,63,64.5,65 parts; parts by weight of an epoxy acrylate may 10,12,13,15, 18,19,19.3,21,23,23.4,24,24.6,25 parts; parts by weight of silicone modified acrylic resin may be 5,6,7,8,8.6,9,9.3,10,10.3,11, 11.3,12,12.6,13,13.4,14,14.6,15 parts; parts by weight of trimethylol propane trimethacrylate may be 2,2.3,2.8,3,3.4,4,4.6,5,5.3, 6,6.7,7 parts; parts by weight of triethylene glycol dimethacrylate may be 5,6,7,8,8.6,9,9.3,9.8,10 parts; parts by weight of the modified titania nanoparticles can parts of 3,4,5,6,6.3,7,7.5,8; parts by weight of nano-alumina may be 2,2.3,2.6,2.8,3,3.4,4,4.6,5,5.3,6,6.7, 7,7.6,8 parts; parts by weight of nano-zinc oxide may be Ul.2,1 .3,1.56,1.8、2、2.3、 .3,1.56,1.8,2,2.3,

2.6,2.68,2.8,2.86、3 份;纳米二氧化硅的重量份可以为2,2.3,2.6,2.85,3,3.4,3.7、4、4.6、5、5.3,5.8、6 份;氮化硅晶须的重量份可以为2,2.3,2.6,2.87,3,3.4、4、4.6、5 份;1-羟基环己基苯基甲酮的重量份可以为0.3,0.6,0.75,0.8,0.86,0.9,0.94、1份;安息香双甲醚的重量份可以为1、1.2,1.3,1.56,1.8,1.89,2,2.3,2.5,2.64,2.8,2.86,2.9,2.94、3份;2-羟基-2-甲基-1-苯基-1-丙酮的重量份可以为2、2.3,2.6,2.85,3,3.4,3.7、4、 2.6,2.68,2.8,2.86,3 parts; parts by weight of nano silica can be 2,2.3,2.6,2.85,3,3.4,3.7,4,4.6,5,5.3,5.8,6 parts; silicon parts by weight of the whiskers may 2,2.3,2.6,2.87,3,3.4,4,4.6,5 parts; 1-hydroxycyclohexyl phenyl ketone may be 0.3,0.6,0.75,0.8,0.86 parts by weight, 0.9,0.94,1 parts; dimethoxybenzoin parts by weight of parts may 1,1.2,1.3,1.56,1.8,1.89,2,2.3,2.5,2.64,2.8,2.86,2.9,2.94,3; hydroxy -2- parts by weight of methyl-1-phenyl-2,2.3,2.6,2.85,3,3.4,3.7,4 may be,

4.5,4.68,4.8,4.89,4.93、5份;2,4,6-三甲基苯甲酰基-二苯基氧化膦的重量份可以为 4.5,4.68,4.8,4.89,4.93,5 parts; 2,4,6-trimethyl benzoyl - diphenyl-phosphine oxide may be parts by weight

0.5,0.6,0.68,0.8,0.9、1、1.2,1.3,1.56,1.8,1.86,1.9,1.94、2 份;溶剂的重量份可以为 0.5,0.6,0.68,0.8,0.9,1,1.2,1.3,1.56,1.8,1.86,1.9,1.94,2 parts; parts by weight of the solvent may be

5、6、7、8、8.6、9、9.3、10、10.6、11、11.3、12、12.6、13、13.4、15、16、18、19、19.3、20 份;流平剂的重量份可以为0.8,0.9、1、1.2、1.3、1.35、1.4、1.46、1.5、1.56、1.6、1.68、1.7、1.75、 5,6,7,8,8.6,9,9.3,10,10.6,11,11.3,12,12.6,13,13.4,15,16,18,19,19.3,20 parts; parts by weight of leveling agent may be as 0.8,0.9,1,1.2,1.3,1.35,1.4,1.46,1.5,1.56,1.6,1.68,1.7,1.75,

1.8 份;缓蚀剂的重量份可以为1、1.2、1.3、1.35、1.4、1.46、1.5、1.53、1.6、1.68、1.7、 1.8 parts; parts by weight of a corrosion inhibitor may be 1,1.2,1.3,1.35,1.4,1.46,1.5,1.53,1.6,1.68,1.7,

1.74、1.8 份。 1.74,1.8 copies.

[0020] 实施例1 [0020] Example 1

[0021] 本发明提出的一种改性纳米二氧化钛紫外光固化涂料,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体35份、环氧丙烯酸酯25份、有机硅改性丙烯酸树脂5份、三羟甲基丙烷三甲基丙烯酸酯7份、二缩三乙二醇二甲基丙烯酸酯5份、改性纳米二氧化钛8份、纳米氧化铝2份、纳米氧化锌3份、纳米二氧化硅2份、氮化硅晶须5份、1-羟基环己基苯基甲酮0.3份、安息香双甲醚3份、2-羟基-2-甲基-1-苯基-1-丙酮2份、2,4,6-三甲基苯甲酰基-二苯基氧化膦2份、醋酸丁酯5份、流平剂1.8份、缓蚀剂I份; [0021] The present invention proposes a modified titanium dioxide UV-curable coating material which comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 35 parts, 25 parts of epoxy acrylate, silicone-modified acrylate 5 parts of a resin, 7 parts of trimethylolpropane trimethacrylate, 5 parts of triethylene glycol dimethacrylate, 8 modified parts titanium dioxide, 2 parts of nano alumina, nano zinc oxide 3 parts, 2 parts of nano-silica, silicon nitride whisker, 5 parts of 1-hydroxy cyclohexyl phenyl ketone 0.3 parts, 3 parts of benzoin methyl ether bis hydroxy-2-methyl-1-phenyl-1 2 parts of acetone, 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 2 parts, 5 parts of butyl acetate, 1.8 parts of a leveling agent, parts I inhibitor;

[0022] 其中,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯-2,4- 二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,其中,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为4.6:1,然后升温至90°C,反应7.5h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2- 丁基-2-乙基-1,3-丙二醇,升温至85°C,反应3h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应12h,其中,一次改性纳米二氧化钛、2-丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5.5: 7,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 [0022] wherein the modified titanium dioxide prepared according to the following process: under the protection of nitrogen gas, toluene-2,4-diisocyanate dilaurate and di-n Dingjixijia into mixed xylenes, followed by addition of titanium dioxide uniformly dispersed wherein the molar ratio of toluene diisocyanate and _2,4- titanium dioxide of 4.6: 1, and then warmed to 90 ° C, 7.5h the reaction, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; and a modified titanium dioxide of xylene was added, was added 2-butyl-1,3-propanediol, warmed to 85 ° C, the reaction 3h, then p-toluenesulfonic acid and vinyltriethoxysilane the reaction 12h, wherein the molar ratio of primary-modified titanium dioxide, 2-butyl-2-ethyl-1,3-propanediol, vinyltriethoxysilane is 1: 5.5: 7, after the reaction was filtered , washed, and dried to obtain the modified titanium dioxide.

[0023] 实施例2 [0023] Example 2

[0024] 本发明提出的一种改性纳米二氧化钛紫外光固化涂料,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体65份、环氧丙烯酸酯10份、有机硅改性丙烯酸树脂15份、三羟甲基丙烷三甲基丙烯酸酯2份、二缩三乙二醇二甲基丙烯酸酯10份、改性纳米二氧化钛3份、纳米氧化铝8份、纳米氧化锌I份、纳米二氧化硅6份、氮化硅晶须2份、1-羟基环己基苯基甲酮I份、安息香双甲醚I份、2-羟基-2-甲基-1-苯基-1-丙酮5份、2,4,6-三甲基苯甲酰基-二苯基氧化膦0.5份、异丁醇12份、醋酸乙酯8份、流平剂0.8份、缓蚀剂 [0024] The present invention proposes a modified titanium dioxide UV-curable coating material which comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 65 parts, 10 parts of epoxy acrylate, silicone-modified acrylate 15 parts of resin, 2 parts of trimethylolpropane trimethacrylate, 10 parts of triethylene glycol dimethacrylate, 3 parts of modified titanium dioxide, 8 parts by nano alumina, nano zinc oxide parts I, nano-silica 6 parts, 2 parts of silicon nitride whiskers, 1-hydroxy cyclohexyl phenyl ketone parts I, I dimethoxybenzoin parts of 2-methyl-1 -phenyl- 1 5 parts of acetone, 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 0.5 parts of isobutanol, 12 parts, 8 parts of ethyl acetate, 0.8 parts of a leveling agent, a corrosion inhibitor

1.8 份; 1.8 parts;

[0025] 其中,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯-2,4- 二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,其中,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为4:1,然后升温至80°C,反应8h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2- 丁基-2-乙基-1,3-丙二醇,升温至80°C,反应5h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应10h,其中,一次改性纳米二氧化钛、2- 丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:6:8,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 [0025] wherein the modified titanium dioxide prepared according to the following process: under the protection of nitrogen gas, toluene-2,4-diisocyanate dilaurate and di-n Dingjixijia into mixed xylenes, followed by addition of titanium dioxide uniformly dispersed wherein the molar ratio of diisocyanate and toluene _2,4- titanium dioxide is 4: 1, then warmed to 80 ° C, the reaction 8h, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; primary modified titanium dioxide of xylene was added, was added 2-butyl-1,3-propanediol, warmed to 80 ° C, the reaction 5h, then p-toluenesulfonic acid and vinyltriethoxysilane, 10H reaction, wherein the molar ratio of a modified titanium dioxide, 2-butyl-2-ethyl-1,3-propanediol, vinyltriethoxysilane is 1: 6: 8, after the reaction was filtered, washed, and dried to obtain the modified titanium dioxide.

[0026] 实施例3 [0026] Example 3

[0027] 本发明提出的一种改性纳米二氧化钛紫外光固化涂料,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体50份、环氧丙烯酸酯20份、有机硅改性丙烯酸树脂12份、三羟甲基丙烷三甲基丙烯酸酯4.6份、二缩三乙二醇二甲基丙烯酸酯8.7份、改性纳米二氧化钛5.8份、纳米氧化铝5份、纳米氧化锌2.2份、纳米二氧化硅5份、氮化硅晶须4份、 [0027] The present invention proposes a modified titanium dioxide UV-curable coating material which comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 50 parts, 20 parts of epoxy acrylate, silicone-modified acrylate 12 parts resin, 4.6 parts of trimethylolpropane trimethacrylate, 8.7 parts of triethylene glycol dimethacrylate, 5.8 parts of modified titanium dioxide, 5 parts of nano alumina, nano zinc oxide 2.2 parts, nano-silica 5 parts, 4 parts of the silicon nitride whiskers,

1-羟基环己基苯基甲酮0.65份、安息香双甲醚2.1份、2-羟基-2-甲基-1-苯基-1-丙酮4份、2,4,6-三甲基苯甲酰基-二苯基氧化膦1.5份、甲苯3份、醋酸丁酯5份、丙二醇甲醚4份、甲基异丁基酮I份、流平剂1.2份、缓蚀剂1.5份; 1-hydroxy cyclohexyl phenyl ketone 0.65 parts, 2.1 parts of benzoin methyl ether bis, 2-methyl-1-phenyl-4 parts of 2,4,6-trimethyl benzoic acyl - diphenyl phosphine oxide, 1.5 parts, 3 parts of toluene, 5 parts of butyl acetate, 4 parts of propylene glycol methyl ether, methyl isobutyl ketone and I parts, 1.2 parts of a leveling agent, 1.5 parts corrosion inhibitor;

[0028] 其中,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯-2,4- 二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,其中,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为5:1,然后升温至95°C,反应6h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2- 丁基-2-乙基-1,3-丙二醇,升温至95°C,反应2h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应15h,其中,一次改性纳米二氧化钛、2-丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5:6,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 [0028] wherein the modified titanium dioxide prepared according to the following process: under the protection of nitrogen gas, toluene-2,4-diisocyanate dilaurate and di-n Dingjixijia into mixed xylenes, followed by addition of titanium dioxide uniformly dispersed wherein the molar ratio of toluene diisocyanate and _2,4- titanium dioxide is 5: 1, then warmed to 95 ° C, the reaction 6h, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; primary modified titanium dioxide of xylene was added, was added 2-butyl-1,3-propanediol, warmed to 95 ° C, the reaction 2h, followed by addition of p-toluenesulfonic acid and vinyltriethoxysilane, 15H reaction, wherein the molar ratio of a modified titanium dioxide, 2-butyl-2-ethyl-1,3-propanediol, vinyltriethoxysilane is 1: 5: 6, after the reaction was filtered, washed, and dried to obtain the modified titanium dioxide.

[0029] 实施例4 [0029] Example 4

[0030] 本发明提出的一种改性纳米二氧化钛紫外光固化涂料,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体48份、环氧丙烯酸酯21份、有机硅改性丙烯酸树脂10份、三羟甲基丙烷三甲基丙烯酸酯5份、二缩三乙二醇二甲基丙烯酸酯8份、改性纳米二氧化钛6.3份、纳米氧化铝4份、纳米氧化锌2.5份、纳米二氧化硅4.7份、氮化硅晶须4.5份、 [0030] The present invention proposes a modified titanium dioxide UV-curable coating material which comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 48 parts, 21 parts of epoxy acrylate, silicone-modified acrylate 10 parts of the resin, 5 parts of trimethylolpropane trimethacrylate, 8 parts of triethylene glycol dimethacrylate, 6.3 parts of modified titanium dioxide, 4 parts of nano alumina, nano zinc oxide 2.5 parts nano-silica 4.7 parts, 4.5 parts of silicon nitride whiskers,

1-羟基环己基苯基甲酮0.6份、安息香双甲醚2.3份、2-羟基-2-甲基-1-苯基-1-丙酮 1-hydroxy cyclohexyl phenyl ketone 0.6 parts, 2.3 parts of benzoin methyl ether bis, 2-methyl-1-phenyl-1-propanone

3.6份、2,4,6-三甲基苯甲酰基-二苯基氧化膦1.7份、甲基异丁基酮10份、流平剂1.5份、缓蚀剂1.3份; 3.6 parts of 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 1.7 parts, 10 parts of methyl isobutyl ketone, 1.5 parts of a leveling agent, 1.3 parts of a corrosion inhibitor;

[0031] 其中,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯-2,4- 二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,其中,甲苯-2,4-二异氰酸酯和纳米二氧化钛的摩尔比为4.3:1,然后升温至84°C,反应7.6h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2-丁基-2-乙基-1,3-丙二醇,升温至88°C,反应3.8h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应12h,其中,一次改性纳米二氧化钛、 [0031] wherein the modified titanium dioxide prepared according to the following process: under the protection of nitrogen gas, toluene-2,4-diisocyanate dilaurate and di-n Dingjixijia into mixed xylenes, followed by addition of titanium dioxide uniformly dispersed wherein the molar ratio of toluene-2,4-diisocyanate and titanium dioxide of 4.3: 1, and then warmed to 84 ° C, the reaction 7.6H, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; and a modified titanium dioxide of xylene was added, was added 2-butyl-1,3-propanediol, warmed to 88 ° C, the reaction 3.8H, followed by addition of p-toluenesulfonic acid and triethoxy vinyl silane, the reaction 12h, wherein a modified titanium dioxide,

2- 丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5.4:7.5,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 2-butyl-1,3-propanediol, vinyltriethoxysilane molar ratio of 1: 5.4: 7.5, after the reaction was filtered, washed, and dried to obtain the modified titanium dioxide.

[0032] 实施例5 [0032] Example 5

[0033] 本发明提出的一种改性纳米二氧化钛紫外光固化涂料,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体53份、环氧丙烯酸酯18份、有机硅改性丙烯酸树脂13份、三羟甲基丙烷三甲基丙烯酸酯4份、二缩三乙二醇二甲基丙烯酸酯9份、改性纳米二氧化钛5份、纳米氧化铝5.6份、纳米氧化锌2份、纳米二氧化硅5.6份、氮化硅晶须3.6份、1-羟基环己基苯基甲酮0.8份、安息香双甲醚1.8份、2-羟基-2-甲基-1-苯基-1-丙酮 [0033] The present invention proposes a modified titanium dioxide UV-curable coating material which comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 53 parts, 18 parts of epoxy acrylate, silicone-modified acrylate 13 parts resin, 4 parts of trimethylol propane trimethacrylate, 9 parts of triethylene glycol dimethacrylate, 5 parts of modified titanium dioxide, 5.6 parts by nano alumina, nano zinc oxide 2 parts nano-silica 5.6 parts, 3.6 parts of silicon nitride whiskers, 1-hydroxy cyclohexyl phenyl ketone 0.8 parts, 1.8 parts of benzoin methyl ether bis hydroxy-2-methyl-1-phenyl-1 acetone

4.2份、2,4,6-三甲基苯甲酰基-二苯基氧化膦1.3份、异丁醇3份、醋酸乙酯4份、甲苯3份、醋酸丁酯3份、丙二醇甲醚I份、甲基异丁基酮3份、流平剂I份、缓蚀剂1.7份; 4.2 parts of 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 1.3 parts, 3 parts of isobutanol, 4 parts of ethyl acetate, 3 parts of toluene, 3 parts of butyl acetate, propylene glycol methyl ether I parts, 3 parts of methyl isobutyl ketone, the I parts of a leveling agent, 1.7 parts corrosion inhibitor;

[0034] 其中,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯-2,4- 二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,其中,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为4.8:1,然后升温至92°C,反应6.6h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2- 丁基-2-乙基-1,3-丙二醇,升温至93°C,反应4h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应14h,其中,一次改性纳米二氧化钛、2- 丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5.8:6.6,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 [0034] wherein the modified titanium dioxide prepared according to the following process: under the protection of nitrogen gas, toluene-2,4-diisocyanate dilaurate and di-n Dingjixijia into mixed xylenes, followed by addition of titanium dioxide uniformly dispersed wherein the molar ratio of toluene diisocyanate and _2,4- titanium dioxide is 4.8: 1, and then warmed to 92 ° C, the reaction 6.6Hz, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; and a modified titanium dioxide of xylene was added, was added 2-butyl-1,3-propanediol, warmed to 93 ° C, the reaction 4h, then p-toluenesulfonic acid and vinyltriethoxysilane , 14H reaction, wherein the molar ratio of primary-modified titanium dioxide, 2-butyl-2-ethyl-1,3-propanediol, vinyltriethoxysilane is 1: 5.8: 6.6, by filtration after the reaction , washed, and dried to obtain the modified titanium dioxide.

[0035] 以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。 [0035] The above are only the preferred specific embodiments of the invention, but the scope of the present invention is not limited thereto, any skilled in the art in the art within the technical scope disclosed by the present invention, according to the present invention its aspect of the inventive concept changes or equivalent replacements to be, shall fall within the scope of the present invention.

Claims (10)

1.一种改性纳米二氧化钛紫外光固化涂料,其特征在于,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体35-65份、环氧丙烯酸酯10-25份、有机硅改性丙烯酸树脂5-15份、三羟甲基丙烷三甲基丙烯酸酯2-7份、二缩三乙二醇二甲基丙烯酸酯5-10份、改性纳米二氧化钛3-8份、纳米氧化铝2-8份、纳米氧化锌1-3份、纳米二氧化硅2-6份、氮化硅晶须2-5份、1-羟基环己基苯基甲酮0.3-1份、安息香双甲醚1-3份、2-羟基-2-甲基-1-苯基-1-丙酮2-5份、2,4,6-三甲基苯甲酰基-二苯基氧化膦0.5-2份、溶剂5_20份、流平剂0.8-1.8份、缓蚀剂1-1.8份。 A titanium dioxide modified UV-curable coatings, characterized in that the material which comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 35-65 parts, 10-25 parts epoxy acrylate, silicone 5-15 parts of modified acrylic resin, 2-7 parts of trimethylol propane trimethacrylate, 5-10 parts of triethylene glycol dimethacrylate, titanium dioxide 3-8 parts of modified nano 2-8 parts of alumina, nano zinc oxide parts 1-3, 2-6 parts by nano silica, 2-5 parts of silicon nitride whiskers, 1-hydroxy cyclohexyl phenyl ketone 0.3-1 parts, benzoin bis 1-3 parts of methyl ether, 2-methyl-1-phenyl-2-5 parts of 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 0.5 parts, 5_20 parts solvent, 0.8 to 1.8 parts of a leveling agent, corrosion inhibitor 1-1.8 parts.
2.根据权利要求1所述改性纳米二氧化钛紫外光固化涂料,其特征在于,其原料中,聚氨酯丙烯酸酯弹性预聚体、环氧丙烯酸酯、有机硅改性丙烯酸树脂、三羟甲基丙烷三甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯的重量比为40-60:13-22:8-15:3-6:7_10。 1 according to the modified titanium dioxide as claimed in claim UV-curable coatings, characterized in that its raw materials, elastomeric polyurethane acrylate prepolymer, epoxy acrylate, silicone-modified acrylic resin, trimethylolpropane trimethacrylate, by weight of triethylene glycol dimethacrylate ratio of 40-60: 13-22: 8-15: 3-6: 7_10.
3.根据权利要求1或2所述改性纳米二氧化钛紫外光固化涂料,其特征在于,其原料中,改性纳米二氧化钛、纳米氧化铝、纳米氧化锌、纳米二氧化硅、氮化硅晶须的重量比为4-7:3-6:1.8-2.8:4_6:3-5。 1 or 2 according to the modified titanium dioxide as claimed in claim UV-curable coatings, characterized in that the raw material, the modified titanium dioxide, nano alumina, nano zinc oxide, nano-silicon dioxide, silicon nitride whiskers weight ratio of 4-7: 3-6: 1.8-2.8: 4_6: 3-5.
4.根据权利要求1-3中任一项所述改性纳米二氧化钛紫外光固化涂料,其特征在于,其原料中,1-羟基环己基苯基甲酮、安息香双甲醚、2-羟基-2-甲基-1-苯基-1-丙酮、2,4, 6-三甲基苯甲酰基-二苯基氧化膦的重量比为0.5-0.9:1.3-2.7:2.9-4.5:1_2。 According to claim 1-3 in any one of titanium dioxide modified UV-curable coatings, characterized in that its raw material, 1-hydroxy cyclohexyl phenyl ketone, benzoin methyl ether bis, 2-hydroxy - 2-methyl-1-phenyl-1-propanone, 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide in a weight ratio of 0.5-0.9: 1.3-2.7: 2.9-4.5: 1_2.
5.根据权利要求1-4中任一项所述改性纳米二氧化钛紫外光固化涂料,其特征在于,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体48-53份、环氧丙烯酸酯18-21份、有机硅改性丙烯酸树脂10-13份、三羟甲基丙烷三甲基丙烯酸酯4-5份、二缩三乙二醇二甲基丙烯酸酯8-9份、改性纳米二氧化钛5-6.3份、纳米氧化铝4-5.6份、纳米氧化锌2-2.5份、纳米二氧化硅4.7-5.6份、氮化硅晶须3.6-4.5份、1-羟基环己基苯基甲酮0.6-0.8份、安息香双甲醚1.8-2.3份、2-羟基-2-甲基-1-苯基_1_丙酮3.6-4.2份、2,4,6-三甲基苯甲酰基-二苯基氧化膦1.3-1.7份、溶剂10-17份、流平剂1-1.5份、缓蚀剂1.3-1.7份;优选地,其原料按重量份包括以下组分:聚氨酯丙烯酸酯弹性预聚体50份、环氧丙烯酸酯20份、有机硅改性丙烯酸树脂12份、三羟甲基丙烷三甲基丙烯酸酯4.6份、二缩三乙二醇二甲基丙烯酸酯8.7 1-4 according to any one of the modified titanium dioxide as claimed in claim UV-curable coatings, wherein the raw material comprises the following components in parts by weight: Flexible polyurethane acrylate prepolymer 48-53 parts, ring oxygen acrylate 18-21 parts, 10-13 parts of a silicone-modified acrylic resin, 4-5 parts of trimethylol propane trimethacrylate, 8-9 parts of triethylene glycol dimethacrylate, modified parts titanium dioxide 5-6.3, 4-5.6 parts by nano alumina, nano zinc oxide to 2.5 parts 4.7-5.6 parts by nano-silica, silicon nitride whiskers 3.6-4.5 parts of 1-hydroxycyclohexyl phenyl 0.6-0.8 parts yl methanone, 1.8 to 2.3 parts of benzoin methyl ether bis, 2-hydroxy-2-methyl _1_ 3.6-4.2 parts of acetone, 2,4,6-trityl acyl - 1.3-1.7 parts of diphenyl phosphine oxide, 10-17 parts solvent, 1.5 parts of a leveling agent, 1.3 to 1.7 parts corrosion inhibitor; preferably, raw materials in parts by weight which comprises the following components: urethane acrylate 50 parts of elastomeric prepolymer, 20 parts epoxy acrylate, 12 parts of silicone-modified acrylic resin, 4.6 parts of trimethylol propane trimethacrylate, triethylene glycol dimethacrylate 8.7 、改性纳米二氧化钛5.8份、纳米氧化铝5份、纳米氧化锌2.2份、纳米二氧化硅5份、氮化硅晶须4份、1-羟基环己基苯基甲酮0.65份、安息香双甲醚2.1份、2-羟基-2-甲基-1-苯基-1-丙酮4份、2,4,6-三甲基苯甲酰基-二苯基氧化膦1.5份、溶剂13份、流平剂1.2份、缓蚀剂1.5份。 , 5.8 parts of modified titanium dioxide, 5 parts of nano alumina, nano zinc oxide 2.2 parts, 5 parts of nano-silica, silicon nitride whiskers, 4 parts of 1-hydroxy cyclohexyl phenyl ketone 0.65 parts benzoin methyl bis ether 2.1 parts of 2-methyl-1-phenyl-4 parts of 2,4,6-trimethyl benzoyl - diphenyl phosphine oxide 1.5 parts, 13 parts of solvent, flow 1.2 parts of a leveling agent, 1.5 parts of a corrosion inhibitor.
6.根据权利要求1-5中任一项所述改性纳米二氧化钛紫外光固化涂料,其特征在于,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯_2,4-二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,升温至80-95°C,反应6-8h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2- 丁基-2-乙基-1,3-丙二醇,升温至80-95°C,反应2_5h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应10-15h,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 According to any of claims 1-5 modified titanium dioxide a UV-curable coating, wherein the modified titanium dioxide prepared according to the following process: under the protection of nitrogen, toluene _2,4- diisocyanate dilaurate and di-n Dingjixijia into mixed xylenes, followed by addition of titanium dioxide dispersed uniformly, was warmed to 80-95 ° C, 6-8h the reaction, after the reaction was filtered, washed, and dried to give a modified nano titanium dioxide; titanium dioxide primary modification of xylene was added, was added 2-butyl-1,3-propanediol, warmed to 80-95 ° C, the reaction 2_5h, then p-toluenesulfonic acid and vinyl triethoxysilane, 10-15h reaction, after the reaction was filtered, washed, and dried to obtain the modified titanium dioxide.
7.根据权利要求1-6中任一项所述改性纳米二氧化钛紫外光固化涂料,其特征在于,改性纳米二氧化钛按照以下工艺进行制备:在氮气的保护下,将甲苯_2,4-二异氰酸酯和二月桂酸二正丁基锡加入二甲苯中混合均匀,然后加入纳米二氧化钛分散均匀,升温至90°C,反应7.5h,反应结束后经过滤、洗涤、干燥得到一次改性纳米二氧化钛;将一次改性纳米二氧化钛加入二甲苯中,加入2- 丁基-2-乙基-1,3-丙二醇,升温至85°C,反应3h,然后加入对甲苯磺酸和乙烯基三乙氧基硅烷,反应12h,反应结束后经过滤、洗涤、干燥得到所述改性纳米二氧化钛。 According to any of claims 1 to 6 in a modified titanium dioxide UV-curable coating, wherein the modified titanium dioxide prepared according to the following process: under the protection of nitrogen, toluene _2,4- diisocyanate and dibutyltindilaurate n Dingjixijia into xylene and uniformly mixed, followed by addition of titanium dioxide dispersed uniformly, heated to 90 ° C, the reaction 7.5h, after the reaction was filtered, washed, and dried to give a modified titanium dioxide; and a modified titanium dioxide of xylene was added, was added 2-butyl-1,3-propanediol, warmed to 85 ° C, the reaction 3h, then p-toluenesulfonic acid and vinyltriethoxysilane the reaction 12h, after the reaction was filtered, washed, and dried to obtain the modified titanium dioxide.
8.根据权利要求6或7所述改性纳米二氧化钛紫外光固化涂料,其特征在于,在改性纳米二氧化钛的制备过程中,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为4-5:1 ;优选地,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为4.3-4.8:1 ;优选地,甲苯_2,4- 二异氰酸酯和纳米二氧化钛的摩尔比为4.6:1。 According to claim 6 or 7 titanium dioxide modified UV-curable coatings, characterized in that, during the preparation of the modified titania nanoparticles, the ratio of two moles of diisocyanate and toluene _2,4- titanium dioxide is 4- 5: 1; preferably, toluene diisocyanate and _2,4- molar ratio of titanium dioxide is 4.3-4.8: 1; preferably, toluene diisocyanate and _2,4- molar ratio of titanium dioxide is 4.6: 1.
9.根据权利要求6-8中任一项所述改性纳米二氧化钛紫外光固化涂料,其特征在于,加入到二甲苯中的一次改性纳米二氧化钛、2- 丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5-6:6-8 ;优选地,加入到二甲苯中的一次改性纳米二氧化钛、2-丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5.4-5.8:6.6-7.5 ;优选地,加入到二甲苯中的一次改性纳米二氧化钛、2-丁基-2-乙基-1,3-丙二醇、乙烯基三乙氧基硅烷的摩尔比为1:5.5:7。 According to claim 6-8 in any one of titanium dioxide modified UV-curable coatings, characterized in that, once added to the xylene-modified titanium dioxide, 2-butyl-2-ethyl -1 the molar ratio of 1,3-propanediol, vinyltriethoxysilane is 1: 5-6: 6-8; preferably, added to a modified titanium dioxide in xylene, 2-butyl-2-ethyl 1,3-propanediol, vinyltriethoxysilane molar ratio of 1: 5.4-5.8: 6.6-7.5; preferably, added to a modified titanium dioxide in xylene, butyl-2 molar ratio of ethyl-1,3-propanediol, vinyltriethoxysilane is 1: 5.5: 7.
10.根据权利要求1-9中任一项所述改性纳米二氧化钛紫外光固化涂料,其特征在于,所述溶剂为异丁醇、醋酸乙酯、甲苯、醋酸丁酯、丙二醇甲醚、甲基异丁基酮中的一种或者多种的组合。 According to any of claims 1-9 in a modified UV-curable coatings titanium dioxide, wherein the solvent is isobutanol, ethyl acetate, toluene, butyl acetate, propylene glycol methyl ether, methyl one butyl group isobutyl ketone or any combination thereof.
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