CN106905837B - 一种光固化含氟防污防指纹树脂涂膜的制备方法 - Google Patents

一种光固化含氟防污防指纹树脂涂膜的制备方法 Download PDF

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CN106905837B
CN106905837B CN201710100932.7A CN201710100932A CN106905837B CN 106905837 B CN106905837 B CN 106905837B CN 201710100932 A CN201710100932 A CN 201710100932A CN 106905837 B CN106905837 B CN 106905837B
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安秋凤
祁刚
权利军
郑安迪
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Shaanxi University of Science and Technology
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Abstract

本发明公开了一种光固化含氟防污防指纹树脂涂膜的制备方法。本发明将羟基含氟树脂与多官能异氰酸酯先进行反应，再加入羟基烯类化合物封端，制成多官能烯基含氟树脂中间体，然后再将中间体与2‑6官能度的丙烯酸酯、烯基改性纳米增强组分、光引发剂等复配制成涂料，涂在玻璃或金属等基材表面，再经流平表干、烘烤、光固化，即可获得防污防指纹透明涂膜。

Description

一种光固化含氟防污防指纹树脂涂膜的制备方法
技术领域
本发明属精细化工领域，具体涉及一种光固化纳米杂化含氟防污防指纹树脂以及基于该树脂所构建的涂膜的制备方法。
背景技术
含氟丙烯酸酯树脂，表面能低、成膜性好、附着力强，拒水拒油性能优异，将它与纳米颜填料结合制成功能涂膜(见US5705276、CN1222929、CN101508755、WO2009/126467、US6126849、US5242487、US2001/0020077)，不仅防水防污效果好，且能防汗渍指纹污染，故在家电涂层、手机与平板电脑触摸屏、光学镜头与可穿戴电子产品等表面防污方面有广泛应用。
在光引发剂作用下，将含氟烯类单体与多官能丙烯酸酯共聚是制备光固化含氟丙烯酸酯防污防指纹树脂涂膜的一条捷径，这点可见CN102504625、CN104893542、CN102634267等。例如，专利CN102504625将UV丙烯酸树脂低聚物与多官能UV丙烯酯单体、改性全氟聚醚、流平剂、溶剂等在光引发剂作用下共聚所制备的透明硬化膜，在赋予基材持久防指纹性能的同时，还能满足透明硬化膜应具备的抗刮性和耐磨性要求。而CN104893542将聚氨酯紫外光固化涂料、UV光固化含氟丙烯酸化合物和稀释剂等喷涂在电子产品表面，再经60℃烘烤45min、UV照射15-20s，所形成的皮膜，既不影响产品原有的外观，又可减少产品表面指纹及污渍附着，并有防刮花、耐磨及易清洁等特点。而CN102634267将UV树脂、光引发剂、丙烯酸改性氟化树脂、溶剂等先制成涂料喷涂于基材表面，再经紫外光固化形成防污防指纹涂膜，据称在涂膜表面，水的接触角可大于80°、油酸的接触角大于40°，且涂膜有抑制指纹油污及汗渍附着、防刮花及抗摩擦作用。但研究发现，单纯用UV光固化树脂所形成的涂膜硬度欠佳，防污性能等达不到要求。
将纳米粉体与氟树脂结合，可改善氟树脂涂膜的耐热稳定性、阻燃性和硬度，提高防污效果(CN101857789、CN101024751)，但物理共混引入的纳米粉体易脱落，且影响紫外光固化效果和涂膜透光率。另外，将多官能烯基含氟树脂与双官能及多官能丙烯酸酯、反应性烯基纳米增强组分共聚来制备耐久透明性含氟防污防指纹涂膜，也未见研究报道。
发明内容
本发明的目的在于提供一种光固化含氟防污防指纹树脂涂膜的制备方法。
为达到上述目的，本发明采用了以下技术方案：
1)多官能烯基含氟树脂中间体的制备
准确称取羟基含氟树脂，用溶剂溶解调制成含固量为50-70％，然后按树脂中所含羟基数目(摩尔数)，再加入以羟基数目计0.9-1.1倍摩尔量的多异氰酸酯，在干燥N2保护条件下于20-35℃搅拌反应5-15min，然后再加入以树脂羟基数目计2-4倍摩尔量的含羟基烯类化合物，控温30-40℃进行封端反应30-60min，所得产物，即分子中含有多个反应性烯基的含氟树脂——多官能烯基含氟树脂中间体，记作PUF。
2)防污防指纹涂料的配制
按质量依次称取25-60份PUF、30-45份双官能丙烯酸酯、10-30份多官能丙烯酸酯、30-50份烯基改性纳米增强组分、0.2-1.0份润湿分散剂以及2.0-6.0份光引发剂，搅拌混匀，用转速为300-1000r/m的磨砂机搅拌分散30-60min，所得透明状流体，即防污防指纹涂料。
3)光固化含氟防污防指纹树脂涂膜的制备
取防污防指纹涂料，用喷涂、棒涂或旋涂工艺将涂料涂覆于玻璃(可预先进行等离子蚀刻)或金属等基材表面，制成厚度约为2-3μm涂膜，在20-35℃流平、表干1-3min，再在50-60℃烘5-6min，然后用光固化机照射10-20s，所得透明涂膜，即负载在玻璃或金属等基材表面的光固化含氟防污防指纹树脂涂膜。
所述的羟基含氟树脂，为分子结构中既含有疏水疏油性氟烃基、又连有羟基的含氟聚合物，主要包括FEVE树脂、含羟基的氟代丙烯酸酯树脂(FR-1)、含羟基的氟代苯丙树脂(FR-2)以及含羟基的全氟聚醚改性丙烯酸酯树脂(FR-3)等；所述的FEVE树脂为偏氟氯乙烯、羟丁基烯醚与全氟烷基乙烯基醚等组分所形成的共聚物，树脂含量100％、羟值为45-55mgKOH/g，从大连振邦氟碳涂料有限公司等单位购买；所述的含羟基的氟代丙烯酸酯树脂(FR-1)，主组分为C6-14氟烃基(甲基)丙烯酸酯与C1-18脂肪族(甲基)丙烯酸酯及(甲基)丙烯酸羟烷基酯等所形成的共聚物；所述含羟基的氟代苯丙树脂(FR-2)，主组分一般为C6-14氟烃基(甲基)丙烯酸酯与C1-8脂肪族(甲基)丙烯酸酯、苯乙烯、(甲基)丙烯酸羟烷基酯、丙烯酸等形成的共聚物；所述含羟基的全氟聚醚改性丙烯酸酯树脂(FR-3)，主组分为全氟聚醚丙烯酸酯、或全氟聚醚烯丙醚分别与C1-6脂肪族丙烯酸酯及(甲基)丙烯酸羟烷基酯或分子中含C3-6的羟基烯醚(如4-羟丁基乙烯基醚、羟乙基烯丙醚)等所形成的共聚物；所述的羟烷基为羟乙基或羟丙基；优先选取FR-1的主组分为全氟烷乙基丙烯酸酯-co-甲基丙烯酸十二醇酯-co-对氯甲基苯乙烯-co-丙烯酸羟丙酯-co-乙烯基三乙氧基硅烷，甲基丙烯酸十二氟庚酯-co-丙烯酸丁酯-co-丙烯酸羟丙酯-co-NN-二甲基丙烯酸氨乙酯，甲基丙烯酸十二氟庚酯-co-丙烯酸丁酯-co-丙烯酸羟丙酯-co-丙烯酸等；优先选取FR-2的主组分为甲基丙烯酸十二氟庚酯-co-丙烯酸丁酯-co-苯乙烯-co-丙烯酸羟丙酯、甲基丙烯酸六氟丁酯-co-苯乙烯-co-甲基丙烯酸甲酯-co-丙烯酸羟丙酯等；优先选取FR-3的主组分为全氟聚醚丙烯酸酯-co-丙烯酸丁酯-co-甲基丙烯酸环己基酯-co-4-羟丁基乙烯基醚，全氟聚醚丙烯酸酯-co-甲基丙烯酸丁酯-co-甲基丙烯酸环己基酯-co-4-羟乙基烯丙醚等。
以上所述的FR-1～FR-3，树脂含固量约为50-70％、羟值为60-108mgKOH/g，参照文献方法(CN103937357、J.App.Polym.Sci.,2013,127(3):1519-1526等)合成或从苏威(上海)有限公司、北京华通瑞驰材料有限公司订购加工。
所述的多异氰酸酯，主要包括分子结构中含有2-3个活泼-NCO基团的二异氰酸酯或异氰酸酯三聚体，如六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、氢化苯二亚甲基二异氰酸酯(又名1,3-二甲基异氰酸酯环己烷，Takenate 600)、二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)以及市售的HDI三聚体、IPDI三聚体等。
所述的含羟基烯类化合物，为分子结构中既含有能与-NCO基团反应的羟基、又连有可聚合烯基的酯类或醚类化合物，主要包括丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、羟乙基烯丙醚、4-羟丁基乙烯基醚等。
所述的双官能丙烯酸酯，为端基连有两个丙烯酸酯基或甲基丙烯酸酯基而中间嵌入有聚乙二醇、或聚丙二醇、或烷基等链段的二元醇酯，主要包括二缩三乙二醇双丙烯酸酯，二缩三乙二醇双甲基丙烯酸酯，三缩丙二醇双丙烯酸酯，三缩丙二醇双甲基丙烯酸酯，1,6-己二醇二丙烯酸酯，1,4-丁二醇二丙烯酸酯，新戊二醇二丙烯酸酯，乙二醇二丙烯酸酯，乙二醇二甲基丙烯酸酯、己二醇双甲基丙烯酸酯等。
所述的多官能丙烯酸酯，为分子结构中含3-6个可聚合丙烯酸酯基的酯类化合物，主要包括甘油、季戊四醇等多元醇与(甲基)丙烯酸所形成的有机酸酯，如甘油三丙烯酸酯，甘油三甲基丙烯酸酯，三羟甲基丙烷三丙烯酸酯，三羟甲基丙烷三甲基丙烯酸酯，季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯，季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯酸酯，二季戊四醇五甲基丙烯酸酯，二季戊四醇六丙烯酸酯，二季戊四醇六甲基丙烯酸酯等，可一种或任意两种混合使用。
所述的烯基改性纳米增强组分，是指粒度处于纳米尺寸、外观透明且表面带有可反应性烯基的纳米硅溶胶、纳米钛溶胶或顶角连有烯基的笼状低聚倍半硅氧烷等中的一种或多种的混合物，所述的烯基为乙烯基或甲基丙烯酰氧丙基；所述的烯基改性纳米增强组分，既能参与光引发的多官能丙烯酸酯类单体的聚合反应，又能键合入涂层中增加涂膜硬度，且不影响涂膜透光性，其中，带有可反应性烯基的纳米硅溶胶或纳米钛溶胶参照文献方法将烯基硅烷如乙烯基三乙氧基硅烷、甲基丙烯酰氧丙基三乙氧基硅烷分别与正硅酸乙酯(TEOS)或钛酸异丙酯以及1,2-双(三乙氧基硅基)乙烷(BTESE)按摩尔比1-3:30:2在35-60℃进行碱性水解缩聚反应24h制备，或从青岛微纳硅胶科技有限公司、陕西安迪吉尔新材料有限公司等单位订制，含固量为20-30％、烯基含量约为0.05-0.2％(即每100g SiO2或TiO2中所含烯基的摩尔数为0.05-0.2mol)，平均粒径为20-100nm，分散介质一般为甲苯。
所述的光引发剂(又名光固化引发剂)为在紫外-可见光区能吸收一定波长的光波、从而产生自由基并引发不饱和单体聚合反应的物质，主要包括2-羟基-2-甲基-1-苯基丙烷-1-酮(1173)、1-羟基环已基苯基酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮(907)、安息香双甲醚(651)、2,4,6-(三甲基苯甲酰基)二苯基氧化膦(TPO)等，可单一组分或多种组分混合使用，引发剂的用量一般为2-6％；优先选取1173和TPO二者(质量比约为1:0.5～2)复合的光引发剂。所述的润湿分散剂，一般为聚丙烯酸的铵盐、聚丙烯酸的碱金属盐类、聚羧酸的有机铵盐，如Rohm&Haas公司的OROTANTM 1124、迪高公司的TEGO WetKL245、TEGO 4200、Win Sperse 3163等。
所述的溶剂一般为能与羟基含氟树脂、双官能或多官能丙烯酸酯单体、烯基改性纳米增强组分同时具有互溶性、且可挥发的物质，主要包括芳烃、酮、醚、酯、醇醚酯，如甲苯(MB)、二甲苯、丙酮、丁酮、环己酮、甲基异丁基酮(MIBK)、乙酸乙酯、醋酸丁酯(BA)、乙二醇丁醚、丙二醇丁醚、丙二醇丁醚醋酸酯(PMA)等，可单组分或多组份复配使用，优先选取芳烃-酮-酯、芳烃-酯、酯-酮等类混合溶剂，如甲苯-MIBK-醋酸丁酯(质量比为40-50:15-25:20-35)、甲苯-醋酸丁酯(质量比为40-50:50-60)或醋酸丁酯-MIBK(质量比为60-75:25-40)溶剂等。
本发明的有益效果体现在：
本发明以低表面能羟基含氟树脂作原料，将它与多官能异氰酸酯先进行反应，然后再用含羟基的烯类化合物进行封端，首先制得分子中含有多个可反应性烯基的含氟树脂中间体PUF；然后，再将PUF与光可固化的双官能丙烯酸酯、多官能丙烯酸酯、烯基改性纳米增强组分、润湿分散剂、光引发剂等复配制成防污防指纹涂料，均匀涂覆在玻璃或金属基材表面，再经流平表干、低温烘烤、光固化形成防污防指纹涂膜，不仅可获得耐久性防污防指纹效果，且涂膜硬度可达到2H，耐摩擦牢度达到3000次以上。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例1
1)多官能烯基含氟树脂中间体的制备
准确称取10.0g、羟值约为50mgKOH/g(含羟基0.0089mol)的羟基含氟树脂(FEVE树脂)，用甲苯-MIBK-醋酸丁酯(质量比50:20:30)混合溶剂溶解调制成含固量为70％的溶液，然后按树脂中所含羟基数目再加入以羟基数目计等摩尔量亦即0.0089mol的HDI，在干燥N2保护条件下于室温搅拌反应15min，然后再加入以树脂羟基数目计4倍摩尔量、即0.0357mol的丙烯酸羟丙酯，在35℃进行封端反应1h，所得产物，即多官能烯基含氟树脂中间体，记作PUF-1。
2)防污防指纹涂料的配制
按质量依次称取25份PUF-1、45份1,6-己二醇二丙烯酸酯、30份季戊四醇四丙烯酸酯、50份含固量为30％的乙烯基改性纳米硅溶胶(平均粒径约为30nm、乙烯基含量为0.05％)、0.2份润湿分散剂(TEGO Wet KL 245)、6份光引发剂(2份1173及4份TPO)，搅拌混匀，再用转速为300r/m的磨砂机搅拌分散30min，所得透明流体，即含氟防污防指纹涂料，记作FC-1。
3)光固化含氟防污防指纹涂膜的制备
取FC-1，用压力为0.5MPa、口径为0.8mm的喷枪均匀喷涂于等离子蚀刻后的平板玻璃表面(等离子蚀刻条件：用YZD08-5C等离子清洗机蚀刻30s，仪器功率为200W、电压220V、主频40KHz、电流1.8A、空气流速为500mL/s)，在室温流平、表干3min，再在60℃烘烤5min，然后用1KW的UV光固化机照射20s，所得透明涂膜，即FC-1防污防指纹涂膜，涂膜厚度约3μm。
实施例2
1)多官能烯基含氟树脂中间体的制备
准确称取20.0g、羟值为108mgKOH/g(含羟基0.0231mol)主组分为甲基丙烯酸十二氟庚酯-co-丙烯酸丁酯-co-苯乙烯-co-丙烯酸羟丙酯的羟基含氟树脂(含羟基的氟代苯丙树脂)，用醋酸丁酯-MIBK(质量比75:25)混合溶剂溶解调制成含固量为60％的溶液，按树脂中所含羟基的摩尔数再加入以羟基数目计1.1倍摩尔量、亦即0.0254mol的异佛尔酮二异氰酸酯(IPDI)，在干燥N2保护条件下于室温搅拌反应5min，然后再加入以树脂羟基数目计2倍摩尔量、即0.0462mol的丙烯酸羟乙酯，在30℃进行封端反应30min，所得产物，即多官能烯基含氟树脂中间体，记作PUF-2。
2)防污防指纹涂料的配制
按质量依次称取60份PUF-2、30份二缩三乙二醇双甲基丙烯酸酯、10份二季戊四醇六丙烯酸酯、30份含固量为20％的乙烯基改性纳米钛溶胶(平均粒径为23nm、乙烯基含量为0.2％)、1.0份润湿分散剂(TEGO 4200)、2份光引发剂(1份1173及1份TPO)，搅拌混合均匀，用1000r/m的磨砂机搅拌分散60min，得透明流体，即防污防指纹涂料，记作FC-2。
3)光固化含氟防污防指纹涂膜的制备
取FC-2，用棒涂法均匀涂于平板玻璃表面，在室温流平、表干1min、再在50℃烘烤6min，然后用1KW的UV固化机照射10s，所得透明涂膜，即FC-2防污防指纹涂膜，涂膜厚度约3μm。
实施例3
1)多官能烯基含氟树脂中间体的制备
准确称取30.0g、羟值为65.8mgKOH/g(含羟基0.018mol)主组分为甲基丙烯酸六氟丁酯-co-苯乙烯-co-甲基丙烯酸甲酯-co-丙烯酸羟丙酯的羟基含氟树脂(含羟基的氟代苯丙树脂)，用甲苯-醋酸丁酯(质量比45:55)混合溶剂溶解调制成含固量为50％的溶液，按树脂中所含羟基数目再加入以羟基数目计0.9倍摩尔量、亦即0.0162mol的HDI三聚体，在干燥N2保护条件下于室温搅拌反应10min，然后再加入以树脂羟基数目计3倍摩尔量、即0.054mol的4-羟丁基乙烯醚，在30℃进行封端反应30min，所得产物，即多官能烯基含氟树脂中间体，记作PUF-3。
2)防污防指纹涂料的配制
按质量依次称取40份PUF-3、30份新戊二醇二丙烯酸酯、30份二季戊四醇五丙烯酸酯、35份含固量约为30％的γ-丙烯酰氧丙基硅烷改性的纳米硅溶胶(平均粒径为25nm、γ-甲基丙烯酰氧丙基含量约0.06％)、0.5份分散剂(Win Sperse 3163)、5份光引发剂(2份1173及3份TPO)，搅拌混匀，用500r/m的磨砂机搅拌分散45min，所得透明流体，即防污防指纹涂料，记作FC-3。
3)光固化含氟防污防指纹涂膜的制备
取FC-3，用旋涂方法均匀涂于马口铁表面，在室温流平表干2min、再在60℃烘烤6min，然后用1KW的UV固化机照射15s，所得透明涂膜，即FC-3防污防指纹涂膜，涂膜厚度约2μm。
实施例4
1)多官能烯基含氟树脂中间体的制备
准确称取20.0g、羟值为65.8mgKOH/g(含羟基0.0141mol)主组分为全氟聚醚丙烯酸酯-co-丙烯酸丁酯-co-甲基丙烯酸环己基酯-co-4-羟丁基乙烯基醚的羟基含氟树脂(含羟基的全氟聚醚改性丙烯酸酯树脂)，用醋酸丁酯-MIBK(质量比75:25)混合溶剂溶解调制成含固量为60％的溶液，按树脂中所含羟基数目再加入与羟基等摩尔量、亦即0.0141mol的六亚甲基二异氰酸酯(HDI)，在干燥N2保护条件下于室温搅拌反应8min，再加入以树脂羟基数目计4倍摩尔量、即0.0564mol的甲基丙烯酸羟乙酯，在40℃进行封端反应45min，所得产物，即多官能烯基含氟树脂中间体，记作PUF-4。
2)防污防指纹涂料的配制
按质量依次称取35份PUF-4、37份己二醇双甲基丙烯酸酯、28份季戊四醇三丙烯酸酯、38份含固量为25％的乙烯基改性纳米二氧化硅溶胶(平均粒径约为100nm、乙烯基含量约为0.08％)、2份乙烯基POSS、0.4份分散剂(TEGO 4200)、6份光引发剂(3.0份1173及3.0份TPO)，搅拌混合均匀，用600r/m的磨砂机搅拌分散40min，得透明流体，即防污防指纹涂料，记作FC-4。
3)光固化含氟防污防指纹涂膜的制备
取FC-4，用压力为0.5MPa、口径为0.8mm的喷枪均匀喷涂于等离子蚀刻后的平板玻璃表面(用YZD08-5C等离子清洗机蚀刻30s，仪器功率为200W、电压220V、主频40KHz、电流1.8A、空气流速为500mL/s)，在室温流平表干1.5min、再在60℃烘烤6min，然后用1KW的UV固化机照射20s，所得透明涂膜，即FC-4防污防指纹涂膜，涂膜厚度约2μm。
实施例1-4制备的防污防指纹涂膜，其防水、防油性能以水、环己烷在涂膜表面的静态接触角(θH2O、θ油)表示，分别用JC2000型接触角测量仪在室温25±2℃测定，液滴大小为5μL；耐摩擦性能用橡皮-酒精耐摩擦牢度仪测定，涂膜的硬度参照GB/T 6739-93方法用QHQ-A型铅笔硬度计测定(结果见表1)，测定结果表明其具有良好的防污防指纹效果及耐久性。
表1.防污防指纹涂膜性能的测定结果
通过对比，可以看出，等离子蚀刻处理的玻璃上，涂膜的静态接触角更大，通过等离子蚀刻可以使玻璃表面出现更多的活性羟基，因而，相比于未经过等离子蚀刻处理的光滑玻璃表面，更利于涂膜性能的提高。

Claims (8)

1.一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：包括以下步骤：
1)多官能烯基含氟树脂中间体的制备
将羟基含氟树脂调制成含固量为50-70％，得物料A，向物料A中加入所述树脂所含羟基摩尔数0.9-1.1倍的多异氰酸酯，然后在N2保护条件下于20-35℃搅拌反应5-15min，得物料B，向物料B中加入所述树脂所含羟基摩尔数2-4倍的含羟基烯类化合物，然后在30-40℃进行封端反应30-60min，得多官能烯基含氟树脂中间体，记作PUF；
所述的羟基含氟树脂选自FEVE树脂、含羟基的氟代苯丙树脂或含羟基的全氟聚醚改性丙烯酸酯树脂；
所述含羟基烯类化合物选自结构中既含有能与-NCO基团反应的羟基、又含有可聚合烯基的酯类或醚类化合物；
2)防污防指纹涂料的配制
将按质量称取的25-60份PUF、30-45份双官能丙烯酸酯、10-30份多官能丙烯酸酯、30-50份烯基改性纳米增强组分、0.2-1.0份润湿分散剂及2.0-6.0份光引发剂搅拌混匀，然后用磨砂机搅拌分散，得透明均匀流体，即防污防指纹涂料；
所述的烯基改性纳米增强组分选自烯基改性的纳米硅溶胶、烯基改性的纳米钛溶胶或顶角连有烯基的笼状低聚倍半硅氧烷中的一种或多种任意比例的混合物，所述的烯基为乙烯基或甲基丙烯酰氧丙基；
3)光固化含氟防污防指纹透明涂膜的制备
将防污防指纹涂料直接涂覆于基材表面，或者，将基材表面进行等离子蚀刻后再涂覆防污防指纹涂料，涂覆厚度均为2-3μm；涂覆后在20-35℃进行流平及表干，然后在50-60℃烘5-6min、再进行光固化，即在基材表面制得含氟防污防指纹透明涂膜。
2.根据权利要求1所述一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：所述的FEVE树脂为至少由偏氟氯乙烯与羟丁基烯醚及全氟烷基乙烯醚所形成的共聚物，羟值为45-55mgKOH/g；所述的含羟基的氟代苯丙树脂为至少由C6-14氟烃基丙烯酸酯或C6-14氟烃基甲基丙烯酸酯与C1-8脂肪族丙烯酸酯或C1-8脂肪族甲基丙烯酸酯及苯乙烯和丙烯酸羟烷基酯或甲基丙烯酸羟烷基酯所形成的共聚物；所述的含羟基的全氟聚醚改性丙烯酸酯树脂为至少由全氟聚醚丙烯酸酯或全氟聚醚烯丙醚与C1-6脂肪族丙烯酸酯及丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯或C3-6的羟基烯醚所形成的共聚物，所述的羟烷基为羟乙基或羟丙基；所述的氟代苯丙树脂及全氟聚醚改性丙烯酸酯树脂的羟值均为65-108mg KOH/g。
3.根据权利要求1一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：所述的多异氰酸酯选自分子结构中含有2-3个活泼-NCO基团的二异氰酸酯或异氰酸酯三聚体。
4.根据权利要求1一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：所述双官能丙烯酸酯选自端基连有两个丙烯酸酯基或甲基丙烯酸酯基而中间嵌入有聚乙二醇、聚丙二醇或烷基链段的二元醇酯。
5.根据权利要求1所述一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：所述的多官能丙烯酸酯选自结构中含3-6个可聚合丙烯酸酯基的酯类化合物中的一种或两种任意比例的混合物。
6.根据权利要求1所述一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：所述的烯基改性的纳米硅溶胶或纳米钛溶胶的含固量为20-30％，烯基含量为0.05％-0.2％，平均粒径为20-100nm。
7.根据权利要求1所述一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：所述的光引发剂选自2-羟基-2-甲基-1-苯基丙烷-1-酮、1-羟基环已基苯基酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、安息香双甲醚或2,4,6-(三甲基苯甲酰基)二苯基氧化膦中的一种或多种任意比例的混合物；所述的润湿分散剂选自聚丙烯酸的铵盐、聚丙烯酸的碱金属盐类或聚羧酸的有机铵盐。
8.根据权利要求1所述一种光固化含氟防污防指纹树脂涂膜的制备方法，其特征在于：所述步骤1)中，用于调制羟基含氟树脂的含固量的溶剂选自与羟基含氟树脂、双官能、多官能丙烯酸酯及烯基改性纳米增强组分均具有互溶性且可挥发的物质中的一种或多种任意比例的混合物。
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