技术领域Technical field
本发明属于光固化涂料领域，具体涉及一种紫外光固化涂料及其制备方法。The invention belongs to the field of light-curing coatings, and specifically relates to an ultraviolet curing coating and a preparation method thereof.
背景技术Background technique
紫外光固化涂料是一种环保节能型涂料，在紫外光照射下进行固化，不仅固化速度快，而且与热固化涂料相比更节省能源。紫外光固化涂料不仅在金属、皮革、木材、塑料等材料表面得到大量应用，而且还在光纤、印刷线路板、电子元器件封装等领域成功应用。然而，市面上大多数紫外光固化涂料存在抗水解性能不佳的问题，限制了其应用范围及应用场景。此外，在实际应用过程中，紫外光固化涂料可能需要长期暴露于环境中，容易因外界环境条件导致腐蚀脱落，因而还要求紫外光固化涂料具有良好的防腐性能。Ultraviolet light curing coating is an environmentally friendly and energy-saving coating that is cured under ultraviolet light irradiation. It not only cures quickly, but also saves more energy than thermal curing coatings. UV curable coatings are not only widely used on the surfaces of metal, leather, wood, plastics and other materials, but are also successfully used in fields such as optical fibers, printed circuit boards, and electronic component packaging. However, most UV-curable coatings on the market have poor hydrolysis resistance, which limits their application scope and application scenarios. In addition, during actual application, UV-curable coatings may need to be exposed to the environment for a long time, and are prone to corrosion and peeling due to external environmental conditions. Therefore, UV-curable coatings are also required to have good anti-corrosion properties.
发明内容Contents of the invention
本发明的目的之一在于针对目前市面上的紫外光固化涂料存在抗水性能不佳且防腐性能较差的不足之处，而提供一种附着性能好、防水性能高且耐酸碱腐蚀性能好的紫外光固化涂料。One of the purposes of the present invention is to provide a UV-curable coating with good adhesion performance, high waterproof performance and good acid and alkali corrosion resistance in view of the shortcomings of poor water resistance and poor anti-corrosion performance of the ultraviolet curable coatings currently on the market. UV curable coatings.
具体地，所述紫外光固化涂料含有质量比为1:(0.5～2.5):(0.3～2):(0.02～0.25):(0.002～0.1):(0～0.1)的改性丙烯酸酯树脂、单官能度稀释剂、多官能度稀释剂、光引发剂、抗水解剂以及任选的助剂；所述单官能度稀释剂和多官能度稀释剂的质量比为1:(0.3～1.5)；所述多官能度稀释剂选自乙氧基化双酚A二丙烯酸酯、乙氧基化双酚A二甲基丙烯酸酯和乙氧基化三羟甲基丙烷三丙烯酸酯中的至少一种；所述改性丙烯酸酯树脂具有如式(1)所示结构；Specifically, the ultraviolet curable coating contains modified acrylate resin with a mass ratio of 1:(0.5~2.5):(0.3~2):(0.02~0.25):(0.002~0.1):(0~0.1) , monofunctional diluent, multifunctional diluent, photoinitiator, anti-hydrolysis agent and optional auxiliaries; the mass ratio of the monofunctional diluent and multifunctional diluent is 1:(0.3~1.5 ); the multifunctional diluent is selected from at least ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate and ethoxylated trimethylolpropane triacrylate. One; the modified acrylate resin has a structure as shown in formula (1);
式(1)中，R1为衍生自二异氰酸酯的基团，R2为C1～C10的亚烷基，R3为C1～C4的亚烷基，R4为H或者甲基，n为1～10的整数。In formula (1), R1 is a group derived from diisocyanate, R2 is a C1 to C10 alkylene group, R3 is a C1 to C4 alkylene group, and R4 is H or methyl. , n is an integer from 1 to 10.
在一种优选的实施方式中，所述改性丙烯酸酯树脂的含量为20～40重量份，所述单官能度稀释剂的含量为25～45重量份，所述多官能度稀释剂的含量为15～35重量份，所述光引发剂的含量为1～5重量份，所述抗水解剂的含量为0.1～2重量份，所述助剂的含量为0～2重量份。In a preferred embodiment, the content of the modified acrylate resin is 20 to 40 parts by weight, the content of the monofunctional diluent is 25 to 45 parts by weight, and the content of the multifunctional diluent is The content of the photoinitiator is 1-5 parts by weight, the content of the anti-hydrolysis agent is 0.1-2 parts by weight, and the content of the auxiliary agent is 0-2 parts by weight.
在一种优选的实施方式中，所述改性丙烯酸酯树脂采用以下方法制备得到：In a preferred embodiment, the modified acrylate resin is prepared by the following method:
S1、将二异氰酸酯和二元胺混合进行加成反应，得到异氰酸酯双封端的聚脲预聚体；S1. Mix diisocyanate and diamine for addition reaction to obtain an isocyanate double-terminated polyurea prepolymer;
S2、将步骤S1所得的聚脲预聚体和端羟基丙烯酸酯在阻聚剂和引发剂的存在下进行封端反应，得到改性丙烯酸酯树脂。S2. The polyurea prepolymer obtained in step S1 and the hydroxyl-terminated acrylate are subjected to an end-capping reaction in the presence of a polymerization inhibitor and an initiator to obtain a modified acrylate resin.
在一种优选的实施方式中，所述二异氰酸酯和二元胺的摩尔比为(1.1～1.3):1。In a preferred embodiment, the molar ratio of the diisocyanate and diamine is (1.1-1.3):1.
在一种优选的实施方式中，所述端羟基丙烯酸酯以使反应体系中的NCO基团基本被完全反应为准。In a preferred embodiment, the hydroxyl-terminated acrylate is such that the NCO groups in the reaction system are substantially completely reacted.
在一种优选的实施方式中，所述阻聚剂的添加量为反应原料总量的0.02～0.04wt％。In a preferred embodiment, the addition amount of the polymerization inhibitor is 0.02 to 0.04 wt% of the total amount of reaction raw materials.
在一种优选的实施方式中，所述引发剂的添加量为反应原料总量的0.1～0.5wt％。In a preferred embodiment, the added amount of the initiator is 0.1 to 0.5 wt% of the total amount of reaction raw materials.
在一种优选的实施方式中，所述二异氰酸酯选自甲苯二异氰酸酯、降冰片烷二异氰酸酯、异佛尔酮二异氰酸酯、间苯二甲基二异氰酸酯、二环已基甲烷-4,4-二异氰酸酯、五亚甲基二异氰酸酯和六亚甲基二异氰酸酯中的至少一种。In a preferred embodiment, the diisocyanate is selected from toluene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, dicyclohexylmethane-4,4- At least one of diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate.
在一种优选的实施方式中，所述二元胺选自乙二胺、1,2-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺和1,10-癸二胺中的至少一种。In a preferred embodiment, the diamine is selected from the group consisting of ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine. At least one of amine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and 1,10-decanediamine.
在一种优选的实施方式中，所述端羟基丙烯酸酯选自丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯中的至少一种。In a preferred embodiment, the hydroxyl-terminated acrylate is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. .
在一种优选的实施方式中，所述改性丙烯酸酯树脂在25℃下的粘度为1000～25000cps。In a preferred embodiment, the viscosity of the modified acrylate resin at 25°C is 1,000 to 25,000 cps.
在一种优选的实施方式中，所述单官能度稀释剂为单官能度的丙烯酸酯单体。In a preferred embodiment, the monofunctional diluent is a monofunctional acrylate monomer.
在一种优选的实施方式中，所述单官能度稀释剂选自丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、3,3,5-三甲基环己基丙烯酸酯(TMCHA)、乙氧基乙基丙烯酸酯、丙烯酸异辛酯(2-EHA)、甲基丙烯酸4-羟基环己酯、四氢呋喃丙烯酸酯和异冰片基丙烯酸酯(IBOA)中的至少一种。In a preferred embodiment, the monofunctional diluent is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate (TMCHA), ethoxy At least one of ethylacrylate, isooctyl acrylate (2-EHA), 4-hydroxycyclohexyl methacrylate, tetrahydrofuran acrylate and isobornyl acrylate (IBOA).
在一种优选的实施方式中，所述抗水解剂为碳化二亚胺类抗水解剂。In a preferred embodiment, the anti-hydrolysis agent is a carbodiimide anti-hydrolysis agent.
本发明的目的之二在于还提供了上述紫外光固化涂料的制备方法，该方法包括：将改性丙烯酸酯树脂、单官能度稀释剂、多官能度稀释剂、光引发剂、抗水解剂以及任选的助剂混合搅拌均匀后避光出料，即得紫外光固化涂料。The second object of the present invention is to also provide a method for preparing the above-mentioned ultraviolet curable coating. The method includes: combining modified acrylate resin, monofunctional diluent, multifunctional diluent, photoinitiator, anti-hydrolysis agent and Mix the optional additives evenly and then discharge in the dark to obtain the UV curable coating.
本发明的关键在于将改性丙烯酸酯树脂、单官能度稀释剂、多官能度稀释剂、光引发剂、抗水解剂和助剂按照特定比例协同配合形成紫外光固化涂料，由此所得的紫外光固化涂料一方面能够通过具有特定结构的改性丙烯酸酯树脂、多官能度稀释剂和抗水解剂的协同作用赋予涂料良好的防水性能，另一方面由于改性丙烯酸酯树脂含有聚脲结构，使涂料体系具有更高的耐酸碱腐蚀性能。此外，单官能度稀释剂和多官能度稀释剂的复配不仅能够提高紫外光固化涂料的防水性能，还能提高体系的交联密度，从而增强紫外光固化涂料附着性。综上所述，本发明所提供的紫外光固化涂料不仅具有良好的附着性能和耐酸碱腐蚀性能，而且在95％RH的环境下放置1500h依旧可以保持外观不变形(变形包括表面起皱不平以及涂层表面出现鼓泡现象)。The key to the present invention is to synergistically combine modified acrylic resin, monofunctional diluent, multifunctional diluent, photoinitiator, anti-hydrolysis agent and auxiliary agent in a specific proportion to form an ultraviolet curable coating. On the one hand, photocurable coatings can give the coating good waterproof properties through the synergistic effect of modified acrylate resin with a specific structure, multifunctional diluents and anti-hydrolysis agents. On the other hand, because the modified acrylate resin contains a polyurea structure, The coating system has higher acid and alkali corrosion resistance. In addition, the combination of monofunctional diluents and multifunctional diluents can not only improve the waterproof performance of UV-cured coatings, but also increase the cross-linking density of the system, thereby enhancing the adhesion of UV-cured coatings. To sum up, the UV curable coating provided by the present invention not only has good adhesion properties and acid and alkali corrosion resistance, but also can maintain its appearance without deformation (deformation includes surface wrinkles and unevenness) even after being placed in an environment of 95% RH for 1500 hours. and bubbling on the coating surface).
具体实施方式Detailed ways
本发明提供的紫外光固化涂料含有质量比为1:(0.5～2.5):(0.3～2):(0.02～0.25):(0.002～0.1):(0～0.1)的改性丙烯酸酯树脂、单官能度稀释剂、多官能度稀释剂、光引发剂、抗水解剂以及任选的助剂。其中，所述改性丙烯酸酯树脂和单官能度稀释剂的质量比为1:(0.5～2.5)，如1:0.5、1:0.8、1:1、1:1.2、1:1.5、1:1.8、1:2、1:2.2、1:2.5或它们之间的任意值；所述改性丙烯酸酯树脂和多官能度稀释剂的质量比为1:(0.3～2)，如1:0.3、1:0.5、1:0.8、1:1、1:1.2、1:1.5、1:1.8、1:2或它们之间的任意值；所述改性丙烯酸酯树脂和光引发剂的质量比为1:(0.02～0.25)，如1:0.02、1:0.05、1:0.08、1:0.1、1:0.12、1:0.15、1:0.18、1:0.2、1:0.22、1:0.25或它们之间的任意值；所述改性丙烯酸酯树脂和抗水解剂的质量比为1:(0.002～0.1)，如1:0.002、1:0.005、1:0.008、1:0.01、1:0.02、1:0.05、1:0.08、1:0.1或它们之间的任意值；所述改性丙烯酸酯树脂和助剂的质量比为1:(0～0.1)，如0、1:0.002、1:0.005、1:0.008、1:0.01、1:0.02、1:0.05、1:0.08、1:0.1或它们之间的任意值。The ultraviolet curable coating provided by the invention contains modified acrylate resin with a mass ratio of 1:(0.5~2.5):(0.3~2):(0.02~0.25):(0.002~0.1):(0~0.1), Monofunctional diluents, polyfunctional diluents, photoinitiators, anti-hydrolysis agents and optional auxiliaries. Wherein, the mass ratio of the modified acrylate resin and the monofunctional diluent is 1: (0.5~2.5), such as 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1: 1.8, 1:2, 1:2.2, 1:2.5 or any value between them; the mass ratio of the modified acrylate resin and the multifunctional diluent is 1: (0.3~2), such as 1:0.3 , 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2 or any value between them; the mass ratio of the modified acrylate resin and photoinitiator is 1: (0.02～0.25), such as 1:0.02, 1:0.05, 1:0.08, 1:0.1, 1:0.12, 1:0.15, 1:0.18, 1:0.2, 1:0.22, 1:0.25 or them Any value between; the mass ratio of the modified acrylate resin and anti-hydrolysis agent is 1: (0.002~0.1), such as 1:0.002, 1:0.005, 1:0.008, 1:0.01, 1:0.02, 1:0.05, 1:0.08, 1:0.1 or any value between them; the mass ratio of the modified acrylate resin and additive is 1: (0~0.1), such as 0, 1:0.002, 1: 0.005, 1:0.008, 1:0.01, 1:0.02, 1:0.05, 1:0.08, 1:0.1 or any value in between.
所述单官能度稀释剂和多官能度稀释剂的质量比为1:(0.3～1.5)，如1:0.3、1:0.5、1:0.8、1:1、1:1.2、1:1.5或它们之间的任意值。所述多官能度稀释剂选自乙氧基化双酚A二丙烯酸酯、乙氧基化双酚A二甲基丙烯酸酯和乙氧基化三羟甲基丙烷三丙烯酸酯中的至少一种。所述多官能度稀释剂的添加不仅能够辅助提高涂料的防水性能，而且能够提高涂层的交联密度，有利于增强涂料与基材的附着力。The mass ratio of the monofunctional diluent and the multifunctional diluent is 1: (0.3~1.5), such as 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5 or any value between them. The multifunctional diluent is selected from at least one of ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxylated trimethylolpropane triacrylate. . The addition of the multifunctional diluent can not only help improve the waterproof performance of the coating, but also increase the cross-linking density of the coating, which is beneficial to enhancing the adhesion between the coating and the substrate.
所述改性丙烯酸酯树脂具有如式(1)所示结构；The modified acrylate resin has a structure shown in formula (1);
式(1)中，R1为衍生自二异氰酸酯的基团，R2为C1～C10的亚烷基，R3为C1～C4的亚烷基，R4为H或者甲基，n为1～10的整数。其中，所述C1～C10的亚烷基可以为亚甲基、亚乙基、正亚丙基、异亚丙基、正亚丁基、仲亚丁基、异亚丁基、叔亚丁基、正亚戊基、异亚戊基、叔亚戊基、新亚戊基、正亚己基、正亚庚基和正亚辛基中的至少一种。所述C1～C4的亚烷基可以为亚甲基、亚乙基、正亚丙基、异亚丙基、正亚丁基、仲亚丁基、异亚丁基和叔亚丁基中的至少一种。所述n为1～10的整数，如1、2、3、5、7、9等。In formula (1), R1 is a group derived from diisocyanate, R2 is a C1 to C10 alkylene group, R3 is a C1 to C4 alkylene group, and R4 is H or methyl. , n is an integer from 1 to 10. Wherein, the C1 to C10 alkylene group can be methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n- At least one of pentylene, isopentylene, tert-pentylene, neopentylene, n-hexylene, n-heptylene and n-octylene. The C1 to C4 alkylene group may be at least one of methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene and tert-butylene. kind. The n is an integer from 1 to 10, such as 1, 2, 3, 5, 7, 9, etc.
在本发明中，所述改性丙烯酸酯树脂的含量优选为20～40重量份，如20、22、25、28、30、32、35、38、40重量份或它们之间的任意值。所述单官能度稀释剂的含量优选为25～45重量份，如25、28、30、32、35、38、40、42、45重量份或它们之间的任意值。所述多官能度稀释剂的含量优选为15～35重量份，如15、18、20、22、25、28、30、32、35重量份或它们之间的任意值。所述光引发剂的含量优选为1～5重量份，如1、2、3、4、5重量份或它们之间的任意值。所述抗水解剂的含量优选为0.1～2重量份，如0.1、0.2、0.5、0.8、1、1.2、1.5、1.8、2重量份或它们之间的任意值。所述助剂的含量优选为0～2重量份，如0、0.2、0.5、0.8、1、1.2、1.5、1.8、2重量份或它们之间的任意值。In the present invention, the content of the modified acrylate resin is preferably 20 to 40 parts by weight, such as 20, 22, 25, 28, 30, 32, 35, 38, 40 parts by weight or any value between them. The content of the monofunctional diluent is preferably 25 to 45 parts by weight, such as 25, 28, 30, 32, 35, 38, 40, 42, 45 parts by weight or any value therebetween. The content of the multifunctional diluent is preferably 15 to 35 parts by weight, such as 15, 18, 20, 22, 25, 28, 30, 32, 35 parts by weight or any value therebetween. The content of the photoinitiator is preferably 1 to 5 parts by weight, such as 1, 2, 3, 4, 5 parts by weight or any value between them. The content of the anti-hydrolysis agent is preferably 0.1 to 2 parts by weight, such as 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2 parts by weight or any value therebetween. The content of the auxiliary agent is preferably 0 to 2 parts by weight, such as 0, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2 parts by weight or any value between them.
在本发明中，所述改性丙烯酸酯树脂在25℃下的粘度优选为1000～25000cps，如1000cps、5000cps、10000cps、15000cps、20000cps、25000cps或它们之间的任意值。In the present invention, the viscosity of the modified acrylate resin at 25° C. is preferably 1,000 to 25,000 cps, such as 1,000 cps, 5,000 cps, 10,000 cps, 15,000 cps, 20,000 cps, 25,000 cps or any value between them.
在本发明中，所述改性丙烯酸酯树脂优选采用以下方法制备得到：In the present invention, the modified acrylate resin is preferably prepared by the following method:
S1、将二异氰酸酯和二元胺混合进行加成反应，得到异氰酸酯双封端的聚脲预聚体；S1. Mix diisocyanate and diamine for addition reaction to obtain an isocyanate double-terminated polyurea prepolymer;
S2、将步骤S1所得的聚脲预聚体和端羟基丙烯酸酯在阻聚剂和引发剂的存在下进行封端反应，得到改性丙烯酸酯树脂。S2. The polyurea prepolymer obtained in step S1 and the hydroxyl-terminated acrylate are subjected to an end-capping reaction in the presence of a polymerization inhibitor and an initiator to obtain a modified acrylate resin.
在上述改性丙烯酸酯树脂的制备过程中，步骤S1中，所述加成反应的时间优选为30～50℃，如30℃、32℃、35℃、38℃、40℃、42℃、45℃、48℃、50℃或它们之间的任意值；所述加成反应的时间优选为1～4h，如1h、1.5h、2h、2.5h、3h、3.5h、4h或它们之间的任意值。In the preparation process of the above modified acrylate resin, in step S1, the addition reaction time is preferably 30 to 50°C, such as 30°C, 32°C, 35°C, 38°C, 40°C, 42°C, 45°C ℃, 48 ℃, 50 ℃ or any value between them; the time of the addition reaction is preferably 1 to 4h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or any value between them Any value.
在上述改性丙烯酸酯树脂的制备过程中，步骤S2中，所述封端反应的温度优选为70～95℃，如70℃、75℃、80℃、85℃、90℃、95℃或它们之间的任意值；所述封端反应的时间优选为2～8h，如2h、3h、4h、5h、6h、7h、8h或它们之间的任意值。In the preparation process of the above-mentioned modified acrylate resin, in step S2, the temperature of the end-capping reaction is preferably 70 to 95°C, such as 70°C, 75°C, 80°C, 85°C, 90°C, 95°C or any of them. Any value between; the time of the end-capping reaction is preferably 2 to 8h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h or any value between them.
在上述改性丙烯酸酯树脂的制备过程中，由于异氰酸酯对水分敏感，因此为了使二异氰酸酯与二元胺、端羟基丙烯酸酯的反应能够顺利进行，在反应加料前需要对反应容器和反应原料进行除水处理并于将反应体系置于惰性气氛下进行。其中，对反应容器进行除水处理的方式通常可以为对反应容器进行干燥，具体可以在130～150℃条件下对反应容器干燥2～4h。对反应原料进行除水处理的方式通常可以为对反应原料采用加热抽真空除水、冷冻干燥、分子筛除水、手套箱抽换气等方式进行处理。将反应体系置于惰性气氛下进行的方式通常可以为往反应容器中通入化学惰性气体、抽换真空等方式以驱除空气并充入惰性气体，从而使反应体系能够保持在惰性气氛下，其中，所述化学惰性气体具体可以为氮气或氩气，优选为氮气。In the preparation process of the above-mentioned modified acrylate resin, since isocyanate is sensitive to moisture, in order to make the reaction between diisocyanate, diamine and hydroxyl-terminated acrylate proceed smoothly, the reaction vessel and reaction raw materials need to be inspected before adding materials. The water removal treatment was carried out under an inert atmosphere. Wherein, the method of removing water from the reaction vessel can usually be to dry the reaction vessel. Specifically, the reaction vessel can be dried at 130-150°C for 2-4 hours. The method of dewatering the reaction raw materials can usually include heating and vacuuming to remove water, freeze drying, molecular sieve dewatering, glove box ventilation, etc. The reaction system can usually be placed under an inert atmosphere by introducing chemical inert gas into the reaction vessel, removing the vacuum, etc. to drive out the air and fill it with inert gas, so that the reaction system can be maintained under an inert atmosphere, where , the chemically inert gas may specifically be nitrogen or argon, preferably nitrogen.
在一种具体的实施方式中，改性丙烯酸酯树脂的制备过程可以为：在氮气氛围下，在三口瓶中加入除水后的二异氰酸酯和二元胺，控制反应温度为30～50℃，搅拌反应1～4h，使二异氰酸酯和二元胺进行封端反应，得到异氰酸酯双封端的聚脲预聚体；然后加入端羟基丙烯酸酯、阻聚剂和引发剂，控制反应温度为70～95℃，搅拌反应2～8h，并在反应过程中每间隔0.5～1.5h检测反应体系中的NCO基团的含量，当NCO基团的质量百分比含量≤0.05％时结束反应，即分子链末端异氰酸酯基团基本完全反应，降温出料，得到改性丙烯酸酯树脂。其中，所述端羟基丙烯酸酯的用量为使反应体系中的NCO基团基本被完全反应时的总质量，优选地，所述端羟基丙烯酸酯可一次性添加，也可以分步添加。In a specific embodiment, the preparation process of the modified acrylate resin can be as follows: under a nitrogen atmosphere, add the dehydrated diisocyanate and diamine into a three-necked bottle, and control the reaction temperature to 30-50°C. Stir the reaction for 1 to 4 hours to allow the diisocyanate and diamine to perform a blocking reaction to obtain an isocyanate double-blocked polyurea prepolymer; then add hydroxyl-terminated acrylate, polymerization inhibitor and initiator, and control the reaction temperature to 70 to 95 ℃, stir the reaction for 2 to 8 hours, and detect the content of NCO groups in the reaction system at intervals of 0.5 to 1.5 hours during the reaction. The reaction ends when the mass percentage of NCO groups is ≤ 0.05%, that is, the terminal isocyanate of the molecular chain The groups are basically completely reacted, and the temperature is lowered and the material is discharged to obtain modified acrylate resin. The amount of the hydroxyl-terminated acrylate is the total mass when the NCO groups in the reaction system are substantially completely reacted. Preferably, the hydroxyl-terminated acrylate can be added at one time or in steps.
在本发明中，所述二异氰酸酯和二元胺的摩尔比优选为(1.1～1.3):1，如1.1:1、1.15:1、1.2:1、1.25:1、1.3:1或它们之间的任意值。所述阻聚剂的添加量优选为反应原料总量的0.02～0.04wt％，如0.02wt％、0.025wt％、0.03wt％、0.035wt％、0.04wt％或它们之间的任意值。所述引发剂的添加量优选为反应原料总量的0.1～0.5wt％，如0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％或它们之间的任意值。所述反应原料包括二异氰酸酯、二元胺和端羟基丙烯酸酯。In the present invention, the molar ratio of the diisocyanate and diamine is preferably (1.1-1.3):1, such as 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1 or between them any value. The addition amount of the polymerization inhibitor is preferably 0.02 to 0.04wt% of the total amount of reaction raw materials, such as 0.02wt%, 0.025wt%, 0.03wt%, 0.035wt%, 0.04wt% or any value between them. The added amount of the initiator is preferably 0.1 to 0.5wt% of the total amount of reaction raw materials, such as 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt% or any value between them. The reaction raw materials include diisocyanate, diamine and hydroxyl-terminated acrylate.
在本发明中，所述二异氰酸酯优选自甲苯二异氰酸酯、降冰片烷二异氰酸酯、异佛尔酮二异氰酸酯、间苯二甲基二异氰酸酯、二环已基甲烷-4,4-二异氰酸酯、五亚甲基二异氰酸酯和六亚甲基二异氰酸酯中的至少一种，更优选地，所述二异氰酸酯可以为五亚甲基二异氰酸酯和/或六亚甲基二异氰酸酯。In the present invention, the diisocyanate is preferably selected from the group consisting of toluene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, dicyclohexylmethane-4,4-diisocyanate, penta At least one of methylene diisocyanate and hexamethylene diisocyanate, more preferably, the diisocyanate can be pentamethylene diisocyanate and/or hexamethylene diisocyanate.
在本发明中，所述二元胺优选自乙二胺、1,2-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺和1,10-癸二胺中的至少一种，更优选地，所述二元胺可以为乙二胺。In the present invention, the diamine is preferably selected from ethylenediamine, 1,2-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1, At least one of 7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and 1,10-decanediamine. More preferably, the diamine can be ethylenediamine.
在本发明中，所述阻聚剂优选自对苯二酚、4-甲氧基苯酚、对羟基苯甲醚、邻甲基对苯二酚和2,6-二叔丁基-4-甲基苯酚中的至少一种。In the present invention, the polymerization inhibitor is preferably selected from hydroquinone, 4-methoxyphenol, p-hydroxyanisole, o-methylhydroquinone and 2,6-di-tert-butyl-4-methyl At least one of the base phenols.
在本发明中，所述引发剂可以为有机锡化合物或有机铋化合物，具体地，所述有机锡化合物优选自乙酸亚锡、三甲基氯化锡、二月桂酸二丁基锡、二丁基二氯化锡和甲基三氯化锡中至少一种，所述有机铋化合物有选自异辛酸铋和/或羧酸铋。In the present invention, the initiator may be an organic tin compound or an organic bismuth compound. Specifically, the organic tin compound is preferably selected from the group consisting of stannous acetate, trimethyltin chloride, dibutyltin dilaurate, and dibutyl dilaurate. At least one of tin chloride and methyltin trichloride, and the organic bismuth compound is selected from bismuth isooctanoate and/or bismuth carboxylate.
在本发明中，所述单官能度稀释剂的添加一方面能够提高光固化涂料的反应速度，另一方面能够降低涂料体系的粘度。优选地，所述所述单官能度稀释剂为单官能度丙烯酸酯单体，其具体实例包括但不限于：丙烯酸丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、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、3,3,5-三甲基环己基丙烯酸酯、乙氧基乙基丙烯酸酯、丙烯酸异辛酯、甲基丙烯酸4-羟基环己酯、四氢呋喃丙烯酸酯和异冰片基丙烯酸酯中的至少一种。In the present invention, the addition of the monofunctional diluent can, on the one hand, increase the reaction speed of the photocurable coating, and on the other hand, can reduce the viscosity of the coating system. Preferably, the monofunctional diluent is a monofunctional acrylate monomer, specific examples thereof include but are not limited to: glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, methacrylic acid Hydroxyethyl ester, hydroxypropyl acrylate, hydroxypropyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxyethyl acrylate, isooctyl acrylate, 4-hydroxycyclomethacrylate At least one of hexyl ester, tetrahydrofuran acrylate and isobornyl acrylate.
在本发明中，所述抗水解剂可以与紫外光固化涂料水解时产生的端羧基、端胺基及端羟基进行反应，生成稳定的无害化产物，有效阻止紫外光固化涂料进一步降解断链，从而提高紫外光固化涂料的防水性。所述抗水解剂优选为碳化二亚胺类抗水解剂，其可以为二环己基碳二亚胺和/或二异丙基碳二亚胺等小分子碳二亚胺，也可以为高分子量碳二亚胺类抗水解剂，如Stabaxol P100、Stabaxol P200等。In the present invention, the anti-hydrolysis agent can react with terminal carboxyl groups, terminal amine groups and terminal hydroxyl groups generated during hydrolysis of UV-cured coatings to generate stable harmless products, effectively preventing further degradation of UV-cured coatings and chain scission. , thereby improving the waterproofness of UV-cured coatings. The anti-hydrolysis agent is preferably a carbodiimide anti-hydrolysis agent, which can be a small molecule carbodiimide such as dicyclohexylcarbodiimide and/or diisopropylcarbodiimide, or a high molecular weight carbodiimide. Carbodiimide anti-hydrolysis agents, such as Stabaxol P100, Stabaxol P200, etc.
在本发明中，所述光引发剂优选自Irgacure184、Irgacure369、Irgacure651、Irgacure754、Irgacure819、Irgacure907、Irgacure1173和TPO中的至少一种。In the present invention, the photoinitiator is preferably at least one selected from Irgacure184, Irgacure369, Irgacure651, Irgacure754, Irgacure819, Irgacure907, Irgacure1173 and TPO.
在本发明中，所述助剂优选为流平剂和/或消泡剂。其中，所述流平剂可以为本领域技术人员公知的各种能够改善涂料流平性能的物质，具体可以优选自BYK307、BYK333、BYK358、BYK361、BYK366、EFKA3600、EFKA3883和EFKA3886中的至少一种。所述消泡剂可以为本领域技术人员公知的各种能够消除涂料中的气泡或减少气泡产生的物质，具体可以优选自BYK020、BKY054、BYK352、BYK354、BYK357、BKY1790和BKY1794中的至少一种。In the present invention, the auxiliary agent is preferably a leveling agent and/or defoaming agent. Wherein, the leveling agent can be a variety of substances known to those skilled in the art that can improve the leveling performance of coatings. Specifically, at least one of BYK307, BYK333, BYK358, BYK361, BYK366, EFKA3600, EFKA3883 and EFKA3886 can be preferred. . The defoaming agent can be a variety of substances known to those skilled in the art that can eliminate bubbles or reduce the generation of bubbles in coatings. Specifically, at least one of BYK020, BKY054, BYK352, BYK354, BYK357, BKY1790 and BKY1794 can be preferred. .
在本发明中，所述防水性UV涂料的制备方法包括将改性丙烯酸酯树脂、单官能度稀释剂、多官能度稀释剂、光引发剂、抗水解剂和助剂混合搅拌均匀后避光出料，即得紫外光固化涂料。在一种具体的实施方式中，该方法包括：将改性丙烯酸酯树脂、单官能度稀释剂、多官能度稀释剂和抗水解剂依次加入双行星混合动力反应釜内，搅拌时间1～3h；然后加入光引发剂和助剂，搅拌1～2h后，抽真空脱泡，出料后密封包装即得到紫外光固化涂料。此外，在整个制备搅拌过程需严格避白光。In the present invention, the preparation method of the waterproof UV coating includes mixing the modified acrylate resin, a monofunctional diluent, a multifunctional diluent, a photoinitiator, an anti-hydrolysis agent and an auxiliary agent, stirring evenly and then protecting from light. After discharging, the UV curable coating is obtained. In a specific embodiment, the method includes: sequentially adding modified acrylate resin, monofunctionality diluent, multifunctionality diluent and anti-hydrolysis agent into the dual planetary hybrid reactor, stirring for 1 to 3 hours ; Then add the photoinitiator and additives, stir for 1 to 2 hours, vacuum and defoam, and seal and package after discharging to obtain the ultraviolet curable coating. In addition, white light must be strictly avoided during the entire preparation and stirring process.
以下将通过具体实施例对本发明进行详细描述。The present invention will be described in detail below through specific embodiments.
以下实施例和对比例中，原料的份数均指重量份。In the following examples and comparative examples, the parts of raw materials refer to parts by weight.
制备例1改性丙烯酸酯树脂的制备Preparation Example 1 Preparation of modified acrylate resin
在氮气氛围下，在三口瓶中加入266.76g(1.2mol)异佛尔酮二异氰酸酯，然后称取60.10g(1mol)乙二胺，分2次添加到三口瓶中，在温度为35℃下搅拌反应2h；然后在氮气氛围保护下，往三口瓶中加入0.09g的邻甲基对苯二酚，加入1.02g二丁基二氯化锡催化剂，升温至90℃，一次性逐渐滴加入43.25g(0.3mol)丙烯酸羟丁酯，搅拌反应1h后监测体系中NCO基团的含量，测得NCO质量百分比含量大于＞0.05％，滴加入14.42g(0.1mol)丙烯酸羟丁酯，搅拌反应1h后监测体系中NCO基团的含量，重复以上步骤直至NCO含量≤0.05％后结束添加丙烯酸羟丁酯并停止加热，此时裸露在分子量末端异氰酸酯基团基本已经反应完全，降温至40℃出料，得到改性丙烯酸酯树脂，记为A1，其25℃粘度为7500cps。Under a nitrogen atmosphere, add 266.76g (1.2mol) isophorone diisocyanate to the three-necked flask, then weigh 60.10g (1mol) ethylenediamine and add it to the three-necked flask in two portions. At a temperature of 35°C Stir the reaction for 2 hours; then, under the protection of nitrogen atmosphere, add 0.09g of o-methylhydroquinone into the three-necked flask, add 1.02g of dibutyltin dichloride catalyst, raise the temperature to 90°C, and gradually add 43.25% at a time. g (0.3 mol) hydroxybutyl acrylate. After stirring and reacting for 1 hour, the content of the NCO group in the system was monitored. The NCO mass percentage content was measured to be greater than 0.05%. 14.42 g (0.1 mol) hydroxybutyl acrylate was added dropwise and stirred and reacted for 1 hour. Finally, monitor the content of NCO groups in the system, repeat the above steps until the NCO content is ≤ 0.05%, then add hydroxybutyl acrylate and stop heating. At this time, the isocyanate groups exposed at the molecular weight terminals have basically reacted completely, and the temperature is cooled to 40°C for discharging. , a modified acrylate resin was obtained, designated as A1, with a viscosity of 7500 cps at 25°C.
制备例2改性丙烯酸酯树脂的制备Preparation Example 2 Preparation of modified acrylate resin
在氮气氛围下，在三口瓶中加入185.00g(1.1mol)六亚甲基二异氰酸酯，然后称取60.10g(1mol)乙二胺，分2次添加到三口瓶中，在温度为46℃下搅拌反应2.5h；然后在氮气氛围保护下，往三口瓶中加入0.08g的对苯二酚，加入0.78g氯化三甲基锡催化剂二丁基二氯化锡催化剂，升温至75℃，一次性逐渐滴加入39.04g(0.3mol)甲基丙烯酸羟乙酯，搅拌反应1h后监测体系中NCO基团的含量，测的NCO质量百分比含量大于＞0.05％，滴加入13.01g(0.1mol)甲基丙烯酸羟乙酯，搅拌反应1h后监测体系中NCO基团的含量，重复以上步骤直至NCO含量≤0.05％后结束添加甲基丙烯酸羟乙酯并停止加热，即将裸露在分子量末端异氰酸酯基团基本完全反应，降温至40℃出料，得到改性丙烯酸酯树脂，记为A2，其25℃为粘度13000cps。Under a nitrogen atmosphere, add 185.00g (1.1mol) hexamethylene diisocyanate to the three-necked flask, then weigh 60.10g (1mol) ethylenediamine and add it to the three-necked flask in two portions. At a temperature of 46°C Stir the reaction for 2.5 hours; then, under the protection of nitrogen atmosphere, add 0.08g of hydroquinone into the three-necked flask, add 0.78g of trimethyltin chloride catalyst, dibutyltin dichloride catalyst, and heat it to 75°C, once 39.04g (0.3mol) hydroxyethyl methacrylate was gradually added dropwise. After stirring for 1 hour, the content of the NCO group in the system was monitored. The measured NCO mass percentage content was greater than 0.05%. 13.01g (0.1mol) methacrylate was added dropwise. After stirring for 1 hour, monitor the content of NCO groups in the system. Repeat the above steps until the NCO content is ≤ 0.05%. Then add hydroxyethyl methacrylate and stop heating. The isocyanate groups at the end of the molecular weight are about to be exposed. After complete reaction, the temperature is lowered to 40°C and the material is discharged to obtain a modified acrylate resin, marked as A2, with a viscosity of 13,000 cps at 25°C.
制备例3改性丙烯酸酯树脂的制备Preparation Example 3 Preparation of modified acrylate resin
在氮气氛围下，在三口瓶中加入341.00g(1.2mol)二环已基甲烷-4,4-二异氰酸酯，然后称取60.10g(1mol)乙二胺，分2次添加到三口瓶中，在温度为38℃下搅拌反应3h；然后在氮气氛围保护下，往三口瓶中加入0.10g的对苯二酚，加入1.08g二丁基二氯化锡催化剂，升温至80℃，一次性逐渐滴加入43.25g(0.3mol)甲基丙烯酸羟丙酯，搅拌反应1h后监测体系中NCO基团的含量，测的NCO质量百分比含量大于＞0.05％，滴加入14.42g(0.1mol)甲基丙烯酸羟丙酯，搅拌反应1h后监测体系中NCO基团的含量，重复以上步骤直至NCO含量≤0.05％后结束添加甲基丙烯酸羟丙酯并停止加热，即将裸露在分子量末端异氰酸酯基团基本完全反应，降温至40℃出料，得到改性丙烯酸酯树脂，记为A3，其25℃为粘度10000cps。Under a nitrogen atmosphere, add 341.00g (1.2mol) dicyclohexylmethane-4,4-diisocyanate to the three-necked flask, then weigh 60.10g (1mol) ethylenediamine and add it to the three-necked flask in two portions. Stir the reaction for 3 hours at a temperature of 38°C; then, under the protection of a nitrogen atmosphere, add 0.10g of hydroquinone and 1.08g of dibutyltin dichloride catalyst into the three-necked flask, raise the temperature to 80°C, and gradually Add 43.25g (0.3mol) hydroxypropyl methacrylate dropwise. After stirring for 1 hour, monitor the content of NCO groups in the system. The measured NCO mass percentage content is greater than 0.05%. Add 14.42g (0.1mol) methacrylic acid dropwise. Hydroxypropyl methacrylate, stir and react for 1 hour, monitor the content of NCO groups in the system, repeat the above steps until the NCO content is ≤ 0.05%, add hydroxypropyl methacrylate and stop heating, that is, the isocyanate groups exposed at the molecular weight end are almost completely reacted , lower the temperature to 40°C and discharge the material to obtain a modified acrylate resin, recorded as A3, with a viscosity of 10,000 cps at 25°C.
实施例1紫外光固化涂料的制备Example 1 Preparation of UV-curable coating
将40份改性丙烯酸酯树脂A1、30份丙烯酸羟丙酯、8份乙氧基化双酚A二甲基丙烯酸、15份乙氧基化三羟甲基丙烷三丙烯酸酯和2份抗水解剂Stabaxol P100依次加入到双行星混合动力反应釜内，搅拌混合2h；然后再加入3.5份Irgacure 369、1份TPO、0.3份BYK361、0.2份BKY054到反应釜内，搅拌混合1.5h后，抽真空脱泡即可出料，即得紫外光固化涂料，记为B1。Combine 40 parts of modified acrylate resin A1, 30 parts of hydroxypropyl acrylate, 8 parts of ethoxylated bisphenol A dimethacrylate, 15 parts of ethoxylated trimethylolpropane triacrylate and 2 parts of anti-hydrolysis Stabaxol P100 was added to the double planetary hybrid reactor in sequence, and stirred for 2 hours; then, 3.5 parts of Irgacure 369, 1 part of TPO, 0.3 parts of BYK361, and 0.2 parts of BKY054 were added to the reactor, stirred and mixed for 1.5 hours, and then vacuumed After degassing, the material can be discharged to obtain the ultraviolet curable coating, which is recorded as B1.
实施例2紫外光固化涂料的制备Example 2 Preparation of UV-curable coating
将25份改性丙烯酸酯树脂A2、40份丙烯酸羟乙酯、30份乙氧基化双酚A二丙烯酸酯、0.5份二环己基碳二亚胺(抗水解剂)依次加入到双行星混合动力反应釜内，搅拌混合2h；然后再加入2份Irgacure 651、2份TPO、0.4份BYK361、0.1份BKY054到反应釜内，搅拌混合1h后，抽真空脱泡即可出料，即得紫外光固化涂料，记为B2。Add 25 parts of modified acrylate resin A2, 40 parts of hydroxyethyl acrylate, 30 parts of ethoxylated bisphenol A diacrylate, and 0.5 parts of dicyclohexylcarbodiimide (anti-hydrolysis agent) to the double planetary mix in sequence In the power reactor, stir and mix for 2 hours; then add 2 parts of Irgacure 651, 2 parts of TPO, 0.4 parts of BYK361, and 0.1 part of BKY054 into the reaction kettle. After stirring and mixing for 1 hour, vacuum and degas the material, and then the UV Light-curing coating, recorded as B2.
实施例3紫外光固化涂料的制备Example 3 Preparation of UV-curable coating
将35份改性丙烯酸酯树脂A3、38份丙烯酸异冰片酯、21份乙氧基化三羟甲基丙烷三丙烯酸酯、1份二异丙基碳二亚胺(抗水解剂)依次加入到双行星混合动力反应釜内，搅拌混合2h；然后再加入1份Irgacure 184、3份TPO、0.4份BYK333、0.6份BKY1790到反应釜内，搅拌混合1h后，抽真空脱泡即可出料，即得紫外光固化涂料，记为B3。Add 35 parts of modified acrylate resin A3, 38 parts of isobornyl acrylate, 21 parts of ethoxylated trimethylolpropane triacrylate, and 1 part of diisopropylcarbodiimide (anti-hydrolysis agent) to In the double planetary hybrid reactor, stir and mix for 2 hours; then add 1 part of Irgacure 184, 3 parts of TPO, 0.4 part of BYK333, and 0.6 part of BKY1790 into the reactor. After stirring and mixing for 1 hour, vacuum and defoaming can be used to discharge the material. That is, the UV-curable coating is obtained, which is recorded as B3.
实施例4紫外光固化涂料的制备Example 4 Preparation of UV-curable coating
将40份改性丙烯酸酯树脂A1、38份乙氧基乙基丙烯酸酯、15份乙氧基化双酚A二甲基丙烯酸酯和0.5份抗水解剂Stabaxol P100依次加入到双行星混合动力反应釜内，搅拌混合2h；然后再加入4份Irgacure 754、1份TPO、0.3份BYK307、0.2份BKY020到反应釜内，搅拌混合1.5h后，抽真空脱泡即可出料，即得紫外光固化涂料，记为B4。Add 40 parts of modified acrylate resin A1, 38 parts of ethoxyethyl acrylate, 15 parts of ethoxylated bisphenol A dimethacrylate and 0.5 parts of anti-hydrolysis agent Stabaxol P100 to the dual planetary hybrid reaction in sequence In the kettle, stir and mix for 2 hours; then add 4 parts of Irgacure 754, 1 part of TPO, 0.3 parts of BYK307, and 0.2 parts of BKY020 into the reaction kettle. After stirring and mixing for 1.5 hours, vacuum and defoaming can be used to discharge the material, and the ultraviolet light can be obtained Cured coating, marked as B4.
实施例5紫外光固化涂料的制备Example 5 Preparation of UV-curable coating
将20份改性丙烯酸酯树脂A1、41份四氢呋喃丙烯酸酯、35份乙氧基化三羟甲基丙烷三丙烯酸酯和2份抗水解剂Stabaxol P200依次加入到双行星混合动力反应釜内，搅拌混合2h；然后再加入1份Irgacure 907、0.5份TPO、0.3份BYK358、0.2份BKY354到反应釜内，搅拌混合1.5h后，抽真空脱泡即可出料，即得紫外光固化涂料，记为B5。Add 20 parts of modified acrylate resin A1, 41 parts of tetrahydrofuran acrylate, 35 parts of ethoxylated trimethylolpropane triacrylate and 2 parts of anti-hydrolysis agent Stabaxol P200 into the dual planetary hybrid reactor in sequence, and stir Mix for 2 hours; then add 1 part of Irgacure 907, 0.5 part of TPO, 0.3 part of BYK358, and 0.2 part of BKY354 into the reaction kettle. After stirring and mixing for 1.5 hours, vacuum and degas the material, and the UV curable coating is obtained. for B5.
对比例1参比紫外光固化涂料的制备Comparative Example 1 Preparation of Reference UV Curable Coating
按照实施例1的方法制备参比紫外光固化涂料，不同的是，将改性丙烯酸酯树脂A1采用相同重量份的二官能聚氨脂丙烯酸酯树脂Trust 7116(25℃下粘度为8500cps)替代，其余条件均与实施例1相同，记为DB1。The reference UV-curable coating was prepared according to the method of Example 1, except that the modified acrylate resin A1 was replaced by the same weight part of the difunctional polyurethane acrylate resin Trust 7116 (viscosity 8500 cps at 25°C). The remaining conditions are the same as those in Example 1 and are designated as DB1.
对比例2参比紫外光固化涂料的制备Comparative Example 2 Preparation of Reference UV Curable Coating
按照实施例2的方法制备参比紫外光固化涂料，不同的是，将乙氧基化双酚A二丙烯酸酯采用相同重量份的二丙二醇二丙烯酸酯(普通二官能丙烯酸酯单体)替代，其余条件均与实施例2相同，记为DB2。The reference UV-curable coating was prepared according to the method of Example 2, except that the ethoxylated bisphenol A diacrylate was replaced by the same weight part of dipropylene glycol diacrylate (common difunctional acrylate monomer). The remaining conditions are the same as those in Example 2, denoted as DB2.
对比例3参比紫外光固化涂料的制备Comparative Example 3 Preparation of Reference UV Curable Coating
按照实施例3的方法制备参比紫外光固化涂料，不同的是，未添加二异丙基碳二亚胺，其余条件均与实施例3相同，记为DB3。The reference UV-curable coating was prepared according to the method of Example 3, except that no diisopropylcarbodiimide was added. The remaining conditions were the same as Example 3, which was recorded as DB3.
测试例test case
将以上实施例和对比例所得的紫外光固化涂料采用395nm波长的汞灯进行光固化，其辐射光强在3000mj/cm2，固化完成后按照以下方法进行性能测试，所得结果如表1所示。The ultraviolet curable coatings obtained in the above examples and comparative examples were cured using a mercury lamp with a wavelength of 395nm, and the radiation intensity was 3000mj/cm2 . After curing, the performance test was performed according to the following method. The results are shown in Table 1 .
(1)附着力测试：将紫外光固化涂料涂覆在厚度为30±5μm的不锈钢基材上，按照上述条件固化后，用百格法测试附着力：用锋利的小刀在待测样件表面划6×6个1mm×1mm的小方格，用胶带贴在形成的格子中心，然后平稳的扯离，观察涂料脱落的现象，并通过以下标准进行判定：(1) Adhesion test: Coat the UV-curable coating on a stainless steel substrate with a thickness of 30±5 μm. After curing according to the above conditions, use the hundred grid method to test the adhesion: use a sharp knife on the surface of the sample to be tested Draw 6 × 6 small squares of 1mm × 1mm, stick it on the center of the formed grid with tape, and then pull it off smoothly to observe the phenomenon of paint peeling off, and judge it according to the following standards:
5B-切口边缘完全光滑，格子边缘和交叉点均无剥落；5B-The cut edge is completely smooth, and there is no peeling at the grid edges or intersections;
4B-在切口的相交处有小片剥落，划格区内实际破损不超过5％；4B-There are small pieces peeling off at the intersection of the cuts, and the actual damage in the cross-hatch area does not exceed 5%;
3B-在切口的边缘和相交处有小片剥落，划格区内实际破损为5％(不含端点值)～15％；3B-There are small pieces peeling off at the edges and intersections of the cuts, and the actual damage in the cross-hatch area is 5% (excluding endpoint values) to 15%;
2B-在切口的边缘和相交处有成片剥落，划格区内实际破损为15％(不含端点值)～35％；2B-There are pieces peeling off at the edges and intersections of the cuts, and the actual damage in the cross-hatch area is 15% (excluding endpoint values) to 35%;
1B-在切口的边缘和相交处有大片剥落，划格区内实际破损为35％(不含端点值)～65％；1B-There are large pieces of peeling at the edges and intersections of the cuts, and the actual damage in the cross-hatch area is 35% (excluding endpoint values) to 65%;
0-一些方格部分或整片剥落，划格区内实际破损大于65％。0-Some squares are partially or completely peeled off, and the actual damage in the cross-hatch area is greater than 65%.
(2)水接触角测试：将紫外光固化涂料涂覆在厚度为30±5μm的不锈钢基材上，按照上述条件固化后，用水接触角测试仪进行测试涂层的水接触角。(2) Water contact angle test: Coat the UV curable coating on a stainless steel substrate with a thickness of 30±5 μm. After curing according to the above conditions, test the water contact angle of the coating with a water contact angle tester.
(3)水气透过率：根据GB/T1037-88《塑料薄膜和片材透水蒸气性试验方法杯式法》，将按照上述条件固化后的涂料制成与杯环相应的圆片，在温度23±0.6℃、相对湿度90±2％条件下，测试其24h内的水蒸气透过量(g/m2·24h)并记录数据。(3) Water vapor transmission rate: According to GB/T1037-88 "Test Method for Water Vapor Permeability of Plastic Films and Sheets, Cup Method", the paint cured according to the above conditions is made into a disc corresponding to the cup ring, and Under the conditions of temperature 23±0.6℃ and relative humidity 90±2%, test the water vapor transmission amount (g/m2 ·24h) within 24h and record the data.
(4)耐酸性测试：将紫外光固化涂料涂覆在厚度为30±5μm的不锈钢基材上，按照上述条件固化后，放入0.1N的硫酸中常温浸泡48h后，观察涂层表面是否发生变形、鼓泡或脱落现象。(4) Acid resistance test: Coat the UV-curable coating on a stainless steel substrate with a thickness of 30±5 μm. After curing according to the above conditions, put it into 0.1N sulfuric acid and soak it at room temperature for 48 hours. Observe whether the surface of the coating is damaged. Deformation, bubbling or shedding.
(5)耐碱性测试：将紫外光固化涂料涂覆在厚度为30±5μm的不锈钢基材上，按照上述条件固化后，放入0.1N的氢氧化钾中常温浸泡48h后，观察涂层表面是否发生变形(变形包括表面起皱不平以及涂层表面出现鼓泡现象)同时测试其附着力。(5) Alkali resistance test: Coat the UV-curable coating on a stainless steel substrate with a thickness of 30±5 μm. After curing according to the above conditions, put it into 0.1N potassium hydroxide and soak it at room temperature for 48 hours. Then observe the coating. Whether the surface is deformed (deformation includes surface wrinkles and bubbling on the coating surface) and test its adhesion.
(6)防水性能测试：将紫外光固化涂料涂覆在厚度为30±5μm的不锈钢基材上，按照上述条件固化后，放入ESPEC的恒温恒湿箱中，温度湿度设定为25℃@95％RH，别分放置500h、750h、1000h、1250h、1500h后取出样件，观察涂层表面是否发生变形(变形包括表面起皱不平以及涂层表面出现鼓泡现象，只要涂层表面形貌出现上述情况，不论情况的严重程度都说明涂层表面发生了变形)同时测试其附着力。(6) Waterproof performance test: Coat the UV-curable coating on a stainless steel substrate with a thickness of 30±5μm. After curing according to the above conditions, place it in an ESPEC constant temperature and humidity box. The temperature and humidity are set to 25℃@ 95%RH, place the sample for 500h, 750h, 1000h, 1250h, and 1500h respectively. Take out the sample and observe whether the coating surface is deformed (deformation includes surface wrinkles and bubbling on the coating surface. As long as the coating surface morphology The occurrence of the above situation, regardless of the severity of the situation, indicates that the surface of the coating has been deformed) and its adhesion is tested at the same time.
表1Table 1
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it can be understood that the above-mentioned embodiments are illustrative and should not be construed as limitations of the present invention. Those of ordinary skill in the art will not deviate from the principles and purposes of the present invention. Under the circumstances, the above-described embodiments can be changed, modified, replaced and modified within the scope of the present invention.
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| CN202311767594.4ACN117757342A (en) | 2023-12-21 | 2023-12-21 | Ultraviolet light curing coating and preparation method thereof |
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| CN202311767594.4ACN117757342A (en) | 2023-12-21 | 2023-12-21 | Ultraviolet light curing coating and preparation method thereof |
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| FI861907A0 (en)* | 1985-05-08 | 1986-05-07 | Desoto Inc | POLYAKRYLERADE OLIGOMERER I ULTRAVIOLETTA HAERDBARA BELAEGGNINGAR FOER OPTISKA FIBER. |
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| CN114605956A (en)* | 2022-03-21 | 2022-06-10 | 深圳市磐石工业科技有限公司 | A kind of ultraviolet curing transfer adhesive and its preparation process and application |
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