CN101463222A - UV curing color coating - Google Patents

UV curing color coating Download PDF

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CN101463222A
CN101463222A CN 200710302243 CN200710302243A CN101463222A CN 101463222 A CN101463222 A CN 101463222A CN 200710302243 CN200710302243 CN 200710302243 CN 200710302243 A CN200710302243 A CN 200710302243A CN 101463222 A CN101463222 A CN 101463222A
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coating
resin
content
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diluent
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CN 200710302243
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CN101463222B (en )
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成仁辉
戚仁宏
柱 杨
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比亚迪股份有限公司
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Abstract

The invention provides a ultraviolet curing coating, comprising a body resin, a diluting agent and a photo-initiator, the body resin comprises polyurethane acrylate resins, wherein, the body resin further comprises silicone acrylate resins with degree of functionality of 6-10, viscosity of 500-2,500cP below 60 DEG C and hardness of 5-8H. The ultraviolet curing coating provided by the invention has, after film forming, relatively low surface energy, and the formed paint film is excellent in water resistance, oil resistance and self-cleaning performance, thus reaching great antifouling effect, and meanwhile, the paint film has high hardness, good scratch resistance, high lustrousness and superb adhesive force.

Description

一种紫外光固化涂料 One kind of UV-curable coatings

技术领域 FIELD

本发明涉及一种紫外光固化涂料。 The present invention relates to a UV-curable coatings. 背景技术 Background technique

紫外光固化涂料是20世纪60年代开发的一种环保节能型涂料,70年代我国开始涉足该技术领域,90年代后才得到长足发展。 UV-curable coatings is the 1960s developed an environmentally friendly energy-saving coatings, our 70s began to get involved in the technical field, after 90 years by leaps and bounds. 紫外光固化涂料在紫外光照射下即可快速固化,不仅固化速度快,而且与热固化涂料相比还节省能源。 UV-curable coatings that cure under ultraviolet light, not only rapid curing rate, but also saves energy compared to heat-curable coatings. 目前,它不仅在木材、金属、塑料、纸张、皮革上大量应用,而且还在光纤、印刷线路板、电子元器件封装等材料上成功应用。 Currently, it is not widely used in the wood, metal, plastic, paper, leather, but also on the optical fiber, the printed wiring board, electronic components and other packaging materials successfully.

CN1778852A公开了一种紫外光固化哑光涂料,该涂料含有主体树脂、 稀释剂、哑光粉和光引发剂,含或不含助剂,其特征在于,该涂料还含有纯丙烯酸酯,以涂料总量为基准,纯丙烯酸酯的含量为1-20重量%。 CN1778852A discloses a matt UV curable coating, the coating comprising a resin body, a diluent, and a photoinitiator matte powder, with or without additives, wherein the coating further comprises pure acrylate, the total of the coating based on the amount of pure acrylate content of 1-20%. 所述主体树脂为聚酯丙烯酸酯、聚氨酯丙烯酸酯和环氧丙烯酸酯中的一种或几种。 One or several of the main body resin is a polyester acrylates, urethane acrylates and epoxy acrylates. 由该专利申请的涂料所形成的漆膜的附着力较高,但该涂料成膜后的表面能较高,导致漆膜的耐水、耐油和自清洁性能较差。 Higher adhesion of the film coating by this patent application to be formed, but after the paint film surface can be higher, leading to the film of water, oil and poor self-cleaning properties.

发明内容 SUMMARY

本发明的目的在于克服上述现有技术中的涂料成膜后的表面能较高的缺陷,提供一种成膜后表面能较低的紫外光固化涂料。 Object of the present invention to overcome the surface of the paint film after the above-described prior art can be higher defect, there is provided a film forming the low surface energy UV-curable coatings.

本发明提供了一种紫外光固化涂料,该涂料含有主体树脂、稀释剂和光引发剂,所述主体树脂含有聚氨酯丙烯酸酯树脂,其中,所述主体树脂还含有有机硅丙烯酸酯树脂,所述聚氨酯丙烯酸酯树脂的官能度为6-10,粘度为6CTC下500-2500 cP,硬度为5-8H。 The present invention provides a UV-curable coatings, the coating contains a main resin, a diluent and a photoinitiator, the host resin containing urethane acrylate resin, wherein the body further comprises a silicone resin, an acrylate resin, a polyurethane multifunctional acrylate resin is 6-10, the viscosity of 500-2500 cP 6CTC, hardness of 5-8H. 根据本发明提供的紫外光固化涂料,由于在主体树脂中还含有有机硅丙烯酸酯树脂,可以很好地降低本发明的涂料成膜后的表面能。 The present invention provides UV-curable coatings, since the body also contains a silicone resin, an acrylic resin, can be well reduced surface energy after deposition of the coating material of the present invention. 本发明采用的 Used in the present invention

6(TC下粘度为500-2500 cP,官能度为6-10,硬度为5-8H的聚氨酯丙烯酸酯树脂,可以提高由本发明的涂料所形成的漆膜的硬度。因此,有机硅丙烯酸树脂和聚氨酯丙烯酸树脂的配合使用,使得本发明的涂料所形成的漆膜有较好的耐水、耐油和自清洁性能,可以达到很好的防污效果。同时又有较高的硬度,从而使该漆膜具有较好的耐擦划性能。 6 (TC viscosity of 500-2500 cP, a functionality of 6-10 and a hardness of 5-8H urethane acrylate resin, the hardness can be improved by the coating film formed by the present invention. Accordingly, a silicone acrylic resin, and urethane acrylate with a resin so that the coating film formed according to the present invention have better water, oil and self-cleaning properties, can achieve a good antifouling effect. At the same time have a higher hardness, so that the paint the film has better abrasion resistance properties.

同时,由本发明提供的紫外光固化涂料所形成的漆膜具有较高的光泽度和较好的附着力。 Meanwhile, the film provided by the present invention is formed of UV-curable coatings having high gloss and good adhesion.

具体实施方式 detailed description

本发明提供的紫外光固化涂料含有主体树脂、稀释剂和光引发剂,所述主体树脂含有聚氨酯丙烯酸酯树脂,其中,所述主体树脂还含有有机硅丙烯酸酯树脂,所述聚氨酯丙烯酸酯树脂的官能度为6-10,粘度为6(TC下500-2500 cP,硬度为5-8H。 The present invention provides UV-curable coatings containing a binder, a diluent and a photoinitiator, the host resin containing urethane acrylate resin, wherein the body further comprises a silicone resin, an acrylate resin, a polyfunctional urethane acrylate resin degree of 6-10 and a viscosity of 6 (TC at 500-2500 cP, hardness of 5-8H.

根据本发明提供的紫外光固化涂料,由于在主体树脂中还含有有机硅丙烯酸酯树脂,可以很好地降低本发明的涂料成膜后的表面能。 The present invention provides UV-curable coatings, since the body also contains a silicone resin, an acrylic resin, can be well reduced surface energy after deposition of the coating material of the present invention. 本发明采用了6(TC下粘度为500-2500 cP,官能度为6-10,硬度为5-8H的聚氨酯丙烯酸酯树脂,可以提高由本发明的涂料所形成的漆膜的硬度。在一定的条件下有机硅丙烯酸树脂和聚氨酯丙烯酸树脂配合使用,而使得本发明所得涂料所形成的漆膜有较好的耐水、耐油和自清洁性能,可以达到很好的防污效果。同时又有较高的硬度,从而使该漆膜具有耐擦划性能。 The present invention employs 6 (TC viscosity of 500-2500 cP, a functionality of 6-10 and a hardness of 5-8H urethane acrylate resin, the film hardness can be improved by the coating of the present invention is formed in a certain under conditions of a silicone acrylic resin and a urethane acrylate resin used in conjunction, such that the resulting coating film formed by the present invention has good water resistance, oil resistance and self-cleaning properties, can achieve a good antifouling effect. at the same time have a higher hardness, so that the film has a scratch-resistant properties.

根据本发明提供的紫外光固化涂料,在优选情况下,基于所述主体树脂的总重量,所述聚氨酯丙烯酸酯树脂的含量为10-90重量%、优选为50-85 重量%,所述有机硅丙烯酸酯树脂的含量为10-90重量%、优选为15-50重量%。 The UV-curable coating material of the present invention provides, in the preferred case, based on the total weight of the main resin, the content of the urethane acrylate resin is 10-90% by weight, preferably 50 to 85% by weight, of the organic silicone acrylate resin content is 10 to 90 wt%, preferably 15 to 50 wt%.

根据本发明提供的紫外光固化涂料,在优选情况下,所述有机硅丙烯酸 The present invention provides UV-curable coatings, in the preferred case, the silicone acrylate

酯树脂25。 Ester resin 25. C下的粘度为2000-50000 cP。 C is a viscosity of 2000-50000 cP.

根据本发明提供的紫外光固化涂料,所述聚氨酯丙烯酸酯树脂可以为各种满足上述性能指标范围的脂肪族聚氨酯丙烯酸酯树脂、脂环族聚氨酯丙烯酸酯树脂和芳香族聚氨酯丙烯酸酯树脂中的一种或几种,优选脂肪族聚氨酯丙烯酸酯树脂。 The present invention provides UV-curable coatings, said urethane acrylate resin can satisfy a variety of performance above the target range of an aliphatic urethane acrylate resin, alicyclic and aromatic urethane acrylate resin, urethane acrylate resin one or several, preferably an aliphatic urethane acrylate resin. 所述聚氨酯丙烯酸酯树脂可以商购得到,例如日本合成化学公司的7605B、 1700B;氰特公司的EB1290;优西比(UCB)公司的EB5129; 盖斯塔夫公司的306;台湾长兴公司的6145-100;中山千叶合成公司的UV3600;中山横兆公司的UA2000和UA2001。 The urethane acrylate resin may be commercially available, for example, Japanese synthetic chemistry company 7605B, 1700B; Cytec EB1290; preferably West ratio (UCB)'s EB5129; Gaisitafu company 306; 6145 Taiwan company Changhsingian -100; Chiba synthesis Zhongshan company UV3600; Zhongshan company UA2000 and cross Katherine UA2001.

根据本发明提供的紫外光固化涂料,所述有机硅丙烯酸酯树脂可以为各种满足上述指标性能范围的有机硅丙烯酸酯树脂中的一种或几种。 The present invention provides UV-curable coatings, said silicone acrylate resin may satisfy one or more silicone acrylate resin in the range of performance indicators in various. 所述有机硅丙烯酸酯树脂可以商购得到,例如,比利时优西比(UCB)公司的有机硅丙烯酸酯树脂EB350和六官能度有机硅丙烯酸酯树脂EB1360;美国沙多玛公司的聚硅氧烷化脂肪族聚氨酯丙烯酸酯树脂CN990;台湾长兴公司的有机硅聚醚丙烯酸酯树脂6225。 The silicone acrylate resin may be commercially available, e.g., preferably West Belgium ratio (UCB) Company EB350 silicone acrylate resin, and hexafunctional silicone acrylate resin EB1360; U.S. silicone Sartomer Company aliphatic urethane acrylate resin CN990; Taiwan company Changhsingian silicone polyether acrylate resin 6225.

根据本发明提供的紫外光固化涂料,所述的主体树脂、稀释剂和光引发剂的含量为常规的紫外光固化涂料中的含量。 The UV-curable coating material of the present invention provides, according to the main resin, a diluent and a photoinitiator for the content of a conventional UV curable coatings. 一般来说,基于所述涂料的总重量,所述主体树脂的含量为5-90重量%、优选为10-80重量%,稀释剂的含量为10-90重量%、优选为20-80重量%,光引发剂的含量为1-10重量%、 优选为2-8重量%。 Generally, based on total weight of the coating, the content of the main resin is 5 to 90 wt%, preferably 10 to 80 wt%, the content of the diluent is 10-90% by weight, preferably 20 to 80 wt. %, content of the photoinitiator is from 1 to 10 wt%, preferably 2-8 wt%.

根据本发明提供的紫外光固化涂料,如本领域技术人员所公知的,所述稀释剂为有机溶剂,所述有机溶剂为甲苯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、乙酸丙酯、乙醇、正丁醇、环己酮、二甲苯、甲基异丁基甲酮、丙酮、 甲乙酮、乙二醇丁醚和丙二醇丁醚中的-一种或几种。 The present invention provides UV-curable coatings, as is well known to those of skill in the diluent is an organic solvent, the organic solvent is toluene, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate , ethanol, butanol, cyclohexanone, xylene, methyl isobutyl ketone, acetone, methyl ethyl ketone, ethylene glycol butyl ether and propylene glycol monobutyl ether - one or several. 根据本发明提供的紫外光固化涂料,所述光引发剂可以使用本领域技术人员所公知的各种光引发剂,例如2-羟基-2-甲基-l-苯基丙酮、1-羟基环己基 The present invention provides UV-curable coatings is, the photoinitiator may be used by the skilled person and various known photoinitiators, such as 2-hydroxy-2-methyl-acetone -l- phenyl, 1-hydroxycyclohexyl hexyl

苯甲酮、2-甲基l-(4-巯基苯基)-2-吗啉-l-丙酮和2-节基-2-二甲氨基-l-(4-吗啉苄基)-l-丁酮中的一种或几种。 Benzophenone, 2-methyl-l- (4- mercapto-phenyl) -2-morpholino -L-acetone and 2-dimethylamino-2-sections -l- (4- morpholin-benzyl) -l - one or several butanone. 所述光引发剂可以选自国内的北京英奇高科技术有限公司的IHT-PI185、 IHT-PI907和瑞士汽巴公司的Irgacure651、 Irgacure184 、 Irgacure369 、 Irgacure754 、 Irgacure2022 、 darocur1173 禾口darocurMBF中的一种或几种。 The photoinitiator can be selected from the domestic Inge Beijing High-Tech Co., Ltd. IHT-PI185, IHT-PI907 and Ciba's Irgacure651, Irgacure184, Irgacure369, Irgacure754, Irgacure2022, darocur1173 Wo mouth darocurMBF one or several.

根据本发明提供的紫外光固化涂料,在优选情况下,所述涂料还含有活性稀释剂,且基于所述涂料的总重量,所述活性稀释剂的含量为1-80重量%。 The UV-curable coating material of the present invention provides, in the preferred case, the coating further contains a reactive diluent, based on the total weight of the coating, the content of the reactive diluent is 1-80 wt%.

根据本发明提供的紫外光固化涂料,采用所述活性稀释剂可以提高本发明的涂料中各种成分之间的相容性,使该涂料更均匀,还可配合涂料中的几种树脂能更好的交联固化反应,在固化的过程中提高涂层的交联度,使得本发明的涂料所形成的漆膜有优良的硬度和附着力。 The present invention provides UV-curable coatings, the reactive diluent may be employed to improve the compatibility between the coating of the present invention, various components, making the coating more uniform, but also with several resins in the coating can be more good crosslinking reaction and increasing the degree of crosslinking in the cured coating process, so that the coating film formed by the present invention has excellent hardness and adhesion. 所述活性稀释剂可以采用二季戊四醇五丙烯酸酯(DPPA)、 二季戊四醇六丙烯酸酯(DPHA)、三羟甲基丙垸三丙烯酸酯(TMPTA)、季戊四醇三丙烯酸酯(PETA)、 1,6-己二醇丙烯酸酯(HDDA)和三丙二醇二丙烯酸酯(TPGDA)中的一种或几种。 The reactive diluent may be employed dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), embankment trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), 1,6- one or more of hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (of TPGDA) in.

根据本发明提供的紫外光固化涂料,在优选情况下,所述涂料还含有助剂,所述助剂的含量为1-15重量%。 The UV-curable coating material of the present invention provides, in the preferred case, the coating further contains adjuvants, the adjuvant in an amount of 1-15 wt%. 根据本发明提供的紫外光固化涂料,所述助剂可以选用本领域技术人员公知的各种助剂,例如该助剂可以选用流平剂、消泡剂、分散剂、偶联剂和表面活性剂中的一种或几种。 The present invention provides UV-curable coatings, which can be selected adjuvant known to a person skilled in the art various adjuvants, the adjuvants may be selected for example leveling agents, defoaming agents, dispersing agents, coupling agents and surfactants one or more agents.

根据本发明提供的紫外光固化涂料,所述各种助剂的含量为本领域技术人员公知的,在优选情况下,基于涂料的总重量,所述流平剂含量为0.1-2 重量%、优选0.5-1.5重量%,所述消泡剂的含量为0.1-2重量%、优选0.5-1.5 重量%,所述分散剂含量为0.1-5重量%、优选1-3重量%,所述偶联剂的含量为0.1-7重量%、优选1-5重量%,所述表面活性剂的含量为0.1-5重量%、优选1-3重量%。 The present invention provides UV-curable coatings, the amount of the various additives known to those skilled in the preferred case, based on the total weight of the coating, the content of the leveling agent is from 0.1 to 2 wt.% Flow, preferably 0.5 to 1.5% by weight, the defoaming agent in an amount of from 0.1 to 2% by weight, preferably 0.5 to 1.5 wt%, the content of the dispersant is 0.1 to 5 wt%, preferably 1-3 wt%, said coupling linking agent content of 0.1 to 7 wt%, preferably 1-5 wt%, the content of the surfactant is 0.1 to 5 wt%, preferably 1-3 wt%.

根据本发明提供的紫外光固化涂料,所述流平剂的种类为本领域的技术人员所公知的,例如,所述流平剂可以选用商购的荷兰爱夫卡公司的 The present invention provides UV-curable coatings, the stream type leveling agent known to those well known in the art, for example, the leveling agent may be selected companies commercially available 荷兰爱夫卡

EFKA3883、 EFKA3886和EFKA3600, BYK公司的BYK366、 BYK333和BYK307,德国迪高公司的DEG0410。 EFKA3883, EFKA3886 and EFKA3600, BYK's BYK366, BYK333 and BYK307, Germany Tego's DEG0410.

根据本发明提供的紫外光固化涂料,所述消泡剂的种类为本领域的技术人员所公知的,例如,所述消泡剂可以选用商购的荷兰爱夫卡公司的EFKA2022、 EFKA2527禾卩EFKA2040, BYK公司的BYK352、 BYK354和BYK357。 The present invention provides UV-curable coatings, said defoamer known to those skilled in the kind known, for example, the commercially available antifoaming agents can be selected 荷兰爱夫卡's EFKA2022, EFKA2527 Wo Jie EFKA2040, BYK's BYK352, BYK354 and BYK357.

根据本发明提供的紫外光固化涂料,所述分散剂为本领域技术人员公知的各种能够改善涂料中的主体树脂在稀释剂中的分散状态的物质,例如可以选用商购的美国Kerper公司的Kerper-602、 Kerper-605和Kerper-630,法国CFC公司的CFC-500HP、 CFC-510、 CFC-637和CFC-604S。 The present invention provides a UV-curable coating material, the dispersing agent known to those skilled in various known substances capable of improving the dispersion state of the resin coating material body in a diluent, for example, can use a commercially available US company Kerper Kerper-602, Kerper-605 and Kerper-630, CFC's French CFC-500HP, CFC-510, CFC-637 and CFC-604S.

根据本发明提供的紫外光固化涂料,所述偶联剂为本领域技术人员公知的各种偶联剂,例如可以选用商购的道康宁公司的KH-550、 6020、 6040和7104以及旭肖子公司的DP7192。 The present invention provides UV-curable coatings, said coupling agent known to those skilled in known various coupling agents, for example, can use commercially available Dow Corning KH-550, 6020, 6040 and 7104 as well as Asahi subsidiary Shaw the DP7192.

根据本发明提供的紫外光固化涂料,所述表面活性剂为本领域技术人员公知的各种表面活性剂,例如可以选用商购的杜邦公司的8857A和Zonyl FSO-100以及旭肖子公司DP-10和DP-20。 The present invention provides UV-curable coatings, said surfactant present skill known in the art various surfactants, commercially available, for example, can use the 8857A and DuPont Zonyl FSO-100 and DP-10 by Asahi subsidiary Shaw and DP-20.

本发明的紫外光固化涂料的制备方法可以将所述主体树脂、稀释剂和光引发剂可以同时进行混合也可以分步进行混合。 The method of preparing the ultraviolet curable coating of the present invention may be the main resin, a diluent and a photoinitiator may be mixed at the same time may be mixed stepwise. 在优选情况下,先将光引发剂与部分稀释剂混合,使光引发剂充分溶解,得到一种含有光引发剂的溶液; 然后将主体树脂与另一部分稀释剂混合均匀,得到一种含有主体树脂的浆液;如果在涂料中还加入活性稀释剂时,则将活性稀释剂与一部分稀释剂混合均匀,得到一种含有活性稀释剂的溶液;接着将含有光引发剂的溶液与含有主体树脂的浆液以及含有活性稀释剂的溶液混合均匀,最后加入剩余的稀释剂混合均匀。 In the preferred case, the first agent and the photoinitiator portion diluent, photoinitiator sufficiently dissolved to obtain a solution containing a photoinitiator; and then the resin body to another part of the diluent uniformly mixed to obtain a body comprising resin slurry; if the paint was also added reactive diluents, reactive diluents and then the portion of the diluent uniformly mixed to obtain a solution containing a reactive diluent; then a solution containing a photoinitiator and a resin body containing the slurry was mixed and a uniform solution containing a reactive diluent, and finally adding the remaining diluent uniformly mixed. 上述混合通常在常温下进行,必要时,可以稍微加热至30-60 Said mixing is generally carried out at ordinary temperature, if necessary, can be slightly heated to 30-60

°c,以加速混合。 ° c, to accelerate the mixing. 在此优选的方法中,对各部分稀释剂的用量没有特别的要 In this preferred method, no particular amounts to each portion of the diluent

求,只要充分溶解或稀释各成分即可。 Seeking, as long as sufficient of each component can be dissolved or diluted.

如果在所述涂料中还加入流平剂、消泡剂、分散剂、偶联剂和表面活性剂等助剂中的一种或几种时,上述制备方法还包括在加入剩余的稀释剂之前,在将含有光引发剂的溶液、含有主体树脂的浆液以及含有活性稀释剂的溶液混合时,再加入上述各种助剂中的一种或几种,并均匀混合。 If the further addition of a coating leveling agents, antifoaming agents, dispersing agents, coupling agents and surfactants aid in or several of the above-described production method further comprising prior to adding the remaining diluent when a solution containing a photoinitiator, a mixed slurry of the resin body containing a reactive diluent and a solution containing one or more of adding the above-described various additives, and uniformly mixed. 各种助剂可以同时加入也可以分步加入,加入的顺序对本发明的涂料的性能没有显著的影响。 Various additives can also be added stepwise added, the order of addition had no significant effect on the performance of the coating of the present invention.

本发明的紫外光固化涂料的制备方法的优选的实施方式为, The preferred embodiment of a method of making UV-curable coatings of the present invention is,

(1) 将光引发剂与部分稀释剂混合,搅拌至充分溶解,得到含有光引 (1) the photoinitiator with some diluent agent, stirring until fully dissolved to give a primer containing a light

发剂的溶液; Initiator solution;

(2) 将主体树脂与另一部分稀释剂混合均匀,得到含有主体树脂的浆 (2) the resin body to another part of the diluent uniformly mixed to obtain a slurry containing a main resin

液; liquid;

(3) 将活性稀释剂与再一部分稀释剂混合,搅拌至充分溶解,得到含有活性稀释剂的溶液; (3) the reactive diluent and then mixed with a portion of the diluent and stirred until fully dissolved to obtain a solution containing a reactive diluent;

(4) 将上述所得到的含有光引发剂的溶液、含有主体树脂的浆液与含有活性稀释剂的溶液混合,得到混合物; (4) The above-obtained solution containing a photoinitiator, a mixed solution containing a slurry containing the active body resin and a diluent, to obtain a mixture;

(5) 在所得到的混合物中继续加入流平剂、消泡剂、分散剂、偶联剂和表面活性剂中的一种或几种,并混合均匀; (5) the resulting mixture was further added a leveling agent, a defoaming agent, one or more dispersing agents, coupling agents, and surface active agent, and mixed well;

(6) 然后过滤除去操作过程中带来的灰尘和杂质产生的残渣,将剩余的稀释剂全部加入并混合均匀。 (6) then filtered to remove the residue from the dust during the operation and the generation of impurities, all of the remaining diluent was added and mixed well.

最终得到本发明的优选的涂料。 Finally obtained preferred coating of the present invention.

本发明所提供的涂料适合用于塑料基材的面漆,如手机壳体表面、手提电脑外売、化妆品包装外壳等的面漆。 The present invention provides a suitable finish coatings for plastic substrates, such as a mobile phone housing surface finish, an outer Laptop bai, cosmetic packaging bag or the like. 将本发明的涂料涂覆到基材上之后, The coatings of the present invention is applied to the substrate after,

将该涂覆了涂料的基材在40-8(TC的温度下烘烤10-15分钟,并采用紫外光照射20-25秒,在基材上形成厚度为10-15微米的漆膜。 The coated substrate coating baking 10-15 minutes (at a temperature of TC 40-8, and 20-25 seconds using UV irradiation to form a film having a thickness of 10-15 microns on the substrate.

本发明提供的紫外光固化涂料形成漆膜后的表面能较低,因而使得由本发明的涂料所形成的漆膜的耐水、耐油和自清洁性能较好,可以达到很好的防污效果。 The low surface energy according to the present invention provides UV-curable coatings form a film, thereby making the water from the coating film to be formed according to the present invention, since the oil and good cleaning performance, can achieve a good antifouling effect. 而且漆膜的硬度较高,使漆膜具有耐擦划性能。 And high film hardness, scratch resistant paint film performance. 另外,漆膜具有较高的光泽度和较好的附着力。 Further, the film has a high gloss and good adhesion.

下面采用实施例的方式对本发明进行进一步详细地描述。 The present invention will be described in further detail by way of embodiments.

实施例1 Example 1

将4克光引发剂(darocur1173)与5克稀释剂(甲苯:乙酸丁酯二l: 1) 混合,搅拌至充分溶解,得到含有光引发剂的溶液; 4 g of photoinitiator (Darocur 1173) and 5 g diluent (toluene: butyl diacetate l: 1) were mixed and stirred until fully dissolved to obtain a solution containing a photoinitiator;

将10克聚硅氧烷脂肪族聚氨酯丙烯酸酯树脂(美国沙多玛产品,型号为CN990, 25T:时的粘度为50000 cP)和50克6官能度聚氨酯丙烯酸酯树脂(日本合成化学株氏会社产品,型号为7605B, 6(TC时的粘度为2000cP, 官能度为6,硬度为5H。)与30克稀释剂(甲苯:乙酸丁酯=1: 1)混合均匀,得到含有上述两种主体树脂的浆液; 10 g of silicone resin, aliphatic urethane acrylate (Sartomer product USA, Model CN990, 25T: viscosity of 50000 cP) and 50 g of 6-functional urethane acrylate resin (Nippon Synthetic Chemical Zhushikuaishe products, model 7605B, 6 (viscosity of 2000cP TC, a functionality of 6, a hardness of 5H.) and 30 g diluent (toluene: butyl acetate = 1: 1) were mixed uniformly, and the two body comprising the slurry of the resin;

将含有光引发剂的溶液与含有上述两种主体树脂的浆液混合,得到混合物;在所得到的混合物中继续添加2.0克的流平剂(BYK333), 2.0克的消泡剂(BYK354)、 5.0克的偶联剂(道康宁Z-6040)和2.0克氟表面活性剂(Zonyl 8857A),混合均匀,接着过滤除去残渣,将剩余的5克稀释剂(甲苯:乙酸丁酯=1: l)全部加入,搅拌均匀,得到本发明的紫外光固化涂料。 The solution containing the photoinitiator and mixing a slurry containing both the main resin, to obtain a mixture; continue adding 2.0 g of a leveling agent (BYK333) in the obtained mixture, 2.0 g of antifoaming agent (BYK354), 5.0 g of coupling agent (Dow Corning Z-6040) and 2.0 g of fluorosurfactant (Zonyl 8857A), mixed well, and then the residue was removed by filtration, the remaining 5 g of diluent (toluene: butyl acetate = 1: l) all was added and stirred uniformly to obtain UV-curable coatings of the present invention.

实施例2 Example 2

将4克光引发剂(darocur1173)与5克稀释剂(甲苯:乙酸丁酯二l: 1)混合,搅拌至充分溶解,得到含有光引发剂的溶液; 4 g of photoinitiator (Darocur 1173) and 5 g diluent (toluene: butyl diacetate l: 1) were mixed and stirred until fully dissolved to obtain a solution containing a photoinitiator;

将20克6官能度有机硅丙烯酸酯树脂(比利时UCB公司,EB1360, 25。C时的粘度为2100 cP)、 20克10官能度聚氨酯丙烯酸酯树脂(日本合成化学株氏会社产品,型号为1700B, 6(TC时的粘度为1500 cP,官能度为10, 硬度为8H)和20克活性稀释剂(DPHA)与30克稀释剂(甲苯:乙酸丁酯=1: 1)混合均匀,得到含有上述两种主体树脂和活性稀释剂的浆液; 20 g of 6-functional silicone acrylate resin (UCB Belgium company, EB1360, viscosity at 25.C to 2100 cP), 20 g of 10 functionality of the urethane acrylate resin (product of Japan Synthetic Chemical K.K., Model 1700B , 6 (TC viscosity of 1500 cP, a functionality of 10, a hardness of 8H) and 20 g of reactive diluent (DPHA) and 30 g diluent (toluene: butyl acetate = 1: 1) were mixed uniformly, comprising both the main resin and the reactive diluent of the slurry;

将上述含有光引发剂的溶液、含有上述两种主体树脂和活性稀释剂的浆液混合,得到混合物;在所得到的混合物中继续添加2.0克的流平剂(BYK333), 2.0克的消泡剂(BYK354)、 5.0克的偶联剂(道康宁Z-6040) 和2.0克氟表面活性剂(Zonyl 8857A),混合均匀,接着过滤以除去残渣, 将剩余的5克稀释剂(甲苯:乙酸丁酯=1: 1)全部加入,搅拌均匀,得到本发明的紫外光固化涂料。 The solution containing the photoinitiator, the two body comprising mixing a resin and a slurry of the reactive diluent, to obtain a mixture; continue adding 2.0 g of a leveling agent (BYK333) in the obtained mixture, 2.0 g of defoamer (BYK354), 5.0 gram coupling agent (Dow Corning Z-6040) and 2.0 g fluorinated surfactant (Zonyl 8857A), mixed well, and then filtered to remove debris, and the remaining 5 g diluent (toluene: butyl acetate = l: l) was added all, stir to give a UV-curable coatings of the present invention.

实施例3 Example 3

将4克光引发剂(darocur1173)与5克稀释剂(甲苯:乙酸丁酯=1: 1) 混合,搅拌至充分溶解,得到含有光引发剂的溶液; 4 g of photoinitiator (Darocur 1173) and 5 g diluent (toluene: butyl acetate = 1: 1) were mixed and stirred until fully dissolved to obtain a solution containing a photoinitiator;

将12克6官能度有机硅丙烯酸酯树脂(比利时UCB公司,EB1360, 25"C时的粘度为2100cP)、 28克IO官能度聚氨酯丙烯酸酯树脂(日本合成化学株氏会社产品,型号为1700B, 6(TC时的粘度为1500 cP,官能度为10, 硬度为8H)和20克活性稀释剂(DPHA)与30克稀释剂(甲苯:乙酸丁酯=1: 1)混合均匀,得到含有上述两种主体树脂和活性稀释剂的浆液; 12 g of a hexafunctional silicone acrylate resin (UCB Belgium company, EB1360, 25 "C at a viscosity of 2100cP), 28 g of IO functionality urethane acrylate resin (product of Japan Synthetic Chemical K.K., Model 1700B, 6 (TC viscosity of 1500 cP, a functionality of 10, a hardness of 8H) and 20 g of reactive diluent (DPHA) 30 g of a diluent (toluene: butyl acetate = 1: 1) and uniformly mixed to obtain containing the two kinds of main resin and reactive diluent slurry;

将上述含有光引发剂的溶液、含有上述两种主体树脂和活性稀释剂的浆液混合,得到混合物;在所得到的混合物中继续添加2.0克的流平剂(BYK333), 2.0克的消泡剂(BYK354)、 5.0克的偶联剂(道康宁Z-6040) 和2.0克氟表面活性剂(Zonyl 8857A),混合均匀,接着过滤以除去残渣,将剩余的5克稀释剂(甲苯:乙酸丁酯二l: l)全部加入,搅拌均匀,得到本发明的紫外光固化涂料。 The solution containing the photoinitiator, the two body comprising mixing a resin and a slurry of the reactive diluent, to obtain a mixture; continue adding 2.0 g of a leveling agent (BYK333) in the obtained mixture, 2.0 g of defoamer (BYK354), 5.0 gram coupling agent (Dow Corning Z-6040) and 2.0 g fluorinated surfactant (Zonyl 8857A), mixed well, and then filtered to remove debris, and the remaining 5 g diluent (toluene: butyl acetate two l: l) was added all, stir to give a UV-curable coatings of the present invention.

对比例1 Comparative Example 1

将4克光引发剂(darocur1173)与5克稀释剂(甲苯:乙酸丁酯=1: 1) 混合,搅拌至充分溶解,得到含有光引发剂的溶液; 4 g of photoinitiator (Darocur 1173) and 5 g diluent (toluene: butyl acetate = 1: 1) were mixed and stirred until fully dissolved to obtain a solution containing a photoinitiator;

将40克10官能度聚氨酯丙烯酸酯树脂(日本合成化学株氏会社产品, 型号为1700B, 60。C时的粘度为1500 cP,官能度为10,硬度为8H)和20 克活性稀释剂(DPHA)与30克稀释剂(甲苯:乙酸丁酯=1: l)混合均匀, 得到含有上述主体树脂和活性稀释剂的浆液; 40 g of 10 functional urethane acrylate resin (product of Japan Synthetic Chemical K.K., Model 1700B, a viscosity at 60.C to 1500 cP, a functionality of 10, a hardness of 8H) and 20 g of reactive diluent (DPHA ) and 30 g diluent (toluene: butyl acetate = 1: l) uniformly mixed to obtain a slurry containing the diluent resin and an active body;

将上述含有光引发剂的溶液、含有上述主体树脂和活性稀释剂的浆液混合,得到混合物;在所得到的混合物中继续添加2.0克的流平剂(BYK333), 2.0克的消泡剂(BYK354)、 5.0克的偶联剂(道康宁Z-6040)和2.0克氟表面活性剂(Zonyl 8857A),混合均匀,接着过滤以除去残渣,将剩余的5克稀释剂(甲苯:乙酸丁酯=1: 1)全部加入,搅拌均匀,得到本发明的紫外光固化涂料。 The solution containing the photoinitiator, reactive diluent containing a main resin and mixing the above slurry, to obtain a mixture; continue adding 2.0 g of a leveling agent (BYK333) in the obtained mixture, 2.0 g of antifoaming agent (BYK354 ), 5.0 g of coupling agent (Dow Corning Z-6040) and 2.0 g fluorinated surfactant (Zonyl 8857A), mixed well, and then filtered to remove debris, and the remaining 5 g diluent (toluene: butyl acetate = 1 : 1) was added all, stir to give a UV-curable coatings of the present invention.

对比例2 Comparative Example 2

将4克光引发剂(darocur1173)与5克稀释剂(甲苯:乙酸丁酯=1: 1) 混合,搅拌至充分溶解,得到含有光引发剂的溶液; 4 g of photoinitiator (Darocur 1173) and 5 g diluent (toluene: butyl acetate = 1: 1) were mixed and stirred until fully dissolved to obtain a solution containing a photoinitiator;

将12克6官能度有机硅丙烯酸酯树脂(比利时UCB公司,EB1360, 25。C时的粘度为2100 cP)、28克聚氨酯丙烯酸酯树脂(沙多玛公司,CN9007, 6(TC时的粘度为4500 cP,官能度为2,硬度为2H)禾P 20克活性稀释剂(DPHA)与30克稀释剂(甲苯:乙酸丁酯=1: 1)混合均匀,得到含有上述两种主体树脂和活性稀释剂的浆液;将上述含有光弓I发剂的溶液、含有上述两种主体树脂和活性稀释剂的浆液混合,得到混合物;在所得到的混合物中继续添加2.0克的流平剂(BYK333), 2.0克的消泡剂(BYK354)、 5.0克的偶联剂(道康宁Z-6040) 和2.0克氟表面活性剂(Zonyl 8857A),混合均匀,接着过滤以除去残渣, 将剩余的5克稀释剂(甲苯:乙酸丁酯二l: l)全部加入,搅拌均匀,得到本发明的紫外光固化涂料。 12 g of a hexafunctional silicone acrylate resin (UCB Belgium company, EB1360, viscosity at 25.C to 2100 cP), 28 g of urethane acrylate resin (Sartomer Company, CN9007, 6 (viscosity of TC 4500 cP, a functionality of 2 and a hardness of 2H) Wo P 20 grams of active diluent (DPHA) and 30 g diluent (toluene: butyl acetate = 1: 1) were mixed uniformly to obtain a resin body containing both an active and diluent slurry; solution containing the above-described light bow I initiator, a slurry containing the mixed resin body and the two reactive diluents, to obtain a mixture; continue adding 2.0 g of a leveling agent (BYK333) in a mixture of the obtained , 2.0 g of antifoaming agent (BYK354), 5.0 gram coupling agent (Dow Corning Z-6040) and 2.0 g fluorinated surfactant (Zonyl 8857A), mixed well, then filtered to remove the residue diluted with 5 grams, the remaining agent (toluene: butyl diacetate l: l) was added all, stir to give a UV-curable coatings of the present invention.

性能测试 Performance Testing

将实施例1-2和对比例1中制备得到的涂料分别喷涂在塑料外壳(60mmxl00mm黑色PC色板)上,在60°C的温度下烘烤10分钟,然后经过紫外光照射25秒,在塑料外壳得到厚度为12微米的漆膜。 1-2 and coatings prepared in Comparative Example 1 obtained in Example embodiments are sprayed on the plastic housing (60mmxl00mm black swatch PC), baked at a temperature of 60 ° C for 10 minutes and then subjected to UV irradiation for 25 seconds in plastic shell having a thickness of 12 micron film. 将所得到的漆膜进行如下的性能测试,结果如表l所示。 The film obtained following performance test results are shown in Table l.

1、 测试附着力 1. Adhesion test

用划格器在漆膜表面上划100个1毫米X 1毫米的正方形格。 Crosshatch designated by 100 is 1 mm X 1 mm square grid on the surface of the film. 用美国3M 公司生产的型号为600的透明胶带平整粘结在方格上,不留一丝空隙,然后以60度角迅速揭起胶带,观察漆膜的划痕边缘处是否有脱漆。 With the American company 3M Model 600 transparent tape adhered to the box flat, without leaving a trace of the gap, then quickly lift the tape 60 degree angle, to see if there is a scratch at the edge of the film stripping.

如没有任何脱漆为5B,脱漆量在0-5面积%之间为4B,脱漆量在5-15 面积M之间为3B,脱漆量在15-35面积。 The stripping is no 5B, stripping between the amount of 0-5% of the area 4B, the amount of paint stripping area between 5-15 M of 3B, an amount of 15-35 paint stripping area. /。 /. 之间为2B,脱漆量在35-65面积% 之间为1B,脱漆量在65面积%以上为0B。 It is between 2B, stripping between the amount of 35-65% of the area 1B, the amount of stripping% or more in an area 65 0B.

2、 硬度测试 2, hardness test

按照GB/6739T中第四章的规定执行。 Accordance with the provisions of Chapter GB / 6739T fourth.

3、 光泽度测试 3, gloss test

采用微型光泽度仪(BYK)在60。 Using micro gloss meter (BYK) at 60. 角下测试得到光泽度数据。 Test data obtained at an angle gloss.

4、 表面能测试 4, the surface can be tested

使用Data physics公司的OCA系列接触角测量仪测量漆膜与水和二碘甲烷的接触角,然后由该测量仪得出涂层的表面能。 Use Data physics series OCA's contact angle meter measured the contact angle of the film with water and diiodomethane, and surface coating can be derived from the meter.

<table>table see original document page 14</column></row> <table> <Table> table see original document page 14 </ column> </ row> <table>

由表1所示的结果可以看出,本发明所提供的紫外光固化涂料固化后的漆膜表面能较低,硬度较高,同时有较高的光泽度和优良的附着力。 As can be seen from the results shown in Table 1, after the surface of the film of the present invention provides a UV curable coating is cured low energy, high hardness, while high gloss and excellent adhesion. 由于所得到的漆膜具有较低的表面能和较高的硬度,因此,具有较好的防污效果和耐擦划性能。 Due to the resulting film has low surface energy and high hardness, and therefore, the antifouling effect and has good abrasion resistance properties.

Claims (10)

  1. 1、一种紫外光固化涂料,该涂料含有主体树脂、稀释剂和光引发剂,所述主体树脂含有聚氨酯丙烯酸酯树脂,其特征在于,所述主体树脂还含有有机硅丙烯酸酯树脂,所述聚氨酯丙烯酸酯树脂的官能度为6-10,粘度为60℃下500-2500cP,硬度为5-8H。 A UV-curable coating material, the coating comprising a resin body, a diluent and a photoinitiator, the host resin containing urethane acrylate resin, wherein said body further comprises a silicone resin, an acrylate resin, a polyurethane multifunctional acrylate resin is 6-10, at a viscosity of 60 ℃ 500-2500cP, hardness of 5-8H.
  2. 2、 根据权利要求1所述的涂料,其中,基于所述主体树脂的总重量,所述聚氨酯丙烯酸酯树脂的含量为10-90重量%,所述有机硅丙烯酸酯树脂的含量为10-90重量%。 2, the coating material according to claim 1, wherein, based on the total weight of the main resin, the content of the urethane acrylate resin is 10-90 wt%, the content of the silicone acrylate resin, 10 to 90 weight%.
  3. 3、 根据权利要求2所述的涂料,其中,基于所述主体树脂的总重量,所述聚氨酯丙烯酸酯树脂的含量为50-85重量%,所述有机硅丙烯酸酯树脂的含量为15-50重量%。 3, the coating according to claim 2, wherein, based on the total weight of the main resin, the content of the urethane acrylate resin of 50 to 85 wt%, the content of the silicone acrylate resin 15-50 weight%.
  4. 4、 根据权利要求1-3中任意一项所述的涂料,其中,所述有机硅丙烯酸酯树脂的粘度为25"C下2000-50000 cP。 4. The coating as claimed in any one of claims, wherein the viscosity of the silicone acrylate resin is at 25 "C 2000-50000 cP.
  5. 5、 根据权利要求1所述的涂料,其中,基于所述涂料的总重量,所述主体树脂的含量为5-90重量%,稀释剂的含量为10-90重量%,光引发剂的含量为1-10重量%。 5. The coating of claim 1, wherein, based on total weight of the coating, the content of the main resin is 5-90 wt%, the content of the diluent is 10 to 90 wt%, the content of the photoinitiator 1 to 10 wt%.
  6. 6、 根据权利要求1或5所述的涂料,其中,所述稀释剂为有机溶剂,所述有机溶剂为甲苯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、乙酸丙酯、乙醇、正丁醇、环己酮、二甲苯、甲基异丁基甲酮、丙酮、甲乙酮、乙二醇丁醚和丙二醇丁醚中的一种或几种;所述光引发剂为2-羟基-2-甲基-l-苯基丙酮、1-羟基环己基苯甲酮、2-甲基l-(4-巯基苯基)-2-吗啉-l-丙酮和2-苄基-2-二甲氨基-l-(4-吗啉苄基)-l-丁酮中的一种或几种。 6, according to claim 1 or coating according to claim 5, wherein said diluent is an organic solvent, the organic solvent is toluene, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, ethanol, n butanol, cyclohexanone, xylene, methyl isobutyl ketone, acetone, methyl ethyl ketone, ethylene glycol butyl ether and propylene glycol monobutyl ether is one or more; the photoinitiator is 2-hydroxy-2- acetone -l- phenyl group, 1-hydroxy cyclohexyl phenyl ketone, 2-methyl-l- (4- mercapto-phenyl) -2-morpholino -l- acetone and 2-benzyl-2-dimethylamino -l- (4- morpholin-benzyl) -L-one or several butanone.
  7. 7、 根据权利要求1所述的涂料,其中,所述涂料还含有活性稀释剂,且基于所述涂料的总重量,所述活性稀释剂的含量为1-80重量%。 7. The coating of claim 1, wherein said coating material further comprises reactive diluents, based on the total weight of the coating, the content of the reactive diluent is 1-80 wt%.
  8. 8、 根据权利要求7所述的涂料,其中,所述活性稀释剂为二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三羟甲基丙垸三丙烯酸酯、季戊四醇三丙烯酸酯、1,6-己二醇丙烯酸酯和三丙二醇二丙烯酸酯中的一种或几种。 8. The coating of claim 7, wherein said reactive diluent is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate embankment, pentaerythritol triacrylate, 1,6 one or more hexanediol diacrylate and tripropylene glycol diacrylate are.
  9. 9、 根据权利要求1或7所述的涂料,其中,所述涂料还含有助剂,且基于所述涂料的总重量,所述助剂的含量为1-15重量%。 9. The coating of claim 1 or claim 7, wherein the coating further comprises additives, based on the total weight of the coating, the auxiliary content is 1-15 wt%.
  10. 10、 根据权利要求9所述的涂料,其中,所述助剂为流平剂、消泡剂、分散剂、偶联剂和表面活性剂中的一种或几种,并且基于涂料的总重量,所述流平剂的含量为0.1-2重量%,所述消泡剂的含量为0.1-2重量%,所述分散剂的含量为0.1-5重量%,所述偶联剂的含量为0.1-7重量%,所述表面活性剂的含量为0.1-5重量%。 10. The coating of claim 9, wherein said adjuvant is a leveling agent, one or more antifoaming agents, dispersing agents, coupling agents, and surface active agent, based on the total weight of the coating the content of the leveling agent is from 0.1 to 2% by weight, the defoaming agent in an amount of from 0.1 to 2 wt%, the content of the dispersant is 0.1 to 5 wt%, the amount of coupling agent 0.1 to 7 wt%, the content of the surfactant is 0.1 to 5 wt%.
CN 200710302243 2007-12-20 2007-12-20 UV curing color coating CN101463222B (en)

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