CN1772820A - Ultraviolet cured paint for plastics and its production process - Google Patents

Ultraviolet cured paint for plastics and its production process Download PDF

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Publication number
CN1772820A
CN1772820A CN 200410090634 CN200410090634A CN1772820A CN 1772820 A CN1772820 A CN 1772820A CN 200410090634 CN200410090634 CN 200410090634 CN 200410090634 A CN200410090634 A CN 200410090634A CN 1772820 A CN1772820 A CN 1772820A
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uv
curable coatings
hardness
plastics according
weight
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CN 200410090634
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谭伟华
董俊卿
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比亚迪股份有限公司
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Abstract

The present invention relates to one kind of ultraviolet cured paint for plastics and its production process. The paint includes matrix resin, active diluent, light initiator and solvent and features its antiwear hardness additive accounting for 0.1-8.0 wt% of the paint. The paint has high hardness, high antiwear performance, forms smooth paint coating through spraying, high toughness, high adhesion and high chemical corrosion resistance.

Description

一种用于塑料的紫外光固化涂料及其制造方法 UV-curable coatings and a manufacturing method for plastic

技术领域 FIELD

本发明属于涂料技术领域,涉及一种用于塑料的紫外光固化涂料及其制造方法,特别是涉及一种具有高硬度和耐磨性能的用于塑料的紫外光固化涂料。 The present invention belongs to the field of coating technology, relates to a method of manufacturing the ultraviolet curable coatings for plastics, in particular to a UV-curable coatings for plastics having a high hardness and wear resistance.

背景技术 Background technique

紫外光固化涂料具有高效、节能,无污染,漆膜层耐磨、硬度高、附着力强、耐腐蚀等特点,已广泛应用于家具涂装、家庭装修及油墨等。 UV-curable coatings with high efficiency, pollution-free, wear-resistant film layer, high hardness, adhesion, corrosion resistance and other characteristics, has been widely used in furniture coating, ink, and other home decoration. 由于紫外光固化涂料的上述特点,目前正将其应用于便携式器件的塑料配件的面漆,如手机壳体表面,手提电脑外壳,化妆品包装外壳等。 Due to the above characteristics of UV curable coatings, it is currently being applied to plastic parts topcoat portable device such as mobile phone housing surface, laptop housings, cosmetic packaging shell. 用紫外光固化涂料喷涂此种塑料件,可使其坚韧耐磨,耐汗水或其他化学品的腐蚀,光泽度高,使用期超长等优点,因此,目前在此方面的应用是该种涂料推广运用的一个热点。 UV-curable coating is sprayed with such a plastic, it can be tough wear-resistant, corrosion-resistant, high gloss, long use of the advantages of sweat or other chemicals, and therefore, the current application in this respect is that the kind of coating promotion of the use of a hot spot.

传统的用于木器、皮革、金属等的紫外光固化涂料,大都采用脂肪族聚氨酯丙烯酸酯、聚酯丙烯酸酯或环氧丙烯酸酯的两种或几种作为主要成膜物质,以1到3个官能团反应性丙烯酸单体作为稀释单体,再添加少量的助剂组成,如CN1277232A、CN1297973A等即采用此种方法。 Traditional UV-curable coatings for wood, leather, metal or the like, mostly using an aliphatic urethane acrylate, of two or more polyester acrylates or epoxy acrylates as the main film-forming substance, to 1-3 functional acrylic monomer as reactive diluent monomer, and then adding a small amount of the composition of additives, such as CN1277232A, CN1297973A, etc. i.e. using this method. 由于其组成和配比的局限性,将该种涂料用于经常受磨损的塑料器件的面漆时,其硬度和耐磨性则显不足。 Due to the limitations of its composition and proportion, the kind often used when coating under the topcoat wear plastic devices, which are increasingly inadequate hardness and wear resistance. CN1436825A谈到在涂料体系中添加占总重量0.5~3%的耐磨添加剂,该种耐磨添加剂型号为BYK920,它为一种反应性助剂,可增进树脂或稀释单体的交联效果,因此可在一定程度上增加固化后漆膜的耐磨性,但难以较大程度地同时增加漆膜的硬度和耐磨性,因此不能达到便携塑料器件涂层的使用要求。 CN1436825A Turning add 0.5-3% by weight of the total of anti-wear additives in the coating system, this type of anti-wear additives model BYK920, which as a reaction auxiliary, or can be diluted promoting resin, the crosslinking effect monomer, therefore to a certain extent increase the abrasion resistance of the cured film, it is difficult to a large extent while increasing the film hardness and wear resistance, and therefore can not achieve the requirements of the portable plastic coating device.

发明内容 SUMMARY

本发明所要解决的技术问题是针对现有技术所存在的便携塑料器件涂层漆膜的硬度和耐磨性达不到使用要求的缺陷,提供一种用于塑料的紫外光固化涂料及其制造方法,通过在涂料中增加一种高强度的硬度和耐磨添加剂粉末,能够同时提高紫外光固化涂料的耐磨度和硬度,使其达到高档塑料器件对漆膜涂料的要求。 The present invention solves the technical problem is not up to the requirements for the prior art drawbacks occurring portable device plastic coating film hardness and wear resistance, provides UV-curable coatings for plastics and a manufacturing method, a high strength by increasing the hardness of the coating powder and anti-wear additives, UV-curable coatings can simultaneously improve the hardness and wear resistance, to reach the high-grade plastic film coating on the device requirements. 喷涂于塑料表面后,用紫外光照射,其固化膜层不仅耐磨性能优异,而且硬度高,能耐汗水及一般化学品腐蚀,涂层的表面质量极好,能很好的满足便携式塑料器件的涂料的要求。 After the spray on the plastic surface, irradiated with ultraviolet light, the cured film is not only excellent wear resistance, and high hardness, the ability to sweat and general chemical corrosion, excellent surface quality of the coating, the plastic can well meet the portable device requirements coatings.

根据本发明,所提供的用于塑料的紫外光固化涂料包括基体树脂、活性稀释剂、光引发剂和溶剂,其特征在于还包括耐磨-硬度添加剂,该耐磨-硬度添加剂在该涂料中的重量百分比含量为0.1~8.0%,优选0.2~5.0%。 According to the present invention, there is provided a UV-curable coatings for plastic comprising a matrix resin, reactive diluent, a photoinitiator and a solvent, characterized by further comprising a wear resistant - hardness additives, the wear resistance - hardness of the additive in the coating the content by weight of 0.1 to 8.0%, preferably 0.2 to 5.0%. 所述耐磨-硬度添加剂是显微硬度在500kgf/mm2以上的固体粉末。 The wear - microhardness hardness additive is a solid powder at 500kgf / mm2 or more.

在一般使用中,对便携式塑料器件漆膜的硬度和耐磨性能较之其他被涂覆件有着更高的要求。 In normal use, compared with other member is coated with higher demands on the portable device the plastic film hardness and wear resistance. 相对于涂层的附着力、耐溶剂性等性能来讲,提高涂料的硬度和耐磨性能的难度往往更大。 With respect to adhesion, solvent resistance and other properties of the coating in terms of difficulty to improve the coating hardness and wear resistance are often greater.

在本发明中,采用向涂料总体系中加入一定量的用于改善硬度及耐磨性的耐磨-硬度添加剂,所述的耐磨-硬度添加剂的材料为具有较高机械强度的固体粉末,当基体树脂和活性稀释剂经光固化后,耐磨-硬度添加剂粉末就混入涂膜层中,由于该耐磨-硬度添加剂是具有较高硬度和强度的材料,这样就大大改善了整个涂膜层的物理机械性能,极大地提高了漆膜的硬度和耐磨性。 In the present invention, a system is added to the total amount of the coating for improving the hardness and wear resistance of wear resistance - hardness additive, the wear - the hardness of the additive material is a solid powder having a high mechanical strength, when the matrix resin and the reactive diluent is cured by light, wear - it is mixed into the additive powder hardness coating layer, since the wear resistance - hardness additive is a material having a higher stiffness and strength, thus greatly improves the overall film physical and mechanical properties of the layer, the paint film greatly improved hardness and wear resistance.

在本发明紫的外光固化涂料中,只要是其显微硬度满足上述要求的固体粉末,都可以用作所述的耐磨-硬度添加剂,例如,该耐磨-硬度添加剂可以为选自碳化物、氮化物、氧化物或有机高聚物中的至少一种。 In the present invention, the ultraviolet light-curable coatings, so long as its hardness satisfying the above requirements solid powder, can be used as the wear - hardness additives, e.g., the wear resistance - may be selected from a carbide hardness of additives at least one, nitride, oxide or organic high polymer. 优选的是,所述碳化物为选自碳化硅、碳化锆、碳化硼、碳化铝、碳化铁、碳化铬中的至少一种;所述氮化物为选自氮化钛、氮化锆、氮化镓、氮化铝、氮化钙中的至少一种;所述氧化物为选自二氧化钛、氧化铝、氧化铬、氧化锡、二氧化硅中的至少一种;所述有机高聚物为选自尼龙、聚乙烯蜡、聚丙烯蜡、聚氯乙烯蜡、聚碳酸酯中的至少一种。 Preferably, said carbide selected from silicon carbide, zirconium carbide, boron carbide, aluminum carbide, iron carbide, chromium carbide in at least one of; the nitride is selected from titanium nitride, zirconium nitride, gallium, aluminum nitride, calcium nitride is at least one; the oxide is selected from titanium dioxide, aluminum oxide, chromium oxide, tin oxide, at least one of silica; the organic polymer is selected from nylon, polyethylene wax, polypropylene wax, wax, polyvinyl chloride, at least one polycarbonate.

所述耐磨-硬度添加剂固体粉末的平均颗粒大小优选为小于10μm,更优选为3μm~8μm。 The wear resistance - hardness additive powder has an average particle size of the solid is preferably less than 10μm, more preferably 3μm ~ 8μm. 其粒径太大时会增加混入主体树脂的难度,并且使漆膜表面流平性能不良,粒径太小有可能会降低对提高漆膜层的硬度和耐磨性的能力。 Which will increase the difficulty of the particle size is mixed into the resin body is too large, and the poor performance of the paint surface leveling, the particle size is too small may reduce the ability of the hardness and wear resistance of the paint film layer.

所述耐磨-硬度添加剂的添加量必须严格控制,添加过少不足以增加固化后膜层的硬度和耐磨性能,太多则会影响漆膜对底材的附着力,使漆膜层对底材的附着力不良。 The wear - added in an amount necessary to strictly control the hardness of the additive added is too small not enough to increase the hardness and wear resistance of the cured film, too much it will affect the coating adhesion to the substrate, so that the film layer poor adhesion to the substrate.

在本发明的紫外光固化涂料中,各组分的重量百分比含量优选的是:基体树脂 15-70%活性稀释剂 10~55%耐磨-硬度添加剂 0.1~8.0%光引发剂 2.0~10.0%溶剂 2~50%在本发明的紫外光固化涂料中,所述基体树脂可以采用现有技术中传统的用于紫外光固化涂料中的基体树脂,本发明对其没有特别的限制,但优选的是玻璃化温度(Tg)在60℃以上的基体树脂,例如,该基体树脂可以为选自脂肪族聚氨酯丙烯酸酯树脂、环氧(甲基)丙烯酸酯树脂和聚酯丙烯酸酯树脂中的至少一种。 UV-curable coating material of the present invention, the content by weight of the components are preferably: 15-70% matrix resin reactive diluent from 10 to 55% wear resistance - Hardness additive 0.1 to 8.0% photoinitiator, 2.0 to 10.0% the solvent 2 ~ 50% in UV-curable coatings of the present invention, the base resin may be employed in conventional prior art for the base resin in UV-curable coatings, particularly no limitation on the present invention, it is preferred glass transition temperature (Tg) in the base resin above 60 ℃, e.g., the matrix resin may be selected from aliphatic urethane acrylate resins, epoxy (meth) acrylate resin and a polyester acrylate resin species. 特别优选的是,所述基体树脂为由脂肪族聚氨酯丙烯酸酯树脂、环氧(甲基)内烯酸酯树脂和聚酯丙烯酸酯树脂所组成的混合树脂,此时相对于所述涂料的总重量,所述混合树脂中各成分的重量百分比含量为:脂肪族聚氨酯丙烯酸酯树脂 5~20%;环氧(甲基)丙烯酸酯树脂 5~30%; Particularly preferred is a mixed resin of an aliphatic urethane acrylate resin, epoxy (meth) acrylate resin and the polyester acrylate resin composed by the base resin, this time with respect to the total coating by weight of the mixed resin content by weight of each component is: an aliphatic urethane acrylate resin is 5 to 20%; epoxy (meth) acrylate resin is 5 to 30%;

聚酯丙烯酸酯树脂 5~20%。 Polyester acrylate resin 5 to 20%.

本发明紫外光固化涂料中的基体树脂可采用Basfu(巴斯夫)或galstaff(盖斯塔夫)等部分型号的产品。 Base resin in UV-curable coatings of the present invention may be employed Basfu (BASF) or galstaff (Gaisitafu) and some other types of products.

在本发明的紫外光固化涂料中,所述活性稀释剂可以采用现有技术中传统的用于紫外光固化涂料中的活性稀释剂,例如采用官能度数从1到3的反应性的丙烯酸酯单体即单官能团丙烯酸酯单体、双官能团丙烯酸酯单体、三官能团丙烯酸酯单体中的至少一种。 UV-curable coating material of the present invention, the reactive diluent may be employed in conventional prior art reactive diluents for UV-curable coatings, for example by from 1 to 3 degrees functional acrylate single reactive i.e. body monofunctional acrylate monomers, difunctional acrylate monomers, trifunctional acrylate monomers at least one ester. 单官能度丙烯酸酯单体有丙烯酸羟乙酯(HEA),丙烯酸异冰片酯,丙烯酸异辛酯,乙氧化羟乙基甲基丙烯酸酯等。 Monofunctional acrylate monomers are hydroxyethyl acrylate (HEA), isobornyl acrylate, isooctyl acrylate, ethoxylated hydroxyethyl methacrylate and the like. 双官能度丙烯酸酯单体通常有二缩三丙二醇二丙烯酸酯(TPGDA)、1,6己二醇二丙烯酸酯(HDDA)、聚乙二醇二丙烯酸酯等,三官能度丙烯酸酯单体有三羟甲基丙烷三丙烯酸酯(TMPTA),季戊四醇三丙烯酸酯等。 Difunctional acrylate monomers are usually tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (of HDDA), polyethylene glycol diacrylate, trifunctional acrylate monomer has three trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate and the like. 通常,官能团越低,其对主体树脂的稀释效果好,但其活性小,交联密度小,因此固化后形成的漆膜耐磨性和硬度往往达不到较高的要求。 Generally, the lower the functional group, which is good for the dilution effect of the resin body, but little activity, low crosslink density, hardness and abrasion resistance film formed after curing tends to reach higher requirements. 高官能团单体属于高反应性单体,具有很高的交联密度,对提高固化后漆膜的耐磨性和硬度很有帮助,形成的膜层的耐溶剂性也好。 Higher functional monomer is a high reactive monomer having a high crosslinking density, helps to improve the wear resistance and hardness of the film after curing, solvent resistance of the film formed is good, too. 但会增加主体树脂的稀释难度,并且可能会较严重地导致漆膜对底材的附着力下降。 But it increases the difficulty of dilution of the resin body, and may lead to more serious film adhesion to the substrate decreases. 在本发明中,所述活性稀释剂特别优选的是采用单官能团丙烯酸酯单体、双官能团丙烯酸酯单体和三官能团丙烯酸酯单体的混合物,此时相对于所述涂料的总重量,优选各单体的重量百分比含量如下:单官能团丙烯酸酯单体 2~15%;双官能团丙烯酸酯单体 4~20%;三官能团丙烯酸酯单体 4~20%。 In the present invention, the reactive diluent is particularly preferred is the use of monofunctional acrylate monomers, difunctional acrylate monomers and trifunctional acrylate ester monomer mixture, this time with respect to the total weight of the coating, preferably content by weight of each monomer are as follows: a monofunctional acrylate monomer, 2 to 15%; bifunctional acrylate monomer having 4 to 20%; trifunctional acrylate monomer having 4 to 20%.

在本发明的紫外光固化涂料中,所述溶剂可以采用现有技术中传统的用于紫外光固化涂料中的溶剂,但为达到合适的溶解力和挥发速度,本发明优选的是采用两种或两种以上不同种有机溶剂所组成的混合溶剂,例如,所述溶剂可以为选自甲苯、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、丙二醇丁醚中的两种或两种以上的溶剂的混合物。 UV-curable coating material of the present invention, the solvent may be employed in the prior art solvents for conventional UV curable coatings, but to achieve suitable solubility and evaporation rate, the present invention is preferably in two or a mixed solvent of two or more different kinds of organic solvents consisting of, for example, the solvent may be selected from toluene, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, ethanol, butanol, cyclohexanol ketone, xylene, methyl isobutyl ketone, acetone, methyl ethyl ketone, ethylene glycol butyl ether, propylene glycol butyl ether mixture of two or more solvents.

在本发明的紫外光固化涂料中,所述光引发剂可以采用现有技术中传统的用于紫外光固化涂料中的光引发剂,本发明对其没有特别的限制,例如,该光引发剂可选用汽巴公司的IHT-PI185、IHT-PI907、Irgacure651、Irgacure184、Irgacure369、Irgacure754,Irgacure2022,darocur1173,Irgacure2959、darocurMBF等产品中的一种或几种的混合物。 UV-curable coating material of the present invention, the photoinitiator is a photoinitiator can be used in UV curable coatings conventional in the prior art for the present invention is not particularly limited, for example, the photoinitiator or may be a mixture of several selected is Ciba IHT-PI185, IHT-PI907, Irgacure651, Irgacure184, Irgacure369, Irgacure754, Irgacure2022, darocur1173, Irgacure2959, darocurMBF other products.

在本发明的紫外光固化涂料中,除上述组分以外,还可以含有流平剂、消泡剂、分散剂等其它助剂。 UV-curable coating material of the present invention, in addition to the above components, may contain a leveling agent, a defoaming agent, dispersing agent other auxiliaries.

所述的流平剂可以采用现有技术中传统的用于紫外光固化涂料中的流平剂,本发明对其没有特别的限制,例如可以采用EFKA3883、EFKA3886、EFKA3600、EFKA3035、BYK366、BYK333、BYK307、DEGO410等中的一种或几种的混合物,其含量可以为涂料总重量的0.1~1.0%。 The leveling agent may be employed in conventional prior art leveling agents for UV-curable coatings, the present invention is not particularly limited, and for example, may be employed EFKA3883, EFKA3886, EFKA3600, EFKA3035, BYK366, BYK333, a mixture of one or more of BYK307, DEGO410 the like, the content thereof may be 0.1 to 1.0% of the total weight of the coating.

所述的消泡剂可以采用现有技术中传统的用于紫外光固化涂料中的消泡剂,本发明对其没有特别的限制,例如可以采用EFKA2022、EFKA2527、EFKA2040、BYK352、BYK354、BYK357、BYK052等中的一种或几种的混合物,其含量可以为涂料总重量的0.1~1.5%。 The antifoaming agent may be employed in conventional prior art defoamer for UV-curable coatings in the present invention is not particularly limited, and for example, may be employed EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354, BYK357, a mixture of one or more of BYK052 the like, the content thereof may be 0.1 to 1.5% of the total weight of the coating.

为了使所述耐磨-硬度添加剂能更好地悬浮于所述涂料中,本发明的紫外光固化涂料优选还含有分散剂。 In order to make the wear resistance - better hardness additive is suspended in the coating, UV-curable coatings of the present invention preferably further contains a dispersant. 所述的分散剂可以采用现有技术中传统的分散剂,本发明对其没有特别的限制,例如可以采用Kerper-602、Kerper-605、Kerper630、CFC-500HP、CFC-510、CFC-637、CFC-604S等中的一种或几种的混合物。 The dispersant may be employed in conventional prior art dispersants, the present invention is not particularly limited, and for example, may be employed Kerper-602, Kerper-605, Kerper630, CFC-500HP, CFC-510, CFC-637, one or a mixture of several of CFC-604S and the like.

根据本发明提供的制造所述用于塑料的紫外光固化涂料的方法包括以下步骤: The method for plastics manufacturing UV-curable coatings of the present invention comprises the steps of:

(1)将占涂料总体系15~70重量%的基体树脂溶解于占总体系10~55重量%的丙烯酸酯单体活性稀释剂中,搅拌均匀;(2)将占涂料总体系2~10重量%的光引发剂与占涂料总体系2~50重量%的溶剂混合,搅拌至充分溶解;(3)将步骤(2)所得混合物与步骤(1)所得混合物搅拌混合均匀;(4)向步骤(3)所得混合物中加入占涂料总体系0.1~8.0重量%的显微硬度在500kgf/mm2以上的耐磨-硬度添加剂固体粉末,高速搅拌使该固体粉末均匀悬浮。 (1) The total coating system will account for 15 to 70 wt% of the base resin is dissolved in 10 to 55% by weight of an acrylate monomer reactive diluent in the total system, stir; (2) the total coating system will account for 2 to 10 wt% of photoinitiator accounting solvent to 2 to 50 wt% of a coating of the total system, and stirring until fully dissolved; (3) obtained in step (2) the resulting mixture of step (1) was evenly stirred and mixed; (4) the the resulting mixture of step (3) was added 0.1 to 8.0% by weight of the total coating system, microhardness wear resistant 500kgf / mm2 or more - hardness of the solid powder additive, a high-speed stirring a homogeneous suspension of the solid powder.

其中步骤(4)还可以包括向步骤(3)所得混合物中加入前面所述的流平剂、消泡剂和分散剂。 Wherein step (4) may further comprise the step of (3) the resulting mixture is added in front of the leveling agents, defoaming agents and dispersing agents.

所述方法中各组分及其用量如前面所述。 The method of the components and amounts thereof as described above.

通过以上制作和处理得到的紫外光固化涂料,其耐磨度和硬度得到了极大的提高,能够很好地满足高档塑料器件对涂料的要求,有很好的硬度和耐磨性能,喷涂后漆膜平整、柔韧性好、附着力强,因此可使用于对便携式塑料器件表面的涂布。 By the above production process and the obtained UV-curable coatings, wear resistance and hardness which has been greatly improved, can satisfy the requirements of high-grade plastic coating device, good hardness and wear resistance, after spraying film formation, good flexibility, adhesion, and thus can be used in the coating of the plastic surface of the portable device. 并且,该种紫外光固化涂料能耐汗水及一般化学品的腐蚀,有光泽度高,使用期超长等优点。 And, the kind of UV-curable coatings and the general corrosion resistance to sweat chemicals, have high gloss, long lifetime and so on.

具体实施方式 Detailed ways

按照本发明所描述的制造方法的步骤,配制具有下列对比例和实施例的重量组成的紫外光固化涂料。 According to the procedure described in the manufacturing method of the present invention, UV-curable coatings formulated with the following Comparative Example and the weight of the composition.

对比例1脂肪族聚氨酯丙烯酸酯树脂(sartomer产品,CN965)10g,环氧丙烯酸酯树脂(galstaff产品,syncryl104)20g,聚酯丙烯酸酯树酯(sartomer产品,CNUVP225)20g,单官能团丙烯酸酯单体HEA 10g,双官能团丙烯酸酯单体HDDA 10g,三官能团丙烯酸酯单体TMPTA 20g,光引发剂Irgacure184为4g,流平剂EFKA3035为0.3g,消泡剂BYK052为0.2g,分散剂Kerper-605为1.0g,丙酮10g,乙酸丁酯8g,正丁醇8g。 Comparative Example 1 Aliphatic urethane acrylate resin (Sartomer product, CN965) 10g, an epoxy acrylate resin (galstaff product, syncryl104) 20g, polyester acrylate resin (Sartomer product, CNUVP225) 20g, monofunctional acrylate monomer HEA 10g, difunctional acrylate monomers HDDA 10g, trifunctional acrylate monomer TMPTA 20g, Irgacure184 as a photoinitiator 4g, EFKA3035 leveling agent is 0.3g, defoaming agent is BYK052 0.2g, Kerper-605 as dispersant 1.0g, acetone 10g, butyl acetate 8g, butanol 8g.

对比例2除添加2.0g的BYK920作为耐磨剂以外,其余和对比例1相同。 , And the rest other than the same as Comparative Example 1 Comparative Example 2 except adding BYK920 2.0g as antiwear agents.

实施例1除添加2.0g的碳化硅粉作为根据本发明的耐磨-硬度添加剂以外,其余和对比例1相同。 Additives other than the hardness, the same as Comparative Example 1, and the rest - for example 1, but the added silicon carbide powder, 2.0g, as the wear-resistant embodiment of the present invention.

实施例2除添加5.0g的碳化硅粉外,其余和对比例1相同。 Example 2 except add 5.0g of silicon carbide powder, the same as Comparative Example 1, and the rest.

实施例3除添加8.0g的碳化硅粉外,其余和对比例1相同。 Example 3 except add 8.0g of silicon carbide powder, the same as Comparative Example 1, and the rest.

实施例4除添加5.0g的氮化钛粉外,其余和对比例1相同。 Example 4 except for the addition of 5.0g of titanium nitride powder, the same as Comparative Example 1, and the rest.

实施例5除添加5.0g的氧化铝粉外,其余和对比例1相同。 Example 5 5.0g of the alumina powder was added in addition to, the other and the same as Comparative Example 1.

实施例6除添加5.0g的尼龙66粉外,其余和对比例1相同。 Example except add 5.0g of nylon 66 powder, the rest Comparative Example 16 and the same.

实施例7将脂肪族聚氨酯丙烯酸酯树脂(sartomer产品,CN965)改为5g,环氧丙烯酸酯树脂(galstaff产品,syncryl104)改为10g,不添加聚酯丙烯酸酯树酯,但添加5.0g的碳化硅粉,其余和对比例1相同。 Example 7 aliphatic urethane acrylate resin (Sartomer product, CN965) to 5g, epoxy acrylate resin (galstaff product, syncryl104) to 10g, polyester acrylate resin was not added, but adding 5.0g of carbonized silica fume, the same as Comparative Example 1, and the rest.

实施例8将脂肪族聚氨酯丙烯酸酯树脂(sartomer产品,CN965)改为40g,环氧丙烯酸酯树脂(galstaff产品,syncryl104)改为50g,聚酯丙烯酸酯树酯(sartomer产品,CNUVP225)改为40g,添加5.0g的碳化硅粉,其余和对比例1相同。 Example 8 aliphatic urethane acrylate resin (Sartomer product, CN965) to 40g, an epoxy acrylate resin (galstaff product, syncryl104) to 50g, polyester acrylate resin (Sartomer product, CNUVP225) to 40g added 5.0g of silicon carbide powder, the same as Comparative Example 1, and the rest.

实施例9双官能团丙烯酸单体HDDA改为7g,三官能团丙烯酸单体TMPTA改为5g,不添加单官能团丙烯酸单体,但添加5.0g的碳化硅粉,其余和对比例1相同。 Example 9 HDDA bifunctional acrylic monomer was changed to 7g, trifunctional acrylic monomer TMPTA to 5g, without addition of monofunctional acrylic monomers, but add 5.0g of silicon carbide powder, the same as Comparative Example 1, and the rest.

实施例10将单官能团丙烯酸单体HEA改为20g,双官能团丙烯酸单体HDDA改为25g,三官能团丙烯酸单体TMPTA改为25g,添加5.0g的碳化硅粉,其余和对比例1相同。 10 HEA monofunctional acrylic monomer to Example 20g, bifunctional acrylic monomer HDDA to 25g, trifunctional acrylic monomer TMPTA to 25g, was added 5.0g of silicon carbide powder, the same as Comparative Example 1, and the rest.

以上实施例及所制成涂料的原漆性能见表1。 The above embodiment the original paint and the paint properties are shown in Table 1 are made.

各实施例所制成的涂料经紫外光固化后的漆膜的性能见表2。 Properties of the film after a coating made of each embodiment by UV curing in Table 2 embodiment.

从表2中可以看出,未添加耐磨-硬度添加剂的实施例1的耐磨次数只有300次,硬度为2H,耐酒精测试不变色。 As can be seen from Table 2, No wear - wear additives embodiment hardness number of 300 in Example 1, only a hardness of 2H, alcohol-resistant test does not change color. 当添加2.0g的碳化硅粉时,其耐磨和硬度大大增加,实施例2的数据结果显示耐磨达到610次,硬度为4H。 When adding the silicon carbide powder 2.0g, which greatly increase the wear resistance and hardness, the data results of Example 2 show wear reaches 610 times, the hardness of 4H. 继续增加耐磨-硬度添加剂的量达到8g,此时耐磨和硬度增幅不大,但附着力出现下降趋势,达到2B,并且耐腐蚀性能也下降。 Continues to increase wear - the amount of additive to reach hardness 8g, this time not increase the hardness and wear resistance, but the adhesion downward trend, to 2B, and also decreases corrosion resistance. 其原因在于耐磨和硬度添加剂消弱了机体树脂和底材的结合力。 The reason is that the hardness and wear resistance additive weakened binding force of the resin body and the substrate. 其他种类的无机添加剂也达到同样的效果,如实施例4、5所示。 Other types of inorganic additives may also achieve the same effect, as shown in Examples 4 and 5 embodiment.

添加少量的有机添加剂也可增加涂膜层的耐磨和硬度,如实施例6所示。 Add a small amount of organic additives may also increase wear resistance and hardness of the coating film layer, as shown in Example 6.

改变基体树脂或活性单体的量,加少量的耐磨和硬度添加剂,同样可以达到增加耐磨和硬度的效果,但基体树脂或活性稀释剂量的减少可能会造成漆膜层附着力及耐腐蚀性能的下降。 Changing the amount of the resin matrix or active monomer, a small amount of additives hardness and wear resistance, can also achieve the effect of increasing wear resistance and hardness, but the matrix resin or reactive diluent to reduce the amount of the film may cause adhesion and corrosion-resistant layer performance degradation. 在同等条件下,基体树脂量的降低造成的后果会更严重一些。 Under the same conditions, the consequences of reducing the amount of resin causes the base will be more serious. 实施例7-10即显示了这一结论。 Examples 7-10 This conclusion is displayed.

测试方法:耐磨性测试:使用美国诺曼仪器设备公司生产的7-IBB型RCA磨耗仪,在175g力的作用下,磨喷涂后的漆膜,漆膜露底材时,橡胶轮转动的次数。 U.S. Norman times using equipment produced 7-IBB RCA type abrasion tester, under the action of force 175g, the film coating after grinding, exposed when the film substrate, the rotating rubber wheel: Test Method: Wear Resistance Test .

硬度测试:采用中华不同H号铅笔,并用1kg力刻划长度超过30mm刻痕,再用橡皮搽试,看有无刻痕,如无,则为此H号硬度。 Hardness Test: A pencil China number of different H and scored with score 30mm longer than 1kg force, then the eraser test to see whether the score, if not, then the hardness numbers for this H.

附着力测试:用划格器在喷涂表面划100个1毫米×1毫米的正方形格,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,然后以最快速度垂直揭起,观察划痕边缘处有无脱漆。 Adhesion Test: Crosshatch designated by spraying the surface 100 in 1 mm × 1 mm square grid, with the American company 3M Model 600 transparent tape adhered to the box flat, leaving no trace of the gap, and then vertical lift fastest speed, at the edge scratches was observed whether or stripping. 如脱漆量在0~5%之间为5B,在5~10%之间为4B,在10~20%之间为3B,在20~30%之间为2B,在30~50%之间为B,在50%以上为0B。 The amount of stripping is between 0 and 5%. 5B, 5 to 10%. 4B, between 10 to 20%. 3B, 20 to 30%. 2B, 30 to 50% of the Room is B, more than 50% 0B.

耐酒精测试:用干净纱布蘸取浓度为99%的酒精,以0.5千克的力在漆膜同一位置搽拭,观察面漆有无变色。 Alcohol Resistance Test: with a clean gauze dipped in 99% alcohol concentration to 0.5 kg of force at the swabbing position of the same film, to observe presence or absence of discoloration of the topcoat.

表1 Table 1

表2 Table 2

Claims (23)

1.一种用于塑料的紫外光固化涂料,包括基体树脂、活性稀释剂、光引发剂、溶剂,其特征在于还包括耐磨-硬度添加剂,该耐磨-硬度添加剂在该涂料中的重量百分比含量为0.1~8.0%。 A UV-curable coatings for plastics, comprising a matrix resin, reactive diluent, light initiator, a solvent, characterized by further comprising a wear resistant - hardness additives, the wear resistance - the hardness of the additive in the coating weight of The percentage content of 0.1 to 8.0%.
2.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于所述耐磨-硬度添加剂是显微硬度在500kgf/mm2以上的固体粉末。 The UV-curable coatings for plastics according to claim 1, characterized in that the wear - the hardness is more than additive microhardness 500kgf / mm2 solid powder.
3.根据权利要求2所述的用于塑料的紫外光固化涂料,其特征在于所述耐磨-硬度添加剂为选自碳化物、氮化物、氧化物或有机高聚物中的至少一种。 The UV-curable coatings for plastics according to claim 2, characterized in that the wear - hardness additive is selected from a carbide, at least one of a nitride, oxide or organic high polymer.
4.根据权利要求3所述的用于塑料的紫外光固化涂料,其特征在于所述碳化物为选自碳化硅、碳化锆、碳化硼、碳化铝、碳化铁、碳化铬中的至少一种。 The UV-curable coatings for plastics according to claim 3, wherein said carbide selected from silicon carbide, zirconium carbide, boron carbide, aluminum carbide, iron carbide, chromium carbide, at least one of .
5.根据权利要求3所述的用于塑料的紫外光固化涂料,其特征在于所述氮化物为选自氮化钛、氮化锆、氮化镓、氮化铝、氮化钙中的至少一种。 The UV-curable coatings for plastics according to claim 3, wherein said nitride is selected from titanium nitride, zirconium nitride, gallium nitride, aluminum nitride, calcium nitride, at least one kind.
6.根据权利要求3所述的用于塑料的紫外光固化涂料,其特征在于所述氧化物为选自二氧化钛、氧化铝、氧化铬、氧化锡、二氧化硅中的至少一种。 The UV-curable coatings for plastics according to claim 3, wherein said oxide is selected from titanium dioxide, aluminum oxide, chromium oxide, tin oxide, at least one silica.
7.根据权利要求3所述的用于塑料的紫外光固化涂料,其特征在于所述有机高聚物为选自尼龙、聚乙烯蜡、聚丙烯蜡、聚氯乙烯蜡、聚碳酸酯中的至少一种。 The UV-curable coatings for plastics according to claim 3, wherein said organic polymer is selected from nylon, polyethylene wax, polypropylene wax, wax, polyvinyl chloride, polycarbonate at least one.
8.根据权利要求2所述的用于塑料的紫外光固化涂料,其特征在于所述耐磨-硬度添加剂固体粉末的平均颗粒大小为小于10μm The UV-curable coatings for plastics according to claim 2, wherein said wear resistant - having an average particle size of the solid powder additive hardness of less than 10μm
9.根据权利要求8所述的用于塑料的紫外光固化涂料,其特征在于所述耐磨-硬度添加剂固体粉末的平均颗粒大小为3μm~8μm。 According to claim UV-curable coatings for plastics according to claim 8, wherein said wear resistant - having an average particle size of the solid powder additive hardness of 3μm ~ 8μm.
10.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于所述涂料含有具有下列重量百分比含量的组分:基体树脂 15-70%活性稀释剂 10~55%耐磨-硬度添加剂 0.1~8.0%光引发剂 2.0~10.0%溶剂 2~50% 10. The UV-curable coatings for plastics according to claim 1, wherein the coating comprising the following components in percentage by weight: 15-70% matrix resin reactive diluent from 10 to 55% wear - hardness additive 0.1 to 8.0% photoinitiator, 2.0 to 10.0% solvent, 2 to 50%
11.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于所述基体树脂为选自脂肪族聚氨酯丙烯酸酯树脂、环氧(甲基)丙烯酸酯树脂和聚酯丙烯酸酯树脂中的至少一种。 11. The UV-curable coatings for plastics according to claim 1, wherein said matrix resin is selected from aliphatic urethane acrylate resins, epoxy (meth) acrylate resin and a polyester acrylate resin at least one.
12.根据权利要求11所述的用于塑料的紫外光固化涂料,其特征在于,相对于所述涂料的总重量,所述涂料含有具有下列重量百分比含量的组分作为所述基体树脂:脂肪族聚氨酯丙烯酸酯树脂 5~20%;环氧(甲基)丙烯酸酯树脂 5~30%;聚酯丙烯酸酯树脂 5~20%。 12. The UV-curable coatings for plastics as claimed in claim 11, characterized in that, relative to the total weight of the coating, said coating comprising the following components having a content by weight of the base resin: Fat aliphatic urethane acrylate resin 5 to 20%; epoxy (meth) acrylate resin is 5 to 30%; polyester acrylate resin 5 to 20%.
13.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于所述活性稀释剂为选自由单官能团丙烯酸酯单体、双官能团丙烯酸酯单体和三官能团丙烯酸酯单体所组成的组中的反应性丙烯酸酯单体中的至少一种。 13. UV-curable coatings for plastics according to claim 1, wherein said reactive diluent is selected from the group consisting of monofunctional acrylate monomers, difunctional acrylate monomers and trifunctional acrylate monomer at least one of the group consisting of reactive acrylate monomers.
14.根据权利要求13所述的用于塑料的紫外光固化涂料,其特征在于,相对于所述涂料的总重量,所述涂料含有具有下列重量百分比含量的组分作为所述活性稀释剂:单官能团丙烯酸酯单体 2~15%;双官能团丙烯酸酯单体 4~20%;三官能团丙烯酸酯单体 4~20%。 According to claim UV-curable coatings for plastics according to claim 13, characterized in that, relative to the total weight of the coating, said coating comprising the following components having a content by weight as the reactive diluent: monofunctional acrylate monomer, 2 to 15%; bifunctional acrylate monomer having 4 to 20%; trifunctional acrylate monomer having 4 to 20%.
15.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于所述溶剂为两种或两种以上不同种有机溶剂所组成的混合溶剂。 15. UV-curable coatings for plastics according to claim 1, wherein a mixed solvent of two or more different kinds of organic solvents consisting of two or more of said solvents.
16.根据权利要求15所述的用于塑料的紫外光固化涂料,其特征在于所述溶剂为选自甲苯、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、丙二醇丁醚中的两种或两种以上的溶剂的混合物。 16. The UV-curable coatings for plastics according to claim 15, wherein the solvent is selected from toluene, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, ethanol, n- alcohol, cyclohexanone, xylene, methyl isobutyl ketone, acetone, methyl ethyl ketone, ethylene glycol butyl ether, propylene glycol butyl ether in a mixture of two or more solvents.
17.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于还含有0.1~1.0重量%的流平剂。 17. UV-curable coatings for plastics according to claim 1, characterized by further containing 0.1 to 1.0 wt% of a leveling agent.
18.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于还含有0.1~1.5重量%的消泡剂。 18. UV-curable coatings for plastics according to claim 1, characterized by further containing 0.1 to 1.5 wt% defoamer.
19.根据权利要求1所述的用于塑料的紫外光固化涂料,其特征在于还含有0.2~3.0重量%的分散剂。 19. UV-curable coatings for plastics according to claim 1, characterized in that it additionally contains 0.2 to 3.0 wt% dispersant.
20.一种制造根据权利要求1的用于塑料的紫外光固化涂料的方法,包括以下步骤:(1)将占涂料总体系15~70重量%的基体树脂溶解于占总体系10~55重量%的丙烯酸酯单体活性稀释剂中,搅拌均匀;(2)将占涂料总体系2~10重量%的光引发剂与占涂料总体系2~50重量%的溶剂混合,搅拌至充分溶解;(3)将步骤(2)所得混合物与步骤(1)所得混合物搅拌混合均匀;(4)向步骤(3)所得混合物中加入占涂料总体系0.1~8.0重量%的显微硬度在500kgf/mm2以上的耐磨-硬度添加剂固体粉末,高速搅拌使该固体粉末均匀悬浮。 20. A method of manufacturing a UV-curable coatings for plastics according to claim 1, comprising the steps of: (1) the total coating system will account for 15 to 70 wt% of the base resin is dissolved in 10 to 55 by weight of the total system % acrylate monomer reactive diluent, stir; solvent are mixed 2 to 50 wt% of the total coating system of 2 to 10 wt% (2) the coating will account for the total photoinitiator system accounts, stirring until fully dissolved; (3) obtained in step (2) the resulting mixture of step (1) was uniformly mixed with stirring; the resulting mixture (4) of step (3) was added 0.1 to 8.0% by weight of the total coating system, microhardness 500kgf / mm2 more wear - solid powder additive hardness, high-speed stirring a homogeneous suspension of the solid powder.
21.根据权利要求20所述的方法,其中步骤(4)还包括向步骤(3)所得混合物中加入占涂料总体系0.1~1.0重量%的流平剂。 21. The method of claim 20, wherein step (4) further comprises the step (3) the resulting mixture was added 0.1 to 1.0% by weight of the total coating system leveling agent.
22.根据权利要求20所述的方法,其中步骤(4)还包括向步骤(3)所得混合物中加入占涂料总体系0.1~1.5重量%的消泡剂。 22. The method of claim 20, wherein step (4) further comprises the step (3) was added the total coating system accounted for 0.1 to 1.5% by weight of an antifoaming agent in the resulting mixture.
23.根据权利要求20所述的方法,其中步骤(4)还包括向步骤(3)所得混合物中加入占涂料总体系0.2~3.0重量%的分散剂。 23. The method according to claim 20, wherein step (4) further comprises the step (3) the resulting mixture is added the dispersing agent comprises 0.2 to 3.0% by weight of the total coating system.
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