CN101979449B - Ultraviolet curing coating for white board - Google Patents

Ultraviolet curing coating for white board Download PDF

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CN101979449B
CN101979449B CN 201010566670 CN201010566670A CN101979449B CN 101979449 B CN101979449 B CN 101979449B CN 201010566670 CN201010566670 CN 201010566670 CN 201010566670 A CN201010566670 A CN 201010566670A CN 101979449 B CN101979449 B CN 101979449B
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modified
organosiloxane
acrylate
molecular weight
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CN101979449A (en
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郭晓娟
陈红娣
刘伟永
陈月霞
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中国乐凯胶片集团公司
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Abstract

一种白板用紫外光固化涂料,所述涂料的组分及其重量份数为:丙烯酸酯树脂预聚体20~60份,丙烯酸酯类单体10~50份,光引发剂3~10份,引发促进剂3~15份,助剂1~2份,所述的助剂由小分子量有机硅氧烷和大分子量改性有机硅氧烷组成,其重量份比为0.1~0.3:1。 One kind of a white UV-curable coatings, the coating components and parts are by weight: acrylate prepolymer resin 20 to 60 parts, from 10 to 50 parts acrylate monomer, 3 to 10 parts of a photoinitiator , initiator 3 to 15 parts accelerator, 1 to 2 parts adjuvant, the adjuvant by a small molecular weight and high molecular weight organosiloxane-modified organosiloxane composition, the weight ratio of which is 0.1 to 0.3: 1. 本发明形成的漆膜的表面能低,擦写与缩墨性能达到平衡状态,解决了当漆膜硬度较高时存在的书写字迹缩墨的缺陷,具有很好的反复涂写和擦拭的功能;耐候性好。 The surface film of the present invention can be formed in a low, ink erasable with a condensing performance reaches an equilibrium state of the solution when present in high film hardness of the writing ink shrinkage defects, and has good repeated graffiti wipe function; good weather resistance.

Description

一种白板用紫外光固化涂料 One kind of ultraviolet light curable coatings whiteboard

技术领域 FIELD

[0001] 本发明涉及一种涂料,特别涉及一种白板用的紫外光固化涂料。 [0001] The present invention relates to a coating, in particular, relates to one kind of UV-curable coatings with a whiteboard.

背景技术 Background technique

[0002] 白板是一种专供白板笔使用的写字板,用于文化教学、办公、会议等场合,其特点是用白板笔书写在写字板上的墨迹可擦除。 [0002] whiteboard is a whiteboard pen tablet designed for use for cultural education, office, meetings and other occasions, which is characterized by a whiteboard pen to write on the tablet erasable ink. 由于具有易擦写又不会产生粉灰的使用特点,已广为大众所使用。 Because they are easy to erase not produce ash of use features, it has been widely used by the general public is.

[0003] 传统的白板采用马口铁作基材,在表面喷上白漆或塑粉后经高温烘烤构成书写板。 [0003] The traditional whiteboard using tin as a substrate, sprayed with white paint or plastic powder constituting the surface of the tablet baked at high temperature. 这种白板马口铁很重,生产工艺复杂,成本较高,无法折叠,携带不方便,应用场合十分有限。 This whiteboard tinplate heavy, complicated production process, high cost, not folded, convenient to carry, applications are limited. 同时使用寿命短,长期使用容易使白漆脱落或者塑粉易磨损,除了字难擦写外,用板擦无论怎样擦拭都会留有字迹。 At the same time short life, long-term use tends to fall off white paint or plastic powder easy to wear, in addition to word hard to erase outside, wipe with eraser will leave no matter how handwriting.

[0004] 为了解决上述问题,迫切需要使用新的基材和工艺降低成本,需要开发新型耐用的白板笔擦写涂层,使得白板笔书写擦除后不残留痕迹,喷涂或是油性笔书写后用溶剂清理时不会破坏涂层。 After [0004] In order to solve the above problems, an urgent need to use the new base and process cost reduction, a need to develop innovative and durable coating erasable whiteboard pen, so that no residue after whiteboard pen erasures, or oil-based pen spraying when cleaning will not damage the coating with a solvent.

[0005] 紫外光固化产品具有节省能源、利于环保、经济和高效等特点,因此广泛地应用于各个领域。 [0005] UV curing products with energy-saving, environmentally friendly, economical and efficient characteristics, it is widely used in various fields. 目前,紫外光固化技术已在涂料、油墨、电子化学品、粘合剂及医用器材等领域得到广泛应用。 Currently, UV curing technology has been widely used in coatings, inks, electronic chemicals, adhesives and medical equipment and other fields. 申请号为200910037056. 3的中国专利公开了一种活性低聚物、其制备方法及含有该低聚物的耐白板笔擦写的紫外光固化涂料,该涂料形成的漆膜的硬度和耐磨性较低,而且高硬度的漆膜的书写字迹缩墨严重。 Application No. of China Patent No. 200910037056.3 discloses a reactive oligomer, and a preparation method comprising the oligomer erasable whiteboard pen resistant UV curable coating, the coating film hardness and wear resistance is formed of low and high film hardness of the writing ink severely reduced.

发明内容 SUMMARY

[0006] 本发明所要解决的技术问题是克服上述已有技术之缺陷、提供一种具有易擦写及缩墨平衡,具有高硬度和高耐磨性的白板用紫外光固化涂料。 [0006] The present invention solves the technical problem is to overcome the drawbacks of the above prior art, there is provided an easily erasable ink and shrinkage balance, having high hardness and wear resistance of UV-curable coatings having a whiteboard.

[0007] 为解决上述技术问题,本本发明采用的技术方案是: [0007] To solve the above technical problem, the technical solution adopted by the invention is the books:

[0008] 一种白板用紫外光固化涂料,所述涂料的组分及其重量份数为: [0008] A UV-curable coating is white, the coating components and parts are by weight:

[0009] 丙烯酸酯树脂预聚体 20〜60份 [0009] The acrylate resin prepolymer 20~60 parts

[0010] 丙烯酸酯类单体 10〜50份 [0010] acrylate monomer 10~50 parts

[0011] 光引发剂 3〜10份 [0011] 3~10 parts photoinitiator

[0012] 引发促进剂 3〜15份 [0012] initiator accelerator 3~15 parts

[0013] 助剂 I〜2份; [0013] aids I~2 parts;

[0014] 所述助剂由小分子量有机硅氧烷和大分子量改性有机硅氧烷组成,其重量份比为 [0014] The additives of small molecular weight and high molecular weight organosiloxane-modified organosiloxane composition, which is a ratio of parts by weight

O. Γο. 3:1。 O. Γο 3:. 1.

[0015] 上述白板用紫外光固化涂料,所述改性有机硅氧烷是不饱和键改性的有机硅氧烷,选自聚酯改性有机硅氧烷和聚醚改性有机硅氧烷中的至少一种。 [0015] The whiteboard UV-curable coatings, said organosiloxane-modified unsaturated bond-modified organosiloxanes, selected from polyester and polyether-modified organosiloxane-modified organosiloxane at least one.

[0016] 上述白板用紫外光固化涂料,所述丙烯酸酯树脂预聚体选自环氧丙烯酸酯类预聚物、聚氨脂丙烯酸酯类预聚物和超支化类预聚物中的至少二种。 [0016] The whiteboard UV-curable coatings, the acrylate prepolymer resin is selected from epoxy acrylate prepolymer, polyurethane acrylate prepolymer and hyperbranched prepolymer least two species. [0017] 上述白板用紫外光固化涂料,所述丙烯酸酯树脂预聚体为官能度大于5的聚酯丙烯酸酯预聚物。 [0017] The whiteboard UV-curable coatings, the acrylate resin prepolymer is a polyester acrylate functionality of more than 5 prepolymers.

[0018] 上述白板用紫外光固化涂料,所述丙烯酸酯类单体为双官能度丙烯酸酯类单体和高官能度丙烯酸酯类单体的混合物。 [0018] The UV-curable coating is white, the acrylate monomer is a difunctional acrylate monomer mixtures and high functionality acrylate monomers.

[0019] 与现有技术相比,本发明通过采用小分子量的有机硅氧烷和大分子量的改性有机硅氧烷组合使用,使涂料形成的漆膜的表面能较低,漆膜的擦写与缩墨性能达到平衡状态,解决了当漆膜硬度较高时存在的书写字迹缩墨的缺陷,具有很好的反复涂写和擦拭的功能;通过超支化类预聚物的加入,在保证书写字迹不缩墨的情况下,漆膜的硬度达到3H以上,耐磨性达数千次以上,同时,漆膜具有良好的耐溶剂性和耐候性。 [0019] Compared with the prior art, the present invention is by modifying the organosiloxane composition and high molecular weight organosiloxane with a small molecular weight is used, the coating can be formed on the lower surface of the film, the film is rubbed write and shrinkage properties of the ink reaches an equilibrium state, when there is solved the higher film hardness of the ink of the writing defect reduction, and has good repeated graffiti wipe function; fed through hyperbranched prepolymer, to ensure Notations case where the writing ink, the film hardness reaches 3H or more, the abrasion resistance of more than thousands of times, at the same time, the film having good solvent resistance and weather resistance.

具体实施方式 Detailed ways

[0020] 紫外光固化产品利用汞灯发出的紫外光快速引发聚合,具有节省能源、利于环保、经济和高效等特点。 [0020] UV-curable products with ultraviolet light to initiate polymerization mercury lamp rapid, with energy saving, environmentally friendly, economical and efficient features. 本发明提供的耐擦写的白板用紫外光固化涂料,是以环氧丙烯酸酯类预聚物、聚氨酯丙烯酸酯类预聚物、超支化类预聚物和丙烯酸酯类单体为主体组分,光引发剂在紫外光照射下,经过裂解或氢转移产生活性自由基,活性自由基攻击其中的不饱和双键,使双键变为单键从而使交联产生固体高聚物。 Endurance whiteboard present invention provides a UV-curable coatings, epoxy acrylate prepolymer is a urethane acrylate prepolymer, and the prepolymer hyperbranched acrylate monomer as a main component photoinitiator under UV irradiation after cleavage or hydrogen transfer generate active radicals attack a living radical wherein the unsaturated double bond, the double bond becomes a single bond so that the cross-linking polymer solids. 高聚物和助剂等呈膜状附着在基材上,形成漆膜。 Polymers and additives in the form of a film adhered on a substrate to form the film. 本发明提供的紫外光固化涂料的组分及重量份数为:丙烯酸酯树脂预聚体20〜60份,丙烯酸酯类单体10〜50份,光引发剂3〜10份,引发促进剂3〜15份,助剂O.1〜2份。 Components and parts by weight of UV curable coatings of the present invention is to provide: an acrylic resin prepolymer parts of 20~60, 10~50 parts of acrylic monomer, a photoinitiator 3~10 parts initiator accelerator 3 ~ 15 parts O.1~2 auxiliary parts.

[0021] 环氧丙烯酸酯类预聚物,是紫外光固化涂料中的重要组成部分,它是使用最为广泛的丙烯酸酯类预聚物,其具有固化速度快、硬度高、光泽度高、耐化学腐蚀性强等特性,但是存在柔韧性差、漆膜脆、耐磨性差、不耐划、耐候性差等缺点;本发明选用的环氧丙烯酸酯类树脂为双酚A环氧丙烯酸酯和改性双酚A型环氧丙烯酸酯的一种或其混合物,双酚A环氧丙烯酸酯具有固化速度快,收缩率高,经固化后产品具有高硬度、高耐磨等特性,优选无锡树脂厂的双酚A环氧丙烯酸酯WSR-U125,台湾长兴化学公司的20%三缩丙二醇二丙烯酸酯稀释的双酚A环氧丙烯酸酯621A-80,台湾长兴化学公司的改性双酚A环氧丙烯酸酯623-100,台湾长兴化学公司20%三缩丙二醇二丙烯酸酯稀释的改性双酚A环氧丙烯酸酯6231A-80。 [0021] The epoxy acrylate prepolymer is an important part of the UV-curable coatings, it is the most widely used acrylic prepolymer having a fast curing, high hardness, high gloss, resistance to chemical resistance and other characteristics, but there is poor flexibility, brittle film, poor wear resistance, scratch intolerance, defects and poor weather resistance; the present invention selects an epoxy acrylate resin is a bisphenol a epoxy acrylates and modified bisphenol a type epoxy acrylate or a mixture thereof, bisphenol a epoxy acrylate having a fast curing speed, high shrinkage, the cured product having a high hardness, high wear-resistant properties, is preferably Wuxi resin factory bisphenol a epoxy acrylate WSR-U125, Taiwan Eternal chemical company 20% tripropylene glycol diacrylate dilution of bisphenol a epoxy acrylate 621A-80, Taiwan Eternal chemical company modified bisphenol a epoxy acrylate 623-100 ester, Taiwan Eternal chemical company 20% tripropylene glycol diacrylate dilution of modified bisphenol a epoxy acrylate 6231A-80.

[0022] 聚氨脂丙烯酸酯类树脂具有低气味、低挥发、低刺激性及优良的成膜性,固化产品具有高抗张强度、卓越的耐磨性和优良的高温稳定性。 [0022] The urethane acrylate resin having a low odor, low volatility, low irritation and excellent film-forming properties, a cured product having high tensile strength, excellent abrasion resistance and excellent high temperature stability. 本发明中加入聚氨酯丙烯酸酯目的在于与环氧丙烯酸酯配合使用,利用聚氨酯丙烯酸酯较好的柔韧性和耐候性,而且随着官能度的增加表现出很好的耐磨性和耐划性,以使漆膜具有高硬度、高光泽、高耐磨、高耐划、良好的柔韧性和耐候性。 The present invention was added with a urethane acrylate object with the use of epoxy acrylate, urethane acrylate using good flexibility and weather resistance, but also with increasing the functionality of a good wear resistance and scratch resistance, such that the film has a high hardness, high gloss, high wear resistance, high scratch resistance, good flexibility and weatherability. 本发明选用的聚氨酯丙烯酸酯类预聚物为选自高官能度脂肪族聚氨酯丙烯酸酯类预聚物和双官能度脂肪族聚氨酯丙烯酸酯类预聚物的一种或其混合物,如台湾长兴化学公司的脂肪族聚氨酯六丙烯酸酯6145-100、6161-100, 15%1,6 —己二醇二丙烯酸酯(HDDA)稀释的脂肪族聚氨酯二丙烯酸酯611B-85,20%乙氧化三羟甲基丙烷三丙烯酸酯稀释的聚酯多元醇,脂肪族聚氨酯二丙烯酸酯6141H-80 ;美国沙多玛公司的脂肪族聚氨酯丙烯酸酯CN9013 (9官能度),美国沙多玛公司15%1,6 —己二醇二丙烯酸酯(HDDA)稀释的脂肪族聚氨酯丙烯酸酯CN966B85 (2官能度),脂肪族聚氨酯丙烯酸酯CN962 (2官能度)。 The present invention is selected as a urethane acrylate prepolymer is selected from high-functionality aliphatic urethane acrylate or a mixture thereof and prepolymers of difunctional aliphatic urethane acrylate prepolymers, such as Taiwan Eternal Chemical company aliphatic urethane hexaacrylate 6145-100,6161-100, 15% 1,6 - hexanediol diacrylate (HDDA) was diluted aliphatic urethane diacrylate 611B-85,20% ethoxylated trimethylolpropane trimethylolpropane triacrylate dilution of polyester polyols, aliphatic urethane diacrylate 6141H-80; US Sartomer company aliphatic urethane acrylate CN9013 (9 functionality), U.S. Sartomer 15% 1,6 - hexanediol diacrylate (HDDA) was diluted aliphatic urethane acrylate CN966B85 (2 functionality), aliphatic urethane acrylate CN962 (2 functionality).

[0023] 为了提高产品的丰满度,本发明提供的产品配方中加入了具有较高折光系数的超支化类预聚物,本发明所选的为高官能度的超支化丙烯酸树脂,如无锡诺克斯公司的超支化聚酯丙烯酸酯预聚体932-100 (6官能度),美国沙多玛公司的超支化聚酯丙烯酸酯预聚体CN2300 (8官能度),CN2301 (9官能度)、CN2302 (16官能度)等。 [0023] In order to increase the fullness of the product, the product formulations of the present invention provides added hyperbranched prepolymer having a higher refractive coefficient for high-functionality hyperbranched selected acrylic resin of the present invention, as Wuxi Connaught Alex's hyperbranched polyester acrylate prepolymer 932-100 (functionality 6), U.S. Sartomer company hyperbranched polyester acrylate prepolymer CN2300 (8 functionality), CN2301 (9 functionality) thereof , CN2302 (16 functionality) and the like.

[0024] 适合本发明的高官能度丙烯酸酯类单体为三官能度、四官能度、五官能度或六官能度丙烯酸酯类单体中的一种或几种,选自三羟甲基丙烷三丙烯酸酯(TMPTA)、季戊四醇三丙烯酸酯(PETA)、季戊四醇四丙烯酸酯(PETTA)、双季戊四醇五丙烯酸酯(DPEPA)、双季戊四醇六丙烯酸酯(DPHA)、丙氧化三羟甲基丙烷三丙烯酸酯(PO-TMPTA)或乙氧基三羟甲基丙烷三丙烯酸酯(EO-TMPTA)。 [0024] suitable for the present invention high functionality acrylate monomer is trifunctional, tetrafunctional, pentafunctional or hexafunctional of acrylate monomers of one or more selected from trimethylol propane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPEPA), dipentaerythritol hexaacrylate (DPHA), propoxylated trimethylol propane tri acrylate (PO-TMPTA) or ethoxylated trimethylol propane triacrylate (EO-TMPTA).

[0025] 适合本发明的双官能度丙烯酸酯类单体选自1,6—己二醇二丙烯酸酯(HDDA)、二缩丙二醇二丙烯酸酯(DPGDA)、三缩丙二醇二丙烯酸酯(TPGDA)、新戊二醇二丙烯酸酯(NPGDA)或乙氧化新戊二醇二丙烯酸酯(PO-NPGDA)。 [0025] The present invention is suitable difunctional acrylic monomer is selected from 1,6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (of TPGDA) , neopentyl glycol diacrylate (NPGDA) or ethoxylated neopentyl glycol diacrylate (PO-NPGDA).

[0026] 适合本发明的光引发剂可以是I 一羟基一环己基苯酮(Irgacure 184)、邻苯甲酰基苯甲酸甲酯(0ΜΒΒ)、二苯甲酮(BP)、2 —甲基一I 一(4 一甲硫基苯基)一2 一吗啉一I 一丙酮(907)、2 —羟基一2 —甲基一I 一苯基丙酮一I (Darocur 1173)或它们的混合物,优选使用I 一羟基一环己基苯酮、邻苯甲酰基苯甲酸甲酯B或它们的混合物,最优选使用Irgacure 184 和OMBB 的组合。 [0026] Suitable photoinitiators of the present invention may be a I a hydroxy phenyl ketone (Irgacure 184), o-benzoyl benzoate (0ΜΒΒ), benzophenone (BP), 2 - methyl- I a (4-methylthiophenyl) a morpholin-2-acetone-I (907), 2 - hydroxy-2 - methyl-I-phenyl-acetone-I (Darocur 1173), or mixtures thereof, preferably using a hydroxy-cyclohexyl phenyl ketone, o-benzoyl benzoate I B or mixtures thereof, most preferably a combination use of Irgacure 184 and OMBB. 其中,Irgacure 184> Darocur 1173 和Irgacure 907 为裂解型光引发剂,其固化快速,有助于产品的深层固化,产品不黄变;BP为氢转移型光引发剂,其有利于产品的表面固化;0ΜΒΒ是一种低气味的引发剂,能使固化后的漆膜气味小有利于涂料在对气味有要求的包装品上使用。 Wherein, Irgacure 184> Darocur 1173 and Irgacure 907 is a cleavage-type photoinitiator, curing fast, it contributes to deep curing, product non-yellowing; on BP is hydrogen transfer type photoinitiators, which is conducive to the surface of a cured product ; 0ΜΒΒ is a low odor initiator, film odor after curing can facilitate small paint used on odors has the request packaging.

[0027] 为了提高光引发剂的引发效率,本发明提供的涂料产品中加入了引发促进剂,适合本发明的引发促进剂可以是UCB公司的P115,其主要成分为三羟甲基丙烷三丙烯酸酯化叔胺,市售的三乙醇胺或活性胺。 [0027] In order to improve the efficiency of initiation of the photoinitiator, the present invention provides a paint product is added in the initiator accelerators, initiators accelerators suitable for the present invention may be UCB's P115, whose main component is trimethylol propane triacrylate esterification tertiary amines, commercially available reactive amine or triethanolamine.

[0028] 为了使漆膜的擦写与缩墨性能达到平衡状态,本发明提供的耐擦写白板用的紫外光固化涂料的配方体系中助剂选用小分子量的有机硅氧烷和大分子量的改性有机硅氧烷组合使用。 [0028] In order to erase the ink film and shrink properties to reach equilibrium, the present invention provides a system of formula UV-curable coatings endurance aid in selection of whiteboard small molecular weight and high molecular weight organosiloxane modified organosiloxane used in combination.

[0029] 本发明中的大分子量的有机硅氧烷主要是不饱和键改性的有机硅氧烷(也称反应性有机硅氧烷),能依靠它的表面活性而迁移到漆膜的表面。 [0029] In the present invention high molecular weight organosiloxane is primarily an unsaturated bond-modified organosiloxane (also known as reactive organosiloxane), it can depend on the surfactant migrate to the surface of the film . 这种反应性有机硅氧烷中所含的不饱和键与体系的树脂和单体一起在紫外光照射下双键断裂进行聚合交联固化在UV体系的网状结构中。 Together with the double bond under UV irradiation fracture of the resin and an unsaturated monomer bond system such reactive polymeric organosiloxane contained in the crosslinked network structure in curing of UV systems. 这样,该助剂就能永久性地固定在涂膜的表面,由有机硅氧烷提供的特定的表面性能也能维持长久,使涂膜表面的具有持久的易擦净性能。 Thus, the aid can be permanently fixed to the surface of the coating, the specific surface properties provided by the organosiloxane can be maintained for a long time, making easy to wipe the lasting properties of the coating film surface. 含不饱和键大分子量的改性有机硅氧烷可以是聚酯改性有机硅氧烷、聚醚改性有机硅氧烷或其混合物,如毕克化学的BYK3500,BYK3530, BYK3570其主要成分是聚酯改性丙烯酸类官能性的聚二甲基硅氧烷;EFKA公司的EFKA3883其主要成分是双键封端聚醚改性有机硅氧烷;AFC0NA公司的AFC0NA3883其主要成分是不饱和键改性的有机硅氧烷;迪高公司的TEG02100,TEG02200N,TEG02250, TEG02300, TEG02500, TEG02600, TEG02700 其主要成分是交联型有机硅丙烯酸酯。 Unsaturated bond-containing high molecular weight organosiloxane-modified organosiloxane may be a polyester-modified, polyether-modified organosiloxane or a mixture thereof, such as BYK-Chemie BYK3500, BYK3530, BYK3570 its main ingredient is polyester modified acrylic-functional polydimethylsiloxane; EFKA3883 its main component is a double bond EFKA company terminated polyether-modified organosiloxane; AFC0NA3883 AFC0NA its main component an unsaturated bond company change of organosiloxane; Tego's TEG02100, TEG02200N, TEG02250, TEG02300, TEG02500, TEG02600, TEG02700 whose main component is a crosslinking type silicone acrylates.

[0030] 由于小分子量有机硅氧烷的表面迁移很快,随着漆膜的形成其表面分布密度即可达到易擦写不缩墨的平衡状态,小分子量的有机硅氧烷包括聚酯/聚醚改性聚硅氧烷化合物、氟碳改性有机硅氧烷或其混合物,如迪高公司的Glide432,毕克化学的BYK333,BYK307其主要成分为聚醚改性聚二甲基硅氧烷,EFKA公司的EFKA3034和AFCONA公司的AFC0NA3034,其主要成分为氟碳有机改性硅氧烷。 [0030] Since the surface migration of low molecular weight organosiloxane quickly, as the film formed on its surface density distribution reaches an equilibrium state can easily erasable ink is indented, small molecular weight organosiloxane include polyester / polyether-modified silicone compound, fluorocarbon-modified organosiloxane or a mixture thereof, such as the company Tego Glide432, BYK-Chemie BYK333, BYK307 the main component is a polyether modified polydimethyl siloxane alkoxy, EFKA EFKA3034 companies and companies AFCONA AFC0NA3034, whose main component is fluorocarbon organomodified silicones. 但其仅现存于漆膜表面,在使用过程中随着反复擦写次数的增多,其会被擦掉,所以配方中不能单用小分子量的有机硅氧烷,否则时间久了字迹不易被擦除或擦不掉;由于大分子量的有机硅氧烷在体系中的迁移速度较慢,如果它在涂料中单独使用,在漆膜刚形成时其表面分布密度很小,所以此时用白板笔写上的字迹不易擦除或擦净,但随着时间的推移,其在漆膜表面的迁移密度越来越大,书写的字迹会越来越容易擦除,所以涂料中也不能单独使用大分子量的有机硅氧烷。 But only existing on the film surface, with the increase in the number of repeated rewriting, it will be erased during use, it can not alone formulation low molecular weight organosiloxane, or writing a long time can not easily be rubbed in addition to or indelible; due to the large molecular weight organosiloxane migrate slower rate in the system, if it is used alone in a paint, when the newly formed film surface distribution density thereof is small, so in this case with a whiteboard pen written on the handwriting is not easy to erase or wipe, but as time goes on, their migration density in the growing film surface, the writing gets easier to erase the writing, so the paint can not be used alone big molecular weight organosiloxane.

[0031] 基于以上原因,本发明涂料的配方体系中助剂选用小分子量的有机硅氧烷和大分子量的改性有机娃氧烧混合使用,其中小分子量的有机娃氧烧和大分子量的有机娃氧烧的配比为O.1〜O. 3 :1。 [0031] Based on the above reasons, the coating formulations of the present invention, the system aids in the use of small molecular weight and high molecular weight organosiloxane-modified organic baby burn oxygen mixture, wherein the organic low molecular weight organic baby burn oxygen and high molecular weight baby ratio of oxygen to burn O.1~O 3:. 1. 当小分子量的有机硅氧烷的用量低于O.1重量份时,所形成的漆膜表面用白板笔很容易书写,但字迹的擦除或擦净性能很差;当其用量高于O. 3重量份时,所形成的漆膜表面用白板笔书写后的字迹缩墨严重,但字迹特别容易擦净。 When the amount of low molecular weight organosiloxane is less than O.1 parts by weight, the film formed on the surface of the whiteboard pen easily write, erase or writing but poor wiping performance; When the amount is higher than O when the parts. 3 by weight, the film surface formed by condensing the whiteboard writing pen ink severe, but the character particularly easy to wipe. 为了保证漆膜的擦写性能和缩墨性能达到平衡状态,小分子量的有机硅氧烷用量优选在O. Γ0. 3重量份的范围内。 To ensure erase shrinkage properties of the film and the ink properties to reach equilibrium, the amount of low molecular weight organosiloxane is preferably in parts by weight O. Γ0. 3.

[0032] 本发明提供的紫外光固化涂料可以通过下述方法制备: [0032] The present invention provides UV-curable coatings may be prepared by the following method:

[0033] 按比例将丙烯酸树脂预聚体、丙烯酸酯类单体、光引发剂混合,升温至50±5°C,搅拌至完全溶解,然后加入引发促进剂,搅拌至混合均匀;再加入助剂搅拌均,降温过滤,得到紫外光固化涂料。 [0033] The proportion of acrylic resin prepolymer, acrylate monomer, photoinitiator, warmed to 50 ± 5 ° C, stirring until completely dissolved, then adding initiator accelerators, stirred until evenly mixed; then add co agents are stirring, cooling was filtered to obtain UV-curable coatings.

[0034] 本发明提供的紫外光固化涂料也可以通过下述方法制备: [0034] The present invention provides UV-curable coatings may also be prepared by the following method:

[0035] ①将助剂加入到部分丙烯酸酯单体中高速分散均匀;©将丙烯酸树脂预聚体、剩余的丙烯酸酯单体、光引发剂混合,升温至50±5°C,搅拌至完全溶解,再加入引发促进剂,搅拌均匀;③将上述①、②混合并搅拌均匀,过滤,得到紫外光固化涂料。 [0035] ① The aid is added to the high-speed portion of the acrylate monomer uniformly dispersed; © acrylic resin prepolymer, the remaining acrylate monomer, photoinitiator, warmed to 50 ± 5 ° C, stirring until completely dissolved, then adding the initiator accelerators, stir; ③ above ①, ② uniformly mixed and stirred and filtered to give a UV-curable coatings.

[0036] 本发明提供的耐擦写白板用紫外光固化涂料可以通过辊涂、喷涂、淋涂或丝网印刷等公知方式涂装式将本发明的涂料涂在塑料、木器、金属、纸张等基材的表面,经过中压汞灯固化,形成各种均匀透明的表面能较低的漆膜。 [0036] The present invention provides endurance whiteboard by roll coating with a UV-curable coating, spray coating, curtain coating or screen printing the coating formula in a known manner according to the present invention, the coating material is coated on plastic, wood, metal, paper, etc. surface of the substrate, after curing medium pressure mercury lamp, to form various uniform transparent film of low surface energy.

[0037] 下面结合具体实施例对本发明作进一步的说明,但不限于此。 [0037] The following specific embodiments of the present invention in conjunction with further illustrated, but is not limited thereto.

[0038] 实施例1 [0038] Example 1

[0039] WSR-U125 10 份 [0039] WSR-U125 10 parts

[0040] 6145-100 10 份 [0040] 6145-10010 parts

[0041] DPGDA 15 份 [0041] DPGDA 15 parts

[0042] TMPTA 25 份 [0042] TMPTA 25 parts

[0043] Irgacure 184 10 份 [0043] Irgacure 184 10 parts

[0044] Pl 15 10 份 [0044] Pl 15 10 parts

[0045] EFKA3034 O. 5 份 [0045] EFKA3034 O. 5 parts

[0046] EFKA38831. 5 份 [0046] EFKA38831. 5 parts

[0047] ①将15份的DPGDA和25份的TMPTA混合均匀; [0047] ① DPGDA 15 parts of TMPTA and 25 parts of a mixed;

[0048] ②将O. 5份的EFKA3034和1. 5份的EFKA3883加入到1/4的①中,高速分散均匀;[0049] ③将10份的胃51?-仍25、10份的6145-100、10份的Irgacure 184和剩余的①混合,升温至50°C,搅拌至完全溶解,然后加入10份P115,搅拌均匀; [0048] ② The O. 5 parts of EFKA3034 and EFKA3883 added 1.5 parts to ① 1/4 of uniformly dispersed high speed; [0049] ③ parts of the stomach 10 51-- parts 25,10 are still 6145? -100,10 parts Irgacure 184 mixed and residual ①, warmed to 50 ° C, stirring until completely dissolved, and then 10 parts of P115, stir;

[0050] ④将②、③混合,搅拌均匀,降温,过滤,得到紫外光固化涂料。 [0050] ④ The ②, ③ mix, stir, cooled and filtered to obtain UV-curable coatings.

[0051] 将得到的涂料通过辊涂的方式涂布到PVC膜上,然后经过一支3000瓦/厘米的中压汞灯照射固化,在PVC膜表面形成均匀透明的表面能较低的漆膜;也可以使用喷涂方式将得到的涂料涂布到PVC膜上,经过红外流平后再经一支5000瓦/厘米的中压汞灯照射固化,在PVC膜表面形成均匀透明的表面能较低的漆膜;还可以通过淋涂或者丝印的方式印刷在PVC膜上,经过中压汞灯照射固化形成均匀透明的表面能较低的漆膜。 [0051] The obtained coating material was applied by roller coating manner to PVC film and then through a medium pressure mercury lamps 3000 watts / cm of radiation curing, the surface of the PVC film is formed on a uniform transparent film of low surface energy ; coating applicator may be used to spraying the resulting PVC film, through the back via an infrared leveling 5000 W / cm medium pressure mercury lamp is cured to form a uniform transparent PVC film on a surface of low surface energy the film; also by curtain coating or screen printing manner in PVC film, after medium pressure mercury lamp is irradiated cured to form a uniform transparent film of low surface energy.

[0052] 实施例2 [0052] Example 2

[0053] 621A-80 20 份 [0053] 621A-80 20 parts

[0054] 932-100 30 份 [0054] 932-10030 parts

[0055] DPHA 5 份 [0055] DPHA 5 parts

[0056] PO-TMPTA 15 份 [0056] PO-TMPTA 15 parts

[0057] TPGDA 10 份 [0057] TPGDA 10 parts

[0058] Irgacure 184 7 份 [0058] Irgacure 184 7 parts

[0059] OMBB 3 份 [0059] OMBB 3 parts

[0060] 三乙醇胺 10份 [0060] 10 parts of triethanolamine

[0061] Glide432 I 份 [0061] Glide432 I parts

[0062] TEG02200N 2 份 [0062] TEG02200N 2 parts

[0063] 以上按组份配比,按实施例1中的步骤得到紫外光固化涂料。 [0063] The ratio of the components by the above, according to the procedure described in Example 1 to obtain UV-curable coatings.

[0064] 按实施例1涂布方式将得到的涂料涂布在PVC、PETG等基材上,得到均匀透明的表面能较低的漆膜。 [0064] The coating was applied by a coating manner as in Example 1 on the obtained PVC, PETG and other substrates, to obtain a uniform transparent film of low surface energy.

[0065] 实施例3 [0065] Example 3

[0066] 623-100 30 份 [0066] 623-10030 parts

[0067] CN2301 15 份 [0067] CN2301 15 parts

[0068] HDDA 10 份 [0068] HDDA 10 parts

[0069] PETTA 18 份 [0069] PETTA 18 parts

[0070] Irgacure 184 2 份 [0070] Irgacure 184 2 parts

[0071] OMBB 4. 2 份 [0071] OMBB 4. 2 parts

[0072] Pl 15 15 份 [0072] Pl 15 15 parts

[0073] BYK333 O.1 份 [0073] BYK333 O.1 parts

[0074] BYK3530 I 份 [0074] BYK3530 I parts

[0075] 以上按组份配比,按实施例1中的步骤得到紫外光固化涂料。 [0075] The ratio of the components by the above, according to the procedure described in Example 1 to obtain UV-curable coatings.

[0076] 按实施例1涂布方式将得到的涂料涂布在PVC、PETG等基材上,得到均匀透明的表面能较低的漆膜。 [0076] The coating was applied by a coating manner as in Example 1 on the obtained PVC, PETG and other substrates, to obtain a uniform transparent film of low surface energy.

[0077] 实施例4 [0077] Example 4

[0078] 6231A-80 30 份 [0078] 6231A-80 30 parts

[0079] CN2302 20 份 [0079] CN2302 20 parts

[0080] PETA 10 份[0081] TMPTA 15 份 [0080] PETA 10 parts [0081] TMPTA 15 parts

[0082] NPGDA 10 份 [0082] NPGDA 10 parts

[0083] Irgacure 184 3 份 [0083] Irgacure 184 3 parts

[0084] Irgacure 907 2 份 [0084] Irgacure 907 2 parts

[0085] Pl 15 9. 7 份 [0085] Pl 15 9. 7 parts

[0086] BYK307 O. 2 份 [0086] BYK307 O. 2 parts

[0087] BYK3570 I 份 [0087] BYK3570 I parts

[0088] 以上按组份配比,按实施例1中的步骤得到紫外光固化涂料。 [0088] The ratio of the components by the above, according to the procedure described in Example 1 to obtain UV-curable coatings.

[0089] 按实施例1涂布方式将得到的涂料涂布在PVC、PETG等基材上,得到均匀透明的表面能较低的漆膜。 [0089] The coating was applied by a coating manner as in Example 1 on the obtained PVC, PETG and other substrates, to obtain a uniform transparent film of low surface energy.

[0090] 实施例5 [0090] Example 5

[0091] 621A-80 25 份 [0091] 621A-80 25 parts

[0092] CN966B85 10 份 [0092] CN966B85 10 parts

[0093] CN2300 25 份 [0093] CN2300 25 parts

[0094] DPEPA 20 份 [0094] DPEPA 20 parts

[0095] PO-TMPTA 20 份 [0095] PO-TMPTA 20 parts

[0096] HDDA 10 份 [0096] HDDA 10 parts

[0097] Darocur 1173 3 份 [0097] Darocur 1173 3 parts

[0098] Pl 15 3 份 [0098] Pl 15 3 parts

[0099] AFC0NA3034 O. 3 份 [0099] AFC0NA3034 O. 3 parts

[0100] AFC0NA38831. 5 份 [0100] AFC0NA38831. 5 parts

[0101] 以上按组份配比,按实施例1中的步骤得到紫外光固化涂料。 [0101] component ratio by the above, according to the procedure described in Example 1 to obtain UV-curable coatings.

[0102] 按实施例1涂布方式将得到的涂料涂布在PVC、PETG等基材上,得到均匀透明的表面能较低的漆膜。 [0102] Coatings applied by a coating manner as in Example 1 on the obtained PVC, PETG and other substrates, to obtain a uniform transparent film of low surface energy.

[0103] 实施例6 [0103] Example 6

[0104] WSR-U125 30 份 [0104] WSR-U125 30 parts

[0105] 611B-85 10 份 [0105] 611B-85 10 parts

[0106] 6160-100 15 份 [0106] 6160-10015 parts

[0107] DPHA 10 份 [0107] DPHA 10 parts

[0108] TMPTA 15 份 [0108] TMPTA 15 parts

[0109] TPGDA 5 份 [0109] TPGDA 5 parts

[0110] Irgacure 184 3 份 [0110] Irgacure 184 3 parts

[0111] OMBB 2 份 [0111] OMBB 2 parts

[0112] Irgacure 907 2 份 [0112] Irgacure 907 2 parts

[0113] 活性胺 10份 [0113] 10 parts of active amine

[0114] BYK333 O. 2 份 [0114] BYK333 O. 2 parts

[0115] Glide432 O.1 份 [0115] Glide432 O.1 parts

[0116] TEG025001. 5 份 [0116] TEG025001. 5 parts

[0117] 以上按组份配比,按实施例1中的步骤得到紫外光固化涂料。 [0117] component ratio by the above, according to the procedure described in Example 1 to obtain UV-curable coatings. [0118] 按实施例1涂布方式将得到的涂料涂布在PVC、PETG等基材上,得到均匀透明的表面能较低的漆膜。 [0118] Coatings applied by a coating manner as in Example 1 on the obtained PVC, PETG and other substrates, to obtain a uniform transparent film of low surface energy.

[0119] 对比例 [0119] Comparative Example

[0120] WSR-U125 10 份 [0120] WSR-U125 10 parts

[0121] 6145-100 10 份 [0121] 6145-10010 parts

[0122] DPGDA 15 份 [0122] DPGDA 15 parts

[0123] TMPTA 25 份 [0123] TMPTA 25 parts

[0124] Irgacure 184 10 份 [0124] Irgacure 184 10 parts

[0125] Pl 15 10 份 [0125] Pl 15 10 parts

·[0126] EFKA3034 O. 5 份 · [0126] EFKA3034 O. 5 parts

[0127] 发明人分别用上述实施例广6所配制的本发明白板用紫外光固化涂料辊涂在贴在高密度板材上的PVC膜表面。 [0127] The inventors are widely formulated whiteboard 6 of the present invention with the above-described embodiments in UV curable coatings roll coating attached to the high-density PVC sheet film surface. 经过红外流平后再经一支5000瓦/厘米的中压汞灯照射固化,对形成的固化膜进行各项性能测试和评定,其结果如表I所示: Medium pressure mercury lamp through a leveling back via an infrared 5000W / cm radiation curing, cured film is formed and the performance evaluation tests, which results are shown in Table I:

[0128] 表I涂膜性能 [0128] Table I Film Properties

[0129] [0129]

Figure CN101979449BD00101

[0130] 表I中,各性能指标为: [0130] Table I, each of the performance indicators:

[0131] (I)附着力:参照国家标准GB/T9286《色漆和清漆漆膜的划格试验》 [0131] (I) Adhesion: according to the national standard GB / T9286 "Paints and varnishes cut test"

[0132] (2)铅笔硬度:参照国家标准GB/T6739《漆膜硬度铅笔测定法》 [0132] (2) Pencil hardness: according to the national standard GB / T6739 "film hardness by pencil test"

[0133] (3)耐磨性:将涂料制成漆膜后用纸带耐磨试验机(BF-RCA)测试,记录漆膜被磨穿的次数。 [0133] (3) Wear Resistance: The coating film made of the sheet strip after wear testing machine (BF-RCA) test, recording the number of times the film is worn out. [0134] X :500次漆膜被磨穿 [0134] X: 500 times the film is worn out

[0135] Δ :500次至1000次之间漆膜被磨穿 [0135] Δ: between 500 to 1000 times the film is worn out

[0136] O :1000次至1500次之间漆膜被磨穿 [0136] O: between 1000 to 1500 times the film is worn out

[0137] ◎ :2500次以上漆膜被磨穿 [0137] ◎: 2500 times the film is worn out

[0138] (4)耐溶剂性:用浸甲乙酮溶液的湿布(负重150g/cm2 )以每分钟摩擦30次的速率来回擦拭试样的样板100次后观察样板的表面情况。 [0138] (4) Solvent resistance: a cloth (weight 150g / cm2) soaked in methyl ethyl ketone at a rate of 30 times per minute rubbed back and forth friction model case where the sample surface was observed after 100 template.

[0139] X :破损 [0139] X: breakage

[0140] Δ :大部分失光,部分破损 [0140] Δ: Most loss of light, part broken

[0141] O :无破损,部分失光 [0141] O: No damage, loss of light portion

[0142] ◎:无破损,无失光 [0142] ◎: no damage, no loss of light

[0143] (5)缩墨情况:白板笔在样板上书写时墨迹收缩情况。 [0143] (5) where shrinkage ink: Ink shrinkage when whiteboard pen to write on the template.

[0144] X :白板笔无法书写上去 [0144] X: whiteboard pen can not write up

[0145] Λ :白板笔能书写,部分地方会缩墨严重 [0145] Λ: whiteboard pen can write, some parts will shrink serious ink

[0146] O :白板笔能书写,部分地方稍有缩墨 [0146] O: whiteboard pen able to write, a slight portion where ink condensing

[0147] ◎:白板笔能书写,完全不缩墨 [0147] ◎: whiteboard pen can write, complete ink Notations

[0148] (6)白板笔擦写性能:一段时间后擦除墨迹的残留情况。 [0148] (6) erasable whiteboard pen performance: erasing residual quantity of ink after a period of time.

[0149] X :隔天擦除墨迹会有残留 [0149] X: the next day will erase ink residue

[0150] Δ :10天内擦除墨迹无残留,大于10天擦除墨迹会有残留 [0150] Δ: 10 days no residue erase ink, greater than 10 days will erase ink residue

[0151] O :20天内擦除墨迹无残留,大于20天擦除墨迹会有残留 [0151] O: 20 days no residue erase ink, greater than 20 days will erase ink residue

[0152] ◎ :30天后擦除墨迹无残留 [0152] ◎: 30 days no residue erase ink

[0153] 从表I可以看出,实施例Γ6漆膜具有良好的书写性能和持久的耐白板笔擦写性能;对比例I在漆膜刚制成时白板笔能书写但部分地方缩墨严重且隔天擦除时墨迹有残留。 [0153] As can be seen from Table I, Example Γ6 embodiment the film has good writing performance and long-lasting resistance to erase whiteboard pen performance; Comparative Example I whiteboard pen able to write but some shrinkage when the film where the ink is made serious just and the next day when the residual ink erasure. 表明含有所述小分子量的有机硅氧烷和大分子量的改性有机硅氧烷的紫外光固化涂料可耐白板笔擦写,使用长久;而未使用组合助剂的配制的涂料虽然白板笔容易书写,但擦拭性能很差。 Showed the presence of the low molecular weight organosiloxane-modified silicones and high molecular weight organic UV-curable coatings resistant erasable whiteboard pen, used for a long time; formulated coating composition without the use of additives, although whiteboard pen easy writing, but the wiping performance is poor.

Claims (1)

1. 一种白板用紫外光固化涂料,其特征在于,所述涂料的组分及其重量份数为: 丙烯酸酯树脂预聚体 20〜60份; 丙烯酸酯类单体 10〜50份; 光引发剂 3〜10份; 引发促进剂 3〜15份;助剂 I〜2份; 所述助剂由小分子量有机硅氧烷和大分子量改性有机硅氧烷组成,其重量份比为O.1〜0.3 :1 ;所述小分子量的有机硅氧烷为聚酯/聚醚改性聚硅氧烷化合物、氟碳改性有机硅氧烷或其混合物,选自迪高公司的Glide432,或者毕克化学的BYK333,BYK307,其主要成分为聚醚改性聚二甲基硅氧烷,或者EFKA公司的EFKA3034和AFCONA公司的AFC0NA3034,其主要成分为氟碳有机改性硅氧烷;所述大分子量改性有机硅氧烷为聚酯改性有机硅氧烷、聚醚改性有机硅氧烷或其混合物;选自毕克化学的BYK3500,BYK3530,BYK3570其主要成分是聚酯改性丙烯酸类官能性的聚二甲基硅氧烷;或者EFKA公司的EFKA3883 A white board, characterized in that a UV-curable coatings, the coating components and parts are by weight: acrylate prepolymer resin 20~60 parts; 10~50 parts acrylic acid ester monomer; light 3~10 parts initiator; initiator accelerator 3~15 parts; I~2 auxiliary parts; the aid of small molecular weight and high molecular weight organosiloxane-modified organosiloxane composition that the weight ratio of O .1~0.3: 1; the low molecular weight organosiloxane is a polyester / polyether-modified silicone compound, fluorocarbon-modified organosiloxane or a mixture thereof, is selected from the company Tego Glide432, or BYK-Chemie BYK333, BYK307, the main component is a polyether modified poly dimethyl siloxane, or EFKA AFCONA companies and companies EFKA3034 AFC0NA3034, the main component of the organic fluorocarbon-modified silicone; the said high molecular weight polyester-modified organosiloxane-modified organic silicone, polyether-modified organosiloxane or a mixture thereof; BYK3500 g Bi selected chemical, BYK3530, BYK3570 whose main component is polyester modified acrylic-functional polydimethylsiloxane; or EFKA company EFKA3883 其主要成分是双键封端聚醚改性有机硅氧烷;或者AFCONA公司的AFC0NA3883,其主要成分是不饱和键改性的有机硅氧烷;或者迪高公司的TEG02100,TEG02200N,TEG02250, TEG02300, TEG02500, TEG02600, TEG02700,其主要成分是交联型有机硅丙烯酸酯;所述丙烯酸酯树脂预聚体选自环氧丙烯酸酯类预聚物、聚氨酯丙烯酸酯类预聚物和超支化类预聚物中的至少二种,所述超支化类预聚物为高官能度的超支化丙烯酸树脂;所述丙烯酸酯类单体为双官能度丙烯酸酯类单体和高官能度丙烯酸酯类单体的混合物;所述高官能度丙烯酸酯类单体为三官能度、四官能度、五官能度或六官能度丙烯酸酯类单体中的一种或几种。 Its main component is a double bond-terminated polyether-modified organosiloxane; AFCONA or company AFC0NA3883, whose main component is an unsaturated bond-modified organosiloxane; or company Tego TEG02100, TEG02200N, TEG02250, TEG02300 , TEG02500, TEG02600, TEG02700, whose main component is a crosslinking type silicone acrylate; the acrylate resin is selected from epoxy acrylate pre-prepolymer, urethane acrylate-based prepolymer and hyperbranched prepolymer copolymer of at least two, the hyperbranched prepolymer is a high-functionality hyperbranched acrylic resin; the acrylate monomer is a difunctional acrylate monomer and high functionality acrylate monomer mixtures thereof; said high functionality acrylate monomer is trifunctional, tetrafunctional, pentafunctional or hexafunctional of one or more acrylic ester monomers.
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