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CN102516859A - Anti-doodling and anti-affixing paint and its preparation method - Google Patents

Anti-doodling and anti-affixing paint and its preparation method Download PDF

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CN102516859A
CN102516859A CN 201110401629 CN201110401629A CN102516859A CN 102516859 A CN102516859 A CN 102516859A CN 201110401629 CN201110401629 CN 201110401629 CN 201110401629 A CN201110401629 A CN 201110401629A CN 102516859 A CN102516859 A CN 102516859A
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anti
parts
paint
component
doodling
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CN 201110401629
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CN102516859B (en )
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刘虎
尚倩倩
肖国民
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东南大学
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Abstract

The invention discloses an anti-doodling and anti-affixing paint and its preparation method. the paint is composed of two components A and B, wherein the component A contains, by weight, 4-20 parts of pseudo-perfluoroalkyl modified polysiloxane, 20-42 parts of hydroxy acrylic resin, 10-35 parts of pigments and fillers, 1-8 parts of an auxiliary agent, 10-36 parts of an organic solvent; and the component B contains, by weight, 12-30 parts of polyisocyanate prepolymer. The mass ratio of the component A to the component B is 2-8:1. The component A is prepared by the following steps of: adding hydroxy acrylic resin, pigments and fillers, the auxiliary agent and the organic solvent into a grinder, uniformly grinding to prepare slurry, pouring the ground slurry and pseudo-perfluoroalkyl modified polysiloxane together into a high-speed dispenser, dispersing at 800-1500 r/min for 0.5-2 hours, filtering and packaging to obtain the required component A. When in use, the anti-doodling and anti-affixing paint is obtained by uniformly mixing the components A and B at the mass ratio of 2-8:1. A paint film formed by the paint has the following advantages of low surface energy, small friction coefficient, excellent anti-doodling and anti-affixing performance and superstrong scrub resistance.

Description

一种防涂鸦抗粘贴涂料及其制备方法技术领域[0001] 本发明涉及涂料及其制备方法,具体涉及一种防涂鸦抗粘贴涂料及其制备方法。 An anti-graffiti and anti-adhesive coating preparation Technical Field [0001] The present invention relates to a coating and a preparation method, particularly relates to an anti-graffiti and anti-adhesive coating preparation. 背景技术[0002] 在城市中,无论是公共设施,如公交站牌、候车亭、电线杆、墙壁上,还是公共交通工具,如地铁、火车、轻轨列车、公交车上,都随处可见到各种乱涂乱画的涂鸦和随意张贴的小广告,俗称“城市牛皮癣”,不仅严重影响了市容市貌,而且为清除这些涂鸦要耗费大量的人力物力,迫切需要开发具有防涂鸦抗粘贴性能的涂料。 [0002] in the city, whether public facilities, such as bus shelters, bus shelters, telephone poles, walls, or public transportation, such as subways, trains, light rail trains, buses are everywhere seen each kinds of graffiti and graffiti feel free to post small ads, commonly known as the "city of psoriasis", not only seriously affect the appearance of the city, and for the removal of graffiti to spend a lot of manpower and resources, the urgent need to develop anti-graffiti anti-stick properties coating. 已有的研究表明,低表面能的表面可有效防止涂鸦附着和污染,通过简单擦除即可轻松除去。 Previous studies showed that the surface of the low surface energy can effectively prevent adhesion and pollution graffiti easily removed by simply erasing can. 聚硅氧烷具有优异的憎水憎油性及润滑性,将其应用于涂料中,可显著降低涂膜的表面能;通过改性,在聚硅氧烷主链上接枝氟烷基侧链,在成膜时,含氟基团由于其极大的表面活性而严格取向涂膜表面,使得涂膜获得更佳的低表面能效果。 Silicone has excellent water repellency and oil repellency lubricity which the coating is applied, it can significantly reduce the surface energy of the coating; by modification, on the polysiloxane backbone of the graft side chain fluoroalkyl group in the film formation, fluorine-containing groups because of its enormous surface active strictly alignment film surface, so that the coating film of low surface energy for better effect. [0003] 科研人员在防涂鸦抗粘贴涂料的研究和开发上也做了一些工作,专利CN101585995B报道了以羟基丙烯酸树脂、氟碳树脂、含羟基聚二甲基硅氧烷树脂、六甲基二异氰酸酯缩二脲为主要原料制备的油性防涂鸦抗粘贴涂料;专利CN 101565579B公开了以氟碳树脂和脂肪族聚异氰酸酯固化剂为组合物的防涂鸦抗粘贴涂料;专利US 5387434报道了以水溶性蜡、硅酸钠、松香及粘合剂为组合物的自损型防涂鸦涂料,使用高压热水清除涂鸦,清洗后,需再涂覆一层涂料。 [0003] Researchers in the anti-anti-graffiti paste also do some work on the research and development of coatings, reported to patent CN101585995B hydroxyl acrylic resin, fluorocarbon resin, hydroxyl group-containing resin, polydimethylsiloxane, hexamethyldisiloxane, isocyanate biuret oily antigraffiti prepared main ingredient an anti-adhesive coating; Patent CN 101565579B discloses a fluorocarbon resin and an aliphatic polyisocyanate curing agent composition antigraffiti anti-adhesive coating; Patent US 5387434 reported a water-soluble waxes, sodium silicate, rosins and self-adhesive type anti-graffiti loss of coating compositions, the use of high pressure hot water graffiti Removal, after cleaning, then coated with a layer of paint required. 尽管有上述关于防涂鸦抗粘贴涂料及其制备方法的报道,但从公开的论文和专利来看,目前国内外尚未见将氟烷基改性聚硅氧烷应用于双组份聚氨酯体系中制备防涂鸦抗粘贴涂料的报道。 Despite these reports of anti-anti-graffiti coatings and methods of making paste, but papers and patents disclosed, the current will be at home and abroad have not been applied fluoroalkyl-modified silicone prepared two-component polyurethane systems anti-graffiti coating anti-paste reports. 发明内容[0004] 技术问题:本发明的目的是提供一种与现有成分不同具有优异的防涂鸦抗粘贴性,超强的耐擦洗性,耐液体介质性,漆膜表面能低,摩擦系数小,易于清洁,使用寿命长的防涂鸦抗粘贴涂料及其制备方法。 [0004] Technical Problem: The purpose of the present invention is to provide an excellent anti-graffiti and anti-adhesive properties different from the conventional composition, superior scrub resistance, liquid chemical resistance, low surface energy film, the coefficient of friction small, easy to clean, long life of the anti-anti-graffiti coating paste and its preparation method. [0005] 技术方案:本发明所述的防涂鸦抗粘贴涂料由A、B两组份组成,按重量份计,[0006] A组份是:[0007] 氟烷基改性聚硅氧烷4〜20份,[0008] 羟基丙烯酸树脂20〜42份,[0009] 颜填料10〜35份,[0010] 助剂1〜8份,[0011] 有机溶剂10〜36份,[0012] B组份为多异氰酸酯预聚物12〜30份;[0013] A组份与B组份的重量比为2〜8 : 1。 [0005] Technical Solution: antigraffiti according to the present invention an anti-adhesive coating consists of two parts A, B composition, in parts by weight, [0006] A component is: [0007] fluoroalkyl-modified silicone 4~20 parts, [0008] hydroxyl acrylic resin 20~42 parts, [0009] fillers 10~35 parts, [0010] auxiliaries 1~8 parts, [0011] parts of 10~36 organic solvent, [0012] B component is a polyisocyanate prepolymer 12~30 parts; [0013] a and B component parts of the group weight ratio of 2~8: 1. [0014] 所述羟基丙烯酸树脂的羟值为5〜200mg KOH/g,数均分子量为4000〜50000。 [0014] The hydroxyl value of the hydroxyl acrylic resin 5~200mg KOH / g, number average molecular weight 4000~50000. [0015] 所述颜填料为气相二氧化硅、金红石型钛白粉、锐钛型钛白粉、聚四氟乙烯微粉、滑石粉、硫酸钡、碳酸钙、云母粉、铝粉或空心玻璃微珠中的一种或多种。 [0015] The pigment filler is fumed silica, rutile titanium dioxide, anatase titanium dioxide, PTFE powder, talc, barium sulfate, calcium carbonate, mica powder, aluminum powder or hollow glass microbeads one or more.

[0016] 所述助剂为润湿分散剂、流平剂、消泡剂、催干剂、耐磨剂、抗划伤剂或附着力促进剂中的一种或多种。 [0016] The auxiliaries are wetting and dispersing agents, leveling agents, defoaming agents, driers, anti-wear agents, anti-scratch agents or one or more adhesion promoting agents.

[0017] 所述有机溶剂为醋酸甲酯、醋酸乙酯、醋酸丁酯、甲苯、对二甲苯、邻二甲苯、间二甲苯、丙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、碳酸二甲酯、丙酮、环己酮中三种或三种以上的组合。 [0017] The organic solvent is methyl acetate, ethyl acetate, butyl acetate, toluene, p-xylene, o-xylene, m-xylene, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, dimethyl carbonate esters, acetone, cyclohexanone three combinations of three or more.

[0018] 所述多异氰酸酯预聚物为HDI三聚体、MDI三聚体、IPDI三聚体或TDI三聚体中的一种。 [0018] The polyisocyanate prepolymers as a trimer HDI, MDI trimer, IPDI trimers or trimers of TDI.

[0019] 防涂鸦抗粘贴涂料的制备方法,其特征在于: [0019] The anti-anti-graffiti coating paste preparation process, wherein:

[0020] 所述A组份的制备: [0020] Preparation of the component A:

[0021] 将羟基丙烯酸树脂与颜填料、助剂、有机溶剂加入到研磨机中,研磨均勻后制成浆料;将研磨好的浆料与氟烷基改性聚硅氧烷一起投入到高速分散机中,在800〜1500转/ 分钟下分散0. 5〜2小时后,过滤包装,即得所需的A组份; [0021] The hydroxyl acrylic resin and pigment, additives, an organic solvent is added to the grinding mill, after the grinding is made uniform slurry; high speed into slurry was triturated with fluoroalkyl-modified silicone dispersing machine, after dispersion at 800~1500 rpm / min 0. 5~2 hours, filtered and packaging, a to yield the desired component;

[0022] 使用时,将A、B两组份按2〜8 : 1重量配比混合均勻即可。 [0022] In use, the A, B two parts by 2~8: 1 weight ratio mix evenly.

[0023] 所述氟烷基改性聚硅氧烷由含氟丙烯酸酯单体与聚甲基氢硅氧烷在催化剂作用下合成得到,其合成方法是:室温下将含氟丙烯酸酯单体、溶剂、催化剂加入到反应器中,搅拌并在惰性气体保护下,升温至80°C以上,滴加聚甲基氢硅氧烷,反应2〜30小时,然后冷却至室温,经旋转蒸发除去溶剂,得到透明、粘稠的氟烷基改性聚硅氧烷。 [0023] The fluoroalkyl-modified silicone synthesized by a fluorine-containing acrylate monomer and methyl hydrogen polysiloxane in the catalyst, its method of synthesis: A mixture of fluorine-containing acrylate monomer , solvent, catalyst was added to the reactor, and stirred under an inert atmosphere, heated up to 80 ° C, was added dropwise methyl hydrogen polysiloxane, the reaction 2~30 hours, then cooled to room temperature, removed by rotary evaporation the solvent to give a clear, viscous fluoroalkyl-modified silicone.

[0024] 所述含氟丙烯酸酯单体为甲基丙烯酸三氟乙酯、丙烯酸四氟丙酯、甲基丙烯酸四氟丙酯、丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、丙烯酸八氟戊酯、甲基丙烯酸八氟戊酯、丙烯酸十二氟庚酯、甲基丙烯酸十二氟庚酯、丙烯酸十三氟辛酯或甲基丙烯酸十三氟辛酯中的一种. [0024] The fluorine-containing acrylate monomer as trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, tetrafluoropropyl methacrylate, butyl acrylate, hexafluoroisopropyl methacrylate, hexafluoroisopropyl acrylate, eight fluoro-amyl methacrylate, octafluoro pentyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, tridecafluoro-octyl acrylate or methacrylate, an ester of tridecafluoro octyl.

[0025] 所述聚甲基氢硅氧烷的结构式为: [0025] The structural formula is methyl hydrogen polysiloxane:

[0026] [0026]

Figure CN102516859AD00051

[0027]式中 10 彡η 彡200。 [0027] wherein η San San 10 200.

[0028] 有益效果:本发明A组份中的羟基丙烯酸树脂能与B组份中的多异氰酸酯预聚物交联固化,生成具有三维立体网状结构的漆膜,这种双组份聚氨酯漆膜交联密度高、结构致密、硬度高、耐擦洗性和耐液体介质性优异;体系中加入了憎水憎油能力极强的氟烷基改性聚硅氧烷,显著地降低了漆膜的表面能和摩擦系数,赋予漆膜以优异的防涂鸦抗粘贴性,能有效防止涂鸦在漆膜上的附着和向漆膜内的渗透,涂鸦经简单擦洗即可除去,各种不干胶、 胶水亦难以粘附在漆膜表面,不干胶反复粘贴500次无任何胶残留物。 [0028] Advantageous Effects: hydroxyl acrylic resin component A in the present invention is capable of and the polyisocyanate component B of the prepolymer crosslinking, the film has generated three-dimensional network structure, such a two-component polyurethane paint high film crosslink density, compact structure, high hardness, scrub resistance and superior resistance to dielectric liquid; added to the system the ability to strong hydrophobic lipophobic fluoroalkyl-modified silicones, film significantly reduces surface energy and coefficient of friction, impart excellent anti-graffiti film Blocking resistance, can effectively prevent graffiti paint film and adhered to the graffiti can be removed by simple penetration of the film to scrubbing, various stickers , glue is also difficult to adhere on the surface of the film, adhesive paste is repeated 500 times without any adhesive residue.

具体实施方式 detailed description

[0029] 下面通过具体实施例,对本发明做进一步说明,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明公开的范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围内。 [0029] The following specific embodiments, the present invention is further illustrated, but the scope of the present invention is not limited thereto, any skilled in the art within the scope of the art disclosed in the present invention can be easily thought variations or replacements It shall fall within the protection scope of the present invention. 因此,本发明的保护范围应该以权利要求保护的范围为准。 Accordingly, the scope of the present invention should be subject to the scope of the claims. [0030] 实施例1 : [0030] Example 1:

[0031] 本实施例提供的防涂鸦抗粘贴涂料由A、B两组份組成,按重量份计包括以下原料: [0031] The present embodiment provides anti-graffiti coating paste consists of two parts of an anti-A, B composition, in parts by weight comprising the following raw materials:

[0032] A 组份: [0032] A component:

[0033] [0033]

氟烷基改性聚硅氧烷 12份 Fluoroalkyl-modified silicone 12 parts

羟基丙烯酸树脂 28份 Hydroxyl acrylic resin 28 parts

颜填料 20份 20 parts of fillers

助剂 4份 4 parts adjuvant

有机溶剂 18份 18 parts of an organic solvent

[0034] B 组份: [0034] Component B:

[0035] HDI三聚体18份 [0035] HDI trimer 18 parts

[0036] 其中,氟烷基改性聚硅氧烷的合成方法是:室温下将60g丙烯酸六氟丁酯、溶剤、 催化剂加入到反应器中,搅拌并在高纯氮气保护下,升温至90°C,然后滴加16. Sg聚甲基氢硅氧烷,反应观小时,然后冷却至室温,经旋转蒸发除去溶剤,得到透明、粘稠的氟烷基改性聚硅氧烷;其中聚甲基氢硅氧烷的结构式为: [0036] wherein the synthetic method fluoroalkyl-modified silicone is: A mixture of 60g of butyl acrylate, hexafluoroisopropyl, Ji solvent, the catalyst added to the reactor, and stirred under high purity nitrogen, warmed to 90 ° C, then a solution of methyl hydrogen polysiloxane 16. Sg reaction concept hours, then cooled to room temperature, Ji solvent removed by rotary evaporation to give a clear, viscous fluoroalkyl-modified silicone; wherein the poly methylhydrogensiloxane formula is:

Figure CN102516859AD00061

[0038] 制备防涂鸦抗粘贴涂料的方法是:将羟基丙烯酸树脂与颜填料、助剂、有机溶剂加入到研磨机中,在2500转/分钟的转速下研磨3小吋,研磨均勻制成浆料;然后将研磨好的浆料与氟烷基改性聚硅氧烷一起投入到高速分散机中,在1000转/分钟的转速下分散1小时后,过滤包装,即得所需的A组份; [0038] Preparation of anti-anti-graffiti coating paste method is: hydroxyl acrylic resin and pigment, additives, an organic solvent is added to the grinding mill at 2500 revolutions / minute for 3 hours inch polishing speed, polishing uniformity pulped materials; milled slurry was then put to the fluoroalkyl-modified silicone with a high-speed dispersing machine, the dispersion at 1000 rev / min speed 1 hour, filtered packaging, to obtain the desired group a parts;

[0039] 使用时,将A、B两组份混合均勻,调整到合适的粘度即可施工。 [0039] In use, the A, B two parts mixed, adjusted to the appropriate viscosity to construction.

[0040] 实施例2 : [0040] Example 2:

[0041] 本实施例提供的防涂鸦抗粘贴涂料由A、B两组份組成,按重量份计包括以下原料: [0041] The present embodiment provides anti-graffiti coating paste consists of two parts of an anti-A, B composition, in parts by weight comprising the following raw materials:

[0042] A 组份: [0042] A component:

[0043] [0043]

氟烷基改性聚硅氧烷 8份 Fluoroalkyl-modified silicone 8 parts

羟基丙烯酸树脂 33份 Hydroxyl acrylic resin 33 parts

颜填料 23份 23 parts of fillers

助剂 4份 4 parts adjuvant

有机溶剂 16份 16 parts of an organic solvent

[0044] B 组份: [0044] Component B:

[0045] MDI三聚体16份[0046] 其中,氟烷基改性聚硅氧烷的合成方法是:室温下将80g甲基丙烯酸十二氟庚酯、 溶剂、催化剂加入到反应器中,搅拌并在高纯氮气保护下,升温至110°C,然后滴加13. 2g聚甲基氢硅氧烷,反应16小时,然后冷却至室温,经旋转蒸发除去溶剂,得到透明、粘稠的氟烷基改性聚硅氧烷;其中聚甲基氢硅氧烷的结构式为: [0047] [0045] MDI trimer 16 parts [0046] wherein the synthetic method fluoroalkyl-modified silicone is: A mixture of 80g of methacrylic acid dodecafluoroheptylmethacrylate, solvent, catalyst was added to the reactor, stirred under high purity nitrogen and heated to 110 ° C, then a solution of 13. 2g methyl hydrogen polysiloxane, for 16 hours, then cooled to room temperature, the solvent was removed by rotary evaporation to give a clear, viscous fluoroalkyl-modified silicone; structural formula wherein methyl hydrogen polysiloxane as: [0047]

Figure CN102516859AD00071

[0048] 制备防涂鸦抗粘贴涂料的方法是:将羟基丙烯酸树脂与颜填料、助剂、有机溶剂加入到研磨机中,在2500转/分钟的转速下研磨池,研磨均勻制成浆料;然后将研磨好的浆料与氟烷基改性聚硅氧烷一起投入到高速分散机中,在1000转/分钟的转速下分散1. 5小时后,过滤包装,即得所需的A组份;[0049][0050][0051] [0048] Preparation of anti-anti-graffiti coating paste method is: hydroxyl acrylic resin and pigment, additives, an organic solvent is added to the grinding mill at 2500 revolutions / minute speed polishing cell, the polishing slurry is made uniform; then the slurry was milled into and fluoroalkyl-modified silicone with a high-speed disperser, and dispersed at 1000 rev / min speed of 1.5 hours, filtered and packaging, to obtain the desired group a parts; [0049] [0050] [0051]

Figure CN102516859AD00072

料:[0052][0053]使用时,将A、B两组份混合均勻,调整到合适的粘度即可施工。 Material: [0052] [0053] In use, the A, B two parts mixed, adjusted to the appropriate viscosity to construction. 实施例3 :本实施例提供的防涂鸦抗粘贴涂料由A、B两组份组成,按重量份计包括以下原A组份氟烷基改性聚硅氧烷 6份羟基丙烯酸树脂 35份颜填料 19份助剂 3份有机溶剂 19份[0054] B 组份:[0055] TDI三聚体18份[0056] 其中,氟烷基改性聚硅氧烷的合成方法是:室温下将IOOg丙烯酸十三氟辛酯、溶剂、催化剂加入到反应器中,搅拌并在高纯氮气保护下,升温至135°C,然后滴加15. 6g聚甲基氢硅氧烷,反应8小时,然后冷却至室温,经旋转蒸发除去溶剂,得到透明、粘稠的氟烷基改性聚硅氧烷;其中聚甲基氢硅氧烷的结构式为:CH3I[0057] H3C-SiO-CH3ICH3I-〒一0"^甲_CH3式中n = 65 ; HCH3Lh JnL3[0058] 制备防涂鸦抗粘贴涂料的方法是:将羟基丙烯酸树脂与颜填料、助剂、有机溶剂加入到研磨机中,在2500转/分钟的转速下研磨4h,研磨均勻制成浆料;然后将研磨好的浆料与氟烷基改性 Example 3: Anti-graffiti embodiment of the present embodiment provides an anti-adhesive coating consists of two parts A, B composition, in parts by weight comprises the following parts of the original A fluoroalkyl group-modified polysiloxane 6 parts acrylic resin 35 parts pigment hydroxy 19 parts 3 parts filler auxiliary organic solvent 19 parts [0054] component B: [0055] TDI trimer 18 parts [0056] wherein the synthetic method fluoroalkyl-modified silicone is: a mixture IOOg thirteen perfluorooctyl acrylate, solvent, catalyst was added to the reactor, and stirred under high purity nitrogen, heated to 135 ° C, then a solution of methyl hydrogen polysiloxane 15. 6g, reacted for 8 hours, then cooled to room temperature, the solvent was removed by rotary evaporation to give a clear, viscous fluoroalkyl-modified silicone; wherein the methyl hydrogen polysiloxane of formula as: CH3I [0057] H3C-SiO-CH3ICH3I-〒 a 0 "^ a _CH3 wherein n = 65; HCH3Lh JnL3 [0058] the method of preparing an anti-anti-graffiti coating paste is: a hydroxyl acrylic resin and pigment, additives, an organic solvent is added to the grinding mill, 2500 rpm / grinding at a rotation speed minutes 4h, the polishing slurry is made uniform; then the slurry was triturated with fluoroalkyl-modified 硅氧烷一起投入到高速分散机中,在1000转/分钟的转速下分散1. 5小时后,过滤包装,即得所需的A组份;[0059] 使用时,将A、B两组份混合均勻,调整到合适的粘度即可施工。[0060] 实施例4 :7[0061]本实施例提供的防涂鸦抗粘贴涂料由A、B两组份组成,按重量份计包括以下原 Silicone together into a high-speed dispersing machine, the dispersion at 1000 rev / min speed of 1.5 hours, filtered and packaging, A to yield the desired component; when [0059] In use, the A, B two parts of mixed, adjusted to the appropriate viscosity to the construction [0060] Example 4: 7 [0061] the present embodiment provides an anti-anti-graffiti coating paste consists of two parts a, B composition, comprising by weight parts of the original

料:[0062] A组份 Material: [0062] A component

[0063]氟烷基改性聚硅氧烷16份 [0063] The fluoroalkyl group-modified silicone 16 parts

羟基丙烯酸树脂28份 Hydroxyl acrylic resin 28 parts

颜填料13份 13 parts of fillers

助剂4份 4 parts adjuvant

有机溶剂 20份[0064] B 组份:[0065] IPDI三聚体19份[0066] 其中,氟烷基改性聚硅氧烷的合成方法是:室温下将85g甲基丙烯酸三氟乙酯、溶剂、催化剂加入到反应器中,搅拌并在高纯氮气保护下,升温至160°C,然后滴加30. 8g聚甲基氢硅氧烷,反应4小时,然后冷却至室温,经旋转蒸发除去溶剂,得到透明、粘稠的氟烷基改性聚硅氧烷;其中聚甲基氢硅氧烷的结构式为: [0067] 20 parts of organic solvent [0064] Component B: [0065] IPDI trimer 19 parts [0066] wherein the synthetic method fluoroalkyl-modified silicone is: at room temperature 85g of trifluoroethyl methacrylate , solvent, catalyst was added to the reactor, and stirred under high purity nitrogen, heated to 160 ° C, then a solution of 30. 8g methyl hydrogen polysiloxane, reaction for 4 hours, then cooled to room temperature, rotated the solvent was evaporated to give a clear, viscous fluoroalkyl-modified silicone; structural formula wherein methyl hydrogen polysiloxane as: [0067]

Figure CN102516859AD00081

[0068] 制备防涂鸦抗粘贴涂料的方法是:将羟基丙烯酸树脂与颜填料、助剂、有机溶剂加入到研磨机中,在3000转/分钟的转速下研磨4h,研磨均勻制成浆料;然后将研磨好的浆料与氟烷基改性聚硅氧烷一起投入到高速分散机中,在1000转/分钟的转速下分散2小时后,过滤包装,即得所需的A组份;[0069] 使用时,将A、B两组份混合均勻,调整到合适的粘度即可施工。 [0068] Preparation of anti-anti-graffiti coating paste method is: hydroxyl acrylic resin and pigment, additives, an organic solvent is added to the grinding mill, grinding 4h at 3000 rev / min speed, polishing uniformity to prepare a slurry; the slurry was then milled into the fluoroalkyl-modified silicone with a high-speed disperser at 1000 rev / min speed dispersion after 2 hours, filtered packaging, a to yield the desired component; [0069] in use, the a, B two parts mixed, adjusted to the appropriate viscosity to construction. [0070] 将上述实施例1〜实施例4的涂料喷涂在规定的基材上,固化成膜后,对所形成的漆膜进行如下技术性能测试:外观、硬度、附着力、耐磨性、耐中性盐雾性、耐人工老化、耐液体介质性、耐溶剂擦拭性、防涂鸦性、抗粘贴性。 [0070] The above embodiments 1 ~ Example 4 sprayed coating on a substrate in a predetermined, after the curing film, the film is formed of the following technical performance test: appearance, hardness, adhesion, abrasion resistance, neutral salt spray resistance, resistance to artificial aging, resistance to liquids, solvent wiping resistance, anti-graffiti, anti-adhesive properties. 各项性能测试结果见下表:[0071] The performance test results in the table below: [0071]

Figure CN102516859AD00091

Claims (10)

  1. 1. 一种防涂鸦抗粘贴涂料,其特征是在于:所述涂料由A、B两组份组成,按重量份计, A组份是:氟烷基改性聚硅氧烷4〜20份, 羟基丙烯酸树脂2(Γ42份,B组份为多异氰酸酯预聚物12〜30份;A组份与B组份的重量比为2〜8: 1。 An anti-anti-graffiti coating paste, which is characterized in that: the coating consists of two parts A, B composition, in parts by weight, the component A is: 4~20 fluoroalkyl-modified silicone parts , hydroxyl acrylic resin 2 (Γ42 parts, component B is a polyisocyanate prepolymer 12~30 parts; a and B component parts of the group weight ratio of 2~8: 1.
  2. 2.根据权利要求1所述的防涂鸦抗粘贴涂料,其特征在于:所述羟基丙烯酸树脂的羟值为5〜200mg KOH/g,数均分子量为4000〜50000。 2. antigraffiti according to claim 1, said anti-adhesive coating, wherein: said hydroxyl acrylic resin has a hydroxyl value 5~200mg KOH / g, number average molecular weight 4000~50000.
  3. 3.根据权利要求1所述的防涂鸦抗粘贴涂料,其特征在于:所述颜填料为气相二氧化硅、金红石型钛白粉、锐钛型钛白粉、聚四氟乙烯微粉、滑石粉、硫酸钡、碳酸钙、云母粉、铝粉或空心玻璃微珠中的一种或多种。 Antigraffiti according to claim 1, said anti-adhesive coating, wherein: the pigment is a fumed silica, rutile titanium dioxide, anatase titanium dioxide, PTFE powder, talc, sulfate barium, calcium carbonate, mica powder, aluminum powder or hollow glass microspheres in one or more.
  4. 4.根据权利要求1所述的防涂鸦抗粘贴涂料,其特征在于:所述助剂为润湿分散剂、 流平剂、消泡剂、催干剂、耐磨剂、抗划伤剂或附着力促进剂中的一种或多种。 The anti-graffiti said anti-adhesive coating according to claim 1, wherein: said adjuvant is a wetting and dispersing agents, leveling agents, defoaming agents, driers, anti-wear agents, anti-scratch agent, or the adhesion promoter one or more agents.
  5. 5.根据权利要求1所述的防涂鸦抗粘贴涂料,其特征在于:所述有机溶剂为醋酸甲酯、醋酸乙酯、醋酸丁酯、甲苯、对二甲苯、邻二甲苯、间二甲苯、丙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、碳酸二甲酯、丙酮、环己酮中三种或三种以上的组合。 The anti-graffiti said anti-adhesive coating according to claim 1, wherein: the organic solvent is methyl acetate, ethyl acetate, butyl acetate, toluene, p-xylene, o-xylene, m-xylene, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, dimethyl carbonate, acetone, cyclohexanone combination of three or more.
  6. 6.根据权利要求1所述的防涂鸦抗粘贴涂料,其特征在于:所述多异氰酸酯预聚物为HDI三聚体、MDI三聚体、IPDI三聚体或TDI三聚体中的一种。 The anti-graffiti said anti-adhesive coating according to claim 1, wherein: said polyisocyanate prepolymer as a HDI trimer, the MDI trimer, IPDI trimers or trimers of TDI .
  7. 7. —种如权利要求1-6所述的防涂鸦抗粘贴涂料的制备方法,其特征在于:所述A组份的制备:将羟基丙烯酸树脂与颜填料、助剂、有机溶剂加入到研磨机中,研磨均勻后制成浆料; 将研磨好的浆料与氟烷基改性聚硅氧烷一起投入到高速分散机中,在80(Γ1500转/分钟下分散0. 5^2小时后,过滤包装,即得所需的A组份;使用时,将Α、Β两组份按2〜8: 1重量配比混合均勻即可。 7. - 1-6 kinds of antigraffiti claim preparing anti-adhesive coating, wherein: the preparing parts A Group: The hydroxyl acrylic resin and pigment, additives, organic solvent is added to the ground machine, after made uniform polishing slurry; polishing slurry was put together with the fluoroalkyl-modified silicone to the high-speed dispersion machine, is dispersed in 80 (/ min at 0.5 revolutions Γ1500 ^ 2 hours after filtration packing, a to yield the desired component; use, the [alpha], Beta two parts by 2~8: 1 weight ratio mix evenly.
  8. 8.如权利要求7所述的防涂鸦抗粘贴涂料的制备方法,其特征在于:所述氟烷基改性聚硅氧烷由含氟丙烯酸酯单体与聚甲基氢硅氧烷在催化剂作用下合成得到,其合成方法是:室温下将含氟丙烯酸酯单体、溶剂、催化剂加入到反应器中,搅拌并在惰性气体保护下, 升温至80°C以上,滴加聚甲基氢硅氧烷,反应2〜30小时,然后冷却至室温,经旋转蒸发除去溶剂,得到透明、粘稠的氟烷基改性聚硅氧烷。 8. antigraffiti according to claim 7 of preparing an anti-adhesive coating, wherein: said modified silicone fluoroalkyl group of the fluorine-containing acrylate monomer and methyl hydrogen polysiloxane in the catalyst synthesized under the action of its method of synthesis: a mixture of fluorine-containing acrylate monomer, solvent, catalyst was added to the reactor, and stirred under an inert atmosphere, heated up to 80 ° C, was added dropwise polymethyl hydrogen siloxane, reaction 2~30 hours, then cooled to room temperature, the solvent was removed by rotary evaporation to give a clear, viscous fluoroalkyl-modified silicone.
  9. 9.如权利要求8所述的防涂鸦抗粘贴涂料的制备方法,其特征在于:所述含氟丙烯酸酯单体为甲基丙烯酸三氟乙酯、丙烯酸四氟丙酯、甲基丙烯酸四氟丙酯、丙烯酸六氟丁酯、 甲基丙烯酸六氟丁酯、丙烯酸八氟戊酯、甲基丙烯酸八氟戊酯、丙烯酸十二氟庚酯、甲基丙烯酸十二氟庚酯、丙烯酸十三氟辛酯或甲基丙烯酸十三氟辛酯中的一种。 9. The antigraffiti according to claim 8 Preparation of anti-adhesive coating, wherein: the fluorinated acrylate monomer is trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, methacrylate, tetrafluoroethylene propyl acrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, butyl acrylate, octafluoropentyl methacrylate, octafluoropentyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, thirteen an ester of one or perfluorooctyl methacrylate tridecafluoro-octyl.
  10. 10.如权利要求8所述的防涂鸦抗粘贴涂料的制备方法,其特征在于:所述聚甲基氢硅氧烷的结构式为:颜填料助剂有机溶剂10〜35份, Γ8份, 10〜36份, 10. antigraffiti according to claim 8 Preparation of anti-adhesive coating, wherein: the structural formula is a methyl hydrogen polysiloxane: fillers aid 10~35 parts of organic solvent, Γ8 parts, 10 ~36 copies,
    Figure CN102516859AC00031
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CN102731743A (en) * 2012-06-26 2012-10-17 华烁科技股份有限公司 Preparation of white thermosetting resin used for LED light having encapsulating film
CN102731743B (en) 2012-06-26 2014-05-07 华烁科技股份有限公司 Preparation of white thermosetting resin used for LED light having encapsulating film
CN102786841A (en) * 2012-08-24 2012-11-21 苏州金海薄膜科技发展有限公司 Scratch-resistant and stain-repellent ink and preparation method thereof
CN103113820A (en) * 2013-03-13 2013-05-22 鹿尼德(上海)表面材料技术有限公司 Double-component liquid protective paint
CN103740220A (en) * 2013-12-11 2014-04-23 甘肃大禹节水集团股份有限公司 High-temperature-resistant burning-resistant under-film drip irrigation zone coating and preparation method thereof
CN103740220B (en) * 2013-12-11 2015-11-18 甘肃大禹节水集团股份有限公司 High temperature resistant, anti-burning coating and preparation method with Drip Irrigation
CN104017480B (en) * 2014-06-24 2016-06-15 博罗县石湾美源涂料有限公司 A fluoropolymer siliconized acrylic urethane paint and preparation method of application
CN104017480A (en) * 2014-06-24 2014-09-03 博罗县石湾美源涂料有限公司 Acrylic polyurethane silicofluoride coating as well as preparation method and application method thereof
CN104293018A (en) * 2014-08-04 2015-01-21 荆门市鑫福瑞交通安全设施有限公司 Low-surface-energy paint with hydrophobic self-cleaning function
CN105518081B (en) * 2014-09-03 2017-09-01 新道公司 For preventing adhesion of advertising sheet using the coating composition and the coating method thereof
CN104356774A (en) * 2014-11-21 2015-02-18 苏州大乘环保建材有限公司 Water-based anti-doodling paint and preparation method thereof
CN105176358A (en) * 2015-10-21 2015-12-23 中航百慕新材料技术工程股份有限公司 Water-based anti-doodling paint
CN105176357A (en) * 2015-10-21 2015-12-23 中航百慕新材料技术工程股份有限公司 Water-based double-component anti-doodling paint
CN106398520A (en) * 2016-09-30 2017-02-15 福建亿尚电气有限公司 Light-reflecting anti-sticking nonskid paint and preparation method thereof

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