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WO2016000537A1 - 一种具有自清洁功能的氨基烤漆组合物及其制备方法 - Google Patents

一种具有自清洁功能的氨基烤漆组合物及其制备方法 Download PDF

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Publication number
WO2016000537A1
WO2016000537A1 PCT/CN2015/081912 CN2015081912W WO2016000537A1 WO 2016000537 A1 WO2016000537 A1 WO 2016000537A1 CN 2015081912 W CN2015081912 W CN 2015081912W WO 2016000537 A1 WO2016000537 A1 WO 2016000537A1
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Prior art keywords
resin
self
parts
cleaning function
amino baking
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French (fr)
Inventor
马永强
张�浩
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Langfang Nippon Paint Co Ltd
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Langfang Nippon Paint Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance

Definitions

  • the invention relates to the technical field of coatings and preparation methods thereof. More specifically, it relates to an amino baking varnish composition having a self-cleaning function and a method of preparing the same.
  • the amino baking varnish is mainly composed of a hydroxy-containing acrylic resin or an alkyd resin or an amino resin, and is packaged in a single component at a normal temperature. At a relatively high temperature (above 140 ° C), a chemical reaction occurs between the components to form a chemical reaction. It has a three-dimensional network structure, high hardness, excellent adhesion, high gloss, good gloss and color retention, and is widely used in the coating of shells for automobiles, ships and airplanes.
  • the coating forms a nano-structure similar to the roughness of the lotus leaf on the surface of the coating during the dry film formation process.
  • the uneven nano coating can make the dust particles adhere to the surface of the coating. Suspended state, the contact angle of water and coating surface is greatly increased, and the accumulation or adsorption of pollution The particles break away from the surface of the coating under the scouring of wind and rain for self-cleaning purposes.
  • a silicone self-cleaning agent is generally added to achieve a certain self-cleaning purpose, but a low surface energy silicone auxiliaries easily migrate to the surface of the paint film, and the auxiliaries are lost over time. The cleaning function will be reduced.
  • the first technical problem to be solved by the present invention is to provide an amino baking paint composition having a self-cleaning function, which utilizes a plurality of terminal hydroxyl functional groups in a nano-scale hyperbranched polyester resin to achieve a high cross-linking density of a paint film. And an amino baking varnish with long-lasting self-cleaning function prepared by anti-graffiti resin which is involved in the cross-linking reaction of paint film.
  • a second technical problem to be solved by the present invention is to provide a method for preparing an amino baking varnish composition having a self-cleaning function, which is simple in preparation process and suitable for industrial production.
  • the present invention adopts the following technical solutions:
  • An amino baking varnish composition having a self-cleaning function comprising the following raw materials by weight:
  • the hyperbranched polyester polyol resin has a hydroxyl value of 240 to 320 mg KOH/g, a viscosity of 20 to 100 cPs, and 25 ° C, based on the solid resin.
  • the blocked isocyanate resin has a deblocking temperature of 110 to 150 °C.
  • the anti-graffiti resin contains a hydroxyl group, and the anti-graffiti resin has a hydroxyl value of 30 to 60 mg KOH/g in terms of a pure solid portion.
  • the coating aid is selected from the group consisting of ultraviolet absorbers, light stabilizers, leveling agents, coupling agents, drier, toughening agents, emulsifiers, thickeners, pigment dispersants, defoamers, and anti-foaming agents.
  • a skinning agent a matting agent, an anti-fungal agent, or an antistatic agent.
  • the coating aid comprises 0.5 to 1.0 part of a UV absorber, 0.5 to 1.0 part of a light stabilizer, 0.5 to 1.0 part of a leveling agent, and 0.5 to 1.0 part of a coupling agent.
  • the diluent is selected from one or more of an ester solvent, a ketone solvent, an alcohol solvent or an alcohol ether solvent;
  • the ester solvent is one or more selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate or amyl acetate;
  • the ketone solvent is selected from one or more of acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone or methyl isobutyl ketone;
  • the alcohol solvent is selected from one or more of methanol, ethanol or butanol;
  • the alcohol ether solvent is selected from the group consisting of ethylene glycol-diethyl ether, ethylene glycol-butyl ether, diethylene glycol-B One or several of the ethers.
  • a method for preparing an amino baking varnish composition having a self-cleaning function comprising the following preparation steps:
  • the stirring speed in the step (1) is: 200 to 250 r/min; and the stirring speed in the step (2) is 300 to 350 r/min.
  • the self-cleaning amino baking varnish of the invention utilizes a plurality of terminal hydroxyl functional groups in the nano-scale hyperbranched polyester resin to achieve a high cross-linking density of the paint film, and the high cross-linking density of the paint film and the low surface energy can effectively reduce the water.
  • the adhesion and infiltration of dust, oil, brakes and bird droppings on the surface of the paint film reduces the frequency of vehicle cleaning to a certain extent.
  • the anti-graffiti resin which participates in the cross-linking reaction of the paint film makes the self-cleaning amino baking varnish of the invention have a long-lasting self-cleaning function.
  • Hyperbranched polyester polyol resin BBHA D5025 (CyGLAZ BB500) or BB D5025, all purchased from Singapore Lishi Technology Co., Ltd.;
  • SETALUX 1215BA-68 was purchased from Nuplex Resin (Suzhou) Co., Ltd., or DESMOPHEN A870BA was purchased from BAYER;
  • Blocked isocyanate resin BL 3175 was purchased from BAYER; BLR 8086, purchased from Deqian (Shanghai) Chemical Co., Ltd.;
  • CYMEL 1158 was purchased from CYTEC, or Luwipal 072 was purchased from BASF;
  • TEGO Protect 5001 or TEGO Protect 5000 are both purchased by Homemade Degussa (China) Investment Co., Ltd.;
  • UV absorbers TINUVIN-1130, TINUVIN-400, CHISOKB5228;
  • Light stabilizer TINUVIN-292, TINUVIN-123, CHISOKB523;
  • Photo coupling agent DC 6040 or KBM 403.
  • CYMEL 1158 25.4 parts of SETALUX 1215BA-68, 25.9 parts of BL 3175, 0.6 parts of Protect 5001, 0.3 parts of BYK-331, 0.7 parts of TINUVIN-400, 0.3 parts of TINUVIN-292 and 0.8 parts of DC 6040, after the completion of the feeding, the stirring speed is increased to 350r/min, and the stirring is continued for 30 minutes, and then filtered and discharged to obtain an amino baking varnish having a self-cleaning function.
  • the prepared amino baking varnish with self-cleaning function is diluted to 24 to 26 seconds (coating-4 viscosity cup, 25 ° C) and sprayed on aluminum plate. (Iwata 101 spray gun, spraying pressure 0.4 MPa, control dry film thickness 25 ⁇ 30 ⁇ m), leveling 6 ⁇ 8min, and finally baking at 140°C ⁇ 30min, which is a self-cleaning amino baking paint coating.
  • the test method for the performance is shown in Table 2:
  • the surface tension test mixture was purchased from Japan Wako Pure Chemical Industries Co., Ltd.
  • the specific test is to use a cotton swab dipped in syrup to scratch the surface of the paint film, leaving scratches, scratches within 3 seconds without shrinkage, which means that the surface tension can reach the surface tension level represented by the number marked on the bottle. The larger the number, the higher the surface tension.
  • Comparative Example 1 was to replace the anti-graffiti resin of Example 1 with a mass such as a commercially available silicone additive, and the amount of other materials was unchanged.
  • Comparative Example 2 is a commercially available SiO 2 nanoparticle and the like, and the amount of other materials of the anti-graffiti resin of Example 1 is unchanged.
  • the baking properties of Example 1 and Comparative Examples 1, 2 are shown in Table 3.
  • the amino baking varnish having the self-cleaning function prepared in Example 1 was excellent in performance, and its surface tension was less than 22.6, which was smaller than the comparative example, and thus had good anti-graffiness. And its anti-graffiti nature does not reduce the anti-graffiti effect with the influence of sunshine, surface scratches and other factors, and has self-cleaning and long-lasting effect. In contrast, the water-resistance and anti-graffiti effect of the paint film of Comparative Example 1 was poor. The SiO 2 nanoparticles added in Comparative Example 2 only filled the paint film, but reduced the physical and chemical properties of the paint film, and did not achieve the ideal anti-graffiti effect.
  • Example 1 The samples prepared in Example 1 and Comparative Examples 1, 2 were placed in an aging tester for about 750 hours, and then taken out, and the graffiti resistance was measured. The results are shown in Table 4.
  • Example 1 was repeated except that the parts by weight of Example 2 were as shown in Table 3.
  • the hyperbranched polyester polyol resin has a hydroxyl value of 240 mg KOH/g as a solid resin and a viscosity of 20 cPs at 25 ° C; the deblocking temperature of the blocked isocyanate resin is 110 ° C; the hydroxyl value of the anti-graffiti resin It was 30 mg KOH/g in terms of pure solids.
  • the weight fraction of the raw materials of Example 3 is shown in Table 4.
  • the hyperbranched polyester polyol resin has a hydroxyl value of 320 mg KOH/g as a solid resin, a viscosity of 100 cPs, 25 ° C; a deblocking temperature of the blocked isocyanate resin is 140 ° C; The hydroxyl value was 30 mg KOH/g in terms of pure solids.
  • Example 2 The same as Example 1, except that the hydroxyl value of the hyperbranched polyester polyol resin was 230 mg KOH/g and 330 mg KOH/g, respectively, based on the solid resin.
  • Example 2 The same as in Example 1, except that the anti-graffiti resin has a hydroxyl value of 25 mg KOH/g and 65 mg KOH/g, respectively, in terms of pure solid parts.
  • the surface tension of the amino baking varnish of Examples 2-8 is shown in Table 6.
  • the anti-graffiti performance of the amino baking varnish of Examples 2-8 was not weakened by the influence of sunlight, surface scratches and the like, and the self-cleaning long-lasting effect was obtained.
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Example 7
  • Example 8 Surface Tension ⁇ 22.6 ⁇ 22.6 ⁇ 22.6 22.6 24.0 24.0 26.8
  • the order of the addition of the step (2) is the sequential addition of a hydroxy acrylic resin, an amino resin, a blocked isocyanate resin, an anti-graffiti resin and a coating aid, and the stirring speed is: 350 r / After stirring at min, the reaction system agglomerated after 10 minutes, and the stirring speed was increased to 400 r/min, and it was still unable to disperse.
  • the feeding sequence of the step (2) is to sequentially add an anti-graffiti resin, an amino resin, a hydroxy acrylic resin, a blocked isocyanate resin and a coating auxiliary agent, and continue the stirring speed: 350r/ After stirring under the conditions of min, the reaction system agglomerated after 5 minutes and could not be dispersed.
  • Example 11 The same as Example 1, except that the materials used in Example 11 are shown in Table 7.
  • Table 7 The test results of the amino baking varnish prepared in Example 11 were similar to those in Example 1.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

一种具有自清洁功能的氨基烤漆组合物，包括以下重量份的原料：超支化聚酯多元醇树脂7.0～12.0，羟基丙烯酸树脂25.0～30.0，封端异氰酸酯树脂25.0～30.0，氨基树脂5.0～10.0，防涂鸦树脂0.5～1.0，涂料助剂2.0～3.0和稀释剂15.0～35.0。其制备方法包括将各成分按顺序加入反应器中搅拌。该组合物具有长效性自清洁功能。

Description

一种具有自清洁功能的氨基烤漆组合物及其制备方法 技术领域
本发明涉及涂料及其制备方法技术领域。更具体地，涉及一种具有自清洁功能的氨基烤漆组合物及其制备方法。
背景技术
氨基烤漆以带有羟基的丙烯酸树脂或醇酸树脂、氨基树脂为主要成膜物质，常温下以单组份包装，在较高温度下(140℃以上)，组分之间发生化学反应，形成具有三维网络的体型结构，具有很高的硬度、优异的附着力、高的光泽、良好的保光保色性等性能，被广泛应用于汽车、船舶和飞机等外壳的涂装。
随着汽车制造业的发展，人们对汽车零部件的涂装要求越来越高，尤其是在环保和具备一定特殊功能方面。汽车铝合金轮毂在车辆行驶中难免会沾有灰尘、油污和刹车削，传统轮毂罩光清漆的耐沾污性能比较差，尤其是对刹车削沾上后很难清理；另外，在中国北方冬季时节，汽车车身、挡风玻璃和后视镜容易结上一层冰霜，影响到汽车外观和行车安全。
根据“荷叶自清洁”原理，使涂料在干燥成膜过程中，在涂层表面形成类似荷叶的凹凸的纳米结构，这种凹凸不平的纳米涂层可以使灰尘颗粒附着在涂层表面呈悬空状态，使水与涂层表面的接触角大大增加，堆积或吸附的污染 性微粒在风雨的冲刷下脱离涂层表面，达到自清洁目的。
现有技术中一般通过加入有机硅助剂以达到一定的自清洁目的，但是低表面能的有机硅助剂容易迁移到漆膜表面，随着时间的推移，助剂有所损失，漆膜自清洁功能会降低。
因此，需要提供一种具有长效性自清洁功能的氨基烤漆及其制备方法。
发明内容
本发明要解决的第一个技术问题是提供一种具有自清洁功能的氨基烤漆组合物，该产品是利用纳米级超支化聚酯树脂中众多的端羟基官能团实现高的漆膜交联密度，并配合参与漆膜交联反应的防涂鸦树脂制备的一种具有长效性自清洁功能的氨基烤漆。
本发明要解决的第二个技术问题是提供一种具有自清洁功能的氨基烤漆组合物的制备方法，该方法制备工艺简单，适宜工业化生产。
为解决上述第一个技术问题，本发明采用下述技术方案：
一种具有自清洁功能的氨基烤漆组合物，包括以下重量份的原料：
Figure PCTCN2015081912-appb-000001
Figure PCTCN2015081912-appb-000002
上述原料均可由市售得到。
优选地，所述超支化聚酯多元醇树脂的羟值按固体树脂计为240～320mg KOH/g、粘度为20～100cPs，25℃。
优选地，所述封端异氰酸酯树脂的解封温度为110～150℃。
优选地，所述防涂鸦树脂含有羟基，所述防涂鸦树脂的羟值按纯固体份计为30～60mg KOH/g。
优选地，所述涂料助剂选自紫外线吸收剂、光稳定剂、流平剂、偶联剂、催干剂、增韧剂、乳化剂、增稠剂、颜料分散剂、消泡剂、抗结皮剂、消光剂、防霉剂或抗静电剂中的一种或几种。更优选地，所述涂料助剂包括0.5～1.0份的紫外线吸收剂、0.5～1.0份光稳定剂、0.5～1.0份的流平剂和0.5～1.0份的偶联剂。
优选地，所述稀释剂选自酯类溶剂、酮类溶剂、醇类溶剂或醇醚类溶剂中的一种或几种；
优选地，所述酯类溶剂选自乙酸乙酯、乙酸丁酯、丙二醇甲醚醋酸酯或乙酸戊酯中的一种或几种；
优选地，所述酮类溶剂选自丙酮、丁酮、环己酮、环戊酮或甲基异丁酮中的一种或几种；
优选地，所述醇类溶剂选自甲醇、乙醇或丁醇中的一种或几种；
优选地，所述醇醚类溶剂选自乙二醇-乙醚、乙二醇-丁醚、二乙二醇-乙 醚中的一种或几种。
为解决上述第二个技术问题，本发明采用下述技术方案：
一种具有自清洁功能的氨基烤漆组合物的制备方法，包括以下制备步骤：
(1)将15.0份～20.0份稀释剂加入带搅拌的反应器中，然后加入7.0份～12.0份超支化聚酯多元醇树脂继续搅拌8-15min；
(2)在步骤(1)的反应器中依次加入5.0份～10.0份氨基树脂、25.0份～30.0份羟基丙烯酸树脂、25.0份～30.0份封端异氰酸酯树脂、0.5份～1.0份防涂鸦树脂和2.0份～3.0份涂料助剂，继续搅拌20～40min后过滤得到具有自清洁功能的氨基烤漆。
优选地，步骤(1)所述搅拌速度为：200～250r/min；步骤(2)所述搅拌速度为：300～350r/min。
本发明的有益效果如下：
本发明的自清洁功能的氨基烤漆，利用纳米级超支化聚酯树脂中众多的端羟基官能团实现高的漆膜交联密度，其高的漆膜交联密度和低的表面能能有效降低水、灰尘、油污、刹车削和鸟粪等在漆膜表面的附着和渗入，在一定程度上降低了车辆清洗的频率。配合参与漆膜交联反应的防涂鸦树脂使得本发明的自清洁功能的氨基烤漆具有长效性自清洁功能。
具体实施方式
下面结合实施例对本发明进一步加以说明。
超支化聚酯多元醇树脂：BBHA D5025(CyGLAZ BB500)或者BB  D5025，均购自新加坡立时科技有限公司；
羟基丙烯酸树脂：SETALUX 1215BA-68购自纽佩斯树脂(苏州)有限公司，或者DESMOPHEN A870BA购自BAYER公司；
封端异氰酸酯树脂：BL 3175均购自BAYER公司；BLR 8086,购自德谦(上海)化学有限公司；
氨基树脂：CYMEL 1158购自CYTEC公司，或者Luwipal 072购自BASF公司；
防涂鸦树脂：TEGO Protect 5001或者TEGO Protect 5000均购自创赢德固赛(中国)投资有限公司；
涂料助剂：
流平剂BYK-331、BYK-358N或OTSN；
紫外线吸收剂：TINUVIN-1130、TINUVIN-400、CHISOKB5228；
光稳定剂：TINUVIN-292、TINUVIN-123、CHISOKB523；
光偶联剂：DC 6040或KBM 403。
实施例1
表1实施例1原料重量份数
Figure PCTCN2015081912-appb-000003
Figure PCTCN2015081912-appb-000004
将12份的乙酸丁酯、9份的丙二醇甲醚醋酸酯和10.6份的环己酮加入搅拌釜中，在200r/min搅拌转速下缓慢加入11.6份的BBHA D5025，搅拌10min后依次缓慢加入10.0份的CYMEL 1158、25.4份的SETALUX 1215BA-68、25.9份的BL 3175、0.6份的Protect 5001、0.3份的BYK-331、0.7份的TINUVIN-400、0.3份的TINUVIN-292和0.8份的DC 6040，投料完毕后升搅拌速率至350r/min继续搅拌30min后过滤、出料得到具有自清洁功能的氨基烤漆。
实施例1制备的具有自清洁功能的氨基烤漆的性能测试
将制得的具有自清洁功能的氨基烤漆粘度稀释至24～26秒(涂-4粘度杯，25℃)，喷涂于铝板上，(岩田101型喷枪，喷涂压力0.4MPa，控制干膜厚25～30μm)，流平6～8min，最后140℃×30min烘烤，即得到自清洁功能的氨基烤漆涂层。
性能的检测方法见表2：其中，表面张力测试用混合液是日本和光纯药工业株式会社购买。具体测试是用沾有药水的棉签划过漆膜表面，留下划痕，3秒钟之内划痕无收缩，即表示表面张力可以达到瓶子上标注的数字所代表的表面张力级别。数字越大，表示表面张力越高。
表2性能检测方法
Figure PCTCN2015081912-appb-000005
Figure PCTCN2015081912-appb-000006
对比例1为用市售的有机硅助剂等质量替代实施例1中防涂鸦树脂，其他物料用量不变。
对比例2为市售的SiO2纳米颗粒等质量替代实施例1防涂鸦树脂其他物料用量不变。实施例1及对比例1、2的烤漆性能见表3。
表3实施例1及对比例的烤漆的性能
Figure PCTCN2015081912-appb-000007
Figure PCTCN2015081912-appb-000008
从表3中可以看出，实施例1制备的具有自清洁功能的氨基烤漆性能优异，其表面张力小于22.6，小于对比例，因此具有良好的防涂鸦性。且其防涂鸦性完全没有随着日照、表面划痕等因素的影响而减弱防涂鸦效果，具有自清洁长效性。而对比例1漆膜的耐水及防涂鸦效果较差，对比例2添加的SiO2纳米颗粒仅在漆膜中起填充作用，反而降低漆膜理化性能，更未达到理想的防涂鸦效果。
老化试验机模拟：将实施例1和对比例1、2制备的样板放在老化试验机中约750小时后取出，再测防涂鸦性，结果见表4。
表4耐老化试验后实施例1及对比例的烤漆的性能
Figure PCTCN2015081912-appb-000009
实施例2
重复实施例1，其不同之处仅在于，实施例2原料重量份数如表3。其中所 述超支化聚酯多元醇树脂的羟值按固体树脂计为240mg KOH/g、粘度为20cPs，25℃；所述封端异氰酸酯树脂的解封温度为110℃；所述防涂鸦树脂的羟值按纯固体份计为30mg KOH/g。
表5实施例2原料重量份数
Figure PCTCN2015081912-appb-000010
实施例3
实施例3原料重量份数如表4。其中所述超支化聚酯多元醇树脂的羟值按固体树脂计为320mg KOH/g、粘度为100cPs，25℃；所述封端异氰酸酯树脂的解封温度为140℃；所述防涂鸦树脂的羟值按纯固体份计为30mg KOH/g。
表6实施例3原料重量份数
原料 份数
超支化聚酯多元醇树脂BBHA D5025 12份
羟基丙烯酸树脂SETALUX 1215BA-68 28份
封端异氰酸酯树脂BL 3175 26份
氨基树脂CYMEL 1158 8份
防涂鸦树脂TEGO Protect 5001 0.8份
颜料分散剂和消泡剂1:1混合 2.5份
乙醇和二乙二醇-乙醚1:1混合 18份
(1)将稀释剂加入带搅拌的反应器中，然后加入超支化聚酯多元醇树脂继续搅拌15min；搅拌速度为200r/min；
(2)在步骤(1)的反应器中依次加入氨基树脂、羟基丙烯酸树脂、封端异氰酸酯树脂、防涂鸦树脂和涂料助剂，继续在搅拌速度为：300r/min的条件下搅拌40min后过滤得到具有自清洁功能的氨基烤漆。
实施例4
实施例4原料重量份数如表5。
表7实施例4原料重量份数
Figure PCTCN2015081912-appb-000011
(1)将稀释剂加入带搅拌的反应器中，然后加入超支化聚酯多元醇树脂继续搅拌8min；搅拌速度为250r/min；
(2)在步骤(1)的反应器中依次加入氨基树脂、羟基丙烯酸树脂、封端异氰酸酯树脂、防涂鸦树脂和涂料助剂，继续在搅拌速度为：350r/min的条件下搅拌20min后过滤得到具有自清洁功能的氨基烤漆。
实施例5、6
同实施例1，其不同之处仅在于，所述超支化聚酯多元醇树脂的羟值按固体树脂计分别为：230mg KOH/g、330mg KOH/g。
实施例7、8
同实施例1，其不同之处仅在于，所述防涂鸦树脂的羟值按纯固体份计分别为25mg KOH/g、65mg KOH/g。
实施例2-8的氨基烤漆涂层的表面张力见表6。实施例2-8的氨基烤漆涂层防涂鸦性完全没有随着日照、表面划痕等因素的影响而减弱防涂鸦效果，具有自清洁长效性。
表8实施例2-8的氨基烤漆涂层的表面张力
  实施例2 实施例3 实施例4 实施例5 实施例6 实施例7 实施例8
表面张力 ＜22.6 ＜22.6 ＜22.6 22.6 24.0 24.0 26.8
实施例9
同实施例4，其不同之处仅在于，步骤(2)的加料顺序是依次加入羟基丙烯酸树脂、氨基树脂、封端异氰酸酯树脂、防涂鸦树脂和涂料助剂，继续在搅拌速度为：350r/min的条件下搅拌，10min后反应体系团聚，将搅拌速度提高到400r/min，依然无法分散开。
实施例10
同实施例4，其不同之处仅在于，步骤(2)的加料顺序是依次加入防涂鸦树脂、氨基树脂、羟基丙烯酸树脂、封端异氰酸酯树脂和涂料助剂，继续在搅拌速度为：350r/min的条件下搅拌，5min后反应体系团聚，无法分散开。
实施例11
同实施例1，其不同之处仅在于，实施例11所用原料见表7。实施例11制备的氨基烤漆涂层测试结果与实施例1接近。
表9实施例11原料重量份数
Figure PCTCN2015081912-appb-000012
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (9)

  1. 一种具有自清洁功能的氨基烤漆组合物，其特征在于，包括以下重量份的原料：
    Figure PCTCN2015081912-appb-100001
  2. 根据权利要求1所述的具有自清洁功能的氨基烤漆组合物，其特征在于，所述超支化聚酯多元醇树脂的羟值按固体树脂计为240～320mg KOH/g、粘度为20～100cPs，25℃。
  3. 根据权利要求1所述的具有自清洁功能的氨基烤漆组合物，其特征在于，所述封端异氰酸酯树脂的解封温度为110～150℃。
  4. 根据权利要求1所述的具有自清洁功能的氨基烤漆组合物，其特征在于，所述防涂鸦树脂含有羟基，所述防涂鸦树脂的羟值按纯固体份计为30～60mg KOH/g。
  5. 根据权利要求1所述的具有自清洁功能的氨基烤漆组合物，其特征在于，所述涂料助剂选自紫外线吸收剂、光稳定剂、流平剂、偶联剂、催干剂、增韧剂、乳化剂、增稠剂、颜料分散剂、消泡剂、抗结皮剂、消光剂、防霉剂或抗静电剂中的一种或几种。
  6. 根据权利要求5所述的具有自清洁功能的氨基烤漆组合物，其特征在于，所述涂料助剂包括0.5～1.0份的紫外线吸收剂、0.3～1.0份光稳定剂、0.3～1.0份的流平剂和0.5～1.0份的偶联剂。
  7. 根据权利要求1所述的具有自清洁功能的氨基烤漆组合物，其特征在于，所述稀释剂选自酯类溶剂、酮类溶剂、醇类溶剂或醇醚类溶剂中的一种或几种；
    优选地，所述酯类溶剂选自乙酸乙酯、乙酸丁酯、丙二醇甲醚醋酸酯或乙酸戊酯中的一种或几种；
    优选地，所述酮类溶剂选自丙酮、丁酮、环己酮、环戊酮或甲基异丁酮中的一种或几种；
    优选地，所述醇类溶剂选自甲醇、乙醇或丁醇中的一种或几种；
    优选地，所述醇醚类溶剂选自乙二醇-乙醚、乙二醇-丁醚、二乙二醇-乙醚中的一种或几种。
  8. 如权利要求1-7所述的具有自清洁功能的氨基烤漆组合物的制备方法，其特征在于，包括以下制备步骤：
    (1)将15.0份～20.0份稀释剂加入反应器中，搅拌；然后加入7.0～12.0份超支化聚酯多元醇树脂继续搅拌8-15min；
    (2)往反应器中依次加入5.0份～10.0份氨基树脂、25.0份～30.0份羟基丙烯酸树脂、25.0份～30.0份封端异氰酸酯树脂、0.5份～1.0份防涂鸦树脂和2.0份～3.0份涂料助剂，搅拌20～40min后过滤得到具有自清洁功能的氨基烤漆。
  9. 根据权利要求8所述的具有自清洁功能的氨基烤漆组合物的制备方法，其特征在于：步骤(1)所述搅拌速度为：200～250r/min；步骤(2)所述搅拌速度为：300～350r/min。
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CN115232521B (zh) * 2022-08-23 2023-07-25 青岛益群漆业集团有限公司 一种油墨结合附着力优异的水性钢桶烤漆及其制备方法

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