CN105705535A - 用于具有改进的耐久性的疏水性涂层的共聚物 - Google Patents

用于具有改进的耐久性的疏水性涂层的共聚物 Download PDF

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CN105705535A
CN105705535A CN201480039380.8A CN201480039380A CN105705535A CN 105705535 A CN105705535 A CN 105705535A CN 201480039380 A CN201480039380 A CN 201480039380A CN 105705535 A CN105705535 A CN 105705535A
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F.吉耶莫
C.卢巴
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Saint Gobain Glass France SAS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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Abstract

本发明涉及：式（I）的共聚物：其中：该R1基团是疏水性的，该R2基团是可交联的，x、z和t>0，且y≥0，且x+y+z+t=1，n为整数；包含该共聚物的涂层的玻璃基底，插入具有能够与可交联的R2基团反应的官能团的硅烷的层；和该玻璃基底作为运输工具的疏水性窗玻璃、沐浴房壁和易于清洁的室内玻璃窗的应用。

Description

用于具有改进的耐久性的疏水性涂层的共聚物
本发明使用聚合物层在玻璃上制备疏水性涂层，调节其组成以获得良好的耐久性：水解耐久性、UV耐久性或机械耐久性。该涂层可以在暴露于外部的面上施加到机动车窗玻璃上以改善雨天的能见度并由此提高安全性。
Saint-GobainSekurit目前以Aquacontrol?注册商标生产涂覆有疏水性处理的汽车侧窗。该涂层通过液体途径以双层体系的形式施加：用于改善耐久性的二氧化硅基底层，和疏水性层。该疏水性层是氟硅烷即1H,1H,2H,2H-全氟癸基硅烷的分子单层。
用于改进的第一途径的目的在于开发与可施加在挡风玻璃上的相同类型的涂层。这种情况下的主要问题是改善机械和水解耐久性以便能够经受与侧窗相比在挡风玻璃上的附加应力。
基于氟硅烷的分子层的疏水性处理表现出导致耐久性问题的两个主要缺点：
-分子经由Si-O-Si键键合到玻璃表面上。这种类型的键合表现出在盐水或碱性介质中可水解的缺点。这常常发生在水滴停留在其上的挡风玻璃上；
-该处理基于仅一个分子层（单分子层）；容易理解的是，在老化过程中，如果分子从该表面上脱离，释放的位置不再是官能性的；由此，表面中任何微小的劣化（划伤、水解等等）将导致缺陷处官能的完全丧失。
本发明意在通过开发有助于该疏水性官能的聚合物材料，从而以不同方式解决疏水性涂层的问题。调节其分子结构以便在疏水性官能、易于加工、水解耐久性、在UV辐射下的稳定性以及最终的机械稳定性方面获得最佳性能。
为此，本发明的主题是式（I）的共聚物：
其中：
该R1基团是疏水性的，
该R2基团是可交联的，
x、z和t>0，且y≥0，且x+y+z+t=1，
n为整数。
本发明的聚合物的骨架由获自四种类型的单体的四种类型的单元组成：
-聚甲基丙烯酸甲酯（PMMA）基底，其摩尔分数为x；
-具有氟甲基的甲基丙烯酸酯组分，贡献了疏水性功能的一部分（摩尔分数为y）；
-带有疏水性官能的甲基丙烯酸酯链段（maillon），其摩尔分数为z；该官能团可以具有-(CF2)mCF3（m=5、7、9、11）形式或-OC(=O)CF(CF3)-(OCF2CF(CF3))p-F（p为2至10的整数）形式；
-带有可交联基团的甲基丙烯酸酯链段（links），其摩尔分数为t；该基团可以带有环氧、甲磺酰基、甲苯磺酰基或异氰酸酯官能团。
根据本发明，该官能存在于涂层的表面处，但是也存在于其主体内。由此，可以预期的是，在适度劣化的情况下，该涂层将保持其疏水性功能。
本发明的另一主题是包含上述共聚物的涂层的玻璃基底，插入具有能够与可交联的R2基团反应的官能团的硅烷的层。该硅烷官能团能够以已知方式键合到该玻璃上。
最后，可以通过在其中混入无机填料来改善该共聚物涂层的机械性质。这些无机填料通常是二氧化硅纳米粒子。它们的尺寸小于50纳米以便不会令该涂层发生光学散射。此外，这些无机填料的表面可以官能化以便能够与该共聚物的可交联R2官能团反应。
本发明的另一主题是上述玻璃基底的应用，其作为
-用于运输工具（陆运、空运或水运，特别是运输车辆）的疏水性窗玻璃；
-沐浴房壁；和
-易于清洁的内部窗玻璃。
现在通过以下实施例来描述本发明。
实施例
a.制备基底
玻璃基底预先通过用Cerox抛光来活化。
其随后用氨基丙级三乙氧基硅烷官能化。为此，使用由Evonik出售的水溶液，其浓度已经调节至1重量%。用抹布将该溶液涂施到该玻璃上，该涂层在110℃下干燥15分钟，并用浸渍有异丙醇的抹布擦拭该玻璃，由此除去任何过量涂层。
b.官能层
使用该共聚物：
组成（摩尔%）MMA：60%
HEMA甲磺酸酯：20%
Zonyl：20%
组成（重量%）MMA：29%
HEMA甲磺酸酯：20%
Zonyl：51%
重量%氟31%
分子量Mn16500克/摩尔
分子量Mw60100克/摩尔
多分散性指数3.7
MMA：甲基丙烯酸甲酯
HEMA：甲基丙烯酸羟乙酯
甲磺酸酯：SO2CH3
Zonyl：该共聚物的氟化单元
该共聚物以3重量%溶解在甲乙酮中并通过旋涂法（2000rpm）沉积在官能化基底上。该涂层在烘箱中在130℃下交联1小时。
c.性质
在官能化基底上测得的与水的接触角测得为114°。
在中性盐喷雾测试72小时后，测得的接触角为103°。
在暴露于UV辐射（WOM）400小时的测试后，测得的接触角为105°。
有可能向该制剂中添加二氧化硅纳米粒子在甲乙酮中的分散体以增强该机械性质。

Claims (10)

1.式（I）的共聚物：
其中：
该R1基团是疏水性的，
该R2基团是可交联的，
x、z和t>0，且y≥0，且x+y+z+t=1，
n为整数。
2.如权利要求1中所要求保护的共聚物，其特征在于该R1基团是-(CF2)mCF3基团，m=5、7、9或11，或-OC(=O)CF(CF3)(OCF2CF(CF3))pF基团，p是2至10的整数。
3.如前述权利要求之一所要求保护的共聚物，其特征在于该R2基团带有环氧、甲磺酰基、甲苯磺酰基或异氰酸酯官能团。
4.包含如权利要求1所要求保护的共聚物的涂层的玻璃基底，插入具有能够与可交联的R2基团反应的官能团的硅烷的层。
5.如权利要求4所要求保护的玻璃基底，其特征在于所述共聚物涂层包含无机填料。
6.如权利要求5所要求保护的玻璃基底，其特征在于所述无机填料是二氧化硅纳米粒子。
7.如权利要求5或6所要求保护的玻璃基底，其特征在于所述无机填料的表面具有能够与可交联R2基团反应的官能团。
8.如权利要求4至7之一所要求保护的玻璃基底作为用于运输工具的疏水性窗玻璃的应用。
9.如权利要求4至7之一所要求保护的玻璃基底作为沐浴房壁的应用。
10.如权利要求4至7之一所要求保护的玻璃基底作为易于清洁的内部窗玻璃的应用。
CN201480039380.8A 2013-07-08 2014-07-03 用于具有改进的耐久性的疏水性涂层的共聚物 Pending CN105705535A (zh)

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FR1356694 2013-07-08
FR1356694A FR3008100B1 (fr) 2013-07-08 2013-07-08 Copolymere pour revetement hydrophobe a durabilite amelioree
PCT/FR2014/051702 WO2015004368A1 (fr) 2013-07-08 2014-07-03 Copolymere pour revetement hydrophobe a durabilite amelioree

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US11059990B2 (en) * 2018-10-15 2021-07-13 Metashield Llc Anti-fouling coatings
WO2020190441A1 (en) 2019-03-19 2020-09-24 Applied Materials, Inc. Hydrophobic and icephobic coating

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US5081165A (en) * 1988-04-15 1992-01-14 Daikin Industries, Ltd. Antifouling coating composition containing fluorinated (meth)acrylates
CN1389489A (zh) * 2001-06-05 2003-01-08 上海绿纳化工材料技术有限公司 水分散含氟杂化树脂的制备方法
EP1571165A1 (en) * 2004-03-01 2005-09-07 Lorenzo Toffano Compositions for the preparation of hydrophobic coatings
CN103408709A (zh) * 2013-08-08 2013-11-27 中科院广州化学有限公司 水性含氟聚合物和二氧化硅杂化材料及其制备而成的透明超双疏涂层

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US5081165A (en) * 1988-04-15 1992-01-14 Daikin Industries, Ltd. Antifouling coating composition containing fluorinated (meth)acrylates
CN1389489A (zh) * 2001-06-05 2003-01-08 上海绿纳化工材料技术有限公司 水分散含氟杂化树脂的制备方法
EP1571165A1 (en) * 2004-03-01 2005-09-07 Lorenzo Toffano Compositions for the preparation of hydrophobic coatings
CN103408709A (zh) * 2013-08-08 2013-11-27 中科院广州化学有限公司 水性含氟聚合物和二氧化硅杂化材料及其制备而成的透明超双疏涂层

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110325484A (zh) * 2017-02-28 2019-10-11 法国圣戈班玻璃厂 含有疏水性窗玻璃的用于湿室的物品

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FR3008100A1 (fr) 2015-01-09
US20160159952A1 (en) 2016-06-09
FR3008100B1 (fr) 2015-06-26
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