WO2017140100A1 - 一种成膜硅溶胶及其制备方法与应用 - Google Patents

一种成膜硅溶胶及其制备方法与应用 Download PDF

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WO2017140100A1
WO2017140100A1 PCT/CN2016/097894 CN2016097894W WO2017140100A1 WO 2017140100 A1 WO2017140100 A1 WO 2017140100A1 CN 2016097894 W CN2016097894 W CN 2016097894W WO 2017140100 A1 WO2017140100 A1 WO 2017140100A1
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film
silica sol
forming
stirring
coating
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French (fr)
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王永霞
刘卫丽
宋志棠
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上海新安纳电子科技有限公司
中国科学院上海微系统与信息技术研究所
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Publication of WO2017140100A1 publication Critical patent/WO2017140100A1/zh

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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the invention belongs to the field of preparation and application of inorganic nano materials, and relates to a film-forming silica sol and a preparation method and application thereof.
  • Silica sol is a colloidal solution of nano-scale inorganic polymetasilicate which uses water as a dispersion medium. It can participate in film formation as a separate film-forming substance during use, but it will have a certain degree of cracking after film formation. The problem affects the continuity of the film.
  • a film forming aid is usually added directly to the silica sol to assist in film formation.
  • a filming aid directly to the silica sol presents a series of problems, one of which is the stability of the filming aid and the silica sol.
  • Silica sol is a thermodynamically unstable system that relies on charge or other stabilizers to assist dispersion. It may cause flocculation, agglomeration or gelation due to changes in environmental conditions during the compounding process. Therefore, the filming aid should have good compatibility with silica sol. compatibility. Therefore, the selection of a suitable filming aid is especially critical.
  • the addition of other adjuvants in the filming aid and silica sol system will contribute to the stability of the filming aid and the silica sol system, and will also facilitate the film formation of the film-forming silica sol after drying. Continuity. In view of this, the development of a film-forming silica sol with good stability is of great significance for its application in a wider field.
  • the object of the present invention is to provide a film-forming silica sol and a preparation method and application thereof, and obtain a film-forming silica sol by a method with simple process and strong controllability, and It is applied to the substrate and finally dried to obtain a coating with high hardness, strong adhesion and adjustable transparency.
  • a first aspect of the present invention provides a film-forming silica sol comprising, by mass percent, the following components:
  • the silica sol is a colloidal aqueous solution containing silica particles.
  • the silica sol has a solid content (i.e., silica particle content) of from 6 to 40% by weight.
  • the silica sol has a solid content (i.e., a silica particle content) of 30% by weight.
  • the silica sol ie, silica particles
  • the silica sol has a particle size of 6-15 nm. More preferably, the silica sol (i.e., silica particles) has a particle diameter of 10 nm.
  • the modifier is selected from one of a silane coupling agent and a surfactant.
  • the silane coupling agent is an epoxy group-containing siloxane compound.
  • the epoxy group-containing siloxane compound is ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane or vinyltriethoxysilane.
  • the ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane has a CAS number of 2530-83-8.
  • the vinyl triethoxysilane has a CAS number of 78-08-0.
  • the surfactant is a low molecular weight polyvinyl alcohol.
  • the polyvinyl alcohol has a CAS number of 9002-89-5.
  • the low molecular weight polyvinyl alcohol has a weight average molecular weight of from 40 to 1,000.
  • the film forming aid is selected from one of an acrylic resin, a polyurethane, a styrene resin, and an epoxy resin.
  • a second aspect of the invention provides a method for preparing a film-forming silica sol, comprising the steps of:
  • the accelerator has a drop acceleration rate of 6-8 ml/min. More preferably, the acetyl coupling agent has a drop acceleration rate of 7 ml/min.
  • the agitation mixing time is 0.5-2 hours. More preferably, the agitation mixing time is 1 hour.
  • step 1) the stirring is continued for a period of from 1 to 72 hours. More preferably, The time to continue stirring was 48 hours.
  • the film forming aid has a drop acceleration rate of 8-12 ml/min. More preferably, the film forming aid has a drop acceleration rate of 10 ml/min.
  • the stirring and mixing time is 0.5-2 hours. More preferably, the agitation mixing time is 1 hour.
  • step 2) the stirring is continued for 1-5 hours. More preferably, the time of continued stirring is 2 hours.
  • the preparation method is carried out at room temperature.
  • the room temperature is 20-25 °C.
  • the stirring and mixing is continuous stirring and mixing.
  • the silica sol is a colloidal aqueous solution containing silica particles.
  • the silica sol has a solid content (i.e., silica particle content) of from 6 to 40% by weight. Further preferably, the silica sol has a solid content (i.e., a silica particle content) of 30% by weight.
  • the silica sol ie, silica particles
  • the silica sol has a particle size of 6-15 nm. More preferably, the silica sol (i.e., silica particles) has a particle diameter of 10 nm.
  • the modifier is selected from one of a silane coupling agent and a surfactant.
  • the silane coupling agent is an epoxy group-containing siloxane compound.
  • the epoxy group-containing siloxane compound is ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane or vinyltriethoxysilane.
  • the surfactant is a low molecular weight polyvinyl alcohol.
  • the low molecular weight polyvinyl alcohol has a weight average molecular weight of from 40 to 1,000.
  • the film forming assistant is selected from one of an acrylic resin, a polyurethane, a styrene resin, and an epoxy resin.
  • the silica sol, the modifier, and the film-forming auxiliary agent are added in a mass percentage of 66 to 91%, 0.1 to 1.8%, and 7.2 to 33.9%, respectively, based on 100% by mass.
  • a third aspect of the invention provides the use of a film-forming silica sol as a coating.
  • the use is the use of the film-forming silica sol as a coating on the surface of a substrate as a film-forming coating.
  • the matrix is selected from one or a combination of metals, wood, ceramics.
  • a fourth aspect of the invention provides a method for using a film-forming silica sol.
  • the prepared film-forming silica sol is coated on a substrate by an applicator, and after drying, a film-forming coating on the surface of the desired substrate is obtained.
  • the applicator is a conventional applicator.
  • the substrate is selected from one or a combination of metals, wood, ceramics.
  • the film-forming coating has a film thickness of 12 to 200 ⁇ m.
  • the film formation thickness can be controlled by an applicator.
  • the drying temperature is from 25 to 100 °C.
  • the drying time is 12-48 h.
  • the present invention provides a film-forming silica sol and a preparation method and application thereof, and a film-forming silica sol is prepared by an optimized condition preparation method.
  • the film-forming silica sol has good transparency and stability of appearance, and is applied to a coating, and the film-forming coating after drying of the coating film has good gloss, high hardness and strong adhesion.
  • the film-forming silica sol of the invention has the advantages of simple process and strong controllability, and has high practical value in the field of coatings.
  • Figure 1 shows a schematic view of Coating 1 in the present invention.
  • Figure 2 shows a schematic view of Coating 2 in the present invention.
  • Figure 3 shows a schematic view of the coating 3 of the present invention.
  • Figure 4 shows a schematic view of coating 4 in the present invention.
  • Figure 5 shows a schematic view of coating 5 in the present invention.
  • Silica sol (MCS-S10, Shanghai Xinanna Electronic Technology Co., Ltd.) used in the following examples, ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560, Hangzhou Jessica) Chemical Co., Ltd.), vinyl triethoxysilane (KH-188, Hangzhou Jessica Chemical Co., Ltd.), polyvinyl alcohol (1788, Shanghai Jinshan Petrochemical), acrylic resin (SYNTRAN 404, Intai Polymer Trade (Shanghai) )), Polyurethane (PU037, Shanghai Haochi Import and Export Co., Ltd.), styrene-acrylic resin (SYNTRAN 1671, Intai Polymer Trading (Shanghai) Co., Ltd.), epoxy resin (CARAPOL WEP 2308, Intai Polymer Trade (Shanghai Co., Ltd).
  • one or more of the method steps recited in the present invention are not exclusive of other method steps that may be present before or after the combination step, or that other method steps can be inserted between the steps specifically mentioned, unless otherwise It should be understood that the combined connection relationship between one or more devices/devices referred to in the present invention does not exclude that other devices/devices may exist before or after the combined device/device or Other devices/devices can also be inserted between the two devices/devices unless otherwise stated.
  • each method step is merely a convenient means of identifying the various method steps, and is not intended to limit the order of the various method steps or to limit the scope of the invention, the relative In the case where the technical content is not substantially changed, it is considered to be a scope in which the present invention can be implemented.
  • silica sol solid content 30%, particle size 10 nm
  • 15.3 g of ⁇ -(2,3-epoxypropoxy group) was taken at room temperature with constant stirring.
  • the propyltrimethoxysilane was added dropwise to the silica sol, and the mixture was stirred and mixed at a dropping rate of 7 ml/min.
  • the stirring and mixing time was 1 h, and the reaction was further stirred for 48 hours to obtain a mixed solution.
  • silica sol solid content 30%, particle size 10 nm
  • 15.3 g of ⁇ -(2,3-epoxypropoxy group) was taken at room temperature with constant stirring.
  • the propyltrimethoxysilane was added dropwise to the silica sol, and the mixture was stirred and mixed at a dropping rate of 7 ml/min.
  • the stirring and mixing time was 1 h, and the reaction was further stirred for 48 hours to obtain a mixed solution.
  • silica sol solid content 30%, particle size 10 nm
  • 15.3 g of ⁇ -(2,3-epoxypropoxy group) was taken at room temperature with constant stirring.
  • the propyltrimethoxysilane was added dropwise to the silica sol, and the mixture was stirred and mixed at a dropping rate of 7 ml/min.
  • the stirring and mixing time was 1 h, and the reaction was further stirred for 48 hours to obtain a mixed solution.
  • silica sol (40% solids, particle size 6 nm) was added to a three-necked flask and stirred; 15.3 g of low molecular weight polyvinyl alcohol was added dropwise to the silica sol while stirring at room temperature with stirring. The mixture was mixed at a dropping rate of 8 ml/min, and the stirring and mixing time was 2 hours, and the reaction was further stirred for 72 hours to obtain a mixed solution.
  • styrene-acrylic resin Under continuous stirring, 500 g of styrene-acrylic resin was added dropwise to the mixed solution, stirred and mixed, the dropping rate was 12 ml/min, and the stirring and mixing time was 2 h, and the stirring reaction was further continued for 5 hours to finally obtain a film-forming silica sol sample 6#.
  • the silica sol was 66%
  • the low molecular weight polyvinyl alcohol was 1%
  • the styrene-acrylic resin was 33%.
  • the pure silica sol which has not been treated by the modifier and the film-forming auxiliary agent is coated on the surface of the aluminum plate, and the film layer is naturally dried to form the coating layer 1.
  • the specific results are shown in Fig. 1.
  • the film-forming silica sol sample 1# was coated on the surface of the aluminum plate by an applicator, and the film layer was naturally dried to form a coating layer 2, and the specific results are shown in Fig. 2.
  • the film-forming silica sol sample 2# was coated on the surface of the aluminum plate by an applicator, and the film layer was naturally dried to form a coating layer 3.
  • the specific results are shown in Fig. 3.
  • the film-forming silica sol sample 3# was coated on the surface of the aluminum plate by an applicator, and the film layer was naturally dried to form a coating layer 4.
  • the specific results are shown in Fig. 4.
  • the film-forming silica sol sample 4# was coated on the surface of the aluminum plate by an applicator, and the film layer was naturally dried to form a coating layer 5.
  • the specific results are shown in Fig. 5.
  • the coating 2-5 with a modifier and a film-forming auxiliary agent has a better hardness than the coating layer 1 to which the modifier and the film-forming auxiliary agent are not added, but the addition amount of the film-forming auxiliary agent is higher. More, the lower the hardness of the film after drying, the hardness of the coating 4 is better than that of the coating 5.
  • the gloss and adhesion information is obtained by visual observation and key scratches, and the gloss of the coating is compared with the coating 1 without the modifier and the filming aid.
  • the amount of the film-forming auxiliary agent is increased, the transparency of the film layer is gradually increased, that is, the more the amount of the film-forming auxiliary agent is added, the better the glossiness, and therefore the coating layer 5 has a good gloss.
  • the hardness, gloss and adhesion of the coating layer can be optimally obtained by adding a moderate amount of the film-forming auxiliary agent.
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.

Abstract

一种成膜硅溶胶，按质量百分比计，包括以下组分：硅溶胶66～91％；改性剂0.1～1.8％；成膜助剂7.2～33.9％。制备获得的成膜硅溶胶具有良好的外观透明度和稳定性，其应用于涂料作为成膜涂层具有良好的光泽度、较高的硬度和较强的附着力，在涂料领域具有较高实用价值。

Description

一种成膜硅溶胶及其制备方法与应用 技术领域
本发明属于无机纳米材料制备和应用领域，涉及一种成膜硅溶胶及其制备方法与应用。
背景技术
硅溶胶是一种以水为分散介质的纳米级无机聚偏硅酸的胶体溶液，在使用过程中可以作为单独成膜物质参与成膜，但是其在成膜后会出现一定程度的龟裂等问题，影响了膜层的连续性。为改善硅溶胶的成膜性，通常在硅溶胶中直接添加成膜助剂以辅助其成膜。
但是，直接在硅溶胶中添加成膜助剂会出现一系列的问题，其中比较重要的一个问题就是成膜助剂与硅溶胶的稳定性。硅溶胶是靠电荷或其它一些稳定剂来辅助分散的热力学不稳定体系，在复合过程中因环境条件发生变化可能引起絮凝、结块或凝胶，所以成膜助剂要与硅溶胶具有良好的相容性。因此，选择合适的成膜助剂尤为关键。除此之外，在成膜助剂和硅溶胶的体系中添加其他的辅助剂，将有利于成膜助剂和硅溶胶体系的稳定性，同时也会有利于成膜硅溶胶干燥后成膜的连续性。鉴于此，开发一种具有良好稳定性的成膜硅溶胶为其在更广领域的应用具有重要意义。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种成膜硅溶胶及其制备方法与应用，通过一种工艺简便、可控性强的方法得到成膜硅溶胶，并将其涂覆于基体上，最终干燥后得到涂层具有较高的硬度、较强的附着力以及可调的透明度。
为实现上述目的及其他相关目的，本发明第一方面提供一种成膜硅溶胶，按质量百分比计，包括以下组分：
硅溶胶   66～91％；
改性剂    0.1～1.8％；
成膜助剂  7.2～33.9％。
优选地，所述硅溶胶为含二氧化硅颗粒的胶体水溶液。
更优选地，所述硅溶胶的固含量(即二氧化硅颗粒含量)为6-40wt％。
进一步优选地，所述硅溶胶的固含量(即二氧化硅颗粒含量)为30wt％。
优选地，所述硅溶胶(即二氧化硅颗粒)的粒径为6-15nm。更优选地，所述硅溶胶(即二氧化硅颗粒)的粒径为10nm。
优选地，所述改性剂选自硅烷偶联剂、表面活性剂中的一种。
更优选地，所述硅烷偶联剂为含环氧基团的硅氧烷化合物。
进一步优选地，所述含环氧基团的硅氧烷化合物为γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷或乙烯基三乙氧基硅烷。所述γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷的CAS号为2530-83-8。所述乙烯基三乙氧基硅烷的CAS号为78-08-0。
更优选地，所述表面活性剂为低分子量聚乙烯醇。所述聚乙烯醇的CAS号为9002-89-5。
进一步优选地，所述低分子量聚乙烯醇的重均分子量为40-1000。
优选地，所述成膜助剂选自丙烯酸树脂、聚氨酯、苯丙树脂、环氧树脂中的一种。
本发明第二方面提供一种成膜硅溶胶的制备方法，包括以下步骤：
1)按配比将改性剂滴加到硅溶胶中搅拌混合后，继续搅拌，得到混合溶液；
2)再将成膜助剂滴加到混合溶液中搅拌混合后，继续搅拌，即得成膜硅溶胶。
优选地，步骤1)中，所述改性剂的滴加速率为6-8ml/min。更优选地，所述硅烷偶联剂的滴加速率为7ml/min。
优选地，步骤1)中，所述搅拌混合的时间为0.5-2小时。更优选地，所述搅拌混合的时间为1小时。
优选地，步骤1)中，所述继续搅拌的时间为1-72小时。更优选地， 所述继续搅拌的时间为48小时。
优选地，步骤2)中，所述成膜助剂的滴加速率为8-12ml/min。更优选地，所述成膜助剂的滴加速率为10ml/min。
优选地，步骤2)中，所述搅拌混合的时间为0.5-2小时。更优选地，所述搅拌混合的时间为1小时。
优选地，步骤2)中，所述继续搅拌的时间为1-5小时。更优选地，所述继续搅拌的时间为2小时。
优选地，所述步骤1)或2)中，所述制备方法在室温下进行。所述室温为20-25℃。
优选地，所述步骤1)或2)中，所述搅拌混合为持续搅拌混合。
优选地，步骤1)中，所述硅溶胶为含二氧化硅颗粒的胶体水溶液。
更优选地，所述硅溶胶的固含量(即二氧化硅颗粒含量)为6-40wt％。进一步优选地，所述硅溶胶的固含量(即二氧化硅颗粒含量)为30wt％。
优选地，所述硅溶胶(即二氧化硅颗粒)的粒径为6-15nm。更优选地，所述硅溶胶(即二氧化硅颗粒)的粒径为10nm。
优选地，步骤1)中，所述改性剂选自硅烷偶联剂、表面活性剂中的一种。
更优选地，所述硅烷偶联剂为含环氧基团的硅氧烷化合物。
进一步优选地，所述含环氧基团的硅氧烷化合物为γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷或乙烯基三乙氧基硅烷。
更优选地，所述表面活性剂为低分子量聚乙烯醇。进一步优选地，所述低分子量聚乙烯醇的重均分子量为40-1000。
优选地，步骤2)中，所述成膜助剂选自丙烯酸树脂、聚氨酯、苯丙树脂、环氧树脂中的一种。
优选地，所述硅溶胶、改性剂、成膜助剂按总质量为100％计，加入的质量百分比分别为66～91％、0.1～1.8％、7.2～33.9％。
本发明第三方面提供一种成膜硅溶胶作为涂料的用途。
优选地，所述用途为所述成膜硅溶胶作为涂料在基体表面涂覆为成膜涂层的用途。
更优选地，所述基体选自金属、木材、陶瓷中的一种或多种组合。
本发明第四方面提供一种成膜硅溶胶的使用方法，将制备得到的成膜硅溶胶经涂布器涂覆在基体上，干燥后即得所需基体表面的成膜涂层。
优选地，所述涂布器为常规的涂布器。
优选地，所述基体选自金属、木材、陶瓷中的一种或多种组合。
优选地，所述成膜涂层的成膜厚度为12～200μm。所述成膜厚度可通过涂布器进行控制。
优选地，所述干燥的温度为25-100℃。所述干燥的时间为12-48h。
如上所述，本发明提供的一种成膜硅溶胶及其制备方法与应用，通过优化条件的制备方法制备一种成膜硅溶胶。该种成膜硅溶胶具有良好的外观透明度和稳定性，其应用于涂料中，涂膜干燥后的成膜涂层具有良好的光泽度、较高的硬度和较强的附着力。本发明所述成膜性硅溶胶，具有工艺简便、可控性强等优点，在涂料领域具有较高实用价值。
附图说明
图1显示为本发明中涂层1示意图。
图2显示为本发明中涂层2示意图。
图3显示为本发明中涂层3示意图。
图4显示为本发明中涂层4示意图。
图5显示为本发明中涂层5示意图。
具体实施方式
下面结合具体实施例进一步阐述本发明，应理解，这些实施例仅用于说明本发明而不用于限制本发明的保护范围。
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
须知，下列实施例中未具体注明的工艺设备或装置均采用本领域内的 常规设备或装置；所有压力值和范围都是指相对压力。
以下实施例中使用的硅溶胶(MCS-S10、上海新安纳电子科技有限公司)，γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷(KH-560、杭州杰西卡化工有限公司)，乙烯基三乙氧基硅烷(KH-188、杭州杰西卡化工有限公司)，聚乙烯醇(1788、上海金山石化)，丙烯酸树脂(SYNTRAN 404、因泰聚合物贸易(上海)有限公司)，聚氨酯(PU037、上海煜驰进出口有限公司)，苯丙树脂(SYNTRAN 1671、因泰聚合物贸易(上海)有限公司)，环氧树脂(CARAPOL WEP 2308、因泰聚合物贸易(上海)有限公司)。
此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明；还应理解，本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备/装置，除非另有说明。而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。
实施例1
将1kg的硅溶胶(固含量为30％，粒径为10nm)加入到三口烧瓶中并进行搅拌；在室温且持续搅拌条件下，取15.3g的γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷滴加到硅溶胶中搅拌混合，滴加速度为7ml/min，搅拌混合时间为1h，再继续搅拌反应48h，得到混合溶液。在持续搅拌条件下，将100g聚氨酯滴加到混合溶液中搅拌混合，滴加速度为10ml/min，搅拌混合时间为1h，再继续搅拌反应2h，最终制得成膜硅溶胶样品1#。成膜硅溶胶样品1#中，硅溶胶为89.6％，γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷为1.4％，聚氨酯为9％。
实施例2
将1kg的硅溶胶(固含量为30％，粒径为10nm)加入到三口烧瓶中 并进行搅拌；在室温且持续搅拌条件下，取15.3g的γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷滴加到硅溶胶中搅拌混合，滴加速度为7ml/min，搅拌混合时间为1h，再继续搅拌反应48h，得到混合溶液。在持续搅拌条件下，将150g聚氨酯滴加到混合溶液中搅拌混合，滴加速度为10ml/min，搅拌混合时间为1h，再继续搅拌反应2h，最终制得成膜硅溶胶样品2#。成膜硅溶胶样品2#中，硅溶胶为85.8％，γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷为1.3％，聚氨酯为12.9％。
实施例3
将1kg的硅溶胶(固含量为30％，粒径为10nm)加入到三口烧瓶中并进行搅拌；在室温且持续搅拌条件下，取15.3g的γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷滴加到硅溶胶中搅拌混合，滴加速度为7ml/min，搅拌混合时间为1h，再继续搅拌反应48h，得到混合溶液。在持续搅拌条件下，将300g聚氨酯滴加到混合溶液中搅拌混合，滴加速度为10ml/min，搅拌混合时间为1h，再继续搅拌反应2h，最终制得成膜硅溶胶样品3#。成膜硅溶胶样品3#中，硅溶胶为76％，γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷为1.2％，聚氨酯为22.8％。
实施例4
将1kg的硅溶胶(固含量为30％，粒径为10nm)加入到三口烧瓶中并进行搅拌；在室温且持续搅拌条件下，取15.3g的γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷滴加到硅溶胶中搅拌混合，滴加速度为7ml/min，搅拌混合时间为1h，再继续搅拌反应48h，得到混合溶液。在持续搅拌条件下，将500g聚氨酯滴加到混合溶液中搅拌混合，滴加速度为10ml/min，搅拌混合时间为1h，再继续搅拌反应2h，最终制得成膜硅溶胶样品4#。成膜硅溶胶样品4#中，硅溶胶为66％，γ―(2,3-环氧丙氧基)丙基三甲氧基硅烷为1％，聚氨酯为33％。
实施例5
将1kg的硅溶胶(固含量为6％，粒径为15nm)加入到三口烧瓶中并 进行搅拌；在室温且持续搅拌条件下，取15.3g的乙烯基三乙氧基硅烷滴加到硅溶胶中搅拌混合，滴加速度为6ml/min，搅拌混合时间为0.5h，再继续搅拌反应1h，得到混合溶液。在持续搅拌条件下，将500g丙烯酸树脂滴加到混合溶液中搅拌混合，滴加速度为8ml/min，搅拌混合时间为0.5h，再继续搅拌反应1h，最终制得成膜硅溶胶样品5#。成膜硅溶胶样品5#中，硅溶胶为66％，乙烯基三乙氧基硅烷为1％，丙烯酸树脂为33％。
实施例6
将1kg的硅溶胶(固含量为40％，粒径为6nm)加入到三口烧瓶中并进行搅拌；在室温且持续搅拌条件下，取15.3g的低分子量聚乙烯醇滴加到硅溶胶中搅拌混合，滴加速度为8ml/min，搅拌混合时间为2h，再继续搅拌反应72h，得到混合溶液。在持续搅拌条件下，将500g苯丙树脂滴加到混合溶液中搅拌混合，滴加速度为12ml/min，搅拌混合时间为2h，再继续搅拌反应5h，最终制得成膜硅溶胶样品6#。成膜硅溶胶样品6#中，硅溶胶为66％，低分子量聚乙烯醇为1％，苯丙树脂为33％。
应用例1
未经过改性剂和成膜助剂处理的纯硅溶胶涂覆在铝板表面上，膜层自然干燥后形成涂层1，具体结果见图1。
应用例2
将成膜硅溶胶样品1#通过涂布器涂覆在铝板表面上，膜层自然干燥后形成涂层2，具体结果见图2。
应用例3
将成膜硅溶胶样品2#通过涂布器涂覆在铝板表面上，膜层自然干燥后形成涂层3，具体结果见图3。
应用例4
将成膜硅溶胶样品3#通过涂布器涂覆在铝板表面上，膜层自然干燥后形成涂层4，具体结果见图4。
应用例5
将成膜硅溶胶样品4#通过涂布器涂覆在铝板表面上，膜层自然干燥后形成涂层5，具体结果见图5。
测试例1
将应用例1-5中自然干燥后的涂层1-5的硬度进行测试，测试结果如表1所示。
表1
样品 涂层1 涂层2 涂层3 涂层4 涂层5
硅溶胶(g) 1000 1000 1000 1000 1000
改性剂(g) - 15.3 15.3 15.3 15.3
成膜助剂添加量(g) - 100 150 300 500
莫式硬度 - 1 2 3 2
根据表1可知，与未添加改性剂和成膜助剂的涂层1相比，添加改性剂和成膜助剂的涂层2-5硬度更好，但成膜助剂添加量越多，其干燥后的膜层硬度越低，所以，相比涂层5，涂层4的硬度更好。
同时，根据图1-5可知，通过肉眼观察和钥匙划痕得到光泽度和附着力相关信息，与未添加改性剂和成膜助剂的涂层1相比，涂层的光泽度随着成膜助剂添加量的增加，膜层的透明度逐渐增加，即成膜助剂添加量越多，光泽度越好，因此涂层5具有良好的光泽度。同时，涂层与膜层与基体间结合力越强，其附着性能越好，而涂层5与膜层与基体间具有较强的结合力，说明其具有良好的附着性能。
结合上述结果，在添加改性剂和成膜助剂后，加入适中的成膜助剂添加量后，涂层的硬度、光泽度和附着力才能得到最佳值。
所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

  1. 一种成膜硅溶胶，按质量百分比计，包括以下组分：
    硅溶胶    66～91％；
    改性剂    0.1～1.8％；
    成膜助剂  7.2～33.9％。
  2. 根据权利要求1所述的成膜硅溶胶，其特征在于，所述硅溶胶为含二氧化硅颗粒的胶体水溶液；所述硅溶胶的固含量为6-40wt％。
  3. 根据权利要求1所述的成膜硅溶胶，其特征在于，所述改性剂选自硅烷偶联剂、表面活性剂中的一种；所述硅烷偶联剂为含环氧基团的硅氧烷化合物；所述表面活性剂为低分子量聚乙烯醇。
  4. 根据权利要求1所述的成膜硅溶胶，其特征在于，所述成膜助剂选自丙烯酸树脂、聚氨酯、苯丙树脂、环氧树脂中的一种。
  5. 根据权利要求1-4任一所述的成膜硅溶胶的制备方法，包括以下步骤：
    1)按配比将改性剂滴加到硅溶胶中搅拌混合后，继续搅拌，得到混合溶液；
    2)再将成膜助剂滴加到混合溶液中搅拌混合后，继续搅拌，即得成膜硅溶胶。
  6. 根据权利要求5所述的成膜硅溶胶的制备方法，其特征在于，步骤1)中，包括以下条件中任一项或多项：
    A1)所述改性剂的滴加速率为6-8ml/min；
    A2)所述搅拌混合的时间为0.5-2小时；
    A3)所述继续搅拌的时间为1-72小时。
  7. 根据权利要求5所述的成膜硅溶胶的制备方法，其特征在于，步骤2)中，包括以下条件中任一项或多项：
    B1)所述成膜助剂的滴加速率为8-12ml/min；
    B2)所述搅拌混合的时间为0.5-2小时；
    B3)所述继续搅拌的时间为1-5小时。
  8. 根据权利要求1-4任一所述的成膜硅溶胶作为涂料的用途。
  9. 根据权利要求8所述的成膜硅溶胶作为涂料的用途，其特征在于， 所述用途为所述成膜硅溶胶作为涂料在基体表面涂覆为成膜涂层的用途。
  10. 一种成膜硅溶胶的使用方法，将如权利要求5-7任一所述的成膜硅溶胶的制备方法，制备得到如权利要求1-4任一所述的成膜硅溶胶经涂布器涂覆在基体上，干燥后即得所需基体表面的成膜涂层。
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