WO2015051598A1 - 一种无机涂料的基体材料及其应用 - Google Patents

一种无机涂料的基体材料及其应用 Download PDF

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WO2015051598A1
WO2015051598A1 PCT/CN2014/070123 CN2014070123W WO2015051598A1 WO 2015051598 A1 WO2015051598 A1 WO 2015051598A1 CN 2014070123 W CN2014070123 W CN 2014070123W WO 2015051598 A1 WO2015051598 A1 WO 2015051598A1
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base material
inorganic coating
calcium carbonate
silica sol
inorganic
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PCT/CN2014/070123
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English (en)
French (fr)
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傅雁
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弗克科技(苏州)有限公司
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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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • 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
    • C09D7/41—Organic pigments; Organic dyes
    • 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

Definitions

  • the invention relates to an inorganic coating, in particular to an inorganic coating using a silica sol, a preparation method and application thereof.
  • Inorganic architectural coatings can be divided into two categories according to the main binder types.
  • One is water glass (alkali metal silicate) as the main binder, and pigment, filler and additives are added.
  • the second is silica sol.
  • the main binder is prepared by adding an appropriate amount of synthetic resin emulsion, pigment, filler and auxiliary agent.
  • the main difference between the two is the amount of alkali.
  • the former can also react with calcium carbonate calcification, and even has a lower shrinkage rate, but because of its higher free base content, it has a hindrance to the silicidation reaction, so the water resistance of the final product is greatly affected, and the associated pan Alkali phenomenon also affects the uniformity of coloration, which poses a bottleneck for practical applications.
  • the latter has a very low alkali content and a high degree of silicidation, so the water resistance and compatibility with the pigment are also better.
  • silica sol when silica sol is used alone, the film is cured at room temperature, and there are often fatal defects such as cracks and internal micropores. At the same time, the price of silica sol is high, and its price has often been several times that of water glass, and is much higher than the same concentration.
  • Synthetic emulsion so silica sol is usually used as an auxiliary agent, often organic organic emulsion is added to make organic - Inorganic composite coatings, and coatings obtained by adding organic polymeric materials are susceptible to aging and have poor weatherability. It has also been reported to modify silica sols with water-soluble melamine and polyols, but such treatments increase the complexity of the preparation.
  • An object of the present invention is to overcome the above-mentioned deficiencies in the prior art, to provide a base material for an inorganic coating, and the use of the base material.
  • the technical solution adopted by the present invention is: A base material of an inorganic coating material, wherein the base material is a mixture of a liquid silica sol and a calcium carbonate having a mass ratio of solid content to calcium carbonate of from 1:3 to 10 ⁇ .
  • the liquid silica sol has a mass ratio of solid content to calcium carbonate of 1:5-8.
  • the liquid silica sol has a solid content of at least 30%, a sodium oxide content of less than 1%, and a pH value of less than 11 .
  • the calcium carbonate is a powder having a purity of 95% or more and a fineness of 200 mesh or more.
  • the present invention provides an inorganic coating composed of the above-mentioned base material and an auxiliary material liquid, which is 20% of the total mass of the inorganic coating material.
  • the auxiliary material is selected from a combination of one or more of a high molecular polymer, a filler, a pigment, and a coating additive.
  • the preparation method of the above inorganic coating comprises the following steps:
  • the auxiliary material is composed of high molecular polymer, filler, pigment and coating additive;
  • the liquid silica sol in the coated inorganic coating reacts with the calcium carbonate to form a hydrated calcium silicate.
  • the process is that the amorphous active silica in the aqueous solution of silica sol reacts with the calcium on the surface of the calcium carbonate particles to form calcium silicate hydrate, and is wrapped on the surface of the calcium carbonate particles, and the calcium carbonate particles are passed through the hydrated calcium silicate.
  • Glue together when in the air, the water in the system evaporates, precipitates hydrated calcium silicate crystals, and forms hydrated calcium silicate crystals / Calcium carbonate is the main component, water-insoluble, mechanically strong artificial stone structure. Thereby, the coating has strong chemical bonding force with the cement base layer, and the coating does not have problems such as cracking.
  • the high molecular polymer is EVA Dispersible polymer powder, acrylate emulsion and its dispersible polymer powder, fluorocarbon emulsion, silicone emulsion, pure acrylic emulsion, waterborne epoxy resin, waterborne polyurethane, aqueous epoxy ester, waterborne alkyd resin or a plurality of combinations;
  • the filler is one or a combination of titanium dioxide, mica, kaolin;
  • the pigment is an organic pigment, an inorganic pigment or a liquid colorant formed by mixing a plurality of pigments;
  • the coating additive is a polyacrylic acid dispersion Agent, silane waterproofing agent, PVA A thickener, a preservative, a calcium-containing compound, one or a combination of zinc-containing compounds.
  • the metal ions in the calcium-containing compound and the zinc-containing compound can react with the silica sol to form a silicate insoluble matter, which can promote the hardening speed of the inorganic coating and improve the crack resistance of the inorgan
  • the lowest film forming temperature (MFT) of the high molecular polymer is about zero degrees.
  • the invention simultaneously provides the use of the base material of the above inorganic coating material in preparing a rigid waterproof material, a colored facing mortar, and an artificial stone material.
  • Adding 20% or less of the above-mentioned base material can be used as an art paint to draw a picture similar to oil painting.
  • the present invention has the following advantages over the prior art:
  • the present invention discloses a valuable gelling chemical reaction characterized by a liquid silica sol which can react with a certain fineness of calcium carbonate to form a water-insoluble, strength-independent hydrated silicon.
  • Calcium acid artificial stone material and based on this, constructed a base material of inorganic coating, and by defining the ratio of liquid silica sol and calcium carbonate, significant technical effects were obtained.
  • the inorganic coating of the invention has outstanding advantages over the existing inorganic silicate coatings: it has anti-aging, strong weather resistance, chemical bonding with the cement base layer, no peeling, heat resistance, fire prevention, non-toxic, no It is characterized by pollution and energy conservation, and it does not contain strong alkaline ions such as potassium and sodium.
  • the pH value is less than 10, the compatibility with the pigment is good, the pan-alkali phenomenon does not occur, and inorganic paints of various colors can be produced.
  • the calcium carbonate utilized in the present invention belongs to a slightly soluble salt, and the free carbonate ions are replaced by silicic acid ions, thereby forming calcium silicate which is insoluble and has better comprehensive performance, and has a certain hiding in white paint.
  • the role can replace the role of a large part of titanium dioxide.
  • Figure 1 is an XRD diffraction pattern of a silica sol in Example 1.
  • Fig. 2 is an XRD diffraction pattern of a hardened product of a silica sol and a calcium carbonate mixed gas in the first embodiment.
  • Embodiment 1 A base material of an inorganic coating material, which is a mixture of liquid silica sol and calcium carbonate, and weigh 100 g respectively Liquid silica sol (solid content: 30%), 100 grams of powdered calcium carbonate, the silica sol is injected into the speed-regulating dispersion tank, calcium carbonate is added while stirring, and then uniformly dispersed by high-speed stirring.
  • an inorganic coating material which is a mixture of liquid silica sol and calcium carbonate
  • Figure 1 is an XRD diffraction pattern of a silica sol raw material, which is an amorphous silica
  • Figure 2 is a product of the present embodiment placed in the air.
  • XRD of hardened products after 3 days In the diffraction pattern, it can be found that the amorphous silica has completely disappeared, and calcium silicate having a good crystal structure is formed, leaving a portion of unreacted calcium carbonate.
  • the amorphous active silica in the aqueous silica sol solution reacts with the calcium on the surface of the calcium carbonate particles to form hydrated calcium silicate and is coated on the surface of the calcium carbonate particles, and the calcium carbonate particles are passed through the hydrated silicic acid.
  • Calcium glues together when placed in the air, the water in the system evaporates, precipitates hydrated calcium silicate crystals, and forms hydrated calcium silicate crystals / Calcium carbonate is the main component, water-insoluble, mechanically strong artificial stone structure.
  • the silica sol used may be: a dispersion of active silica colloid in water having a pH greater than 8, and the solid content range thereof is 30-40%.
  • the calcium carbonate may be a powder obtained by pulverizing and grinding natural calcium carbonate ore, or a synthetic calcium carbonate having a calcium carbonate content of not less than 95%.
  • the whiteness is not less than 85% and the fineness is not less than 200 mesh.
  • the use of heavy calcium carbonate gives greater density and better performance than light calcium carbonate.
  • the high molecular polymer can be a flexible latex powder, emulsion and aqueous resin dispersion, including EVA Re-dispersible latex powder, acrylate-based dispersible polymer powder, fluorocarbon emulsion (performed fluorocarbon emulsion is preferred), silicone-acrylic emulsion, pure acrylic emulsion, styrene-acrylic emulsion, and waterborne epoxy resin, waterborne polyurethane , water-based epoxy esters, water-based alkyd resins, and the like.
  • the use of high molecular weight polymer can improve 'silica sol - Calcium carbonate 'system stability and workability, and can increase the crack resistance and flexibility of its hardened materials.
  • Auxiliary materials such as pigments, fillers, and coating additives can be adjusted according to the performance requirements of the coating.
  • Example 3 First, 100 grams of silica sol, about 200 grams of powdered calcium carbonate, 20 grams of expanded perlite, and 10 G glass temperature MFT EVA at around zero The dispersible polymer powder is mixed and dispersed uniformly in the same manner in the speed-regulating dispersion tank.
  • the product can be used as an inorganic fireproof thermal insulation coating, and the storage time after using the barrel is 6 Months. The crack resistance is improved compared to the product of the second embodiment.
  • Example 4 First, 100 g of silica sol, about 150 g of powdered calcium carbonate, 30 g of titanium dioxide, 10 g The acrylate latex powder and 2 grams of iron oxide pigment are mixed and dispersed evenly in the speed-regulating dispersion tank. This product can be used as an inorganic exterior wall coating. The storage time after barreling reaches 6 Months. Compared with the second and third products, it can present rich colors.
  • the obtained product adopts JG/T 26-2002 "External Wall Inorganic Architectural Coatings" standard test, and the technical indicators are shown in Table 1. As shown,
  • the inorganic coating prepared by using the second to fourth embodiments after being painted on the wall and dried in the air, the amorphous silica sol (silica) will react with the calcium carbonate, and after dehydration, cross-link into a network-like hydration. Calcium silicate 'structure, thereby forming an artificial stone coating with compressive and tensile strength. The final product is dominated by ionic bonds and covalent bonds, supplemented by van der Waals bonds, and its properties are similar to those of rock minerals.
  • the inorganic coating is applied to the cement-based wall surface (such as concrete, cement-based putty, cement-based insulation surface layer, etc.), can penetrate into the surface of the cement-based wall, and react with the calcium material in the cement to form water-insoluble silicon. Calcium acid forms an anchoring effect that firmly bonds the paint to the wall.
  • Example 5 First, 100 g of silica sol, about 200 g of powdered calcium carbonate, 20 g of titanium dioxide, 20 g The fluorocarbon emulsion and 3 grams of chrome green pigment are mixed and dispersed evenly in the speed-regulating dispersion tank. This product can be used as an inorganic exterior wall coating, and the storage time after barreling reaches 6 Months. Compared with the second and third products, it can exhibit a green color.
  • Example 6 First 100 g of silica sol, about 250 g of powdered calcium carbonate, 20 g of kaolin, 20 g The styrene-acrylic emulsion and 5 grams of ultramarine blue pigment are mixed and dispersed evenly in the speed-regulating dispersion tank. This product can be used as an inorganic exterior wall coating. The storage time after barreling reaches 6 Months. Compared to the second and third products, it can exhibit a blue color.
  • Example 7 100 g of silica sol, about 150 g of powdered calcium carbonate, 20 g of acrylic emulsion and 100 The iron oxide red pigment is mixed and dispersed evenly in the speed-regulating dispersion tank. This product can be used as an art paint, and the storage time after barreling reaches 6 months.
  • Example 8 First 100 g of silica sol, about 250 g of powdered calcium carbonate and 15 g The hydrophobic dispersible polymer powder is uniformly dispersed in a thick slurry after being mixed in a speed-regulating dispersion tank.
  • the product can be used as a rigid waterproof material, and its impermeability can reach 0.3 MPa.
  • Example 9 First, 100 grams of silica sol, 250 grams of powdered calcium carbonate, 100 grams of graded sand, 10 grams Acrylate Latex Powder and 4g
  • the iron oxide pigment and the appropriate amount of thickened powder (pulp), lignocellulose and the like are uniformly mixed with the thixotropic mortar, and the material can be used as a colored veneer mortar which does not require pan-alkali and does not need to be covered.
  • Example 10 First, 100 grams of silica sol, about 200 grams of powdered calcium carbonate, 150 grams of graded sand, 20 Gram EVA redispersible powder, 4 g The iron oxide pigment and the appropriate amount of leveling agent are mixed and dispersed in a speed-regulating dispersing tank, and then uniformly dispersed into a rheological mortar, which is then poured into a mold of an artificial stone plate, reinforced and vibrated, and a surface is polished after demolding to obtain a bright light. Artificial slate.
  • Example 11 Weigh two samples separately, 100 g of liquid silica sol, 200 g The powdered calcium carbonate is then injected into the speed-controlled dispersion tank, and then calcium carbonate is gradually added. Add 1 gram of calcium chloride to one sample and no sample to another. At the same time, the mixture is uniformly dispersed at a high speed to form a slurry, which is sealed and stored after being packed in a barrel, and the storage time is up to 6 months. As a result, it was found that the sample after adding calcium chloride hardened faster than the sample without calcium chloride.
  • the technical solution of the invention has outstanding advantages compared with the existing inorganic silicate coatings: it has anti-aging, strong weather resistance, chemical bonding with the cement base layer, no peeling, heat resistance, fire prevention, non-toxic, It is non-polluting and energy-saving, and it does not contain strong alkaline ions such as potassium and sodium. pH less than 10 It has good compatibility with pigments, does not produce pan-alkali phenomenon, and can produce inorganic paints of various colors. It realizes an alkali-free and open-end controllable inorganic cementitious material with good coloring properties. Can be used in inorganic coatings, color finish mortar , artificial platen and art paints and other industries.

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Abstract

一种无机涂料的基体材料，基体材料为由液态硅溶胶和碳酸钙的混合物，液态硅溶胶以含固量计与碳酸钙的质量比为1:3-10。还提供了一种无机涂料，由基体材料与辅配材料液组成，其中辅配材料为无机涂料总质量20%以下的选自高分子聚合物、填料、颜料、涂料添加剂中的一种或多种的组合。该基体材料可应用于制备刚性防水涂料，彩色饰面砂浆、人造石材料和美术颜料。

Description

一种无机涂料的基体材料及其应用 技术领域
本发明涉及一种无机涂料，具体涉及一种采用硅溶胶的无机涂料及其制备方法和应用。
背景技术
根据国家行业标准 JG/26-2002 ， 无机建筑涂料按主要粘结剂种类可分为两类，一是以水玻璃（碱金属硅酸盐）为主要粘结剂，加入颜料、填料及助剂配制而成；二是以硅溶胶为主要粘结剂，加入适量的合成树脂乳液、颜料、填料及助剂配制而成。
常规用于制备无机涂料的硅酸钾及硅溶胶其主要物化指标如下表所示：
项目 指标
硅酸钾 硅溶胶
密度（ g/cm3 ） 1.35 - 1.4 1.15 - 1.2
氧化钾（ % ） 11.5 ~
氧化钠（ % ） ~ 0.5
二氧化硅（ % ） 25 30
粘度（ cps ） 100 10
pH 值 11 - 12 9 - 10
。
从硅酸钾与硅溶胶的组成上看，两者的主要区别在含碱量。虽然前者也能与碳酸钙发生钙化反应，甚至有着更低的收缩率，但由于其游离碱含量较高，对硅化反应有阻碍作用，因此对最终产物的耐水性影响较大，而伴生的泛碱现象也会影响着色的均匀性，对实际应用构成了瓶颈。而后者含碱量极低，硅化程度较高，所以耐水性及与颜料的相容性也更好。
然而，单独使用硅溶胶时，常温固化成膜往往存在裂纹、内部微孔等致命缺陷，同时，硅溶胶的价格偏高，一直以来其价格往往是水玻璃的数倍，也远高于同样浓度的合成乳液，因此目前通常将硅溶胶当作助剂使用，常常是加入有机高分子乳液制得有机 - 无机复合型涂料，而加入有机高分子材料获得的涂料易老化，耐候性差。也有报道采用水溶性三聚氰胺和多元醇对硅溶胶进行改性的，但这类处理会增加制备的复杂性。
近年来，随着硅粉一步水解法生产硅溶胶工艺逐步取代传统的离子交换法生产硅溶胶工艺，硅溶胶的价格已逐步下降到低于水玻璃的水平，所以如今的硅溶胶已成为一种应用前景广阔的基本化工原料。因此，如果能够克服硅溶胶成膜存在裂纹、内部微孔等问题，将能获得性能良好的无机涂料。
 技术问题
本发明的发明目的是克服现有技术中存在的上述不足，提供一种无机涂料的基体材料，以及该基体材料的应用。
技术解决方案
为达到上述发明目的，本发明采用的技术方案是： 一种无机涂料的基体材料，所述基体材料为液态硅溶胶和碳酸钙的混合物，所述液态硅溶胶以含固量计与碳酸钙的质量比为 1 ∶ 3 ～ 10 。
优选的技术方案，所述液态硅溶胶以含固量计与碳酸钙的质量比为 1 ∶ 5 ～ 8 。
上述技术方案中，所述液态硅溶胶的含固量至少为 30% ，氧化钠含量小于 1% ， pH 值小于 11 。
所述碳酸钙为纯度 95% 以上、细度 200 目以上的粉末。
作为上述基体材料的一种应用，本发明提供了一种无机涂料，由上述基体材料与辅配材料液配组成，所述辅配材料为无机涂料总质量的 20% 以下，辅配材料选自高分子聚合物、填料、颜料、涂料添加剂中的一种或多种的组合。
上述无机涂料的制备方法，包括以下步骤：
Ⅰ、按上述质量比称量液态硅溶胶、碳酸钙以及辅配材料，所述辅配材料由高分子聚合物、填料、颜料、涂料添加剂组成；
Ⅱ、将液态硅溶胶加入到调速分散釜中，搅拌并缓缓加入碳酸钙及辅配材料，添加完毕后加速搅拌至均匀，制成浆状物并密封保存。
使用时，涂布的无机涂料中的液态硅溶胶与碳酸钙发生气硬性反应，生成水化硅酸钙。其过程为，硅溶胶水溶液中的无定型活性二氧化硅与碳酸钙颗粒表面上的钙反应生成水化硅酸钙，并包裹在碳酸钙颗粒的表面，将碳酸钙颗粒通过水化硅酸钙胶联起来，当处于空气中时，体系中的水蒸发，析出水化硅酸钙晶体，并形成水化硅酸钙晶体 / 碳酸钙为主要成分的、不溶于水的、具有力学强度的人造石结构。由此使涂层与水泥基层具有较强的化学结合力，并使涂层不会发生开裂等问题。
上述技术方案中，所述高分子聚合物为 EVA 可再分散乳胶粉、丙烯酸酯类乳液及其可再分散乳胶粉、氟碳乳液、硅丙乳液、纯丙乳液、水性环氧树脂、水性聚氨酯、水性环氧酯、水性醇酸树脂之一或多种组合；所述填料为钛白粉、云母、高岭土之一或多种组合；所述颜料为有机颜料、无机颜料或由多种颜料混合成的液体色浆；所述涂料添加剂为聚丙烯酸分散剂、硅烷防水剂、 PVA 增稠剂、防腐剂、含钙化合物、含锌化合物之一或多种组合。含钙化合物和含锌化合物中的金属离子可与硅溶胶反应生成硅酸盐不溶解物，可促进无机涂料的硬化速度，提高无机涂料的抗裂强度。
优选的，高分子聚合物的最低成膜温度（ MFT ）在零度左右。
本发明同时提供上述无机涂料的基体材料在制备刚性防水材料、彩色饰面砂浆、人造石材料中的应用。
上述基体材料中加 20% 以下颜料，可以作为美术颜料使用，用于绘制类似油画的图画。
 有益效果
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
1 、本发明揭示了一种很有价值的胶凝性化学反应，这种化学反应的特点是液体硅溶胶可以和一定细度的碳酸钙发生气硬性反应生成不溶于水、具有强度的水化硅酸钙人造石材料，并据此构建了一种无机涂料的基体材料，通过限定液体硅溶胶和碳酸钙的比例，获得了显著的技术效果。
2 、本发明的无机涂料较之于现有无机硅酸盐涂料具有突出的优点：它具有耐老化、耐候性强、与水泥基层有化学结合力、不脱皮、耐热、防火、无毒、无污染及节约能源等特点，而且它不含钾、钠等强碱性离子， pH 值小于 10 ，与颜料的相容性好，不会产生泛碱现象，可制作各种颜色的无机涂料。
3 、本发明利用的碳酸钙属于一种微溶性盐，其游离出的碳酸离子会被硅酸离子置换，从而形成不溶性且综合性能更好的硅酸钙，其在白色涂料中还具有一定的遮盖作用，可以取代一大部分的钛白粉的作用。
 附图说明
图 1 是实施例一中硅溶胶的 XRD 衍射图。
图 2 是实施例一中硅溶胶和碳酸钙混合气硬化产物的 XRD 衍射图。
 本发明的实施方式
下面结合附图及实施例对本发明作进一步描述：
实施例一： 一种无机涂料的基体材料，所述基体材料为液态硅溶胶和碳酸钙的混合物，分别称取 100 克 液态硅溶胶（含固量为 30% ）、 100 克 粉体碳酸钙，将硅溶胶注入调速分散釜中，边搅拌边加入碳酸钙，再高速搅拌分散均匀。
图 1 为硅溶胶原料的 XRD 衍射图，它是一种无定型的二氧化硅；图 2 为本实施例的产物放置在空气中 3 天后的硬化产物的 XRD 衍射图，其中能够发现无定型的二氧化硅已经全部消失，生成了具有晶体结构良好的水化硅酸钙，余留部分未反应的碳酸钙。从机理上讲，硅溶胶水溶液中的无定型活性二氧化硅与碳酸钙颗粒表面上的钙反应生成水化硅酸钙，并包裹在碳酸钙颗粒的表面，将碳酸钙颗粒通过水化硅酸钙胶联起来，当放于空气中时，体系中的水蒸发，析出水化硅酸钙晶体，并形成水化硅酸钙晶体 / 碳酸钙为主要成分的、不溶于水的、具有力学强度的人造石结构。
以下实施例中，使用的硅溶胶可为： pH 值大于 8 的活性二氧化硅胶体在水中的分散液，其固含量范围为 30-40% 。
碳酸钙可为：由天然碳酸钙矿石经粉碎、研磨而成的粉体，或人工合成的碳酸钙，其碳酸钙含量不少于 95% ，白度不小于 85% ，细度不小于 200 目。特别地，采用重质碳酸钙比轻质碳酸钙所获的密度更大、性能更好。
高分子聚合物可为具有柔韧性的乳胶粉、乳液及水性树脂分散液，其中包括 EVA 可再分散乳胶粉，丙烯酸酯类可再分散乳胶粉，氟碳乳液（经过增塑的氟碳乳液为佳）、硅丙乳液、纯丙乳液、苯丙乳液，及水性环氧树脂、水性聚氨酯、水性环氧酯、水性醇酸树脂等。采用高分子聚合物的作用可提高'硅溶胶 - 碳酸钙'体系的稳定性和施工性，而且能增加其硬化材料的抗裂性和柔韧性。
颜料、填料、涂料添加剂等辅配材料可根据涂料的使用性能要求进行调整。
实施例二：先分别称取 100 克 的液态硅溶胶（含固量 =30% ，以下简称硅溶胶，下同）、 300 克 的粉体碳酸钙，然后将硅溶胶注入调速分散釜中，再逐步加入碳酸钙及辅配材料，辅配材料用量不大于总质量的 20% ，再高速搅拌分散均匀，制成浆状物，装桶后密封保存，贮存时间达到 6 个月，其七天测试的抗压强度大于 12MPa ，白度大于 85% ，莫氏硬度大于 5 。
实施例三：先将 100 克 的硅溶胶、约 200 克 的粉体碳酸钙、 20 克 的膨胀珍珠岩及 10 克 的玻璃化温度 MFT 在零度左右的 EVA 可再分散乳胶粉混合后在调速分散釜中以同样方法分散均匀，本产品可作为一种无机防火保温涂料使用，使用装桶后贮存时间达到 6 个月。与实施例二产品相比，其抗开裂性能得到改善。
实施例四：先将 100 克 的硅溶胶、约 150 克 的粉体碳酸钙、 30 克 的钛白粉、 10 克 的丙烯酸酯乳胶粉及 2 克 的氧化铁颜料混合后在调速分散釜中分散均匀，本产品可作为一种无机外墙涂料使用，装桶后贮存时间达到 6 个月。与实施例二、三产品相比，其可呈现丰富的色彩。
所得产品采用 JG/T 26-2002 《外墙无机建筑涂料》标准试验，得技术指标如表 1 所示，
项目 技术指标
容器中状态 搅拌后无结块，呈均匀状态
施工性 刷涂二道无障碍
涂膜外观 涂膜外观正常
对比率（白色和浅色） ≥0.95
热贮存稳定性（30d） 无结块 凝聚 霉变现象
低温贮存稳定性(3次) 无结块 凝聚现象
表干时间/h ≤2
耐洗刷性(次) ≥1000
耐水性(168h) 无起泡、裂纹、剥落
耐碱性(168h) 无起泡、裂纹、剥落
耐温变性(10次) 无起泡、裂纹、剥落
耐沾污性/% ≤20
耐人工老化性 白色和浅色 ( 800h ) 无起泡、裂纹、剥落、粉化≤1 级，变色≤2级
。
采用实施例二至四制备的无机涂料，经涂刷上墙后，在空气中干燥时，无定型硅溶胶（二氧化硅）将与碳酸钙反应，脱水后交联成网状的'水化硅酸钙'结构，从而形成具有抗压、抗拉强度的人造石涂层。其最终产物以离子键与共价键为主，范德华键为辅，其性能类似于岩石矿物。该无机涂料涂刷于水泥基墙面后（如混凝土、水泥基腻子、水泥基保温面层等），能渗透进入水泥基墙表面，并和水泥中的钙质材料反应生成不溶于水的硅酸钙，形成锚固效应，使涂料与墙面牢固地结合为一体。
实施例五：先将 100 克 的硅溶胶、约 200 克 的粉体碳酸钙、 20 克 的钛白粉、 20 克 的氟碳乳液及 3 克 的铬绿颜料混合后在调速分散釜中分散均匀，本产品可作为一种无机外墙涂料使用，装桶后贮存时间达到 6 个月。与实施例二、三产品相比，其可呈现绿的色彩。
实施例六：先将 100 克 的硅溶胶、约 250 克 的粉体碳酸钙、 20 克 的高岭土、 20 克 的苯丙乳液及 5 克 的群青蓝颜料混合后在调速分散釜中分散均匀，本产品可作为一种无机外墙涂料使用，装桶后贮存时间达到 6 个月。与实施例二、三产品相比，其可呈现蓝的色彩。
实施例七：先将 100 克 的硅溶胶、约 150 克 的粉体碳酸钙、 20 克 的丙烯酸乳液及 100 克 的氧化铁红颜料混合后在调速分散釜中分散均匀，本产品可作为一种美术颜料使用，装桶后贮存时间达到 6 个月。
实施例八：先将 100 克 的硅溶胶、约 250 克 的粉体碳酸钙及 15 克 的疏水型可再分散乳胶粉在调速分散釜中混合后分散均匀呈厚浆状，本产品可作为一种刚性防水材料使用，其抗渗性可达 0.3MPa 。
实施例九：先将 100 克 的硅溶胶、 250 克 的粉体碳酸钙、 100 克 的级配砂石、 10 克 的丙烯酸酯乳胶粉及 4 克 的氧化铁颜料及适量的稠化粉（浆）、木质纤维素等混合均匀呈触变性砂浆，本材料可作为一种不泛碱、无需罩面处理的彩色饰面砂浆使用。
实施例十：先将 100 克 的硅溶胶、约 200 克 的粉体碳酸钙、 150 克 的级配砂石、 20 克 的 EVA 可再分散乳胶粉、 4 克 的氧化铁颜料及适量流平剂在调速分散釜中混合后分散均匀呈流变性砂浆，然后倒入人造石板的模具中，加筋并震动成型，脱模后经表面抛光可得到一种光亮的人造石板。
实施例十一：先分别称取二个样品， 100 克 的液态硅溶胶、 200 克 的粉体碳酸钙，然后将硅溶胶注入调速分散釜中，再逐步加入碳酸钙。一个样品中加 1 克 氯化钙，另一个样品不加， 再同时高速搅拌分散均匀，制成浆状物，装桶后密封保存，贮存时间达到 6 个月。结果发现，加氯化钙的样品上墙后的硬化速度大于不加氯化钙的样品。
应用本发明的技术方案，较之于现有无机硅酸盐涂料具有突出的优点：它具有耐老化、耐候性强、与水泥基层有化学结合力、不脱皮、耐热、防火、无毒、无污染及节约能源等特点，而且它不含钾、钠等强碱性离子， pH 值小于 10 ，与颜料的相容性好，不会产生泛碱现象，可制作各种颜色的无机涂料，它实现了一种无碱且开放期可控的无机胶凝材料，并具有良好的着色性，可用于无机涂料、彩色饰面砂浆 、 人造台板及美术颜料等行业。

Claims (10)

  1. 一种无机涂料的基体材料，其特征在于：所述基体材料为液态硅溶胶和碳酸钙的混合物，所述液态硅溶胶以含固量计与碳酸钙的质量比为 1 ∶ 3 ～ 10 。
  2. 根据权利要求 1 所述的无机涂料的基体材料，其特征在于：所述液态硅溶胶以含固量计与碳酸钙的质量比为 1 ∶ 5 ～ 8 。
  3. 根据权利要求 1 所述的无机涂料的基体材料，其特征在于：所述液态硅溶胶的含固量至少为 30% ，氧化钠含量小于 1% ， pH 值小于 11 。
  4. 根据权利要求 1 所述的无机涂料的基体材料，其特征在于：所述碳酸钙为纯度 95% 以上、细度 200 目以上的粉末。
  5. 一种无机涂料，其特征在于：由权利要求 1 所述基体材料与辅配材料液配组成，所述辅配材料为无机涂料总质量的 20% 以下，辅配材料选自高分子聚合物、填料、颜料、涂料添加剂中的一种或多种的组合。
  6. 根据权利要求 5 所述的无机涂料，其特征在于：所述高分子聚合物为 EVA 可再分散乳胶粉、丙烯酸酯类可再分散乳胶粉、氟碳乳液、硅丙乳液、纯丙乳液、水性环氧树脂、水性聚氨酯、水性环氧酯、水性醇酸树脂之一或多种组合；所述填料为钛白粉、云母、高岭土之一或多种组合；所述颜料为有机颜料、无机颜料或由多种颜料混合成的液体色浆；所述涂料添加剂为聚丙烯酸分散剂、硅烷防水剂、 PVA 增稠剂、防腐剂、含钙化合物、含锌化合物、水玻璃之一或多种组合。
  7. 权利要求 1 所述无机涂料的基体材料在制备刚性防水材料中的应用。
  8. 权利要求 1 所述无机涂料的基体材料在制备彩色饰面砂浆中的应用。
  9. 权利要求 1 所述无机涂料的基体材料在制备人造石材料中的应用。
  10. 权利要求 1 所述无机涂料的基体材料在制备美术颜料中的应用。
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CN110644703B (zh) * 2019-11-08 2022-09-27 广州科源新材料有限公司 一种a1级防火水性无机浮雕板及其制备方法
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CN112479671A (zh) * 2020-11-30 2021-03-12 富思特新材料科技发展股份有限公司 一种仿洞石质感涂料及其制备方法和使用方法
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