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Publication numberCN102725359 A
Publication typeApplication
Application numberCN 201080059071
PCT numberPCT/IB2010/003246
Publication date10 Oct 2012
Filing date15 Dec 2010
Priority date23 Dec 2009
Also published asCA2785302A1, EP2338940A1, EP2338940B1, US9777163, US20120328875, WO2011077211A1
Publication number201080059071.9, CN 102725359 A, CN 102725359A, CN 201080059071, CN-A-102725359, CN102725359 A, CN102725359A, CN201080059071, CN201080059071.9, PCT/2010/3246, PCT/IB/10/003246, PCT/IB/10/03246, PCT/IB/2010/003246, PCT/IB/2010/03246, PCT/IB10/003246, PCT/IB10/03246, PCT/IB10003246, PCT/IB1003246, PCT/IB2010/003246, PCT/IB2010/03246, PCT/IB2010003246, PCT/IB201003246
InventorsA奥尔特加穆尔吉亚德利, D科尔德罗埃切巴瑞, E舍内菲尔德, F桑奇斯布里内斯, J戈麦斯科尔东, MD洛伦兹阿卡
Applicant斯拉加纳公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Composition for coating
CN 102725359 A
Abstract
Provided is a method which consists of the formation of a layer over a stone substrate to increase its hardness, chemical resistance, wear and scratch resistance, comprising applying on the substrate a coating matrix incorporating an organic material and fillers including inorganic nanoparticles and/or microparticles; chemically binding said matrix to the substrate,by a self-assembly process and/or a binding process by covalent bonding, electrostatic bonding, van der Waals bonding or hydrogen bonds; and finally drying said matrix. The mentioned organic material is selected from organosilanes, organophosphates, polycarboxylic compounds, compounds based on triazine heterocycles and said nanoparticles are nanoparticles of oxides, carbides, borides, nitrides of metals or of semimetals.
Claims(14)  translated from Chinese
1.用于涂覆石型基底的方法,其包括在所述基底上形成涂层以提高其硬度、耐化学性、耐磨性和耐划伤性,所述方法的特征在于其包括: 在所述基底上施用涂层基料,其包含至少一种有机材料作为粘结助剂和包括无机纳米粒子、或纳米粒子和微米粒子的填料; 将所述基料化学地粘结到所述基底上;和干燥所述基料, 其中所述的涂层基料进一步包括有机粘结剂和/或无机粘结剂和有机溶剂和/或无机溶剂; 其中所述的石型基底是基于石灰质材料和/或白云化石灰石的石骨料混合物,通过选自标准聚酯树脂、环氧树脂和丙烯酸树脂的粘结剂成团块;和其中所述的有机材料是有机硅烷,其包括Si-OH、SiOR(R =有机化合物)、或Si-Cl、醛或酮或C00H、NH2、磷酸根、膦酸根、磺酸根、硫酸根、或其组合中至少一种的官能团。 A method for coating a substrate of rock type, which comprises a coating layer formed on the substrate in order to improve their hardness, chemical resistance, abrasion resistance and scratch resistance, the method being characterized in that it comprises: applying the coating on the substrate base material, which comprises at least one organic material and a binder additive comprises inorganic nanoparticles, or nanoparticles and micron filler particles; the base material chemically bonded to the substrate on; and drying said binder, wherein said binder coating further comprises an organic binder and / or an inorganic binder and an organic solvent and / or inorganic solvent; wherein said substrate is a graphite-type materials based on lime and / or clouds of limestone stone aggregate mixture by standard selected from a polyester resin, an epoxy resin and an acrylic resin binder into a mass; and wherein said organic material is an organic silane, which comprises Si-OH , SiOR (R = organic compound), or Si-Cl, aldehyde or ketone or C00H, NH2, phosphate, phosphonate, sulfonate, sulfate, or combinations thereof at least one functional group.
2.根据权利要求I的方法,其中所述的纳米粒子是用权利要求I中的官能团进行官能化的金属或半金属的氧化物、碳化物、硼化物、氮化物的纳米粒子,选自氧化铝、碳化硼、氮化硼、硅酸盐、玻璃微球、碳化硅、二氧化硅、石英、氧化铜、微米纤维和纳米纤维、核-壳粒子、n-Na2Si03或其组合。 2. The method according to claim I, wherein said nanoparticle is as claimed in claim I functional group functionalized metal oxide or semi-metal carbides, borides, nitrides nanoparticles, oxide selected aluminum, boron carbide, boron nitride, silicates, glass microspheres, silicon carbide, silica, quartz, copper oxide, micron fibers and nanofibers, core - shell particles, n-Na2Si03 or combinations thereof.
3.根据权利要求I的方法,其中所述的粘结剂是热固性水基聚合物,所述的溶剂是水性或醇性介质。 3. The method according to claim I, wherein said binder is a thermosetting water-based polymer, said solvent is an aqueous or alcoholic medium.
4.根据权利要求5的方法,其特征在于所述的热固性聚合物为三嗪杂环类。 4. The method according to claim 5, wherein said thermosetting polymer is a triazine heterocycles.
5.根据权利要求1-4中之一的方法,其特征在于在所述基底上施用所述的涂层基料是通过有机材料和纳米粒子和/或微米粒子的共沉积来完成的。 5. The method according to one of claim 1-4, characterized in that on the base of the applying base material is coated by an organic material and nanoparticles and / or co-deposited to complete micron particles.
6.根据权利要求I的方法,其特征在于所述基料的干燥包括施加热到涂覆的基底上,以加速自由官能团的脱水过程和提高其交联性。 6. The method according to claim I, wherein said binder comprises the application of heat to the drying the coated substrate to accelerate the dehydration process free functional groups and improving the crosslinking.
7.由石材制成的板,包括天然石灰质基底或含石灰质材料和/或白云化石灰石的人造石,并具有根据权利要求1-6中之一的方法形成的涂层。 7. Stone made by the board, including natural calcareous or calcareous substrate material and / or artificial clouds of limestone stone, and a coating method according to one of claims 1-6 formation.
8.根据权利要求7的板,其特征在于所述的人造石包括粉末状的石灰质和/或白云石材料和粘结剂树脂。 8. A plate according to claim 7, characterized in that said artificial stone comprising powdered limestone and / or dolomite and a binder resin material.
9.根据权利要求7或8的板,其特征在于所述的涂层包括具有高硬度的选自氧化铝、碳化硼、氮化硼、硅酸盐、玻璃微球、碳化硅、二氧化硅、石英、氧化铜、微米纤维和纳米纤维、核-壳粒子、n-Na2Si03或其组合中至少一种材料的无机纳米粒子、或纳米粒子和微米粒子。 9. A plate according to claim 7 or 8, wherein said coating is selected from the group comprising alumina having a high hardness, boron carbide, boron nitride, silicates, glass microspheres, silicon carbide, silicon dioxide , quartz, copper oxide, microfiber and nanofiber core - shell particles, n-Na2Si03 or a combination of inorganic nanoparticles of at least one material, or nanoparticles and micron particles.
10.用于涂覆由石材制成的板状元件的组合物,其特征在于其包括用具有Si-OH、SiOR(R =有机化合物)、或Si-Cl、醛或酮或C00H、NH2、磷酸根、膦酸根、磺酸根中至少一种官能团的分子来官能化的无机纳米粒子、或纳米粒子和微米粒子的混合物,其通过自组装方法和/或其他化学结合或静电或化学相互作用方法被粘结于基料中。 10. A composition for coating the plate-like element made of stone, characterized in that it comprises having Si-OH, SiOR (R = organic compound), or Si-Cl, aldehyde or ketone or C00H, NH2, phosphate, phosphonate, sulfonate at least one functional group of molecules to the functionalized inorganic nanoparticles or a mixture of particles and micro-particles, which is incorporated by self-assembly and / or other chemical or chemical interactions electrostatic method, or It is bonded to the base compound.
11.根据权利要求10的组合物,其特征在于其还包含水基有机粘结剂、水性、醇性、水醇性溶剂和反应促进剂。 11. A composition according to claim 10, characterized in that it further comprises a water-based organic binder, an aqueous, alcoholic, aqueous alcoholic solvent and reaction accelerator.
12.根据权利要求10或11的组合物,其特征在于所述的第一有机硅烷材料是有机官能化的硅烷,其选自以下材料:TE0S(原硅酸四乙酯)、Y -甲基丙烯酰氧基丙基三甲氧基硅烷、BTSE (1,2-双(三乙氧基硅烷))、十六烷基三甲氧基硅烷、(3-缩水甘油基氧基丙基三甲氧基硅烷)、二氯(二苯基)硅烷、二氯二甲基硅烷、有机膦酸酯、聚羧酸化合物、基于三嗪杂环类的化合物或具有选自1,3,5-三嗪的三嗪基团或具有选自二氨基-PEG的自由氨基基团的有机材料,且其中所述的纳米粒子和微米粒子选自以下材料:氧化铝、碳化硼、氮化硼、硅酸盐、玻璃微球、碳化硅、二氧化硅、石英、氧化铜、微米纤维和纳米纤维、核-壳粒子、Ii-Na2SiO3、或其组合。 12. A composition according to claim 10 or 11, wherein said first material is an organic silane organofunctional silane selected from the following materials: TE0S (tetraethyl orthosilicate), Y - methyl acryloxy propyl trimethoxy silane, BTSE (1,2- bis (triethoxysilane)), hexadecyl trimethoxysilane, (3-glycidoxypropyl trimethoxysilane ), dichloro (diphenyl) silane, dichloro dimethyl silane, organic phosphonates, polycarboxylic acid compounds, triazine-based or heterocyclic compounds having 1,3,5-triazine of the three selected or a group selected from piperazinyl diamino -PEG free amino groups of the organic material, and wherein said nanoparticles and micron particles are selected from the following materials: aluminum oxide, boron carbide, boron nitride, silicates, glass microspheres, silicon carbide, silica, quartz, copper oxide, micron fibers and nanofibers, core - shell particles, Ii-Na2SiO3, or combinations thereof.
13.根据权利要求12的组合物,其特征在于所述的纳米粒子和微米粒子用膦酸根、氨基、醛、磺酸根、硫酸根、羧酸基或有机硅烷官能化。 13. The composition of claim 12, wherein said nanoparticles and micron particles with phosphonate, amino, aldehyde, sulfonate, sulfate, carboxylic acid or an organic silane functional group.
14.根据权利要求11、12或13的组合物,其特征在于有机粘结剂是带有反应性官能团的热固性聚合物。 14. A composition according to claim 11, 12 or 13, characterized in that the organic binder is a thermosetting polymer having a reactive functional group.
Description  translated from Chinese

涂料组合物 The coating composition

技术领域 Technical Field

[0001] 本发明在第一方面涉及一种用于涂覆石材基底的方法,所述石材基底在本说明书应被理解为天然大理石或包括石灰质材料和/或白云化石灰石(dolomitic limestone)通过粘结剂成团块的石骨料(stone aggregate),这种方法提供了一种涂层,其能够提高所述石材基底的硬度,提高耐化学性,耐磨性和耐划伤性。 [0001] In a first aspect of the present invention relates to a method for coating a substrate of the stone, the stone base in the present specification should be understood to include natural marble or calcareous material and / or clouds of limestone (dolomitic limestone) by stick coalescent agglomerated stone aggregates (stone aggregate), this method provides a coating which is possible to improve the hardness of the stone base, improve chemical resistance, abrasion and scratch resistance. 本发明的涂层提高了表面抵抗化学物质蚀刻的稳定性和减少了沾污。 Coating of the present invention improves the stability of the surface resistance to chemical etching and reduce the contamination.

[0002] 本发明的工艺允许在最佳状态下提闻使用石材基底例如人造大理石板的寿命的同时,显著扩大此类产品(考虑到暴露表面所显示出的对多种因素的抵抗性)的使用范围,以及减少在处理、运输和安装过程中的划伤块或缺陷块的数量。 [0002] The process of the present invention allows the smell in the best condition to mention the use of stone substrates such as artificial marble slabs life while significantly expanding such product (taking into account the exposed surface exhibited resistance to a variety of factors) of range, and reduce handling, transport and installation of scratching block or blocks of the number of defects.

[0003] 本发明所述的第一方面的方法提供了一种基于自组装技术的涂层,自组装技术允许连接纳米结构材料。 [0003] The first aspect of the present invention to provide a coating technology based on self-assembly, self-assembly technology allows connection nanostructure materials. [0004] 本发明的第二方面涉及一种由包含根据所建议的方法形成的涂层的石材所制成的板状元件。 [0004] The second aspect relates to a coating formed by the method comprising the recommendations based on the stone of the present invention is made of a plate-like member.

[0005] 本发明的第三方面提供一种组合物,其用于涂覆由石材所制成的板状元件,该组合物包括通过自组装方法将第一有机硅烷材料和无机纳米粒子和/或微米粒子粘结到基料中。 [0005] The third aspect of the present invention provides a composition which is coated by a plate-like member made of stone used, the composition comprises by self-assembly of the first organic silane material and inorganic nanoparticles and / or micron particles bonded to the base compound.

背景技术 Background

[0006] 在用于获得人造大理石板的现有工艺中,使用具有优异可控粒度的大理石骨料的混合物,其代表超过90%的材料组合物。 [0006] In the means for obtaining an artificial marble plate prior art, the use of a controlled particle size has excellent marble aggregate mixture, which represents more than 90% of the material composition. 事先用催化剂和促进剂来达到所要求的情况的热固性树脂一般作为填料的粘结剂成分。 Advance with catalyst and promoter to achieve the desired situation is generally a thermosetting resin as a binder component filler. 由于所用矿物质的岩类学性质和聚酯树脂的固有特性,人造大理石铺材有着低耐化学性,当发生摩擦和划伤时会降低基底的使用寿命。 Due to the nature of the rocks with mineral properties and a polyester resin, artificial marble flooring material has low resistance and chemical resistance, friction and scratches when the base will reduce the life. 耐划伤性和耐磨性与材料的硬度或抵抗性有关,一种材料被另一个划伤所呈现出的抵抗性定义为材料的莫氏耐划伤性和耐磨损性。 Scratch resistance and hardness or abrasion resistance and materials related to a material being exhibited by another scratch resistance is defined as a material Mohs scratch resistance and abrasion resistance. 这种情况是包括天然和人造大理石(aggIomeratemarble)的大理石型石材基底的主要缺点之一。 This situation is one of the main drawbacks include natural and artificial marble (aggIomeratemarble) marble type stone base.

[0007] 基于硅氧烷或其他聚合物的传统透明涂层有着良好的对间歇的冲击或攻击的抵抗性,但是它们对经受持续的压力,例如通道地区时,有着低的抵抗性,这归因于基于硅氧烷和塑料的产品的低的耐磨损和耐划伤性。 [0007] The silicone-based or other conventional clear coating polymers have good resistance to impact or intermittent attacks, but they continued to withstand the pressure, for example, the channel region, has a low resistance, which is owned by Based due to low wear silicone and plastic products and scratch resistance.

[0008] 有不同的技术来解决上述缺陷。 [0008] There are different techniques to solve the above-mentioned drawbacks. 基于硅氧烷的填料(钙硅石,纳米粘土)光滑剂或添加剂一般成批使用。 The silicone-based fillers (wollastonite, nanoclay) Smooth agents or additives are generally batch use. 这些技术仅仅对有低耐磨性要求的应用的有效。 The technology is only valid for low wear resistance applications. 当需要更高的耐磨性时,含有无机填料和层压材料的树脂的涂层技术被使用。 When you need higher wear resistance, an inorganic filler and coating technology containing resin laminate is used. 但是这种解决方法产生了一种在高端装饰产品市场不被看好的塑料视觉的表面。 However, this solution results in a high-end decorative product market is not optimistic about the surface of the plastic vision.

[0009] 使用涂层是最先进的技术之一。 [0009] The coating is one of the most advanced technology. 涂层一般适用于保护、提高或装饰不同的产品。 Coatings are generally applicable to protect, enhance or decorate different products. 然而,在涂层与聚合物材料之间由于后者的低极性而有着低粘结力。 However, between the coating and the polymeric material of the latter due to the low polarity and it has a low adhesion. 提高粘结力的方法一般包括通过不同的方法提高塑料的表面能:暴露于高能量源例如火焰,电晕,等离子体和UV辐射处理。 Improve adhesion improving method generally includes plastic surface energy in different ways: exposure to high energy sources such as flame, corona, plasma, and UV irradiation treatment. 一般来说,通过涂层让具有高表面能的表面变“潮湿”是很容易的,因此也将会更容易提高喷涂基底和相之间的粘结力。 In general, by coating the surface with a high energy so that the surface becomes "wet" it is very easy, and therefore it will be easier to improve the adhesion between the coating and the phase substrate. 然而,当使用这些方法时仍然有些缺点,主要由于环境原因,这一事实它们是慢而且不是很均一的工艺,另外存在这些限制由于这些材料热稳定性不好的事实。 However, when using these methods still have some drawbacks, mainly due to environmental reasons, the fact that they are slow and not very homogeneous process, the presence of these additional restrictions due to the poor thermal stability of these materials facts.

[0010] 特殊的涂覆工艺例如物理气相沉积(PVD),化学蒸汽沉积(CVD),和湿法沉积涂覆(或溶胶-凝胶),均是已知的技术用于将无机涂料(SiO2,碳化物,氮化物,金属氧化物...)沉积在不同的基底(包括塑料)上。 [0010] a special coating processes such as physical vapor deposition (PVD), chemical vapor deposition (CVD), deposition and wet coating (or sol - gel), are known in the art for the inorganic coating (SiO2 , carbides, nitrides, metal oxides ...) deposited on different substrates (including plastic) on. 然而,在塑料材料上这一类型的技术有一定的限制例如高成本,低沉积速度,高能量消耗和尤其产生毒气。 However, the plastic material of this type of technology has certain limitations such as high cost and low deposition rate, high energy consumption and, especially, produce toxic gases.

[0011] 专利US5751018公开了一种包括通过SAM工艺在无机基底上应用半导体涂层的方法。 [0011] Patent US5751018 discloses a method for process applications including through the SAM semiconductor coating on the inorganic substrate. 特别是,它主张通过第一官能团共价键连结桥结构到无机基底的表面,和通过它的其他官能团也是共价键连结到半导体纳米晶体。 In particular, it advocates covalent bridge structure coupled to the surface of the inorganic substrate via a first functional group, and by its other functional groups is covalently coupled to the semiconductor nanocrystals. 这一专利的这一技术不适用于石材基底的涂层,因为均没有考虑所述基底的性质和涂层的要求。 The technology in this patent does not apply to the stone base coat, because the requirements are not considered the nature of the substrate and coating.

[0012] 申请W02004094303A2提出通过纳米纤维连接两种物品,其中对于一个实施方案,物品之一是石制的。 [0012] The application W02004094303A2 connecting the two articles proposed by nanofibers, which for one embodiment, one of the article is made of stone. 在它的说明书中描述了SAM工艺与微接触喷涂工艺相结合以构造用于上述连接的纳米纤维。 It's described in the specification in the SAM process and micro-contact coating technology combine to construct nano-fiber used for such connections.

[0013] 申请EP1802455A2提出了应用磷酸铝涂层到基底上。 [0013] Application EP1802455A2 proposed aluminum phosphate coating applied to the substrate. 在它的说明书中它描述了这样的涂层,尤其,提供更高的硬度。 In its specification which describes such coatings, in particular, provide higher hardness. 它也描述了一种附加涂层,“保护涂层”,能够通过自组装单层或SAM工艺应用于所述涂层。 It also describes an additional coating, "protective coating", the coating can be applied by process of self-assembled monolayer or SAM. 此附加涂层可以包括有机分子或聚合物,涂料基于硅烷,和提出的硫酸铝材料本身一样。 This additional coating can include organic molecules or polymers, silane-based coatings, and aluminum sulfate material presented itself. 它也描述了所提供的涂料可以包括有机或无机添加剂,例如金属离子如硅,铁,锌和镁或其混合物,和纳米晶体锌,钛氧化物或它们的混合物。 It also describes the coating provided may include organic or inorganic additives, such as metal ions such as silicon, iron, zinc and magnesium, or mixtures thereof, and nanocrystalline zinc, titanium oxide or mixtures thereof.

[0014] 考虑到关于保护石材基底的所提及的现有技术的不足,一种新的涂料已经取得了发展,其在石材基底和透明涂层之间形成有高抵抗性的共价键、静电、范德华力等化学键,石材基底是包括石灰质材料和/或白云化石灰石的骨料,以达到与具有石材视觉的石英板相似的抵抗性。 [0014] Taking into account the shortage on proposed protect the stone base and the prior art, a new kind of paint has made the development of its high resistance to the formation of a covalent bond between the stone base and clear coat, electrostatic, van der Waals bond, etc., including lime stone base material and / or clouds of limestone aggregates, in order to achieve the vision of a quartz plate with a stone similar resistance.

发明内容 DISCLOSURE

[0015] 本发明提供一种用于涂覆石材基底的方法,该方法通过在其上形成涂层以提高所述基底的硬度,耐磨性和抗划伤性。 [0015] provides a method for coating the stone base of the present invention, the method by which to form a coating on the substrate to increase hardness, wear resistance and scratch resistance. 所提供的涂层也使得表面更加地耐刻蚀和耐污。 Coatings offer also makes the surface more to etch and stain resistant.

[0016] 所提及的石材基底是基于,在一个优选方案中,包括石灰质材料和/或白云化石灰石石骨料混合物,通过粘结剂成团块。 [0016] mentioned the stone base is based, in a preferred embodiment, it includes a calcareous material and / or clouds of limestone rock aggregate mixture, by an adhesive into clumps.

[0017] 该方法包括如下步骤: [0017] The method comprises the steps of:

[0018] 在所述基底上施用包括至少一种有机材料和包括无机纳米粒子和/或微米粒子的填料的涂层基料(coating matrix); [0018] applied on the substrate comprises at least one organic material and include inorganic nanoparticles and / or micro-particle filler coating binder (coating matrix);

[0019] 将所述的基料通过实施自组装工艺和/或通过共价键结合、静电结合、范德华力结合或氢键结合的粘结工艺而化学地粘结到基底上;和 [0019] The base material through the implementation of the self-assembly process and / or by covalent bonding, electrostatic bonding, van der Waals forces or hydrogen bonding of the bonding process and chemically bonded to the substrate; and

[0020] 采用合适的方法一般来说通过提供热能来干燥所述基料, [0020] The use of appropriate methods in general by providing heat to dry the base material,

[0021 ] 特别地,数量为至少一种有机材料、和/或纳米粒子和/或微米粒子具有含Si-OH,SiOR (R =有机化合物),或Si-Cl,醛或酮或C00H,NH2,磷酸根,膦酸根,磺酸根,硫酸根,或它们的组合中至少一种基团的分子。 [0021] In particular, the amount of at least one organic material and / or nanoparticles and / or micro-particles having a containing Si-OH, SiOR (R = organic compound), or Si-Cl, aldehyde or ketone or C00H, NH2 , phosphate, phosphonate, sulfonate, sulfate, or a combination thereof in the molecule at least one group.

[0022] 因此在本质上,本发明的方法包括使能够形成三维网络的有机和无机前体通过自组装工艺形成纳米结构的涂层,其通过化学键牢固地粘结于基底,包封不同的纳米粒子和/或微米粒子,并且获得的涂层具有高耐磨损性和耐划伤性。 [0022] Thus, in essence, the method of the present invention include organic and inorganic capable of forming a three dimensional network precursor coating nanostructure formed by self-assembly process, which is firmly bonded to the substrate by chemical bonding, encapsulating different nano particles and / or micro-particles, and the coating obtained has a high abrasion resistance and scratch resistance.

[0023] 关于有机材料,根据一个实施方案,它选自有机硅烷,有机磷酸酯,聚羧酸化合物,基于三嗪杂环类的化合物,并且所述的纳米粒子是所述纳米粒子和/或微米粒子成分官能化的金属或半金属的氧化物、碳化物,硼化物,氮化物的纳米粒子,选自氧化铝,碳化硼,氮化硼,硅酸盐,玻璃微球,碳化硅,二氧化硅,石英,氧化铜,微米纤维和纳米纤维,核-壳粒子,Ii-Na2SiO3或其组合。 [0023] As the organic material, according to one embodiment, it is selected from organosilanes, organic phosphates, polycarboxylic acid compounds, heterocyclic compounds based on triazine, and the said nanoparticles are nanoparticles and / or micron particle component oxide nanoparticles functionalized metal or semi-metal carbides, borides, nitrides, selected from alumina, boron carbide, boron nitride, silicates, glass microspheres, silicon carbide, titanium silica, quartz, copper oxide, micron fibers and nanofibers, core - shell particles, Ii-Na2SiO3, or combinations thereof.

[0024] 涂层基料进一步包括有机或无机粘结剂和有机或无机溶剂。 [0024] The coating further comprises an organic binder or an inorganic binder and an organic or inorganic solvent.

[0025] 所述的粘结剂特别是热固性水基聚合物,和所述的溶剂是水性或醇性介质,和所述的热固性聚合物是基于三嗪杂环的化合物,例如甲氧基化的三聚氰胺。 Binder [0025] The particular water-based thermosetting polymer, and said solvent is an aqueous or alcoholic medium, a thermosetting polymer and said heterocyclic compound is a triazine-based, e.g., methoxylated melamine.

[0026] 关于施用涂层基料的方法,优选通过有机材料和纳米粒子和/或微米粒子的共沉积进行。 [0026] For the method of applying the coating base material, preferably by an organic material and nanoparticles and / or co-micron particle deposition.

[0027] 为了在干燥所述基料的过程中加快自由官能团的脱水过程和提高其交联性能的目的,所述方法进一步包括对于涂覆的基底的受控的加热步骤。 [0027] In order to accelerate the dehydration process free functional groups and improving the crosslinking performance of the object in the drying process of the base material, the method further comprising the coated substrate for a controlled heating step.

[0028] 本发明的第二方面关于具有由本发明的第一方面所提供的方法形成的涂层的板状元件,其包括天然石灰质基底或含有石灰质材料和/或白云化石灰石的人造石。 [0028] The second aspect of the present invention has a plate-like member on the coating formed by the method of the first aspect of the present invention, there is provided, which includes natural calcareous substrate or contain calcareous material and / or clouds of limestone artificial stone.

[0029] 根据一个实施方案,本发明的第二方面所提供的由石材材料所制成的板的基底的人造石包括粉末状的石灰质和/或白云化石灰石和粘结剂树脂。 [0029] According to one embodiment of the second aspect of the present invention, there is provided a plate made from stone material base of artificial stone include powdered limestone and / or clouds of limestone and a binder resin.

[0030] 在另一个实施方案中,所述涂层包含了陷入所述基料中的选自氧化铝,碳化硼,氮化硼,硅酸盐,玻璃微球,碳化硅,二氧化硅,石英,氧化铜,微米-和纳米纤维,核-壳粒子,Ii-Na2SiO3或它们的组合中至少一种材料的高硬度的无机微米-和/或纳米粒子。 [0030] In another embodiment, the coating comprises a compound selected from the group into the alumina, boron carbide, boron nitride, silicates, glass microspheres, silicon carbide, silicon dioxide, quartz, copper oxide, micro - and nano fiber, core - shell particles, Ii-Na2SiO3 or a combination thereof, at least one inorganic material with high hardness of micron - and / or nanoparticles.

[0031] 根据第三方面,本发明也涉及用于涂覆例如刚刚所描述的石材制的板状元件的组合物,包括第一有机硅烷材料和无机纳米粒子和/或微米粒子,其具有选自Si-OH,SiOR(R=有机化合物),或Si-Cl,醛或酮CO或C00H,磷酸根,膦酸根,磺酸根,硫酸根基团中至少一种的分子,其中所述的纳米粒子和有机硅烷材料通过实行自组装工艺和/或其他化学结合或静电或化学相互作用方法而被粘结在基料中。 [0031] According to a third aspect, the present invention also relates to a composition for coating such as a plate-like member made of stone just described, comprising a first material and an organosilane inorganic nanoparticles and / or micro-particles, having a selected Since Si-OH, SiOR (R = organic compound), or Si-Cl, or an aldehyde or ketone CO C00H, phosphate, phosphonate, sulfonate, sulfate group in the molecule at least one, wherein said nanoparticles and organic silane material through the introduction of self-assembly process and / or other chemical bonding or electrostatic interaction or chemical methods is bonded to the base compound.

[0032] 在一个实施方案中,根据第三方面所提出的组合物也包括水基的有机粘结剂,水性、醇性、水醇性溶剂和反应促进剂。 [0032] In one embodiment, according to the third aspect of the proposed composition may also include water-based organic binder, an aqueous, alcoholic, aqueous alcoholic solvent and reaction accelerator.

[0033] 在一个优选方案中,所述的第一有机娃烧材料为有机官能化的娃烧,其选自如下的材料:TE0S(原硅酸四乙酯),Y-甲基丙烯酰氧基丙基三甲氧基硅烷,BTSE (I,2-二三乙氧基娃烧),十TK烧基二甲氧基娃烧,(3-缩水甘油基氧基丙基二甲氧基娃烧),_■氣_■苯基硅烷,二氯二甲基硅烷,有机膦酸酯类,聚羧酸化合物,基于三嗪杂环的化合物、或具有选自I,3,5-三嗪的三嗪基团或具有选自二氨基-PEG的自由氨基基团的有机材料。 [0033] In a preferred embodiment, the first organic material is organic baby burn baby burn functionalized, selected from the following materials: TE0S (tetraethylorthosilicate), Y- -methacryloyloxy- propyl trimethoxysilane, BTSE (I, 2- twenty-three ethoxy baby burn), ten TK dimethoxy burn baby burn, (3-glycidoxypropyl dimethoxy baby burn ), _ ■ _ ■ gas phenyl silane, dichloro dimethyl silane, organic phosphonates, polycarboxylic acid compounds, heterocyclic compounds based on triazine, or selected from I, 3,5- triazine triazine group or selected from Diamino -PEG of free amino groups of the organic material. 另外,所述的纳米粒子和微米粒子选自氧化铝,碳化硼,氮化硼,硅酸盐,玻璃微球,碳化硅,硅石,石英,氧化铜,微米-和纳米纤维,核-壳粒子,Ii-Na2SiO3或它们的组合中的材料。 Further, the nanoparticles and micron particles selected from alumina, boron carbide, boron nitride, silicates, glass microspheres, silicon carbide, silica, quartz, copper oxide, m - and nanofibers, core - shell particles , Ii-Na2SiO3 or combinations of materials.

[0034] 根据一个优选方案,本发明第三方面所提出的组合物设想,形成它的纳米-和微米粒子,共同或选择性地,被膦酸根、氨基、醛、磺酸根、硫酸根盐、羧酸基团或有机硅烷官能化。 [0034] In accordance with one preferred embodiment of the third aspect of the proposed composition of the present invention is contemplated, it is formed of nano - and micron particles, jointly or alternatively, by phosphonate, amino, aldehyde, sulfonate, sulfate salt, carboxylic acid group or an organic silane functional.

[0035] 关于有机粘结剂,带有反应性官能团的热固性聚合物被使用。 [0035] As the organic binder, a thermosetting polymer having a reactive functional group is used. [0036] 前述的优点和其他的优点和特点将通过下面的几个实施例的详细描述和附图来更好地理解,这必须看作是非限制性描述。 [0036] The foregoing advantages and other advantages and features of the detailed description and drawings to be better understood through an example of some the following examples, which must be seen as a non-restrictive description.

附图说明 Brief Description

[0037] 在附图中: [0037] In the drawings:

[0038] 图I图示基底上的自组装过程,这层是由水醇性有机硅烷溶液形成的。 [0038] Figure I illustrates the process of self-assembly on the substrate, which layer is made of water-alcoholic organic silane solution formed. 由于SiOH. . . HOSi单元的脱水反应和生成Si-O-Si键而导致的交联发生在低温热处理后; ... Since the SiOH HOSi dehydration reaction unit and generating Si-O-Si bonds resulting from the cross-linking occurs after low temperature heat treatment;

[0039] 图2显示了纳米粒子,其结构由2个单元、一种组成的核、不同组成的外面部分形成;洋葱型的纳米粒子; [0039] Figure 2 shows the nanoparticles, its core structure consists of two units, a composition, forming part of the outside of different compositions; onion-type nanoparticles;

[0040] 图3显示了基底表面上的薄的自组装层,其中展示了八核Si4O4单元; [0040] Figure 3 shows a thin layer of self-assembled on the surface of the substrate, which shows the eight-core Si4O4 unit;

[0041] 图4显示了表面功能化的其它实施例,基于使用氨基和醛官能团的自组装; [0041] Figure 4 shows the surface functionalization of other embodiments, the use of self-assembly based on the amino and aldehyde functional groups;

[0042] 图5显示了其中使用含有醛官能团的分子和三嗪用于自组装过程的实例。 [0042] Figure 5 shows the use of molecules which contain an aldehyde functional group and a triazine for instance self-assembly process. 包含的三嗪允许产生三维网络; Containing triazine allows the generation of three-dimensional network;

[0043] 图6图示了在基底上的自组装过程,其根据本发明的原理:表面的轻度氧化,纳米复合材料的自组装和沉积。 [0043] FIG. 6 illustrates a self-assembly process on a substrate, which according to the principles of the invention: mild oxidation of the surface of the self-assembly and depositing nanocomposites. 这个过程可以发生在3步内,2步内,甚至在一步内发生。 This process can take place in three steps, within 2 steps, or even in a single step.

[0044] 图7显示了因自发的自组装而导致的基料中的硅烷醇的结合。 [0044] Figure 7 shows the combined result of spontaneous self-assembly resulting binder of silanol. 在这个过程中发生了脱水和键的形成; Dehydration and bond formation occurs in this process;

[0045] 图8在其顶部显示了根据本发明的仅仅有微米粒子的涂层结构,而在底部描述了微米粒子和纳米粒子的组合的结构。 [0045] Figure 8 shows a top coated structure according to just-micron particles of the present invention, and in the bottom of the description of the structure of the combination of micron particles and nanoparticles.

具体实施方式 DETAILED DESCRIPTION

[0046] 本发明提供了一种高硬度涂层,其基于纳米填料和/或微米填料和TE0S,硅烷粘 [0046] The present invention provides a high hardness coating, the nano-fillers and / or micro-fillers and TE0S, silane-based adhesive

结基料等。 Results-based materials.

[0047] 本发明提供的硬涂层配方允许石材基底的表面硬度增加超过2或3个点的莫氏硬度,该硬涂层是基于所述的纳米填料和/或微米填料在醇性或水醇性水性溶剂中的分散体。 [0047] Hard coating formulations of the present invention is provided to allow the stone surface of the substrate hardness increase by more than 2 or 3-point Mohs hardness of the hard coating is based on a nano-filler and / or micro-fillers in alcohol or water alcoholic aqueous solvent dispersion.

[0048] 该进展由多官能分子的基料组成,其中官能团之一是能够自组装或共价键结合,因此分子至少包括下述基团的一种:Si-0(R =有机化合物)或Si-Cl,醛或酮,CO或C00H,磷酸根,硫酸根,或者这些官能团的组合例如硫醇膦酸根,其由于自发的自组装将产生三维网络。 [0048] The progress of the multi-functional molecule binders, one of which is capable of self-assembly of functional group or a covalent bond, so molecules comprise at least one of the following groups: Si-0 (R = organic compound) or Si-Cl, a combination of an aldehyde or ketone, CO or C00H, phosphate, sulfate, or these functional groups such as thiols phosphonate, which due to the spontaneous self-assembly to produce a three-dimensional network. 一些所用的分子是:硫醇类,烷氧基硅烷类,羧酸类,烷氧基金属盐类(alkoxymetalIates)和勝酸类。 Some molecules are used: thiols, alkoxysilanes, carboxylic acids, alkoxy metal salts (alkoxymetalIates) and wins acids.

[0049] 第二官能团是在受控的方式下能够引发单体聚合的基团。 [0049] The second functional group is in a controlled manner capable of initiating polymerization of the monomer groups.

[0050] 一些所使用的官能分子是:原硅酸四乙酯,二-1,2 (三乙氧基甲硅烷基)乙烷, [0050] Some functional molecules used are: tetraethylorthosilicate, two-1,2 (triethoxysilyl) ethane,

3-缩水甘油氧基丙基二甲氧基娃烧,Y -氨基丙基娃烧,二氯二甲基娃烧,二_ 二氯甲基苯基硅烷,十六烷基三甲氧基硅烷。 3- glycidoxypropyl dimethoxy baby burn, Y - aminopropyl baby burn baby burn dichlorodimethylsilane, two _ dichloromethyl phenyl silane, hexadecyl trimethoxysilane.

[0051] 为了促进基底与填料的粘结,水性/水醇性介质可以通过添加乙酸,盐酸,酒石酸,乙二胺四乙酸等进行酸化,此类的酸通过产生硅烷醇,羧基或膦酸根基团促进自组装。 [0051] In order to promote adhesion of the substrate with a filler, an aqueous / alcoholic aqueous medium by adding acetic acid, hydrochloric acid, tartaric acid, ethylenediaminetetraacetic acid, etc. acidification, by generating such an acid silanol, carboxyl or phosphonate Mission to promote self-assembly.

[0052] 最终选择的微米粒子和纳米粒子在水性介质和/或胶体溶液中是稳定的,并且可以在形成分子的低聚反应过程中添加,从而纳米填料在添加剂中有很好控制的百分比。 [0052] the final choice of micron particles and nano-particles in an aqueous medium and / or colloidal solution stability, and can be added to the oligomerization process of the formation of molecules, thereby Nanofillers Percentage of well-controlled in the additive. [0053] 所用填料的选择基于组合物,结构,尺寸和成本等。 [0053] As used filler is selected based on the composition, structure, size and cost. 一些所考虑的填料是: Some fillers are considered:

[0054]氧化铝(Al2O3) [0054] Alumina (Al2O3)

[0055]碳化硼(B4C) [0055] The boron carbide (B4C)

[0056]氮化硼(BN) [0056] The boron nitride (BN)

[0057] 硅酸盐 [0057] Portland

[0058] 玻璃微球 [0058] Glass microspheres

[0059]碳化硅(SiC) [0059] Silicon carbide (SiC)

[0060] 二氧化硅(SiO2) [0060] Silica (SiO2)

[0061] 石英 [0061] Quartz

[0062]氧化铜(CuO) [0062] copper oxide (CuO)

[0063] 微米和纳米纤维 [0063] micro- and nano-fiber

[0064] 为了提升石材基底表面和多官能纳米结构涂层之间的分子交联性,采用自组装(self-assembly, SAM)技术,其能产生强键而不需要考虑待粘结表面的极性,而且可维持原始片的外观。 [0064] In order to enhance the intermolecular crosslinking of the stone surface of the substrate and between multifunctional nanostructured coatings, the use of self-assembly (self-assembly, SAM) technology, which can produce extremely strong bond without the need to consider the surface to be bonded resistance, and can maintain the original appearance of the sheet.

[0065]自组装技术是基于这样的事实,某些材料的表面能够通过表面活化进行改性,表面活化可以包括所述的轻度氧化,和/或采用具有自组装能力的分子的化学官能化方法。 [0065] Self-assembly technique is based on the fact that certain materials can be surface modified by surface activation, the surface activation may include mild oxidation, and / or the use of the ability of self-assembly molecules having chemical functional Methods.

[0066] 这项新技术提供了在材料表面和包括微米和纳米粒子的涂层之间有效的结合,这归因于在保持原始片的外观的同时在表面上形成分子交联的可能性。 [0066] This new technology provides an effective bond between the material surface and including micro- and nano-particle coating, which is attributed to the sheet while maintaining the original appearance of the surface of the possibility of intermolecular crosslinking formation.

[0067] 分子锚结方法包括3步:活化,自组装和微米和纳米粒子的共沉积。 [0067] Molecular anchor knot method includes three steps: activation, self-assembly and co-deposition of micro- and nano-particles. 当负责活化和负责在基底的表面上形成三维网络的分子和微米和纳米填料是在同一组合物中时,如图6所描述的活化、自组装和微米和纳米粒子的共沉积这3步可以在一步内完成。 When it is in charge and responsible for the formation of activated molecules and micro- and nano-filler three-dimensional network on the surface of the substrate in the same composition, as described activation 6, self-assembly and co-deposition of micro- and nano-particles of these three steps can completed in a single step.

[0068] 第一步涉及为了使待处理基底的表面功能化的目的在适宜条件下的活化,在上述表面上产生用于有机分子的自组装的最佳官能化基团,从而提高所述表面发生自组装反应的可能性。 [0068] The first step involved in order to make the surface of the substrate to be processed functional purpose of activation under appropriate conditions, to produce the best functional groups for self-assembly of organic molecules onto the surface, thereby improving the surface the possibility of self-assembly reactions.

[0069] 在活化过程(第一步)中形成的羧基和羟基提供了活化点,因此分子与合适的官能团进行自组装(第二步)。 [0069] carboxyl and hydroxyl groups in the activation process (first step) is provided in the form of active sites, so the molecule functional groups with suitable self-assembly (second step). 在所述的第二步中基于共价键和其他弱的相互作用例如静电或在活化基底表面的官能团和双或多官能团有机分子之间的范德华力的形成的自组装技术被应用。 Covalent interaction based on other weak self-assembly technology such as electrostatic or between the activation of the substrate surface functional groups and double or polyfunctional organic molecules formed by van der Waals force is applied in the second step. 因此,稳定的分子化学地粘结于部件表面必须是自发产生的。 Therefore, a stable molecule chemically bonded to the surface of the part must be spontaneous.

[0070] 在第三步,高硬度的无机微米和纳米粒子(SiC,BN, SiO2, TiO2, ZrO2,石英,氧化铝,B4C等)的共沉积发生在基底表面以获得高质量的涂层。 [0070] In the third step, the inorganic microns high hardness and nanoparticles (SiC, BN, SiO2, TiO2, ZrO2, quartz, alumina, B4C, etc.) occur in the co-deposition surface of the substrate in order to obtain high quality coatings. 微米和/或纳米粒子陷入由所述的分子能够形成的网络中,最大化基料-粒子的相互作用。 Micro- and / or nano-particles into the network by the molecules capable of forming the maximization binder - interacting particles. 自组装的分子通过化学吸附方法(被吸附物质通过其能量水平与那些化学键相近的力结合到固体表面,)粘结到表面,提供了在基底和分子间的有效结合。 The self-assembled molecules by chemisorption method (adsorbed substances bound to a solid surface through a chemical bond energy levels similar to those forces,) bonded to the surface, it provides effective binding between the substrate and molecules.

[0071] 这三步可以减少为一步,为了那个结果必须将三个步骤中的硬的微米粒子和纳米粒子在同一配方中使用,其将会与能够使基底表面活化并通过自组装产生三维网络的分子共沉积在涂层里。 [0071] These three steps can be reduced to one step, in order that the results of the three steps necessary to hard-micron particles and nanoparticles used in the same recipe, which will be able to make the surface of the substrate and activated by self-assembly to produce a three-dimensional network Molecular co-deposited coating inside.

[0072] 通过化学的或静电的相互作用或键的粘结获得硬的透明的涂层,其具有高耐磨损性,同时维持机械性能。 [0072] to obtain a hard transparent coating or bonding by electrostatic interaction or a chemical bond, which has a high abrasion resistance, while maintaining mechanical properties.

[0073] 使用这一技术,使与微米和/或纳米粒子不同的且有能力形成三维网络的有机和、无机前体被封装。 [0073] Using this technology, the micro- and / or nano-particles and has the ability to form different organic and inorganic precursors three-dimensional network is encapsulated.

[0074] 图7中显示了由于自发的自组装在基料中多官能分子的结合产生了三维网络(例如硅烷醇基团的情况),多官能分子具有选自至少以下一种基团:Si-0或Si-Cl,CO或C00H,胺,羰基,游离醛基团,羧酸,磷酸根,硫酸根,或者这些官能团的组合例如硫醇膦酸根。 [0074] Figure 7 shows a spontaneous self-assembly due to the binder in the binding of the polyfunctional molecule produced three-dimensional network (e.g., the case of silanol groups), the polyfunctional molecule selected from at least one of the following groups: Si -0 or Si-Cl, a combination of CO or C00H, amine, carbonyl, free aldehyde group, carboxylic acid, phosphate, sulfate, or these functional groups such as thiols phosphonate.

[0075] 关于附图中的图形,需要强调的是,当主要由结晶结构的金属碳酸盐(主要是碳酸钙)构成的大理石表面用化合物例如有机硅烷、膦酸酯、硫醇、具有氨基、醛或羧酸基团的化合物处理时,薄涂层的沉积出现了XCO3单元,生成了-OXO-Si类型键,例如有机硅烧。 [0075] For drawing graphics should be emphasized that, when the crystal structure mainly composed of a metal carbonates (mainly calcium carbonate) constituting the marble surface with an organosilane compound, for example, phosphonates, thiol, an amino When an aldehyde compound or a carboxylic acid group treatment, depositing a thin coating appeared XCO3 unit, generated -OXO-Si type bonds, e.g., silicone burning.

[0076] 对于这一类型的材料,硅化合物形成Si-O-Si-O类型键,从而形成与大理石基底具有优异粘结力的三维结构。 [0076] For this type of material, a silicon compound formed Si-O-Si-O type bond, thereby forming a three-dimensional structure and marble having excellent adhesion of the substrate. ,

[0077] 如果有机硅烷的基于水醇性的溶液在低温下热处理,它引起硅烷醇单元的脱水,其将从Si-OH变成Si-O-Si类型键(有或没有有机链),使得在层间交联(图I)。 [0077] If the organic silane-based water-alcoholic solution heat treatment at a low temperature, it causes dehydration of silanol unit, which from the Si-OH into Si-O-Si type bonds (with or without an organic chain), such that In the inter-layer crosslinking (Figure I).

[0078] 根据所用硅烷分子(BTSE ;TE0S, GLYMO,等.• •),通过八核单元(SiO) 4(图3),洋葱型(图2),等...形成纳米粒子结构。 [0078] Depending on the silane molecule (BTSE;. TE0S, GLYMO, etc. • •), by eight-core units (SiO) 4 (FIG. 3), the onion-type (Fig. 2), etc ... formed nanoparticle structure. 这些在原处产生的氧化硅(SiO)纳米粒子沉积在基底的表面,并且通过自组装方法化学地粘结于表面。 The silica produced in situ (SiO) nanoparticles deposited on the surface of the substrate, and by self-assembly chemically bonded to the surface.

[0079] 表面的官能化和自组装的另一个例子是在二官能或多官能醛和胺基化学改性的表面之间的反应。 [0079] surface functionalization and another example of self-assembly is a reaction between the surface of the titanium-functional or multi-functional aldehyde and amine groups of chemically modified. 在这种情况下,自组装反应将在胺基官能团和醛基团之间发生(图4)。 In this case, the self-assembly reaction will occur between the amine functional groups and aldehyde groups (Figure 4). 当带有醛官能团的分子用于引起自组装反应时,可以使用不同类型的试剂,其能够通过与自由醛基或羟基的反应产生三维网络。 When a functional group with an aldehyde molecule for inducing self-assembly reaction, you can use different types of agents capable of producing three-dimensional network through reaction with the free aldehyde or hydroxyl groups. 这些分子必须有至少3个自由氨基基团例如三聚氰胺,三胺或四胺,等。 These molecules must have at least three free amino groups such as melamine, triamine or tetramine, and the like. (图5)。 (Figure 5).

[0080] 具有高硬度的微米粒子和/或纳米粒子将会被添加到配方中以更多地提高涂层的硬度和耐磨性。 [0080] micron particles having a high hardness and / or nano-particles will be added to the formulation to further improve the coating hardness and wear resistance. 一些纳米结构的涂层的抵抗性比普通使用的涂层的抵抗性大近似三倍和持续多于40 %。 Some resistance nano-structured coating is greater than the resistance to commonly used coating approximately three times more than 40 percent and sustained. 采用这种方法,纳米粒子可以直接应用于涂层表面,最终成本可以显著减少。 With this method, the nanoparticles can be directly applied to the coating surface, the final cost can be significantly reduced. 而且,获得从纳米层到微米层的可定制厚度的可能性有助于成本的减少。 Moreover, the possibility of obtaining from the nano-layer thickness can be customized to the micron layer helps to reduce costs.

[0081] 形成的产品包括厚度为100nm-500iim的新涂层,其借助具有高硬度的微米粒子和纳米粒子的自组装通过共沉积而形成,为了此目的,使用具有在基底的表面和配方组分之间引起自组装反应的能力的有机或有机金属基料,允许形成三维网络。 Products [0081] include forming a thickness of 100nm-500iim new coating, which means having a high hardness micron particles and nanoparticle self-assembly is formed by co-deposition, for this purpose, the substrate having a surface and the formulation groups The reaction occurs between the sub-assembly capacity from organic or organometallic material, allowing the formation of a three-dimensional network.

[0082] 检测不同类型的官能分子、溶剂、以及填料在化学组成中的变化,组合物的结构和粒径,直到获得涂料的最佳配方。 [0082] to detect different types of functional molecules, solvents, as well as changes in the chemical composition of the filler, and the composition of the structure and size, until the best formula to get the paint.

[0083] 应用的参数(涂层厚度,干燥温度...),处理方式(浸涂,辊涂...),等...也影响涂层的质量结果和最终性能。 [0083] Applications of the parameter (coating thickness, drying temperature ...), treatment (dip coating, roll coating, ...), ... etc. also affect the quality of the results and the final properties of the coating.

[0084] 所有这些因素影响涂层的疏水性、产生的表面张力、分子间的正确交联、或多或少的透明外观、气泡的产生、粘结性的损失例如其后粘性的表面、开裂等... [0084] All of these factors affect the hydrophobicity of the coating, the surface tension of the proper cross-linking between molecules, more or less transparent appearance, resulting, for example, loss of adhesion of subsequent adhesive surface bubbles, cracks and so on ...

[0085] 因此,正确粘结剂、适宜溶剂介质的活化、最佳的填料的组合,也包括应用方法和某些具体的应用参数,最终导致获得有效和化学上稳定的涂层。 [0085] Thus, the correct adhesive, the activation of a suitable solvent medium, the best combination of fillers, including application methods and application specific parameters, resulting in an effective and chemically stable coatings.

[0086] 下面通过非限制性详细说明本发明的几个实施例的实现。 [0086] The following detailed description of several embodiments of the realization of the present invention by way of non-limiting.

[0087] 实施例I [0087] Example I

[0088] Iml盐酸在磁力搅拌下加入到乙醇/水(80ml乙醇;20ml水)水醇溶液中,加入55ml的TEOS (原硅酸四乙酯)和23ml的GLYMO (3-缩水甘油基氧基丙基三甲氧基硅烷)。 [0088] Iml hydrochloric acid was added under magnetic stirring in ethanol / water (80ml of ethanol; 20ml water) aqueous alcohol solution was added 55ml of TEOS (tetraethyl orthosilicate) and 23ml of GLYMO (3- glycidyloxy propyl trimethoxy silane). 溶液持续搅拌10分钟,加入粒径为80nm的a -碳化硅5. 4g。 Solution was continuously stirred for 10 minutes, the particle size of 80nm a - SiC 5. 4g. 混合物被持续搅拌5分钟,之后施用于人造大理石板的表面。 The mixture was continuously stirred for 5 minutes, then applied to the surface of the artificial marble plate.

[0089] 在120C的烘箱中干燥25分钟。 [0089] and dried in an oven to 120 C for 25 minutes.

[0090] 实施例2 [0090] Example 2

[0091] Iml盐酸在磁力搅拌下加入到乙醇/水(80ml乙醇;20ml水)水醇溶液中,加入40ml的TEOS (原硅酸四乙酯)和40ml GLYMO (3-缩水甘油基氧基丙基三甲氧基硅烷)。 [0091] Iml hydrochloric acid was added under magnetic stirring in ethanol / water (80ml of ethanol; 20ml water) aqueous alcohol solution was added 40ml of TEOS (tetraethyl orthosilicate) and 40ml GLYMO (3- glycidyloxy propyl trimethoxysilane). 溶液持续搅拌10分钟,加入粒径为IU m的a -碳化硅5. 4g。 Solution was continuously stirred for 10 minutes, the particle size of IU m a - SiC 5. 4g. 混合物被持续搅拌5分钟,之后施用于人造大理石板的表面。 The mixture was continuously stirred for 5 minutes, then applied to the surface of the artificial marble plate.

[0092] 在85 C的烘箱中干燥45分钟。 [0092] dried at 85 C oven for 45 minutes. [0093] 实施例3 [0093] Example 3

[0094] 人造大理石板(基底)在25C下3. 5体积%的HCl水溶液中处理40秒。 [0094] artificial marble plate (substrate) for 40 seconds in aqueous HCl 3.5% by volume at 25 C in. 基底经过3次水洗,之后被干燥。 After 3 washes the substrate, after being dried.

[0095] Iml盐酸在磁力搅拌下加入到乙醇/水(80ml乙醇;20ml水)水醇溶液中,加入25ml的TEOS (原硅酸四乙酯)和55ml GLYMO (3-缩水甘油基氧基丙基三甲氧基硅烷)。 [0095] Iml hydrochloric acid was added under magnetic stirring in ethanol / water (80ml of ethanol; 20ml water) aqueous alcohol solution was added 25ml of TEOS (tetraethyl orthosilicate) and 55ml GLYMO (3- glycidyloxy propyl trimethoxysilane). 溶液持续搅拌10分钟,加入粒径为IU m的a -碳化娃4. 4g和粒径为80nm的a -碳化娃lg。 Solution continued stirring for 10 minutes, adding a particle size of IU m of a - baby 4. 4g carbide particle size of 80nm and a - carbonation baby lg. 混合物被持续搅拌5分钟,并施用于基底。 The mixture was continuously stirred for 5 minutes, and applied to a substrate.

[0096] 在85 C的烘箱中干燥45分钟。 [0096] dried at 85 C oven for 45 minutes.

[0097] 实施例4 [0097] Example 4

[0098] 人造大理石板(基底)在25C下3. 5体积%的HCl水溶液中处理40秒。 [0098] artificial marble plate (substrate) for 40 seconds in aqueous HCl 3.5% by volume at 25 C in. 基底经过3次水洗,之后经过干燥。 After 3 washes the substrate, after drying.

[0099] Iml盐酸在磁力搅拌下加入到乙醇/水(80ml乙醇;20ml水)水醇溶液中,加入55ml的TEOS (原硅酸四乙酯)和25ml GLYMO (3-缩水甘油基氧基丙基三甲氧基硅烷)。 [0099] Iml hydrochloric acid was added under magnetic stirring in ethanol / water (80ml of ethanol; 20ml water) aqueous alcohol solution was added 55ml of TEOS (tetraethyl orthosilicate) and 25ml GLYMO (3- glycidyloxy propyl trimethoxysilane). 溶液持续搅拌10分钟,加入粒径为6 um的二氧化硅25g。 Solution stirred continuously for 10 minutes, particle size 6 um silica 25g. 混合物被持续搅拌5分钟,之后施 The mixture was continuously stirred for 5 minutes after application

用于基底。 For the substrate.

[0100] 在85C的烘箱中干燥45分钟。 [0100] dried at 85 C oven for 45 minutes.

[0101] 通过基于微米-和/或纳米填料和所述的硅烷(或膦酸盐)粘结基料的新的硬涂层和使用基底的该粘结技术的组合: [0101] micron-based - and / or nanofiller and the silane (or phosphonate) new hard coat layer and the adhesive base material of the substrate bonding techniques using a combination of:

[0102]-在基底上获得了稳定的涂层。 [0102] - access to a stable coating on the substrate.

[0103]-基底硬度的提高得以实现。 [0103] - to improve the hardness of the substrate is achieved.

[0104]-改善基底的耐划伤性得以实现。 [0104] - to improve the scratch resistance of the substrate can be achieved.

[0105]-由于在涂层和聚酯树脂间产生了化学键,因此提高了涂层与基底间的粘结性。 [0105] - Since between the coating and the polyester resin to produce a chemical bond, thereby increasing the adhesion between the coating and the substrate.

[0106]-测试样品的耐化学性和耐清洁剂性得到了提高。 [0106] - the chemical resistance and resistance to cleaning agents test sample has been improved.

[0107]-在低温下施工得以实现。 [0107] - at low construction can be achieved.

[0108]-因为所用的溶剂是水性的或水醇性介质,所以实现了在低毒性介质中施工,因此防止了有害挥发性气体的排放和对于处理溶液的人没有刺激性或其他健康危险。 [0108] - because the solvent used is aqueous or aqueous alcoholic medium, so to achieve the construction of low toxicity in the medium, thereby preventing harmful volatile gases and irritating or other health risks for people handling solutions.

[0109] 实施例5 :蚀刻测试 [0109] Example 5: Test Etching

[0110] 一些大理石块被抛光紧接着在其上完成蚀刻和沾污测试,并与未被抛光的块进行比较。 [0110] Some polished marble blocks are etched and stained immediately complete the test, and the comparison is not polished blocks thereon. 结果是抛光的块已经没有了涂层和很容易被盐酸腐蚀。 The result is a polished piece has no coating and can easily be hydrochloric acid corrosion. [0111] 观察到仍有涂层的这些区域保持没有改变。 [0111] observed that the coating is still maintained in these areas has not changed. 这样的话,与未被处理的为3相比,所获得的硬度达到了莫氏硬度6。 In this case, as compared to untreated 3, the obtained hardness Mohs hardness 6 reached. 发现一定的分离但是没有观察到划伤也没有材料损耗的发生。 Find some isolated but no scratches were observed and no material loss occurs.

[0112] 当盐酸和碱液被倾注时,没有气泡并且直到几个小时已经过去也没有反应发生。 [0112] When the hydrochloric acid and lye is poured, no air bubbles and until a few hours have passed and no reaction. 相反,未被处理的块直接被蚀刻和大理石立即被损耗了。 Instead, the block is not processed directly by etching and loss of marble immediately.

[0113] 本发明的方法能够达到接下来的具体目标: [0113] The method of the present invention can achieve the following specific objectives:

[0114]-在没有改变基底原始外观的情况下提高了耐磨损性能。 [0114] - without changing the original appearance of the substrate to improve the wear resistance.

[0115]-它没有影响最终产品的其他性能(弯曲,耐冲击性,加工性能,物理特性,机械性能等。) [0115] - it does not affect the other properties of the final product (bending, impact resistance, processability, physical properties, mechanical properties and the like.)

[0116]-采用这个新处理方法,形成了持久的稳定涂层,主要归因于通过在涂层与基底之间形成静电、共价键类型等坚固的相互作用而获得与基底的高粘结性。 [0116] - Using this new approach, the formation of a lasting and stable coating, mainly due to the bond between the coating by high strong electrostatic interaction with the substrate, forming a covalent bond types, and the substrate is obtained sex.

[0117]-它作用于宽范围的基于通过有机粘结剂成团块的石骨料的混合物的石材基底。 [0117] - it acts on a wide range of organic-based binder by clumps of a mixture of stone aggregate stone base. 粘结剂作为石材的粘结组分可以为热固性和热塑的。 Binder as the binder component stone for thermoset and thermoplastic,. 矿物质的性质根据所选用的天然石头(大理石,石灰石,石英,花岗岩等•••)的岩类学起源而变化。 Properties of minerals according to the selected natural stone (marble, limestone, quartz, granite and other •••) of Petrographic origin change.

[0118]-它防止了当成批使用时的结块问题。 [01] - it prevents caking problems when used as a batch.

[0119]-它减少了在产品加工之后废品的产生:减少了划伤块的废弃物。 [0119] - It reduces the generation of waste after processing: reducing waste scratches block.

[0120]-最终产品的额外成本是最小的。 [0120] - the extra cost of the final product is minimal.

[0121]-因为它们是基于无挥发溶剂的处理方法,所以没有环境风险或健康风险。 [0121] - because they are based on non-volatile solvent treatment method, so there is no environmental risk or health risks.

[0122]-在低温下操作可以有没有明显的退化的块,不像当更苛刻的沉积体系例如等离子或电晕这些所发生的。 [0122] - at low temperature operation may have no obvious degradation of the block, unlike the more demanding when deposition system such as plasma or corona these occurred.

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Classifications
International ClassificationC09D5/00
Cooperative ClassificationY10T428/269, Y10T428/31942, Y10T428/31663, C04B41/009, C04B41/64, C04B41/4922, C08K3/28, C09D7/1216, C09D5/00, C08K3/38, C08K3/14, C08G77/14, C08K3/0008, C08K3/22, C08K3/36, C09D183/06, C08K3/34, C09D183/08, B82Y30/00
European ClassificationC09D5/00, C09D7/12D2, B82Y30/00
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