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CN113321952A - High-water-resistance silicate coating and preparation method thereof - Google Patents

High-water-resistance silicate coating and preparation method thereof Download PDF

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Publication number
CN113321952A
CN113321952A CN202110802105.9A CN202110802105A CN113321952A CN 113321952 A CN113321952 A CN 113321952A CN 202110802105 A CN202110802105 A CN 202110802105A CN 113321952 A CN113321952 A CN 113321952A
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water
preparation
potassium silicate
silicate
parts
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朱开兴
隋玮红
李松梅
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Qingdao University of Science and Technology
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Qingdao University of Science and Technology
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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
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明公开了一种高耐水硅酸盐涂料及其制备方法；该涂料由成膜物质改性硅酸钾树脂、耐高温颜料、填料、助剂、水组成；该发明中涂料的制备方法：首先通过将水性环氧树脂、硅烷偶联剂、异丙酮、氧化镁、硅酸钾、硅溶胶、去离子水按照特定配比和步骤制备成改性硅酸钾树脂，然后将颜填料进行特定的处理，再将制备好的改性硅酸钾树脂、疏水剂、处理过的耐高温颜料以及金属氧化物，进行分散、研磨，最后加入助剂和水搅拌，制成高耐水硅酸盐涂料；其施工便捷、涂装VOC排放低，具备高附着力、高耐水性能，是耐水性领域涂装的极佳选择。The invention discloses a highly water-resistant silicate paint and a preparation method thereof; the paint is composed of a film-forming substance modified potassium silicate resin, high temperature resistant pigments, fillers, auxiliary agents and water; the preparation method of the paint in the invention: First, the modified potassium silicate resin is prepared by using water-based epoxy resin, silane coupling agent, isoacetone, magnesium oxide, potassium silicate, silica sol, and deionized water according to specific proportions and steps, and then the pigments and fillers are specifically Then, the prepared modified potassium silicate resin, hydrophobic agent, treated high temperature resistant pigment and metal oxide are dispersed and ground, and finally additives and water are added to stir to make high water resistant silicate coating ; Its convenient construction, low VOC emission, high adhesion, high water resistance, is an excellent choice for water resistance coating.

Description

High-water-resistance silicate coating and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a high-water-resistance silicate coating formula and a preparation method thereof.
Background
The silicate paint is a paint taking potassium silicate and sodium silicate as film forming substances, and the main components of the silicate paint comprise the film forming substances, a curing agent, a filling material, a pigment, an auxiliary agent and the like; the solid content of the inorganic silicate coating can be increased along with the reduction of water, silicon-oxygen bonds are gradually polymerized to form polysilicone, and finally a silicon-oxygen network structure is formed, so that the inorganic silicate coating has excellent weather resistance, good chemical stability under the irradiation of ultraviolet rays, difficulty in decomposition, excellent heat resistance, film forming property and better stain resistance; when the coating is in contact with water, partial metal ions are dissolved in the water, and water molecules gradually replace the positions of the metal ions to cause the coating to absorb water and damage the structure of the coating film, which is the main reason causing the poor water resistance of the silicate coating and is one of the defects of the silicate coating in the using process; therefore, the water resistance of the silicate coating needs to be improved, and the problem of poor water resistance of the inorganic silicate coating can be well solved by modifying the film forming material potassium silicate.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems of poor water resistance and easy damage of the surface structure of the existing silicate coating, the high-water-resistance inorganic silicate coating and the preparation method thereof are provided.
The above object of the present invention is achieved by the following technical solutions:
a high-water-resistance silicate coating and a preparation method thereof are disclosed, which mainly comprise the following components in parts by weight: comprises 6 to 9 portions of aluminum oxide, 2 to 4 portions of titanium dioxide, 0.5 to 1.5 portions of methyl trioxymethylsilane, 10 to 14 portions of modified potassium silicate resin, 0 to 1.5 portions of flatting agent, 0.5 to 1 portion of hydrophobic agent, 1 to 5 portions of wetting dispersant, 0.5 to 1 portion of stabilizer and 8 to 13 portions of deionized water; the modified potassium silicate resin is prepared from water-based epoxy resin, a silane coupling agent, isopropyl ketone, magnesium oxide, potassium silicate, silica sol and deionized water, and comprises the following steps:
a: slowly adding waterborne epoxy resin, a silane coupling agent and isopropyl ketone into deionized water, and fully stirring to prepare epoxy resin polymer emulsion;
b: adding potassium silicate and silica sol into deionized water, stirring in a water bath at 40 ℃ for 3h at 300r/min, adding magnesium oxide, and stirring until the magnesium oxide is completely dissolved to obtain a mixed binder;
c: and adding a mixed binder into the epoxy resin polymer emulsion, and uniformly ball-milling to prepare the modified potassium silicate resin.
A preparation method of a high-water-resistance silicate coating comprises the following steps:
(1) burning titanium dioxide and aluminum oxide powder in a vacuum furnace at 1100 ℃ for 1h, cooling for a period of time, and then ball-milling and uniformly mixing on a ball mill to prepare mixed powder A;
(2) adding the mixed powder A into deionized water, adding methyl trioxymethylsilane under the stirring condition, and uniformly mixing to obtain a mixed solution;
(3) drying the mixed solution in a 60 ℃ oven for 1-2 h, and cooling at normal temperature to obtain mixed powder B;
(4) and fully stirring the prepared modified potassium silicate resin, the mixed powder B, the auxiliary agent and the deionized water, and performing ball milling uniformly to obtain the coating.
The invention takes modified potassium silicate resin as a main film forming substance, and takes titanium dioxide, aluminum oxide and other metal oxides as pigment and filler; the silane coupling agent interacts with the waterborne epoxy resin and the potassium silicate in a molecular scale to form a composite structure of an organic matrix, the silane coupling agent and an inorganic matrix, so that the film forming property and the water resistance of the coating are improved; magnesium ions in the magnesium oxide can slow the dissolution of colloidal silica particles and the deposition rate of silicon monomers in the potassium silicate on silica sol nanoparticles in the mixing process of the potassium silicate and the silica sol, and slow the occurrence of a gelation phenomenon, so that the coating is more stable; the addition of the stabilizer can keep chemical balance, reduce the generation of gel and improve the storage stability of the coating; the addition of the phosphate can disperse the pigment and the filler through hydrogen bonds and chemical adsorption, so that the dispersion effect in the coating process is enhanced; the water-based hydrophobing agent promotes the film-forming surface of the coating to form a special water-resistant structure (changing a contact angle) similar to a lotus leaf, so that the coating has good hydrophobicity and waterproofness; the addition of the leveling agent can effectively reduce the surface tension of the coating liquid and improve the permeability of the coating, and promote the coating to form a flat, smooth and uniform coating film in the drying film-forming process.
The invention aims to provide a high-water-resistance silicate coating and a preparation method thereof, and the high-water-resistance silicate coating comprises, by weight, 6-9 parts of aluminum oxide, 2-4 parts of titanium dioxide, 0.5-1.5 parts of methyl trioxymethylsilane, 10-14 parts of modified potassium silicate resin, 0-1.5 parts of a leveling agent, 0.5-1 part of a hydrophobing agent, 1-5 parts of a wetting dispersant, 0.5-1 part of a stabilizer and 8-12 parts of deionized water.
In conclusion, the beneficial technical effects of the invention are as follows:
(1) the modified potassium silicate resin increases the wet binding power of the coating, can buffer the brittle cracks generated by dehydration shrinkage during the film formation of silicic acid, and can also improve the water resistance of the coating;
(2) the wetting dispersant taking phosphate as a raw material is added with a more obvious dispersing effect, so that the modified potassium silicate resin is well combined with pigments and fillers, and the storage stability of the coating is improved.
Detailed Description
Example 1
A high-water-resistance silicate coating comprises, by weight, 4 parts of aluminum oxide, 2 parts of titanium dioxide, 0.5 part of methyl trioxymethylsilane, 14 parts of modified potassium silicate resin (the addition amount of waterborne epoxy resin is 15% of the total amount of the modified potassium silicate resin), 1 part of a leveling agent, 8 parts of deionized water, 1 part of a hydrophobing agent, 1 part of a wetting dispersant and 0.8 part of a stabilizer; wherein, according to the weight portion, the waterborne epoxy resin is 2.1 portions, the silane coupling agent is 0.5 portion, the isopropyl ketone is 0.5 portion, the magnesium oxide is 0.5 portion, the potassium silicate is 4.5 portions, the deionized water is 4.5 portions, the silica sol is 1.4 portions, and the modified potassium silicate resin comprises the following steps:
a: slowly adding waterborne epoxy resin, a silane coupling agent and isopropyl ketone into deionized water, and fully stirring to prepare epoxy resin polymer emulsion;
b: adding potassium silicate and silica sol into deionized water, stirring in a water bath at 40 ℃ for 3h at 300r/min, adding magnesium oxide, and stirring until the magnesium oxide is completely dissolved to obtain a mixed binder;
c: and adding a mixed binder into the epoxy resin polymer emulsion, and uniformly ball-milling to prepare the modified potassium silicate resin.
Example 2
A high-water-resistance silicate coating comprises, by weight, 3 parts of aluminum oxide, 2 parts of titanium dioxide, 0.5 part of methyl trioxymethylsilane, 14 parts of modified potassium silicate resin (the addition amount of waterborne epoxy resin is 20% of the total amount of the modified potassium silicate resin), 1 part of a leveling agent, 8 parts of deionized water, 1 part of a hydrophobing agent, 1 part of a wetting dispersant and 0.8 part of a stabilizer; wherein, according to the parts by weight, 2.8 parts of waterborne epoxy resin, 0.2 part of silane coupling agent, 0.5 part of isopropyl ketone, 0.5 part of magnesium oxide, 4 parts of potassium silicate, 4.5 parts of deionized water and 1.5 parts of silica sol, and the modified potassium silicate resin comprises the following steps:
a: slowly adding waterborne epoxy resin, a silane coupling agent and isopropyl ketone into deionized water, and fully stirring to prepare epoxy resin polymer emulsion;
b: adding potassium silicate and silica sol into deionized water, stirring in a water bath at 40 ℃ for 3h at 300r/min, adding magnesium oxide, and stirring until the magnesium oxide is completely dissolved to obtain a mixed binder;
c: and adding a mixed binder into the epoxy resin polymer emulsion, and uniformly ball-milling to prepare the modified potassium silicate resin.
Example 3
A high-water-resistance silicate coating comprises, by weight, 3 parts of aluminum oxide, 2 parts of titanium dioxide, 0.5 part of methyl trioxymethylsilane, 14 parts of modified potassium silicate resin (the addition amount of waterborne epoxy resin is 15% of the total amount of the modified potassium silicate resin), 1 part of a leveling agent, 9 parts of deionized water, 0 part of a hydrophobing agent, 1 part of a wetting dispersant and 0.8 part of a stabilizer; wherein, according to the weight portion, the waterborne epoxy resin is 2.1 portions, the silane coupling agent is 0.5 portion, the isopropyl ketone is 0.5 portion, the magnesium oxide is 0.5 portion, the potassium silicate is 4.5 portions, the deionized water is 4.5 portions, the silica sol is 1.4 portions, and the modified potassium silicate resin comprises the following steps:
a: slowly adding waterborne epoxy resin, a silane coupling agent and isopropyl ketone into deionized water, and fully stirring to prepare epoxy resin polymer emulsion;
b: adding potassium silicate and silica sol into deionized water, stirring in a water bath at 40 ℃ for 3h at 300r/min, adding magnesium oxide, and stirring until the magnesium oxide is completely dissolved to obtain a mixed binder;
c: and adding a mixed binder into the epoxy resin polymer emulsion, and uniformly ball-milling to prepare the modified potassium silicate resin.
Example 4
A high-water-resistance silicate coating comprises, by weight, 6 parts of aluminum oxide, 2 parts of titanium dioxide, 0.5 part of methyl trioxymethylsilane, 16 parts of modified potassium silicate resin (the addition amount of waterborne epoxy resin is 20% of the total amount of the modified potassium silicate resin), 1 part of a leveling agent, 9 parts of deionized water, 1 part of a hydrophobing agent, 1 part of a wetting dispersant and 0.8 part of a stabilizer; wherein, the modified potassium silicate resin comprises 3.2 parts of water-based epoxy resin, 0.5 part of silane coupling agent, 0.5 part of isopropyl ketone, 0.5 part of magnesium oxide, 4.5 parts of potassium silicate, 4.8 parts of deionized water and 2 parts of silica sol by weight:
a: slowly adding waterborne epoxy resin, a silane coupling agent and isopropyl ketone into deionized water, and fully stirring to prepare epoxy resin polymer emulsion;
b: adding potassium silicate and silica sol into deionized water, stirring in a water bath at 40 ℃ for 3h at 300r/min, adding magnesium oxide, and stirring until the magnesium oxide is completely dissolved to obtain a mixed binder;
c: and adding a mixed binder into the epoxy resin polymer emulsion, and uniformly ball-milling to prepare the modified potassium silicate resin.
In conclusion, the modified potassium silicate resin is added in the invention, so that the water resistance of the silicate coating can be improved, and in addition, the wetting dispersant and the stabilizer are used, so that the silicate coating has better adhesive force, the possibility of sedimentation and agglomeration of the silicate coating is reduced, and the comprehensive performance of the silicate coating is improved.

Claims (9)

1.一种高耐水硅酸盐涂料及其制备方法，其特征在于：按重量份计，包括三氧化二铝6-9份、二氧化钛2-4份、甲基三氧甲基硅烷0.5-1.5份、改性硅酸钾树脂10-14份、流平剂0-1.5份、疏水剂0.5-1份、湿润分散剂1-5份、稳定剂0.5-1份、去离子水8-13份。1. a high water-resistant silicate coating and preparation method thereof, is characterized in that: by weight, comprising 6-9 parts of aluminum oxide, 2-4 parts of titanium dioxide, 0.5-1.5 parts of methyltrioxymethylsilane parts, 10-14 parts of modified potassium silicate resin, 0-1.5 parts of leveling agent, 0.5-1 part of hydrophobic agent, 1-5 parts of wetting and dispersing agent, 0.5-1 part of stabilizer, 8-13 parts of deionized water . 2.根据权利要求1所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于：所述改性硅酸钾树脂由水性环氧树脂、硅烷偶联剂、异丙酮、氧化镁、硅酸钾、硅溶胶、去离子水制备而来，步骤为：2. a kind of high water-resistant silicate coating according to claim 1 and preparation method thereof, it is characterized in that: described modified potassium silicate resin is made of water-based epoxy resin, silane coupling agent, isoacetone, magnesium oxide , potassium silicate, silica sol, deionized water, the steps are: a：向去离子水中缓慢加入水性环氧树脂、硅烷偶联剂、异丙酮，充分搅拌，制得环氧树脂聚合物乳液；a: Slowly add water-based epoxy resin, silane coupling agent and isoacetone into deionized water, and stir well to prepare epoxy resin polymer emulsion; b：向去离子水中加入硅酸钾、硅溶胶，用水浴锅进行搅拌，温度为40℃，300r/min搅拌3h，加入氧化镁，搅拌至完全溶解，制得混合粘结剂；b: add potassium silicate and silica sol to deionized water, stir with a water bath, the temperature is 40°C, stir at 300r/min for 3h, add magnesium oxide, stir until completely dissolved, and prepare a mixed binder; c：在环氧树脂聚合物乳液中加入混合粘结剂，球磨均匀，制备成改性硅酸钾树脂。c: adding a mixed binder to the epoxy resin polymer emulsion, and ball milling uniformly to prepare a modified potassium silicate resin. 3.根据权利要求1所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于：所述三氧化二铝粒径为100±20nm；所述二氧化钛为金红石型，粒径为200±10nm。3. a kind of high water-resistant silicate coating according to claim 1 and preparation method thereof, it is characterized in that: the particle diameter of described Al2O3 is 100±20nm; Described titanium dioxide is rutile type, and particle diameter is 200 nm ±10nm. 4.根据权利要求1所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于：所述分散剂选用六偏磷酸钠；所述流平剂选用BYK-333；所述疏水剂选用含氟丙烯酸树脂；稳定剂选用无机硅酸盐稳定剂。4. a kind of high water-resistant silicate coating according to claim 1 and preparation method thereof, it is characterized in that: described dispersing agent selects sodium hexametaphosphate; described leveling agent selects BYK-333; Select fluorine-containing acrylic resin; stabilizer select inorganic silicate stabilizer. 5.根据权利要求2所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于：所述硅酸钾的模数为3.5；所述硅溶胶为碱性硅溶胶，固含量为30％。5. a kind of high water-resistant silicate coating according to claim 2 and preparation method thereof, is characterized in that: the modulus of described potassium silicate is 3.5; Described silica sol is alkaline silica sol, and solid content is 30%. 6.根据权利要求2所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于：所述水性环氧树脂的添加量为改性硅酸钾树脂总量的15％-25％。6. a kind of high water-resistant silicate coating according to claim 2 and its preparation method, it is characterized in that: the addition amount of described water-based epoxy resin is 15%-25% of the total amount of modified potassium silicate resin . 7.根据权利要求2所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于：所述氧化镁的粒径800-1200目。7 . The highly water-resistant silicate coating according to claim 2 and the preparation method thereof, wherein the particle size of the magnesium oxide is 800-1200 meshes. 8 . 8.根据权利要求2所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于：所述硅烷偶联剂选用KH-560。8 . The highly water-resistant silicate coating according to claim 2 and the preparation method thereof, characterized in that: the silane coupling agent is selected from KH-560. 9.根据权利要求1所述的一种高耐水硅酸盐涂料及其制备方法，其特征在于，还涉及一种制备方法，其步骤如下：9. a kind of high water-resistant silicate paint and preparation method thereof according to claim 1, is characterized in that, also relates to a kind of preparation method, and its steps are as follows: (1)将二氧化钛、三氧化二铝粉末在1100℃真空炉中灼烧1h，一段时间冷却后，在球磨机上球磨混合均匀，制得混合粉末A；(1) Firing the titanium dioxide and aluminum oxide powders in a vacuum furnace at 1100°C for 1 hour, and after cooling for a period of time, ball milling and mixing them on a ball mill to obtain mixed powder A; (2)在去离子水中加入混合粉末A，在搅拌的条件下加入甲基三氧甲基硅烷，混合均匀，制得混合溶液；(2) adding mixed powder A in deionized water, adding methyltrioxymethylsilane under stirring conditions, and mixing evenly to obtain a mixed solution; (3)将混合溶液置于60℃的烘箱中干燥1～2h，常温冷却，制得混合粉末B；(3) drying the mixed solution in an oven at 60°C for 1-2 hours, and cooling at room temperature to obtain mixed powder B; (4)将已经制备好的改性硅酸钾树脂、混合粉末B、助剂、去离子水，进行充分搅拌，球磨均匀后即为涂料。(4) The prepared modified potassium silicate resin, mixed powder B, auxiliary agent and deionized water are fully stirred, and the coating is obtained after ball milling evenly.
CN202110802105.9A 2021-07-15 2021-07-15 High-water-resistance silicate coating and preparation method thereof Pending CN113321952A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113801503A (en) * 2021-09-29 2021-12-17 上海宜瓷龙新材料股份有限公司 Finishing paint with slow-release deodorization function and preparation method thereof
CN114806298A (en) * 2022-04-27 2022-07-29 沈阳化工大学 Preparation method of single-component water-based zinc-rich metal coating with long-term storage stability
CN115894001A (en) * 2023-03-10 2023-04-04 湖南康纳新材料有限公司 High-hardness wear-resistant resin-permeable ceramic composite material and preparation method and application thereof
CN116478597A (en) * 2023-04-28 2023-07-25 佛山市谭龙建材有限公司 Composite antibacterial plate and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113801503A (en) * 2021-09-29 2021-12-17 上海宜瓷龙新材料股份有限公司 Finishing paint with slow-release deodorization function and preparation method thereof
CN114806298A (en) * 2022-04-27 2022-07-29 沈阳化工大学 Preparation method of single-component water-based zinc-rich metal coating with long-term storage stability
CN115894001A (en) * 2023-03-10 2023-04-04 湖南康纳新材料有限公司 High-hardness wear-resistant resin-permeable ceramic composite material and preparation method and application thereof
CN116478597A (en) * 2023-04-28 2023-07-25 佛山市谭龙建材有限公司 Composite antibacterial plate and preparation method thereof
CN116478597B (en) * 2023-04-28 2024-02-13 佛山市谭龙建材有限公司 Composite antibacterial plate and preparation method thereof

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