免燒仿釉塗料及其製備方法和應用Non-burning imitation glaze coating and preparation method and application thereof
【01】 本發明涉及瓷釉塗料技術領域，特別揭露一種免燒仿釉塗料及其製備方法和應用。[01] The present invention relates to the field of enamel coating technology, and particularly discloses a burn-free imitation glaze coating and a preparation method and application thereof.
【02】 陶瓷釉是附著在陶瓷坯體表面的一種矽酸鹽玻璃質薄層，陶瓷器上所施的釉一般以石英、長石、黏土為原料，經研磨、加水調製後，塗敷於坯體表面，經一定溫度的焙燒而熔融，溫度下降時，形成陶瓷表面的玻璃質薄層。它使陶瓷器增加機械強度、熱穩定性、介電強度和防止液體、氣體的侵蝕。釉還有增加瓷器美觀和便於洗拭、不被塵土黏染等作用。我們日常使用的陶瓷器，一般都穿著一身光潤、平滑的衣裳，特別是日用陶瓷，對“衣裳”更為講究，有的潔白如玉，有的五彩繽紛，十分美觀。陶瓷的這種衣裳，名叫“釉”。陶瓷釉按製備方法分類，有生料釉、熔塊釉；按釉的組成分類，有石灰釉、長石釉、鉛釉、硼釉、熔鹽釉、土釉等；按坯體類型分類，有硬瓷釉、軟瓷釉、陶釉；按燒成溫度分類，有易熔釉（1100℃以下）、中溫釉（1100～1250℃）和高溫釉（1250℃以上）；按釉面外觀分類，有透明釉、乳濁釉、結昌釉、碎紋釉等。生產中常用的分類法是前兩種，它可直接反映出釉的製備方法和性能。 【03】 施釉工藝是古陶瓷器製作工藝技術的一種，是指在成型的陶瓷坯體表面施以釉漿。主要有蘸釉、蕩釉、澆釉、刷釉、灑釉、輪釉等六種方法，按坯體的不同形狀、厚薄，採用相應的施釉方法。因為施釉工藝是古陶瓷器製作工藝技術的一種，施釉工藝較為複雜，而且基本都需要高溫煆燒，造成環境污染，不僅費事而且大量耗能。 【04】 近些年，仿釉塗料得到了深入的研究。中國專利第CN104231816A號揭露了一種仿釉塗料及其製備方法，含有如下重量份數的組分：聚合物乳液500~600，奈米氧化鋯50~150，該仿釉塗料解決了以往塗料特性的單一性，顯著從抗劃傷性能、耐高溫性能、耐老化性能方面得到提高，而且該塗料具有絕佳的外觀仿釉效果，提高了塗覆產品的檔次。中國專利第CN105176284A號一種水性仿釉塗料及製備方法，所述水性仿釉塗料中物料組分A的物料及重量配比分別是：丙烯酸丁酯90份、甲基丙烯酸甲酯45份、過硫酸銨1.3份、聚乙二醇辛基苯基醚2.2份、丙烯酸-甲基丙烯酸共聚物銨鹽1.1份、水210份。物料組分B的物料及重量配比分別是：水乳型成膜物80份、金紅石型鈦白粉7.5份、六偏磷酸鈉0.8份、乙二醇丁醚6.2份、水61份。本發明適用於建築內、外牆及屋頂瓦面裝飾的水性仿釉塗料，具有表面平整光滑，光澤度高，附著力強的特性，具有耐水、耐老化、耐酸堿、耐洗刷、耐污染性強等積極效果，可抗100℃以上的高溫；成本較低。中國專利第CN106905794A號揭露了一種無毒仿釉塗料配方，其原料組成為：聚羧酸甜菜堿：25‑30份；丙磺酸：3‑5份；白炭黑：5‑10份；氫氧化鈉：0.8‑1.2份；螢光增白劑：0.7‑1份；去離子水：500‑600份；輕質碳酸鈣：40‑50份；灰鈣粉：250‑280份；防黴劑：0.08‑0.12份；合成樹脂乳液：10‑15份；防腐劑：0.8‑1.2份；耐沾汙劑：0.5‑1.5份；滑石粉：38‑45份；甲醛：15‑20份；黏度穩定劑：0.5‑1份；上述份數均為品質份數。上述的無毒仿釉塗料配方，耐擦洗，成本低，可保持牆面的平整光亮。但是，上述專利技術產品在耐候性、可清潔性方面並非得到特別的關注和研究。[02] Ceramic glaze is a thin layer of bismuth silicate which adheres to the surface of ceramic body. The glaze applied on ceramics is usually made of quartz, feldspar and clay. After grinding and adding water, it is applied to the slab. The surface of the body is melted by firing at a certain temperature, and when the temperature is lowered, a thin glass layer of the ceramic surface is formed. It increases the mechanical strength, thermal stability, dielectric strength and corrosion of liquids and gases. The glaze also has the effect of increasing the appearance of the porcelain and facilitating the washing and not being stained by the dust. The ceramics we use every day are generally dressed in light and smooth clothes, especially for daily-use ceramics. They are more particular about "clothing", some are white as jade, some are colorful and beautiful. This kind of clothes of ceramics is called "glaze". The ceramic glaze is classified according to the preparation method, and has raw glaze and frit glaze; according to the composition of the glaze, there are lime glaze, feldspar glaze, lead glaze, boron glaze, molten salt glaze, earth glaze, etc.; according to the type of the blank, it is hard. Enamel, soft enamel, pottery glaze; according to firing temperature classification, there are fusible glaze (below 1100 °C), medium temperature glaze (1100~1250 °C) and high temperature glaze (above 1250 °C); classified according to glazed appearance, transparent Glaze, opaque glaze, knot glaze, broken glaze, etc. The classifications commonly used in production are the first two, which directly reflect the preparation method and properties of the glaze. [03] The glazing process is a kind of ancient ceramics manufacturing process technology, which means applying glaze slurry on the surface of the formed ceramic body. There are mainly six methods of enamel glaze, glaze glaze, glaze, brush glaze, sprinkling glaze, wheel glaze, etc. According to the different shapes and thickness of the blank, the corresponding glazing method is adopted. Because the glazing process is one of the ancient ceramics manufacturing process technology, the glazing process is more complicated, and basically requires high temperature smoldering, causing environmental pollution, which is not only troublesome but also consumes a lot of energy. [04] In recent years, imitation glaze coatings have been studied in depth. Chinese Patent No. CN104231816A discloses a glaze-like paint and a preparation method thereof, comprising the following components by weight: polymer emulsion 500-600, nano zirconia 50-150, the glaze coating solves the characteristics of the prior paint. Uniformity, significantly improved from scratch resistance, high temperature resistance, and aging resistance, and the coating has an excellent appearance and glaze effect, which improves the grade of the coated product. Chinese Patent No. CN105176284A, an aqueous imitation glaze coating and a preparation method thereof, wherein the material and weight ratio of material component A in the aqueous imitation glaze coating are: 90 parts of butyl acrylate, 45 parts of methyl methacrylate, persulfuric acid 1.3 parts of ammonium, 2.2 parts of polyethylene glycol octylphenyl ether, 1.1 parts of an acrylic acid-methacrylic acid copolymer ammonium salt, and 210 parts of water. The material and weight ratio of material component B were: water emulsion type film former 80 parts, rutile type titanium dioxide 7.5 parts, sodium hexametaphosphate 0.8 parts, ethylene glycol butyl ether 6.2 parts, and water 61 parts. The invention is applicable to the water-based imitation glaze paint for interior, exterior wall and roof tile decoration of buildings, has the characteristics of smooth surface, high gloss and strong adhesion, and has water resistance, aging resistance, acid resistance, washing resistance and pollution resistance. Strong positive effect, can resist high temperature above 100 °C; lower cost. Chinese Patent No. CN106905794A discloses a non-toxic imitation glaze coating formulation whose raw material composition is: polycarboxylate beet pulp: 25-30 parts; propanesulfonic acid: 3-5 parts; white carbon black: 5-10 parts; Sodium: 0.8-1.2 parts; Fluorescent brightener: 0.7-1 part; Deionized water: 500-600 parts; Light calcium carbonate: 40-50 parts; Gray calcium powder: 250-280 parts; Anti-fungal agent: 0.08‐0.12 parts; synthetic resin emulsion: 10‐15 parts; preservative: 0.8‐1.2 parts; stain resistance: 0.5‐1.5 parts; talcum powder: 38‐45 parts; formaldehyde: 15-20 parts; viscosity stabilizer : 0.5-1 part; the above parts are all quality parts. The above-mentioned non-toxic imitation glaze coating formula is scrub-resistant and low in cost, and can keep the wall surface smooth and bright. However, the above patented products have not received special attention and research in terms of weather resistance and cleanability.
【05】 本發明的目的在於提供一種免燒仿釉塗料，免煆燒即可形成類似釉效果，既可以保證塗層的超高強度、高抗劃傷、高耐磨性，又可以具有優異的戶外耐候性能。 【06】 本發明的另一個目的在於提供一種免燒仿釉塗料的製備方法，其製備技術簡單，易大批量產業化生產，獲得的塗料綜合性能優異。 【07】 本發明的又一個目的在於提供一種免燒仿釉塗料在戶外基礎設施和戶外工藝品中的應用。 【08】 本發明提供一種免燒仿釉塗料，包括如下重量份的組分：有機矽改性丙烯酸樹脂 28-35，聚氨酯有機矽改性丙烯酸樹脂 26-32，矽烷偶聯劑 3-5，奈米顏料3-30，功能性助劑 6-10和混合溶液 10-20。 【09】 較佳的，所述的有機矽改性丙烯酸樹脂是由含有活性基團的聚丙烯酸酚樹脂與含有活性羚基(或烷氧基)的有機矽低聚物反應製成的一類改性樹脂，較佳地為中國常州市嘉諾有機矽有限公司的FJNS-4有機矽改性丙烯酸樹脂。它是由含一苯基三乙氧基矽烷和八甲基環四矽氧烷為改性劑與丙烯酸單體或中間體在催化劑作用下接枝反應合成的改性丙烯酸樹脂，使得有機矽改性丙烯酸樹脂產生三維網狀交聯結構，可以明顯提高塗層的耐候性、耐高低溫、耐水性、保光性和耐久性等，同時可單組份室溫乾燥。該樹脂在產品體系中起到成膜物的作用。 【010】 較佳的，所述的聚氨酯有機矽改性丙烯酸樹脂是自乾型聚氨酯有機矽改性丙烯酸樹脂，較佳地為中國樅陽縣三金顏料有限責任公司的聚氨酯有機矽改性丙烯酸樹脂SJ-5021。它主要是利用先進的合成技術將聚有機矽氧烷分子中的烷氧基與聚氨酯預聚物中的部分羥基進行酯交換反應合成，不僅明顯提高有機矽的附著力、耐磨性耐油性、耐化學性，而且保持聚氨酯優良的耐候性和機械性，同時具有高度交聯的網狀結構，分子上含有活性基團，藉由預聚物中的-NCO與空氣中的水份反應生成脲鍵常溫交聯固化乾燥成膜，其能保證漆膜的超高硬度。該樹脂在產品體系中起到改性增硬和促進附著力的雙重功效。 【011】 矽烷偶聯劑是一類在分子中同時含有兩種不同化學性質基團的有機矽化合物。本配方中，它可以充當交聯劑，提高樹脂的交聯性，改善樹脂的附著力、耐水柔韌性，能明顯提高塗料的附著力、密著性能，能改善丙烯酸膠乳、密封劑、聚氨酯和環氧樹脂的黏合力，提高塗層柔韌性，防水性、耐磨性、耐擦洗性、耐劃傷性和耐化學品性等，較佳地為美國道康寧公司矽烷偶聯劑Z-6040。 【012】 較佳的，所述的奈米顏料為奈米氧化鋁、奈米鈦白粉、奈米有機中黃或者奈米有機大紅，其對應的重量份配比為奈米氧化鋁 3-5，奈米鈦白粉 26-30，奈米有機中黃 12-16，或者奈米有機大紅 12-16。其中，添加奈米氧化鋁則形成高硬度透明防陶瓷耐磨清漆，添加奈米鈦白粉則形成白色免燒仿釉塗料，添加奈米有機中黃則形成黃色免燒仿釉塗料，添加奈米有機大紅則形成紅色免燒仿釉塗料。 【013】 較佳的，功能性助劑包括消泡劑、流平劑、分散劑、抗汙助劑和抗紫外線助劑的一種或多種。 【014】 更佳的，所述消泡劑為德國迪高公司810消泡劑，該消泡劑為聚醚矽氧烷類消泡劑。所述流平劑為埃夫卡EFKA-3700流平劑，該流平劑是高氟碳含量的聚丙烯酸酯流平劑，具有很強的降表面張力，優異的抗縮孔，良好的底材潤濕和促進立面流平。所述的分散劑是英國的650U分散劑，該分散劑是丙烯酸分散劑，能分散有機無機顏料。所述的抗汙助劑是BYK®-SILCLEAN 3700；所述抗紫外線助劑較佳地為巴斯夫的1130紫外光吸收劑和抗氧化劑292，1130是羥基苯並三唑類液態紫外光吸收劑，292是液體受阻胺類光穩定劑，兩種複配使用，塗層起到非常好的抗紫外光的作用。 【015】 較佳的，所述混合溶劑選自水溶性醇類溶劑、水溶性醚類溶劑中的多種的混合物。所述水溶性醇類溶劑為正丁醇、異丁醇、乙醇等；所述水溶性醚類溶劑可以為二丙二醇二甲醚、二乙二醇丁醚、二丙二醇丁醚等。選用的溶劑為可以溶於水的水溶性溶劑，該類溶劑比有機溶劑苯、甲苯、二甲苯更加環保，對人體無毒害作用，對環境不會造成污染，具有很高的環保性。 【016】 更佳的，混合溶劑為正丁醇、二丙二醇二甲醚的混合物，品質比為1:1至1:2。正丁醇在塗料中起到了穩定劑的作用，防止塗料膠化，延長塗料儲存時間，二丙二醇二甲醚起到溶解和調整油漆乾燥時間，降低表面張力，幫助成膜的作用。 【017】 本發明還提供上述免燒仿釉塗料的製備方法，當添加的奈米顏料無需研磨時，其步驟為：將有機矽改性丙烯酸樹脂、聚氨酯改性有機矽樹脂、部分混合溶劑、功能性助劑混合、進行攪拌均勻，最後用剩餘的混合溶劑調節黏度、過濾；當添加的奈米顏料需要研磨時，其步驟為：將有機矽改性丙烯酸樹脂、聚氨酯改性有機矽樹脂、奈米顏料、部分混合溶劑、功能性助劑混合、進行攪拌均勻，轉至研磨工序利用砂磨機進行研磨分散至細度符合要求，最後用剩餘的混合溶劑調節黏度、過濾。 【018】 本發明的免燒仿釉塗料利用潮固化自然乾燥，形成超高硬度的塗膜，潮氣固化的主要原理是產品中的主要成膜物—預聚物中的-NCO反應活性很大，可以與空氣中的水份作用反應生成脲鍵而常溫交聯固化乾燥成膜，產品要在適當的溫度和濕度下進行乾燥。溫度在25-27℃，濕度在75-80%最為適合。必要的時候在地面灑水或噴水，以提高室內濕度，從而促使塗膜潮固化乾燥。該技術成本低廉、能耗小且操作簡單，不需要高溫煆燒和高溫烘烤，屬於高節能、高環保產品，適合工業化生產。 【019】 本發明提供上述免燒仿釉塗料在戶外基礎設施和戶外工藝品中的應用。 【020】 本發明的免燒仿釉塗料可以直接與環氧防銹底漆、電泳底漆、粉末塗料、丙烯酸漆等防銹漆或各類底面漆搭配形成完整塗裝，可以應用於城市道路兩旁的電線杆、防護欄杆、路燈杆、交通信號燈、配電櫃、垃圾桶等需要高硬度、高耐候要求的戶外基礎設施，如花盆、花台、椅凳、動物雕像等戶外工藝品。 【021】 本發明的有益效果有： 【022】 1、本發明免燒仿釉塗料不僅施工技術簡單，而且免煆燒潮固化自然乾燥48小時即可形成類似釉的效果，大大減少了為燒制釉而消耗的能源；同時該塗料製備方法簡易，成本較低，施工方式也簡易，利用率高，避免造成浪費，節約了生產和施工成本。 【023】 2、有機矽改性丙烯酸樹脂和自乾型聚氨酯有機矽改性丙烯酸樹脂複配精緻而成的仿釉塗料，經潮固化自然乾燥後形成漆膜，成膜塗層具有：a、高硬度，固化成膜後塗層表面硬度可達到9H（三菱鉛筆）；b、耐高低溫，能耐500℃以上高溫和-40℃低溫並且塗層不脆化；c、高耐磨性，具有超高耐磨性，耐磨性可與陶瓷相媲美；d、具有良好的附著力，在各種底材上的附著力可以達到0級；e、耐候性極好，特別適合戶外具有防水防潮、抗紫外線要求的基材上使用，正常使用30年不老化。 【024】 3、能長時間保持塗膜特性的低表面能，傑出的疏油疏水性和抗塗鴉易清潔性能。 【025】 4、選用的溶劑為可以溶於水的水溶性溶劑，該類溶劑比有機溶劑苯、甲苯、二甲苯更加環保，對人體無毒害作用，對環境不會造成污染，具有很高的環保性。[05] The object of the present invention is to provide a non-burning imitation glaze paint, which can form a similar glaze effect without smoldering, and can ensure the ultra high strength, high scratch resistance, high wear resistance of the coating, and can be excellent. Outdoor weather resistance. [06] Another object of the present invention is to provide a method for preparing a burn-free imitation glaze paint, which has simple preparation technology and is easy to mass-produce industrially, and the obtained coating has excellent comprehensive performance. [07] Still another object of the present invention is to provide an application of a burn-free imitation glaze paint in outdoor infrastructure and outdoor crafts. [08] The present invention provides a burn-free imitation glaze coating comprising the following components by weight: an organic hydrazine-modified acrylic resin 28-35, a polyurethane organic hydrazine-modified acrylic resin 26-32, a decane coupling agent 3-5, Nano pigment 3-30, functional additive 6-10 and mixed solution 10-20. [09] Preferably, the organic hydrazine-modified acrylic resin is a type of modification obtained by reacting a polyacrylic phenol resin containing a reactive group with an organic cerium oligomer containing an active antelope (or alkoxy group). The resin is preferably FJNS-4 organic hydrazine modified acrylic resin of Changzhou Jianuo Organic Co., Ltd., China. It is a modified acrylic resin synthesized by grafting reaction of acrylic acid monomer or intermediate with a monophenyltriethoxydecane and octamethylcyclotetraoxane as a modifier to cause organic tampering. The acrylic resin produces a three-dimensional network cross-linked structure, which can significantly improve the weather resistance, high and low temperature resistance, water resistance, gloss retention and durability of the coating, and can be dried at room temperature in a single component. The resin acts as a film former in the product system. Preferably, the polyurethane organic hydrazine modified acrylic resin is a self-drying polyurethane organic hydrazine modified acrylic resin, preferably a polyurethane organic hydrazine modified acrylic acid of China Shuyang County Sanjin Pigment Co., Ltd. Resin SJ-5021. It mainly uses advanced synthesis technology to synthesize alkoxy groups in polyorganosiloxane molecules with partial hydroxyl groups in polyurethane prepolymers, which not only significantly improves the adhesion, wear resistance and oil resistance of organic germanium. Chemical resistance, and maintain excellent weatherability and mechanical properties of polyurethane, while having a highly crosslinked network structure, containing reactive groups on the molecule, and reacting with -NCO in the prepolymer to form urea in the air. The bond is cured at a normal temperature and dried to form a film, which can ensure the ultra-high hardness of the paint film. The resin plays a dual role of modifying hardening and promoting adhesion in the product system. [011] A decane coupling agent is a class of organic cerium compounds containing two different chemical groups in a molecule. In this formulation, it can act as a crosslinking agent, improve the crosslinkability of the resin, improve the adhesion of the resin, water resistance and flexibility, can significantly improve the adhesion and adhesion of the coating, and can improve the acrylic latex, sealant, polyurethane and The adhesive strength of the epoxy resin improves the flexibility of the coating, water repellency, abrasion resistance, scrub resistance, scratch resistance and chemical resistance, and is preferably the Dow Corning Copolymer Z-6040. [012] Preferably, the nano pigment is nano alumina, nano titanium dioxide, nano organic yellow or nano organic red, and the corresponding weight ratio is nano alumina 3-5 , nano titanium dioxide 26-30, nano organic yellow 12-16, or nano organic red 12-16. Among them, the addition of nano-alumina forms a high-hardness transparent anti-ceramic wear-resistant varnish, and the addition of nano-titanium white powder forms a white non-burning imitation glaze coating, and the addition of nano-organic yellow forms a yellow non-burning glaze coating, adding nano Organic red color forms a red, non-burning glaze paint. Preferably, the functional auxiliary agent comprises one or more of an antifoaming agent, a leveling agent, a dispersing agent, an antifouling auxiliary agent and an anti-UV auxiliary agent. More preferably, the antifoaming agent is a Degas 810 defoamer from Germany, and the defoaming agent is a polyether siloxane defoaming agent. The leveling agent is Evka EFKA-3700 leveling agent, the leveling agent is a high fluorocarbon content polyacrylate leveling agent, has strong surface tension, excellent anti-cratering, good bottom Wetting and promoting the leveling of the facade. The dispersing agent is a 650 U dispersing agent in the United Kingdom, and the dispersing agent is an acrylic dispersing agent capable of dispersing an organic inorganic pigment. The anti-fouling agent is BYK®-SILCLEAN 3700; the anti-UV agent is preferably a 1130 ultraviolet light absorber and an antioxidant 292 of BASF, and 1130 is a hydroxybenzotriazole liquid ultraviolet light absorber. 292 is a liquid hindered amine light stabilizer, which is used in two combinations, and the coating acts very well against ultraviolet light. Preferably, the mixed solvent is selected from the group consisting of water-soluble alcohol solvents and water-soluble ether solvents. The water-soluble alcohol solvent is n-butanol, isobutanol, ethanol or the like; and the water-soluble ether solvent may be dipropylene glycol dimethyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether or the like. The solvent selected is a water-soluble solvent which is soluble in water. The solvent is more environmentally friendly than the organic solvents benzene, toluene and xylene, has no toxic effect on the human body, does not cause pollution to the environment, and has high environmental protection. More preferably, the mixed solvent is a mixture of n-butanol and dipropylene glycol dimethyl ether, and the mass ratio is 1:1 to 1:2. N-butanol acts as a stabilizer in the coating to prevent gelation of the coating and prolong the storage time of the coating. Dipropylene glycol dimethyl ether dissolves and adjusts the drying time of the paint, reduces the surface tension and helps the film formation. [017] The present invention also provides a method for preparing the above-mentioned non-burning glaze paint. When the added nano pigment does not need to be ground, the steps are: organic hydrazine modified acrylic resin, polyurethane modified organic hydrazine resin, partially mixed solvent, The functional additives are mixed and stirred uniformly. Finally, the remaining mixed solvent is used to adjust the viscosity and filtration. When the added nano pigment needs to be ground, the steps are as follows: organic hydrazine modified acrylic resin, polyurethane modified organic resin, The nano pigment, a part of the mixed solvent, and the functional auxiliary are mixed and uniformly stirred, and transferred to a grinding process for grinding and dispersing to a fineness by a sand mill, and finally, the remaining mixed solvent is used to adjust the viscosity and filter. [018] The burn-free imitation glaze paint of the invention is naturally dried by moisture solidification to form an ultra-high hardness coating film, and the main principle of moisture solidification is that the main film-forming material in the product---------- It can react with water in the air to form a urea bond and solidify and solidify at room temperature to form a film. The product should be dried at an appropriate temperature and humidity. The temperature is 25-27 ° C, and the humidity is 75-80%. When necessary, sprinkle water or spray water on the ground to increase the humidity in the room, thus promoting the curing and drying of the coating film. The technology has the advantages of low cost, low energy consumption and simple operation, does not require high temperature simmering and high temperature baking, and is a high energy saving and high environmental protection product, and is suitable for industrial production. The present invention provides the use of the above-mentioned burn-free imitation glaze paint in outdoor infrastructure and outdoor handicrafts. [020] The burn-free imitation glaze paint of the invention can be directly combined with an anti-rust primer such as an epoxy antirust primer, an electrophoretic primer, a powder coating, an acrylic paint or a variety of primers to form a complete coating, which can be applied to cities. Outdoor poles such as flower pots, flower beds, chair stools, animal statues, etc. [021] The beneficial effects of the present invention are as follows: [022] 1. The non-burning imitation glaze coating of the invention not only has simple construction technology, but also forms a glaze-like effect by drying the natural moisture for 48 hours without drying, and greatly reduces the burning effect. The energy consumed by the glaze is simple; the preparation method is simple, the cost is low, the construction method is simple, the utilization rate is high, waste is avoided, and production and construction costs are saved. [023] 2. The organic enamel modified acrylic resin and the self-drying polyurethane organic cerium modified acrylic resin are compounded and exquisitely formed into a glaze coating, which is dried by moisture to form a paint film, and the film-forming coating has: a. High hardness, the surface hardness of the coating can reach 9H (Mitsubishi pencil) after curing film formation; b, high and low temperature resistance, high temperature above 500 °C and low temperature of -40 °C and coating is not embrittled; c, high wear resistance, with Ultra high wear resistance, wear resistance comparable to ceramics; d, good adhesion, adhesion on a variety of substrates can reach 0; e, weather resistance is excellent, especially suitable for outdoor waterproof and moisture, It is used on substrates that are resistant to UV rays and does not age after 30 years of normal use. [024] 3, can maintain the low surface energy of the film characteristics for a long time, outstanding oleophobic hydrophobicity and anti-graffiti easy to clean performance. [025] 4. The selected solvent is a water-soluble solvent which is soluble in water. The solvent is more environmentally friendly than the organic solvents benzene, toluene and xylene, and has no toxic effect on the human body, and does not cause pollution to the environment. Environmentally friendly.
【027】 藉由下述給出的本發明具體實施例和比較實施例可以進一步清楚地瞭解本發明，但它們不是對本發明的限定。具體實施例和比較實施例中沒有詳細敘述的部分是採用現有技術、習知技術手段和行業標準獲得的。 【028】 若未特別指明，實施例中所採用的技術手段為本領域技術人員所熟知的常規手段，所採用的試劑和產品也均為可商業獲得的。所用試劑的來源、商品名以有必要列出其組成成分者，均在首次出現時標明。 【029】 除非另有說明，本發明中所採用的百分數均為重量百分數。 【030】 該發明的具體實施方式中有用到主要的測試方法或儀器如下： 【031】 測塗膜厚：德國進口尼克斯（Qanix8500）測厚儀（膜厚計），適用於測量鋁銅鎂鋅鐵等鐵金屬和非鐵金屬件基材厚度，PosiTector200非金屬數顯測厚儀,適用於測量塑膠底材、木材、混凝土、氧化鎂等基材塗層厚度。 【032】 鉛筆硬度：廣州標哥達實驗室儀器用品有限公司的組合型鉛筆硬度計。 【033】 附著力：廣州標哥達實驗室儀器用品有限公司的漆膜劃格器（百格刀）。 【034】 耐濕熱性：臺灣眾志CZ-A-150D可程式恆溫恆濕試驗機設置溫度濕度並設定測試時間800h耐濕熱測試條件進行測試。 【035】 光澤：廣州標哥達實驗室儀器用品有限公司的智慧三角度光澤儀BGD516進行精密測試。 【036】 色差：美國愛色麗（亞太）有限公司的CI6X分光光度儀進行精密測試。 【037】 耐鹽霧性：廣州標哥達實驗室儀器用品有限公司BGD 881連續式鹽水噴霧鹽霧腐蝕試驗機，設置溫度濕度並設定測試時間800h耐鹽霧測試條件進行測試。 【038】 耐人工氣候老化性：美國Q=LAB公司生產的Q-SUN-XE-3型光穩定性試驗箱設置光波在340nm，輻照度0.51W/m2，光照溫度63℃，濕度在80%進行連續性耐人工氣候老化性測試1200h，後用廣州標哥達實驗室儀器用品有限公司的智慧三角度光澤儀BGD516和美國愛色麗（亞太）有限公司的CI6X分光光度儀進行光澤度和色差變化測試。 【039】 實施例 1
【040】 免燒仿釉的透明清漆，包括以下重量份的各組分：有機矽改性丙烯酸樹脂32.5重量份，聚氨酯改性有機矽樹脂32重量份，矽烷偶聯劑4.5重量份，奈米氧化鋁5.0重量份，功能性助劑 9.5重量份，混合溶劑（正丁醇：二丙二醇二甲醚=1:1）16.5重量份。 【041】 其生產方法，包括以下步驟： 【042】 在配漆罐內投入有機矽改性丙烯酸樹脂、聚氨酯改性有機矽樹脂、混合溶劑、矽烷偶聯劑、分散劑、消泡劑，奈米氧化鋁用攪拌機攪拌均勻，攪拌機的轉速為1000轉每分鐘，攪拌到完全均勻後將功能性助劑中的流平劑、抗汙助劑和抗紫外線助劑依次加入，再次攪拌均勻，攪拌機轉速為800轉每分鐘，再用混合溶劑將黏度調至塗4#杯25±22S（25℃），待檢驗合格後用200目過濾網過濾並包裝。 【043】 其施工方法如下： 【044】 噴塗或滾塗免燒仿釉塗料：打開包裝桶，攪拌均勻即可施工，採用空氣噴塗、輥塗或刷塗。 【045】 實施例 2
【046】 免燒仿釉白色塗料，包括以下重量份的各組分：有機矽改性丙烯酸樹脂 28.3重量份，聚氨酯改性有機矽樹脂 26重量份，矽烷偶聯劑4.0重量份，奈米氧化鋁2.0重量份，奈米二氧化鈦26重量份，功能性助劑 8.5重量份，混合溶劑（正丁醇：二丙二醇二甲醚=1:1）15.9重量份。 【047】 其生產方法，包括以下步驟： 【048】 在配漆罐內投入上半部分有機矽改性丙烯酸樹脂、聚氨酯改性有機矽樹脂、混合溶劑、矽烷偶聯劑、分散劑、消泡劑，奈米氧化鋁，奈米二氧化鈦，用攪拌機攪拌均勻，攪拌機的轉速為1000轉每分鐘，攪拌到完全均勻後用大流量高效率砂磨機研磨至細度≤20um，後將下半部分合成有機矽改性丙烯酸樹脂、聚氨酯改性有機矽樹脂、功能性助劑中的流平劑、抗汙助劑和抗紫外線助劑依次加入，再次攪拌均勻，攪拌機轉速為800轉每分鐘，再用混合溶劑將黏度調至塗4#杯22±2S（25℃），待檢驗合格後用200目過濾網過濾並包裝。 【049】 實施例 3
【050】 免燒仿釉黃色塗料包括以下重量份的各組分：有機矽改性丙烯酸樹脂 29.2重量份，聚氨酯改性有機矽樹脂 26重量份，矽烷偶聯劑4.0重量份，奈米氧化鋁2.2重量份，奈米有機中黃粉12重量份，功能性助劑 8.5重量份，混合溶劑（正丁醇：二丙二醇二甲醚=1:1）14.3重量份。 【051】 其生產方法，包括以下步驟： 【052】 在配漆罐內投入有機矽改性丙烯酸樹脂、聚氨酯改性有機矽樹脂、混合溶劑、矽烷偶聯劑、消泡劑、分散劑，奈米氧化鋁，奈米有機中黃粉，用攪拌機攪拌均勻，攪拌機的轉速為1000轉每分鐘，攪拌到完全均勻後用大流量高效率砂磨機研磨至細度≤20um，後將轉入配漆罐中，再加入下半部分有機矽改性丙烯酸樹脂、聚氨酯改性有機矽樹脂、功能性助劑中的流平劑、抗汙助劑和抗紫外線助劑依次加入，再次攪拌均勻，攪拌機轉速為800轉每分鐘，再用混合溶劑將黏度調至塗4#杯22±2S（25℃），待檢驗合格後用200目過濾網過濾並包裝。 【053】 對比例 1
【054】 普通陶瓷烤漆包括以下重量份的各組分：熱固性丙烯酸樹脂33重量份，混合溶劑（正丁醇：二甲苯=1:1）13重量份，潤濕分散劑1重量份，消泡劑0.3重量份，鐵紅粉20重量份，填料11重量份，防沉劑0.4重量份，氨基樹脂（582-2）14重量份，飽和聚酯樹脂6重量份，流平劑0.4重量份，抗紫外線助劑0.4重量份。 【055】 其生產方法，包括以下步驟： 【056】 在配漆罐內投入熱固性丙烯酸樹脂、混合溶劑、防沉劑、潤濕分散劑、消泡劑、金紅石型鈦白粉、填料後，用攪拌機攪拌均勻，攪拌機的轉速為1000轉每分鐘，攪拌到完全均勻後將其研磨至細度≤20um，研磨細度合格後，轉入配漆罐中，再加入氨基樹脂、飽和聚酯樹脂、流平劑、抗紫外線助劑、降溫劑，再次攪拌均勻，攪拌機轉速為800轉每分鐘，再用混合溶劑將黏度調至塗4#杯22±2S（25℃），待檢驗合格後用200目過濾網過濾並包裝。 【057】 對上述各個實施例和對比例的免燒仿釉塗料進行測試，得到的性能測試結果如圖1所示。 【058】 以上所揭露的僅為本發明的較佳地實施例而已，當然不能以此來限定本發明之專利範圍，因此依本發明申請專利範圍所作的等同變化，仍屬本發明所涵蓋的範圍。The invention is further clarified by the specific examples and comparative examples of the invention given below, but they are not intended to limit the invention. Portions of the specific embodiments and comparative examples that are not described in detail are obtained using prior art, conventional techniques, and industry standards. Unless otherwise specified, the technical means employed in the examples are conventional means well known to those skilled in the art, and the reagents and products employed are also commercially available. The source and trade name of the reagents used are listed on the first appearance when they are necessary to list their constituents. [029] The percentages used in the present invention are by weight unless otherwise indicated. [030] The main test methods or instruments used in the specific embodiment of the invention are as follows: [031] Film thickness: German imported Knicks (Qanix 8500) thickness gauge (film thickness gauge), suitable for measuring aluminum copper magnesium The thickness of ferrous and non-ferrous metal parts such as zinc and iron, PosiTector 200 non-metallic digital thickness gauge, suitable for measuring the thickness of substrate coatings such as plastic substrates, wood, concrete and magnesium oxide. [032] Pencil Hardness: The combined pencil hardness tester of Guangzhou Gotthard Laboratory Instrument Co., Ltd. [033] Adhesion: Guangzhou film Gotthard Laboratory Instrument Co., Ltd. paint film cross-cutting device (Hundred Grid knife). [034] Moisture and heat resistance: Taiwan Zhongzhi CZ-A-150D programmable constant temperature and humidity tester set temperature and humidity and set test time 800h humidity and heat test conditions for testing. [035] Gloss: Guangzhou Gotthard Laboratory Instrument Co., Ltd.'s intelligent three-angle gloss meter BGD516 for precision testing. [036] Chromatic aberration: Precision testing by CI6X spectrophotometer from X-Rite (Asia Pacific) Co., Ltd. [037] Salt spray resistance: Guangzhou Borgda Laboratory Equipment Co., Ltd. BGD 881 continuous salt spray salt spray corrosion test machine, set the temperature and humidity and set the test time 800h salt spray test conditions for testing. [038] Artificial weathering resistance: Q-SUN-XE-3 light stability test chamber produced by Q=LAB Company of USA set light wave at 340nm, irradiance 0.51W/m2, illumination temperature 63°C, humidity at 80% Conducted continuous artificial weathering resistance test for 1200h, and then used the wisdom three-angle gloss meter BGD516 of Guangzhou Standard Gotthard Laboratory Instrument Co., Ltd. and CI6X spectrophotometer of American X-Rite (Asia Pacific) Co., Ltd. for gloss and color difference. Change test. [039] Example 1 [040] A clear varnish free of glaze, comprising the following components by weight: 32.5 parts by weight of an organic cerium-modified acrylic resin, 32 parts by weight of a urethane-modified organic cerium resin, a decane coupling agent 4.5 parts by weight, 5.0 parts by weight of nano alumina, 9.5 parts by weight of a functional auxiliary, and 16.5 parts by weight of a mixed solvent (n-butanol: dipropylene glycol dimethyl ether = 1:1). [041] The production method comprises the following steps: [042] Injecting an organic hydrazine-modified acrylic resin, a urethane-modified organic hydrazine resin, a mixed solvent, a decane coupling agent, a dispersing agent, an antifoaming agent, and a naphtha in a paint tank The rice alumina is stirred evenly with a mixer, the rotation speed of the mixer is 1000 rpm, and after stirring until completely uniform, the leveling agent, anti-fouling agent and anti-UV agent in the functional additive are sequentially added, and the mixture is stirred again, the mixer is stirred. The rotation speed was 800 rpm, and the viscosity was adjusted to 4# cup 25±22S (25°C) with a mixed solvent. After passing the test, it was filtered and packaged with a 200 mesh filter. [043] The construction method is as follows: [044] Spray or roll-on non-burning imitation glaze paint: Open the drum and mix it evenly to apply it, using air spray, roller or brush. [045] Example 2 [046] A non-burning glaze white paint comprising the following components by weight: 28.3 parts by weight of an organic hydrazine-modified acrylic resin, 26 parts by weight of a urethane-modified organic hydrazine resin, a decane coupling agent 4.0 Parts by weight, 2.0 parts by weight of nano alumina, 26 parts by weight of nano titanium dioxide, 8.5 parts by weight of a functional auxiliary, and 15.9 parts by weight of a mixed solvent (n-butanol: dipropylene glycol dimethyl ether = 1:1). [047] The production method comprises the following steps: [048] The upper part of the organic hydrazine-modified acrylic resin, the urethane-modified organic hydrazine resin, the mixed solvent, the decane coupling agent, the dispersing agent, and the defoaming are put into the paint tank. Agent, nano alumina, nano titanium dioxide, stir evenly with a mixer, the speed of the mixer is 1000 rpm, stir until completely uniform, then grind to a fineness ≤ 20um with a large flow high efficiency sander, then the lower half Synthetic organic hydrazine modified acrylic resin, polyurethane modified organic hydrazine resin, leveling agent in functional auxiliaries, anti-fouling auxiliaries and anti-UV auxiliaries are sequentially added, stirred again, and the speed of the mixer is 800 rpm, and then The viscosity was adjusted to 4# cup 22±2S (25 ° C) with a mixed solvent, and after passing the test, it was filtered and packaged with a 200 mesh filter. [049] Example 3 [050] The burn-free imitation glaze yellow paint comprises the following components by weight: 29.2 parts by weight of an organic cerium-modified acrylic resin, 26 parts by weight of a urethane-modified organic cerium resin, and a decane coupling agent of 4.0 weight. The fraction was 2.2 parts by weight of nano alumina, 12 parts by weight of yellow powder in nano organic, 8.5 parts by weight of a functional auxiliary, and 14.3 parts by weight of a mixed solvent (n-butanol: dipropylene glycol dimethyl ether = 1:1). [051] The production method comprises the following steps: [052] Into the paint tank, an organic hydrazine-modified acrylic resin, a urethane-modified organic hydrazine resin, a mixed solvent, a decane coupling agent, an antifoaming agent, a dispersing agent, Rice alumina, nano-organic yellow powder, stir evenly with a mixer, the speed of the mixer is 1000 rpm, stir until completely uniform, and then grind to a fineness ≤ 20um with a large flow high-efficiency sander, then transfer to the distribution In the paint can, the lower half of the organic hydrazine-modified acrylic resin, the urethane-modified organic hydrazine resin, the leveling agent in the functional auxiliaries, the anti-fouling auxiliaries and the anti-UV auxiliaries are sequentially added, and the mixture is stirred again, the mixer is stirred. The rotation speed was 800 rpm, and the viscosity was adjusted to 4# cup 22±2S (25° C.) with a mixed solvent. After passing the test, it was filtered and packaged with a 200 mesh filter. [053] Comparative Example 1 [054] Ordinary ceramic baking varnish comprises the following components by weight: 33 parts by weight of thermosetting acrylic resin, 13 parts by weight of mixed solvent (n-butanol: xylene = 1:1), wetting and dispersing agent 1 part by weight, antifoaming agent 0.3 parts by weight, iron red powder 20 parts by weight, filler 11 parts by weight, anti-settling agent 0.4 parts by weight, amino resin (582-2) 14 parts by weight, saturated polyester resin 6 parts by weight, leveling 0.4 parts by weight of the agent and 0.4 parts by weight of the ultraviolet-resistant auxiliary agent. [055] The production method comprises the following steps: [056] After putting a thermosetting acrylic resin, a mixed solvent, an anti-settling agent, a wetting and dispersing agent, a defoaming agent, a rutile titanium dioxide, and a filler in a paint can, Stir the mixer evenly, the speed of the mixer is 1000 rpm, stir it until it is completely uniform, then grind it to a fineness ≤ 20um. After passing the fineness, transfer it to the paint tank, then add amino resin, saturated polyester resin, Leveling agent, anti-UV additive, cooling agent, stir again, the speed of the mixer is 800 rpm, and then adjust the viscosity to 4# cup 22±2S (25°C) with mixed solvent. After passing the test, use 200. The filter is filtered and packaged. [057] The fire-free imitation glaze paints of the above respective examples and comparative examples were tested, and the obtained performance test results are shown in FIG. The above disclosure is only a preferred embodiment of the present invention, and of course, the scope of the present invention is not limited thereto, and thus equivalent changes made by the scope of the present invention remain covered by the present invention. range.
無no
【026】 圖1示出本發明之免燒仿釉塗料的性能測試結果。Fig. 1 shows the results of performance test of the burn-free imitation glaze paint of the present invention.