WO2021196736A1 - 耐沸水煮水性玻璃涂覆料及其制备方法 - Google Patents

耐沸水煮水性玻璃涂覆料及其制备方法 Download PDF

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WO2021196736A1
WO2021196736A1 PCT/CN2020/136222 CN2020136222W WO2021196736A1 WO 2021196736 A1 WO2021196736 A1 WO 2021196736A1 CN 2020136222 W CN2020136222 W CN 2020136222W WO 2021196736 A1 WO2021196736 A1 WO 2021196736A1
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water
boiling
component
stirring
resistant
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PCT/CN2020/136222
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English (en)
French (fr)
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张涛
花魁昌
汪小峰
徐宏
赵奔
欧阳旭频
鲁斌
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苏州市贝特利高分子材料股份有限公司
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Publication of WO2021196736A1 publication Critical patent/WO2021196736A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C09D7/80—Processes for incorporating ingredients
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to coating technology, and in particular relates to a boiling water-resistant glass coating material and a preparation method thereof.
  • Glass coatings are widely used in cosmetic glass bottles, wine bottles, gift decoration bottles, etc. in daily life. They play the role of beautiful decoration, covering glass defects or protecting glass from scratches. When using these glass products, they will The surface coating of glass products is in direct contact. With people's awareness of environmental protection, health and safety, the requirements for surface coating of glass products are becoming increasingly strict. At present, according to incomplete statistics of the market, 70-80% of glass coatings are water-based paints, of which 80-90% are water-soluble glass paints, the rest are water-based dispersion glass paints, and water-based dispersion glass paints.
  • the proportion of water dilution for construction is 100 :0-10, the dilution ratio is smaller, the cost is higher, and the brightness and vividness of the dried coating are slightly worse, and it is rarely used in the market at present;
  • water-based glass coatings use water as the solvent, which is different from traditional oil-based glass coatings ,
  • the paint itself has a low odor, and the organic solvent evaporates less during baking, which will not cause physical harm to the user; because water is the solvent, the cost is lower and it is safe and environmentally friendly, which can bring cost and environmental advantages to the enterprise.
  • the existing water-based glass coatings have several shortcomings and deficiencies: 1 Whether it is water-soluble glass coating or water-based dispersion glass coating, the coating is not water-resistant after drying, or the water-resistant is only normal temperature, when it is soaked in boiling water at 100°C for boiling After testing for 0.5H, the paint film will fall off, wrinkle and swell, or the 100 grid test 0B-4B does not meet the requirements of 5B.
  • the coating of glass products will often contact boiling water, resulting in damage to the surface coating; especially , After adding sky blue color concentrate (1%-20%), after the coating is dried, the coating is soaked in boiling water at 100°C for 0.5H and then tested for adhesion.
  • the invention discloses a boiling water-resistant water-based glass coating material and a preparation method and application thereof.
  • the main component of a water-soluble glass coating is a water-soluble epoxy modified acrylic resin matched with a water-based amino resin, and then neutralized with an ammonia alkaline solvent. , Dilute with deionized water, add 1-3wt% silane coupling agent and color paste; when the water-soluble glass coating of the present invention is made into a finished product, it can be used directly, or color paste or color concentrate can be added as needed, according to different color requirements Blending ratio.
  • the invention discloses a boiling water-resistant water-based glass coating material, which is composed of a mixture of component A, component B, water, and colorant; said component A is composed of water-soluble epoxy modified acrylic resin, water-based amino resin, It is composed of amine neutralizer, water-based wetting agent, water-based defoamer, co-solvent, and deionized water; the B component is a silane coupling agent; and the colorant is a color paste or a color concentrate.
  • the invention discloses a method for preparing a boiling water-resistant water-based glass coating material, which comprises the following steps: mixing component A with component B, water, and colorant to obtain a boiling water-resistant water-based glass coating material;
  • the components are composed of a water-soluble epoxy-modified acrylic resin, a water-based amino resin, an amine neutralizer, a water-based wetting agent, a water-based defoamer, a co-solvent, and deionized water;
  • the B component is a silane coupling agent.
  • the invention discloses the application of the above-mentioned boiling water-resistant water-boiling glass coating material in preparing a boiling water-resistant water-boiling glass coating, and the boiling water-resistant glass coating is a color paint coating.
  • the boiling water-resistant glass coating is a color paint coating.
  • mixing A component and B component with water and colorant to obtain boiling water resistant glass coating material; then coating the boiling water resistant glass coating material on the glass, and drying to obtain boiling water resistant glass Coating;
  • the A component is composed of a water-soluble epoxy-modified acrylic resin, a water-based amino resin, an amine neutralizer, a water-based wetting agent, a water-based defoamer, a co-solvent, and deionized water;
  • the B component It is a silane coupling agent;
  • the colorant is a color paste or a color concentrate.
  • the present invention it is a conventional technology to coat the boiling water-resistant water-based glass coating material on the glass, and the existing coating method can be used, such as the spraying method.
  • the area of spraying application leads to the problem that the production capacity is too low and cannot meet the market demand.
  • the public paint blending paint can be sprayed on a large area, and the VOC in the actual spraying application is less than 200g/L, which meets the national environmental protection coating standards and is different The matching of co-solvents is reasonable.
  • the coating After drying, the coating has no orange peel, high gloss, and bright color. It only needs to be dried at 150°C for 20 minutes to cure to obtain the coating, especially when it is immersed in boiling water at 100°C for 2 hours. The film will not fall off or wrinkle or swell, and the 100 grid test meets the requirements of 5B.
  • component A based on 100 parts by mass of component A, water-soluble epoxy-modified acrylic resin, water-based amino resin, amine neutralizer, water-based wetting agent, water-based defoamer, cosolvent, deionized water
  • the mass parts are respectively 30-50 parts, 6-15 parts, 0.4-8 parts, 0.2-0.5 parts, 0.2-0.5 parts, 5-10 parts, and the remainder.
  • the water-soluble epoxy-modified acrylic resin The mass parts of, water-based amino resin, amine neutralizer, water-based wetting agent, water-based defoamer, co-solvent, and deionized water are 35-45, 8-12, 2-5, 0.3-0.4, respectively Parts, 0.3-0.4 parts, 6-8 parts, balance; the amount of component B is 1-3% of the mass of component A.
  • the above water-soluble epoxy-modified acrylic resins, water-based amino resins, amine neutralizers, water-based wetting agents, water-based defoamers, co-solvents, and deionized water are all conventional commercially available products.
  • the mass ratio of the A component, the B component, water and the coloring agent is 100:1-3:20-30:1-20.
  • the paint of the present invention can be added with color paste or color essence, both of which have good color development and vividness. After the coating is dried, it can be boiled for 2 hours without exception, and especially solves the problem of adding sky blue color essence to the existing water-based glass paint on the market. There is no problem of adhesion and intolerance to boiling water.
  • a component, B component, water or A component, B component, water, and colorant are mixed by stirring and dispersing to prepare boiling water-resistant glass coating material; preferably, the stirring rate is 800-1000 rpm and the time is 3-5 minutes.
  • the water-soluble epoxy-modified acrylic resin is one or more of ETERAC 7228-1-B-55, Longwood New Material CM-1060, and HOMAAC 5202. They all use a small amount of Or a large amount of methyl methacrylate and then a large molecular weight water-soluble resin synthesized through an external epoxy group. It has excellent adhesion on the glass substrate. According to the different characteristics of these resins, the appropriate ratio is matched.
  • the use can improve the performance of boiling water immersion resistance to 100°C for 2 hours, and at the same time, it can also take into account high gloss, high fullness, good flexibility, high hardness, and excellent recoatability; no matter the varnish or the color with added color paste or color precision Lacquer, including sky blue color concentrate.
  • After the coating is baked at 150°C*20min, cool for 30min, and do a boiling test at 100°C for 2h. The surface of the coating maintains the gloss, fullness and transparency before the boiling test.
  • the appearance of the coating There is no phenomenon of shedding, wrinkling or swelling when cooling, and the 100 grid test is performed after cooling, and the result is 5B; the water-soluble resin of the present invention can withstand boiling water up to the performance standard of 2h after being combined with the auxiliary agent, and it can be cured at 150°C*20min. There is no need to add a drier or a cooling agent, thus solving the problems that the prior art coating is not resistant to boiling and the curing temperature is high.
  • the water-based amino resin used in the present invention is methyl etherified high imino melamine water-based amino resin, specifically one of Changchun Chemical MR-625, MR-627, Allnex CYMEL-325, CYMEL-327, and CYMEL-385 Or several, good solubility in water, reducing the amount of co-solvents used, reducing the VOC content, and can effectively crosslink with the hydroxyl and carboxyl functional groups in the main resin, without the need to add additional acid catalysts, and have high reactivity Reactivity, under the temperature conditions of 100-150 °C, can obtain effective curing, and has a high self-condensation tendency, so the coating has very good gloss, boiling water resistance.
  • the amine neutralizer used in the present invention is Deqian DMEA, AMP-95, one or more of ammonia water, and the components of Deqian DMEA and AMP-95 are dimethylethanolamine or alcohol amine organics, which can neutralize The role of water-soluble resin, the resin is excellent in water dilution; in addition, it can also provide excellent storage stability for the resin.
  • the water-based wetting agent used in the present invention is one or more of BYK-346, BYK-333, Evonik Tego 270, Tego KH 245, and the wetting agent used in the present invention has a relatively low molecular weight. It has high wetting activity; its function makes the coating film wet the glass substrate better and spreads the coating more evenly on the surface of the glass material. The glass material is relatively well wetted, which can reduce the amount of wetting agent. Usage amount.
  • the water-based defoaming agent used in the present invention is one or more of BYK-028, BYK-022, Evonik Tego810, Deqian DAPRO DF 677, and its main components are mineral oil, wax and organic Silicon has a good effect of eliminating microbubbles and breaking bubbles in coatings; since the baking temperature of water-based glass coatings is greater than 100°C, it is easy to produce microbubbles on the coating surface during baking, especially in thick coating. Micro bubbles are generated on the surface of the coating, and the use of water-based defoamers avoids the defects of microbubbles in the coating film during the construction process and during the baking after the construction.
  • the co-solvent used in the present invention is one or more of ethanol, isopropanol, ethylene glycol butyl ether, and propylene glycol monomethyl ether; their characteristics can be co-volatile and compatible with water, making the coating surface Drying is faster, it is not easy to produce micro-bubble defects during baking, and at the same time, the water-soluble resin has better color development; the amount of co-solvent used in the coating formulation is ⁇ 15wt%, and the VOC ⁇ 200g/L in the spray application meets the environmental protection coating standard ; When the mass ratio of ethanol, isopropanol, ethylene glycol butyl ether, and propylene glycol monomethyl ether is: 5-20:5-30:20-40:5-30, the co-solvent has an effect on the water-soluble resin used in the present invention It has the best solubility.
  • the content of co-solvent used at this time is the lowest. After drying, the coating is smooth, high-gloss, and bright in color. The reasonable use of co-solvents reduces the VOC content while increasing the co-volatility with water. Improve the efficiency of large-area spraying, increase productivity, and make the coating less likely to produce defects, especially the mixing ability of the components, the reaction effect, and the adhesion of the coating.
  • the deionized water used in the present invention removes cations such as sodium, calcium, iron and the like and anions such as chlorine and bromine, which greatly improves the storage stability of the coating.
  • the silane coupling agent used in the present invention is: one or more of KH-560, FD-560A, MP200, SCA-E87M; its component is epoxy modified polysiloxane, which has good epoxy reaction Active, improve the mechanical properties of water-soluble resin, such as: bending strength, impact strength, etc., prevent the coating from being too brittle, easy to fall off and not impact resistant; at the same time, it greatly improves the adhesion between the resin and the glass material, and it is resistant to boiling and boiling. Resistance to cold water immersion and other properties.
  • the preparation method of the boiling water-resistant water-based glass coating material of the present invention includes the following steps. After stirring and dispersing the water-soluble epoxy-modified acrylic resin for the first time, an amine neutralizer is added; Antifoaming agent, then add water-based wetting agent after stirring and dispersing, adding deionized water after stirring and dispersing, and finally adding water-based amino resin after stirring and dispersing, and stirring evenly to obtain component A; , The coloring agent is mixed to obtain the boiling water-resistant glass coating material.
  • the mixing is stirring and dispersing, and the stirring parameters are conventional techniques, which are not limited in the present invention.
  • the stirring rate for first stirring and dispersing is 600-800 rpm and the time is 2-3 minutes
  • the stirring rate for re-stirring and dispersing is 600-800 rpm and the time is 3-5 minutes
  • the stirring rate for continuing to stir and disperse is 600-800 rpm.
  • 800rpm the time is 3-5 minutes
  • the stirring rate of stirring and dispersing is 1000-1200rpm
  • the time is 15-20 minutes
  • the stirring rate of continuous stirring and dispersing is 800-1000rpm
  • the time is 3-5 minutes
  • the final stirring and dispersing is stirring
  • the speed is 600-800rpm and the time is 2-3 minutes
  • the stirring speed for uniform stirring is 600-800rpm and the time is 5-10 minutes.
  • the feeding sequence and process parameters can make the water-soluble resin better dissolve in water and reduce the use of co-solvents.
  • the additives can be dispersed more uniformly and stably in the coating system to ensure product quality.
  • the water-based glass coating of the present invention adopts a unique epoxy-modified water-soluble acrylic resin, and is reasonably matched with water-based amino resin, which can greatly improve the boiling water resistance of the coating, regardless of whether any color paste or color is added. Fine. After the coating is dried, it can be immersed in boiling water at 100°C for 2 hours. The surface coating will not fall off, wrinkle and swell, and maintain the original luster.
  • the 100 grid test 5B greatly improves the use environment of glass products;
  • the water-based glass coating of the present invention can be completely dried at 150°C*20min without adding a drier or cooling agent, which reduces energy consumption and costs;
  • the water-based glass coating of the present invention has fewer raw materials, simple manufacturing process, and reasonable matching to reduce the content of co-solvents, and does not affect the gloss, color, surface smoothness, etc. of the coating after drying.
  • the paint of the present invention can be added with any color paste or color essence, and has good color development and vividness; after the coating is dried, it can be boiled for 2 hours without exception, and especially solves the problem of common water-based glass coatings on the market after adding sky blue color essence. Adhesion and intolerance to boiling water.
  • Figure 1 is a photo of Example 2 after the adhesion test of the boiling water-resistant water-based glass coating (marked 1) and the commercially available water-based glass coating (marked 2);
  • Figure 2 is a photograph of the boiling water resistant water-based glass coating (note 1), the commercially available water-based glass coating (note 2), and the commercially available water-based glass dispersion layer (note 3) after the adhesion test after boiling water resistance in Example 1. .
  • the preparation method of the boiling water-resistant water-based glass coating material disclosed in the present invention is as follows: component A is mixed with component B, water, and colorant to obtain boiling water-resistant water-based glass coating material; Epoxy modified acrylic resin, water-based amino resin, amine neutralizer, water-based wetting agent, water-based defoaming agent, co-solvent, and deionized water; the B component is a silane coupling agent.
  • the boiling water-resistant water-based glass coating material is coated on the glass by a conventional spraying method, and the boiling water-resistant water-based glass coating is obtained after drying.
  • the raw materials of the present invention are all commercially available products.
  • Example 1 to Example 3 and Comparative Example 1 and Comparative Example 2 respectively A component of water-based glass coating.
  • the A component of the boiling water-resistant water-based glass coating material of the above-mentioned Examples 1 to 3 and the A component of the water-based glass coating of Comparative Example 1 and Comparative Example 2 were respectively stirred and dispersed with the B component, water, and colorant, and mixed Obtain the boiling water-resistant water-based glass coating material, corresponding to the first color paint of the embodiment, the second color paint of the embodiment, the third color paint of the embodiment, the first color paint of the comparative example, and the second color paint of the comparative example; wherein, the colorants are selected as follows.
  • Example 2 Comparative Example 1 uses sky blue color concentrate (Shanghai Jinlian Daily Chemical Technology Co., Ltd.
  • Example 3 Comparative Example 2 uses another color paste (Shanghai Xiyan Chemical Technology Co., Ltd. NW-1457); In all examples, the mass ratio of component A, component B, and water is 100:2:30.
  • the amount of colorant used is based on the mass of A-component 10%. In the color paint of Example 1, the amount of colorant is 20% of the mass of component A.
  • the B component of Example 1, Comparative Example 1, and Comparative Example 2 is KH-560, the B component of Example 2 is FD-560A, and the B component of Example 3 is MP200.
  • the above-mentioned colored paints are respectively coated on the same conventional glass by a conventional spraying method, and after drying treatment at 150°C*20min, a boiling water-resistant glass coating is obtained.
  • the commercially available water-based glass coating (manufacturer: Hangzhou Mingquan New Materials, brand: water-based bright paint) is coated on the same conventional glass by the same conventional spraying method, 170°C*20min, to obtain the commercial water-based glass coating ( With 10% sky blue color essence).
  • the commercially available water-based dispersion (Hangzhou Zeyu Coating Technology Co., Ltd., water-based glass coating) was coated on the same conventional glass by the same conventional spraying method, 170°C*20min, to obtain a commercially available water-based glass dispersion layer (with 10 % Sky blue color essence).
  • Figure 1 is a photograph of the adhesion test of the boiling water-resistant water-based glass coating (marked 1) and the commercially available water-based glass coating (marked 2) in Example 2. It can be seen that the coating of the present invention reaches 5B, and the commercially available coating The layer is 0B.
  • Figure 2 shows the results of the boiling water-resistant water-based glass coating (labeled 1) and the commercially available water-based glass coating (labeled 2) and the commercially available water-based glass dispersion layer (labeled 3) after the adhesion test after boiling water boiling resistance in Example 1. From the photo, it can be seen that the coating of the present invention reaches 5B, and the two commercially available coatings are 0B, and there is a small amount of peeling and a large amount of peeling respectively; Figure 1 and Figure 2 are all blue.
  • the present invention has high flexibility.
  • the user can spray varnish, or add any color paste or color concentrate, especially the most difficult sky blue color concentrate on the market, to bring color to the user It is extremely convenient; and the coating dryness and general performance test after drying at 150°C*20min are consistent or even better with the water-based glass coatings on the market after baking and drying at 170°C*20min, and at the same time.
  • Excellent performance of resistance to boiling water for 2 hours; in terms of storage stability, reasonable use of amine neutralizer and appropriate ratio of co-solvent can stabilize the storage performance of the coating for a long time.
  • the A component can have a minimum of 12
  • the shelf life of three months is three times higher than the three-month shelf life of products on the market.

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Abstract

一种耐沸水煮水性玻璃涂覆料及其制备方法，将水溶性环氧改性丙烯酸树脂首次搅拌分散后加入胺中和剂，再次搅拌分散后加入助溶剂，继续搅拌分散后加入水性消泡剂，接着搅拌分散后加入水性润湿剂，持续搅拌分散后加入去离子水，最后搅拌分散后加入水性氨基树脂，搅拌均匀，得到A组分；将A组分、B组分、水、着色剂混合，得到耐沸水煮水性玻璃涂覆料；所述B组分为硅烷偶联剂。采用这样的加料顺序、工艺参数，可以使水溶性树脂更好的在水中溶解减少助溶剂的使用，同时使各助剂在涂料体系中分散更均匀稳定，保证产品质量。获得的涂料可以添加色浆或色精，都具有很好的展色性和鲜艳性，涂层干燥后耐沸水煮2h无异常，解决了现有水性玻璃涂料添加天蓝色色精后无附着和不耐沸水煮的问题。

Description

耐沸水煮水性玻璃涂覆料及其制备方法 技术领域
本发明属于涂料技术，具体涉及一种耐沸水煮水性玻璃涂覆料及其制备方法。
背景技术
玻璃涂料在日常生活中被广发应用于化妆品玻璃瓶、酒瓶、礼品装饰瓶等上，起到装饰美观、遮盖玻璃本身缺陷或保护玻璃被划伤的作用；在使用这些玻璃制品时，都会与玻璃制品的表面涂层直接接触，随着人们对环保、健康、安全意识的提高，对玻璃制品表面涂层的要求日益严格。目前玻璃涂料据市场不完全统计，70-80％为水性涂料，其中80-90％为水溶性玻璃涂料，其余为水性分散体玻璃涂料，水性分散体玻璃涂料，其施工时用水稀释比例为100:0-10，稀释比例较小，成本更高，且干燥后的涂层亮度和鲜艳度稍差，目前很少被市场使用；水性玻璃涂料是以水为溶剂，区别与传统的油性玻璃涂料，涂料本身气味小，烘烤时有机溶剂挥发少，不会对使用者造成身体伤害；因用水为溶剂，成本更低且安全环保，可以为企业带来成本和环保上的优势。
现有的水性玻璃涂料存在几个缺点和不足：①无论是水溶性玻璃涂料还是水性分散体玻璃涂料干燥后涂层不耐水，或者耐水性仅为常温，当用100℃的沸水浸泡做水煮测试0.5H后，漆膜会脱落、发皱发胀或者百格测试0B-4B，达不到5B要求，而实际中玻璃制品的涂层会经常接触沸水，导致表面涂层受损；尤其是，当添加天蓝色色精(1％-20％)后，涂层干燥后做100℃的沸水浸泡水煮0.5H后测试附着，结果为0B，对使用者造成极大的困扰；②现有的水性分散体玻璃涂料由于成分中的分散体树脂和助溶剂混溶性不好，及易出现分散体树脂与助溶剂和水发生分层现象，导致存储过程中涂料容易变质且施工喷涂不均匀，所以助溶剂含量添加很少或者不添加，在实际应用中很难大面积进行喷涂应用，导致产能过低，无法满足市场需求；③现有的大部分水溶性玻璃涂料助溶剂添加过多，导致实际喷涂应用中VOC＞200g/L，超过国家环保涂料的标准，且因不同助溶剂搭配不合理，干燥后涂层会有橘皮和光泽不高、色彩不够鲜艳的现象；④目前市场上的水性玻璃涂料大多数需要最低170-180℃烘烤，且部分还需要添加催干剂或降温剂，提升了能源消耗和增加了成本。
发明内容
本发明公开了一种耐沸水煮水性玻璃涂覆料及其制备方法与应用，水溶性玻璃涂料主要成分为水溶性环氧改性丙烯酸树脂搭配水性氨基树脂，再用氨类碱性溶剂中和后，用去离子水稀释，添加1-3wt％的硅烷偶联剂以及色浆；本发明水溶性玻璃涂料做成成品时可以直接使用还可以根据需要加入色浆或色精，根据不同的颜色要求调配比。
本发明公开了一种耐沸水煮水性玻璃涂覆料，由A组分、B组分、水、着色剂混合组成；所述A组分由水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水组成；所述B组分为硅烷偶联剂；所述着色剂为色浆或者色精。
本发明公开了一种耐沸水煮水性玻璃涂覆料的制备方法，包括以下步骤，将A组分与B组分、水、着色剂混合，得到耐沸水煮水性玻璃涂覆料；所述A组分由水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水组成；所述B组分为硅烷偶联剂。
本发明公开了上述耐沸水煮水性玻璃涂覆料在制备耐沸水煮水性玻璃涂层中的应用，耐沸水煮水性玻璃涂层为色漆涂层。比如，将A组分、B组分与水、着色剂混合得到耐沸水煮水性玻璃涂覆料；然后将耐沸水煮水性玻璃涂覆料涂覆在玻璃上，干燥后得到耐沸水煮水性玻璃涂层；所述A组分由水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水组成；所述B组分为硅烷偶联剂；所述着色剂为色浆或者色精。本发明将耐沸水煮水性玻璃涂覆料涂覆在玻璃上为常规技术，采用现有涂料涂覆方法即可，比如喷涂的方法，但是本发明解决了现有技术在实际应用中很难大面积进行喷涂应用导致产能过低、无法满足市场需求的问题，公开的涂料调配的色漆可以大面积进行喷涂应用，而且实际喷涂应用中VOC≤200g/L，符合国家环保涂料的标准，且不同助溶剂搭配合理，干燥后涂层没有橘皮、光泽高、色彩鲜艳，只需要150℃干燥20分钟即可固化得到涂层，尤其是当用100℃的沸水浸泡做水煮测试2h后，漆膜不会脱落或者发皱发胀，百格测试达到5B要求。
本发明中，以A组分质量份数为100份计，水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水的质量份数分别为30-50份、6-15份、0.4-8份、0.2-0.5份、0.2-0.5份、5-10份、余量，优选的，水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水的质量份数分别为35-45份、8-12份、2-5份、0.3-0.4份、0.3-0.4份、6-8份、余量；B组分用量为A组分质量的1-3％。以上水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水都为常规市购产品。
本发明耐沸水煮水性玻璃涂覆料中，A组分、B组分、水、着色剂的质量比为100:1-3:20-30：1-20。本发明的涂料可以添加色浆或色精，都具有很好的展色性和鲜艳性，涂层干燥后耐沸水煮2h无异常，尤其解决了市场上现有水性玻璃涂料添加天蓝色色精后无附着和不耐沸水煮的问题。A组分、B组分、水或者A组分、B组分、水、着色剂通过搅拌分散的方法混合制备耐沸水煮水性玻璃涂覆料；优选的，搅拌速率为800-1000rpm、时间为3-5分钟。
本发明中，水溶性环氧改性丙烯酸树脂为长兴化学ETERAC 7228-1-B-55、长木新材料CM-1060、金团化学HOMAAC 5202中的一种或几种，它们都是用少量或多量的甲基丙烯酸甲酯再通过外接环氧基团合成的大分子量水溶性树脂，在玻璃基材上都具有 优异的附着力，根据这几种树脂的不同特性，经过合适的比列搭配使用可以提升耐100℃的沸水浸泡水煮2h的性能，同时还可以兼顾高光泽、高丰满度、柔韧性好、硬度高、卓越的重涂性；无论清漆还是添加色浆或色精的色漆，包括天蓝色色精，涂层经过150℃*20min烘烤后，冷却30min，做100℃的沸水煮测试2h，涂层外表保持水煮测试之前的光泽、丰满度和透明度，测试涂层外观时没有脱落、发皱发胀的现象，冷却后再进行百格测试，结果为5B；本发明水溶性树脂结合助剂后可以耐沸水煮达到2h性能标准，且150℃*20min即可固化，无需添加催干剂或降温剂，因此解决了现有技术涂层不耐水煮、固化温度高的问题。
本发明使用的水性氨基树脂为甲基醚化高亚氨基三聚氰胺类水性氨基树脂，具体为长春化工MR-625、MR-627，湛新CYMEL-325、CYMEL-327、CYMEL-385中的一种或几种，在水中的溶解性好，减少了助溶剂的使用量，降低了VOC含量，可以与主体树脂中的羟基、羧基官能团有效的交联，不需要添加额外的酸催化剂，具有高反应活性，在100-150℃的温度条件下，均可获得有效的固化，并且具有较高的自缩合倾向，因此使涂层具有非常好的光泽、耐沸水性。
本发明使用的胺中和剂为德谦DMEA、AMP-95，氨水中的一种或几种，德谦DMEA、AMP-95成分为二甲基乙醇胺或醇胺类有机物，可以起到中和水溶性树脂的作用，树脂水稀释性优异；此外还可以为树脂提供优异的存储稳定性。
本发明使用的水性润湿剂为毕克化学BYK-346、BYK-333,赢创迪高Tego 270、Tego KH 245、的一种或几种，本发明所使用的润湿剂分子量较低，具有很高的润湿活性；它的作用使涂膜更好的润湿玻璃基材，让涂料更均匀的铺展在玻璃材质表面，玻璃材质相对而言比较好润湿，可以减少润湿剂的使用量。
本发明使用的水性消泡剂为毕克化学BYK-028、BYK-022，赢创迪高Tego810，德谦DAPRO DF 677中的一种或几种，它的主要成分为矿物油和蜡以及有机硅，在涂料中具有很好的消除微泡和破泡的效果；由于水性玻璃涂料烘烤温度大于100℃，很容易在烘烤时涂层表面产生微小气泡，尤其在厚涂时更容易在涂层表面产生微小气泡，而水性消泡剂的使用避免了施工过程中和施工后烘烤中涂膜产生微泡缺陷。
本发明使用的助溶剂为乙醇、异丙醇、乙二醇丁醚、丙二醇单甲醚中的一种或几种；它们的特性可以与水有共挥发性、相容性，使涂膜表干加快，烘烤时不易产生微泡缺陷，同时使水溶性树脂具有更好的展色性；助溶剂在涂料配方中使用量≤15wt％，在喷涂应用中VOC＜200g/L符合环保涂料标准；当乙醇、异丙醇、乙二醇丁醚、丙二醇单甲醚质量比例为：5-20:5-30：20-40:5-30时，助溶剂对本发明中所使用的水溶性树脂具有最佳的溶解性，此时使用的助溶剂含量最低，且干燥后涂层平整光滑、光泽高、色彩鲜艳，助溶剂的合理搭配使用，降低VOC含量的同时提升与水的共挥发性，提升大面积喷的效率，，提高了产能，涂层不易产生缺陷，尤其是提高了组分的 混合能力，增加反应效果，提升涂层粘接力。
本发明使用的去离子水其去掉了钠、钙、铁等阳离子以及氯、溴等阴离子，对涂料的存储稳定性有较大的提升。
本发明使用的硅烷偶联剂为：KH-560、FD-560A、MP200、SCA-E87M中的一种或几种；它的成分为环氧改性聚硅氧烷，具有良好的环氧反应活性，提高水溶性树脂的力学性能，如：弯曲强度、冲击强度等，防止涂层过脆，容易脱落和不抗冲击；同时极大提升树脂与玻璃材质之间的附着力，耐沸水煮、耐冷水浸泡等性能。
本发明耐沸水煮水性玻璃涂覆料的制备方法包括以下步骤，将水溶性环氧改性丙烯酸树脂首次搅拌分散后加入胺中和剂，再次搅拌分散后加入助溶剂，继续搅拌分散后加入水性消泡剂，接着搅拌分散后加入水性润湿剂，持续搅拌分散后加入去离子水，最后搅拌分散后加入水性氨基树脂，搅拌均匀，得到A组分；将A组分、B组分、水、着色剂混合，得到耐沸水煮水性玻璃涂覆料。其中所述混合为搅拌分散，搅拌参数为常规技术，本发明不做限定。
本发明优选的，首次搅拌分散的搅拌速率为600-800rpm、时间为2-3分钟，再次搅拌分散的搅拌速率为600-800rpm、时间为3-5分钟，继续搅拌分散的搅拌速率为600-800rpm、时间为3-5分钟，接着搅拌分散的搅拌速率为1000-1200rpm、时间为15-20分钟，持续搅拌分散的搅拌速率为800-1000rpm、时间为3-5分钟，最后搅拌分散的搅拌速率为600-800rpm、时间为2-3分钟，搅拌均匀的搅拌速率为600-800rpm、时间为5-10分钟。这样加料顺序、工艺参数，可以使水溶性树脂更好的在水中溶解减少助溶剂的使用，同时使各助剂在涂料体系中分散更均匀稳定，保证产品质量。
1、本发明的水性玻璃涂料采用独特的环氧改性水溶性丙烯酸树脂，再与水性氨基树脂合理搭配比列，可以大幅度提升涂层的耐沸水性能，无论添加任何颜色的色浆或色精，涂层干燥后可以100℃的沸水浸泡做水煮测试2h，表面涂层不会脱落、发皱发胀，且保持原有的光泽，百格测试5B，大大提升玻璃制品的使用环境；
2、本发明的水性玻璃涂料150℃*20min即可完全干燥，不需要添加催干剂或降温剂，降低了能耗，减少了成本；
3、本发明的水性玻璃涂料原物料种类少，制程简单，经过合理搭配减少助溶剂含量使用，且不影响干燥后涂层的光泽、色彩、表面平整度等。本发明涂料可以添加任意色浆或色精，都具有很好的展色性和鲜艳性；涂层干燥后耐沸水煮2h无异常，尤其解决了市场上一般水性玻璃涂料添加天蓝色色精后无附着和不耐沸水煮的问题。
附图说明
图1为实施例二耐沸水煮水性玻璃涂层(标注1)与市售水性玻璃涂层(标注2)附着力测试后的照片；
图2为实施例一耐沸水煮水性玻璃涂层(标注1)与市售水性玻璃涂层(标注2)、市 售水性玻璃分散体层(标注3)耐沸水煮后附着力测试后的照片。
具体实施方式
本发明公开的耐沸水煮水性玻璃涂覆料的制备方法如下，将A组分与B组分、水、着色剂混合，得到耐沸水煮水性玻璃涂覆料；所述A组分由水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水组成；所述B组分为硅烷偶联剂。本发明将耐沸水煮水性玻璃涂覆料采用常规喷涂的方法涂覆在玻璃上，干燥后得到耐沸水煮水性玻璃涂层。本发明原料都是市购产品。
实施例
表1 实施例以及对比例A组分配方，总100份
Figure PCTCN2020136222-appb-000001
Figure PCTCN2020136222-appb-000002
将表1中水溶性环氧改性丙烯酸树脂加入到容器中，并以搅拌速率为800rpm的速度分散2分钟；然后在800rpm搅拌速率下将加入胺中和剂，分散4分钟；然后在600rpm搅拌速率下加入助溶剂，分散4分钟；然后在1000rpm搅拌速率下加入水性消泡剂，分散20分钟；然后在1000rpm搅拌速率下加入水性润湿剂，分散4分钟；然后在700rpm搅拌速率下加入去离子水，分散2分钟；然后在800rpm搅拌速率下加入水性氨基树脂，分散8分钟，分别得到实施例一至实施例三的耐沸水煮水性玻璃涂覆料A组分以及对比例一、对比例二的水性玻璃涂料A组分。
将上述实施例一至实施例三的耐沸水煮水性玻璃涂覆料A组分以及对比例一、对比例二的水性玻璃涂料A组分分别与B组分、水、着色剂常规搅拌分散，混合得到耐沸水煮水性玻璃涂覆料，对应实施例一色漆、实施例二色漆、实施例三色漆、对比例一色漆、对比例二色漆；其中，着色剂选用如下，实施例一、实施例二、对比例一采用天蓝色色精(上海锦连日化科技有限公司RB-61)，实施例三、对比例二采用另一种色浆(上海喜颜化工科技有限公司NW-1457)；所有例子中A组分、B组分、水的质量比为100:2:30，实施例二、对比例一、实施例三、对比例二色漆中，着色剂用量为A组分质量的10％、实施例一色漆中，着色剂用量为A组分质量的20％。实施例一、对比例一、对比例二的B组分为KH-560，实施例二的B组分为FD-560A，实施例三的B组分为MP200。
采用常规的喷涂方法将上述色漆分别涂覆在同样的常规玻璃上，150℃*20min干燥处理后，得到耐沸水煮水性玻璃涂层。将市售水性玻璃涂料(厂家：杭州明泉新材料有些公司，牌号：水性亮光涂料)采用同样的常规喷涂方法覆在同样的常规玻璃上，170℃*20min，得到市售水性玻璃涂层(带有10％天蓝色色精)。将市售水性分散体(杭州泽宇涂料科技有限公司，水性玻璃涂料)采用同样的常规喷涂方法覆在同样的常规玻璃上，170℃*20min，得到市售水性玻璃分散体层(带有10％天蓝色色精)。
表2 水性玻璃涂料性能测试
Figure PCTCN2020136222-appb-000003
Figure PCTCN2020136222-appb-000004
按照表2的方法进行性能测试，结果见表3。
表3 涂层测试结果
Figure PCTCN2020136222-appb-000005
Figure PCTCN2020136222-appb-000006
附图1为实施例二耐沸水煮水性玻璃涂层(标注1)与市售水性玻璃涂层(标注2)附着力测试后的照片，可以看出，本发明涂层达到5B，市售涂层为0B。附图2为实施例一耐沸水煮水性玻璃涂层(标注1)与市售水性玻璃涂层(标注2)、市售水性玻璃分散体层(标注3)耐沸水煮后附着力测试后的照片，可以看出，本发明涂层达到5B，两种市售涂层为0B，且分别存在少量脱落、大量脱落；附图1、附图2都为蓝色。
与现有技术相比，本发明的灵活度高，使用者可以喷涂清漆，也可以添加任意的色浆或色精，尤其是可以添加市场上最难的天蓝色色精，给使用者带来色彩上的极大便利；而且经150℃*20min干燥后的涂层干燥性和一般的性能测试与市面上的水性玻璃涂料经170℃*20min烘烤干燥后保持一致甚至更优，且同时兼具耐沸水煮2h的优异性能；在存储稳定性方面，合理的使用胺中和剂的使用量，同时恰当的搭配助溶剂的比例，可以长时间稳定涂料的存储性能，A组分可以最低具有12个月的保质期，比市场上产品的3个月保质期提升了3倍。

Claims (10)

  1. 一种耐沸水煮水性玻璃涂覆料，其特征在于，由A组分、B组分、水、着色剂混合组成；所述A组分由水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水组成；所述B组分为硅烷偶联剂；所述着色剂为色浆或者色精。
  2. 根据权利要求1所述耐沸水煮水性玻璃涂覆料，其特征在于，所述耐沸水煮水性玻璃涂覆料的制备方法包括以下步骤，将水溶性环氧改性丙烯酸树脂首次搅拌分散后加入胺中和剂，再次搅拌分散后加入助溶剂，继续搅拌分散后加入水性消泡剂，接着搅拌分散后加入水性润湿剂，持续搅拌分散后加入去离子水，最后搅拌分散后加入水性氨基树脂，搅拌均匀，得到A组分；将A组分、B组分、水、着色剂混合，得到耐沸水煮水性玻璃涂覆料。
  3. 根据权利要求1所述耐沸水煮水性玻璃涂覆料，其特征在于，以A组分质量份数为100份计，水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水的质量份数分别为30-50份、6-15份、0.4-8份、0.2-0.5份、0.2-0.5份、5-10份、余量。
  4. 根据权利要求1所述耐沸水煮水性玻璃涂覆料，其特征在于，A组分、B组分、水、着色剂的质量比为100:1-3:20-30：1-20。
  5. 根据权利要求1所述耐沸水煮水性玻璃涂覆料，其特征在于，助溶剂为乙醇、异丙醇、乙二醇丁醚、丙二醇单甲醚中的一种或几种。
  6. 根据权利要求5所述耐沸水煮水性玻璃涂覆料，其特征在于，助溶剂由乙醇、异丙醇、乙二醇丁醚、丙二醇单甲醚组成时；乙醇、异丙醇、乙二醇丁醚、丙二醇单甲醚质量比例为：5-20:5-30：20-40:5-30。
  7. 权利要求1所述耐沸水煮水性玻璃涂覆料的制备方法，其特征在于，包括以下步骤，将水溶性环氧改性丙烯酸树脂首次搅拌分散后加入胺中和剂，再次搅拌分散后加入助溶剂，继续搅拌分散后加入水性消泡剂，接着搅拌分散后加入水性润湿剂，持续搅拌分散后加入去离子水，最后搅拌分散后加入水性氨基树脂，搅拌均匀，得到A组分；将A组分、B组分、水、着色剂混合，得到耐沸水煮水性玻璃涂覆料。
  8. 根据权利要求7所述耐沸水煮水性玻璃涂覆料的制备方法，其特征在于，以A组分质量份数为100份计，水溶性环氧改性丙烯酸树脂、水性氨基树脂、胺中和剂、水性润湿剂、水性消泡剂、助溶剂、去离子水的质量份数分别为30-50份、6-15份、0.4-8份、0.2-0.5份、0.2-0.5份、5-10份、余量；A组分、B组分、水、着色剂的质量比为100:1-3:20- 30：1-20。
  9. 根据权利要求7所述耐沸水煮水性玻璃涂覆料的制备方法，其特征在于，首次搅拌分散的搅拌速率为600-800rpm、时间为2-3分钟，再次搅拌分散的搅拌速率为600-800rpm、时间为3-5分钟，继续搅拌分散的搅拌速率为600-800rpm、时间为3-5分钟，接着搅拌分散的搅拌速率为1000-1200rpm、时间为15-20分钟，持续搅拌分散的搅拌速率为800-1000rpm、时间为3-5分钟，最后搅拌分散的搅拌速率为600-800rpm、时间为2-3分钟，搅拌均匀的搅拌速率为600-800rpm、时间为5-10分钟。
  10. 权利要求1所述耐沸水煮水性玻璃涂覆料在制备耐沸水煮水性玻璃涂层中的应用。
PCT/CN2020/136222 2020-03-30 2020-12-14 耐沸水煮水性玻璃涂覆料及其制备方法 WO2021196736A1 (zh)

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