阅读说明：本技术 一种玻璃涂料及其制备方法 (Glass coating and preparation method thereof ) 是由 马晓英 贾继霞 张晓菊 杨鉴政 于 2020-06-09 设计创作，主要内容包括：本发明公开一种玻璃涂料,由以下重量份数的原料制成：丙烯酸复合乳液65-70份、填料4-7份、玉米醇溶蛋白0.1-0.2份、纳米陶瓷纤维0.3-0.5份、硫酸钙晶须0.3-0.5份、氨丙基三乙氧基硅烷0.6-1份、偏硼酸钡0.2-0.6份、纳米二氧化钛1-2份、碳酸锶0.2-0.5份、去离子水10-15份、乙二醇1-2份、消泡剂0.5-1份、分散剂2-3份；该涂料通过改进配方以及制备工艺,形成的涂膜与基材的附着力高,硬度高,且耐磨耐酸碱,性能优异。(The invention discloses a glass coating which is prepared from the following raw materials in parts by weight: 65-70 parts of acrylic acid composite emulsion, 4-7 parts of filler, 0.1-0.2 part of zein, 0.3-0.5 part of nano ceramic fiber, 0.3-0.5 part of calcium sulfate whisker, 0.6-1 part of aminopropyl triethoxysilane, 0.2-0.6 part of barium metaborate, 1-2 parts of nano titanium dioxide, 0.2-0.5 part of strontium carbonate, 10-15 parts of deionized water, 1-2 parts of ethylene glycol, 0.5-1 part of defoamer and 2-3 parts of dispersant; by improving the formula and the preparation process, the coating formed by the coating has high adhesion with a base material, high hardness, wear resistance, acid and alkali resistance and excellent performance.)

1. A glass coating is characterized in that: the feed is prepared from the following raw materials in parts by weight: 65-70 parts of acrylic acid composite emulsion, 4-7 parts of filler, 0.1-0.2 part of zein, 0.3-0.5 part of nano ceramic fiber, 0.3-0.5 part of calcium sulfate whisker, 0.6-1 part of aminopropyl triethoxysilane, 0.2-0.6 part of barium metaborate, 1-2 parts of nano titanium dioxide, 0.2-0.5 part of strontium carbonate, 10-15 parts of deionized water, 1-2 parts of ethylene glycol, 0.5-1 part of defoaming agent and 2-3 parts of dispersing agent.

2. A glass coating according to claim 1, characterized in that: the dispersant is stearic acid monoglyceride and sodium dodecyl sulfate according to a weight ratio of 1-2: 1 are mixed.

3. A glass coating according to claim 1, characterized in that: the filler is organic bentonite and mica powder according to the weight ratio of 1-2: 1, mixing and modifying;

the specific modification method comprises the following steps:

1) dissolving stearic acid in 75% ethanol with 3-4 times volume fraction to obtain mixed solution;

2) soaking the organobentonite and mica powder in 2-3 times of 12% hydrochloric acid solution, acidifying for 1-2h, deionizing and washing to neutrality, mixing with the mixed solution, ball milling for 1-2h, and drying at 50-60 deg.C to obtain the final product; the weight ratio of the total amount of the organic bentonite and the mica powder to the stearic acid is 10: 0.5-0.8.

4. A glass coating according to claim 1, characterized in that: the strontium carbonate is coated strontium carbonate, and the specific preparation method comprises the following steps:

dispersing strontium carbonate in ethanol with the weight volume fraction of 7-8 times of that of 75%, then adding ammonia water to adjust the pH to 8-9, adding tetraethoxysilane, stirring to react for 3-4h, washing the product with deionized water, and drying at 50 ℃ to obtain the product;

the mol ratio of the strontium carbonate to the ethyl orthosilicate is 1: 2.

5. a glass coating according to claim 1, characterized in that: the preparation method of the acrylic acid composite emulsion comprises the following steps:

(1) stirring and mixing polyether glycol, pentanediol and N, N-dimethylethanolamine under a nitrogen environment, heating to 80-85 ℃, adding diphenylmethane diisocyanate and 2-3 drops of dibutyltin dilaurate, and stirring to react for 3-4 hours;

(2) then adding aminopropyltriethoxysilane for reaction for 1h, then adding styrene, butyl acrylate and hydroxyethyl methacrylate, stirring for reaction for 1-2h, cooling to room temperature, adding acetic acid, stirring for 0.5h, then adding deionized water, stirring for emulsification for 1h, continuing heating to 80-85 ℃, and then adding an azo initiator for reaction for 2-3h to obtain an acrylic acid composite emulsion;

the weight ratio of the polyether glycol, the diphenylmethane diisocyanate, the pentanediol, the N, N-dimethylethanolamine, the styrene, the butyl acrylate, the hydroxyethyl methacrylate, the aminopropyltriethoxysilane, the azo initiator and the acetic acid is as follows: 5.2-5.36: 7.2-7.3: 0.15: 1.65: 5.01: 10: 0.27: 0.2: 0.15: 0.8.

6. a method for preparing the glass coating according to claim 1, characterized in that: the method comprises the following steps:

(1) mixing the acrylic acid composite emulsion, deionized water and ethylene glycol, adding into a dispersion kettle, and stirring at high speed for 5-8 min;

(2) adding defoaming agent and dispersant, stirring for 5-8min, adding the rest components, stirring for 20-30min to form a mixed solution, and grinding in a grinder until the fineness is less than 18 μm to obtain the final product.

7. The method for preparing a glass coating according to claim 6, wherein: and (3) fully stirring and mixing the nano ceramic fibers, the calcium sulfate whiskers and the aminopropyltriethoxysilane in the step (2) and then mixing and stirring the mixture with other components.

Technical Field

The invention relates to the technical field of glass paint, in particular to glass paint and a preparation method thereof.

Background

The glass material is a commonly used material for decoration, packaging and the like, and the glass surface coating can not only protect glass products and increase the strength, hardness, heat resistance, corrosion resistance and other properties of the glass products, but also beautify the glass products and increase the aesthetic property of the glass products. The common wine bottles in daily life are generally glass bottles, along with the higher living standard of people, the appearance of the wine bottles is more and more emphasized, and the requirements on the coating film on the surfaces of the wine bottles are higher and higher, such as the requirements on good decoration, weather resistance, adhesiveness, high temperature resistance and the like, low toxicity, environmental protection, high hardness and long service life are required; the prior art improves the formulation of glass coatings in order to improve their performance.

Chinese patent document (application No. 2015100677238) discloses a method for preparing organosilane acrylic polyurethane, and the organosilane acrylic polyurethane is used as a matrix resin for a boiling-resistant ultraviolet-curable glass paint. The method comprises the steps of firstly, reacting diisocyanate with hydroxy acrylate to prepare a prepolymer containing a carbon-carbon double bond single-ended end, and then reacting the prepolymer containing the carbon-carbon double bond single-ended end with metered polyether diol and an amino-containing silane coupling agent in two steps to prepare the organosilane acrylic polyurethane. The polyurethane is used as matrix resin, and is prepared into glass paint with adhesion promoters, diluents and photoinitiators under the action of ultraviolet light, so that the glass paint has relatively high surface hardness and extremely low shrinkage; after boiling for 2 hours at 100 ℃, the paint film does not foam and fall off, and the adhesion of the hundred-grid knife test is excellent. The matrix resin in the patent is organosilane acrylic polyurethane, the specific preparation method is complex and tedious in process, and diisocyanate and acrylic hydroxyl ester form carbon-carbon prepolymer which is then reacted with metered polyether diol and amino-containing silane coupling agent in two steps to form mainly linear polymer, and the mechanical property of the formed paint film is poorer than that of the paint film formed by network polymer. Chinese patent document (application No. 2016102733699) discloses a nano indium modified transparent heat-insulating nano glass coating which is prepared from the following raw materials in parts by weight: 20-21 parts of nano antimony tin oxide, 0.3-0.3 part of dispersing agent SN-50400.2, 79-81 parts of waterborne polyurethane resin, 30-35 parts of deionized water, 40-50 parts of N, N' -dimethylformamide, 20-22 parts of 20% sulfuric acid solution, 20-22 parts of perfluorooctanoic acid, 3-4 parts of methyl methacrylate, 0.1-0.2 part of potassium persulfate, 3-3.5 parts of isocyanate, 0.7-0.9 part of nano indium, 0.4-0.6 part of 10-undecylenic acid and 0.4-0.6 part of ferrocenecarboxaldehyde. The invention discloses a method for improving the compatibility of nano indium and resin by mixing and modifying auxiliary materials of nano indium, 10-undecylenic acid and ferrocene formaldehyde in a formula, so that the nano indium is dispersed more uniformly, and the mechanical property of the coating is improved. However, the auxiliary materials in the formula are simply improved, the improvement effect on the adhesive force of the paint film is not obvious, and the factors such as the adhesive force, the hardness and the heat resistance of the paint film need to be comprehensively considered.

Disclosure of Invention

In view of the above, the present invention aims to provide a glass coating, which is formed by improving a formula and a preparation process, and has the advantages of high adhesion between a coating film and a substrate, high hardness, wear resistance, acid and alkali resistance, impact resistance, and excellent performance.

In order to achieve the purpose, the invention adopts the following technical scheme:

the glass coating is prepared from the following raw materials in parts by weight: 65-70 parts of acrylic acid composite emulsion, 4-7 parts of filler, 0.1-0.2 part of zein, 0.3-0.5 part of nano ceramic fiber, 0.3-0.5 part of calcium sulfate whisker, 0.6-1 part of aminopropyl triethoxysilane, 0.2-0.6 part of barium metaborate, 1-2 parts of nano titanium dioxide, 0.2-0.5 part of strontium carbonate, 10-15 parts of deionized water, 1-2 parts of ethylene glycol, 0.5-1 part of defoaming agent and 2-3 parts of dispersing agent.

Further, the dispersant is stearic acid monoglyceride and sodium dodecyl sulfate according to a weight ratio of 1-2: 1 are mixed.

Further, the filler is organic bentonite and mica powder in a weight ratio of 1-2: 1, mixing and modifying;

the specific modification method comprises the following steps:

1) dissolving stearic acid in 75% ethanol with 3-4 times volume fraction to obtain mixed solution;

2) soaking the organobentonite and mica powder in 2-3 times of 12% hydrochloric acid solution, acidifying for 1-2h, deionizing and washing to neutrality, mixing with the mixed solution, ball milling for 1-2h, and drying at 50-60 deg.C to obtain the final product; the weight ratio of the total amount of the organic bentonite and the mica powder to the stearic acid is 10: 0.5-0.8.

Further, the strontium carbonate is coated strontium carbonate, and the specific preparation method comprises the following steps:

dispersing strontium carbonate in ethanol with the weight volume fraction of 7-8 times of that of 75%, then adding ammonia water to adjust the pH to 8-9, adding tetraethoxysilane, stirring to react for 3-4h, washing the product with deionized water, and drying at 50 ℃ to obtain the product;

the mol ratio of the strontium carbonate to the ethyl orthosilicate is 1: 2.

further, the preparation method of the acrylic composite emulsion comprises the following steps:

(1) stirring and mixing polyether glycol, pentanediol and N, N-dimethylethanolamine under a nitrogen environment, heating to 80-85 ℃, adding diphenylmethane diisocyanate and 2-3 drops of dibutyltin dilaurate, and stirring to react for 3-4 hours;

(2) then adding aminopropyltriethoxysilane for reaction for 1h, then adding styrene, butyl acrylate and hydroxyethyl methacrylate, stirring for reaction for 1-2h, cooling to room temperature, adding acetic acid, stirring for 0.5h, then adding deionized water, stirring for emulsification for 1h, continuing heating to 80-85 ℃, and then adding an azo initiator for reaction for 2-3h to obtain an acrylic acid composite emulsion;

the weight ratio of the polyether glycol, the diphenylmethane diisocyanate, the pentanediol, the N, N-dimethylethanolamine, the styrene, the butyl acrylate, the hydroxyethyl methacrylate, the aminopropyltriethoxysilane, the azo initiator and the acetic acid is as follows: 5.2-5.36: 7.2-7.3: 0.15: 1.65: 5.01: 10: 0.27: 0.2: 0.15: 0.8.

a preparation method of a glass coating comprises the following steps:

(1) mixing the acrylic acid composite emulsion, deionized water and ethylene glycol, adding into a dispersion kettle, and stirring at high speed for 5-8 min;

(2) adding defoaming agent and dispersant, stirring for 5-8min, adding the rest components, stirring for 20-30min to form a mixed solution, and grinding in a grinder until the fineness is less than 18 μm to obtain the final product.

Further, the nano ceramic fiber, the calcium sulfate whisker and the aminopropyltriethoxysilane in the step (2) are fully stirred and mixed, and then are mixed and stirred with other components.

The invention has the beneficial effects that:

1. the invention discloses a glass coating, which is prepared by improving a formula, improving both matrix resin and an additive component of the coating, and fully considering the factors of the adhesion, heat resistance, hardness, mechanical property and the like of a coating film.

2. The matrix resin adopted in the application is acrylic acid composite emulsion, namely acrylic acid/polyurethane/organosilicon composite emulsion, and as the acrylic acid resin has the characteristics of corrosion resistance, acid and alkali resistance, water resistance, good film forming property, no pollution and the like, but the acrylic acid resin has insufficient heat resistance, low hardness, low mechanical strength, poor solvent resistance and the like, and the polyurethane has strong adhesion with a substrate, and is wear-resistant and solvent-resistant, the acrylic acid resin and the polyurethane are copolymerized to prepare the composite emulsion, so that the performances of wear resistance, heat resistance, solvent resistance and the like of a coating film can be greatly improved; and siloxane is introduced into a polymer chain, so that the adhesive force of the coating to the surface of the glass can be improved, the water resistance of the coating layer and the intersolubility with other inorganic materials are improved, and the comprehensive performance of the coating is improved.

Therefore, the specific preparation method of the acrylic composite emulsion in the application is as follows: firstly, reacting-NCO of diphenylmethane diisocyanate with hydroxyl in alcohol to form-NCO-terminated prepolymer, then reacting with aminopropyltriethoxysilane and hydroxyethyl methacrylate, reacting one end with the aminopropyltriethoxysilane to form a silicon-oxygen bond, and reacting the other end with the hydroxyethyl methacrylate to form a carbon-carbon double bond, and initiating butyl acrylate and hydroxyethyl methacrylate monomers to perform free radical polymerization reaction with the carbon-carbon double bond under the action of an initiator to form interpenetrating network type high-molecular composite emulsion.

3. The coating is also added with a filler, wherein the main components of the filler are organic bentonite and mica powder, and the filler is formed by modification; the organic bentonite has higher viscosity, strong plasticity and good film forming property, and the mica powder has better elasticity and toughness, and can be mixed and added into the coating to adjust the viscosity of the coating, increase the stability of the coating and the binding force with a glass substrate, and also increase the toughness and high temperature resistance of the coating. In addition, in order to improve the binding force between the organic bentonite, the mica powder and the high molecular resin, the surface of the organic bentonite, the mica powder and the high molecular resin is coated by stearic acid, and the stearic acid has a hydrophilic end and a lipophilic end simultaneously, so that the binding force between the filler and the base material can be greatly improved, and the mechanical property and the thermodynamic property of the coating are improved.

4. The coating is also added with nano ceramic fibers and calcium sulfate whiskers, the ceramic fibers have the advantages of light weight, high temperature resistance, good thermal stability, low thermal conductivity, small specific heat, mechanical shock resistance and the like, and the calcium sulfate whiskers have high strength, high toughness, wear resistance and corrosion resistance; the two components are added into the coating, so that the advantages of the two components can be integrated, the dispersibility of the two different materials in a polymer matrix is different, the aggregation and sedimentation can be reduced, the ceramic fibers and the calcium sulfate whiskers are uniformly dispersed in a polymer network structure and can be used as structural binders of organic materials and inorganic materials, and the mechanical property of the coating is integrally enhanced; in order to increase the dispersibility of the modified epoxy resin in resin, the modified epoxy resin can be mixed with aminopropyltriethoxysilane in advance when preparing a coating, so that the bonding force between the modified epoxy resin and the resin is improved.

5. In addition, barium metaborate and nano titanium dioxide are added into the coating, so that the coating can be used as a reinforcing agent on one hand and can enhance the antibacterial effect of the coating on the other hand; while a small amount of strontium carbonate can improve the stability of the emulsion and the stability, hardness and solvent resistance of the paint film, strontium carbonate is also subjected to surface treatment in order to increase the compatibility of the strontium carbonate with the resin. In addition, the coating is also added with zein, and a small amount of zein can improve the film forming property of the resin when being dispersed in a base material.

6. In addition, transparent red pigment, yellow pigment, black pigment and the like can be added according to the requirements in the process of preparing the coating, so that glass coatings with different colors can be prepared.

Detailed Description

The invention is further described below with reference to specific embodiments.