Water-based environment-friendly glass coating and preparation method thereof

Abstract

The invention discloses a water-based environment-friendly glass coating, which relates to the technical field of glass coatings and is prepared from the following raw materials in parts by weight: 55 to 65 parts of polyurethane-polyacrylate emulsion, 22 to 28 parts of filler, 1 to 2 parts of ethanol, 8 to 12 parts of water, 0.2 to 0.3 part of defoaming agent and 0.1 to 0.15 part of glycerin monostearate. The polyurethane-polyacrylate composite emulsion is adopted, and the filler is subjected to surface modification, so that the adhesive force and the water resistance of the coating are improved, and the comprehensive performance is excellent.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass coating, in particular to a water-based environment-friendly glass coating and a preparation method thereof. BACKGROUND

[0002] The glass coating is suitable for surface decoration of glass wine bottles, decorative glass, household appliance glass, kitchen glass, communication glass and the like. Initially, the glass coating mainly plays a decorative role. However, with the difference of application environment of different glass products, the construction process and performance requirements of the glass coating are diversified. For example, the glass used in the bathroom needs to be in contact with high-temperature water vapor for a long time, and thus requires the glass coating to be water-resistant and high-temperature-resistant. In addition, the glass coating used for glass wine bottles requires a beautiful coating and high hardness.

[0003] At present, the glass coatings on the market are solvent-based and water-soluble. Due to the enhancement of people's environmental protection and health awareness, the application of traditional solvent-based coatings is limited to a certain extent. Compared with solvent-based coatings, water-soluble coatings are more widely used due to the low emission of organic compounds, low odor and low toxicity. However, the main problems of the current water-soluble glass coating are as follows: on the one hand, due to the use of water-based coating, the adhesion of the coating to the glass surface is not good; on the other hand, the water resistance is poor. SUMMARY

[0004] Therefore, the present application aims at the deficiencies of the prior art, and provides a water-based environment-friendly glass coating. The polyurethane-polyacrylate composite emulsion is used, and the filler is subjected to surface modification treatment, so that the adhesion and water resistance of the coating are improved.

[0005] To achieve the above-mentioned purposes, the following technical solutions are adopted in the present application. A water-based environment-friendly glass coating is prepared from the following raw materials in parts by weight: polyurethane-polyacrylate emulsion 55-65 parts, filler 22-28 parts, ethanol 1-2 parts, water 8-12 parts, defoaming agent 0.2-0.3 parts, and glycerol monostearate 0.1-0.15 parts.

[0006] Further, the polyurethane-polyacrylate emulsion is prepared by the following steps: (1) After mixing isophorone diisocyanate and sulfonate polyester polyol, nitrogen is passed, and the mixture is reacted at 70-80℃ for 1h. After cooling to 60-65℃, dimethylol propionic acid, 1, 4-butanediol and dibutyl tin dilaurate are added and reacted for 2h. After cooling to 35℃, triethylamine is added for neutralization, and emulsification is performed for 3-5min to obtain a PU emulsion; (2) mixing PU emulsion, methyl methacrylate, half of butyl acrylate and sodium dodecyl sulfate, stirring and reacting at 80 DEG C in nitrogen environment for 1h, then adding half of azobisisobutyronitrile dropwise, keeping for 1h after dropping, then adding the rest of butyl acrylate and azobisisobutyronitrile dropwise, keeping for 2-3h after dropping, and discharging after cooling to obtain polyurethane-polyacrylate emulsion; The weight ratio of the isophorone diisocyanate, the sulfonic acid type polyester diol, the dimethylol propionic acid, the 1, 4-butanediol, the dibutyl tin dilaurate, the triethylamine, the methyl methacrylate, the butyl acrylate, the azobisisobutyronitrile and the sodium dodecyl sulfate is 30:24-28:2.5:5.5:0.1:2.0-2.2:5-6:8.5:0.1:0.2-0.3.

[0007] Further, in the step (1), after cooling to 60-65 DEG C, the dimethylol propionic acid, the 1, 4-butanediol and the dibutyl tin dilaurate are added and reacted for 2h, then the vinyl versatate is added and the reaction is continued for 1-2h, and the addition amount of the vinyl versatate is 5-6% of the total amount of the isophorone diisocyanate and the sulfonic acid type polyester diol.

[0008] Further, the filler is mixed by the weight ratio of 1.5-2:1 of titanium white powder and nanocellulose.

[0009] Further, the filler is subjected to surface modification treatment, and the surface modification step specifically comprises: (1) dispersing the filler in water, adding sodium dodecyl sulfate and stirring for 12h, and then filtering, washing, drying and grinding to obtain the filler subjected to surface modification. (2) dispersing the SDS-filler in water, adding amino silane, and stirring for 12h, and then filtering, washing, drying and grinding to obtain the filler subjected to surface modification.

[0010] A preparation method of a water-based environment-friendly glass coating, comprising the following steps: mixing and uniformly dispersing polyurethane-polyacrylate emulsion, filler, ethanol and water, adding defoaming agent and glycerol monostearate, uniformly mixing, and discharging to obtain the product.

[0011] The application has the following beneficial effects: 1. The application discloses a water-based environment-friendly glass coating, which adopts polyurethane-polyacrylate composite emulsion, carries out emulsion polymerization of acrylate in the polyurethane, and has high compatibility and excellent comprehensive performance. In the polyurethane, sulfonate polyester polyol is adopted, and a hydrophilic group is provided. When the acrylate emulsion copolymerization is carried out in the polyurethane water dispersion, the hydrophilic chain on the polyurethane is close to the water phase to form a shell, and the hydrophobic polyacrylate is far away from the water phase to form a core, thereby forming a stable core-shell structure, greatly improving the adhesion and water resistance of the coating, and the coating uses less organic solvent, is energy-saving and environment-friendly.

[0012] In addition, during the emulsion polymerization, vinyl versatate is used to further graft modify the shell phase and the core phase, so that the overall crosslinking degree and the polymerization degree of the polymer are improved, and the comprehensive performance of the coating film is further improved.

[0013] 2. In the application, the filler is a titanium white powder and a nanocellulose composite filler. The nanocellulose is added to the titanium white powder, so that the agglomeration of the titanium white powder is reduced, and the dispersibility of the titanium white powder in the coating is increased. In the use process, the filler is modified in two steps. First, a surfactant is used for modification, and then the surfactant is intercalated in the filler. Then, amino silane is used for coating, so that the dispersibility of the filler in the coating is enhanced, and the adhesion between the coating and the glass is improved. DETAILED DESCRIPTION

[0014] The application will be further described in combination with the specific embodiments. In the following examples, the sulfonate polyester polyol is sulfonate polyester diol BY-3303 (molecular weight 1100, hydroxyl value 97 mgKOH / g), and sodium dodecyl sulfate is referred to as SDS. EMBODIMENT

[0015] The water-based environment-friendly glass coating is prepared from the following raw materials in parts by weight: 55 parts of polyurethane-polyacrylate emulsion, 22 parts of filler, 1 part of ethanol, 8 parts of water, 0.2 parts of defoamer BYK028, and 0.1 part of glycerol monostearate.

[0016] The polyurethane-polyacrylate emulsion is prepared by the following steps: (1) After vacuum dehydration, the isophorone diisocyanate and the sulfonate polyester polyol (sulfonate polyester diol) are mixed, nitrogen is passed, and the reaction is carried out at 80℃ for 1h. After cooling to 65℃, dimethylol propionic acid, 1, 4-butanediol and dibutyl tin dilaurate are added, and the reaction is carried out for 2h. Then, vinyl versatate is added, and the reaction is continued for 1-2h. After cooling to 35℃, triethylamine is added for neutralization, and emulsification is carried out for 5min to obtain the PU emulsion. The addition amount of the vinyl versatate is 5% of the total amount of the isophorone diisocyanate and the sulfonate polyester diol. (2) PU emulsion, methyl methacrylate, half of the butyl acrylate and sodium dodecyl sulfate were mixed, stirred at 80℃ for 1h in nitrogen environment, then half of the azobisisobutyronitrile was added dropwise, 1h drop, after dropping, the reaction was kept for 1h, then the remaining butyl acrylate and azobisisobutyronitrile were added dropwise, 1h drop, after dropping, the reaction was kept for 3h, and the temperature was lowered to discharge the polyurethane-polyacrylate emulsion; The weight ratio of isophorone diisocyanate, sulfonate polyester diol, dimethylol propionic acid, 1, 4-butanediol, dibutyl tin dilaurate, triethylamine, methyl methacrylate, butyl acrylate, azobisisobutyronitrile and sodium dodecyl sulfate is 30:24:2.5:5.5:0.1:2:5:8.5:0.1:0.2.

[0017] The filler is titanium white powder and nanocellulose mixed in a weight ratio of 1.5:1.

[0018] The filler is surface modified, and the modification steps are as follows: (1) the filler is dispersed in 10 times the weight of water, SDS is added and stirred for 12h, filtered, washed and dried to obtain SDS-filler, and the weight ratio of the filler and SDS is 2:1; (2) the SDS-filler is dispersed in 10 times the weight of water, amino silane is added, the weight ratio of the SDS-filler and amino silane is 2:0.8, stirring reaction for 12h, then filtering, washing, drying and grinding to obtain the surface modified filler with an average particle size of 100μm.

[0019] A preparation method of a water-based environmentally friendly glass coating, comprising the following steps: mixing and dispersing polyurethane-polyacrylate emulsion, filler, ethanol and water uniformly, adding defoaming agent and glycerol monostearate, mixing uniformly, and discharging the product. Embodiment

[0020] A water-based environmentally friendly glass coating is made from the following raw materials by weight: polyurethane-polyacrylate emulsion 58 parts, filler 24 parts, ethanol 1.2 parts, water 9 parts, defoaming agent BYK028 0.25 parts, glycerol monostearate 0.12 parts.

[0021] The polyurethane-polyacrylate emulsion is prepared by the following steps: (1) isophorone diisocyanate, sulfonate polyester polyol after vacuum dehydration, nitrogen, 80℃ for 1h, cooling to 65℃, then adding dimethylol propionic acid, 1, 4-butanediol and dibutyl tin dilaurate, reaction for 2h, then adding vinyl versatate, continue to react for 1.5h, cool to 35℃, then add triethylamine, emulsify for 5min, get PU emulsion; the addition amount of vinyl versatate is 5.5% of the total amount of isophorone diisocyanate and sulfonate polyester diol; (2) mixing PU emulsion, methyl methacrylate, half of butyl acrylate and sodium dodecyl sulfate, stirring in nitrogen environment, heating to 80℃ for 1h, then adding half of azobisisobutyronitrile dropwise, 1h drop, after dropping, keeping for 1h, then adding the remaining butyl acrylate and azobisisobutyronitrile dropwise, 1h drop, after dropping, keeping for 3h, cooling and discharging to obtain polyurethane-polyacrylate emulsion; The weight ratio of isophorone diisocyanate, sulfonate polyester diol, dimethylol propionic acid, 1, 4-butanediol, dibutyl tin dilaurate, triethylamine, methyl methacrylate, butyl acrylate, azobisisobutyronitrile and sodium dodecyl sulfate is 30:25:2.5:5.5:0.1:2.2:6:8.5:0.1:0.25.

[0022] The filler is titanium white powder and nanocellulose mixed in a weight ratio of 2:1.

[0023] The filler is surface modified, and the surface modification step is specifically as follows: (1) dispersing the filler in water, adding SDS and stirring for 12h, filtering, washing and drying to obtain SDS-filler, and the weight ratio of the filler and SDS is 2:1.5; (2) dispersing the SDS-filler in water, adding amino silane, and the weight ratio of the SDS-filler and amino silane is 2:0.9, stirring for 12h, then filtering, washing, drying and grinding to obtain the surface modified filler.

[0024] A preparation method of a water-based environmentally friendly glass coating, comprising the following steps: mixing and uniformly dispersing polyurethane-polyacrylate emulsion, filler, ethanol and water, adding defoaming agent and glycerol monostearate, uniformly mixing, and discharging to obtain the product. Embodiment

[0025] A water-based environmentally friendly glass coating is prepared from the following raw materials in parts by weight: polyurethane-polyacrylate emulsion 60 parts, filler 25 parts, ethanol 1.5 parts, water 10 parts, defoaming agent BYK028 0.28 parts, and glycerol monostearate 0.14 parts.

[0026] The polyurethane-polyacrylate emulsion is prepared by the following steps: (1) mixing isophorone diisocyanate and sulfonate polyester polyol after vacuum dehydration, passing nitrogen, and reacting at 80℃ for 1h, then cooling to 65℃, adding dimethylol propionic acid, 1, 4-butanediol and dibutyl tin dilaurate, and reacting for 2h, then adding vinyl versatate, continuing to react for 2h, cooling to 35℃, then adding triethylamine for neutralization, and emulsifying for 5min to obtain PU emulsion; the addition amount of vinyl versatate is 6% of the total amount of isophorone diisocyanate and sulfonate polyester diol; (2) mixing PU emulsion, methyl methacrylate, half of butyl acrylate and sodium dodecyl sulfate, stirring in nitrogen environment, heating to 80℃ for 1h, then adding half of azobisisobutyronitrile dropwise, 1h drop, after dropping, keeping for 1h, then adding the remaining butyl acrylate and azobisisobutyronitrile dropwise, 1h drop, after dropping, keeping for 3h, cooling and discharging to obtain polyurethane-polyacrylate emulsion; The weight ratio of isophorone diisocyanate, sulfonate polyester diol, dimethylol propionic acid, 1, 4-butanediol, dibutyl tin dilaurate, triethylamine, methyl methacrylate, butyl acrylate, azobisisobutyronitrile and sodium dodecyl sulfate is 30:28:2.5:5.5:0.1:2.2:6:8.5:0.1:0.3.

[0027] The filler is titanium white powder and nanocellulose mixed in a weight ratio of 1.8:1.

[0028] The filler is surface modified, and the surface modification step is specifically as follows: (1) dispersing the filler in water, adding SDS and stirring for 12h, filtering, washing and drying to obtain SDS-filler, and the weight ratio of the filler and SDS is 2:1; (2) dispersing the SDS-filler in water, adding amino silane, and the weight ratio of the SDS-filler and amino silane is 2:1, stirring for 12h, then filtering, washing, drying and grinding to obtain the surface-modified filler.

[0029] A preparation method of a water-based environmentally friendly glass coating, comprising the following steps: mixing and uniformly dispersing polyurethane-polyacrylate emulsion, filler, ethanol and water, adding defoaming agent and glycerol monostearate, uniformly mixing, and discharging to obtain the product. Embodiment

[0030] A water-based environmentally friendly glass coating is prepared from the following raw materials in parts by weight: polyurethane-polyacrylate emulsion 65 parts, filler 28 parts, ethanol 2 parts, water 12 parts, defoaming agent BYK028 0.3 parts, and glycerol monostearate 0.15 parts.

[0031] The polyurethane-polyacrylate emulsion is prepared by the following steps: (1) mixing isophorone diisocyanate and sulfonate polyester polyol after vacuum dehydration, passing nitrogen, and reacting at 80℃ for 1h, then cooling to 65℃, adding dimethylol propionic acid, 1, 4-butanediol and dibutyl tin dilaurate, and reacting for 2h, then adding vinyl versatate, continuing to react for 2h, cooling to 35℃, then adding triethylamine for neutralization, and emulsifying for 5min to obtain PU emulsion; the addition amount of vinyl versatate is 6% of the total amount of isophorone diisocyanate and sulfonate polyester diol; (2) PU emulsion, methyl methacrylate, half butyl acrylate and sodium dodecyl sulfate were mixed, stirred at 80℃ for 1h in nitrogen environment, then half of azobisisobutyronitrile was added dropwise, 1h drop, after dropping, 1h was kept, then the remaining butyl acrylate and azobisisobutyronitrile were added dropwise, 1h drop, after dropping, 3h was kept, and the temperature was lowered to discharge the polyurethane-polyacrylate emulsion; The weight ratio of isophorone diisocyanate, sulfonate polyester diol, dimethylol propionic acid, 1, 4-butanediol, dibutyl tin dilaurate, triethylamine, methyl methacrylate, butyl acrylate, azobisisobutyronitrile and sodium dodecyl sulfate is 30:28:2.5:5.5:0.1:2:5:8.5:0.1:0.25.

[0032] The filler is titanium white powder and nanocellulose mixed in a weight ratio of 2:1.

[0033] The filler is surface modified, and the surface modification step is specifically: (1) dispersing the filler in water, adding SDS and stirring for 12h, filtering, washing and drying to obtain SDS-filler, and the weight ratio of the filler and SDS is 2:1; (2) dispersing the SDS-filler in water, adding amino silane, and the weight ratio of the SDS-filler and amino silane is 2:1, stirring for 12h, then filtering, washing, drying and grinding to obtain the surface modified filler.

[0034] A preparation method of a water-based environmentally friendly glass coating, comprising the following steps: mixing and dispersing polyurethane-polyacrylate emulsion, filler, ethanol and water uniformly, adding defoaming agent and glycerol monostearate, mixing uniformly, and discharging the product.

[0035] Comparative Example 1 Comparative Example 1 is a comparative example of Example 4, and the difference between Example 4 and Comparative Example 1 is that: In the preparation step (1) of the polyurethane-polyacrylate emulsion, no vinyl versatate is added, that is: (1) After vacuum dehydration of isophorone diisocyanate, sulfonate polyester polyol, nitrogen was passed, and the mixture was reacted at 80℃ for 1h, then cooled to 65℃, and then dimethylol propionic acid, 1, 4-butanediol and dibutyl tin dilaurate were added and reacted for 2h, cooled to 35℃, then added triethylamine for neutralization, emulsified for 5min, and PU emulsion was obtained.

[0036] Comparative Example 2 Comparative Example 2 is a comparative example of Example 4, and the difference between Example 4 and Comparative Example 2 is that: The filler is not surface modified.

[0037] Comparative Example 3 Comparative Example 3 is a comparative example of Example 4, which is different from Example 4 in that: The filler was subjected to a first step of surface modification treatment, and the surface modification step was specifically as follows: (1) the filler was dispersed in water, SDS was added, and stirring was performed for 12 h, and the product was obtained by suction filtration, washing, and drying, and the weight ratio of the filler to SDS was 2:1.

[0038] Performance detection: The products prepared in Examples 1-4 and Comparative Examples 1-3 were sprayed on the surface of a glass plate, with a dry film thickness of 30 μm, and were self-dried at room temperature for 7 days, and their performances were detected, gloss (60°) was detected according to GB / T 1743-1979, wear resistance was detected according to GB / T 1768-2006, hardness was detected according to GB / T 6739, adhesion was detected according to GB / T 9286-1998, and the tensile strength and elongation at break of the emulsion film were detected according to GB / T 528-2009.

[0039] Water resistance: the polymer film was cut into 3 cm x 3 cm, placed in a vacuum drying oven and dried to constant weight, accurately weighed, then placed in deionized water at room temperature for 24 h, taken out, absorbed the free water on the surface, quickly weighed the wet film mass m2, and calculated the water absorption rate = (m2-m1) / m1*100%.

[0040] Water boiling resistance (100℃): the glass plate and the coating film thereon were placed in 100℃ water (coating film area 10*10 cm), and the time when the coating film started to bubble / peel off was recorded, and the results are shown in Table 1.

[0041] Table 1 Performance detection data Hardness Tensile strength (MPa) Adhesion / grade Wear resistance / g (1000g / 500r) Water resistance (%) Boiling resistance (100°C) Example 1 4H 55.56 0 grade 0.0181 2.20% 6h Example 2 4H 56.31 0 grade 0.0185 2.51% 6h Example 3 4H 56.16 0 grade 0.0170 2.32% 6.5h Example 4 4H 57.32 0 grade 0.0178 2.19% 6h Comparative Example 1 3H 48.91 2 grade 0.0256 3.54% 4.5h Comparative Example 2 4H 51.12 1 grade 0.0215 2.74% 5.5h Comparative Example 3 4H 54.25 1 grade 0.0207 2.69% 6h As can be seen from Table 1, the coating prepared by the coating of the present application has excellent mechanical properties, with a tensile strength of 54.31-57.16 MPa, high hardness, good wear resistance, and good water resistance and water boiling resistance, and excellent comprehensive performance.

[0042] As can be seen from Comparative Example 1, in Comparative Example 1, no vinyl versatate was added, and its water resistance, water boiling resistance, adhesion, and mechanical properties were all reduced to different degrees compared with Example 4, indicating that the introduction of vinyl versatate into the emulsion polymerization system can graft and crosslink the double bonds of polyurethane and polyacrylate, greatly improving the comprehensive performance of the coating film. In Comparative Example 2, the filler was not modified, and its adhesion was lower than that of Example 4, and other properties were also reduced to different degrees, indicating that the surface modification method of the filler can increase the adhesion and water resistance of the coating, and increase the mechanical properties of the coating film; and in Comparative Example 3, the filler was only subjected to one step of modification, and its performance was better than that of Comparative Example 2, but still had certain gaps compared with Example 4, indicating that the surface coating of amino silane has a certain influence on the comprehensive performance of the coating.

[0043] Finally, it is to be explained that the above embodiments are only used to illustrate the technical solutions of the present application but not to limit the present application, and other modifications or equivalent replacements made by those skilled in the art to the technical solutions of the present application should be covered in the scope of claims of the present application as long as they do not depart from the spirit and scope of the technical solutions of the present application.

Claims

1. A water-based environmentally friendly glass coating, characterized by: The invention is prepared from the following raw materials in parts by weight: 55-65 parts of polyurethane-polyacrylate emulsion, 22-28 parts of filler, 1-2 parts of ethanol, 8-12 parts of water, 0.2-0.3 parts of defoaming agent and 0.1-0.15 parts of glyceryl monostearate.

2. The water-based environmentally friendly glass coating according to claim 1, characterized in that: The polyurethane-polyacrylate emulsion is prepared by the following steps: (1) After mixing isophorone diisocyanate and sulfonate polyester polyol, nitrogen is passed through the mixture and the mixture is reacted at 70-80°C for 1 hour. After cooling to 60-65°C, dimethylolpropionic acid, 1,4-butanediol and dibutyltin dilaurate are added and the mixture is reacted for 2 hours. After cooling to 35°C, triethylamine is added for neutralization and the mixture is emulsified for 3-5 minutes to obtain PU emulsion. (2) PU emulsion, methyl methacrylate, half of butyl acrylate and sodium lauryl sulfate were mixed, heated to 80 ° C in a nitrogen environment, stirred and reacted for 1 hour, and then half of azobisisobutyl cyanide was added dropwise, and the reaction was kept warm for 1 hour after the addition was completed. Then, the remaining butyl acrylate and azobisisobutyl cyanide were added dropwise, and the reaction was kept warm for 2-3 hours after the addition was completed. The temperature was lowered and the material was discharged to obtain polyurethane-polyacrylate emulsion; The weight ratio of isophorone diisocyanate, sulfonic acid polyester diol, dimethylol propionic acid, 1,4-butanediol, dibutyltin dilaurate, triethylamine, methyl methacrylate, butyl acrylate, azobisisobutyl cyanide, and sodium lauryl sulfate is 30:24-28:2.5:5.5:0.1:2.0-2.2:5-6:8.5:0.1:0.2-0.

3.

3. The water-based environmentally friendly glass coating according to claim 2, characterized in that: In the step (1), after cooling to 60-65°C, dimethylolpropionic acid, 1,4-butanediol and dibutyltin dilaurate are added and reacted for 2 hours, and then tert-butyl carbonate is added and the reaction is continued for 1-2 hours. The amount of tert-butyl carbonate added is 5-6% of the total amount of isophorone diisocyanate and sulfonic acid type polyester diol.

4. The water-based environmentally friendly glass coating according to claim 1, characterized in that: The filler is a mixture of titanium dioxide and nanocellulose in a weight ratio of 1.5-2:

1.

5. The water-based environmentally friendly glass coating according to claim 4, characterized in that: The filler is subjected to surface modification treatment, and the surface modification step is specifically as follows: (1) Dispersing the filler in water, adding sodium lauryl sulfate and stirring for 12 hours, filtering, washing and drying to obtain SDS-filler, wherein the weight ratio of the filler to sodium lauryl sulfate is 2:1-1.5; (2) Dispersing the SDS-filler in water, adding aminosilane, wherein the weight ratio of the SDS-filler to the aminosilane is 2:0.8-1, stirring and reacting for 12 hours, and then filtering, washing, drying, and grinding to obtain a surface-modified filler.

6. A method for preparing the water-based environmentally friendly glass coating according to claim 1, characterized in that: The following steps are involved: The polyurethane-polyacrylate emulsion, filler, ethanol and water are mixed and dispersed uniformly, a defoamer and glyceryl monostearate are added, mixed uniformly, and the product is obtained by discharging.