阅读说明：本技术 一种环保型玻璃烤漆及其制备方法 (Environment-friendly glass baking varnish and preparation method thereof ) 是由 刘艳蕊 翟江 由文颖 于 2019-11-04 设计创作，主要内容包括：本发明公开了一种环保型玻璃烤漆,所述玻璃烤漆是有如下重量份的原料组成的：水溶性含氟硒氰基氨基三嗪类树脂45-65份,阳离子型水性聚氨酯15-25份,封闭型交联剂UN-7038 2-5份,流平剂1-5份,去离子水20-30份,颜料3-7份,消泡剂1-3份。本发明还公开了所述环保型玻璃烤漆的制备方法。本发明公开的环保型玻璃烤漆干湿附着力良好,耐醇性、耐水性、耐磨性优异,硬度高,综合性能优异,生产和使用过程安全环保,漆膜耐候性佳,使用寿命长。(The invention discloses an environment-friendly glass baking varnish, which is prepared from the following raw materials in parts by weight: 45-65 parts of water-soluble fluorine-containing selenium cyano amino triazine resin, 15-25 parts of cationic waterborne polyurethane, 1-5 parts of a closed cross-linking agent UN-70382, 1-5 parts of a leveling agent, 20-30 parts of deionized water, 3-7 parts of a pigment and 1-3 parts of a defoaming agent. The invention also discloses a preparation method of the environment-friendly glass baking varnish. The environment-friendly glass baking varnish disclosed by the invention is good in dry and wet adhesive force, excellent in alcohol resistance, water resistance and wear resistance, high in hardness, excellent in comprehensive performance, safe and environment-friendly in production and use processes, good in weather resistance of a paint film and long in service life.)

1. The environment-friendly glass baking varnish is characterized by comprising the following raw materials in parts by weight: 45-65 parts of water-soluble fluorine-containing selenium cyano amino triazine resin, 15-25 parts of cationic waterborne polyurethane, 1-5 parts of a closed cross-linking agent UN-70382, 1-5 parts of a leveling agent, 20-30 parts of deionized water, 3-7 parts of a pigment and 1-3 parts of a defoaming agent;

wherein the water-soluble fluorine-containing selenium cyanoamino triazine resin is prepared from 4,4 '-bis [ (4-anilino-6-hydroxyethyl amino-1, 3, 5-triazine-2-yl) amino ] stilbene-2, 2' -disulfonic acid disodium salt, 3- (2-propenyl seleno) -L-alanine, 1,1,1,7,7, 7-hexafluoro-2, 6-bis (trifluoromethyl) -3-heptene-2, 6-diol and N-trimethylolpropane acrylamide, [4- [ bis (2-hydroxyethyl) amino ] phenyl ] -1,1, 2-vinyltrimethylonitrile, tetra- (4-aminostyrene) ethylene and 2- (methacryloyloxy) ethyl 3-hydroxybutyrate are prepared by copolymerization.

2. The environment-friendly glass baking varnish as claimed in claim 1, wherein the leveling agent is one or more of a polyacrylate leveling agent, a cellulose acetate butyrate leveling agent and a polyvinyl butyral leveling agent.

3. The environment-friendly glass baking paint as claimed in claim 1, wherein the antifoaming agent is one or more of tributyl phosphate, antifoaming agent humble 3100, and antifoaming agent BYK 088.

4. The environment-friendly glass baking varnish according to claim 1, wherein the pigment is one or a combination of titanium dioxide, carbon black, organic pigment, dye, transparent pigment, pearlescent pigment, multi-angle effect pigment and metal pigment water-based color paste, and the fineness of the pigment is not more than 10 μm.

5. The environment-friendly glass baking varnish according to claim 1, wherein the preparation method of the water-soluble fluorine-containing selenium cyano amino triazine resin comprises the following steps: adding 4,4 '-bis [ (4-anilino-6-hydroxyethylamino-1, 3, 5-triazin-2-yl) amino ] stilbene-2, 2' -disulfonic acid disodium salt, 3- (2-propenyl seleno) -L-alanine, 1,1,1,7,7, 7-hexafluoro-2, 6-bis (trifluoromethyl) -3-heptene-2, 6-diol, N-trimethylol methacrylamide, [4- [ bis (2-hydroxyethyl) amino ] phenyl ] -1,1, 2-vinyltrimethylnitrile, tetra- (4-aminobenzene) ethylene, 2- (methacryloyloxy) ethyl 3-hydroxybutyrate, an emulsifier and an initiator into a high boiling point solvent, stirring and reacting for 6-8 hours at 65-80 ℃ in nitrogen or inert gas atmosphere, then precipitating in ethanol, and removing the solvent by rotary evaporation to obtain the water-soluble fluorine-containing selenium cyano amino triazine resin.

6. The environment-friendly glass baking varnish according to claim 5, wherein the 4,4 '-bis [ (4-anilino-6-hydroxyethylamino-1, 3, 5-triazin-2-yl) amino ] stilbene-2, 2' -disulfonic acid disodium salt, 3- (2-propenylseleno) -L-alanine, 1,1,1,7,7, 7-hexafluoro-2, 6-bis (trifluoromethyl) -3-heptene-2, 6-diol, N-trimethylolmethacrylamide, [4- [ bis (2-hydroxyethyl) amino ] phenyl ] -1,1, 2-vinyltrimethylnitrile, tetrakis- (4-aminophenyl) ethylene, 2- (methacryloyloxy) ethyl 3-hydroxybutyrate, N-trimethylenenitrile, The mass ratio of the emulsifier to the initiator to the high-boiling point solvent is 1:1:1:2:2:1:3:0.5 (0.2-0.4) to (25-35).

7. The environment-friendly glass baking varnish according to claim 5, wherein the inert gas is selected from helium, neon and argon; the initiator is at least one selected from azobisisobutyronitrile, azobisisoheptonitrile, di-tert-butyl peroxide and cyclohexanone peroxide.

8. The environment-friendly glass baking varnish according to claim 5, wherein the high boiling point solvent is at least one selected from dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the emulsifier is one or more selected from phenethyl phenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, oleic acid polyoxyethylene ester and polyacrylamide emulsifier.

9. The environment-friendly glass baking varnish according to any one of claims 1 to 8, wherein the preparation method of the environment-friendly glass baking varnish comprises the following steps: mixing the raw materials according to the parts by weight, and dispersing for 15-25min by using a high-speed dispersion machine with the rotating speed of 900-1200r/min to prepare the glass baking varnish.

10. The environment-friendly glass baking varnish according to claim 9, wherein the use method of the environment-friendly glass baking varnish comprises the following steps: coating the glass baking paint on a corrugated product, and baking for 15-25min at the temperature of 130-160 ℃.

Technical Field

The invention relates to the technical field of chemical coatings, in particular to an environment-friendly glass baking varnish and a preparation method thereof.

Background

With the development of economy and the promotion of global industrialization process, resource and environmental problems become a pair of main contradictions of the sustainable development of the society at present. The chemical coating industry is particularly prominent, the market competition of price and quality is increasingly intense, and meanwhile, the discharge of VOC directly brings serious threats to the environment and the physical health of people. Therefore, the development of environment-friendly chemical coatings is a necessary trend in the chemical coating industry.

Glass and glass products are widely applied as common materials and are closely related to the life of people. Glass products such as cosmetic bottles, perfume bottles, wine bottles, lamps and the like in daily life all need to be protected and decorated with coatings to achieve the best effect. The material for coating and protecting glass and glass products is glass baking varnish, and along with the increase of attention on appearance characteristics of various glass products and deep understanding on environmental problems, the requirements on various performances of the glass baking varnish are higher and higher.

According to different dispersion media, the glass bottle baking varnish mainly comprises two types of oily and aqueous, and the oily glass bottle baking varnish can volatilize toluene, xylene, industrial alcohol and other substances which seriously damage the environment and harm the human health in the use process. The water-based glass wine bottle paint takes water as a dispersion medium, thoroughly eliminates the harm of an organic solvent to a human body, and has the advantages of health, environmental protection, low carbon, energy conservation, high utilization rate and good safety. However, the aqueous glass baking varnish in the prior art has the defects of poor aqueous transparency even milky white, poor dispersibility, non-compact film formation, generally low glossiness, poor ethanol and high-alcohol resistance, poor recoatability, poor adhesion, water resistance, wear resistance, low hardness and the like on a glass substrate.

Therefore, the development of the environment-friendly glass baking varnish with better comprehensive performance and stronger adhesive force has very important significance and has great promotion effect on promoting the development of the water-based paint industry.

Disclosure of Invention

The invention aims to solve the problems and provides the environment-friendly glass baking paint which has good dry and wet adhesive force, excellent alcohol resistance, water resistance and wear resistance, high hardness, excellent comprehensive performance, safe and environment-friendly production and use processes, good weather resistance of a paint film and long service life; meanwhile, the invention also provides a preparation method of the environment-friendly glass baking varnish.

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

the environment-friendly glass baking varnish is prepared from the following raw materials in parts by weight: 45-65 parts of water-soluble fluorine-containing selenium cyano amino triazine resin, 15-25 parts of cationic waterborne polyurethane, 1-5 parts of a closed cross-linking agent UN-70382, 1-5 parts of a leveling agent, 20-30 parts of deionized water, 3-7 parts of a pigment and 1-3 parts of a defoaming agent;

wherein the water-soluble fluorine-containing selenium cyanoamino triazine resin is prepared from 4,4 '-bis [ (4-anilino-6-hydroxyethyl amino-1, 3, 5-triazine-2-yl) amino ] stilbene-2, 2' -disulfonic acid disodium salt, 3- (2-propenyl seleno) -L-alanine, 1,1,1,7,7, 7-hexafluoro-2, 6-bis (trifluoromethyl) -3-heptene-2, 6-diol and N-trimethylolpropane acrylamide, [4- [ bis (2-hydroxyethyl) amino ] phenyl ] -1,1, 2-vinyltrimethylonitrile, tetra- (4-aminostyrene) ethylene and 2- (methacryloyloxy) ethyl 3-hydroxybutyrate are prepared by copolymerization.

Preferably, the leveling agent is one or more of a polyacrylate leveling agent, a cellulose acetate butyrate leveling agent and a polyvinyl butyral leveling agent.

Preferably, the antifoaming agent is one or more of tributyl phosphate, antifoaming agent dele 3100 and antifoaming agent BYK 088.

Preferably, the pigment is one or a combination of more of titanium dioxide, carbon black, organic pigment, dye, transparent pigment, pearlescent pigment, multi-angle effect pigment and metal pigment water-based color paste, and the fineness of the pigment is not more than 10 mu m.

Preferably, the preparation method of the water-soluble fluorine-containing selenium cyanoamino triazine resin comprises the following steps: adding 4,4 '-bis [ (4-anilino-6-hydroxyethylamino-1, 3, 5-triazin-2-yl) amino ] stilbene-2, 2' -disulfonic acid disodium salt, 3- (2-propenyl seleno) -L-alanine, 1,1,1,7,7, 7-hexafluoro-2, 6-bis (trifluoromethyl) -3-heptene-2, 6-diol, N-trimethylol methacrylamide, [4- [ bis (2-hydroxyethyl) amino ] phenyl ] -1,1, 2-vinyltrimethylnitrile, tetra- (4-aminobenzene) ethylene, 2- (methacryloyloxy) ethyl 3-hydroxybutyrate, an emulsifier and an initiator into a high boiling point solvent, stirring and reacting for 6-8 hours at 65-80 ℃ in nitrogen or inert gas atmosphere, then precipitating in ethanol, and removing the solvent by rotary evaporation to obtain the water-soluble fluorine-containing selenium cyano amino triazine resin.

Preferably, the 4,4' -bis [ (4-anilino-6-hydroxyethylamino-1, 3, 5-triazin-2-yl) amino ] stilbene-2, 2' -disulfonic acid disodium salt, 3- (2-propenylseleno) -L-alanine, 1,1,1,7,7, 7-hexafluoro-2, 6-bis (trifluoromethyl) -3-heptene-2, 6-diol, N-trimethylolmethacrylamide, [4- [ bis (2-hydroxyethyl) amino ] phenyl ] -1,1, 2-vinyltrimethylnitrile, tetrakis- (4-aminobenzene) ethylene, 2- (methacryloyloxy) ethyl 3-hydroxybutyrate, emulsifier, di (2-propenoic acid) ethyl 3-hydroxybutyrate, di (2-propenylseleno) -1,1, 2' -diol, di (trifluoromethyl) -3-heptene, 2, 6-diol, di (trifluoromethyl) -2, 6-bis (trifluoromethyl, The mass ratio of the initiator to the high-boiling point solvent is 1:1:1:2:2:1:3:0.5 (0.2-0.4) to (25-35).

Preferably, the inert gas is selected from one of helium, neon and argon.

Preferably, the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, di-tert-butyl peroxide and cyclohexanone peroxide.

Preferably, the high boiling point solvent is at least one selected from the group consisting of dimethylsulfoxide, N-dimethylformamide, and N-methylpyrrolidone.

Preferably, the emulsifier is one or more selected from phenethyl phenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, oleic acid polyoxyethylene ester and polyacrylamide emulsifier.

Further, the preparation method of the environment-friendly glass baking varnish comprises the following steps: mixing the raw materials according to the parts by weight, and dispersing for 15-25min by using a high-speed dispersion machine with the rotating speed of 900-1200r/min to prepare the glass baking varnish.

Further, the use method of the environment-friendly glass baking varnish comprises the following steps: coating the glass baking paint on a corrugated product, and baking for 15-25min at the temperature of 130-160 ℃.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

(1) the environment-friendly glass baking varnish provided by the invention has the advantages of simple and easy preparation and use methods, low preparation cost, low requirements on equipment and reaction conditions, suitability for large-scale production, and safe and environment-friendly preparation and use.

(2) The environment-friendly glass baking paint provided by the invention overcomes the defects of poor water-based transparency, even milky white color, poor dispersibility, non-compact film forming, generally low glossiness, poor ethanol and high-alcohol resistance and poor recoatability, poor adhesive force, water resistance, abrasion resistance and low hardness of a glass substrate in the traditional water-based glass baking paint, and has the advantages of good dry-wet adhesive force, excellent alcohol resistance, water resistance and abrasion resistance, high hardness, excellent comprehensive performance, safe and environment-friendly production and use processes, good weather resistance of a paint film and long service life.

(3) The environment-friendly glass baking varnish provided by the invention does not use toxic and harmful organic solvents in the production and use processes, and is safer and more environment-friendly; the film forming material is composed of water-soluble fluorine-containing selenium cyano amino triazine resin and cationic waterborne polyurethane, and the two materials are connected through ionic bonds to form an organic whole, so that the comprehensive performance of the film layer is improved; the water-soluble fluorine-containing selenium cyano amino triazine resin is prepared by copolymerizing various monomers, wherein a selenium structure is introduced, so that the performances of flame retardance, weather resistance and the like of a film layer are improved, and a health-care effect is achieved; a fluorine structure and an amino triazine structure are introduced, so that the weather resistance of the film layer is improved; active hydroxyl, quaternary ammonium cation, anilino and amino introduced on a molecular chain are easy to form firm adhesion with the surface of a glass product, and the adhesion and the wear resistance of the film layer are improved; the introduced cyano group can enhance the film forming property and the mechanical property of the resin; the introduced tertiary amine and secondary amine can also provide a catalyst for cross-linking and curing in the curing stage of the paint film, so that the small molecules of the paint film are not required to be externally added to cause the exosmosis in the long-term use process, the stability of the paint film is improved, and the service life of the paint film is prolonged; by adding the enclosed cross-linking agent UN-7038, a three-dimensional network structure is formed through cross-linking and curing, so that the comprehensive performance of the baking varnish is improved; the components and the structure have synergistic effect, so that the paint film has more excellent heat resistance, weather resistance, chemical resistance, alcohol resistance and physical and mechanical properties.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

Wherein, the raw materials related in the examples are all purchased commercially.