CN109181461B - Environment-friendly water-based automobile metal flashing paint and preparation method thereof - Google Patents
Environment-friendly water-based automobile metal flashing paint and preparation method thereof Download PDFInfo
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- CN109181461B CN109181461B CN201811169790.0A CN201811169790A CN109181461B CN 109181461 B CN109181461 B CN 109181461B CN 201811169790 A CN201811169790 A CN 201811169790A CN 109181461 B CN109181461 B CN 109181461B
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
Abstract
The invention discloses an environment-friendly water-based automobile metal flashing paint and a preparation method thereof. The environment-friendly water-based automobile metal flashing paint comprises the following components: the water-based polyurethane graft acrylic emulsion comprises water-based amino resin, water-based aluminum paste, a defoaming agent, a wetting agent, a thickening agent, an amine neutralizer and deionized water. The water-based automobile metallic flashing paint provided by the invention has good dispersibility and stability, the formed paint film is rich in color and strong in metal texture, the distinctness of image DOI grade of the paint film meets the coating requirement of high-grade cars (DOI is more than or equal to 1.0), and the paint film is good in weather resistance and durability, environment-friendly and pollution-free, and meets the decorative requirement of high-grade cars.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an environment-friendly water-based automobile metal flashing paint and a preparation method thereof.
Background
In recent two years, with the improvement of global environmental protection requirements and the continuous deepening of energy conservation and emission reduction of automobile industry, automobile coatings are developing towards water-based, high-solid and powder coatings, wherein the water-based coating is one of the most promising technologies. Automotive paint suppliers have been working on developing water-based automotive paints with superior appearance and color to replace traditional solvent-based paints. The automobile metallic paint occupies the half-wall Jiangshan of the automobile paint, and the silver color occupies nearly 20 percent of the color.
The effect pigment of the silver paint is fine scale-shaped aluminum powder which has the characteristics of metallic luster and being parallel to a coated object, and in a carrier containing transparent pigment, the glossiness and the color depth of the aluminum powder change with the change of incident light angle and visual angle to generate light and color change, so that the silver paint has the appearance performance of different brightness and constantly changing color and having metallic texture. The silver paint greatly meets the requirements of people on the colorful and vivid appearance of the automobile.
However, the aqueous metallic flashing paints using aluminum powder as an effect pigment have many problems as follows: 1) in order to prevent the aluminum powder from reacting with water to generate aluminum oxide and aluminum hydroxide and release hydrogen to cause the surface of the aluminum powder to be dark and influence the appearance of a paint film, the aluminum powder needs to be subjected to surface treatment such as coating or passivation, and the water-based aluminum powder subjected to the surface treatment is generally difficult to disperse and easy to agglomerate, so that the development of the metallic flashing paint is greatly limited. 2) The dispersed aluminum powder has poor stability and is sensitive to pH value, and acidic substances mixed in the paint can form acidic particles, so that the water-based paint is gelatinized and damaged. 3) The water-based paint contains a large amount of water which can not be volatilized quickly in the spraying process, so that the arrangement orientation of aluminum powder pigment of the metal paint is influenced, the color is poor, and the defects of paint films, such as easy sagging, poor flattening property, easy generation of pinholes, shrinkage cavities and the like, are generated. 4) The water resistance, chemical resistance and weather resistance of the paint film can not reach the level of solvent type metallic flashing paint. 5) The physical and mechanical properties of the paint film are poorer than those of the solvent type metallic flashing paint.
The prior art mainly overcomes the defects by improving the formula composition of the metallic flashing paint. For example, chinese patent application with publication number CN102604497A discloses an aqueous metallic flashing paint and a preparation method thereof, wherein the aqueous metallic flashing paint comprises the following components: the acrylic copolymer aqueous dispersion-1, amino resin, BYK-028, dimethylethanolamine, water, aqueous aluminum powder, a dispersing agent, ethylene glycol monobutyl ether, BYK-347, BYK-425, aqueous polyurethane, a polyurethane dispersing agent and cellulose acetate butyrate. In addition, chinese patent application publication No. CN 106916497a discloses a method for preparing a dispersion-stable type water-based metallic flashing paint for automobiles, which comprises extracting polysaccharides from the interior of tea leaves, performing carboxymethylation modification to prepare a modification solution, preparing water-based aluminum powder from the modification solution, and compounding with water-based resin to prepare a water-based excellent dispersion metallic flashing paint.
Although the improvement of the prior art on the metallic flashing paint has obtained a lot of progress, a new environment-friendly aqueous metallic flashing paint formula is still needed to be provided, the advantages and the disadvantages are raised on the basis of the characteristics of the original paint, the performance indexes of the paint are further improved, and the market demand is better met.
Disclosure of Invention
The invention aims to provide the environment-friendly water-based automobile metallic flashing paint and the preparation method thereof.
The invention is realized by the following technical scheme:
an environment-friendly water-based automobile metal flashing paint comprises the following components in parts by weight:
preferably, the environment-friendly water-based automobile metal flashing paint comprises the following components in parts by weight:
the invention also provides a formula and a preparation method of the waterborne aluminum paste, so that the prepared waterborne aluminum paste not only keeps high metal luster, but also has better dispersion performance and stability, and the waterborne aluminum paste comprises the following components in parts by weight: 50-60 parts of flake aluminum powder, 20-30 parts of ethyl orthosilicate, 603-5 parts of quaternized silane BFS, 4-8 parts of dimethyl methanol, 4-10 parts of 2-amino-2-methyl-1-propanol, 20-30 parts of butyl glycol ether and a proper amount of ammonia water, and a silane coupling agent KH-5605-10 parts.
Preferably, the particle size of the flaky aluminum powder is 10-25 μm.
The preparation method of the waterborne aluminum paste comprises the following steps:
s1: putting aluminum flake, quaternary ammonium silane BFS60, a silane coupling agent KH-560, dimethyl methanol, 2-amino-2-methyl-1-propanol and ethylene glycol butyl ether into a reaction kettle, stirring and mixing for 1-2 h at a speed of 100-200 r/min to obtain a dispersed mixture;
s2: adding a proper amount of ammonia water into the dispersed mixture of S1, adjusting the pH value to 8-9, slowly dropwise adding ethyl orthosilicate at the temperature of 50-60 ℃, and continuously reacting for 5-6 hours while dropwise adding to obtain a reaction solution;
s3: and after cooling the reaction liquid, dispersing for 30-60 min at a speed of 500-600 r/min, and sieving with a 400-mesh sieve to obtain the waterborne aluminum paste.
The quaternary ammonium silane BFS60 is added into the formula of the waterborne aluminum paste provided by the invention, so that the positive charge of the surface of the flaky aluminum powder can be increased, the surface tension of the aluminum powder is reduced, and the SiO generated by hydrolyzing ethyl orthosilicate is reduced2Uniformly and compactly distributed on the surface of the aluminum powder to form a layer of uniform and compact SiO2The film is added with silane coupling agent KH-560, 2-amino-2-methyl-1-propanol and other auxiliary components, which is beneficial to improving the dispersibility and stability of the aqueous aluminum paste in the aqueous coating, so that the aqueous aluminum paste can be uniformly dispersed in the aqueous coating without adding a dispersant after being added into the aqueous coating, and the storage stability of the aqueous coating can be improved, so that the coating does not have the defects of tank expansion, blackening and the like of common aqueous silver paint.
The defoaming agent is DigaAirex 902W;
the wetting agent is American gas chemical surfynol 104.
The thickening agent is composed of an alkali swelling thickening agent and an associated thickening agent in a mass ratio of 1 (0.2-0.3).
Preferably, the alkali swelling thickener is Rohm and Haas ASE60, and the associative thickener is Haas 1070.
The amine neutralizer is Haimax MA-95.
The waterborne polyurethane grafted acrylic emulsion is provided by Shanghai Tuojia printing material company Limited, and the product name of the waterborne polyurethane grafted acrylic emulsion is TJ-0650%.
The waterborne amino resin is Zhan Xin Cymel 325, Zhan Xin Cymel 327, basf Luwipal 052 or basf Luwipal 073.
The polyurethane grafted acrylic emulsion is selected as a main film forming substance, has the characteristics of wear resistance, brightness, softness, elasticity, good mechanical property, weather resistance and the like, and is added with the water-based amino resin for crosslinking and curing, so that the coating has excellent water resistance.
In addition, the invention also provides a preparation method of the environment-friendly water-based automobile metal flashing paint, which comprises the following steps:
s1: sequentially adding the waterborne polyurethane grafted acrylic emulsion, the waterborne amino resin, the defoaming agent, the wetting agent, the thickening agent and the amine neutralizing agent into deionized water at a stirring speed of 400-500 rpm, and stirring for 30-60 min;
s2: and then adding the water-based aluminum paste into the material obtained in the step S1, stirring at the speed of 100-200 rpm for 20-30 minutes to obtain the aluminum paste.
Compared with the prior art, the invention has the following beneficial effects:
(1) the environment-friendly water-based automobile metallic flashing paint provided by the invention has the advantages of high drying speed, flat, full and smooth formed paint film, uniform color, high glossiness, good adhesiveness, excellent water resistance, good wear resistance, solvent resistance, weather resistance and the like, and good storage stability, and does not have the defects of tank expansion, blackening and the like of common water-based silver paint.
(2) The environment-friendly water-based automobile metal flashing paint provided by the invention meets the requirements of a 2C1B coating process on the paint, greatly saves the cost, reduces the energy consumption, and has the advantages of energy conservation and emission reduction.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1 preparation of aqueous aluminum paste
The waterborne aluminum paste of the embodiment comprises the following components in parts by weight as shown in the following table 1:
TABLE 1 formulation composition of aqueous aluminum paste
The preparation of the aqueous aluminum paste of formula 1 comprises the following steps:
s1: putting aluminum flake powder, quaternary ammonium silane BFS60, a silane coupling agent KH-560, dimethyl methanol, 2-amino-2-methyl-1-propanol and ethylene glycol butyl ether into a reaction kettle, and stirring and mixing for 1.5h at the speed of 150r/min to obtain a dispersed mixture;
s2: adding a proper amount of ammonia water into the dispersed mixture of S1, adjusting the pH value to 9, slowly dropwise adding tetraethoxysilane at the temperature of 60 ℃, and continuously reacting for 6 hours while dropwise adding to obtain a reaction solution;
s3: and after the reaction liquid is cooled, dispersing for 40min at 550r/min, and sieving by a 400-mesh sieve to obtain the waterborne aluminum paste.
Formulations 2-5 preparation procedure for aqueous aluminum paste reference was made to formulation 1 above.
EXAMPLE 2 preparation of aqueous metallic flashing paint
The water-based metallic flashing paint of the embodiment comprises the following components in parts by weight as shown in the following table 2:
TABLE 2 formulation composition of aqueous metallic flashing paints
(1) The preparation method comprises the following steps:
s1: sequentially adding the waterborne polyurethane grafted acrylic emulsion, the waterborne amino resin, the defoaming agent, the wetting agent, the thickening agent and the amine neutralizing agent into deionized water at a stirring speed of 450 revolutions per minute, and stirring for 60 min;
s2: and then adding waterborne aluminum paste into the material obtained in the step S1, rotating at 100 rpm, and stirring for 30 minutes to obtain the aluminum-silicon-aluminum-based composite material.
(2) And (3) detecting the performance of the water-based metal flashing paint:
the base material is a cold-rolled steel plate, after degreasing, cleaning and drying, template manufacturing is carried out according to the process flow requirement of 2C1B, the thickness of the metal flashing paint is 14 micrometers, the thickness of the finishing varnish is 40 micrometers, the metal flashing paint is prepared according to the formula 1-5, the varnish is solvent type amino polyester baking varnish, and the detection result is shown in table 3.
TABLE 3 detection results of the properties of aqueous metallic flashing paints
The result shows that the water-based metallic flashing paint provided by the invention has good construction performance, high metallic luster, high distinctness of image grade of more than 1.0DOI value, mirror imaging definition, excellent water resistance, acid and alkali resistance, weather aging resistance, humidity resistance and high adhesion, and meets the coating requirement of high-grade cars.
EXAMPLE 3 preparation of aqueous metallic flashing paints
Example 3 is a feeding formula for changing the content of each substance under the condition that the variety of each substance in the formula 1 of example 2 is not changed, and the water-based metallic flashing paint is prepared according to the process of example 2 as shown in the following table 4.
TABLE 4 formulation composition of aqueous metallic flashing paints
The performance of the aqueous metallic flashing paint prepared by the formulas 6-8 is shown in table 5, and the comparison with the performance in table 3 shows that when the content of each substance in the formula of the aqueous metallic flashing paint exceeds the range disclosed by the invention, the performance of the aqueous metallic flashing paint is obviously reduced, especially when the ratio of TJ-0650% polyurethane grafted acrylic emulsion to aqueous amino resin exceeds the range disclosed by the invention, the performance detection result of the aqueous metallic flashing paint is greatly influenced.
TABLE 5 Water-based metallic flashing paint Performance test results
Comparative examples 1 to 3 preparation of aqueous metallic flashing paints
Comparative examples 1 to 3 the aqueous metallic flashing paint comprises the following components in parts by weight as shown in table 6:
TABLE 6 formulation composition of aqueous metallic flashing paints
The results of the performance tests of the aqueous metallic flashing paints of comparative examples 1 to 3 are shown in Table 7.
TABLE 7 detection results of the properties of aqueous metallic flashing paints
The results show that the performances of all aspects of the waterborne metallic flashing paint prepared in the comparative examples 1-3 are weakened, and the aqueous aluminum paste not only influences the board surface effect of the metallic paint film, but also influences the mechanical property and weather resistance of the paint film. As can be seen from comparative examples 1 and 2, when the waterborne aluminum paste prepared by the formulas 4 and 5 in example 1 is added into a metallic flashing paint formula for preparation, the obtained metallic flashing paint has obviously reduced construction performance and board surface effect, the distinctness of image DOI grade of a paint film can not meet the coating requirement of high-grade cars (DOI is more than or equal to 1.0), and the glossiness is obviously reduced. As can be seen from the comparative example 3, the waterborne aluminum paste provided by the invention is replaced by the commercially available waterborne aluminum paste, so that the obtained metallic flashing paint has poor construction performance, the board surface effect is reduced, and the distinctness of image DOI grade of a paint film can not meet the coating requirements of high-grade cars.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The environment-friendly water-based automobile metal flashing paint is characterized by comprising the following components in parts by weight:
the waterborne aluminum paste comprises the following components in parts by weight: 50-60 parts of flake aluminum powder, 20-30 parts of ethyl orthosilicate, 603-5 parts of quaternized silane BFS, 4-8 parts of dimethyl methanol, 4-10 parts of 2-amino-2-methyl-1-propanol, 20-30 parts of butyl glycol ether and a proper amount of ammonia water, and a silane coupling agent KH-5605-10 parts.
2. The environment-friendly water-based automobile metallic flashing paint as claimed in claim 1, which is characterized by comprising the following components in parts by weight:
3. the environment-friendly water-based automobile metallic flashing paint as claimed in claim 1, wherein the particle size of the flake aluminum powder is 10-25 μm.
4. The environment-friendly water-based automobile metal flashing paint as claimed in claim 1, wherein the preparation of the water-based aluminum paste comprises the following steps:
s1: putting aluminum flake, quaternary ammonium silane BFS60, a silane coupling agent KH-560, dimethyl methanol, 2-amino-2-methyl-1-propanol and ethylene glycol butyl ether into a reaction kettle, stirring and mixing for 1-2 h at a speed of 100-200 r/min to obtain a dispersed mixture;
s2: adding a proper amount of ammonia water into the dispersed mixture of S1, adjusting the pH value to 8-9, slowly dropwise adding ethyl orthosilicate at the temperature of 50-60 ℃, and continuously reacting for 5-6 hours while dropwise adding to obtain a reaction solution;
s3: and after cooling the reaction liquid, dispersing for 20-30 min at a speed of 200-300 r/min, and sieving with a 400-mesh sieve to obtain the waterborne aluminum paste.
5. The environmentally friendly waterborne automotive metallic glitter paint of claim 1, wherein the defoamer is digauerex 902W; the wetting agent is American gas chemical surfynol 104.
6. The environment-friendly water-based automobile metal flashing paint as claimed in claim 1, wherein the thickener is an alkali swelling thickener and an associated thickener in a mass ratio of 1 (0.2-0.3).
7. The eco-friendly aqueous automotive metal flash paint as claimed in claim 6, wherein the alkali swelling thickener is Rohm and Haas ASE60, and the associative thickener is Haas 1070.
8. The eco-friendly aqueous automotive metallic glitter paint of claim 1, wherein the amine neutralizing agent is Haimax MA-95.
9. A method for preparing the environmentally friendly aqueous automotive metallic glitter of claim 1, which comprises the steps of: s1: sequentially adding the waterborne polyurethane grafted acrylic emulsion, the waterborne amino resin, the defoaming agent, the wetting agent, the thickening agent and the amine neutralizing agent into deionized water at a stirring speed of 400-500 rpm, and stirring for 30-60 min;
s2: and then adding the water-based aluminum paste into the material obtained in the step S1, stirring at the speed of 100-200 rpm for 20-30 minutes to obtain the aluminum paste.
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| CN110343432A (en) * | 2019-06-27 | 2019-10-18 | 河北晨阳工贸集团有限公司 | A kind of water paint and preparation method thereof |
| CN112266720B (en) * | 2020-09-27 | 2021-10-26 | 广东美涂士建材股份有限公司 | Metallic acrylic coating |
| CN115895446A (en) * | 2022-11-24 | 2023-04-04 | 江苏四方威凯科技有限公司 | Water-based low-temperature anti-freezing coating suitable for automobile hub and preparation method thereof |
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| CN101380620A (en) * | 2008-10-16 | 2009-03-11 | 马显贵 | Superhard wear UV surface paint for vehicle spray painting and solidification device |
| CN104371381B (en) * | 2014-09-29 | 2016-05-25 | 合肥旭阳铝颜料有限公司 | A kind of antimicrobial form aluminium pigment and preparation method thereof |
| CN104962135A (en) * | 2015-06-12 | 2015-10-07 | 广州擎天材料科技有限公司 | Waterborne aluminum paste for decorative waterborne metallic shining coating and soaking production process thereof |
| CN104927635A (en) * | 2015-07-17 | 2015-09-23 | 广东华兹卜化学工业有限公司 | Waterborne polyurethane modified acrylic resin and butylated amino resin binary syllabification metal baking paint and preparation method thereof |
| CN106916497A (en) * | 2017-03-28 | 2017-07-04 | 常州大学 | A kind of preparation method of the automobile water-based property metal flash paint of stably dispersing type |
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| CN102220080A (en) * | 2011-05-31 | 2011-10-19 | 浙江大学 | Quaternary ammonium salt modified organosilicon polyurethane ocean antifouling paint and preparation method and application thereof |
| CN103043683A (en) * | 2012-09-24 | 2013-04-17 | 中国海洋石油总公司 | Method for preparing silicoaluminophosphate 11 (SAPO-11) molecular sieve with adjustable mesoporous aperture |
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