CN109705278B - Water-based acrylic emulsion for automobile electrophoresis finish paint and preparation method thereof - Google Patents
Water-based acrylic emulsion for automobile electrophoresis finish paint and preparation method thereof Download PDFInfo
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Abstract
The water-based acrylic emulsion for the automobile electrophoresis finish coat belongs to the technical field of automobile finish coat emulsion, and comprises, by weight, 50-80 parts of styrene, 50-100 parts of methyl methacrylate, 250 parts of n-butyl acrylate 200-. The invention also provides a preparation method of the water-based acrylic emulsion, and the emulsion and the synthesized water-based automobile finish emulsion do not contain APEO, have low formaldehyde, no benzene series and other pollution emissions, narrow particle size distribution and good product stability.
Description
Technical Field
The invention belongs to the technical field of automobile finish paint emulsion, relates to aqueous acrylic emulsion for automobile finish paint, and particularly relates to aqueous acrylic emulsion for automobile electrophoretic finish paint and a preparation method thereof.
Background
With the development and progress of science and technology, the international requirement on VOC emission is more and more, and the standard of coming out is more and more strict. Since the 90 s of the 20 th century, the European and American automobile factories have gradually adopted environment-friendly automobile coatings to replace the traditional organic solvent-based coatings in order to meet the environmental standards. In the automobile coating trend in China, the automobile coating is developed towards green environmental protection and pollution-free, the water-based paint is generally adopted, and the automobile water-based paint and the coating technology thereof are mature day by day. The coating can be compared favorably with the traditional solvent type in the aspects of variety matching and coating quality. The technology is an advanced vehicle body priming process from the aspects of environmental protection, resource availability, coating quality and the like, almost 100 percent of vehicle bodies produced in a large amount of flow are subjected to cathodic electrophoresis priming, and then a top coating is coated on the outside. The existing common water-based acrylic emulsion can not meet the harsh requirements, the adhesion force on the electrophoretic paint is poor, and a paint film is easy to peel off; in the high-temperature spraying process, the leveling property is poor, and the appearance effects such as luster and the like are seriously influenced.
Disclosure of Invention
The invention aims to solve the problems and provides the water-based acrylic emulsion for the automobile electrophoresis finish paint and the preparation method thereof.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the water-based acrylic emulsion for the automobile electrophoresis finish paint comprises, by weight, 50-80 parts of styrene, 50-100 parts of methyl methacrylate, 250 parts of n-butyl acrylate 200-.
The reactive polymerizable emulsifier is an emulsifier which has a double bond at one end and participates in emulsion polymerization reaction. For example, one or two selected from reactive polymerizable emulsifier AR-10 or reactive polymerizable emulsifier ER-10 are compounded, but not limited to the two. When two compositions are selected, the mass ratio of the reactive polymerizable emulsifier AR-10 to the reactive polymerizable emulsifier ER-10 is 1:9 to 9: 1.
The aliphatic polyurethane acrylate is aliphatic polyurethane acrylate CN9002 and/or aliphatic polyurethane acrylate CN 996.
The compounding ratio of the aliphatic polyurethane acrylate CN9002 to the aliphatic polyurethane acrylate CN996 is 2:8 to 8: 2.
The selected water-based solid acrylic resin is one or more of basf 678 or Korea 60L, 70, 74 and 90.
The initiator is one of ammonium persulfate, sodium persulfate and potassium persulfate.
The preparation method of the water-based acrylic emulsion for the automobile electrophoresis finish paint comprises the following steps:
A. preparing raw materials: weighing 50-80 parts of styrene, 50-100 parts of methyl methacrylate, 250 parts of n-butyl acrylate 200-one, 2-10 parts of methacrylic acid, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic polyurethane acrylate, 2-10 parts of a reactive polymerizable emulsifier, 0-10 parts of aqueous solid acrylic resin, 1-5 parts of an initiator, 600 parts of water 430-one, 0-5 parts of ammonia water, 0-3 parts of a defoaming agent and 0-3 parts of a bactericide for later use;
B. preparation of monomer pre-emulsion: taking 100 portions of water, 150 portions of organic solvent and 2 to 10 portions of reactive polymerizable emulsifier, fully stirring, sequentially adding 50 to 80 portions of styrene, 50 to 100 portions of methyl methacrylate, 250 portions of n-butyl acrylate, 2 to 10 portions of methacrylic acid, 0 to 50 portions of acrylonitrile and 1 to 8 portions of aliphatic polyurethane acrylate into a reaction kettle, and stirring for 1 to 1.5 hours to obtain a monomer pre-emulsion;
C. preparation of initiator solution: dissolving an initiator in 30-50 parts of water, and stirring to obtain an initiator solution for later use;
D. preparation of the emulsion: mixing 400 parts of water 300-containing materials, 1-5 parts of reactive polymerizable emulsifier and 0-10 parts of aqueous solid acrylic resin, stirring and heating to 80-85 ℃, adding 1-10% of monomer pre-emulsion, preserving heat for 515min, then adding 5-15% of initiator solution, preserving heat for 30-40min, then beginning to simultaneously dropwise add the rest monomer pre-emulsion and the rest initiator solution, finishing dropwise adding within 2.5-3.5h, then preserving heat for 1-1.5h, carrying out post-treatment and cooling, then adjusting the pH to 7-8 by using ammonia water, adding defoamer and bactericide, and filtering to obtain the final finished emulsion.
The invention has the beneficial effects that:
the invention introduces the water-based solid acrylic resin, greatly improves the adhesive force with the electrophoretic primer, and supports the reactive polymerizable emulsifier (preferably compounded with AR10 and ER10) in function, thereby improving the overall water resistance of a paint film, reducing the possibility of stripping the emulsifier and emulsion particles, and ensuring that the emulsion has good leveling and luster in the spraying process. By introducing the water-based solid acrylic resin, the emulsion has very good adhesive force with the electrophoretic primer, and can be effectively prevented from forming a film in the high-temperature spraying process, so that a paint film has very good leveling and spreading properties after being attached to a base material, and can effectively keep the gloss.
In addition, special polyurethane monomers CN9002 and CN996 which can be copolymerized with acrylate monomers are introduced, so that the adhesive force with pigments, fillers and base materials is further improved, the base materials are well combined, and the overall toughness and weather resistance of a paint film can be improved.
The water-based automobile finish emulsion product synthesized by the emulsion of the invention does not contain APEO, has low formaldehyde, no benzene series and other pollution emissions, narrow particle size distribution and good product stability. Compared with the main competitors at home and abroad, the paint has excellent adhesive force and water resistance in key performance, has good spraying effect in the later construction process, and has excellent performance of the final product and environmental protection.
By compounding the reactive polymerizable emulsifier AR10 and ER10, the reactive polymerizable emulsifier can well react with monomers and is grafted on the surface of emulsion particles, so that the flow-off of the emulsifier is reduced, emulsion particles are well protected in the spraying process of the emulsion, and the stability of the emulsion is improved.
The invention also has the following advantages:
1. the aliphatic polyurethane acrylate is added into the emulsion as a special polyurethane monomer, and has the effect of high curing speed; due to the existence of the acrylate, a plurality of hydrogen bonds can be formed among molecular chains of the high molecular polymer, so that the paint film has excellent mechanical wear resistance, flexibility, chemical resistance and high and low temperature resistance. According to the invention, the drying speed can be balanced by controlling the proportion of the two aliphatic polyurethane acrylates, and the paint film does not shrink or crack in the drying process, so that the paint film has better compactness. Meanwhile, the proportion control of the two aliphatic polyurethane acrylates can also adjust the viscosity of the emulsion and the paint film, increase the wettability of the paint film and improve the leveling effect, so that the paint film has stronger water absorption before curing and stronger water resistance after curing, and simultaneously participates in the reaction in the curing process to form a cross-linking network, so that the cured paint film is prevented from migrating and escaping, and the quality of the paint film is ensured; and because the methyl methacrylate, the n-butyl acrylate and the methacrylic acid are added, and are crosslinked with the aliphatic polyurethane acrylate, a crosslinking network is formed, so that a paint film is uniformly adhered to the electrophoretic primer, and the adhesion force of the paint film to the electrophoretic primer is improved.
2. According to the invention, after styrene, acrylonitrile and aliphatic polyurethane acrylate are crosslinked, an interpenetrating network structure is formed on the basis of a crosslinking network, and the water-based solid acrylic resin is distributed in each network structure in a shuttling mode, so that the network structures are connected compactly, the emulsion can be effectively protected from forming a film in the high-temperature spraying process, the problems of reducing the viscosity of the emulsion and generating bubbles due to the addition of an emulsifier are solved, the mechanical property of a paint film is improved due to the compact structure, the ductility of the paint film is good, and the elongation at break is improved; meanwhile, the water-based solid acrylic resin enables the cross-linking monomer to be distributed on the surfaces of the colloidal particle, so that the water resistance and the mechanical property of the adhesive film are greatly improved, and the emulsion with stability and good glossiness is obtained.
3. The addition of the aqueous solid resin can better adjust the molecular weight of the emulsion, so that the molecular weight distribution is wider. The low molecular weight part can improve the fluidity of the emulsion and the film forming speed, and on the other hand, the adhesion with the base material is greatly improved; the high molecular weight portion imparts better mechanical properties, toughness, temperature change resistance, and the like to the emulsion. The strength, the adhesive force and the water resistance of the paint film can be further improved by controlling the using amount of the waterborne solid acrylic resin.
4. The invention adopts the compounded polymerizable emulsifiers AR-10 and ER-10, the two emulsifiers are combined with the two aliphatic polyurethane acrylates, the effect of reducing the surface tension of a paint film is achieved, the addition of a leveling agent and a leveling auxiliary agent can be omitted when the finish paint is prepared, and the excellent leveling effect is still obtained.
Detailed Description
The present invention will be further described with reference to the following examples.
Detailed description of the preferred embodiments
Example 1
The preparation method comprises the following steps of preparing raw materials, by weight, 60 parts of styrene, 50 parts of methyl methacrylate, 220 parts of n-butyl acrylate, 2 parts of methacrylic acid, 10 parts of acrylonitrile, 90024 parts of aliphatic urethane acrylate CN, 103 parts of reactive polymerizable emulsifier AR, 103 parts of ER, 5 parts of aqueous solid acrylic resin, 1 part of initiator, 500 parts of water, ammonia water, a defoaming agent and a bactericide.
Taking 150 parts of water, a reactive polymerizable emulsifier AR10 and an ER10, fully stirring, sequentially adding styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, acrylonitrile and aliphatic urethane acrylate CN9002 into a reaction kettle, and stirring for 1h to obtain a monomer pre-emulsion for later use.
Dissolving an initiator in 50 parts of water, and stirring to obtain an initiator solution for later use.
Mixing 300 parts of water, a reactive polymerizable emulsifier and aqueous solid acrylic resin, stirring, heating to 80 ℃, adding 5% of monomer pre-emulsion, preserving heat for 5min, sequentially adding 5% of initiator solution, preserving heat for 30min, then beginning to simultaneously dropwise add the rest monomer pre-emulsion and the rest initiator solution, finishing dropwise adding within 2.5h, preserving heat for 1h, carrying out post-treatment and cooling, then adjusting the pH to 7 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
Example 2
The preparation method comprises the following steps of preparing raw materials, by weight, 60 parts of styrene, 50 parts of methyl methacrylate, 220 parts of n-butyl acrylate, 2 parts of methacrylic acid, 10 parts of acrylonitrile, 9964 parts of aliphatic urethane acrylate CN, 103 parts of reactive polymerizable emulsifier AR, 103 parts of ER, 5 parts of aqueous solid acrylic resin, 2 parts of initiator, 500 parts of water, ammonia water, defoaming agent and bactericide.
100 parts of water, reactive polymerizable emulsifiers AR10 and ER10 are fully stirred, and then styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, acrylonitrile and aliphatic urethane acrylate CN996 are sequentially added into a reaction kettle and stirred for 1.5 hours to obtain a monomer pre-emulsion for later use.
Dissolving an initiator in 30 parts of water, and stirring to obtain an initiator solution for later use.
Taking 370 parts of water, mixing with a reactive polymerizable emulsifier and aqueous solid acrylic resin, stirring, heating to 85 ℃, adding 10% of monomer pre-emulsion, preserving heat for 15min, sequentially adding 15% of initiator solution, preserving heat for 40min, then beginning to simultaneously dropwise add the rest monomer pre-emulsion and the rest initiator solution within 3.5h, finishing dropwise adding, preserving heat for 1.5h, performing post-treatment and cooling, then adjusting the pH to 8 with ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
Example 3
The preparation method comprises the following steps of preparing raw materials, by weight, 60 parts of styrene, 50 parts of methyl methacrylate, 220 parts of n-butyl acrylate, 2 parts of methacrylic acid, 10 parts of acrylonitrile, CN 90022 parts and CN 9962 parts of aliphatic urethane acrylate, 103 parts of reactive polymerizable emulsifier AR, 103 parts of ER, 5 parts of aqueous solid acrylic resin, 3 parts of initiator, 500 parts of water, ammonia water, defoamer and bactericide.
120 parts of water, reactive polymerizable emulsifiers AR10 and ER10 are fully stirred, then styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 are sequentially added into a reaction kettle, and stirred for 1.2 hours to obtain a monomer pre-emulsion for later use.
Dissolving an initiator in 40 parts of water, and stirring to obtain an initiator solution for later use.
Mixing 340 parts of water, a reactive polymerizable emulsifier and aqueous solid acrylic resin, stirring, heating to 83 ℃, adding 8% of monomer pre-emulsion, preserving heat for 10min, sequentially adding 10% of initiator solution, preserving heat for 35min, simultaneously dropwise adding the rest monomer pre-emulsion and the rest initiator solution within 3h, preserving heat for 1.3h, performing post-treatment and cooling, adjusting the pH value to 8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
Example 4
The preparation method comprises the following steps of preparing raw materials, by weight, 60 parts of styrene, 50 parts of methyl methacrylate, 220 parts of n-butyl acrylate, 2 parts of methacrylic acid, 10 parts of acrylonitrile, CN 90022 parts and CN 9962 parts of aliphatic urethane acrylate, 103 parts of reactive polymerizable emulsifier AR, 103 parts of ER, 7.5 parts of aqueous solid acrylic resin, 4 parts of initiator, 500 parts of water, ammonia water, defoamer and bactericide.
130 parts of water, reactive polymerizable emulsifiers AR10 and ER10 are fully stirred, then styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic polyurethane acrylate CN996 and CN9002 are sequentially added into a reaction kettle, and the mixture is stirred for 1.2 hours to obtain a monomer pre-emulsion for later use.
Dissolving an initiator in 35 parts of water, and stirring to obtain an initiator solution for later use.
Mixing 335 parts of water, a reactive polymerizable emulsifier and aqueous solid acrylic resin, stirring, heating to 82 ℃, adding 3% of monomer pre-emulsion, preserving heat for 8min, sequentially adding 12% of initiator solution, preserving heat for 38min, then beginning to simultaneously dropwise add the rest monomer pre-emulsion and the rest initiator solution within 2.8h, preserving heat for 1.2h, performing post-treatment and cooling, then adjusting the pH to 8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
Example 5
The preparation method comprises the following steps of preparing raw materials, by weight, 60 parts of styrene, 75 parts of methyl methacrylate, 250 parts of n-butyl acrylate, 4 parts of methacrylic acid, 5 parts of acrylonitrile, CN 90023 parts and CN 9963 parts of aliphatic urethane acrylate, 102 parts of reactive polymerizable emulsifier AR, 102 parts of ER, 6 parts of aqueous solid acrylic resin, 5 parts of initiator, 550 parts of water, ammonia water, defoamer and bactericide.
145 parts of water, reactive polymerizable emulsifiers AR10 and ER10 are fully stirred, then styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 are sequentially added into a reaction kettle, and stirring is carried out for 1.2 hours to obtain a monomer pre-emulsion for later use.
Dissolving an initiator in 45 parts of water, and stirring to obtain an initiator solution for later use.
Mixing 360 parts of water, a reactive polymerizable emulsifier and aqueous solid acrylic resin, stirring, heating to 84 ℃, adding 2% of monomer pre-emulsion, preserving heat for 14min, sequentially adding 11% of initiator solution, preserving heat for 33min, simultaneously dropwise adding the rest monomer pre-emulsion and the rest initiator solution within 3.2h, preserving heat for 1.4h, performing post-treatment and cooling, adjusting the pH value to 8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
Example 6
The preparation method comprises the following steps of preparing raw materials, by weight, 50 parts of styrene, 60 parts of methyl methacrylate, 200 parts of n-butyl acrylate, 5 parts of methacrylic acid, 90022 parts of aliphatic polyurethane acrylate, 102 parts of a reactive polymerizable emulsifier ER, 2.5 parts of an initiator, 450 parts of water, ammonia water, a defoaming agent and a bactericide.
100 parts of water and a reactive polymerizable emulsifier ER10 are fully stirred, and then styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid and aliphatic urethane acrylate CN9002 are sequentially added into a reaction kettle and stirred for 1.1h to obtain a monomer pre-emulsion for later use.
Dissolving an initiator in 50 parts of water, and stirring to obtain an initiator solution for later use.
Mixing 300 parts of water and a reactive polymerizable emulsifier, stirring and heating to 82 ℃, adding 1% of monomer pre-emulsion, preserving heat for 12min, sequentially adding 12% of initiator solution, preserving heat for 32min, then beginning to simultaneously dropwise add the rest monomer pre-emulsion and the rest initiator solution, finishing dropwise adding within 2.7h, preserving heat for 1.1h, carrying out post-treatment and cooling, then adjusting the pH to 8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
Example 7
The preparation method comprises the following steps of preparing raw materials, by weight, 70 parts of styrene, 80 parts of methyl methacrylate, 235 parts of n-butyl acrylate, 7 parts of methacrylic acid, 25 parts of acrylonitrile, CN 90023 parts and CN 9964 parts of aliphatic urethane acrylate, 105 parts of reactive polymerizable emulsifier AR, 103 parts of ER, 3 parts of aqueous solid acrylic resin, 3.5 parts of initiator, 580 parts of water, ammonia water, defoamer and bactericide.
130 parts of water, reactive polymerizable emulsifiers AR10 and ER10 are fully stirred, then styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic polyurethane acrylate CN996 and CN9002 are sequentially added into a reaction kettle, and stirring is carried out for 1 hour to obtain a monomer pre-emulsion for later use. In this example, polyurethane monomers CN9002 and CN996 were added and pre-treated by ultrasonic oscillation for 3-5min and then washed with nitrogen for 0.2-0.3 s. The pretreatment of the aliphatic polyurethane acrylate enables the aliphatic polyurethane acrylate to be better combined with two emulsifiers, the aliphatic polyurethane acrylate and the emulsifiers are enabled to be mutually supported in function, the effect of reducing the surface tension of the monomers and water can be achieved, the monomers and the water form a stable uniform system, the synergistic effect is achieved, the pigment and the filler can be soaked more quickly during the preparation of the finish paint, and the pigment and the filler can penetrate into pores of pigment and filler particle aggregates, so that the pigment and filler dispersing effect and the stability of an emulsion system are improved, the finish paint has better wetting, adhering and soaking effects on the surface of the electrophoretic primer paint, the leveling property is improved, the film surface is smoother, and the glossiness is higher.
Dissolving an initiator in 50 parts of water, and stirring to obtain an initiator solution for later use.
Mixing 400 parts of water, a reactive polymerizable emulsifier and aqueous solid acrylic resin, stirring, heating to 80 ℃, adding 4% of monomer pre-emulsion, preserving heat for 7min, sequentially adding 10% of initiator solution, preserving heat for 30min, then beginning to simultaneously dropwise add the rest monomer pre-emulsion and the rest initiator solution, finishing dropwise adding within 2.5h, preserving heat for 1h, carrying out post-treatment and cooling, then adjusting the pH to 8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
The ammonia water is not only used for adjusting the pH value, but also used for pre-treating special polyurethane monomers CN9002 and CN996, and surprisingly shows that the ammonia water also acts on the pre-treated aliphatic polyurethane acrylate, so that the cross-linking effect can be enhanced, the curing speed is accelerated, the generation of pores is reduced, and the curing regularity is further improved.
Example 8
The preparation method comprises the following steps of preparing raw materials, by weight, 80 parts of styrene, 100 parts of methyl methacrylate, 250 parts of n-butyl acrylate, 10 parts of methacrylic acid, 50 parts of acrylonitrile, 90025 parts of aliphatic urethane acrylate and 9963 parts of CN, 104 parts of reactive polymerizable emulsifier AR, 106 parts of ER, 10 parts of aqueous solid acrylic resin, 4.5 parts of initiator, 600 parts of water, ammonia water, defoamer and bactericide.
Taking 150 parts of water, a reactive polymerizable emulsifier AR10 and an ER10, fully stirring, sequentially adding styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 into a reaction kettle, and stirring for 1h to obtain a monomer pre-emulsion for later use. In this example, polyurethane monomers CN9002 and CN996 were added and pre-treated by ultrasonic oscillation for 3-5min and then washed with nitrogen for 0.2-0.3 s.
Dissolving an initiator in 50 parts of water, and stirring to obtain an initiator solution for later use.
Mixing 400 parts of water, a reactive polymerizable emulsifier and aqueous solid acrylic resin, stirring, heating to 85 ℃, adding 6% of monomer pre-emulsion, preserving heat for 12min, sequentially adding 7% of initiator solution, preserving heat for 34min, simultaneously dropwise adding the rest monomer pre-emulsion and the rest initiator solution within 3h, preserving heat for 1.5h, performing post-treatment and cooling, adjusting the pH value to 8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the final finished emulsion.
Comparative example
The prior acrylic acid-polyurethane emulsion comprises raw materials such as acrylic acid, polyurethane, emulsifier and the like, and the selected polyurethane and emulsifier are not the polyurethane and emulsifier of the invention.
Secondly, testing and characterizing the application performance of the coating
The acrylic emulsion prepared according to the above method is compared with commercially available competitive product emulsion for testing application performance. The comparison is mainly made from the following aspects: water resistance, adhesion test, leveling property and the like.
1. Comparison of Water resistance
And (3) wiping and drying the prepared emulsion for 24 hours, then soaking in water, and observing the change of the water resistance of the paint film.
| Soaking in water for 12h | Soaking in water for 24h | Soaking in water for 38h | |
| Example 1 | Without any change | Without any change | Slightly bluish |
| Example 2 | Without any change | Without any change | Slightly bluish |
| Example 3 | Without any change | Without any change | Slightly bluish |
| Example 4 | Without any change | Without any change | Slightly bluish |
| Example 5 | Without any change | Without any change | Slightly bluish |
| Example 6 | Without any change | Without any change | Slightly bluish |
| Example 7 | Without any change | Without any change | Slightly bluish |
| Example 8 | Without any change | Without any change | Slightly bluish |
| Comparative example | Slightly bluish | Apparent bluing | Severe bluing |
| Competition emulsion | Slightly bluish | Apparent bluing | Severe bluing |
2. Adhesion test
The prepared acrylic emulsion is prepared into paint, after the paint is sprayed on an electrophoretic primer, the adhesion is tested by a cross-grid drawing method, and the obtained results are as follows:
| results of adhesion | Score value | |
| Example 1 | The paint film is complete and has no shedding | 5 |
| Example 2 | The paint film is complete and has no shedding | 5 |
| Example 3 | The paint film is complete and has no shedding | 5 |
| Example 4 | The paint film is complete and has no shedding | 5 |
| Example 5 | The paint film is complete and has no shedding | 5 |
| Example 6 | The paint film is complete and has no shedding | 5 |
| Example 7 | The paint film is complete and has no shedding | 5 |
| Example 8 | The paint film is complete and has no shedding | 5 |
| Comparative example | Severe film peeling | 2 |
| Competition emulsion | Severe film peeling | 2 |
Wherein the best score of 5 is that the paint film has no shedding and any change; 1 min, the paint film completely falls off.
3. Leveling property
The prepared acrylic emulsion is prepared into paint, after the paint is sprayed on an electrophoretic primer, the leveling condition of the paint film is observed, and the obtained result is as follows:
| leveling property | |
| Example 1 | Slight wrinkles |
| Example 2 | The leveling is very good |
| Example 3 | The leveling is very good |
| Example 4 | Slight wrinkles |
| Example 5 | The leveling is very good |
| Example 6 | Slight wrinkling and lower leveling than the others |
| Example 7 | The leveling is very good |
| Example 8 | The leveling is very good |
| Comparative example | The paint film is wrinkled and does not spread |
| Competition emulsion | The paint film is wrinkled and does not spread |
In conclusion, the acrylic emulsion has good water resistance, good adhesive force and leveling property on the automobile electrophoretic primer, is superior to the emulsion of a comparative example and the emulsion of a competitive product purchased on the market, and has good application prospect in the market of water-based automobile paint.
4. Properties of the emulsion
Note: calcium ion stability: adding 1%, 3%, 5% CaCl2The solution and emulsion were mixed at 4: 1 (mass ratio), standing for 72h, and observing no layering or gel, namely, the product is qualified.
Centrifugal stability: injecting 1ml of the emulsion into a centrifuge tube, placing into a high-degree centrifuge, centrifuging at 12000r/min, 20000r/min for 60min, and observing the state of the emulsion until the emulsion is not broken.
5. Properties of emulsion formulated topcoats
Note: the finishing paint does not contain a leveling agent, a leveling auxiliary agent, an anti-ultraviolet agent and an anti-aging agent. Comparative example preparation of a topcoat composition.
Water resistance: the best score of 5 is no change, and no foaming or falling off exists; 1 min worst.
Adhesion force: the best score of 5 is, and a paint film does not fall off; 1 min worst.
QUV: the first-level paint film has no change and no color difference; the worst five grades, the paint film has serious chromatic aberration.
According to the data, the unexpected discovery shows that the paint film of the invention has good leveling effect and still has excellent ultraviolet resistance under the condition of not containing assistants such as a leveling agent, a leveling assistant, an ultraviolet-resistant agent, an anti-aging agent and the like, and the analysis shows that the paint film has ultraviolet resistance due to the fact that two emulsifiers are adsorbed in an interface orientation mode, cross-linked and polymerized with two polyurethanes and interfered with ultraviolet light, so that the anti-aging agent or the ultraviolet-resistant agent can be omitted when the finish paint is prepared, and the defect of shrinkage cavity on the surface of the paint film caused by the addition of the anti-aging agent or the ultraviolet-resistant agent is avoided.
Claims (6)
1. The water-based acrylic emulsion for the automobile electrophoresis finish paint is characterized by comprising 50-80 parts of styrene, 50-100 parts of methyl methacrylate, 200-250 parts of n-butyl acrylate, 2-10 parts of methacrylic acid, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic polyurethane acrylate, 3-15 parts of a reactive polymerizable emulsifier, 0-10 parts of water-based solid acrylic resin, 1-5 parts of an initiator, 600 parts of water 430-containing acrylic resin, 0-5 parts of ammonia water, 0-3 parts of a defoaming agent and 0-3 parts of a bactericide by weight; the aliphatic polyurethane acrylate is aliphatic polyurethane acrylate CN9002 and/or aliphatic polyurethane acrylate CN 996.
2. The aqueous acrylic emulsion for an automotive electrophoretic finish according to claim 1, characterized in that the reactive polymerizable emulsifier is an emulsifier having a double bond at one end and participating in the emulsion polymerization reaction.
3. The aqueous acrylic emulsion for an automotive electrophoretic finish according to claim 1, characterized in that the compounding ratio of the aliphatic urethane acrylate CN9002 and the aliphatic urethane acrylate CN996 is from 2:8 to 8: 2.
4. The aqueous acrylic emulsion for an automotive electrophoresis finish according to claim 1 wherein the aqueous solid acrylic resin is used in combination of basf 678 or one or more of hanhua 60L, hanhua 70, hanhua 74 and hanhua 90.
5. The aqueous acrylic emulsion for an automotive electrophoretic finish according to claim 1 wherein the initiator is one of ammonium persulfate, sodium persulfate and potassium persulfate.
6. The preparation method of the water-based acrylic emulsion for the automobile electrophoresis finish paint is characterized by comprising the following steps:
A. preparing raw materials: weighing 50-80 parts of styrene, 50-100 parts of methyl methacrylate, 250 parts of n-butyl acrylate 200-one, 2-10 parts of methacrylic acid, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic polyurethane acrylate, 2-10 parts of a reactive polymerizable emulsifier, 0-10 parts of aqueous solid acrylic resin, 1-5 parts of an initiator, 600 parts of water 430-one, 0-5 parts of ammonia water, 0-3 parts of a defoaming agent and 0-3 parts of a bactericide for later use; the aliphatic polyurethane acrylate is aliphatic polyurethane acrylate CN9002 and/or aliphatic polyurethane acrylate CN 996;
B. preparation of monomer pre-emulsion: taking 100 portions of water, 150 portions of organic solvent and 2 to 10 portions of reactive polymerizable emulsifier, fully stirring, sequentially adding 50 to 80 portions of styrene, 50 to 100 portions of methyl methacrylate, 250 portions of n-butyl acrylate, 2 to 10 portions of methacrylic acid, 0 to 50 portions of acrylonitrile and 1 to 8 portions of aliphatic polyurethane acrylate into a reaction kettle, and stirring for 1 to 1.5 hours to obtain a monomer pre-emulsion;
C. preparation of initiator solution: dissolving an initiator in 30-50 parts of water, and stirring to obtain an initiator solution for later use;
D. preparation of the emulsion: mixing 400 parts of water 300-containing materials, 1-5 parts of reactive polymerizable emulsifier and 0-10 parts of aqueous solid acrylic resin, stirring and heating to 80-85 ℃, adding 1-10% of monomer pre-emulsion, preserving heat for 5-15min, then adding 5-15% of initiator solution, preserving heat for 30-40min, then beginning to simultaneously dropwise add the rest monomer pre-emulsion and the rest initiator solution, finishing dropwise adding within 2.5-3.5h, then preserving heat for 1-1.5h, carrying out post-treatment and cooling, then adjusting the pH to 7-8 by using ammonia water, adding defoamer and bactericide, and filtering to obtain the final finished emulsion.
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Address after: 512400 5 North Road, Nanxiong fine chemical park, Shaoguan, Guangdong. Applicant after: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Address before: 512400 Dalingshan (Nanxiong) Industrial Transfer Industrial Park, Dongguan City, Guangdong Province, No. 5 North National Road Applicant before: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. |
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Denomination of invention: Waterborne acrylic lotion for automotive electrophoretic finish and its preparation method Effective date of registration: 20230506 Granted publication date: 20211008 Pledgee: Agricultural Bank of China Limited Nanxiong Sub branch Pledgor: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980039881 |