Waterborne acrylic resin as well as preparation method and application thereof

Abstract

The invention discloses water-based acrylic resin as well as a preparation method and application thereof. The water-based acrylic resin is prepared from the following components in parts by weight: 50 to 90 parts of acrylic polymeric monomer, 0.5 to 2 parts of initiator, 0.5 to 2 parts of emulsifier, 10 to 15 parts of diethanol amine and 60 to 80 parts of water. The acrylic polymeric monomer is prepared from acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in a weight ratio of 10: (5-15): (10-30): (3-8). The water-based acrylic resin is synthesized by selecting acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate and controlling the dosage of the acrylic acid, the tetrahydrofurfuryl acrylate, the trimethylolpropane triacrylate and the 4-hydroxybutyl acrylate, so that the adhesive force, the hardness and the wear resistance of the water-based paint prepared from the water-based acrylic resin can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and more specifically to a water-based acrylic resin and a preparation method and application thereof. Background Art

[0002] As a daily means of transportation, cars are widely used. During use, they often encounter scratches, collisions and other behaviors that damage the car paint film, making the car paint film no longer intact, affecting the appearance of the car. Moreover, if the primer, original anti-rust coating or steel plate is exposed at the crack of the car paint film, it means that the protective effect of the car paint film has been damaged, which can easily cause the steel plate to oxidize and rust. The rust may also spread to the entire body, eventually posing a threat to the safety of the vehicle. Therefore, it is necessary to repair the damaged parts of the car paint film in time to ensure the integrity and protective effectiveness of the paint film.

[0003] At present, the paints used to repair damaged parts of automobile paint films include oil-based paints and water-based paints. However, most of the paints currently used are oil-based paints. However, the VOCs (volatile organic compounds) generated by oil-based paints during use will cause great pollution to the environment. In recent years, with the improvement of environmental awareness, water-based paints have gradually become the development trend of the paint industry due to their environmental protection and low VOCs emissions, and are favored by consumers. However, the performance of existing water-based paints in the three aspects of adhesion, hardness, and wear resistance is still lacking and needs to be improved.

[0004] Therefore, it is of great significance to develop a water-based acrylic resin that can improve the adhesion, hardness and wear resistance of water-based coatings. Summary of the invention

[0005] The purpose of the present invention is to solve the problem of poor adhesion, hardness and wear resistance of water-based paint used for automobile paint film repair, and to provide a water-based acrylic resin and a preparation method and application thereof.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] In a first aspect, the present invention provides a water-based acrylic resin comprising the following components in parts by weight:

[0008] 50-90 parts of acrylic acid polymerization monomer, 0.5-2 parts of initiator, 0.5-2 parts of emulsifier, 10-15 parts of diethanolamine, 60-80 parts of water;

[0009] The acrylic acid polymerization monomers are acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in a weight ratio of 10:(5-15):(10-30):(3-8).

[0010] The invention selects acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate and controls the dosage of the synthesized water-based acrylic resin, so as to improve the adhesion, hardness and wear resistance of the water-based coating prepared by using the water-based acrylic resin.

[0011] The water-based acrylic resin of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate has a dense network structure and is uniformly dotted with rigid five-membered heterocyclic rings and hydroxyl-terminated alkyl side chains that participate in the formation of intermolecular and intramolecular hydrogen bonds that can improve the structural stability of the water-based acrylic resin. The wettability of the water-based coating on a substrate is enhanced, and the rigidity, compactness and crosslinking degree of the water-based coating are improved, thereby facilitating the improvement of the adhesion, hardness and wear resistance of the water-based coating prepared by using the water-based acrylic resin.

[0012] By regulating the weight ratio of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate, the density of the water-based acrylic resin network structure, the distribution uniformity and quantity of the rigid five-membered heterocyclic ring and the hydroxyl-terminated alkyl side chains forming hydrogen bonds can be controlled, thereby enhancing the wettability of the water-based coating to the substrate, improving the rigidity, density and cross-linking degree of the water-based coating, and further improving the adhesion, hardness and wear resistance of the water-based coating prepared using the water-based acrylic resin.

[0013] Preferably, the acrylic acid polymerization monomers are acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in a weight ratio of 10:10:20:5.

[0014] Preferably, the weight proportion of the acrylic acid polymerizable monomer is 60-80 parts.

[0015] Preferably, the initiator is at least one of ammonium persulfate and potassium persulfate.

[0016] Preferably, the emulsifier is at least one of sodium lauryl sulfate and OP-10.

[0017] In a second aspect, the present invention provides a method for preparing a water-based acrylic resin, comprising:

[0018] The components are mixed and reacted to obtain water-based acrylic resin.

[0019] Preferably, the reaction temperature is 60-80°C.

[0020] Preferably, the reaction time is 1-5 h.

[0021] In a third aspect, the present invention provides a use of a water-based acrylic resin in a water-based coating.

[0022] In a fourth aspect, the present invention provides a water-based coating comprising the following components in parts by weight:

[0023] 40-60 parts of water-based acrylic resin, 5-20 parts of curing agent, 5-20 parts of filler, and 15-25 parts of water.

[0024] Preferably, the curing agent is a water-based isocyanate curing agent, such as Bayhydur XP2655 from Bayer, Germany.

[0025] Preferably, the filler is at least one of hydrotalcite, mica powder, calcium carbonate and wollastonite.

[0026] Preferably, the filler is hydrotalcite and mica powder in a weight ratio of 1:(0.5-2.5).

[0027] More preferably, the filler is hydrotalcite and mica powder in a weight ratio of 1:(1-2).

[0028] Preferably, the water-based paint further comprises at least one of a pigment and an additive.

[0029] More preferably, the weight proportion of the pigment is 5-25 parts.

[0030] More preferably, the auxiliary agent is at least one of a defoamer, a leveling agent and a film-forming agent, the weight proportion of the defoamer is 0.1-2 parts, the weight proportion of the leveling agent is 0.1-1.5 parts, and the weight proportion of the film-forming agent is 0.1-2 parts.

[0031] Pigments, defoamers, leveling agents, and film-forming agents commonly used in the art can be used in the present invention, such as:

[0032] The pigment is at least one of an azo pigment and a phthalocyanine pigment, and the azo pigment is at least one of pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment yellow 128, pigment red 144, pigment red 166, pigment red 214, etc.;

[0033] The defoamer is a silicone defoamer, specifically BYK-021, etc.

[0034] The leveling agent is an organic silicon leveling agent, specifically BYK-333, etc.;

[0035] The film-forming agent may specifically be 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and the like.

[0036] In a fifth aspect, the present invention provides a method for preparing a water-based coating, comprising:

[0037] Firstly mix the other components except the curing agent, then add the curing agent and mix, thus obtaining the water-based paint.

[0038] In a sixth aspect, the present invention provides an application of a water-based paint in an automobile.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The invention selects acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate and controls the dosage of the synthesized water-based acrylic resin, so as to improve the adhesion, hardness and wear resistance of the water-based coating prepared by using the water-based acrylic resin.

[0041] The water-based acrylic resin of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate has a dense network structure and is uniformly dotted with rigid five-membered heterocyclic rings and hydroxyl-terminated alkyl side chains that participate in the formation of intermolecular and intramolecular hydrogen bonds that can improve the structural stability of the water-based acrylic resin. The wettability of the water-based coating on a substrate is enhanced, and the rigidity, compactness and crosslinking degree of the water-based coating are improved, thereby facilitating the improvement of the adhesion, hardness and wear resistance of the water-based coating prepared by using the water-based acrylic resin.

[0042] By regulating the weight ratio of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate, the density of the water-based acrylic resin network structure, the distribution uniformity and quantity of the rigid five-membered heterocyclic ring and the hydroxyl-terminated alkyl side chains forming hydrogen bonds can be controlled, thereby enhancing the wettability of the water-based coating to the substrate, improving the rigidity, density and cross-linking degree of the water-based coating, and further improving the adhesion, hardness and wear resistance of the water-based coating prepared using the water-based acrylic resin. DETAILED DESCRIPTION

[0043] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0044] The experimental methods without specific conditions in the following examples, comparative examples, application examples and comparative application examples are generally carried out according to conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets.

[0045] In each embodiment, comparative example, application example and comparative application example of the present invention, the use of reagents is as follows:

[0046] Curing agent, water-based isocyanate curing agent, Bayhydur XP2655, Bayer, Germany;

[0047] Hydrotalcite, magnesium aluminum hydrotalcite, H875612, McLean;

[0048] Mica powder, dry mica powder, D875286, McLean;

[0049] Pigment, Pigment Yellow 93, N832630, Maclean;

[0050] Defoamer, silicone defoamer, BYK-021, BYK;

[0051] Leveling agent, silicone leveling agent, BYK-333, BYK;

[0052] Film former, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, commercially available.

[0053] Example 1

[0054] This embodiment provides a water-based acrylic resin, comprising the following components in parts by weight:

[0055] 70 parts of acrylic acid polymerization monomer, 1.5 parts of initiator ammonium persulfate, 1 part of emulsifier sodium lauryl sulfate, 12 parts of diethanolamine, 70 parts of water;

[0056] The acrylic acid polymerization monomers are acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in a weight ratio of 10:10:20:5.

[0057] The preparation method of the water-based acrylic resin comprises:

[0058] The components were mixed and reacted at 70°C for 3 hours to obtain a water-based acrylic resin.

[0059] Examples 2-7 and Comparative Examples 1-6

[0060] Examples 2-7 and Comparative Examples 1-6 provide different water-based acrylic resins, which differ from Example 1 in that the weight ratios of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate are different, and the rest are consistent with Example 1, as shown in the following table:

[0061] Table 1 Weight ratio of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in Examples 1-7 and Comparative Examples 1-6

[0062]

[0063] Examples 8-11 and Comparative Examples 7-8

[0064] Examples 8-11 and Comparative Examples 7-8 provide different water-based acrylic resins, which differ from Example 1 in that the weight fractions of acrylic acid polymerized monomers are different, and the rest are consistent with Example 1, as shown in the following table:

[0065] Table 2 Weight parts of acrylic acid polymerization monomers in Examples 1, 8-11 and Comparative Examples 7-8

[0066]

[0067]

[0068] Example 12

[0069] This embodiment provides a water-based acrylic resin, comprising the following components in parts by weight:

[0070] 70 parts of acrylic acid polymerization monomer, 0.5 parts of initiator ammonium persulfate, 0.5 parts of emulsifier sodium lauryl sulfate, 10 parts of diethanolamine, 60 parts of water;

[0071] The acrylic acid polymerization monomers are acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in a weight ratio of 10:10:20:5.

[0072] The preparation method of the water-based acrylic resin comprises:

[0073] The components were mixed and reacted at 70°C for 3 hours to obtain a water-based acrylic resin.

[0074] Embodiment 13

[0075] This embodiment provides a water-based acrylic resin, comprising the following components in parts by weight:

[0076] 70 parts of acrylic acid polymerization monomer, 2 parts of initiator ammonium persulfate, 2 parts of emulsifier sodium lauryl sulfate, 15 parts of diethanolamine, 80 parts of water;

[0077] The acrylic acid polymerization monomers are acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in a weight ratio of 10:10:20:5.

[0078] The preparation method of the water-based acrylic resin comprises:

[0079] The components were mixed and reacted at 70°C for 3 hours to obtain a water-based acrylic resin.

[0080] Application examples and comparative application examples

[0081] Application Example 1

[0082] This application example provides a water-based coating, comprising the following components in parts by weight:

[0083] 50 parts of the water-based acrylic resin of Example 1, 13 parts of a curing agent, 15 parts of a filler, 20 parts of water, 10 parts of a pigment, 1 part of a defoaming agent, 1 part of a leveling agent, and 1 part of a film-forming agent;

[0084] The filler is hydrotalcite and mica powder in a weight ratio of 1:1.5;

[0085] The preparation method of the water-based coating comprises:

[0086] Firstly mix the other components except the curing agent, then add the curing agent and mix, thus obtaining the water-based paint.

[0087] Application Example 2-13

[0088] Application Examples 2-13 provide different water-based coatings, which differ from Application Example 1 in that Application Examples 2-13 use the water-based acrylic resins of Examples 2-13 to replace the water-based acrylic resin of Example 1, and the rest is consistent with Application Example 1.

[0089] Comparative Application Examples 1-8

[0090] Comparative Application Examples 1-8 provide different water-based coatings, which differ from Application Example 1 in that Comparative Application Examples 1-7 use the water-based acrylic resins of Comparative Examples 1-8 to replace the water-based acrylic resin of Example 1, and the rest are consistent with Application Example 1.

[0091] Application Examples 14-19

[0092] Application Examples 14-19 provide different water-based coatings, which differ from Application Example 1 in that the weight ratio of hydrotalcite to mica powder is different, and the rest is consistent with Application Example 1, as shown in the following table:

[0093] Table 3 Weight ratio of hydrotalcite and mica powder in application examples 1, 14-19

[0094] Weight ratio of hydrotalcite and mica powder Application Example 1 1:1.5 Application Example 14 1:1 Application Example 15 1:2 Application Example 16 1:0.5 Application Example 17 1:2.5 Application Example 18 1:0 Application Example 19 0:1

[0095] Application Example 20

[0096] This application example provides a water-based coating, comprising the following components in parts by weight:

[0097] 40 parts of the water-based acrylic resin of Example 1, 5 parts of a curing agent, 5 parts of a filler, 15 parts of water, 5 parts of a pigment, 0.1 parts of a defoaming agent, 0.1 parts of a leveling agent, and 0.1 parts of a film-forming agent;

[0098] The filler is hydrotalcite and mica powder in a weight ratio of 1:1.5;

[0099] The preparation method of the water-based coating comprises:

[0100] Firstly mix the other components except the curing agent, then add the curing agent and mix, thus obtaining the water-based paint.

[0101] Application Example 21

[0102] This application example provides a water-based coating, comprising the following components in parts by weight:

[0103] 60 parts of the water-based acrylic resin of Example 1, 20 parts of a curing agent, 20 parts of a filler, 25 parts of water, 25 parts of a pigment, 2 parts of a defoaming agent, 1.5 parts of a leveling agent, and 2 parts of a film-forming agent;

[0104] The filler is hydrotalcite and mica powder in a weight ratio of 1:1.5;

[0105] The preparation method of the water-based coating comprises:

[0106] Firstly mix the other components except the curing agent, then add the curing agent and mix, thus obtaining the water-based paint.

[0107] Performance Testing

[0108] The performance tests of the water-based coatings in each application example and comparative application example are as follows:

[0109] (1) Preparation of test samples:

[0110] 20g of the water-based paint of each application example or comparative application example was applied on a 50mm*50mm*2mm tinplate plane, and dried at 60°C for 18h to obtain a test sample;

[0111] (2) Adhesion test:

[0112] According to GB / T 9286-2021, the adhesion test of the test samples prepared from the water-based coatings of each application example or comparative application example is performed. The larger the adhesion level, the worse the adhesion of the water-based coating;

[0113] (3) Pencil hardness test:

[0114] According to GB / T 6739-2006, the pencil hardness test is performed on the test samples prepared from the water-based paint of each application example or comparative application example. The greater the pencil hardness, the greater the hardness of the water-based paint.

[0115] (4) Wear resistance test:

[0116] According to GB / T 1768-2006, the test samples prepared from the water-based coatings of each application example or comparative application example were subjected to a wear resistance test. Specifically, under the conditions of a rubber grinding wheel load of 1000 g and a test rotation number of 1000 revolutions, the wear mass of the water-based coating (accurate to 0.1 mg) was measured. The greater the wear mass, the worse the wear resistance of the water-based coating.

[0117] The experimental results are shown in the following table:

[0118] Table 4 Performance test results of water-based coatings in various application examples and comparative application examples

[0119]

[0120]

[0121] As can be seen from Table 4, the present invention can improve the adhesion, hardness and wear resistance of the water-based coating prepared by using the water-based acrylic resin synthesized by selecting acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate and controlling their dosage.

[0122] The water-based acrylic resin of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate has a dense network structure and is uniformly dotted with rigid five-membered heterocyclic rings and hydroxyl-terminated alkyl side chains that participate in the formation of intermolecular and intramolecular hydrogen bonds that can improve the structural stability of the water-based acrylic resin. The wettability of the water-based coating on a substrate is enhanced, and the rigidity, compactness and crosslinking degree of the water-based coating are improved, thereby facilitating the improvement of the adhesion, hardness and wear resistance of the water-based coating prepared by using the water-based acrylic resin.

[0123] It can be seen from Application Examples 1-7 and Comparative Application Examples 1-6 that by regulating the weight ratio of acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate, the density of the water-based acrylic resin network structure, the distribution uniformity and quantity of rigid five-membered heterocyclic rings and hydroxyl-terminated alkyl side chains forming hydrogen bonds can be controlled, thereby enhancing the wettability of the water-based coating to the substrate, improving the rigidity, density and cross-linking degree of the water-based coating, and further improving the adhesion, hardness and wear resistance of the water-based coating prepared using the water-based acrylic resin.

[0124] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A water-based acrylic resin, It is characterized in that The composition comprises the following components in parts by weight: 50-90 parts of acrylic acid polymerization monomer, 0.5-2 parts of initiator, 0.5-2 parts of emulsifier, 10-15 parts of diethanolamine, 60-80 parts of water; The acrylic acid polymerization monomers are acrylic acid, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate and 4-hydroxybutyl acrylate in a weight ratio of 10:(5-15):(10-30):(3-8).

2. The water-based acrylic resin according to claim 1, It is characterized in that The weight proportion of the acrylic acid polymerization monomer is 60-80 parts.

3. A method for preparing a water-based acrylic resin as claimed in any one of claims 1 to 2, It is characterized in that include: The components are mixed and reacted to obtain water-based acrylic resin.

4. Use of the water-based acrylic resin as claimed in any one of claims 1 to 2 in water-based coatings.

5. A water-based paint, It is characterized in that The composition comprises the following components in parts by weight: 40-60 parts of the water-based acrylic resin according to any one of claims 1-2, 5-20 parts of a curing agent, 5-20 parts of a filler, and 15-25 parts of water.

6. The water-based paint according to claim 5, It is characterized in that Including at least one of the following (1)-(3): (1) The curing agent is a water-based isocyanate curing agent; (2) The filler is at least one of hydrotalcite, mica powder, calcium carbonate, and wollastonite; (3) The water-based paint further comprises at least one of a pigment and an additive.

7. The water-based paint according to claim 6, It is characterized in that Including at least one of the following (1)-(3): (1) The filler is hydrotalcite and mica powder in a weight ratio of 1: (0.5-2.5); (2) The weight proportion of the pigment is 5-25 parts; (3) The auxiliary agent is at least one of a defoaming agent, a leveling agent, and a film-forming agent.

8. The water-based paint according to claim 6, It is characterized in that Including at least one of the following (1)-(4): (1) The filler is hydrotalcite and mica powder in a weight ratio of 1:(1-2); (2) The weight proportion of the defoaming agent is 0.1-2 parts; (3) The weight proportion of the leveling agent is 0.1-1.5 parts; (4) The weight proportion of the film-forming agent is 0.1-2 parts.

9. A method for preparing a water-based coating as claimed in any one of claims 5 to 8, It is characterized in that include: Firstly mix the other components except the curing agent, then add the curing agent and mix, thus obtaining the water-based paint.

10. Use of the water-based paint according to any one of claims 5 to 8 in automobiles.

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