CN116694175A - Water-based self-cleaning scratch-resistant automobile coating and preparation method thereof - Google Patents
Water-based self-cleaning scratch-resistant automobile coating and preparation method thereof Download PDFInfo
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- CN116694175A CN116694175A CN202310110629.0A CN202310110629A CN116694175A CN 116694175 A CN116694175 A CN 116694175A CN 202310110629 A CN202310110629 A CN 202310110629A CN 116694175 A CN116694175 A CN 116694175A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000004140 cleaning Methods 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 25
- 239000011248 coating agent Substances 0.000 title claims abstract description 22
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003973 paint Substances 0.000 claims abstract description 29
- 229920003180 amino resin Polymers 0.000 claims abstract description 22
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 17
- 239000003899 bactericide agent Substances 0.000 claims abstract description 17
- 239000002562 thickening agent Substances 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 12
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 11
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000000080 wetting agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 27
- 238000005303 weighing Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- -1 methyl butyl Chemical group 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000003873 salicylate salts Chemical class 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims 1
- 150000008366 benzophenones Chemical class 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000003075 superhydrophobic effect Effects 0.000 description 9
- 239000000428 dust Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 241000237858 Gastropoda Species 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000006115 industrial coating Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 244000241796 Christia obcordata Species 0.000 description 1
- 241000931705 Cicada Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000208720 Nepenthes Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a water-based self-cleaning scratch-resistant automobile paint and a preparation method thereof, belonging to the technical field of automobile paint, and comprising the following components in percentage by mass: 30-60 parts of water-based hydrophilic acrylic resin, 10-20 parts of water-based amino resin, 5-20 parts of water-based nano silica sol, 2-10 parts of modified nano alumina, 0.5-4 parts of ultraviolet absorber, 2-10 parts of film forming auxiliary agent, 0.1-0.6 part of flatting agent, 0.1-0.8 part of adhesion promoter, 2-6 parts of dispersing agent, 0.2-5 parts of thickening agent, 0.1-0.5 part of defoaming agent, 0.2-0.6 part of wetting agent, 0.1-0.5 part of bactericide, 1-6 parts of pH regulator and 10-35 parts of deionized water. The super-hydrophilic self-cleaning coating prepared by the method can lead water drops to be quickly spread into a water film, has good self-cleaning function, has the characteristics of high weather resistance, high scratch resistance, high wear resistance and the like, is simple and easy to manufacture, requires less equipment and is very convenient for industrial production.
Description
Technical Field
The invention belongs to the technical field of automobile coatings, and particularly relates to a water-based self-cleaning scratch-resistant automobile coating and a preparation method thereof.
Background
Automotive coatings, particularly automotive topcoats, represent the highest level of industrial coatings, automotive topcoats have very high performance index requirements for the coating, general aqueous industrial coatings cannot be compared favorably with solvent-based coatings, and related performance requirements are difficult to achieve, but aqueous automotive topcoats with certain self-cleaning are less.
Self-cleaning refers to the inherent property of a special material, and substances such as impurity dust attached to the surface of the special material can be spontaneously removed in different modes. In fact, this phenomenon was originally derived from human observations of nature, the "silt-out but not stain" lotus leaf, which is a typical natural self-cleaning surface. In addition, many other animal and plant parts of the surface of nature have natural self-cleaning capabilities, such as rice leaves, nepenthes, wings of cicada, butterfly wings, gecko's feet, snail shells, fish scales, shark skin, etc. From the mechanism point of view, most natural self-cleaning surfaces have special wettability, namely super-hydrophilicity and super-hydrophobicity, and the self-cleaning function is realized through the interaction of water and the surface of an object.
Firstly, the super-hydrophilic and super-hydrophobic self-cleaning surfaces are both made use of the special wettability of the material surface. Wettability, also called wettability, refers to the ability or tendency of a liquid to spread on a solid surface. For example, a drop of water on a solid surface may occur in two different situations: water droplets tend to spread into a thin water layer, which indicates that water wets on such solid surfaces, which are hydrophilic; or the water droplets tend to bunch up into spherical droplets, which indicates that the water does not infiltrate at such solid surfaces, which are hydrophobic. Contact angles greater than 90 degrees are hydrophobic surfaces and less than 90 degrees are hydrophilic surfaces. Further, it is defined that the solid surface has superhydrophobicity when the contact angle is close to or more than 150 degrees, and superhydrophilicity when the contact angle approaches 0 degrees. How does the superhydrophilic and superhydrophobic surfaces achieve self-cleaning? On one hand, water can spontaneously spread into a water film with a large area and a thin thickness on the super-hydrophilic surface, so that the direct contact of pollutants such as grease, dust particles and the like with the surface is prevented; the completely spread water film can evaporate quickly, so that impurities attached to the surface of the water film are taken away, and a self-cleaning function is realized. In nature, snail shells are the case. On the other hand, water spontaneously forms aggregated water drops under superhydrophobic condition, and when the water drops roll on an inclined surface, some dust particles attached to the surface can be spontaneously taken away, so that a self-cleaning function is realized. In nature, the wings of some butterflies have similar functions, in addition to the previously mentioned lotus leaves. The super-hydrophobic self-cleaning coating is required to realize a self-cleaning function, and has a relatively small rolling angle besides a relatively high contact angle. The super-hydrophobic self-cleaning coating mainly corresponds to the movement mode of liquid drops on the surface of the self-cleaning coating, and has important application in the aspects of ship antifouling, radar signal attenuation prevention, high-voltage power transmission antifouling, textile finishing and sports equipment because the super-hydrophobic self-cleaning coating has the advantages of water repellency, small friction coefficient, strong weather resistance and the like. However, in the actual use process of the super-hydrophobic self-cleaning coating, the surface hydrophobicity of the super-hydrophobic coating is reduced due to the adhesion of oily organic pollution, and the super-hydrophobic self-cleaning performance is further lost.
Disclosure of Invention
The invention provides a water-based self-cleaning scratch-resistant automobile paint which is characterized by comprising the following components in percentage by weight: 30-60 parts of water-based hydrophilic acrylic resin, 10-20 parts of water-based amino resin, 5-20 parts of water-based nano silica sol, 2-10 parts of modified nano alumina, 0.5-4 parts of ultraviolet absorber, 2-10 parts of film forming auxiliary agent, 0.1-0.6 part of flatting agent, 0.1-0.8 part of adhesion promoter, 2-6 parts of dispersing agent, 0.2-5 parts of thickening agent, 0.1-0.5 part of defoaming agent, 0.2-0.6 part of wetting agent, 0.1-0.5 part of bactericide, 1-6 parts of pH regulator and 10-35 parts of deionized water.
Preferably, the hydrophilic acrylic resin is one or more of styrene-acrylic emulsion and pure acrylic emulsion.
Preferably, the aqueous amino resin is at least one of a fully methylated amino resin, a partially methylated amino resin, a butylated amino resin and a methyl butyl mixed etherified amino resin.
Preferably, the adhesion promoter is: any one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent are mixed.
Preferably, the ultraviolet absorbent is any one or a mixture of more than one of water-soluble benzotriazoles, salicylates and phenones.
Preferably, the defoamer is: any one or more of polyether siloxane, mineral oil, acrylic ester, polyether modified dimethyl siloxane and polyester modified polysiloxane.
Preferably, the pH adjuster is: ammonia, AMP95, monoethanolamine, dimethylethanolamine.
Preferably, the aqueous silica sol is one or more of acidic silica sol, alkaline silica sol and neutral silica sol.
Preferably, the modified nano-alumina is organic modified nano-alumina.
The invention is mainly characterized in that the synthesized water-based hydrophilic resin is taken as a main resin, and raw materials such as amino resin, water-based silica sol, nano alumina and the like are properly matched to prepare the water-based automobile paint with super-hydrophilic self-cleaning performance, good scratch resistance and the like, and meanwhile, the water-based automobile paint has good drying performance, weather resistance, low VOC and the like.
In order to achieve the purpose of the invention, the following technical scheme is adopted: the water-based self-cleaning scratch-resistant automobile paint and the preparation method thereof are characterized by comprising the following steps:
(1) Synthesis of aqueous hydrophilic acrylic resin:
pre-emulsification of monomers: adding a certain amount of modified fatty alcohol polyoxyethylene ether sodium sulfate, water, methyl methacrylate, butyl acrylate, styrene, methacrylic acid and hydroxypropyl acrylate, and stirring for about 10min to prepare a pre-emulsified mixture;
b, firstly adding a mixture of water and modified fatty alcohol polyoxyethylene ether sodium sulfate into a reaction kettle, and then adding N 2 Firstly, 300ml/min is used for 10min, then 30ml/min is used for reducing N 2 After the usage amount is used, the temperature is raised to 80 ℃; wherein when the temperature is raised to 75 ℃, addAdding a certain amount of the pre-emulsified mixture in the step a, continuously heating to 80 ℃, adding a certain amount of 2.5wt% potassium persulfate, and maintaining the temperature at 80 ℃ for 15min; simultaneously dropwise adding the pre-emulsified mixture in the step (a) and 2.5wt% of potassium persulfate for 3 hours;
c, continuing to keep the temperature for 1h, and heating to 85 ℃ and keeping the temperature for 1h; cooling to below 50 ℃; filtering the mixture to obtain the material with 400 meshes, and testing the parameters such as solid content, viscosity, pH value and the like.
(2) Sequentially weighing 30-60 parts of water-based hydrophilic acrylic resin and 10-20 parts of water-based amino resin according to parts by weight, dispersing for about 10min under the condition of 800r/min, sequentially adding 2-10 parts of film forming auxiliary agent, 5-20 parts of water-based nano silica sol, 2-6 parts of dispersing agent and 2-10 parts of modified nano alumina, and dispersing for about 30min under the condition of 1000r/min until the dispersion is uniform;
(3) Weighing 0.1-0.5 part of defoaming agent, 0.2-0.6 part of wetting agent, 0.5-4 parts of ultraviolet absorber, 0.1-0.6 part of flatting agent and 0.1-0.8 part of adhesion promoter in sequence according to parts by weight, and dispersing for about 30min under the condition of 800r/min until the dispersion is uniform;
(4) And sequentially weighing 0.2-5 parts by weight of thickener and 0.1-0.5 part by weight of bactericide, dispersing for about 20min under the condition of 800r/min until the thickener and the bactericide are uniformly dispersed, then adding 1-6 parts by weight of pH regulator and 10-35 parts by weight of deionized water, and adjusting the paint to a certain pH value and viscosity to prepare the water-based self-cleaning scratch-resistant automobile paint.
A self-cleaning scratch-resistant water-based automobile paint is applied to the surface of an automobile in a spraying manner.
Compared with the existing common automobile paint, the invention has the following good results: the invention adopts the water-based hydrophilic resin as the main resin to further increase the hydrophilic performance of the paint film surface, so that the coating has good self-cleaning performance, and the scratch resistance, hardness and other performances of the automobile paint film are obviously improved by properly adding related auxiliaries such as silica sol and the like. In addition, the invention belongs to water-based paint, can obviously reduce the VOC emission of the paint, has extremely high economic and social benefits, and promotes the healthy development of society and enterprises.
Drawings
Fig. 1 is a graph of contact angles provided by an embodiment of the present invention.
Detailed Description
In order to better explain the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with examples in the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
Embodiment one:
(1) Synthesis of aqueous hydrophilic acrylic resin:
pre-emulsification of monomers: sequentially adding 0.6 part of modified fatty alcohol polyoxyethylene ether sodium sulfate, 20 parts of water, 13 parts of methyl methacrylate, 12 parts of butyl acrylate, 8 parts of styrene, 1 part of methacrylic acid and 7 parts of hydroxypropyl acrylate in sequence, and stirring for about 10 minutes to prepare a pre-emulsified mixture;
b, firstly adding a certain amount of mixture of water and modified fatty alcohol polyoxyethylene ether sodium sulfate into a reaction kettle, and then introducing N 2 Firstly, 300ml/min is used for 10min, then 30ml/min is used for reducing N 2 After the usage amount is used, the temperature is raised to 80 ℃; wherein when the temperature is raised to 75 ℃, 4% of the pre-emulsified mixture in the step a is added, the temperature is continuously raised to 80 ℃, 10 parts of 2.5wt% potassium persulfate is added, and the temperature is maintained at 80 ℃ for 15min; simultaneously dropwise adding the pre-emulsified mixture in the step (a) and 5 parts of 2.5wt% potassium persulfate for 3 hours;
c, continuing to keep the temperature for 1h, and heating to 85 ℃ and keeping the temperature for 1h; cooling to below 50 ℃; filtering the mixture to obtain the material with 400 meshes, and testing the parameters such as solid content, viscosity, pH value and the like.
(2) 40 parts of water-based hydrophilic acrylic resin and 10 parts of water-based amino resin are sequentially weighed according to parts by weight, dispersed for about 10min under the condition of 800r/min, and then 8 parts of film forming auxiliary agent, 10 parts of water-based nano silica sol, 3 parts of dispersing agent and 8 parts of modified nano alumina are sequentially added, and dispersed for about 30min under the condition of 1000r/min until the dispersion is uniform;
(3) Weighing 0.5 part of defoaming agent, 0.2 part of wetting agent, 2 parts of ultraviolet absorber, 0.1 part of flatting agent and 0.8 part of adhesion promoter in sequence according to parts by weight, and dispersing for about 30min under the condition of 800r/min until the dispersion is uniform;
(4) And sequentially weighing 0.6 part of thickener and 0.1 part of bactericide according to parts by weight, dispersing for about 20 minutes under the condition of 800r/min until the thickener and the bactericide are uniformly dispersed, then adding 2 parts of pH regulator and 20 parts of deionized water, and adjusting the paint to a certain pH value and viscosity to prepare the water-based self-cleaning scratch-resistant automobile paint.
Embodiment two:
(1) Synthesis of aqueous hydrophilic acrylic resin:
pre-emulsification of monomers: adding 0.7 part of modified fatty alcohol polyoxyethylene ether sodium sulfate, 25 parts of water, 15 parts of methyl methacrylate, 15 parts of butyl acrylate, 10 parts of styrene, 2 parts of methacrylic acid and 8 parts of hydroxypropyl acrylate in sequence, and stirring for about 10 minutes to prepare a pre-emulsified mixture;
b, firstly adding a certain amount of mixture of water and modified fatty alcohol polyoxyethylene ether sodium sulfate into a reaction kettle, and then introducing N 2 Firstly, 300ml/min is used for 10min, then 30ml/min is used for reducing N 2 After the usage amount is used, the temperature is raised to 80 ℃; wherein when the temperature is raised to 75 ℃, adding 6% of the pre-emulsified mixture in the step a, continuously raising the temperature to 80 ℃, adding 12 parts of 2.5wt% potassium persulfate, and maintaining the temperature at 80 ℃ for 15min; simultaneously dropwise adding the pre-emulsified mixture in the step (a) and 6 parts of 2.5wt% potassium persulfate for 3 hours;
c, continuing to keep the temperature for 1h, and heating to 85 ℃ and keeping the temperature for 1h; cooling to below 50 ℃; filtering the mixture to obtain the material with 400 meshes, and testing the parameters such as solid content, viscosity, pH value and the like.
(2) Sequentially weighing 45 parts of water-based hydrophilic acrylic resin and 12 parts of water-based amino resin according to parts by weight, dispersing for about 10min under the condition of 800r/min, sequentially adding 8 parts of film forming auxiliary agent, 12 parts of water-based nano silica sol, 2 parts of dispersing agent and 7 parts of modified nano alumina, and dispersing for about 30min under the condition of 1000r/min until the dispersion is uniform;
(3) Weighing 0.2 part of defoaming agent, 0.2 part of wetting agent, 2 parts of ultraviolet absorber, 0.2 part of flatting agent and 0.8 part of adhesion promoter in sequence according to parts by weight, and dispersing for about 30min under the condition of 800r/min until the dispersion is uniform;
(4) And (3) weighing 0.7 part of thickener and 0.1 part of bactericide in sequence according to parts by weight, dispersing for about 20min under the condition of 800r/min until the thickener and the bactericide are uniformly dispersed, then adding 2 parts of pH regulator and 22 parts of deionized water, and adjusting the paint to a certain pH value and viscosity to prepare the water-based self-cleaning scratch-resistant automobile paint.
Embodiment III:
(1) Synthesis of aqueous hydrophilic acrylic resin:
pre-emulsification of monomers: adding 0.5 part of modified fatty alcohol polyoxyethylene ether sodium sulfate, 23 parts of water, 13 parts of methyl methacrylate, 12 parts of butyl acrylate, 12 parts of styrene, 3 parts of methacrylic acid and 10 parts of hydroxypropyl acrylate in sequence, and stirring for about 10 minutes to prepare a pre-emulsified mixture;
b, firstly adding a certain amount of mixture of water and modified fatty alcohol polyoxyethylene ether sodium sulfate into a reaction kettle, and then introducing N 2 Firstly, 300ml/min is used for 10min, then 30ml/min is used for reducing N 2 After the usage amount is used, the temperature is raised to 80 ℃; wherein when the temperature is raised to 75 ℃, 8% of the pre-emulsified mixture in the step a is added, the temperature is continuously raised to 80 ℃, 11 parts of 2.5wt% potassium persulfate is added, and the temperature is maintained at 80 ℃ for 15min; simultaneously dropwise adding the pre-emulsified mixture in the step (a) and 8 parts of 2.5wt% potassium persulfate for 3 hours;
c, continuing to keep the temperature for 1h, and heating to 85 ℃ and keeping the temperature for 1h; cooling to below 50 ℃; filtering the mixture to obtain the material with 400 meshes, and testing the parameters such as solid content, viscosity, pH value and the like.
(2) Sequentially weighing 48 parts of water-based hydrophilic acrylic resin and 14 parts of water-based amino resin according to parts by weight, dispersing for about 10min under the condition of 800r/min, sequentially adding 8 parts of film forming auxiliary agent, 12 parts of water-based nano silica sol, 2 parts of dispersing agent and 9 parts of modified nano alumina, and dispersing for about 30min under the condition of 1000r/min until the dispersion is uniform;
(3) Weighing 0.2 part of defoaming agent, 0.2 part of wetting agent, 3 parts of ultraviolet absorber, 0.2 part of leveling agent and 0.8 part of adhesion promoter in sequence according to parts by weight, and dispersing for about 30min under the condition of 800r/min until the dispersion is uniform;
(4) And (3) weighing 0.6 part of thickener and 0.2 part of bactericide in sequence according to parts by weight, dispersing for about 20min under the condition of 800r/min until the thickener and the bactericide are uniformly dispersed, then adding 2 parts of pH regulator and 23 parts of deionized water, and adjusting the paint to a certain pH value and viscosity to prepare the water-based self-cleaning scratch-resistant automobile paint.
Comparative example one:
(1) Sequentially weighing 48 parts of common aqueous acrylic resin and 12 parts of aqueous amino resin according to parts by weight, dispersing for about 10min under the condition of 800r/min, sequentially adding 8 parts of film forming auxiliary agent, 12 parts of filler and 2 parts of dispersing agent, and dispersing for about 30min under the condition of 1000r/min until the dispersion is uniform;
(2) Weighing 0.2 part of defoaming agent, 0.2 part of wetting agent, 3 parts of ultraviolet absorber, 0.2 part of leveling agent and 0.8 part of adhesion promoter in sequence according to parts by weight, and dispersing for about 30min under the condition of 800r/min until the dispersion is uniform;
(3) And (3) weighing 0.6 part of thickener and 0.2 part of bactericide in sequence according to parts by weight, dispersing for about 20 minutes under the condition of 800r/min until the thickener and the bactericide are uniformly dispersed, and then adding 2 parts of pH regulator and 20 parts of deionized water to adjust the paint to a certain pH value and viscosity to prepare the water-based automobile paint.
Control II:
(1) Sequentially weighing 50 parts of common aqueous acrylic resin and 13 parts of aqueous amino resin according to parts by weight, dispersing for about 10min under the condition of 800r/min, sequentially adding 9 parts of film forming auxiliary agent, 10 parts of filler and 2 parts of dispersing agent, and dispersing for about 30min under the condition of 1000r/min until the dispersion is uniform;
(2) Weighing 0.2 part of defoaming agent, 0.2 part of wetting agent, 4 parts of ultraviolet absorber, 0.2 part of leveling agent and 0.6 part of adhesion promoter in sequence according to parts by weight, and dispersing for about 30min under the condition of 800r/min until the dispersion is uniform;
(3) And (3) sequentially weighing 0.5 part of thickener and 0.2 part of bactericide according to parts by weight, dispersing for about 20min under the condition of 800r/min until the thickener and the bactericide are uniformly dispersed, then adding 3 parts of pH regulator and 25 parts of deionized water, and regulating the paint to a certain pH value and viscosity to prepare the water-based automobile paint.
The performance of paint film coatings prepared by the products of the first to third examples and the comparison examples is compared and tested, the test results are shown in a table 1, the contact angle of the examples is shown in a table 1, wherein the more the number of plus is more dust, the better the examples are than the comparison examples in terms of hydrophilicity, dust resistance, scratch resistance, hardness, wear resistance, salt spray resistance, acid and alkali resistance, substrate adhesion and the like, because the examples are compared with the comparison examples, the hydrophilic performance of the examples is obviously improved compared with the performance of the common acrylic resin by using the water-based hydrophilic acrylic resin as the main resin, the hardness and the wear resistance of the examples are further improved by properly matching with the raw materials such as water-based silica sol, nano modified alumina and the like, and the crosslinking density of the paint is further improved by matching with the proper amino resin, so that the overall performance of the paint is further improved.
TABLE 1
Claims (10)
1. An aqueous self-cleaning scratch-resistant automotive coating, which is characterized in that: the composition of the material in percentage by weight is as follows: 30-60 parts of water-based hydrophilic acrylic resin, 10-20 parts of water-based amino resin, 5-20 parts of water-based nano silica sol, 2-10 parts of modified nano alumina, 0.5-4 parts of ultraviolet absorber, 2-10 parts of film forming auxiliary agent, 0.1-0.6 part of flatting agent, 0.1-0.8 part of adhesion promoter, 2-6 parts of dispersing agent, 0.2-5 parts of thickening agent, 0.1-0.5 part of defoaming agent, 0.2-0.6 part of wetting agent, 0.1-0.5 part of bactericide, 1-6 parts of pH regulator and 10-35 parts of deionized water.
2. The aqueous self-cleaning scratch-resistant automotive coating according to claim 1, wherein the hydrophilic acrylic resin is one or more of styrene-acrylic emulsion and pure acrylic emulsion.
3. The aqueous self-cleaning scratch-resistant automotive coating of claim 1, wherein the aqueous amino resin is at least one of a fully methylated amino resin, a partially methylated amino resin, a butylated amino resin, and a methyl butyl mixed etherified amino resin.
4. The aqueous self-cleaning scratch-resistant automotive coating of claim 1, wherein the adhesion promoter is: any one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent are mixed.
5. The aqueous self-cleaning scratch-resistant automotive coating of claim 1, wherein the ultraviolet absorber is any one or more of water-soluble benzotriazoles, salicylates and benzophenones.
6. The aqueous self-cleaning scratch-resistant automotive coating according to claim 1, wherein the defoamer is: any one or more of polyether siloxane, mineral oil, acrylic ester, polyether modified dimethyl siloxane and polyester modified polysiloxane.
7. The aqueous self-cleaning scratch-resistant automotive coating of claim 1, wherein the pH adjuster is: ammonia, AMP95, monoethanolamine, dimethylethanolamine.
8. The aqueous self-cleaning scratch-resistant automotive coating of claim 1, wherein the aqueous silica sol is one or more of an acidic silica sol, an alkaline silica sol, and a neutral silica sol.
9. The aqueous self-cleaning scratch-resistant automotive coating of claim 1, wherein the modified nano-alumina is an organic modified nano-alumina.
10. The method for preparing the aqueous self-cleaning scratch-resistant automotive coating according to any one of claims 1 to 9, comprising the following steps:
(1) Synthesis of aqueous hydrophilic acrylic resin:
pre-emulsification of monomers: adding a certain amount of modified fatty alcohol polyoxyethylene ether sodium sulfate, water, methyl methacrylate, butyl acrylate, styrene, methacrylic acid and hydroxypropyl acrylate, and stirring for about 10min to prepare a pre-emulsified mixture;
b, firstly adding a mixture of water and modified fatty alcohol polyoxyethylene ether sodium sulfate into a reaction kettle, and then adding N 2 Firstly, 300ml/min is used for 10min, then 30ml/min is used for reducing N 2 After the usage amount is used, the temperature is raised to 80 ℃; wherein when the temperature is raised to 75 ℃, adding a certain amount of the pre-emulsified mixture in the step a, continuously raising the temperature to 80 ℃, adding a certain amount of 2.5wt% of potassium persulfate, maintaining the temperature at 80 ℃ for about 15min, and simultaneously dropwise adding the rest of the pre-emulsified mixture in the step a and 2.5wt% of potassium persulfate, wherein the whole dropwise addition is completed for 3 hours;
c, continuing to keep the temperature for 1h, and heating to 85 ℃ and keeping the temperature for 1h; cooling to below 50 ℃; filtering the mixture to obtain a 400-mesh material, and testing solid content, viscosity and pH value parameters;
(2) Sequentially weighing 30-60 parts of water-based hydrophilic acrylic resin and 10-20 parts of water-based amino resin according to parts by weight, dispersing for about 10min under the condition of 800r/min, sequentially adding 2-10 parts of film forming auxiliary agent, 5-20 parts of water-based nano silica sol, 2-6 parts of dispersing agent and 2-10 parts of modified nano alumina, and dispersing for about 30min under the condition of 1000r/min until the dispersion is uniform;
(3) Weighing 0.1-0.5 part of defoaming agent, 0.2-0.6 part of wetting agent, 0.5-4 parts of ultraviolet absorber, 0.1-0.6 part of flatting agent and 0.1-0.8 part of adhesion promoter in sequence according to parts by weight, and dispersing for about 30min under the condition of 800r/min until the dispersion is uniform;
(4) And sequentially weighing 0.2-5 parts by weight of thickener and 0.1-0.5 part by weight of bactericide, dispersing for about 20min under the condition of 800r/min until the thickener and the bactericide are uniformly dispersed, then adding 1-6 parts by weight of pH regulator and 10-35 parts by weight of deionized water, and adjusting the paint to a certain pH value and viscosity to prepare the water-based self-cleaning scratch-resistant automobile paint.
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| CN116904077A (en) * | 2023-09-13 | 2023-10-20 | 山东森博斯特塑胶科技有限公司 | PO film coating liquid and preparation method thereof |
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