CN115449269A - Water-based fluorine-modified siloxane acrylic coating and preparation method and application thereof - Google Patents
Water-based fluorine-modified siloxane acrylic coating and preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 90
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 21
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 7
- 239000000080 wetting agent Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000002562 thickening agent Substances 0.000 claims abstract description 6
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 12
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 11
- 229960002887 deanol Drugs 0.000 claims description 11
- 239000012972 dimethylethanolamine Substances 0.000 claims description 11
- -1 aliphatic isocyanate Chemical class 0.000 claims description 8
- RNFAKTRFMQEEQE-UHFFFAOYSA-N Tripropylene glycol butyl ether Chemical compound CCCCOC(CC)OC(C)COC(O)CC RNFAKTRFMQEEQE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 150000002632 lipids Chemical class 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001023 inorganic pigment Substances 0.000 claims description 2
- 229940116423 propylene glycol diacetate Drugs 0.000 claims description 2
- 125000003473 lipid group Chemical group 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 description 24
- 238000005187 foaming Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000002932 luster Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001330498 Corsia Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a water-based fluorine modified siloxane acrylic coating, a preparation method and application thereof, wherein the coating comprises a component A and a component B, the mass ratio of the component A to the component B is (3-5): 1, the component A comprises the following components in percentage by mass: 70-80% of water-based fluorine modified acrylic resin, 20-25% of water, 0.1-0.3% of neutralizing agent, 3-5% of film forming additive, 0-0.2% of wetting agent, 0-0.2% of defoaming agent, 0-0.2% of flatting agent, 0-0.5% of thickening agent, and the component B comprises the following components in percentage by mass: 95-97% of isocyanate, 3-5% of silane coupling agent A, 0-5% of cosolvent, 50-1500 cps of viscosity of aqueous fluorine modified acrylic resin, and RSi (OCH) of the structure of the silane coupling agent A 3 ） 3 . The water-based acrylic coating has the advantages of weather resistance, impact resistance, fine surface and high glossiness。
Description
Technical Field
The invention relates to the field of coatings, and in particular relates to a water-based fluorine modified siloxane acrylic coating as well as a preparation method and application thereof.
Background
At present, the conventional coating is mature in water-based technology and market application, and gradually replaces the traditional solvent-based coating. The water-based acrylic resin has the advantages of excellent chemical medium resistance and corrosion resistance, and the water-based acrylic coating is mainly applied to the field of corrosion resistance.
At present, the weather resistance of the water-based acrylic coating is poor, and the water-based acrylic coating is not beneficial to long-term outdoor use, so that the application range of the water-based acrylic coating is limited.
Disclosure of Invention
In order to improve the weather resistance of the water-based acrylic coating, the application provides a water-based fluorine modified siloxane acrylic coating and a preparation method and application thereof.
In a first aspect, the application provides a water-based fluorine-modified siloxane acrylic coating, which adopts the following technical scheme:
the water-based fluorine-modified siloxane acrylic coating comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 3-5:1, wherein the component A comprises the following components in percentage by mass:
70-80% of water-based fluorine modified acrylic resin
20 to 25 percent of water
0.1 to 0.3 percent of neutralizer
3 to 5 percent of film-forming additive
0 to 0.2 percent of wetting agent
0 to 0.2 percent of defoaming agent
0 to 0.2 percent of flatting agent
0 to 0.5 percent of thickening agent
The component B comprises the following components in percentage by mass:
95 to 97 percent of isocyanate
3 to 5 percent of silane coupling agent A
0 to 5 percent of cosolvent,
the viscosity of the waterborne fluorine modified acrylic resin is 50-1500 cps, and the structure of the silane coupling agent A is RSi (OCH) 3 ） 3 。
In the aqueous fluorine modified acrylic resin, hydrogen atoms are replaced by F atoms, a tight protective layer is formed by enclosing carbon chains, so that the aqueous fluorine modified acrylic resin is not easy to be attacked by the outside, and an F-C bond is a chemical bond with high bond energy, so that the aqueous fluorine modified acrylic resin has excellent weather resistance, and simultaneously has better chemical inertia, the hydrophobicity of the coating can be improved, but the coating prepared by the aqueous fluorine modified acrylic resin serving as a main base material has poor adhesive force, is easy to be brittle and is easy to generate cracks under the impact.
In the invention, the silane coupling agent A and the isocyanate are added into the component B to be used as the cross-linking agent, so that the coating does not need to be heated and can be applied to the surface of a substrateThe coating is cured at room temperature, so that the adhesive force, flexibility, impact resistance and wear resistance of the coating can be effectively improved, and the fineness, glossiness and hydrophobic effect of the surface of the coating are improved. This is because the silane coupling agent A has a high activity, and when the A component and the B component are mixed, the silane coupling agent A is sufficiently hydrolyzed by the water in the A component to form RSi (OH) 3 ，RSi（OH） 3 The hydroxyl in the component (A) reacts with carboxylic acid in the aqueous fluorine modified acrylic resin, the active isocyanate group in the isocyanate also reacts with the carboxylic acid in the aqueous fluorine modified acrylic resin, and the active isocyanate group in the isocyanate also reacts with water in the component (A) to generate RSi (OH) after being hydrolyzed with a silane coupling agent MPS 3 The reaction is carried out to form a multiple cross-linked network interpenetrating structure, the prepared coating is mutually interpenetrated and combined through silicon atoms and carbon atoms, so that the effects of adhesion, flexibility, impact resistance, wear resistance and the like of the coating are improved, and meanwhile, the surface fineness, the glossiness and the hydrophobic effect of the coating prepared by the method are excellent, so that the coating prepared by the method can be directly used as a coating for a surface layer.
In addition, the silane coupling agent A and the isocyanate are mixed in advance to serve as the component B, and the isocyanate absorbs a small amount of moisture in the air in the storage process, so that the moisture in the air and the silane coupling agent A can be prevented from acting and hydrolyzing, the activity of the silane coupling agent A is prevented from being excited in the storage process, and the smooth reaction is ensured after the component A and the component B are mixed.
Preferably, the silane coupling agent A is 3-methacryloxypropyltrimethoxysilane.
Preferably, the isocyanate is an aliphatic isocyanate.
3-Methacryloxypropyltrimethoxysilane (MPS) and aliphatic isocyanate are jointly used as a component B, the storage stability is good, hydrolysis reaction is not easy to occur, MPS and isocyanate are jointly used as a cross-linking agent of the coating after the 3-Methacryloxypropyltrimethoxysilane (MPS) and the aliphatic isocyanate are mixed with the component A, the cross-linking density is favorably improved, the bonding stability of the prepared coating and a base material is enhanced, the drying speed is high, and the effects of improving the glossiness and the surface fineness of the coating are very excellent.
Preferably, the neutralizing agent is dimethylethanolamine.
By adding the dimethyl ethanolamine according to the proportion, when the component A is mixed with the component B, the pH value of the coating is 7.5-8.5, on one hand, the other auxiliary agents contain more organic matter components which have poor compatibility in the water-based coating, and after the dimethyl ethanolamine is added, the dispersibility of the organic matters in the water-based coating is improved, and the coating is changed from milky color to transparent in the pH range, on the other hand, the reaction effect of each component of the coating in the pH value range of 7.5-8.5 is better after the components of the coating are mixed, and the integral performance of the coating is favorably improved.
Preferably, the film-forming assistant comprises one or more of tripropylene glycol butyl ether TPNB, dipropylene glycol butyl ether DPNB and propylene glycol methyl ether PMA, and the addition amount in the formula is 3-5%.
The film-forming assistant has a high boiling point and a strong dissolving power, can volatilize and escape in a short time after the coating is formed into a film, does not influence the glass transition temperature of the coating film, enables the coating film not to be easily sticky at a high temperature, has a certain plasticizing effect, can improve the coalescence of the coating film, and enables the coating to form the film in a wide temperature range.
Preferably, the co-solvent is generally a lipid solvent, such as PMA propylene glycol methyl ether acetate, PGDA propylene glycol diacetate.
The lipid solvent has excellent effect of improving the solubility of the isocyanate and the silane coupling agent A, so that the raw materials of the component B are fully and uniformly mixed, and the stability of the component B is improved.
Preferably, the pigment is an inorganic pigment. For example, trace nano titanium dioxide and nano silicon dioxide dispersion can be added to the high-gloss transparent finish paint as an auxiliary, and the matte additive is generally prepared by selecting nano titanium dioxide, zirconium UG-T25 and stone-like CR-95 titanium dioxide as titanium dioxide, precipitating barium sulfate, high-gloss barium (generally with fine meshes), sericite and the like.
Preferably, the defoamer is a silicone defoamer, such as BASF FoamStar SI 2292, the wetting agent is a polyether modified polymethylsiloxane wetting agent, such as BASF Hydropalat WE 3323, the leveling agent is a modified polydimethylsiloxane, such as Efka SL3239, and the thickener is an associative polyurethane, such as rhelate 299.
In a second aspect, a preparation method of the water-based fluorine modified siloxane acrylic coating adopts the following technical scheme:
a preparation method of a water-based fluorine modified siloxane acrylic coating comprises the following steps: mixing the aqueous fluorine modified acrylic resin, the film forming additive, the neutralizer, water and other additives, and uniformly stirring to obtain a component A, wherein the preparation method of the component B comprises the following steps: stirring the silane coupling agent and the isocyanate, mixing until the silane coupling agent and the isocyanate are uniformly dispersed, adding the cosolvent, continuously stirring, and uniformly mixing to obtain the component B.
When the fluorine-modified silicone acrylic coating is used, the component A and the component B are uniformly mixed according to the mass ratio of 3-5.
In a third aspect, the application of the water-based fluorine modified siloxane acrylic coating adopts the following technical scheme:
an application of a water-based fluorine modified siloxane acrylic coating, which uses the coating as a finish paint of stainless steel and plastic substrates.
The water-based paint prepared by the method has the advantage of environmental protection, can be applied to the fields of automobiles and new energy, has good adhesiveness with stainless steel and plastics, is fine and smooth in prepared coating, is high in glossiness, and is particularly suitable for being used as automobile finish paint.
In summary, the present application has the following beneficial effects:
1. according to the paint, the silane coupling agent with a specific structure and the isocyanate are added into the component B to serve as the crosslinking agent, the paint can be cured at room temperature without being heated, the adhesive force, flexibility, impact resistance and wear resistance of the coating can be effectively improved, and the surface fineness, glossiness and hydrophobic effect of the coating are improved.
2. MPS and aliphatic isocyanate are jointly used as the component B, the storage stability is good, hydrolysis reaction is not easy to occur, after the MPS and the aliphatic isocyanate are mixed with the component A, the MPS and the isocyanate are jointly used as a cross-linking agent, the cross-linking density is favorably improved, the bonding stability of the prepared coating and a base material is enhanced, the drying speed is high, and the effects of improving the glossiness and the surface fineness of the coating are very excellent.
3. By adding the dimethyl ethanolamine according to the proportion, when the component A is mixed with the component B, the pH value of the coating is 7.5-8.5, on one hand, the other auxiliary agents contain more organic matter components which have poor compatibility in the water-based coating, and after the dimethyl ethanolamine is added, the dispersibility of the organic matters in the water-based coating is improved, and the coating is changed from milky color to transparent in the pH range, on the other hand, the reaction effect of each component of the coating in the pH value range of 7.5-8.5 is better after the components of the coating are mixed, and the integral performance of the coating is favorably improved.
Detailed Description
Example 1
A water-based fluorine modified siloxane acrylic coating consists of a component A and a component B.
The preparation method of the component A comprises the following steps: 80kg of aqueous fluorine-modified acrylic resin (RICH F-830 is selected in this example), 14.83kg of water, 0.17kg of dimethylethanolamine and 5kg of tripropylene glycol butyl ether were mixed uniformly to obtain component A.
The preparation method of the component B comprises the following steps: 97kg of isocyanate (Corsikon Bayer XP-2655) and 3kg of 3-Methacryloxypropyltrimethoxysilane (MPS) are mixed and stirred uniformly to prepare the component B.
During storage, the component A and the component B of the waterborne fluorine modified siloxane acrylic coating are stored separately, so that the component A and the component B are mixed according to a mass ratio of 4.
Example 2
A water-based fluorine-modified siloxane acrylic paint is different from that of example 1 in that 2kg of propylene glycol monomethyl ether acetate is added to the component B, and the addition amounts of the components in the component A and the component B are different.
Specifically, the preparation method of the component A comprises the following steps: 70kg of aqueous fluorine modified acrylic resin, 26.75kg of water, 0.25kg of dimethylethanolamine and 3kg of tripropylene glycol butyl ether are uniformly mixed to obtain a component A.
The preparation method of the component B comprises the following steps: 95kg of isocyanate (Corsika Bayer XP-2655 is selected), 3kg of 3-Methacryloxypropyltrimethoxysilane (MPS) and 2kg of propylene glycol monomethyl ether acetate are mixed and stirred uniformly to prepare the component B.
Example 3
An aqueous fluorine-modified silicone acrylic coating material differs from example 2 in the amount of each component added in the component A.
Specifically, the preparation method of the component A comprises the following steps: 75kg of aqueous fluorine-modified acrylic resin, 20.8kg of water, 0.2kg of dimethylethanolamine and 4kg of tripropylene glycol butyl ether are uniformly mixed to obtain a component A.
Example 4
A difference of the aqueous fluorine modified siloxane acrylic paint from the example 2 is that a wetting agent (BASF Hydropalat WE 3323 selected in the example), an antifoaming agent (BASF FoamStar SI 2292 selected in the example), a leveling agent (Efka SL3239 selected in the example), a pigment filler (UG-T25 zirconium selected in the example) and a thickening agent (RHEOLATE 299 selected in the example) are added into the component A.
Specifically, the preparation method of the component A comprises the following steps: 75kg of aqueous fluorine-modified acrylic resin, 19.5kg of water, 0.2kg of dimethylethanolamine, 4kg of tripropylene glycol butyl ether, BASF Hydropalat WE 3323, BASF FoamStar SI 2292, efka SL3239, UG-T25 zirconium and RHEOLATE 299 are mixed uniformly to obtain a component A.
Comparative example 1
An aqueous fluorine-modified silicone acrylic coating differing from example 4 in that: only isocyanate was added as crosslinker, in particular the B component consisted of 100kg of isocyanate.
Comparative example 2
An aqueous fluorine-modified silicone acrylic coating differing from example 4 in that: gamma-aminopropyltriethoxysilane equally replaces 3-methacryloxypropyltrimethoxysilane.
The amounts of the components of the above examples and comparative examples are summarized in Table 1.
TABLE 1
| Component A | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Aqueous fluorine modified acrylic resin | 80 | 70 | 75 | 75 | 75 | 75 |
| Water (I) | 14.83 | 26.75 | 20.8 | 19.5 | 19.5 | 19.5 |
| Dimethylethanolamine | 0.17 | 0.25 | 0.2 | 0.2 | 0.2 | 0.2 |
| Tripropylene glycol butyl ether | 5 | 3 | 4 | 4 | 4 | 4 |
| Wetting agent BASF Hydropalat WE 3323 | - | - | - | 0.2 | 0.2 | 0.2 |
| Defoaming agent BASF FoamStar SI 2292 | - | - | - | 0.2 | 0.2 | 0.2 |
| Leveling agent Efka SL3239 | - | - | - | 0.2 | 0.2 | 0.2 |
| UG-T25 YOU zirconium | - | - | - | 0.2 | 0.2 | 0.2 |
| Thickener rheelate 299 | - | - | - | 0.5 | 0.5 | 0.5 |
| B component | ||||||
| Isocyanate Corsia Bayer XP-2655 | 97 | 95 | 95 | 95 | 98 | 95 |
| MPS | 3 | 3 | 3 | 3 | 0 | 0 |
| Propylene glycol methyl ether acetate | 0 | 2 | 2 | 2 | 2 | 2 |
| Gamma-aminopropyltriethoxysilane | - | - | - | - | - | 3 |
Experiment of
The coatings prepared in the above examples and comparative examples were sprayed on a stainless steel plate to a coating thickness of 30um, left for one week to cure in a test environment (23 + -5 deg.C, humidity 78% Rh) to prepare test samples, and the properties of the test samples were measured.
(1) Hardness of pencil
Experiments were carried out according to GB/T6739 using the Mitsubishi Uni pencil, the pencil hardness of the coating being expressed as the maximum pencil hardness at which the paint film exhibited no visible scratch or mar phenomena.
(2) Adhesion force
A checkerboard with scratch intervals of 1mm penetrating through a coating film and reaching a base material is scratched on a sample by using a checkerboard device, glass gummed paper is pasted on the scratched checkerboard, gummed paper is wiped by using an eraser, so that gummed paper bubbles are tightly attached to the coating film, and then the gummed paper is quickly torn off along the 45-degree direction of a coating surface.
The results are expressed as residual lattice number/100.
The number of remaining cells was calculated by counting the remaining cells of 50% or more of the coating film for each tray cell, and replacing the cutter blade with a new one every 1 sample.
(3) Degree of specular gloss
The residual gloss was measured in accordance with GB 9754, and the residual gloss was expressed as a percentage of the specular gloss before the test divided by the specular gloss after the test.
(4) Impact resistance
According to the test of GB/T20624.2, the weight of the weight is 1000g, the sample size is 70X 150mm, the thickness is 3mm, and the weight is supposed to fall on the spray surface of the test plate.
(5) Temperature and water resistance
The coating film was immersed in deionized water at 40 ℃ for 240 hours (unit conductivity: 2. Mu.s/cm or less), washed with water, left to stand for 2 hours, and then examined for the state of the coating film.
(6) Acid resistance
A0.1N sulfuric acid solution was prepared from sulfuric acid having a purity of 95% or more, 2mL of the solution was dropped into a ring (inner diameter: 35 mm) attached to a sample plate, and the solution was left to stand at 23 ℃ and 50% RH for 24 hours, washed with water and evaluated.
(7) Alkali resistance
A0.1N sodium hydroxide solution was prepared from sodium hydroxide having a purity of 96% or more, 2mL of the solution was dropped into a circular ring (inner diameter: 35 mm) attached to a sample plate, and the solution was left to stand at a temperature of 23 ℃ and a 50% RH for 24 hours, washed with water and evaluated.
(8) Enhanced weatherability
The outdoor test piece is carried out according to SAE J2527, and the irradiation dose is 2500KJ/m 2 。
(9) Outdoor weather resistance
The outdoor weatherability was evaluated after 2 years of outdoor exposure according to GB/T9576-1996, and the residual gloss was evaluated after 12 months.
The results of the above experiments are shown in table 2.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Pencil hardness Degree of rotation | HB | HB | HB | HB | 2B | B |
| Adhesion force- Stage (division grid) Method) | 100/100 | 100/100 | 100/100 | 100/100 | 84/100 | 88/100 |
| Gloss of （20°/ 60°） | 89%/94% | 83%/89% | 92%/96% | 97%/99% | 73%/76% | 74%/80% |
| Impact-resistant/durable kg.cm | 52 | 45 | 60 | 66 | 58 | 49 |
| Water resistance （40°* 240 is small Time) | Color change 0 grade, bubbling 0 Adhesion force of grade and grid Grade no more than 1 | Color change 1 grade, bubbling 0 Adhesion force of grade and grid Grade no more than 1 | Color change 0 grade, foaming 0 Adhesion force of grade and grid Not more than 0 grade | Color change 0 grade, foaming 0 Grade, cross-cut adhesion 0 Stage | Color change 1 grade, foaming 1 Adhesion force of grade and grid Grade less than or equal to 1 | Color change 1 grade, foaming 1 Adhesion force of grade and grid Grade no more than 1 |
| Acid resistance (0.05mo l/ LH2SO4 Solution(s) 24H) | Color change 0 grade, foaming 0 Adhesion force of grade and grid Grade less than or equal to 1 | Color change 1 grade, foaming 1 Adhesion force of grade and grid Grade less than or equal to 1 | Color change 0 grade, foaming 0 Adhesion force of grade and grid Grade less than or equal to 1 | Color change 0 grade, foaming 0 Stage, division and lattice attachedActing force Grade no more than 1 | Color change 2 grade, foaming 2 Adhesion force of grade and grid Grade no more than 1 | Color change 2 grade, foaming 1 Adhesion force of grade and cross Grade less than or equal to 1 |
| Alkali resistance (0.1mol /LNA0H Solutions of 24H) | Color change 0 grade, foaming 0 Adhesion force of grade and cross Grade no more than 1 | Color change 1 grade, foaming 1 Adhesion force of grade and grid Grade less than or equal to 1 | Color change 0 grade, foaming 0 Adhesion force of grade and cross Grade less than or equal to 1 | Color change 0 grade, foaming 0 Adhesion force of grade and cross Grade less than or equal to 1 | Color change 2 grade, foaming 1 Adhesion force of grade and grid Grade no more than 1 | Color change 2 grade, foaming 1 Adhesion force of grade and grid Grade no more than 1 |
| Aging test Test (not less than) 1500 small Time) | Flaking grade 0, powdering 0 Grade, bubble 0 grade, light Change in luster: less than or equal to 10 percent, the adhesive force of the scratch lattice is less than or equal to 1 Stage | Flaking grade 0, powdering 1 Grade, bubble 0 grade, light Change in luster: less than or equal to 15 percent, the adhesive force of the grid is less than or equal to 1 Stage | Flaking grade 0, powdering 0 Grade, bubble 0 grade, light Change in luster: less than or equal to 8 percent of the total weight of the rice The grid adhesion force is less than or equal to 1 grade | Flaking grade 0, powdering 0 Grade, bubble 0 grade, light Change in luster: less than or equal to 5 percent of the total weight of the rice The lattice adhesion force is less than or equal to 1 grade | Flaking grade 0, powdering 1 Grade, bubble 0 grade, light Change in luster: less than or equal to 10 percent, the adhesive force of the grid is less than or equal to 1 Stage | Flaking grade 0, powdering 1 Grade, bubble 0 grade, light Change in luster: less than or equal to 10 percent, the adhesive force of the grid is less than or equal to 1 Stage |
| Aging test Test gloss Guarantee Rate/%) | 97% | 93% | 99% | 99% | 81% | 86% |
According to the comparison of the data of example 4 and comparative example 1 in table 2, compared with the comparative example 1 which only uses isocyanate as the crosslinking agent, the hardness, adhesion, gloss, impact resistance, aging resistance and gloss assurance rate in aging test of the coating of example 4 in the application are all improved, and the effect of adding MPS and isocyanate together as the crosslinking agent of the coating of the application is proved to be very outstanding. In combination with comparative example 2, which replaces MPS with gamma-aminopropyltriethoxysilane in equal amount, the coating prepared in comparative example 2 is significantly inferior in performance in all respects to that of example 1, and it is proved that the silane coupling agent used in comparative example 2 has low reactivity with the aqueous fluorine-modified silicone acrylic resin and isocyanate in the coating after hydrolysis and cannot sufficiently react to form a plurality of crosslinked interpenetrating network polymers having high crosslink density, and thus the coating in comparative example 2 has significantly lower performance in all respects than that of comparative example 2.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A water-based fluorine modified siloxane acrylic coating is characterized in that: the paint comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 3-5:1, the component A comprises the following components in percentage by mass:
70-80% of water-based fluorine modified acrylic resin
20 to 25 percent of water
0.1 to 0.3 percent of neutralizer
3 to 5 percent of film-forming additive
0 to 0.2 percent of wetting agent
0 to 0.2 percent of defoaming agent
0 to 0.2 percent of flatting agent
0 to 0.5 percent of thickening agent
The component B comprises the following components in percentage by mass:
95 to 97 percent of isocyanate
3 to 5 percent of silane coupling agent A
0 to 5 percent of cosolvent,
the viscosity of the waterborne fluorine modified acrylic resin is 50-1500 cps, and the structure of the silane coupling agent A is RSi (OCH) 3 ） 3 。
2. The aqueous fluorine-modified silicone acrylic coating according to claim 1, wherein: the silane coupling agent A is 3-methacryloxypropyltrimethoxysilane.
3. The aqueous fluorine-modified silicone acrylic coating according to claim 1, wherein: the isocyanate is aliphatic isocyanate.
4. The aqueous fluorine-modified silicone acrylic coating according to claim 1, wherein: the neutralizing agent is dimethylethanolamine.
5. The aqueous fluorine-modified silicone acrylic coating according to claim 1, wherein: the film-forming assistant comprises one or more of tripropylene glycol butyl ether TPNB, dipropylene glycol butyl ether DPNB and propylene glycol methyl ether PMA.
6. The aqueous fluorine-modified silicone acrylic coating according to claim 1, wherein: the cosolvent is a lipid solvent.
7. The aqueous fluorine-modified silicone acrylic coating according to claim 6, wherein: the lipid solvent comprises one or two of PMA propylene glycol methyl ether acetate and PGDA propylene glycol diacetate.
8. The aqueous fluorine-modified silicone acrylic coating according to claim 1, characterized in that: the pigment is an inorganic pigment.
9. A method of preparing the aqueous fluorine-modified silicone acrylic coating material as claimed in any one of claims 1 to 8, characterized in that: the preparation method of the component A comprises the following steps: mixing the aqueous fluorine modified acrylic resin, the film forming additive, the neutralizer, water and other additives, and uniformly stirring to obtain a component A, wherein the preparation method of the component B comprises the following steps: stirring the silane coupling agent A and the isocyanate, mixing until the silane coupling agent A and the isocyanate are uniformly dispersed, adding the cosolvent, continuously stirring, and uniformly mixing to obtain the component B.
10. Use of an aqueous fluorine-modified silicone acrylic coating according to any one of claims 1 to 8, characterized in that: the paint is used as finish paint of stainless steel and plastic base materials.
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Application publication date: 20221209 |