CN114773995B - High-durability fluorine-containing fingerprint resistant agent and preparation method thereof - Google Patents
High-durability fluorine-containing fingerprint resistant agent and preparation method thereof Download PDFInfo
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- CN114773995B CN114773995B CN202210439457.7A CN202210439457A CN114773995B CN 114773995 B CN114773995 B CN 114773995B CN 202210439457 A CN202210439457 A CN 202210439457A CN 114773995 B CN114773995 B CN 114773995B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 139
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 125
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 49
- 239000011737 fluorine Substances 0.000 title claims abstract description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 230000003666 anti-fingerprint Effects 0.000 claims abstract description 83
- 239000000203 mixture Substances 0.000 claims abstract description 69
- -1 phenyl vinyl Chemical group 0.000 claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 claims abstract description 62
- 239000000839 emulsion Substances 0.000 claims abstract description 59
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920002050 silicone resin Polymers 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 230000035515 penetration Effects 0.000 claims description 39
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000005543 nano-size silicon particle Substances 0.000 claims description 24
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 14
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 235000010413 sodium alginate Nutrition 0.000 claims description 14
- 229940005550 sodium alginate Drugs 0.000 claims description 14
- 239000000661 sodium alginate Substances 0.000 claims description 14
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 19
- 239000011253 protective coating Substances 0.000 description 35
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
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- 230000008569 process Effects 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
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- 150000001875 compounds Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to a high-durability fluorine-containing anti-fingerprint agent and a preparation method thereof, and the high-durability fluorine-containing anti-fingerprint agent comprises the following raw materials: the water-based fluorocarbon resin emulsion comprises water-based fluorocarbon emulsion resin, phenyl vinyl silicone resin, a permeation assistant, a compatibilizer, nanoparticles, a silane coupling agent, polytetrafluoroethylene emulsion and a curing agent. The preparation method comprises the following steps: step 1, uniformly mixing 15-20 parts by mass of aqueous fluorocarbon emulsion resin, 1-3 parts by mass of permeation assistant, 1-2 parts by mass of compatibilizer and 30-35 parts by mass of phenyl vinyl silicone resin at 40-50 ℃ to obtain a mixture A; step 2, mixing 10-15 parts by mass of nano particles and 3-5 parts by mass of silane coupling agent with the mixture A to obtain a mixture B; and 3, mixing 5-7 parts by mass of polytetrafluoroethylene emulsion, 2-3 parts by mass of compatibilizer and 1-2 parts by mass of curing agent with the mixture B at 60-65 ℃, reacting for 3-5h, and cooling to 21-23 ℃ to obtain the anti-fingerprint agent. This application has the effect that promotes anti fingerprint agent wear-resisting scratch resistance.
Description
Technical Field
The application relates to the field of anti-fingerprint agents, in particular to a high-durability fluorine-containing anti-fingerprint agent and a preparation method thereof.
Background
With the variety and wide use of intelligent multimedia devices, represented by the display of a mobile phone, the touch panel of a screen has become a normal technology, but fingerprints, grease on skin, sweat and cosmetic traces are easily left on the surface of the screen of the device which is often touched, which not only affects the appearance of the product, but also affects the usability of the product, so that an anti-fingerprint agent is often required to be applied on the surface of the touch screen.
The main component of the commonly used fingerprint resisting agent at present is a fluorine-containing high molecular compound with a special functional group, and the fluorine-containing high molecular compound has excellent physicochemical properties such as hydrophobic and oleophobic properties, chemical resistance and the like. The fingerprint resisting agent containing the fluorine-containing high molecular compound can form an ultrathin transparent coating on the surface of a base material, and has excellent functions of water resistance, oil resistance, easy cleaning, corrosion resistance and the like. Although the ultrathin fingerprint resistant agent coating has good barrier property, the wear resistance of the coating is poor, and the coating is easy to scratch and wear in the long-term use process, so that the protective barrier effect on a base material cannot be achieved for a long time.
In order to solve the technical problems, the inventor thinks that the existing fingerprint resisting agent has the defects of poor abrasion resistance and scratch resistance and insufficient durability.
Disclosure of Invention
In order to improve the wear resistance and scratch resistance of the anti-fingerprint agent, the application provides a high-durability fluorine-containing anti-fingerprint agent and a preparation method thereof.
In a first aspect, the preparation method of the fluorine-containing anti-fingerprint agent with high durability provided by the application adopts the following technical scheme:
a preparation method of a fluorine-containing anti-fingerprint agent with high durability comprises the following steps:
step 1, mixing 15-20 parts by mass of aqueous fluorocarbon emulsion resin, 1-3 parts by mass of permeation aid, 1-2 parts by mass of compatibilizer and 30-35 parts by mass of phenyl vinyl silicone resin, and uniformly mixing at 40-50 ℃ to obtain a mixture A;
step 2, adding 10-15 parts by mass of nano particles and 3-5 parts by mass of silane coupling agent into the mixture A, and uniformly stirring to obtain a mixture B;
and 3, adding 5-7 parts by mass of polytetrafluoroethylene emulsion, 2-3 parts by mass of compatibilizer and 1-2 parts by mass of curing agent into the mixture B, mixing and stirring uniformly at 60-65 ℃, reacting for 3-5h, and cooling to 21-23 ℃ while stirring to obtain the fluorine-containing anti-fingerprint agent with high durability.
By adopting the technical scheme, the waterborne fluorocarbon emulsion resin, the permeation assistant, the compatibilizer and the phenyl vinyl silicone resin are mixed according to a certain combination proportion, and in the mixing process, the waterborne fluorocarbon emulsion resin and the phenyl vinyl silicone resin can be fully dispersed and fused by the synergistic cooperation of the permeation assistant and the compatibilizer at a specific temperature, so that a uniformly dispersed mixture A is obtained; then filling the nano particles into the mixture A, and improving the compatibility between the nano particles and the mixture A through the auxiliary matching of the silane coupling agent and the compatibilizer in the mixture A; so that the nano particles can be well embedded in the structural system of the mixture A to obtain an inorganic-organic hybrid combined mixture B; finally, the polytetrafluoroethylene emulsion, the compatibilizer, the curing agent and the mixture B are mixed and stirred uniformly at 60-65 ℃, in the mixing process, the compatibilizer, the curing agent, the polytetrafluoroethylene emulsion and the mixture B have a synergistic effect to form a colloid substance with tightly linked structural molecules, the colloid substance has a good film forming characteristic after being coated on the surface of a matrix, and a protective coating with good permeability is formed after solidification and coagulation;
the protective coating is tightly adhered to the surface of the matrix, and good adhesiveness is generated between the protective coating and the matrix; the nano particles dispersed in the protective coating form densely distributed strength supporting points, and when the protective coating is impacted, a plurality of strength supporting points connected by the solidified colloid matrix in a wrapping manner can bear larger impact load, so that a better impact resistance effect is achieved; the cured film layer on the surface of the protective coating has certain surface lubricity and barrier property, so that the coating can resist water and oil; the coating formed by curing the anti-fingerprint agent has excellent wear resistance, scratch resistance and high durability under the conditions of strength support and excellent surface lubricity of nano particles in the coating.
Preferably, in the step 1, 17 to 18 parts by mass of the aqueous fluorocarbon emulsion resin, 2.3 parts by mass of the penetration assistant, 1.6 parts by mass of the compatibilizer and 32 to 34 parts by mass of the phenyl vinyl silicone resin are mixed.
By adopting the technical scheme, the addition of the penetration auxiliary agent is beneficial to mutual penetration and fusion between the waterborne fluorocarbon emulsion resin and the phenyl vinyl silicone resin, so that the waterborne fluorocarbon emulsion resin and the phenyl vinyl silicone resin can be uniformly dispersed and fused; the compatibilizer is beneficial to improving the compatibility between the aqueous fluorocarbon emulsion resin and the phenyl vinyl silicone resin, and can be used for bonding the aqueous fluorocarbon emulsion resin and the phenyl vinyl silicone resin to enhance the bonding property between the aqueous fluorocarbon emulsion resin and the phenyl vinyl silicone resin; when the waterborne fluorocarbon emulsion resin, the penetration assistant, the compatibilizer and the phenyl vinyl silicone resin are in a combination ratio in a certain range, the waterborne fluorocarbon emulsion resin, the penetration assistant, the compatibilizer and the phenyl vinyl silicone resin can be matched with each other to assist each other, so that the prepared mixture A has a stable structural system with uniform components and sufficient connection.
Preferably, the compatibilizer is prepared from triethanolamine, 2-hydroxyethyl methacrylate phosphate, trimellitic anhydride, sodium alginate and water according to a mass ratio of (0.5-0.7): (0.3-0.5): (1.2-1.6): (0.8-1.2): 5, mixing at 50-60 ℃.
By adopting the technical scheme, the triethanolamine can play a good role of a surfactant and a complexing agent; 2-hydroxyethyl methacrylate phosphate serving as an adhesion promoter and a coupling agent can show good adhesion and bonding functions and can promote the adhesion polymerization among components in a free radical polymerization system; trimellitic anhydride can be used to promote gum formation; the aqueous solution of the sodium alginate has high viscosity, has the performances of thickening, stabilizing, emulsifying and the like, has certain adhesiveness in the aqueous solution, and can quickly form gel under extremely mild conditions. Triethanolamine, 2-hydroxyethyl methacrylate phosphate, trimellitic anhydride, sodium alginate and water are compounded according to a specific proportion, and can act synergistically under a certain temperature condition to obtain a compatibilizer with a good compatibilization effect, and the compatibilizer is added into a mixture system, so that the components in the compatibilizer can be matched with each other, the compatibility among the components in the system is greatly increased, the cross-linking adhesion among the components is promoted, and the structural performance of the fingerprint inhibitor cured coating is further promoted.
Preferably, the penetration assistant is prepared from polydimethylsiloxane, N-butanol and N-vinyl pyrrolidone according to the mass ratio of (0.2-0.5): (0.9-1.1): (0.5-0.7) mixing.
By adopting the technical scheme, the penetration auxiliary agent prepared by combining and compounding the polydimethylsiloxane, the N-butanol and the N-vinyl pyrrolidone in a specific proportion has good lubricity and dispersibility, can be matched with the compatibilizer, promotes the improvement of the compatibility among the components in the mixture system, ensures that the components in the mixture system are uniformly dispersed and blended, and further contributes to improving the stability of the mixture system; the penetration aid prepared by mixing the polydimethylsiloxane, the N-butanol and the N-vinyl pyrrolidone also has good foam inhibiting and defoaming performance, is beneficial to inhibiting the generation of bubbles in the process of stirring and mixing the mixture, and is further beneficial to reducing the influence of the bubbles generated in the production process on the performance of the anti-fingerprint agent product.
Preferably, the curing agent is diethylenetriamine or triethylenetetramine.
By adopting the technical scheme, the diethylenetriamine or the triethylene tetramine is adopted, the compatibility of the diethylenetriamine or the triethylene tetramine is better, the reaction activity is more appropriate, the cross-linking and bonding of the mixture can be promoted, and the performance stability of the protective coating formed after the prepared anti-fingerprint agent product is cured is favorably improved.
Preferably, the nanoparticles comprise the following raw materials in percentage by mass: 55-60% of nano silicon dioxide, 30-35% of nano titanium dioxide and 5-15% of nano hydroxyapatite; the average particle size of the nano silicon dioxide is 10-50nm, the average particle size of the nano titanium dioxide is 5-30nm, and the average particle size of the nano hydroxyapatite is 5-25nm.
Preferably, the nanoparticles comprise the following raw materials in percentage by mass: 58% of nano silicon dioxide, 30% of nano titanium dioxide and 12% of nano hydroxyapatite; the average particle size of the nano silicon dioxide is 35nm, the average particle size of the nano titanium dioxide is 20nm, and the average particle size of the nano hydroxyapatite is 10nm.
By adopting the technical scheme, the nano-hydroxyapatite has better adsorption performance and strength performance, and is beneficial to enhancing the strength performance of the mixture system after being cured and the adsorption and adhesion of inorganic particles and mixture colloid; the nano titanium dioxide and the nano silicon dioxide are beneficial to improving the strength performance and simultaneously can improve the gloss transparency and the wear resistance of the protective coating after the anti-fingerprint agent is cured; three inorganic nanoparticles of nano-silica, nano-titanium dioxide and nano-hydroxyapatite are mixed, the three inorganic nanoparticles with different contents and different particle sizes are mutually matched and act synergistically, and the strength supporting structure with uniform stress can be formed after the inorganic nanoparticles are dispersed in a system, so that the wear resistance, the scratch resistance and the impact strength of the protective coating after the anti-fingerprint agent is cured can be improved, the protective coating can be closely combined with an anti-fingerprint agent colloid matrix, and the overall performance of the protective coating is improved.
Preferably, the penetration aid is added in the step 1, and the compatibilizer is added after stirring for 5 min.
By adopting the technical scheme, the penetration aid is added firstly, so that the waterborne fluorocarbon emulsion resin is favorably and fully dispersed and blended with the phenyl vinyl silicone resin under the assistance of the penetration aid, and then the compatibilizer is added and matched with the penetration aid to further promote the interactive bonding between the waterborne fluorocarbon emulsion resin and the phenyl vinyl silicone resin, so as to form a mixture B with a uniform and stable system.
In a second aspect, the fluorine-containing anti-fingerprint agent with high durability provided by the application adopts the following technical scheme:
the fluorine-containing anti-fingerprint agent with high durability is prepared by the preparation method of the fluorine-containing anti-fingerprint agent with high durability.
By adopting the technical scheme, the anti-fingerprint agent prepared by reacting and mixing the raw materials such as the waterborne fluorocarbon emulsion resin, the polytetrafluoroethylene emulsion, the phenyl vinyl silicone resin, the nano particles, the permeation assistant, the compatibilizer, the curing agent, the silane coupling agent and the like has better water and oil resistance, and the anti-fingerprint agent is spread, formed and cured on the surface of a substrate to form a protective coating with better permeability; the internal structure of the protective coating is tightly and stably connected, and the protective coating is firmly adhered to the substrate; the nano particles dispersed in the protective coating form densely distributed strength supporting points, so that the protective coating has strong impact strength; under the support of the surface with good lubricity and barrier property and the internal strength of the protective coating, the coating has excellent wear resistance and scratch resistance, is durable, and provides durable protection for the surface of a substrate.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the application, components such as water-based fluorocarbon emulsion resin, a penetration auxiliary agent, a compatibilizer, phenyl vinyl silicone resin, nano particles, a silane coupling agent, polytetrafluoroethylene emulsion, a curing agent and the like are gradually mixed and blended according to a certain sequence, and finally, an anti-fingerprint agent with colloid property is formed; the nano particles doped in the protective coating provide strength support for the protective coating, and excellent surface lubricity and barrier property are endowed to the protective coating through the connection polymerization of fluorine-containing substances on the surface of the protective coating, so that the water-resistant and oil-resistant effects of the coating are outstanding; under the conditions of strength support and excellent surface lubricity of nano particles in the coating, the coating formed by curing the anti-fingerprint agent has excellent wear resistance, scratch resistance and high durability;
2. the compatibilizer is compounded by triethanolamine, 2-hydroxyethyl methacrylate phosphate, trimellitic anhydride, sodium alginate and water according to a specific proportion, mixed and supported under a certain temperature condition, the compatibilizer is added into a mixture system, and all components in the compatibilizer can be matched with one another, so that the compatibility among all components in the system is greatly improved, the cross-linking adhesion among all components is promoted, and the structural performance of the fingerprint inhibitor cured coating is improved;
3. in the application, nano particles formed by mixing three inorganic particles of nano silicon dioxide, nano titanium dioxide and nano hydroxyapatite are used as filling materials to be added into a mixture system, and the nano hydroxyapatite can contribute to enhancing the strength performance of the mixture system after being cured; the nano titanium dioxide and the nano silicon dioxide are beneficial to improving the strength performance and simultaneously can improve the gloss transparency and the wear resistance of the protective coating after the anti-fingerprint agent is cured; three inorganic nanoparticles of nano-silica, nano-titanium dioxide and nano-hydroxyapatite are mixed, and the three inorganic nanoparticles are mutually matched and act synergistically, so that a strength supporting structure with uniform stress can be formed after the inorganic nanoparticles are dispersed in a system, the wear resistance, the scratch resistance and the impact strength of the protective coating after the anti-fingerprint agent is cured can be improved, the protective coating can be closely combined with an anti-fingerprint agent colloid matrix, and the overall performance of the protective coating is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The sources of the raw materials of the examples, comparative examples and comparative examples of the present application are detailed in table 1.
TABLE 1
Preparation examples
Preparation example 1
The preparation example discloses a method for preparing a compatibilizer, which specifically comprises the following steps: adding 6.41g of triethanolamine, 3.85g of 2-hydroxyethyl methacrylate phosphate, 15.38g of trimellitic anhydride, 10.26g of sodium alginate and 64.10g of water into a high-speed stirrer, and stirring for 10min at the temperature of 50 ℃ and the rotating speed of 1200r/min to obtain a compatibilizer; wherein the mass ratio of the triethanolamine to the 2-hydroxyethyl methacrylate phosphate to the trimellitic anhydride to the sodium alginate to the water is 0.5:0.3:1.2:0.8:5.
preparation example 2
The preparation example discloses a method for preparing a compatibilizer, which specifically comprises the following steps: adding 7.78g of triethanolamine, 5.56g of 2-hydroxyethyl methacrylate phosphate, 17.77g of trimellitic anhydride, 13.33g of sodium alginate and 55.56g of water into a high-speed stirrer, and stirring for 10min at the temperature of 60 ℃ and the rotating speed of 1200r/min to obtain a compatibilizer; wherein the mass ratio of triethanolamine, 2-hydroxyethyl methacrylate phosphate, trimellitic anhydride, sodium alginate to water is 0.7:0.5:1.6:1.2:5.
preparation example 3
The preparation example discloses a method for preparing a compatibilizer, which specifically comprises the following steps: adding 7.14g of triethanolamine, 4.76g of 2-hydroxyethyl methacrylate phosphate, 16.67g of trimellitic anhydride, 11.90g of sodium alginate and 59.53g of water into a high-speed stirrer, and stirring for 10min at the temperature of 55 ℃ and the rotating speed of 1200r/min to obtain a compatibilizer; wherein the mass ratio of the triethanolamine to the 2-hydroxyethyl methacrylate phosphate to the trimellitic anhydride to the sodium alginate to the water is 0.6:0.4:1.4:1:5.
preparation example 4
The preparation example discloses a method for preparing a compatibilizer, which specifically comprises the following steps: adding 12.5g of triethanolamine, 12.5g of 2-hydroxyethyl methacrylate phosphate, 6.25g of trimellitic anhydride, 6.25g of sodium alginate and 62.5g of water into a high-speed stirrer, and stirring for 10min at the temperature of 50 ℃ and the rotating speed of 1200r/min to obtain a compatibilizer; wherein the mass ratio of triethanolamine, 2-hydroxyethyl methacrylate phosphate, trimellitic anhydride, sodium alginate to water is 1:1:0.5:0.5:5.
preparation example 5
In this preparation, a commercially available maleic anhydride graft compatibilizer was selected.
Preparation example 6
The preparation example discloses a preparation method of a penetration aid, which specifically comprises the following steps: adding 12.5g of polydimethylsiloxane, 56.25g of N-butanol and 31.25g of N-vinyl pyrrolidone into a high-speed stirrer, and stirring for 10min at normal temperature and the rotating speed of 1000r/min to obtain a penetration aid; wherein the mass ratio of the polydimethylsiloxane to the N-butanol to the N-vinyl pyrrolidone is 0.2:0.9:0.5.
preparation example 7
The preparation example discloses a preparation method of a penetration aid, which specifically comprises the following steps: adding 21.74g of polydimethylsiloxane, 47.83g of N-butanol and 30.43g of N-vinyl pyrrolidone into a high-speed stirrer, and stirring at normal temperature and the rotation speed of 1000r/min for 10min to obtain a penetration aid; wherein the mass ratio of the polydimethylsiloxane to the N-butanol to the N-vinyl pyrrolidone is 0.5:1.1:0.7.
preparation example 8
The preparation example discloses a preparation method of a penetration aid, which specifically comprises the following steps: adding 17.95g of polydimethylsiloxane, 51.28g of N-butanol and 30.77g of N-vinyl pyrrolidone into a high-speed stirrer, and stirring at normal temperature and the rotation speed of 1000r/min for 10min to obtain a penetration aid; wherein the mass ratio of the polydimethylsiloxane to the N-butanol to the N-vinyl pyrrolidone is 0.35:1:0.6.
preparation example 9
The preparation example discloses a preparation method of a penetration aid, which specifically comprises the following steps: adding 40g of polydimethylsiloxane, 20g of N-butanol and 40g of N-vinyl pyrrolidone into a high-speed stirrer, and stirring for 10min at normal temperature and the rotating speed of 1000r/min to obtain a penetration aid; wherein the mass ratio of the polydimethylsiloxane to the N-butanol to the N-vinyl pyrrolidone is 1:0.5:1.
preparation example 10
The preparation example selects the commercial isooctanol polyoxyethylene ether penetration auxiliary agent.
Preparation example 11
The preparation example discloses a preparation method of nanoparticles, which specifically comprises the following steps:
s1, weighing 55g of nano silicon dioxide with the average particle size of 50nm, 30g of nano titanium dioxide with the average particle size of 5nm and 15g of nano hydroxyapatite with the average particle size of 25 nm;
and S2, adding the weighed nano silicon dioxide, nano titanium dioxide and nano hydroxyapatite into a stirrer, and stirring for 1h at normal temperature and at the rotating speed of 60r/min to obtain a nano particle mixture.
Preparation example 12
The preparation example discloses a preparation method of nanoparticles, which specifically comprises the following steps:
s1, weighing 60g of nano silicon dioxide with the average particle size of 10nm, 35g of nano titanium dioxide with the average particle size of 30nm and 5g of nano hydroxyapatite with the average particle size of 5 nm;
and S2, adding the weighed nano silicon dioxide, nano titanium dioxide and nano hydroxyapatite into a stirrer, and stirring for 1h at normal temperature and at the rotating speed of 60r/min to obtain a nano particle mixture.
Preparation example 13
The preparation example discloses a preparation method of nanoparticles, which specifically comprises the following steps:
s1, weighing 57.5g of nano silicon dioxide with the average particle size of 30nm, 17.5g of nano titanium dioxide with the average particle size of 20nm and 10g of nano hydroxyapatite with the average particle size of 15 nm;
and S2, adding the weighed nano silicon dioxide, nano titanium dioxide and nano hydroxyapatite into a stirrer, and stirring for 1 hour at normal temperature and at the rotating speed of 60r/min to obtain a nano particle mixture.
Preparation example 14
The preparation example discloses a preparation method of nanoparticles, which specifically comprises the following steps:
s1, weighing 58g of nano silicon dioxide with the average particle size of 35nm, 30g of nano titanium dioxide with the average particle size of 20nm and 12g of nano hydroxyapatite with the average particle size of 10 nm;
and S2, adding the weighed nano silicon dioxide, nano titanium dioxide and nano hydroxyapatite into a stirrer, and stirring for 1h at normal temperature and at the rotating speed of 60r/min to obtain a nano particle mixture.
Preparation example 15
The preparation example discloses a preparation method of nanoparticles, which specifically comprises the following steps:
s1, weighing 33.34g of nano silicon dioxide with the average particle size of 25nm, 33.33g of nano titanium dioxide with the average particle size of 25nm and 33.33g of nano hydroxyapatite with the average particle size of 25 nm;
and S2, adding the weighed nano silicon dioxide, nano titanium dioxide and nano hydroxyapatite into a stirrer, and stirring for 1h at normal temperature and at the rotating speed of 60r/min to obtain a nano particle mixture.
Preparation example 16
The difference between the present preparation example and preparation example 11 is that: and replacing the nano titanium dioxide and the nano hydroxyapatite in the S1 with the same amount of nano silicon dioxide.
Preparation example 17
The difference between the present preparation example and preparation example 11 is that: and replacing the nano silicon dioxide and the nano hydroxyapatite in the S1 with the same amount of nano titanium dioxide.
Preparation example 18
The difference between the present preparation example and preparation example 11 is that: and replacing the nano titanium dioxide and the nano silicon dioxide in the S1 with the same amount of nano hydroxyapatite.
Examples
Example 1
The embodiment discloses a high-durability fluorine-containing anti-fingerprint agent, which comprises the following raw materials: the water-based fluorocarbon resin emulsion comprises water-based fluorocarbon emulsion resin, phenyl vinyl silicone resin, a permeation assistant, a compatibilizer, nanoparticles, a silane coupling agent, polytetrafluoroethylene emulsion and a curing agent.
The embodiment also discloses a preparation method of the fluorine-containing fingerprint resistant agent with high durability, which comprises the following steps:
step 1, mixing 150g of aqueous fluorocarbon emulsion resin, 10g of permeation assistant, 10g of compatibilizer and 300g of phenyl vinyl silicone resin, adding the mixture into a high-speed dispersion machine, and stirring the mixture for 10min at the temperature of 40 ℃ and the stirring speed of 1500r/min to obtain a mixture A (wherein the compatibilizer prepared in the preparation example 1 is used as the compatibilizer, the permeation assistant prepared in the preparation example 6 is used as the permeation assistant, and the mass ratio of the aqueous fluorocarbon emulsion resin to the permeation assistant to the phenyl vinyl silicone resin is 15;
step 2, adding 100g of nanoparticles and 30g of silane coupling agent into the mixture A, and stirring for 10min at the normal temperature and the stirring speed of 2000r/min to obtain a mixture B; wherein the nano-particles are prepared from the preparation example 11, and the silane coupling agent is silane coupling agent KH-550;
step 3, adding 50g of polytetrafluoroethylene emulsion, 20g of compatibilizer and 10g of curing agent into the mixture B, reacting for 5 hours at 60 ℃ and a stirring speed of 1000r/min while stirring, continuously stirring at a cooling rate of 1 ℃ per minute, and stopping stirring after cooling to 21 ℃ to obtain the fluorine-containing anti-fingerprint agent with high durability; wherein the compatibilizer is prepared in preparation example 1, and the curing agent is diethylenetriamine.
Example 2
The embodiment discloses a preparation method of a fluorine-containing fingerprint resistant agent with high durability, which comprises the following steps:
step 1, mixing 200g of aqueous fluorocarbon emulsion resin, 30g of permeation aid, 20g of compatibilizer and 350g of phenyl vinyl silicone resin, adding the mixture into a high-speed dispersion machine, and stirring the mixture for 10min at the temperature of 50 ℃ and the stirring speed of 1500r/min to obtain a mixture A (wherein the compatibilizer is prepared by the preparation example 2, the permeation aid is prepared by the preparation example 7, and the mass ratio of the aqueous fluorocarbon emulsion resin, the permeation aid, the compatibilizer and the phenyl vinyl silicone resin is 20;
step 2, adding 150g of nanoparticles and 50g of silane coupling agent into the mixture A, and stirring for 10min at the normal temperature and the stirring speed of 2000r/min to obtain a mixture B; wherein the nano-particles are prepared from the preparation example 12, and the silane coupling agent is silane coupling agent KH-560;
step 3, adding 70g of polytetrafluoroethylene emulsion, 30g of compatibilizer and 20g of curing agent into the mixture B, reacting for 3 hours at 65 ℃ and at a stirring speed of 1000r/min while stirring, continuously stirring at a cooling rate of 1 ℃ per minute, and stopping stirring after cooling to 23 ℃ to obtain the fluorine-containing anti-fingerprint agent with high durability; wherein the compatibilizer is prepared in preparation example 2, and the curing agent is triethylene tetramine.
Example 3
The embodiment discloses a preparation method of a fluorine-containing anti-fingerprint agent with high durability, which comprises the following steps:
step 1, mixing 175g of aqueous fluorocarbon emulsion resin, 20g of permeation assistant, 15g of compatibilizer and 325g of phenyl vinyl silicone resin, adding the mixture into a high-speed dispersion machine, and stirring the mixture for 10min at the temperature of 45 ℃ and the stirring speed of 1500r/min to obtain a mixture A (wherein the compatibilizer prepared in preparation example 3 is used as the compatibilizer, the permeation assistant prepared in preparation example 8 is used as the permeation assistant, and the mass ratio of the aqueous fluorocarbon emulsion resin to the permeation assistant to the phenyl vinyl silicone resin is 17.5;
step 2, adding 125g of nanoparticles and 40g of silane coupling agent into the mixture A, and stirring for 10min at the normal temperature and the stirring speed of 2000r/min to obtain a mixture B; wherein the nano-particles are prepared from the preparation example 13, and the silane coupling agent is silane coupling agent KH-550;
step 3, adding 60g of polytetrafluoroethylene emulsion, 25g of compatibilizer and 15g of curing agent into the mixture B, reacting for 4 hours at 63 ℃ and at a stirring speed of 1000r/min while stirring, continuously stirring at a cooling rate of 1 ℃ per minute, and stopping stirring after cooling to 23 ℃ to obtain the fluorine-containing anti-fingerprint agent with high durability; wherein the compatibilizer is prepared in preparation example 3, and the curing agent is triethylene tetramine.
Example 4
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in step 1, 170g of aqueous fluorocarbon emulsion resin, 23g of permeation aid, 16g of compatibilizer and 320g of phenyl vinyl silicone resin are mixed, namely the mass ratio of the aqueous fluorocarbon emulsion resin to the permeation aid to the compatibilizer to the phenyl vinyl silicone resin is 17:2.3:1.6:32.
example 5
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in step 1, mixing 180g of aqueous fluorocarbon emulsion resin, 23g of permeation aid, 16g of compatibilizer and 340g of phenyl vinyl silicone resin, wherein the mass ratio of the aqueous fluorocarbon emulsion resin to the permeation aid to the compatibilizer to the phenyl vinyl silicone resin is 18:2.3:1.6:34.
example 6
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in the step 1, 175g of aqueous fluorocarbon emulsion resin, 20g of permeation assistant and 325g of phenyl vinyl silicone resin are mixed and added into a high-speed dispersion machine together, the mixture is stirred for 5min at the temperature of 45 ℃ and the stirring speed of 1500r/min, 15g of compatibilizer is added, and the mixture is continuously stirred for 5min to obtain a mixture A.
Example 7
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in the step 1, 175g of aqueous fluorocarbon emulsion resin, 15g of compatibilizer and 325g of phenyl vinyl silicone resin are mixed and added into a high-speed dispersion machine together, the mixture is stirred for 5min at the temperature of 45 ℃ and the stirring speed of 1500r/min, 20g of permeation assistant is added, and the mixture is continuously stirred for 5min to obtain a mixture A.
Example 8
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in the step 1 and the step 3, the compatibilizer prepared in the preparation example 4 is used as the compatibilizer.
Example 9
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in the step 1 and the step 3, the compatibilizer prepared in the preparation example 5 is used as the compatibilizer.
Example 10
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in step 1, the permeation assistant prepared in preparation example 9 is used as the permeation assistant.
Example 11
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in step 1, the penetration aid prepared in preparation example 10 is used as the penetration aid.
Example 12
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in step 2, the nanoparticles prepared in preparation example 14 were selected as the nanoparticles.
Example 13
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in step 2, the nanoparticles prepared in preparation example 15 were selected as the nanoparticles.
Example 14
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in the step 1, 170g of aqueous fluorocarbon emulsion resin, 23g of permeation assistant and 320g of phenyl vinyl silicone resin are mixed and added into a high-speed dispersion machine together, the mixture is stirred for 5min at the temperature of 45 ℃ and the stirring speed of 1500r/min, 16g of compatibilizer is added, and the mixture is continuously stirred for 5min to obtain a mixture A; namely, the mass ratio of the aqueous fluorocarbon emulsion resin to the penetration assistant to the compatibilizer to the phenyl vinyl silicone resin is 17:2.3:1.6:32, a first step of removing the first layer; in step 2, the nanoparticles prepared in preparation example 14 were selected as the nanoparticles.
Comparative example
Comparative example 1
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in the step 1, the temperature during stirring and dispersing is 23 ℃; in step 3, the reaction temperature was 23 ℃.
Comparative example 2
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in the step 1, the temperature during stirring and dispersing is 60 ℃; in step 3, the reaction temperature was 70 ℃.
Comparative example 3
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in step 1, 100g of aqueous fluorocarbon emulsion resin, 50g of permeation aid, 5g of compatibilizer and 100g of phenyl vinyl silicone resin are mixed, namely the mass ratio of the aqueous fluorocarbon emulsion resin to the permeation aid to the compatibilizer to the phenyl vinyl silicone resin is 10:5:0.5:10.
comparative example 4
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in the step 1, 300g of aqueous fluorocarbon emulsion resin, 5g of permeation assistant, 50g of compatibilizer and 400g of phenyl vinyl silicone resin are mixed, that is, the mass ratio of the aqueous fluorocarbon emulsion resin to the permeation assistant to the compatibilizer to the phenyl vinyl silicone resin is 30:0.5:5:40.
comparative example 5
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in step 2, the nanoparticles prepared in preparation example 16 were selected as the nanoparticles.
Comparative example 6
The preparation method of the fluorine-containing fingerprint resistant agent with high durability is different from that of the embodiment 3 in that: in step 2, the nanoparticles prepared in preparation example 17 were selected as the nanoparticles.
Comparative example 7
The preparation method of the fluorine-containing anti-fingerprint agent with high durability is different from the preparation method of the embodiment 3 in that: in step 2, the nanoparticles prepared in preparation example 18 were selected as the nanoparticles.
Performance test
Preparation of a detection sample: the base material used for detection limitation is completely placed in the anti-fingerprint agent prepared in the examples 1-14 and the comparative examples 1-7 to be soaked for 30s and then taken out, the base material is baked for 2h at the temperature of 130 ℃, and the anti-fingerprint agent on the surface of the base material is cured to form a protective coating. The thickness of the protective coating is 8 +/-1 mu m, and the following related performance detection is carried out on the protective coating;
1. and (3) testing water resistance and oil resistance: dropping 2 mul of test liquid (water and n-hexadecane) on the surface of the protective coating, and testing the contact angle of the water and the n-hexadecane;
2. and (3) testing an antifouling oily pen: the black oily ink with the Dili model 9090 and the model S550 is drawn on a coating sample one line, then the change of ink traces is observed carefully, and the judgment standard is as follows: excellent-ink is quickly removed; preferably, the printing ink is removed; good-ink partial recession; poor-ink not repelled;
3. fingerprint resistance test: the same finger was pressed with the same pressing force on the surface of the coated sample, and then the fingerprint was wiped off with a dry Kimtech Science Kimwipes (0131-10) low dust wipe and evaluated according to the number of times of wiping off the fingerprint essentially removed, with the evaluation criteria being: preferably, the fingerprint can be removed within 2 times of erasing; fingerprint can be completely removed after 3-5 good erasures; poor-not completely clear the fingerprint;
4. and (3) testing the adhesive force: the adhesive force test is carried out according to the test standard and test method in ISO 2409 paint and varnish grid test, and the test result comprises the following specific steps: level 0-cutting edge is completely smooth, no square lattice falls off; level 1-there is little film separation of the coating at the cut intersection, but the cross-cut area is significantly affected by no more than 5%; level 2-the coating at the cut edges or intersections shed significantly more than 5%, but is affected significantly by no more than 15%; level 3-the coating falls off partially or completely in large fragments along the cut edge, or partially or completely in different parts of the grid, significantly greater than 15%, but affected significantly by no more than 35%; class 4-coating along the cut edge, large chips flaking, or some squares coming off partially or completely, significantly greater than 35%, but affected significantly less than 65%; grade 5-severe spallation greater than grade 4;
5. and (3) testing impact strength: carrying out test tests according to test standards and test methods in GB/T9753-2007 test on cup bursting of colored paint and varnish, and recording data;
6. and (3) wear resistance test: rubbing the surface of the protective coating back and forth by using steel wool wear-resisting equipment at 100fg for 1 time, testing for 120 circles in total, checking for 1 time every 30 circles, dropping 2 mul of water on the surface of the protective coating after the rubbing is finished, and testing a contact angle; 7. scratch resistance test: rubbing the surface of the protective coating at a speed of 10 mm/sec by using a Revetest Scratch Tester (Switzerland CSM instruments Co., ltd.) under the action of an initial load of 1N; the scratch load was increased by increasing the force by 1N every 1 second until the surface to be coated was scratched, and the force of the hand load at which the surface of the coating was scratched was recorded.
The specific data of the performance test tests of the anti-fingerprint agents prepared in examples 1-14 and comparative examples 1-7 are shown in tables 2-5.
TABLE 2
According to the performance detection data of the examples 1-3 and the comparative examples 1 and 2 in the table 2, the fingerprint resisting agent obtained by the preparation process disclosed by the application in the examples 1-3 is cured into a protective coating after being coated on the surface of a base material, the water contact angle and the n-hexadecane contact angle are larger, the hydrophobic oil resistance is good, the results of an oil pen test and fingerprint resistance are better, the adhesion level is 0 grade, and the adhesive force is stronger; the anti-impact strength and the anti-scratch strength are high, the degree of reduction of the surface hydrophobic property after multiple times of friction is small, and the wear resistance and the durability are excellent.
The inventor analyzes that: according to the application, the anti-fingerprint agent is prepared by adopting a specific preparation process, the raw material components of the anti-fingerprint agent contain aqueous fluorocarbon emulsion resin and polytetrafluoroethylene emulsion with excellent hydrophobic lubricity, and the water resistance and oil resistance of the anti-fingerprint agent are improved, in the process of mixing preparation, a penetration assistant and a compatibilizer are also added into the raw materials, so that the cross-linking fusion of all components in a system, particularly high-molecular organic components such as phenyl vinyl silicone resin, is promoted, the prepared anti-fingerprint agent becomes a colloid with better structural performance, and after the anti-fingerprint agent is cured on the surface of a substrate, the colloid viscosity of the anti-fingerprint agent enables a formed anticorrosive coating to have better adhesive force and be not easy to peel off from the surface of the substrate; inorganic nanoparticles are mixed in the anti-fingerprint agent to provide better strength support for the anti-fingerprint agent, so that the wear resistance and the scratch resistance of a cured coating of the anti-fingerprint agent are improved, and the anti-fingerprint agent has good durability.
Comparative example 1 in the preparation process of the anti-fingerprint agent, the components are mixed and reacted at the temperature of 23 ℃, and the components cannot react with each other well at the temperature of 23 ℃, so that the prepared anti-fingerprint agent has poor performance and cannot meet the use requirement; in comparative example 2, high temperature conditions beyond the temperature range limited in the application are selected in the preparation process of the anti-fingerprint agent, and the components are mixed and reacted, although the components may have certain reaction effect, the temperature still has certain inhibition effect on the reaction effect and effect, so that the performance of the prepared anti-fingerprint agent is not as good as that of the anti-fingerprint agents prepared in examples 1 to 3.
TABLE 3
According to the performance detection data of examples 4 and 5 and comparative examples 3 and 4 in table 3, the proportioning amounts of the aqueous fluorocarbon emulsion resin, the permeation assistant, the compatibilizer and the phenyl vinyl silicone resin in examples 4 and 5 are further limited, so that the anti-fingerprint agents prepared in examples 4 and 5 have more excellent surface hydrophobicity oil resistance and wear resistance compared with the anti-fingerprint agents prepared in examples 1 to 3, and the adhesion, impact strength and scratch strength of the anti-fingerprint agents are further improved in a more accurate proportioning range.
The proportion ranges of the waterborne fluorocarbon emulsion resin, the permeation assistant, the compatibilizer and the phenyl vinyl silicone resin in the comparative examples 3 and 4 are not in the component dosage range defined in the application, the performances of the anti-fingerprint agents prepared in the comparative examples 3 and 4 are obviously reduced, and the combination and the proportion of the waterborne fluorocarbon emulsion resin, the permeation assistant, the compatibilizer and the phenyl vinyl silicone resin have important influence on the performance of the anti-fingerprint agent prepared by the preparation method.
The inventor analyzes that: when the waterborne fluorocarbon emulsion resin, the penetration assistant, the compatibilizer and the phenyl vinyl silicone resin are in a certain range of combination proportion, the waterborne fluorocarbon emulsion resin, the penetration assistant, the compatibilizer and the phenyl vinyl silicone resin can be matched with each other, the penetration assistant and the compatibilizer play a special synergistic effect while exerting the effects of the penetration assistant and the compatibilizer, and then the prepared mixture has a stable structure system with uniform components and full connection, and the performance stability of the prepared anti-fingerprint agent product is facilitated. When the component ratio of the four components breaks through the limit and changes greatly, the synergistic effect between the four components disappears, and the good effect generated by the combination of the four components is difficult to obtain.
TABLE 4
According to the performance detection data of the embodiments 6 and 7 in table 4, the processing technology of adding the penetration assistant and stirring for 5min and then adding the compatibilizer for continuous stirring is adopted in the preparation process of the embodiment 6, so that the fingerprint resistant agent prepared in the embodiment 6 is further improved in the aspects of hydrophobic oil resistance, wear resistance, scratch resistance, compressive strength and the like compared with the fingerprint resistant agent prepared in the embodiments 1 to 3 by adopting the processing of adding the penetration assistant and the compatibilizer for mixing. In the preparation process of example 7, the treatment process of adding the compatibilizer firstly, stirring for 5min, and then adding the permeation assistant for continuous stirring is adopted, so that the performance of the anti-fingerprint agent prepared in example 7 is reduced.
The inventor analyzes that: the penetration auxiliary agent and the compatibilizer are added according to a certain sequence, and because the effects generated by the penetration auxiliary agent and the compatibilizer are different, the penetration auxiliary agent and the compatibilizer are matched with other components in a system, so that a synergistic effect and an inhibition and inhibition effect can be generated when the penetration auxiliary agent and the compatibilizer are added, and then the penetration auxiliary agent and the compatibilizer can generate a synergistic effect with other components, so that the prepared mixture is uniform in structure and stable in performance, and the performance of the final anti-fingerprint agent product is promoted to be improved.
According to the performance detection data of the embodiments 8 and 9 in table 4, the compatibilizer prepared in preparation example 4 is selected in embodiment 8, and the combination proportion relationship among the components in the compatibilizer in preparation example 4 is beyond the proportion range defined in the application, so that the compatibilizer prepared in preparation example 4 cannot achieve a good compatibilization and melting promotion effect, and the performance of the anti-fingerprint agent prepared in embodiment 8 is reduced. In example 9, the compatibilizer prepared in preparation example 5 is selected, and the compatibilizer in preparation example 5 is a commercially available maleic anhydride grafted compatibilizer, which has a better beneficial effect and is more conducive to improving the performance of the prepared anti-fingerprint agent compared with a compatibilizer specially prepared in a certain ratio from triethanolamine, 2-hydroxyethyl methacrylate phosphate, trimellitic anhydride, sodium alginate and water.
According to the performance detection data of the examples 10 and 11 in table 4, the permeation assistant prepared in the preparation example 9 is selected in the example 10, and the combination proportion relationship among the components in the permeation assistant in the preparation example 9 exceeds the ratio range defined in the application, so that the permeation assistant prepared in the preparation example 9 cannot achieve a good permeation and dispersion effect, and the performance of the anti-fingerprint agent prepared in the example 10 is reduced. In example 11, the permeation assistant prepared in preparation example 10 is selected, the permeation assistant in preparation example 10 is a commercially available isooctanol polyoxyethylene ether permeation assistant, and the performance of the anti-fingerprint agent prepared in example 11 is lower than that of the anti-fingerprint agents prepared in examples 1 to 3.
TABLE 5
According to the performance detection data of examples 12 and 13 in table 5, the nanoparticles prepared in preparation example 14 are selected in example 12, the nanoparticles prepared in preparation example 15 are selected in example 13, the particle size distribution and content control among the inorganic particles in the nanoparticles are more finely limited in preparation examples 14 and 15, and the nano-silica, nano-titania and nano-hydroxyapatite with different contents and particle sizes are used in combination, so that the compatibility and the binding property between inorganic and organic components in a system can be further promoted, the structure among the inorganic components is more uniform and stable, and further, the performance of the anti-fingerprint agent prepared in examples 12 and 13 is further improved compared with that of the anti-fingerprint agent prepared in examples 1 to 3.
In comparative examples 5 to 7, the nanoparticles prepared in preparation examples 16 to 18 were selected respectively, the nanoparticles in preparation examples 16 to 18 had only a single inorganic component, a certain inorganic particle content and similar particle size, and the inorganic particles selected in comparative examples 5 and 7 had inferior strength support and abrasion and scratch resistance to the fingerprint resisting agent to those of the nanoparticles of examples 1 to 3 and examples 12 to 14, which were reasonably graded.
The inventor analyzes that: with nanometer silica, nanometer titanium dioxide, three kinds of inorganic nanoparticles of nanometer hydroxyapatite mix, three kinds of inorganic particles mutually support, synergistic effect, can help forming the even intensity bearing structure of atress after the dispersion in the system, not only can promote the compressive strength and the impact strength of protective coating after anti-fingerprint agent solidification, but also help closely combining with anti-fingerprint agent colloid base member, promote protective coating's wholeness ability, the inorganic particle of single component can't play this kind of effect of cooperateing, and then can make the performance of anti-fingerprint agent receive great influence.
In example 14, the combination ratio of the raw material components is limited and optimized, and the treatment mode in the preparation process is optimized, so that the anti-fingerprint agent prepared in example 14 has the best performance and the best effect under the cooperation of multiple parties.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (6)
1. A preparation method of a fluorine-containing fingerprint resistant agent with high durability is characterized by comprising the following steps: the method comprises the following steps:
step 1, mixing 15-20 parts by mass of aqueous fluorocarbon emulsion resin, 1-3 parts by mass of permeation aid, 1-2 parts by mass of compatibilizer and 30-35 parts by mass of phenyl vinyl silicone resin, and uniformly mixing at 40-50 ℃ to obtain a mixture A;
step 2, adding 10-15 parts by mass of nano particles and 3-5 parts by mass of silane coupling agent into the mixture A, and uniformly stirring to obtain a mixture B;
step 3, adding 5-7 parts by mass of polytetrafluoroethylene emulsion, 2-3 parts by mass of compatibilizer and 1-2 parts by mass of curing agent into the mixture B, mixing and stirring uniformly at 60-65 ℃, reacting for 3-5 hours, and cooling to 21-23 ℃ while stirring to obtain the fluorine-containing anti-fingerprint agent with high durability;
the compatibilizer is prepared from triethanolamine, 2-hydroxyethyl methacrylate phosphate, trimellitic anhydride, sodium alginate and water according to the mass ratio of (0.5-0.7): (0.3-0.5): (1.2-1.6): (0.8-1.2): 5, mixing at 50-60 ℃;
the penetration auxiliary agent is prepared from polydimethylsiloxane, N-butanol and N-vinyl pyrrolidone according to the mass ratio of (0.2-0.5): (0.9-1.1): (0.5-0.7) mixing;
the nano particles comprise the following raw materials in percentage by mass: 55-60% of nano silicon dioxide, 30-35% of nano titanium dioxide and 5-15% of nano hydroxyapatite; the average grain diameter of the nano silicon dioxide is 10-50nm, the average grain diameter of the nano titanium dioxide is 5-30nm, and the average grain diameter of the nano hydroxyapatite is 5-25nm.
2. The method for preparing the fluorine-containing fingerprint resistant agent with high durability as claimed in claim 1, wherein: in the step 1, 17-18 parts by mass of aqueous fluorocarbon emulsion resin, 2.3 parts by mass of permeation assistant, 1.6 parts by mass of compatibilizer and 32-34 parts by mass of phenyl vinyl silicone resin are mixed.
3. The preparation method of the fluorine-containing anti-fingerprint agent with high durability according to claim 1, wherein the preparation method comprises the following steps: the curing agent in the step 3 is diethylenetriamine or triethylenetetramine.
4. The method for preparing the fluorine-containing fingerprint resistant agent with high durability as claimed in claim 1, wherein: the nano particles comprise the following raw materials in percentage by mass: 58% of nano silicon dioxide, 30% of nano titanium dioxide and 12% of nano hydroxyapatite; the average particle size of the nano silicon dioxide is 35nm, the average particle size of the nano titanium dioxide is 20nm, and the average particle size of the nano hydroxyapatite is 10nm.
5. The method for preparing the fluorine-containing anti-fingerprint agent with high durability according to claim 1 or 2, wherein: in the step 1, the penetration auxiliary agent is added, and the compatibilizer is added after the mixture is stirred for 5 min.
6. A fluorine-containing anti-fingerprint agent with high durability is characterized in that: the fluorine-containing fingerprint resisting agent with high durability is prepared by the preparation method of any one of claims 1 to 5.
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