CN116987440A - High wear-resistant hardening coating and high-gloss flexible high wear-resistant durable fingerprint-resistant hardening film prepared from same - Google Patents

High wear-resistant hardening coating and high-gloss flexible high wear-resistant durable fingerprint-resistant hardening film prepared from same Download PDF

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Publication number
CN116987440A
CN116987440A CN202310908437.4A CN202310908437A CN116987440A CN 116987440 A CN116987440 A CN 116987440A CN 202310908437 A CN202310908437 A CN 202310908437A CN 116987440 A CN116987440 A CN 116987440A
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coating
resistant
parts
wear
fluorine
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崔旭龙
刁锐敏
罗灵
朱金东
邓登月
郭辉
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Sichuan Longhua Film Co ltd
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Sichuan Longhua Film Co ltd
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • 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
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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

Abstract

The invention discloses a high wear-resistant hardened coating and a high-gloss flexible high wear-resistant durable fingerprint-resistant hardened film prepared from the same, wherein the high wear-resistant hardened coating comprises organic and inorganic hybrid polyurethane acrylate with the functionality of 9-15, organic and inorganic hybrid polyurethane acrylate with the functionality of 3-6, high molecular mercaptan, a photoinitiator, a hardening wear-resistant agent, an auxiliary agent and a diluent, and can provide higher hardness and wear resistance for a base material; the high-gloss flexible high-wear-resistance durable fingerprint-proof hardened film is a multilayer laminated structure formed by forming a high-wear-resistance hardened coating, a nanoscale interface layer and a nanoscale fluorine coating on a substrate, and has the functions of high glossiness, high wear resistance, high flexibility, fingerprint resistance and the like through controlling the formula proportion of specific raw materials in the coating and the mutual matching of the coatings, so that the durability of the fingerprint-proof performance is realized.

Description

High wear-resistant hardening coating and high-gloss flexible high wear-resistant durable fingerprint-resistant hardening film prepared from same
Technical Field
The invention belongs to the technical field of optical coatings, and particularly relates to a high-wear-resistance hardening coating and a high-gloss flexible high-wear-resistance durable fingerprint-resistant hardening film prepared from the same.
Background
The main preparation methods of the high wear-resistant anti-fingerprint coating at present are vacuum coating and fluorine-containing coating wet coating, the anti-fingerprint coating is prepared by adopting inorganic fluoride for evaporation, the water contact angle can reach 110-113 degrees, the anti-fingerprint effect is durable, but the anti-fingerprint coating is made of inorganic materials, has poor binding force on PC/PMMA (polycarbonate/polymethyl methacrylate) and other organic materials, the coating is hard and has insufficient toughness, and the preparation method is intermittent production, and the treated product has smaller size, large equipment investment, low productivity and large environmental pollution. The other fluorine-containing coating wet coating scheme is mainly to add fluorine-containing materials into the photo-curing coating for coating, the water contact angle of the coating prepared by the scheme is low, only 105-108 degrees, and the fingerprint-proof effect is not durable, but the preparation method can realize continuous coating production of large-size products, and has high production efficiency and low cost.
In the prior art, the invention patent with publication number of CN102634267A discloses a coating composition for preventing dirt and fingerprints of a touch screen panel and a preparation method of the dirt and fingerprint coating, which mainly comprises 10-90 parts of ultraviolet light curing film forming resin, 0-5 parts of photoinitiator, 0.1-10 parts of acrylic acid modified fluorinated resin and 10-90 parts of solvent, wherein the coating composition is prepared by mixing and stirring, and the coating composition is uniformly coated on a substrate and can form an optical dirt and fingerprint coating with excellent performance after ultraviolet light curing, so that the contact angle between the fingerprint and water is larger than 80 degrees, the dirt and fingerprint coating has good dirt and fingerprint preventing effect, and can be widely applied to the functional treatment of the dirt and fingerprint prevention on the surface of various films or plates in the touch screen industry. According to the scheme, hydroxyl-containing organic fluorine modified acrylic ester can form a net structure with ultraviolet light curing film-forming resin through hydroxyl and carbon-carbon unsaturated bond of acrylic ester, so that fluorine is facilitated to be permanently fixed on the surface of a coating film, and the fluorine is not easy to erase. However, the proposal uses the resin containing hydroxyl groups for fluorine modification, and the resin cannot realize high fluorine content, so that the coating prepared by the method has the problems of relatively low water contact angle, relatively poor compatibility with other resins, easy fogging of the coating and the like although the durability is relatively good; in addition, the molecular weight of the modified resin is larger after modification, the olefin bond density capable of participating in UV reaction is reduced, a three-dimensional network structure cannot be realized after curing, the wear resistance of the coating is poor, fluorine elements on the surface after friction resistance are removed by friction, the water contact angle is rapidly reduced, and the pollution resistance is obviously reduced after long-term use in application scenes with touch and friction.
The invention patent with publication number of CN107603462A discloses an ultraviolet light curing type anti-fingerprint coating and a preparation method and a use method thereof, wherein UV curing type resin is adopted as a main body, and an anti-fingerprint effect is achieved by adding an efficient reactive anti-fingerprint auxiliary agent. However, in order to ensure good compatibility of the fluorine-containing auxiliary agent and other components, the fluorine-containing auxiliary agent generally adopts fluorine-modified acrylic resin, and the surface fluorine content is higher than that of the fluorine-modified resin, but the antifouling effect of the water contact angle of the fluorine-containing auxiliary agent is still difficult to reach 110 degrees, and the water contact angle is obviously reduced through friction.
The invention patent with publication number of CN106433411A provides an anti-fingerprint coating liquid and an anti-fingerprint hardening film, wherein the coating liquid is prepared by compounding fluorine modified resin and fluorine auxiliary agent, the obtained anti-fingerprint hardening film can realize higher water contact angle and wear resistance, the water contact angle can reach 112.21 degrees at most, and the wear-resistant 0000# steel wool rubs and bears 1kg (1 cm multiplied by 1 cm) of friction 5000 cycles; however, the solution still cannot solve the problem that the water contact angle is reduced after wear resistance and the water contact angle is reduced under the conditions of high temperature, high temperature and high humidity. And the smoothness of the product is not comparable with that of a glass product.
The invention patent publication No. CN103252937B and publication No. CN107344817A both provide a method for preparing an anti-fingerprint coating by using a coating process, and the process method is mainly suitable for SiO 2 The glass material of the component, although the water contact angle of the scheme can reach 110-113 degrees, the fingerprint-proof effect is durable, the surface is smooth, but the coating process is complex, the preparation period of the fingerprint-proof film is long, the equipment investment is large, the production efficiency is low, and the large-area product production cannot be satisfied.
Disclosure of Invention
The invention aims to provide a high wear-resistant hardened coating, which is prepared by taking organic-inorganic hybrid polyurethane acrylic ester with different functionalities as raw materials and adding macromolecule mercaptan, photoinitiator and the like, and can improve the hardness and wear resistance of a base material by forming an anti-fingerprint hardened film with the base material, a nanoscale interface layer and a nanoscale fluorine coating.
The invention is realized by the following technical scheme: the high wear-resistant hardened coating comprises the following raw material components in parts by weight: 10 to 30 parts of organic-inorganic hybrid polyurethane acrylate with the functionality of 9 to 15, 5 to 15 parts of organic-inorganic hybrid polyurethane acrylate with the functionality of 3 to 6, 1 to 5 parts of macromolecule mercaptan, 1 to 5 parts of photoinitiator, 1 to 5 parts of hardening wear-resistant agent, 0.1 to 1 part of auxiliary agent and 30 to 60 parts of diluent,
the organic-inorganic hybrid polyurethane acrylic ester is prepared by crosslinking polyurethane acrylic ester and metal oxide, wherein the polyurethane acrylic ester can be poly-synthesized by two-step reaction of polyisocyanate, long-chain diol and acrylic ester hydroxy ester, and the metal oxide can be silicon dioxide, zirconium dioxide or aluminum oxide;
the high molecular mercaptan comprises acrylic mercaptan, allylic mercaptan or olefinic mercaptan;
the photoinitiator comprises at least one of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone dimethoxy phenyl acetophenone, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone;
the hardening antiwear agent comprises at least one of nano silica sol, nano titanium sol, nano aluminum sol and nano zirconium sol;
the auxiliary agents include, but are not limited to, defoamers, leveling agents or polymerization inhibitors, wherein defoamers such as: polyether silicone defoamers, polyester silicone defoamers or acrylate defoamers; leveling agents include, for example: an organosilicon leveling agent, an acrylate leveling agent, or a fluoro leveling agent; examples of the polymerization inhibitor include: hydroquinone, tetrachlorobenzoquinone or l, 4-naphthoquinone.
Such diluents include, but are not limited to, ketone, ester, ether, or alcohol solvents.
The high-gloss flexible high-wear-resistance durable fingerprint-proof hardened film comprises a base material, the high-wear-resistance hardened coating, a nanoscale interface layer and a nanoscale fluorine coating, wherein the high-wear-resistance hardened coating, the nanoscale interface layer and the nanoscale fluorine coating are sequentially arranged on the base material.
The substrate is a film or sheet of optical high polymer polycarbonate, polymethyl methacrylate, polyethylene terephthalate and polyimide.
The nanoscale interface layer comprises the following raw material components in parts by weight: 0.1 to 1 part of silane coupling agent, 99 to 99.9 parts of organic solvent and 0 to 0.5 part of acetic acid;
the silane coupling agent comprises at least one of vinyl triethoxysilane, vinyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and amino ethyl aminopropyl trimethoxysilane.
The organic solvent comprises at least one of ethanol, isopropanol, n-propanol and n-butanol.
The nanoscale fluorine coating comprises the following raw material components in parts by weight: 0.01 to 0.2 part of fluorine-containing surfactant resin and 99.8 to 99.99 parts of fluorine-containing solvent.
The fluorosurfactant resin includes a fluoroacrylate or a fluoropolyester.
The fluorine-containing solvent comprises 1, 2-tetrafluoro-1- (2, 2-trifluoroethoxy) ethane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, at least one of hexafluoropropanol, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts the high wear-resistant hardening coating with specific formula proportion, can improve the hardness and wear resistance of a base material, can be used for preparing the anti-fingerprint hardening film, namely adopts a coating formula system consisting of the high wear-resistant hardening coating formula, the nanoscale interfacial layer coating formula and the nanoscale fluorine coating formula, and has a water contact angle which is 10-15 degrees higher than that of the commercial anti-fingerprint product, and the secondary water contact angle after abrasion resistance of steel wool is more than 105 degrees, and the secondary water contact angle after alcohol friction and water boiling is more than 110 degrees, so as to realize the durability of the anti-fingerprint performance.
(2) The fingerprint-proof hardened film provided by the invention adopts the nanoscale interface layer with a specific formula proportion besides the high wear-resistant hardened coating, can provide a surface rich in SI-OH, provides reaction points for the solidification of the nanoscale fluorine coating, increases the adhesion of the nanoscale fluorine coating, and prevents migration of fluorine-containing surfactant, thereby ensuring durable fingerprint-proof performance.
(3) According to the invention, a special fluorine surfactant is selected in the nano fluorine coating paint formula, and a fluorine-containing solvent is used as a dissolving reagent of the fluorine-containing surfactant, so that the enrichment of fluorine elements with the maximum concentration on the surface of an interface layer can be fully ensured in the drying process, the characteristic that the water contact angle is more than 113 DEG is realized, the limitation that the water contact angle of wet coating can only reach 108 DEG is broken through, the durability of fingerprint prevention is improved, and the product performance can be comparable with an electroplating product and even better in the water contact angle characteristic.
(4) According to the invention, the design of nanometer thickness is adopted for the nanoscale interface layer and the nanoscale fluorine coating, the coating is thin, the cost is controllable, and compared with the additive type (the fluorine auxiliary agent is added in the coating), the independent coating of the nanoscale fluorine coating can effectively and accurately realize the aggregation of the fluorine material on the surface of the coating, avoid the embedding of the fluorine material in the middle of the coating, and further effectively improve the use efficiency of the fluorine material.
(5) The invention adopts a laminated structure design, namely a laminated design of a base material, a high wear-resistant hardened coating, a nanoscale interface layer and a nanoscale fluorine coating, realizes excellent fingerprint resistance of a product, has simple preparation process, can adopt coating methods such as curtain coating, coil coating and Ping Tu, can realize large-area coating of the base material, greatly improves the production efficiency, and is suitable for large-scale production.
(6) The invention is a highlight flexible high wear-resistant durable fingerprint-proof hardening film, the initial water contact angle of the hardening film can reach 114-117 degrees, the fingerprint-proof effect is good, and the hardening film has durable fingerprint-proof performance: 0000# steel wool friction load 1kg (1 cm multiplied by 1 cm) friction 5000 cycles, water contact angle after steel wool friction >105 degrees, alcohol dust-free cloth load 1kg (1 cm multiplied by 1 cm) friction 1000 cycles, water contact angle after alcohol friction >110 degrees, water contact angle after water boiling 100 ℃/30min >110 degrees; the wear resistance is good: the dynamic friction coefficient of the coating is less than 0.05; characteristics of high light flexibility: the glossiness of the coating at 60 degrees is up to 150-160 GU, and the flexibility phi of the coating is less than 20mm (cylindrical shaft test method).
Drawings
FIG. 1 is a schematic view of the structure of a cured film according to the present invention.
Detailed Description
The objects, technical solutions and advantageous effects of the present invention will be described in further detail below.
It is noted that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed, and unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention provides a high wear-resistant hardening coating and a high-light flexibility high wear-resistant durable fingerprint-resistant hardening film with a structure shown in figure 1, which are prepared by laminating four layers of structures of a base material, the high wear-resistant hardening coating, a nanoscale interface layer and a nanoscale fluorine coating, wherein the high wear-resistant hardening coating, the nanoscale interface layer and the nanoscale fluorine coating are prepared by adopting a special coating formula system, compared with the hardening film of a single-component fingerprint-resistant coating, a fluorine-containing resin single-component fingerprint-resistant coating and a fluorine-containing resin and fluorine-containing auxiliary agent mixed coating which are externally added with fluorine auxiliary agents in the market, the water contact angle of the product is 10-15 degrees higher, and the organic-inorganic hybridization high wear-resistant hardening coating can improve the hardness and wear resistance of the base material, and the interface layer provides a surface rich in SI-OH, provides a reaction point for the solidification of the fluorine coating, and increases the adhesion of the fluorine coating, so that the fluorine-containing surfactant is prevented from migrating, and the durability of the fingerprint-resistant performance is realized, so that the secondary water contact angle of the product after velvet friction and the water contact angle of the steel wire after water boiling is more than 105 degrees, and the water contact angle of the product is 110 degrees, and the high wear-resistant property of the product is also provided. In the preparation process, the wet coating process is adopted, so that the water contact angle of the product is more than 113 degrees, the fluorine coating is atomized by means of high-speed rotary spraying and the like, the fluorine surfactant is scattered to form nanoscale liquid drops, the fluorine aggregation density on the interface layer is increased, further, the excellent fingerprint-proof characteristic is realized, the performance is superior to that of an electroplating product, the large-area coating of a substrate can be realized, the large-scale production is met, and the production efficiency is improved.
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. In the following examples of the present invention,
the base material is a PC film purchased from Sichuan dragon Hua Guangdian film Co., ltd, the light transmittance of the PC film is more than 90%, the haze is less than 0.5%, the surface hardness is 500g/6B, the surface dyne value is more than 36dyn, the tensile strength is more than 60Mpa, and the elongation at break is more than 90%.
The coating adopts a wet coating process, and adopts a nanometer high-speed rotary spray head for spraying.
Example 1: hardened film 1#
High abrasion-resistant hardening paint:
weighing the following raw materials in parts by weight: 25 parts of polyurethane acrylate/silicon dioxide hybrid material with 10 degrees of functionality, 6 parts of polyurethane acrylate/silicon dioxide hybrid material with 4 degrees of functionality, 5 parts of acrylic ester mercaptan, 4 parts of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2 parts of nano silica sol, 1 part of nano zirconium sol, 0.1 part of polyether siloxane defoamer, 0.5 part of fluorine leveling agent, 0.1 part of l, 4-naphthoquinone and 56.2 parts of methanol. Adding methanol into a reaction kettle, sequentially adding the raw material components, stirring at a low speed of 500 rpm for 35min, and stirring at a speed of 1200 rpm for 15min until the solution is clear and transparent, thus obtaining the organic-inorganic hybrid high-wear-resistance hardening paint.
And (3) interfacial layer coating:
weighing the following raw materials in parts by weight: and mixing 0.9 part of gamma-methacryloxypropyl trimethoxy silane, 99 parts of ethanol and 0.1 part of acetic acid to obtain the interface layer coating.
Fluorine coating:
weighing the following raw materials in parts by weight: 0.1 part of fluorine-containing acrylic ester and 99.9 parts of 1, 2-tetrafluoro-1- (2, 2-trifluoroethoxy) ethane are mixed to obtain the fluorine paint.
The substrate, the organic-inorganic hybrid high-wear-resistance hardening paint, the interface layer paint and the fluorine paint are taken to prepare the highlight flexible high-wear-resistance durable fingerprint-resistant hardening film, and the preparation method comprises the following specific steps:
step one:
the surface of the base material is cleaned by adopting the conventional treatment modes such as electrostatic ion wind dust removal, ultrasonic dust removal or solvent cleaning, and the like, after the treatment, the organic-inorganic hybrid high wear-resistant hardening coating is uniformly coated on the surface of the base material, and then the leveling procedure treatment is carried out, the leveling temperature is controlled to be 25 ℃, the leveling time is controlled to be 2min, and then the base material is sequentially sent into a heating area and a UV areaTreating, heating at 70deg.C for 3min in a heating zone, and controlling UV intensity to 200mw/cm in a UV zone 2 The UV energy is 550mj/cm, the temperature in the UV area is lower than 105 ℃, the UV time is 5s, and a high wear-resistant hardened coating is formed, and the thickness of the coating is controlled to be 6um.
Step two:
and (3) carrying out corona or plasma treatment on the surface of the high wear-resistant hardened coating formed in the step (A), wherein the contact angle of surface water is required to be reduced to be between 30 and 50 degrees so as to realize good surface wettability, then coating interface layer coating on the surface of the treated coating, then sending the coating into a drying area, controlling the temperature of the drying area to be 100 ℃, and the drying time to be 180 seconds so as to form a nanoscale interface layer, wherein the thickness of the coating is controlled to be 225nm.
Step three:
and (3) coating fluorine paint on the surface of the nanoscale interface layer formed in the step two, then sending the coated material into a drying area, controlling the temperature of the drying area to be 90 ℃ and the drying time to be 2.5 hours, and forming a nano fluorine coating, wherein the thickness of the coating is controlled to be 25nm. Thereby preparing a hardened film 1#.
Example 2: hardening film 2#
This embodiment differs from embodiment 1 in that: the raw materials of the organic-inorganic hybrid high-wear-resistance hardening paint are selected and the technological parameters for forming the high-wear-resistance hardening paint on the base material are different. The other raw material components and the preparation process parameters are the same, so that the hardened film No. 2 is prepared.
Specifically, the raw material proportions of the organic-inorganic hybrid high-wear-resistance hardening paint are selected as follows: 30 parts of polyurethane acrylate/zirconium dioxide hybrid material with the functionality of 9, 10 parts of polyurethane acrylate/zirconium dioxide hybrid material with the functionality of 3, 1 part of acrylic ester mercaptan, 3 parts of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 2 parts of nano titanium sol, 0.1 part of polyether siloxane defoamer, 0.2 part of acrylate leveling agent, 0.2 part of hydroquinone and 53.5 parts of acetone.
When a high wear-resistant hardened coating is formed on the surface of a substrate, controlling the leveling temperature to be 20 ℃ and the leveling time to be 3min; controlling the heating temperature to 90 ℃ and the heating time to 3min; the UV light intensity is controlled to be 110mw/cm <2 >, the UV energy is 800mj/cm, the temperature of the UV area is lower than 105 ℃, the UV time is controlled to be 2s, and the thickness of the coating is controlled to be 4.5um.
Example 3: hardened film 3#
This embodiment differs from embodiment 1 in that: the raw materials of the interface layer coating are selected and the technological parameters for forming the nanoscale interface layer on the high-wear-resistance hardening coating are different. The other raw material components and the preparation process parameters are the same, so that the hardened film 3# is prepared.
Specifically, the raw material ratio of the interfacial layer coating is selected as follows: 1 part of gamma-aminopropyl triethoxysilane and 99 parts of isopropanol.
When the nanoscale interface layer is formed on the high-wear-resistance hardening coating, the temperature of a drying area is controlled to be 110 ℃, the drying time is controlled to be 120s, and the thickness of the coating is controlled to be 205nm.
Example 4: hardened film 4#
This embodiment differs from embodiment 1 in that: the raw materials of the fluorine coating are selected and the technological parameters for forming the nano fluorine coating on the nano interface layer are different. The other raw material components and the preparation process parameters are the same, so that the hardening film No. 4 is prepared.
Specifically, the raw material ratio of the interfacial layer coating is selected as follows: 0.05 part of fluorine-containing acrylic ester or fluorine-containing polyester, and 99.95 parts of 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
When the nano fluorine coating is formed on the nano interface layer, the temperature of a drying area is controlled to be 80 ℃, the drying time is controlled to be 3 hours, and the thickness of the coating is controlled to be 28nm.
Example 5: hardened film 5#
This embodiment differs from embodiment 1 in that: the raw materials of the organic-inorganic hybrid high-wear-resistance hardening paint are different. The other raw material components and the preparation process are the same, so that the hardened film No. 5 is prepared.
Specifically, the raw material proportions of the organic-inorganic hybrid high-wear-resistance hardening paint are selected as follows: 25 parts of polyurethane acrylate/silicon dioxide hybrid material with 10 degrees of functionality, 15 parts of polyurethane acrylate/silicon dioxide hybrid material with 5 degrees of functionality, 3 parts of olefin mercaptan, 2 parts of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone dimethoxy phenylacetophenone, 3 parts of nano aluminum sol, 0.15 part of polyester siloxane defoamer, 0.1 part of organosilicon leveling agent, 0.25 part of tetrachlorobenzoquinone and 49.5 parts of isopropanol.
Example 6: hardened film 6#
This embodiment differs from embodiment 1 in that: the materials of the interfacial layer coating are selected differently. The components and the preparation process of the other raw materials are the same, so that the hardened film 6# is prepared.
Specifically, the raw material ratio of the interfacial layer coating is selected as follows: 0.25 part of vinyl triethoxysilane, 0.25 part of gamma-aminopropyl triethoxysilane, 99 parts of isopropanol and 0.5 part of acetic acid.
Example 7: hardened film 7#
This embodiment differs from embodiment 1 in that: the raw materials of the fluorine coating are different. The other raw material components and the preparation process are the same, so that the hardened film 7# is prepared.
Specifically, the raw material ratio of the interfacial layer coating is selected as follows: 0.15 part of fluorine-containing polyester and 99.85 parts of hexafluoropropanol.
Example 8: hardened film 8#
This embodiment differs from embodiment 1 in that: the process parameters of coating and preparing the high-gloss flexible high-wear-resistance durable fingerprint-proof hardened film on the base material are different, and the base material, the organic-inorganic hybrid high-wear-resistant hardened paint, the interface layer paint and the fluorine paint adopted by the method are the same, so that the hardened film 8# is prepared.
Specifically, in the first step, the leveling temperature is controlled to be 30 ℃, and the leveling time is controlled to be 3min; controlling the heating temperature to 90 ℃ and the heating time to 2.5min; controlling the UV light intensity to be 150mw/cm <2 >, the UV energy to be 600mj/cm <2 >, the temperature of a UV region to be lower than 105 ℃, the UV time to be 3s, and controlling the thickness of the high wear-resistant hardened coating to be 2um; in the second step, the temperature of the drying area is controlled to be 90 ℃, the drying time is 240s, and the thickness of the nanoscale interface layer is controlled to be 255nm; in the third step, the temperature of the drying area is controlled to be 90 ℃, the drying time is controlled to be 2.5 hours, and the thickness of the nano fluorine coating is controlled to be 19.2nm.
Comparative example 1: control hardened film 1#
Weighing the following raw materials in parts by weight: 30 parts of polyurethane acrylate with 10 degrees of polyfunctional, 10 parts of polyurethane acrylate with 4 degrees of polyfunctional, 5 parts of fluorinated acrylic monomer, 2.5 parts of nano silicon dioxide particles, 2 parts of acrylic mercaptan, 2 parts of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2 parts of nano silica sol, 1 part of nano zirconium sol, 0.1 part of polyether siloxane defoamer, 0.2 part of fluorine leveling agent, 0.1 part of l, 4-naphthoquinone and 45.1 parts of ethyl acetate.
Adding ethyl acetate into a reaction kettle, sequentially adding the raw material components, stirring at a low speed of 500 rpm for 40min, and stirring at a low speed of 1000 rpm for 10min until the solution is uniformly mixed, thus obtaining the fingerprint-resistant nano coating.
The same substrate of example 1 was taken, after the substrate surface was cleaned, an anti-fingerprint nano-coating was applied to the substrate surface, and then a leveling process treatment was performed, wherein the leveling temperature was controlled to 25 ℃ and the leveling time was 5min, and then the substrate was sequentially fed into a heating zone and a UV zone for treatment, wherein the heating temperature was controlled to 80 ℃ and the heating time was 5min, and wherein the UV light intensity was controlled to 300mw/cm in the UV zone 2 The UV energy is 600mj/cm, the temperature of the UV area is lower than 105 ℃, the UV time is 8s, and the hardened fingerprint-resistant nano coating (contrast hardened film 1#) is formed, and the thickness of the coating is controlled to be 12.2um.
Comparative example 2: control hardened film 2#
Weighing the following raw materials in parts by weight: 30 parts of polyurethane acrylate/silicon dioxide hybrid material with 10 degrees of multifunctionality, 8 parts of polyurethane acrylate/silicon dioxide hybrid material with 4 degrees of functionality, 2 parts of fluorinated acrylic acid monomer, 2 parts of acrylic ester mercaptan, 1 part of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 1 part of gamma-methacryloxypropyl trimethoxysilane, 1 part of nano silica sol, 1 part of nano zirconium sol, 0.25 part of polyether siloxane defoamer, 0.5 part of fluorine leveling agent, 0.25 part of l, 4-naphthoquinone and 43 parts of ethyl acetate.
Adding ethyl acetate into a reaction kettle, sequentially adding the raw material components, stirring at a low speed of 500 rpm for 40min, and stirring at a low speed of 1000 rpm for 10min until the solution is uniformly mixed, thus obtaining the fingerprint-resistant nano coating.
The same substrate of example 1 was taken, after the substrate surface was cleaned, an anti-fingerprint nano-coating was applied to the substrate surface, and then a leveling process treatment was performed, wherein the leveling temperature was controlled to 30 ℃ and the leveling time was 3min, and then the substrates were sequentially fed into a heating zone and a UV zone for treatment, wherein the heating temperature was controlled to 60 ℃ and the heating time was 2min, and wherein the UV light intensity was controlled to 280mw/cm in the UV zone 2 The UV energy is 800mj/cm, the temperature of the UV area is lower than 105 ℃, the UV time is 5s, and the hardened fingerprint-resistant nano coating (contrast hardened film 21#) is formed, and the thickness of the coating is controlled to be 13.1um.
The following tests were performed on the above cured films 1# to 8#, the control cured film 1# and the control cured film 2# respectively:
water contact angle
A small droplet of 3ul was added dropwise to the surface of the sample coating at room temperature using a german gram Lv Shishui contact angle automatic tester, and the static contact angle of the water droplet with the coating was tested by the device imaging system. The test results are shown in table 1 below.
TABLE 1
(II) wear resistance
The dynamic friction coefficient of the coating of the hardened film was measured by using Labthink MXD-02 dynamic friction coefficient test equipment according to the method of standard GB 10006-88. The detection results are shown in the following table 2.
TABLE 2
(III) gloss
The gloss of the cured film was measured using a BYK 4563 new micro three-angle gloss meter according to the method of standard ASTM D523. The detection results are shown in table 3 below.
TABLE 3 Table 3
(IV) flexibility
The flexibility of the hardened film was measured by the method of standard ISO 1519-2011 using a cylindrical shaft as a measuring device. The detection results are shown in the following table 4.
TABLE 4 Table 4
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.

Claims (8)

1. A high wear resistant hardened coating, characterized by: the composite material comprises the following raw material components in parts by weight: 10 to 30 parts of organic-inorganic hybrid polyurethane acrylate with the functionality of 9 to 15, 5 to 15 parts of organic-inorganic hybrid polyurethane acrylate with the functionality of 3 to 6, 1 to 5 parts of macromolecule mercaptan, 1 to 5 parts of photoinitiator, 1 to 5 parts of hardening wear-resistant agent, 0.1 to 1 part of auxiliary agent and 30 to 60 parts of diluent,
the organic-inorganic hybrid polyurethane acrylic ester is prepared by crosslinking polyurethane acrylic ester with metal oxide;
the high molecular mercaptan comprises acrylic mercaptan, allylic mercaptan or olefinic mercaptan;
the photoinitiator comprises at least one of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone dimethoxy phenyl acetophenone, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone;
the hardening antiwear agent comprises at least one of nano silica sol, nano titanium sol, nano aluminum sol and nano zirconium sol;
such adjuvants include, but are not limited to, defoamers, leveling agents or inhibitors;
such diluents include, but are not limited to, ketone, ester, ether, or alcohol solvents.
2. The utility model provides a durable fingerprint hardening film that prevents of highlight flexibility high wear-resisting which characterized in that: the high wear-resistant hard coating comprises a base material, the high wear-resistant hard coating, the nanoscale interface layer and the nanoscale fluorine coating, wherein the high wear-resistant hard coating, the nanoscale interface layer and the nanoscale fluorine coating are sequentially arranged on the base material.
3. The highlight flexible high wear-resistant durable fingerprint-resistant hardened film according to claim 2, wherein: the nanoscale interface layer comprises the following raw material components in parts by weight: 0.1 to 1 part of silane coupling agent, 99 to 99.9 parts of organic solvent and 0 to 0.5 part of acetic acid.
4. A highlight flexible high wear resistant durable fingerprint resistant hardened film according to claim 3, characterized in that: the silane coupling agent comprises at least one of vinyl triethoxysilane, vinyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and amino ethyl aminopropyl trimethoxysilane.
5. A cured film according to claim 3, wherein: the organic solvent comprises at least one of ethanol, isopropanol, n-propanol and n-butanol.
6. The highlight flexible high wear-resistant durable fingerprint-resistant hardened film according to claim 2, wherein: the nanoscale fluorine coating comprises the following raw material components in parts by weight: 0.01 to 0.2 part of fluorine-containing surfactant resin and 99.8 to 99.99 parts of fluorine-containing solvent.
7. The cured film according to claim 6, wherein: the fluorosurfactant resin includes a fluoroacrylate or a fluoropolyester.
8. The cured film according to claim 6, wherein: the fluorine-containing solvent comprises 1, 2-tetrafluoro-1- (2, 2-trifluoroethoxy) ethane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, at least one of hexafluoropropanol, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
CN202310908437.4A 2023-07-24 2023-07-24 High wear-resistant hardening coating and high-gloss flexible high wear-resistant durable fingerprint-resistant hardening film prepared from same Pending CN116987440A (en)

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