CN113150679B - Fingerprint-resistant fluorine-free coating and preparation method thereof - Google Patents

Fingerprint-resistant fluorine-free coating and preparation method thereof Download PDF

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CN113150679B
CN113150679B CN202110513030.2A CN202110513030A CN113150679B CN 113150679 B CN113150679 B CN 113150679B CN 202110513030 A CN202110513030 A CN 202110513030A CN 113150679 B CN113150679 B CN 113150679B
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photoinitiator
fingerprint
fluorine
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CN113150679A (en
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沈丽香
朱明晶
李冠荣
孔婉仪
黄艳轶
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Guangzhou Huigu New Materials Technology Co ltd
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Guangzhou Human Chem 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
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
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    • 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

Abstract

The invention discloses an anti-fingerprint fluorine-free coating and a preparation method thereof, wherein the anti-fingerprint fluorine-free coating is prepared from 10 to 30 parts by weight of hyperbranched polyol, 40 to 150 parts by weight of semi-addition acrylate modified organic silicon resin and 0.18 to 1 part by weight of photoinitiator. The fluorine-free coating has good fingerprint resistance, and the use of expensive fluorine-containing compounds and fingerprint resistance auxiliary agents is effectively avoided; the invention utilizes the unique rheological property of the hyperbranched structure to ensure that the reaction system keeps relatively low viscosity. In the synthesis process, no organic solvent is additionally added to adjust the viscosity of the system, so that the emission of toxic gas is reduced. According to the invention, the hyperbranched polyol is automatically synthesized by a molecular design mode, and ultraviolet/sunlight curing is realized by flexibly controlling the branching degree and the final structure of the product, so that the limitation of high-temperature curing is avoided, and the application field of the anti-fingerprint coating is effectively expanded.

Description

Fingerprint-resistant fluorine-free coating and preparation method thereof
Technical Field
The invention relates to the technical field of coatings, in particular to a fingerprint-resistant fluorine-free coating and a preparation method thereof.
Background
In recent years, high and new technology products such as mobile phones, notebook computers, digital wristbands and wearable electronic products are favored by consumers, but the shells and the screen surfaces of the electronic products are very easily polluted by fingerprints, grease on the skin, sweat, cosmetics and the like in the frequent use process. The dirt not only seriously affects the relevant performances of the product such as the beauty, the light transmittance and the like, but also can breed a large amount of bacteria and threaten the health. Therefore, how to make the surface of the electronic product antifouling and fingerprint-proof is very important.
The existing method for realizing the surface anti-fingerprint function mainly comprises two methods of surface coating and anti-fingerprint coating. The surface coating mainly adopts a vacuum coating or radio frequency magnetron sputtering method, the required coating equipment is high in cost, the coating thickness and the process need to be strictly controlled, the multilayer coating efficiency is low, and the industrial production is not facilitated; the existing fingerprint-proof coating with better effect is fluorine-containing coating, and a smooth and transparent protective coating can be formed on a base material after thermosetting, but the technology needs high temperature, is not applicable to heat-sensitive base materials such as PC, PET and the like, and the characteristics of high price, poor compatibility and the like of fluorine-containing compounds seriously limit the industrialized development of the coating.
In the patent CN104559761A, a silane coupling agent, water, a cosolvent and heptadecafluorodecyltriethoxysilane react at 60-80 ℃ for 2-4h to prepare an anti-fingerprint coating, the anti-fingerprint coating is coated on a substrate, and the coating is baked at 180-220 ℃ for 3-7min to obtain the fluorine-containing anti-fingerprint coating. Although the coating has fingerprint resistance and good adhesion with a substrate, the film formation needs high-temperature baking, contains a fluorine compound, and has a hydrolytic group only at one end of a molecule, so that the durability of the coating has a certain problem, and the practical application of the coating is severely limited.
In patent CN111363428A, polydimethylsiloxane modified polyacrylate is adopted as a matrix, trimethylolpropane tris [3- (2-methyl aziridinyl) propionate ] is adopted as a cross-linking agent, and dysprosium-doped nano titanium oxide/strontium titanate core-shell material is adopted as a reinforcing filler, so that fingerprint prevention and pollution prevention can be realized, but the preparation process involves high-temperature calcination and is not beneficial to industrial production.
Patent CN101570653A uses an anti-fingerprint photo-curing coating material composed of a stain-resistant oligomer, a polyfunctional aliphatic urethane acrylate, a polyester modified acrylate, a tripropylene glycol diacrylate, 1-hydroxycyclohexyl benzophenone, a stain-resistant photo-curing assistant, a leveling agent and a diluent to realize an anti-fingerprint effect, but the curing mode is fixed.
The patent CN110922886A polyurethane acrylate UV coating has the advantages of both organic silicon resin and acrylate, and has excellent weather resistance, stain resistance, low surface energy and other properties; the resin is compatible with the first photocuring system and the second photocuring system to obtain the steel wool-resistant and fingerprint-resistant UV coating, the polyurethane acrylate, the first photocuring system and the second photocuring system are inevitably required to achieve the effects of stain resistance, fingerprint resistance and steel wool resistance, the used raw materials are complicated, and the preparation process is complicated.
Therefore, the preparation of the prior anti-fingerprint coating has the defects of dependence on special equipment, complex process, high-temperature curing, single curing mode, potential danger and the like. The defects not only cause great energy consumption waste, but also increase the production cost and time, and simultaneously limit the anti-fingerprint functionalization of the heat-sensitive material and severely limit the application field of the heat-sensitive material.
Disclosure of Invention
The invention provides a fingerprint-resistant fluorine-free coating and a preparation method thereof.
The invention adopts the following technical scheme for solving the technical problems:
an anti-fingerprint fluorine-free coating is prepared from 10 to 30 parts by weight of hyperbranched polyol, 40 to 150 parts by weight of semi-additive acrylate modified organic silicon resin and 0.18 to 1 part by weight of photoinitiator;
the preparation method of the semi-addition acrylate modified organic silicon resin comprises the following steps:
s1, adding 20 to 35 parts by weight of diisocyanate into a reaction container, vacuumizing, adding 30 to 60 parts by weight of hydroxyl-containing polysiloxane and 0.1 to 1 part by weight of catalyst, and carrying out heat preservation reaction at 65 to 90 ℃ for 0.8 to 2h until the-NCO content reaches a theoretical value;
s2, dripping 1 to 5 parts by weight of a dihydric alcohol chain extender into a reaction container, carrying out heat preservation reaction for 0.5 to 2h at 65 to 90 ℃, cooling to 45 to 80 ℃ after the theoretical value of-NCO is measured, adding 0.3 to 1 part by weight of a polymerization inhibitor, dripping 10 to 30 parts by weight of hydroxyl acrylate, carrying out heat preservation reaction for 2 to 4h, and stopping the reaction when the numerical value of-NCO content is constant to obtain the semi-addition acrylate modified organic silicon resin.
As a preferable mode, the diisocyanate in S1 is at least one of isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, ditolyl methane diisocyanate, dimethyl biphenyl diisocyanate, polymethylene polyphenyl isocyanate, dicyclohexyl diisocyanate, and cyclohexanedimethylene diisocyanate;
preferably, the hydroxyl-containing polysiloxane in S1 is at least one of hydroxyl-terminated hydroxyl polysiloxane, hydroxyl side-chain hydroxyl siloxane and water-based modified hydroxyl siloxane, wherein the hydroxyl functionality of the hydroxyl-terminated polysiloxane is 1 to 4, and the molecular weight of the hydroxyl-terminated hydroxyl polysiloxane is 500 to 6000;
as a preferable scheme, the diol chain extender in S2 is at least one of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol or octanediol;
preferably, the hydroxyl acrylate in S2 is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate or pentaerythritol triacrylate;
the invention can adjust the double bond content by changing the type and the content of the acrylic hydroxyl ester, thereby controlling the film forming time and the film forming hardness of the final product and greatly expanding the application range of the final product.
Preferably, the polymerization inhibitor in S2 is at least one of hydroxyanisole, hydroquinone, 2, 5-di-tert-butylhydroquinone and 2-tert-butylhydroquinone.
As a preferable scheme, the preparation method of the hyperbranched polyol comprises the following steps:
s11, adding 30-50 parts by weight of diisocyanate into a reaction container, vacuumizing, adding 0.2-3 parts by weight of catalyst, dropwise adding part of low-molecular polyol, and reacting at 40-75 ℃ for 0.5-4 h until the-NCO content of the system reaches a theoretical value;
s12, dropwise adding the rest of low-molecular-weight polyol for end capping, reacting for 1 to 5 hours at the temperature of 40 to 75 ℃, stopping the reaction when the-NCO content is constant, and drying to obtain hyperbranched polyol;
the total weight of the low-molecular-weight polyol is 50 to 70 parts.
As a preferable mode, the diisocyanate in S11 is at least one of isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, ditolyl methane diisocyanate, dimethyl biphenyl diisocyanate, polymethylene polyphenyl isocyanate, dicyclohexyl diisocyanate, and cyclohexanedimethylene diisocyanate;
in a preferable embodiment, the low molecular weight polyol in S11 is at least one of trimethylolpropane, pentaerythritol, dipentaerythritol, and ditrimethylolpropane.
Preferably, the photoinitiator is at least one of photoinitiator 1173, photoinitiator TPO, photoinitiator 184, photoinitiator 2959, photoinitiator 500, photoinitiator 907, photoinitiator 651, photoinitiator TPO-L, photoinitiator MBB and photoinitiator BP.
The invention also provides a preparation method of the fingerprint-resistant fluorine-free coating, which comprises the following steps:
s21, adding 20 to 35 parts by weight of diisocyanate into a reaction container, vacuumizing, adding 30 to 60 parts by weight of polysiloxane containing hydroxyl, 0.1 to 1 part by weight of catalyst, carrying out heat preservation reaction at 65 to 90 ℃ for 0.8 to 2h until the-NCO content reaches a theoretical value, dropwise adding 1 to 5 parts by weight of glycol chain extender into the reaction container, carrying out heat preservation reaction at 65 to 90 ℃ for 0.5 to 2h, cooling to 45 to 80 ℃ after measuring that-NCO reaches the theoretical value, adding 0.3 to 1 part by weight of polymerization inhibitor, dropwise adding 10 to 30 parts by weight of hydroxy acrylate, carrying out heat preservation reaction for 2 to 4h, and stopping the reaction when the-NCO content is constant to obtain the semi-acrylate modified organic silicon resin;
s22, adding hyperbranched polyol into the semi-addition acrylate modified organic silicon resin prepared in the S21, carrying out heat preservation reaction for 2-4h at the temperature of 45-80 ℃, stopping the reaction when the-NCO content of the system is less than 0.1%, and cooling to room temperature to obtain a product;
s23, adding 0.18 to 1 weight part of photoinitiator into the product, and uniformly stirring to obtain the fingerprint-resistant fluorine-free coating.
As a preferable mode, the diisocyanate in S21 is at least one of isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, ditolyl methane diisocyanate, dimethyl biphenyl diisocyanate, polymethylene polyphenyl isocyanate, dicyclohexyl diisocyanate, and cyclohexanedimethylene diisocyanate;
preferably, the hydroxyl-containing polysiloxane in S21 is at least one of hydroxyl-terminated hydroxyl polysiloxane, hydroxyl side-chain hydroxyl siloxane and water-based modified hydroxyl siloxane, wherein the hydroxyl functionality of the hydroxyl-terminated polysiloxane is 1 to 4, and the molecular weight of the hydroxyl-terminated hydroxyl polysiloxane is 500 to 6000;
as a preferable scheme, the diol chain extender in S21 is at least one of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol or octanediol;
as a preferable scheme, the hydroxy acrylate in S22 is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate or pentaerythritol triacrylate;
preferably, the polymerization inhibitor in S21 is at least one of hydroxyanisole, hydroquinone, 2, 5-di-tert-butylhydroquinone, and 2-tert-butylhydroquinone.
As a preferable scheme, the preparation method of the hyperbranched polyol comprises the following steps:
s31, adding 30 to 50 parts by weight of diisocyanate into a reaction container, vacuumizing, adding 0.2 to 3 parts by weight of catalyst, dropwise adding part of low-molecular polyol, and reacting at the temperature of 40 to 75 ℃ for 0.5 to 4 hours until the content of the system-NCO reaches a theoretical value; and (3) dropwise adding the rest of low-molecular-weight polyol to terminate, reacting for 1 to 5 hours at the temperature of 40 to 75 ℃, stopping the reaction when the-NCO content is constant, and drying to obtain the hyperbranched polyol.
As a preferable mode, the diisocyanate in S31 is at least one of isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, ditolyl methane diisocyanate, dimethyl biphenyl diisocyanate, polymethylene polyphenyl isocyanate, dicyclohexyl diisocyanate, and cyclohexanedimethylene diisocyanate;
the low-molecular polyol in S31 is at least one of trimethylolpropane, pentaerythritol, dipentaerythritol and ditrimethylolpropane.
Preferably, the photoinitiator is at least one of photoinitiator 1173, photoinitiator TPO, photoinitiator 184, photoinitiator 2959, photoinitiator 500, photoinitiator 907, photoinitiator 651, photoinitiator TPO-L, photoinitiator MBB and photoinitiator BP.
The structure of the hyperbranched polyol is as follows (pentaerythritol is used as low molecular weight polyol, isophorone diisocyanate is diisocyanate, if other low molecular weight polyol and diisocyanate are used as raw materials, the structure is different):
Figure 675564DEST_PATH_IMAGE001
the structure of the semi-addition acrylate modified silicone resin is (wherein,
Figure 610022DEST_PATH_IMAGE002
the chain segment is formed by reacting diisocyanate, polysiloxane containing hydroxyl and a dihydric alcohol chain extender, hydroxyethyl acrylate is used as a blocking monomer in the structure, and if other (methyl) hydroxyl acrylate is used as a raw material, the structure is different; ):
Figure 868965DEST_PATH_IMAGE003
the structure of the product is as follows:
Figure 888874DEST_PATH_IMAGE004
wherein A is hyperbranched polyol, and n ranges from 1 to 30.
The fluorine-free fingerprint-resistant coating has the advantages of high curing speed, high efficiency and the like, is suitable for industrial production, and promotes the industrialization of the fingerprint-resistant coating; the sunlight curing anti-fingerprint coating has the advantages of no dependence on equipment, safe use and the like, and the applicable crowd and the use scene range of the anti-fingerprint coating can be further expanded by the selectable curing mode.
The fluorine-free coating realizes good fingerprint resistance through a hyperbranched polyol and a semi-addition acrylate modified organic silicon resin synthetic product, and effectively avoids the use of expensive fluorine-containing compounds and fingerprint resistance auxiliary agents;
the invention utilizes the unique rheological property of the hyperbranched structure to keep the relatively low viscosity of a reaction system, does not need to add an organic solvent to adjust the viscosity of the system in the synthesis process, and reduces the emission of toxic gas.
The invention has the beneficial effects that: (1) The hyperbranched polyol is automatically synthesized by a molecular design mode, and ultraviolet/sunlight curing is realized by flexibly controlling the branching degree and the final structure of the product, so that the limitation of high-temperature curing is avoided, and the application field of the anti-fingerprint coating is effectively expanded; (2) The fluorine-free fingerprint-resistant coating has the advantages of high curing speed, high efficiency and the like, is suitable for industrial production, and promotes the industrialization of the fingerprint-resistant coating; the sunlight curing anti-fingerprint coating has the advantages of being independent of equipment, safe to use and the like, and the applicable crowd and the use scene range of the anti-fingerprint coating can be further expanded by the selectable curing mode; (3) The fluorine-free coating has good fingerprint resistance, and the use of expensive fluorine-containing compounds and fingerprint resistance auxiliary agents is effectively avoided; (4) The invention utilizes the unique rheological property of the hyperbranched structure to ensure that the reaction system keeps relatively low viscosity. In the synthesis process, no organic solvent is additionally added to adjust the viscosity of the system, so that the emission of toxic gas is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, the parts are all parts by weight unless otherwise specified.
Example 1
A preparation method of fingerprint-resistant fluorine-free coating comprises the following steps:
(1) Preparation of hyperbranched polyol:
adding 88.8 parts of isophorone diisocyanate into a reaction vessel, vacuumizing for 30min at 110 ℃, adding 1.19 parts of dibutyltin dilaurate, dropwise adding 29.8 parts of pentaerythritol, reacting for 1.5h at 70 ℃, dropwise adding 119.2 parts of pentaerythritol for end capping, reacting for 3h at 70 ℃, and drying to obtain hyperbranched polyol;
(2) Preparation of semi-addition acrylate modified silicone resin:
adding 105.5 parts of isophorone diisocyanate into a reaction vessel, vacuumizing for 30min at 110 ℃, adding 200 parts of hydroxyl polysiloxane and 4.0 parts of dibutyltin dilaurate catalyst, reacting for 1h at 90 ℃, then dropwise adding 6.0 parts of 1, 4-butanediol into the reaction vessel, reacting for 2h at 90 ℃, cooling to 75 ℃, adding 2.0 parts of p-hydroxyanisole, dropwise adding 89.4 parts of pentaerythritol triacrylate, and reacting for 2h at a constant temperature to obtain semi-addition acrylate modified organic silicon resin;
(3) Adding the hyperbranched polyol prepared in the step (1) into the semi-addition acrylate modified organic silicon resin prepared in the step (2), carrying out heat preservation reaction for 2h at the temperature of 75 ℃, and cooling to room temperature to obtain a product;
(4) 32.2 parts of photoinitiator 1173 is added into the product and stirred evenly, thus obtaining the fingerprint-resistant fluorine-free coating.
The parts described in this example are parts by weight.
The product contains a hyperbranched polyol structure, the hyperbranched polyol is automatically synthesized by a molecular design mode, ultraviolet/sunlight solidifiable is realized by flexibly controlling the branching degree and the final structure of the product, the limitation of high-temperature solidification is avoided, and the application field of the anti-fingerprint coating is effectively expanded.
Example 2
A preparation method of fingerprint-resistant fluorine-free coating comprises the following steps:
(1) Preparation of hyperbranched polyol:
adding 88.8 parts of isophorone diisocyanate into a reaction container, vacuumizing for 35min at 110 ℃, adding 1.9 parts of stannous octoate, dropwise adding 29.8 parts of pentaerythritol, reacting for 1h at 75 ℃, dropwise adding 119.2 parts of pentaerythritol end capping, reacting for 3h at 70 ℃, and drying to obtain hyperbranched polyol;
(2) Preparation of semi-addition acrylate modified silicone resin:
adding 195.4 parts of isophorone diisocyanate into a reaction container, vacuumizing for 35min at 110 ℃, adding 300 parts of hydroxyl polysiloxane and 2.9 parts of stannous octoate catalyst, reacting for 1.5h at 85 ℃, then dropwise adding 11.8 parts of 1, 6-hexanediol into the reaction container, reacting for 2h at 90 ℃, cooling to 75 ℃, adding 3.0 parts of hydroquinone, dropwise adding 81.2 parts of hydroxyethyl acrylate, and reacting for 3h at the temperature to obtain semi-addition acrylate modified organic silicon resin;
(3) Adding the hyperbranched polyol prepared in the step (1) into the semi-addition acrylate modified organic silicon resin prepared in the step (2), carrying out heat preservation reaction for 2h at the temperature of 75 ℃, and cooling to room temperature to obtain a product;
(4) And adding 24.8 parts of photoinitiator 184 into the product, and uniformly stirring to obtain the fingerprint-resistant fluorine-free coating.
The parts described in this example are parts by weight.
Example 3
(1) Preparation of hyperbranched polyol:
adding 50.4 parts of 1, 6-hexamethylene diisocyanate into a reaction container, vacuumizing for 30min at 110 ℃, adding 1.0 part of bismuth neodecanoate, dropwise adding 13.4 parts of trimethylolpropane, reacting for 2h at 70 ℃, dropwise adding 40.2 parts of trimethylolpropane, reacting for 3h at 70 ℃, and drying to obtain hyperbranched polyol;
(2) Preparation of semi-addition acrylate modified silicone resin:
adding 142.8 parts of 1, 6-hexamethylene diisocyanate into a reaction container, vacuumizing for 30min at 110 ℃, adding 150.0 parts of hydroxyl polysiloxane and 3.5 parts of bismuth neodecanoate catalyst, reacting for 1h at 90 ℃, dropwise adding 21.2 parts of diethylene glycol into the reaction container, reacting for 2h at 85 ℃, cooling to 75 ℃, adding 2.6 parts of 2, 5-di-tert-butylhydroquinone, dropwise adding 119.2 parts of pentaerythritol triacrylate, and reacting for 3h at the temperature to obtain semi-addition acrylate modified organic silicon resin;
(3) Adding the hyperbranched polyol prepared in the step (1) into the semi-addition acrylate modified organic silicon resin prepared in the step (2), carrying out heat preservation reaction for 2.5h at the temperature of 70 ℃, and cooling to room temperature to obtain a product;
(4) And adding 32.5 parts of photoinitiator TPO into the product, and uniformly stirring to obtain the fingerprint-resistant fluorine-free coating.
The parts described in this example are parts by weight.
Example 4
(1) Preparation of hyperbranched polyol:
adding 104.8 parts of 4,4' -dicyclohexylmethane diisocyanate into a reaction vessel, vacuumizing for 25min at 110 ℃, adding 1.8 parts of dibutyltin dilaurate, dropwise adding 29.8 parts of pentaerythritol, reacting for 1h at 65 ℃, dropwise adding 119.2 parts of pentaerythritol for end capping, reacting for 2h at 70 ℃, and drying to obtain hyperbranched polyol;
(2) Preparation of semi-addition acrylate modified silicone resin:
adding 243.7 parts of 4,4' -dicyclohexylmethane diisocyanate into a reaction vessel, vacuumizing for 25min at 110 ℃, adding 600 parts of hydroxyl polysiloxane and 9.1 parts of dibutyltin dilaurate catalyst, reacting for 1h at 90 ℃, dropwise adding 15 parts of 1, 4-butanediol into the reaction vessel, reacting for 2h at 90 ℃, cooling to 75 ℃, adding 5.0 parts of p-hydroxyanisole, dropwise adding 149.0 parts of pentaerythritol triacrylate, and reacting for 2h at a constant temperature to obtain the semi-addition acrylate modified organic silicon resin;
(3) Adding the hyperbranched polyol prepared in the step (1) into the semi-addition acrylate modified organic silicon resin prepared in the step (2), carrying out heat preservation reaction for 2.5h at the temperature of 75 ℃, and cooling to room temperature to obtain a product;
(4) And adding 63.1 parts of photoinitiator 1173 and 100 parts of propylene glycol monomethyl ether acetate into the product, and uniformly stirring to obtain the fingerprint-resistant fluorine-free coating.
The parts described in this example are parts by weight.
The invention can increase the solvent according to the product requirement when preparing the fingerprint-resistant fluorine-free coating.
To further demonstrate the effectiveness of the present invention, the coatings prepared in the above examples were applied to a desired substrate by roll coating, spray coating or curtain coating, wherein examples 1-3 were applied with a light intensity of 20 mW/cm 2 The ultraviolet lamp is used for curing for 1min, and the ultraviolet lamp in example 4 is used for curing for 1h under the sun, so that the uniform and transparent fingerprint-resistant coating without cracks is respectively obtained.
The test method is provided as follows:
1. adhesion force: cut hundred squares and test 3 times with 3M 600 tape.
2. Pencil hardness: scratch testing was performed with a mitsubishi pencil at 750 g.
3. Contact angle of coating with water: the contact angle of the coating surface with distilled water was measured using an AC-A contact angle meter.
4. Anti-fingerprint performance
(1) Coating a layer of vaseline on the solidified anti-fingerprint coating, placing the coating at 50 ℃ for 24 hours under the environment with the relative humidity of 90%, lightly wiping the coating with dust-free cloth, comparing the result with the coating without the vaseline coating, judging that the measured delta E of the coating and the measured delta E is OK if the delta E is smaller than 3, and the smaller the delta E is, the better the performance is;
(2) Writing on the solidified anti-fingerprint coating by using an oily pen, wiping the cured anti-fingerprint coating by using a dust-free cloth, and recording the times of wiping the oily pen marks clean, wherein the times is more than 50, the OK is judged, and the larger the times is, the better the quality is.
TABLE 1 test Properties
Figure 157044DEST_PATH_IMAGE005
As can be seen from Table 1, the fingerprint-resistant fluorine-free coating of the invention has good fingerprint resistance, abrasion resistance and antifouling performance.
The fingerprint-resistant fluorine-free coating prepared from the hyperbranched polyol, the semi-addition acrylate modified organic silicon resin and the photoinitiator which are optimized by the formula has good fingerprint resistance, friction resistance and antifouling performance.
In light of the foregoing description of the preferred embodiment of the present invention, it is to be understood that various changes and modifications may be made by those skilled in the art without departing from the scope and spirit of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (4)

1. The fingerprint-resistant fluorine-free coating is characterized by being prepared from 10 to 30 parts by weight of hyperbranched polyol, 40 to 150 parts by weight of semi-addition acrylate modified organic silicon resin and 0.18 to 1 part by weight of photoinitiator;
the preparation method of the semi-addition acrylate modified organic silicon resin comprises the following steps:
s1, adding 20 to 35 parts by weight of diisocyanate into a reaction vessel, vacuumizing, adding 30 to 60 parts by weight of polysiloxane containing hydroxyl and 0.1 to 1 part by weight of catalyst, and carrying out heat preservation reaction at 65 to 90 ℃ for 0.8 to 2h;
s2, dripping 1 to 5 parts by weight of a dihydric alcohol chain extender into a reaction container, carrying out heat preservation reaction for 0.5 to 2h at the temperature of 65 to 90 ℃, cooling to 45 to 80 ℃, adding 0.3 to 1 part by weight of a polymerization inhibitor, dripping 10 to 30 parts by weight of hydroxyl acrylate, and carrying out heat preservation reaction for 2 to 4h to obtain semi-addition acrylate modified organic silicon resin;
the preparation method of the hyperbranched polyol comprises the following steps:
s11, adding 30-50 parts by weight of diisocyanate into a reaction container, vacuumizing, adding 0.2-3 parts by weight of catalyst, dropwise adding part of low-molecular polyol, and reacting at 40-75 ℃ for 0.5-4 h;
s12, dropwise adding the rest of low-molecular-weight polyol to terminate, keeping the temperature at 40 to 75 ℃ for reaction for 1 to 5 hours, stopping the reaction, and drying to obtain hyperbranched polyol;
the total weight of the low-molecular polyol is 50 to 70 parts;
wherein, diisocyanate in the preparation process of the semi-addition acrylate modified organic silicon resin and the hyperbranched polyol is 1, 6-hexamethylene diisocyanate;
the preparation method of the fingerprint-resistant fluorine-free coating comprises the following steps:
s21, preparing a semi-addition acrylate modified organic silicon resin;
s22, adding hyperbranched polyol into the semi-addition acrylate modified silicone resin prepared in the S21
Keeping the temperature at 45-80 ℃ for reaction for 2-4h, stopping the reaction when the-NCO content of the system is less than 0.1%, and cooling to room temperature to obtain a product;
s23, adding 0.18 to 1 weight part of photoinitiator into the product, and uniformly stirring to obtain the fingerprint-resistant fluorine-free coating.
2. The fingerprint-resistant fluorine-free paint according to claim 1, wherein the hydroxyl acrylate in S2 is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate or pentaerythritol triacrylate.
3. The fingerprint-resistant fluorine-free paint according to claim 1, wherein the low molecular polyol in S11 is at least one of trimethylolpropane, pentaerythritol, dipentaerythritol and ditrimethylolpropane.
4. The method for preparing the fluorine-free coating according to claim 1, wherein the photoinitiator is at least one of photoinitiator 1173, photoinitiator TPO, photoinitiator 184, photoinitiator 2959, photoinitiator 500, photoinitiator 907, photoinitiator 651, photoinitiator TPO-L, photoinitiator MBB and photoinitiator BP.
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