TW201512340A - High-skid, anti-fouling material and its preparation method - Google Patents

Abstract

A high-skid, anti-fouling material and its preparation method, whose high-skid, anti-fouling material comprises an anti-fouling solution and a plurality of composite bodies. The anti-fouling solution comprises a dilution solvent and a plurality of perfluorinated polyether adducts containing two characteristic functional groups. Each of the characteristic functional groups comprises a plurality of silane side chains, while each of the composite bodies comprises ZnO nanoparticles and a plurality of surface modifiers wrapping the ZnO nanoparticles. Those surface modifiers comprise at least an amino group. Those composite bodies are connected by coupling with those perfluorinated polyether adducts by the at least one amino group. And dispersed into the anti-fouling solution after connection. The high-skid, anti-fouling material not only increases the abrasion resistance property by means of adding those composite bodies, but also enhances the skid due to those perfluorinated polyether adducts containing two characteristic functional groups to further increase the anti-fouling and self-cleaning capabilities.

Description

High-slip anti-fouling material and preparation method thereof

The invention relates to a transparent substrate coating, in particular to a high-slip abrasion and anti-fouling material.

In the age of technological development, electronic products such as personal computers, notebook computers, and even mobile phones or tablets have become an indispensable part of life; with the popularity of these personalized electronic products, related maintenance and maintenance It has also received increasing attention.

Alkoxyfluorene alkyl perfluorinated adducts (perfluoropolyether-silane, PFPE-silane) have long-lasting anti-fouling properties, mainly used in glass displays and optical samples, especially on glass substrates or On the substrate of the anti-reflection film. In general, materials coated with AS (Anti-Smudge) ability can resist almost all types of dirt, such as water, oil, fingerprints, dust, etc., and have durability.

Although the self-cleaning ability of AS coating materials is unquestionable, it is still the focus of research to continuously improve its anti-fouling ability, and the coating material of perfluoropolyether decane still has its shortcomings, that is, the static electricity generated during friction, Further attenuating the stain or abrasion resistance of the coating material. In order to increase the anti-staining and self-cleaning ability of the AS coating material and the wear resistance, it is often necessary to add a lot of materials, which leads to an increase in cost.

The main object of the present invention is to improve the slip to improve the anti-staining and self-cleaning ability.

In order to achieve the above object, the present invention provides a high-slip antifouling material comprising an anti-fouling solution and a plurality of complexes, the anti-fouling solution comprising a diluent solvent and a plurality of perfluoropolyether adducts comprising di-functional functional groups Each of the characteristic functional groups comprises a plurality of decane branches, each of the composites comprising zinc oxide nano particles and a plurality of surface modifying materials coated on the zinc oxide nano particles, the surface modifying materials comprising at least one amine group, The composites are coupled to each other with the at least one amine group and the perfluoropolyether adducts, and are uniformly dispersed in the antifouling solution after the connection.

The invention further discloses a method for preparing the high-slip anti-fouling material, the steps of which are as follows: S1: mixing a perfluoropolyether precursor containing at least one ester functional group with a decane coupling agent to obtain a plurality of Fluoropolyether adducts comprising a plurality of decane branches.

S2: the perfluoropolyether adduct is placed in a solvent of hexafluorobutyl methyl ether, and the perfluoropolyether adduct is diluted to 0.5 wt.% to 1 wt.% by using the nonafluorobutyl methyl ether solvent. A perfluoropolyether adduct dilute solution.

S3: adding a plurality of zinc oxide nanoparticles to an ethanol solution containing a plurality of γ-aminopropyltriethoxydecane, and after mixing, removing the ethanol solution to form a complex complex.

S4: The composites are placed in a solution of nonafluorobutyl methyl ether, and the composites are uniformly dispersed in the nonafluorobutyl methyl ether solution to form a suspension solution.

S5: mixing the suspension solution with the diluted solution of the perfluoropolyether adduct such that the concentration of the composites is between 0.005 wt.% and 0.01 wt.% to complete the preparation of the high-slip antifouling material.

As can be seen from the above description, the present invention has the following features:

1. Antifouling material using a perfluoropolyether adduct having at least a tetradecane branch The material can increase the slip of the anti-fouling material and improve the anti-staining and self-cleaning ability.

Second, the combination of the perfluoropolyether adduct and the zinc oxide nanoparticle can improve the wear resistance of the antifouling material, and avoid the static electricity generated by the wiping type, thereby attenuating the stain resistance or wear resistance of the coating material.

10‧‧‧Anti-fouling solution

11‧‧‧Diluted solvent

12‧‧‧Perfluoropolyether adduct

20‧‧‧Compound

21‧‧‧Zinc Oxide Nanoparticles

22‧‧‧ Surface modification

Figure 1 is a schematic view showing the structure of surface modification of zinc oxide nanoparticles.

Figure 2 is a schematic view showing the structure of a high-sliding antifouling material.

Figure 3 is a chemical structural diagram of a perfluoropolyether adduct according to a first embodiment of the present invention.

Figure 4 is a chemical structural diagram of a perfluoropolyether adduct according to a second embodiment of the present invention.

Figure 5 is a flow chart of a method for manufacturing a high-slip anti-fouling material.

The detailed description and technical contents of the present invention will now be described with reference to the following figures: Please refer to "FIG. 1", "FIG. 2", "FIG. 3" and "FIG. 4", and the present invention is a high-slipness. The antifouling material comprises an antifouling solution 10 and a plurality of complexes 20, the antifouling solution 10 comprising a dilution solvent 11 and a plurality of perfluoropolyether adducts 12 comprising two characteristic functional groups, each of the characteristic functional groups comprising a plurality of decane branches, wherein the diluent solvent 11 is a non-nuclear butyl methyl ether having a purity of 99.5%, and each of the characteristic functional groups may be as shown in formula (I) or formula (II):

Each of the composites 20 includes a zinc oxide nanoparticle 21 having an average particle diameter of less than 10 nm and a surface modification 22 coated on the zinc oxide nanoparticle 21, and the surface modification 22 comprises at least one amine group. The composite body 20 is coupled to the perfluoropolyether adduct 12 by the at least one amine group, and uniformly dispersed in the antifouling solution 10, wherein the surface modifying materials 22 are γ-aminopropyl three. 3-aminopropyl triethoxysilane (APTES).

Referring to FIG. 5, the present invention further discloses a method for preparing the wear-resistant antifouling material, the steps of which are as follows: S1: a perfluoropolyether adduct 12 prepared by mixing a perfluoropolyether precursor comprising at least one ester functional group with a monooxane coupling agent, wherein the average molecular weight of the perfluoropolyether precursor is Between 1500 and 3000 grams per mole, the two are mixed and reacted in an environment of 25 ° C to 50 ° C for 6-8 hours to obtain a plurality of perfluoropolyether adducts 12, wherein the perfluoropolyethers are added. The product 12 comprises a plurality of decane branches; in the first embodiment, the decane coupling agent is an amino decane having two identical alkoxyalkyl groups, such as bis(3-trimethoxycarbamidopropyl)amine ( Bis(triethoxysilylpropyl)amine), in turn, gave a perfluoropolyether adduct 12 having four decane branches, as shown in Figure 3.

In the second embodiment, step S1 further includes the following steps: S1A: preparing an intermediate product having two decane branches, wherein the perfluoropolyether precursor is mixed with the decane coupling agent to obtain an intermediate product, wherein the decane coupling agent is a functional group having a diamine series a decane such as N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, the intermediate product having one decane branch Perfluoropolyether decane, the dioxane branch is a diaminoalkoxydecane branch.

S1B: preparing a perfluoropolyether adduct 12 comprising two diaminodecanes having different alkoxyalkylene groups, mixing the intermediate product with a glycidoxy-type decane coupling agent at 35 ° C The reaction is carried out for 6-8 hours to add a propoxytrimethoxydecane functional group to each of the diaminoaloxane branches to obtain the perfluoropolyether adducts 12, wherein the perfluoropolyethers are obtained. Adduct 12 has four alkoxydecane branches. The perfluoropropoxy decane coupling agent is selected from γ-glycidoxypropyl trimethoxysilane, and the perfluoropolyether adduct 12 prepared by the method is as shown in Fig. 4. Show.

S2: the perfluoropolyether adduct 12 is placed in a solvent of hexafluorobutyl methyl ether, and the perfluoropolyether adduct 12 is first diluted with the nonafluorobutyl methyl ether solvent and purified, and then The excess decane is removed by a monoethanol detergent, and finally the perfluoropolyether adduct 12 is diluted to 0.5 wt.% to 1 wt.% with the nonafluorobutyl methyl ether solvent to form a perfluoropolyether adduct. Dilute the solution.

S3: The composite 20 is prepared by adding a zinc oxide nanoparticle 21 having a complex average particle diameter of less than 10 nm to an ethanol solution containing a plurality of γ-aminopropyltriethoxydecane at 40 to 60 ° C, and ultrasonic waves. The surface modification of the zinc oxide nanoparticles 21 was carried out by reacting for one hour in a turbulent environment. After the reaction was completed, the ethanol solution was removed, and washed three times with the ethanol detergent, and finally dried at 80 ° C for one hour to completely remove excess γ-aminopropyl three. Ethoxy decane and an ethanol solution give a complex complex 20.

S4: uniformly dispersing the composites 20, and placing the composites 20 into a solution of nonafluorobutyl methyl ether at room temperature, and uniformly dispersing the composites 20 in the nonafluorobutyl methyl ether by ultrasonic vibration. The solution forms a suspension solution.

S5: preparing the high-slip anti-fouling material, mixing the suspension solution with the perfluoropolyether adduct dilute solution to make the concentration of the composites 20 between 0.005 wt.% and 0.01 wt.%, completing the high-slip Preparation of anti-fouling materials.

In addition, in order to detect the high-slip anti-fouling material, the high-sliding anti-fouling material is first sprayed on a substrate to form a high-slip anti-fouling substrate; the experiments carried out by the present invention are as follows:

1. Water droplet contact angle test: Water droplets with a conductivity of 0.3 to 1 μS were placed on a substrate to be tested, and a contact angle of water droplets with the substrate within 10 seconds was measured under conditions of a relative humidity of 65% and a temperature of 23 ± 5 °C.

Results: The high-slip antifouling material made of the perfluoropolyether adduct 12 disclosed in the first embodiment has a contact angle of 102 degrees, and the perfluoropolyether addition disclosed in the second embodiment is utilized. The high-sliding antifouling material made of the material 12 has a contact angle of 104.86 degrees. Therefore, the representative water droplets are less likely to be adsorbed on the substrate produced by the present invention, and have better stain resistance.

2. Static friction coefficient test: The angle of inclination is measured by a friction ramp tester at a rate of 1.5±0.5° per second, and the static friction coefficient is obtained after conversion.

Results: The high-slip antifouling material made of the perfluoropolyether adduct 12 disclosed in the first embodiment has a static friction coefficient of 0.19; using the perfluoropolyether adduct 12 disclosed in the second embodiment. The high-slip anti-fouling material produced has a static friction coefficient of 0.25; and the conventional substrate made of perfluoropolyether decane as the anti-fouling coating material has a static friction coefficient of 0.27. From the above It is known that the substrate produced by the present invention is superior in performance to the conventional substrate made of the perfluoropolyether decane as the antifouling coating material.

In summary, the present invention has the following features:

1. The antifouling material of the perfluoropolyether adduct comprising at least four alkoxydecane branches can increase the slip of the antifouling material and improve the antifouling and self-cleaning ability.

Second, the combination of the perfluoropolyether adduct and the zinc oxide nanoparticle can improve the wear resistance of the antifouling material, and avoid the static electricity generated by the wiping type, thereby attenuating the stain resistance or wear resistance of the coating material.

3. The substrate prepared by using the high-slip anti-fouling material disclosed in the present invention has a large contact angle and is matched with the high-sliding property to make the substrate made of the high-slip anti-fouling material of the present invention. It has better stain resistance.

10‧‧‧Anti-fouling solution

11‧‧‧Diluted solvent

12‧‧‧Perfluoropolyether adduct

20‧‧‧Compound

Claims (9)

A high-slip anti-fouling material comprising: an anti-fouling solution comprising a diluent solvent and a plurality of perfluoropolyether adducts comprising a di-functional functional group, each of the characteristic functional groups comprising a plurality of decane branches And the perfluoropolyether adduct is uniformly dispersed in the diluting solvent; and a plurality of complexes dispersed in the diluting solvent, each of the composites comprising zinc oxide nanoparticles and a plurality of coatings on the zinc oxide naphthalene A surface modification of the rice particles, the surface modification comprising at least one amine group, the composites being coupled to each other with the at least one amine group and the perfluoropolyether adducts. The high-slip antifouling material according to claim 1, wherein the diluting solvent is nonafluorobutyl methyl ether having a purity of 99.5%, and the surface modifying substances are γ-aminopropyltriethoxydecane. The high-slip antifouling material according to claim 1, wherein each of the characteristic functional groups is as shown in formula (I): The high-slip antifouling material according to claim 1, wherein each of the characteristic functional groups is as shown in formula (II): The high-slip antifouling material according to claim 1, wherein the zinc oxide nanoparticles have an average particle diameter of less than 10 nm. A method for preparing a high-slip anti-fouling material comprises the steps of: S1: mixing a perfluoropolyether precursor comprising at least one ester functional group with a decane coupling agent to obtain a plurality of perfluoropolyether additions And the perfluoropolyether adduct comprises a plurality of decane branches; S2: the perfluoropolyether adduct is placed in a solvent of hexafluorobutyl methyl ether, and the perfluorocarbon is used in the solvent The polyether adduct is diluted to 0.5 wt.% to 1 wt.% to form a difluoropolyether adduct dilute solution; S3: the complex zinc oxide nanoparticle is added to a plurality of gamma-aminopropyl triethoxy groups In the ethanol solution of decane, after mixing, the ethanol solution is removed to form a complex complex; S4: the complexes are placed in a solution of hexafluorobutyl methyl ether to uniformly disperse the complexes in the nonafluorobutyl methyl ether. Solution, forming a suspension solution; S5: mixing the suspension solution with the perfluoropolyether adduct dilute solution to make the concentration of the composite between 0.005 wt.% and 0.01 wt.%, completing the high-slip anti-fouling material Preparation. The method for preparing a high-sliding antifouling material according to claim 6, wherein in the step S1, the decane coupling agent is an amino decane having two identical alkoxyalkyl groups to make the perfluoro The polyether adduct has four identical alkoxydecane branches. The method for preparing a high-slip anti-fouling material according to the sixth aspect of the invention, wherein the step S1 further comprises the following steps: S1A: mixing the perfluoropolyether precursor with the decane coupling agent, Obtaining an intermediate product, wherein the decane coupling agent is a decane having a diamine series functional group, the intermediate product being a perfluoropolyether decane having two diamine alkoxy decane branches; S1B: the middle The product is mixed with a monoglycidoxy decane coupling agent and reacted at 35 ° C for 6-8 hours to add a propoxytrimethoxydecane functional group to each of the diaminoaloxane branches. The perfluoropolyether adduct is obtained, wherein the perfluoropolyether adduct has four alkoxydecane branches. The method for preparing a high-sliding antifouling material according to claim 6, wherein in the step S3, the zinc oxide nanoparticles have an average particle diameter of less than 10 nm.