CN1986651B - Transparent coating structure with ultraviolet shielding function and hydrophobic/lipophobic function - Google Patents
Transparent coating structure with ultraviolet shielding function and hydrophobic/lipophobic function Download PDFInfo
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- CN1986651B CN1986651B CN 200510132398 CN200510132398A CN1986651B CN 1986651 B CN1986651 B CN 1986651B CN 200510132398 CN200510132398 CN 200510132398 CN 200510132398 A CN200510132398 A CN 200510132398A CN 1986651 B CN1986651 B CN 1986651B
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- oxide powder
- zinc oxide
- transparent coating
- ultraviolet shielding
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Abstract
The transparent coating structure with ultraviolet sheltering function and hydrophobic/lipophobic function includes zinc oxide powder, transparent insulating layer on the surface of zinc oxide powder, and polymer coating for the surface modification of the transparent insulating layer. The present invention includes amino group for the surface modification of the transparent insulating layer. The transparent insulating layer of SiO2 and the zinc oxide powder form one ZnO-SiO2 core-shell structure. The present invention adopts polymer with carbofluoro functional group in surface modification of nanometer zinc oxide powder to form fine hairy rough surface structure and the transparent coating structure with ultraviolet sheltering function and hydrophobic/lipophobic function.
Description
Technical field
The present invention relates to a kind of coating structure, particularly a kind of tool carbon fluorine (CF that utilizes
X), hydrocarbon (CH
X) or above two kinds of functional groups' polymer to the nanometer Zinc oxide powder surfaction, form the transparent coating structure of tool ultraviolet shielding and hydrophobic/functional oil.
Background technology
On the many plant leaf surfaces of nature because having unique microstructure and surperficial voltinism demonstrates its super-hydrophobicity, being characterized as water and can forming approximate spherical drop thereon of super hydrophobic surface, the lotus flower leaf of occurring in nature for example, when water droplet forms on the blade face and rolls, can simultaneously dust be taken away, the blade face can be kept clean beautiful, and have self-cleaning (self-cleaning) function.The self-cleaning phenomenon that causes lotus leaf surface is low surface tension and the surfaceness of lotus flower leaf.
When fluid drips was on solid surface, the angle of solid surface and tangent was namely so-called contact angle θ.When gas-solid interfacial tension (being also solid surface energy) is larger, contact angle will be less, and represent that solid surface is more easily by moistening this moment; When contact angle is 0 when spending, express liquid forms moisture film and moistening solid surface completely.On the contrary, when gas-solid interfacial tension is lower, contact angle will be larger, represents that solid surface is more difficult by moistening; When contact angle is 180 when spending, represent that liquid forms spherical drop and fully can not be moistening in solid surface.
In addition, when solid has uneven surface, also can make liquid contact angle from the teeth outwards become large.The surface that surfaceness is the size indentation to the effect of adhesional wetting property can make adsorbed gas atom stable existence, be equivalent to the gas membrane that has one deck stable on macro surface, liquid can't directly be contacted with the surface of solid, and namely the surface in contact of liquid and solid includes the mixed interface of solid and gas.
Existing many making now have hydrophobic coating or have the method on hydrophobic surface, for example United States Patent (USP) the 5th, 693, be to provide a kind of method that making has water repellent surface No. 236, its step includes: at first, but the mixture of preparation needle-like material and solid liquid is coated in body surface and type liquid admittedly with this mixture, then forms to contain needle-like material and with the coating of solid type liquid base.In the situation of the etched speed of base material greater than the etched speed of needle-like material, form recess and the ridge of needle-like material on the surface by etch layer, at last with hydrophobic substance on this layer plated surface.
Generally will have after hydrophobic coating coats solid surface, though can have the character of waterproof, after dust was stained with solid surface, liquid can not efficiently roll dusting out on solid surface, therefore can't effectively reach self-cleaning function.Moreover, after coating solid surface with hydrophobic coating, can't prevent effectively that also UV-light is to human body and organic infringement.
Therefore, a kind of low surface energy is provided, has rough surface structure, covers ultraviolet hydrophobic coating, it can overcome the shortcoming of prior art.
Summary of the invention
Technical problem to be solved by this invention is to provide the transparent coating of a kind of tool ultraviolet shielding and hydrophobic/functional oil, makes apparatus carbon fluorine functional group (CF
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymer upgrading is carried out on the nanometer Zinc oxide powder surface, form and have fine ciliate rough surface structure, and have the transparent coating of the function of ultraviolet shielding and hydrophobic/oil.
To achieve these goals, the invention provides the transparent coating structure of a kind of tool ultraviolet shielding and hydrophobic/functional oil, its characteristics are, include: a Zinc oxide powder; And a polymer coating, with a polymer, this Zinc oxide powder surfaction is formed.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this polymer is a carbon containing fluorine functional group polymkeric substance.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this polymer is one to contain hydrocarbon functional group's polymkeric substance.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder is a nanometer Zinc oxide powder.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder has Wurzite structure.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder is the powder of a four-footed taper.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, the diameter of each of the Zinc oxide powder of this four-footed taper rhabdolith is between 10nm to 100nm, between length 50nm to 1000nm.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder is a bar-shaped powder.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, the diameter of each of the Zinc oxide powder that this is bar-shaped rhabdolith is between 10nm to 100nm, between length 50nm to 1000nm.
The present invention also provides the transparent coating structure of a kind of tool ultraviolet shielding and hydrophobic/functional oil, and its characteristics are, include: a Zinc oxide powder; And a printing opacity barrier layer, block material by a printing opacity and be plated on this oxide powder and zinc surface and form; And a polymer coating, by a polymer, this printing opacity barrier layer is done surfaction and formed.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics are, also include an amino, and this printing opacity barrier layer is done surfaction.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, it is a silicon-dioxide that this printing opacity blocks material, and forms a ZnO-SiO
2The core-shell structure nanopowder body.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics are, this ZnO-SiO
2The thickness of the shell of core-shell structure nanopowder body is between 1nm to 20nm.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this polymer is a carbon containing fluorine functional group polymkeric substance.
Above-mentioned tool ultraviolet shielding and hydrophobic/by the transparent coating structure of function, its characteristics be, this polymer is one to contain hydrocarbon functional group's polymkeric substance.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder is a nanometer Zinc oxide powder.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder has Wurzite structure.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder is the powder of a four-footed taper.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, each of the Zinc oxide powder of this four-footed taper rhabdolith diameter is between 10nm to 100nm, between length 50nm to 1000nm.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, this Zinc oxide powder is a bar-shaped powder.
The transparent coating structure of above-mentioned tool ultraviolet shielding and hydrophobic/functional oil, its characteristics be, each of the Zinc oxide powder that this is bar-shaped rhabdolith diameter is between 10nm to 100nm, between length 50nm to 1000nm.
Effect of the present invention is to make apparatus carbon fluorine functional group (CF
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymer upgrading is carried out on the nanometer Zinc oxide powder surface, form and have fine ciliate rough surface structure, and have the transparent coating of the function of ultraviolet shielding and hydrophobic/oil.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Description of drawings
Figure 1A is the electron micrograph of the nanometer Zinc oxide powder of four-footed cone-shaped;
Figure 1B is the electron micrograph of bar-shaped nanometer Zinc oxide powder;
Fig. 2 is the first specific embodiment according to transparent coating structure of the present invention;
Fig. 3 is the second specific embodiment according to transparent coating structure of the present invention; And
Fig. 4 is according to nano-ZnO-SiO of the present invention
2The electron micrograph of nucleocapsid structure particle.
Wherein, Reference numeral:
10 meters Zinc oxide powder 15 printing opacity barrier layers
20 polymer coating
Embodiment
According to transparent coating structure provided by the invention, be to utilize the nanometer Zinc oxide powder 10 of four-footed taper (Tetrapod) or bar-shaped (rod) to reach absorption and ultraviolet shielding effect, then by containing carbon fluorine functional group (CF
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymer upgrading is carried out on nanometer Zinc oxide powder 10 surfaces, have fine ciliate rough surface structure with formation, and have the transparent coating structure of the function of ultraviolet shielding and hydrophobic/oil.
and, the manufacture of four-footed taper or bar-shaped nanometer Zinc oxide powder 10, adopt at normal pressure and contain under the atmosphere control of nitrogen, with non-consumable electrode formula direct current plasma, the solid zinc raw material is imported plasma zone (plasma zone) make it vaporization, make the metal particle of vaporization with the oxidation of homogeneous nucleation mode to contain in a large number oxygen and oxide gas again, and pass through the mode of the size of control plasma spray outlet, form plasma jet at a high speed, cooling with large quantity of air again, prevent particle coarsening and condense reunion, have the four-footed taper (Tetrapod) of wurtzite (HCP Wurztite) structure or the nanometer Zinc oxide powder 10 of bar-shaped (rod) and generate, as shown in Taiwan patent No. I233321 and 200528186.
In addition, the nanometer Zinc oxide powder 10 of four-footed cone (Tetrapod) shape in transparent coating structure provided by the invention is to be hexagonal bar-shaped nanometer Zinc oxide powder 10 by four cross sections to be consisted of, shown in Figure 1A, each bar-shaped (rod) nanometer Zinc oxide powder 10 diameter is between 10nm to 100nm, and length is between 50nm to 1000nm.Be in the nanometer Zinc oxide powder 10 of bar-shaped (Rod) with reference to Figure 1B, each bar-shaped (rod) nanometer Zinc oxide powder 10 diameter is between 10nm to 100nm, and length is between 50nm to 1000nm.
According to the transparent coating structure of tool ultraviolet shielding provided by the invention and hydrophobic/functional oil, will be appended graphic by following specific embodiment cooperation, be described in detail as follows.
Seeing also " the 2nd figure " is transparent coating structure according to the first specific embodiment that the invention provides.This transparent coating structure is to include: can absorb and ultraviolet shielding, and have the four-footed taper (Tetrapod) of wurtzite (HCPWurztite) structure or the nanometer Zinc oxide powder 10 of bar-shaped (rod), and with polymer (carbon fluorine functional group (CF for example
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymkeric substance) polymer coating 20 that nanometer Zinc oxide powder 10 surfactions are formed.This transparent coating structure is the rough surface structure of the function of ultraviolet shielding and hydrophobic/oil.
Fig. 3 is the transparent coating structure according to the second specific embodiment provided by the invention.This transparent coating structure includes nanometer Zinc oxide powder 10, printing opacity barrier layer 15 and polymer coating 20.Nanometer Zinc oxide powder 10 is take metallic zinc as raw material, and generates by direct current slurry technology and have the four-footed taper (Tetrapod) of wurtzite (HCP Wurztite) structure or the nanometer Zinc oxide powder 10 of bar-shaped (rod).
Then, for fear of the photocatalyst effect, plate printing opacity at nanometer Zinc oxide powder 10 and block material (silicon-dioxide (SiO for example
2)) forming printing opacity barrier layer 20, its thickness is about between 1nm to 20nm, and forms ZnO-SiO
2Nucleocapsid (core-shell) structure nano-powder.
Next, to printing opacity barrier layer 15 surfactions, be also to ZnO-SiO with amino
2Nucleocapsid (core-shell) structure powder surfaction changes ZnO-SiO
2The surface electrical behavior of nucleocapsid (core-shell) structured particles that is to say in order further to increase polymer to ZnO-SiO
2The compatibility of nucleocapsid (core-shell) structure powder.
But this amino surface upgrading is not certain needs, but determines whether needing to make surperficial upgrading with amino with follow-up macromolecular property.
At last, then with tool carbon fluorine functional group (CF
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymer the surface through the printing opacity barrier layer 15 of amino upgrading is carried out surfaction and is formed polymer coating 20.
Seeing also Fig. 4 is by the captured microcosmic photograph of field emission microscope, plates silicon-dioxide (SiO on nanometer Zinc oxide powder 10
2) and the ZnO-SiO of formation
2Nucleocapsid (core-shell) structure nano particle, the SiO of this structure
2Thickness of the shell is about 5nm.
Learn by aforementioned, transparent coating structure of the present invention utilizes tool carbon fluorine functional group (CF
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymer to nanometer Zinc oxide powder 10 surfactions; Or with tool carbon fluorine functional group (CF
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymer effects on surface be coated with nanometer Zinc oxide powder 10 surfactions of printing opacity barrier layer 15, form the transparent coating structure of tool ultraviolet shielding and hydrophobic/functional oil.
In addition, if coat respectively on the timber substrate with difform nanometer Zinc oxide powder, then with tool carbon fluorine functional group (CF
X), hydrocarbon functional group (CH
X) or above two kinds of functional groups' polymer coat powder surface, form transparent coating, then measure the static contact angle of this transparent coating.The nanometer Zinc oxide powder 10 that result shows the four-footed taper than bar-shaped and spherical nanometer Zinc oxide powder have better hydrophobic/functional oil.In addition, transparent coating structure provided by the invention can apply to glass, timber, ceramic tile and baking finish for car etc.
Certainly; the present invention also can have other various embodiments; in the situation that do not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art can make according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of claim of the present invention.
Claims (7)
1. the transparent coating structure of a tool ultraviolet shielding and hydrophobic/functional oil, is characterized in that, includes:
Zinc oxide powder, this Zinc oxide powder are the powder of four-footed taper;
One printing opacity barrier layer blocks material by a printing opacity and is plated on this oxide powder and zinc surface and forms; And
One polymer coating is done surfaction and forms this printing opacity barrier layer by a macromolecular material;
Wherein, it is silicon-dioxide that this printing opacity blocks material, and forms ZnO-SiO
2The core-shell structure nanopowder body, this ZnO-SiO
2The thickness of the shell of core-shell structure nanopowder body is 5nm.
2. the transparent coating structure of tool ultraviolet shielding according to claim 1 and hydrophobic/functional oil, is characterized in that, also includes an amino, and this printing opacity barrier layer is done surfaction.
3. the transparent coating structure of tool ultraviolet shielding according to claim 1 and hydrophobic/functional oil, is characterized in that, this macromolecular material is a carbon containing fluorine functional group polymkeric substance.
4. the transparent coating structure of tool ultraviolet shielding according to claim 1 and hydrophobic/functional oil, is characterized in that, this macromolecular material is one to contain hydrocarbon functional group's polymkeric substance.
5. the transparent coating structure of tool ultraviolet shielding according to claim 1 and hydrophobic/functional oil, is characterized in that, this Zinc oxide powder is nanometer Zinc oxide powder.
6. the transparent coating structure of tool ultraviolet shielding according to claim 5 and hydrophobic/functional oil, is characterized in that, this Zinc oxide powder has Wurzite structure.
7. the transparent coating structure of tool ultraviolet shielding according to claim 1 and hydrophobic/functional oil, is characterized in that, each of the Zinc oxide powder of this four-footed taper rhabdolith diameter is between 10nm to 100nm, between length 50nm to 1000nm.
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| CN 200510132398 CN1986651B (en) | 2005-12-23 | 2005-12-23 | Transparent coating structure with ultraviolet shielding function and hydrophobic/lipophobic function |
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| CN 200510132398 CN1986651B (en) | 2005-12-23 | 2005-12-23 | Transparent coating structure with ultraviolet shielding function and hydrophobic/lipophobic function |
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| CN201310140395.0A Division CN103360792B (en) | 2005-12-23 | 2005-12-23 | Transparent plated film structure with ultraviolet light shielding and water/oil draining functions |
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| CN1986651B true CN1986651B (en) | 2013-11-06 |
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| CN101381593B (en) * | 2007-09-03 | 2012-05-30 | 财团法人工业技术研究院 | Super-hydrophobic self-cleaning powder and manufacturing method thereof |
| WO2012064745A2 (en) | 2010-11-08 | 2012-05-18 | University Of Florida Research Foundation, Inc. | Articles having superhydrophobic and oleophobic surfaces |
| CN103060773B (en) * | 2011-10-19 | 2016-08-10 | 合肥杰事杰新材料股份有限公司 | A kind of preparation method of superhydrophobic surface material |
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