CN110527325B - Visible light photocatalytic functional surface coating for wood surface and preparation method thereof - Google Patents
Visible light photocatalytic functional surface coating for wood surface and preparation method thereof Download PDFInfo
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- CN110527325B CN110527325B CN201910772323.5A CN201910772323A CN110527325B CN 110527325 B CN110527325 B CN 110527325B CN 201910772323 A CN201910772323 A CN 201910772323A CN 110527325 B CN110527325 B CN 110527325B
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a visible light photocatalytic functional surface coating for a wood surface and a preparation method thereof, wherein the visible light photocatalytic functional surface coating comprises the following components in percentage by weight: 1-10% of silica sol, 1-10% of titanium dioxide quantum dots doped with noble metal ions, 0.02-2% of silicon nanoparticles, 0-2% of FeOOH nanoparticles, 0.1-1% of dispersing agent, 0.1-1% of thickening agent, 0.1-1% of defoaming agent, 0.1-1% of flatting agent, 0.1-1% of anti-settling agent and the balance of water. Compared with the traditional photocatalytic coating, the visible light photocatalytic functional surface coating for the surface of the woodware can obviously improve the photocatalytic effect of the coating, can continuously and efficiently remove harmful substances such as formaldehyde, benzene, ammonia, TVOC (total volatile organic compound), PM (particulate matter) 2.5 and the like, purify the indoor air environment, remove haze outdoors, kill bacteria, viruses, fungi, microorganisms and the like in a broad spectrum manner, is safe to use, is coated once and is used for the whole life.
Description
Technical Field
The invention relates to the field of coatings, in particular to a visible light photocatalytic functional surface coating for a woodware surface and a preparation method thereof.
Background
Since the discovery of the photodecomposition phenomenon of titanium dioxide single crystal under ultraviolet irradiation in 1972 by Taeniculia of photochemistry, photocatalysis has gradually become a novel environment-friendly environmental pollution cleaning technology. The photocatalyst absorbs light, electrons on the surface of the photocatalyst absorb enough energy to be separated, positive holes are formed at the positions where the electrons are separated, the electrons and the holes react with oxygen, water and hydroxyl groups to generate superoxide ions with strong oxidizing property and hydroxyl radicals with strong reducing property, and the superoxide ions and the hydroxyl radicals oxidize and decompose organic pollutants and bacteria into harmless water and carbon dioxide, so that the aims of removing pollutants and reducing bacteria are fulfilled.
There are many photocatalyst materials, and titanium dioxide is currently the most important photocatalyst material because of its strong oxidizing ability, chemical stability and non-toxicity. The photocatalyst adopted by the anti-formaldehyde odor-removing full-effect environment-friendly water-based woodenware white paint disclosed in CN102146257B is nano titanium dioxide. However, the forbidden band width of the titanium dioxide is large, and the photocatalyst has higher catalytic activity only under the irradiation of ultraviolet light; for visible light with the most significant solar energy of 400-700nm, the titanium dioxide has weak responsiveness, does not have catalytic activity basically in the visible light range, and has low utilization rate for the visible light.
In order to improve the responsiveness of titanium dioxide to visible light, patent publication No. CN102277051B proposes a method of doping titanium dioxide with a nonmetal such as carbon in a coating, but the visible light-responsive photocatalyst obtained in this way has weak light absorption capability, low catalytic activity, easy loss of doping elements, and easy loss of catalytic activity. However, the photosensitive dye is an organic substance, and its chemical bond is broken and separated by photocatalysis, so that the response to visible light is not durable, and the life of the photosensitive dye gradually decreases with time. Patent publication No. CN1013756376B proposes adding semiconductors with narrow energy gap such as modified iron oxide to absorb visible light, the refractive index of the iron oxide material is high, generally 2.8-2.9, and compared with a coating substrate with a refractive index of generally only about 1.4-1.6, iron oxide particles have strong scattering on visible light, so that there is a defect that the photocatalytic activity is not high when visible light is irradiated, although visible light is absorbed. In addition, the document also proposes to add semiconductors with narrow energy gap such as cadmium sulfide, tin dioxide and the like, but the semiconductors have certain toxicity and cannot meet the requirement of environmental protection.
Furthermore, with existing photocatalytic coatings, the effect of photocatalytic degradation is limited because light absorption is substantially concentrated at the surface of the coating. How to improve the photocatalytic effect of the coating is a problem to be solved urgently. In addition, organic components in the coating, including organic additives, organic base materials of the coating main body and the like, are difficult to avoid bond breaking under the photocatalysis, and how to avoid the deterioration of the coating after film formation is also very important.
Disclosure of Invention
The invention aims to overcome the defects and provide the visible light photocatalytic functional surface coating for the wood surface, which has high photocatalytic efficiency, good visible light responsiveness and long service life.
The invention also aims to provide a preparation method of the visible light photocatalytic functional surface coating for the wood surface, which has high photocatalytic efficiency, good visible light responsiveness and long service life.
One of the objects of the invention is achieved by: a visible light photocatalytic functional topcoat for the surface of a woodware comprises the following components in percentage by weight:
the balance being water.
The titanium dioxide is doped with the noble metal ions, and the titanium dioxide particles are subjected to quantum dot formation, so that the titanium dioxide has responsiveness to visible light; the added silicon nanoparticles are used for converting ultraviolet light and low-wavelength visible light into high-wavelength visible light, so that titanium dioxide in a system can absorb natural light from the environment and can also receive self-generated visible light from the visible light photocatalytic function treatment liquid after the treatment liquid is cured into a film, the photocatalytic effect of the coating is limited to a light source absorbed by the surface of the coating, the light absorption efficiency is greatly improved, and the catalytic efficiency is greatly improved. In addition, the silica sol used herein is a film-forming material which is self-dried at room temperature, has a large bond energy, is not easily photolyzed, has good weather resistance and high temperature resistance, and does not deteriorate, age or deteriorate. The coating forms a rigid microporous framework structure after film forming, forms a microenvironment for adsorbing external toxic organic matters, and is also beneficial to improving the photocatalytic efficiency.
The visible light photocatalytic function surface coating is matched with the visible light photocatalytic function treatment liquid for use, the visible light photocatalytic function treatment liquid for the surface of the wood lacquer coating and the visible light photocatalytic function surface coating for the surface of the wood lacquer coating are sequentially coated on the surface of the wood lacquer coating, and indoor and outdoor air can be efficiently purified for a long time.
The further preferable technical scheme is that the particle size of the titanium dioxide quantum dots is 2-10 nm. The noble metal is preferably one of Pt, Au and Pd.
The silicon nano-particles have rich resources, low price and no toxicity to human bodies, and the surface of the silicon nano-particles is provided with Si-H bonds, can generate Si-OH and Si-O-Si bonds which are well compatible with silicate coating resin when meeting water, and has good compatibility with base materials. Bulk silicon can only fluoresce weakly. The preferable technical scheme is that the particle size of the silicon nano-particles is less than 8 nm. When the particle size of the silicon nano-particles is less than 8nm, the fluorescence effect is enhanced, and the visible light photocatalytic functional surface coating shows higher photocatalytic performance.
In order to improve the photocatalytic effect, the preferable technical scheme is that the weight percentage of the FeOOH nano particles is 0.02-2%. The FeOOH nano particles can absorb visible light to generate photoproduction electrons and photoproduction holes, and can endow the photoproduction electrons with higher reduction capability by matching with the noble metal ions doped with the titanium dioxide quantum dots, widen the absorption wavelength range of the visible light and improve the photocatalytic activity. It is preferred here that the FeOOH nanoparticles have a particle size of less than 20 nm.
The preferable technical scheme is that the silica sol is alkaline silica sol, and the particle size is 5-100 nm. The alkaline silica sol is more suitable for being used as a coating and has the advantages of good caking property, low shrinkage and the like.
In order to facilitate construction and improve film-forming performance, the preferable technical scheme is that the thickening agent is a modified polyurethane thickening agent, the dispersing agent is a polyethylene glycol octyl phenyl ether dispersing agent, the defoaming agent is a polyether modified polysiloxane defoaming agent, the leveling agent is carboxymethyl cellulose, and the anti-settling agent is fumed silica.
The second purpose of the invention is realized by the following steps: a preparation method of visible light photocatalytic functional surface coating for the surface of woodware comprises the following steps:
a) adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions and FeOOH nano particles according to the proportion, and ball-milling uniformly by using a ball mill to form a suspension;
b) adding silica sol into the suspension obtained in the step a), and ball-milling uniformly by using a ball mill; and adding a dispersing agent, a thickening agent, a defoaming agent, a flatting agent and an anti-settling agent, ball-milling uniformly by using a ball mill to obtain a visible light photocatalytic functional surface coating for the surface of the woodware, and packaging.
The process disperses silicon nano particles in water to form Si-OH and Si-O-Si bonds compatible with silica sol, then mixes the silicon nano particles with titanium dioxide quantum dots doped with noble metal ions and FeOOH nano particles, and then mixes the silicon nano particles with organic components; based on similar compatibility, the periphery of the photocatalytic active component is surrounded by silica sol, so that the organic components in the coating are isolated and protected, and the performance of the coating is more stable.
Compared with the traditional photocatalytic coating, the visible light photocatalytic functional surface coating for the surface of the woodware has the following advantages.
(1) The photocatalysis effect can be obviously improved. Because the noble metal ions are doped with titanium dioxide quantum dots, silicon nanoparticles and the like, the photocatalytic reaction activity is improved, the photodecomposition capability is greatly enhanced, the photocatalytic efficiency is improved, the coating is decomposed when light is emitted, and the coating has multispectral responsiveness, so that harmful substances such as formaldehyde, benzene, ammonia, TVOC (total volatile organic compound), PM (particulate matter) 2.5 and the like can be continuously and efficiently removed, the indoor air environment is purified, the haze is removed outdoors, the removal rate of volatile organic compounds can reach more than 90%, bacteria, viruses, fungi, microorganisms and the like can be killed in a broad spectrum, and the killing rate of virus protobacteria such as cold viruses and the like can reach more than 90%.
(2) And (3) food-grade safety: the coating can decompose harmful substances to clean air purely by means of sunlight or illumination, can realize active air purification without any energy consumption, has no secondary pollution, is nontoxic and tasteless, and does not contain substances harmful to the environment.
(3) The photocatalyst has long service life, the coating has uniform and stable performance, and the photocatalyst is coated once and is used for the whole life.
(4) The coating also has a self-cleaning effect. The coating has small contact angle, good self-cleaning effect and long-term self-cleaning effect.
Detailed Description
The following further describes the embodiments of the present invention with reference to the accompanying examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A visible light photocatalytic functional surface coating for the surface of a woodware comprises the following components in percentage by weight:
the balance being water.
The preparation method comprises the following steps:
a) adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions, and ball-milling for 0.25-1 hour by using a ball mill at the speed of 70-1500 rpm until the mixture is uniform to form a suspension;
b) adding silica sol into the suspension obtained in the step a), and ball-milling for 0.25-1 hour by using a ball mill at the speed of 70-1500 rpm until the mixture is uniform; and adding a dispersing agent, a thickening agent, a defoaming agent, a leveling agent and an anti-settling agent, ball-milling for 0.5-6 hours at the speed of 70-1500 revolutions per minute by using a ball mill until the mixture is uniform to obtain a visible light photocatalytic functional surface coating for the surface of the woodware, packaging the visible light photocatalytic functional surface coating, and filling nitrogen with the pressure of 0.10-0.13MPa for packaging.
Example 2
The formulation and preparation method in this example are similar to those in the first example, except that silicon nanoparticles having a particle size of less than 8nm are not used in this example, but silicon nanoparticles having a particle size of 20-200nm are used. The rest is the same as in example 1.
Example 3
A visible light photocatalytic functional surface coating for the surface of a woodware comprises the following components in percentage by weight:
the balance being water.
The preparation method comprises the following steps:
a) adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions and FeOOH nano particles, and ball-milling for 0.25-1 hour by using a ball mill at the speed of 70-1500 rpm until the mixture is uniform to form a suspension;
b) adding silica sol into the suspension obtained in the step a), and ball-milling for 0.25-1 hour by using a ball mill at the speed of 70-1500 rpm until the mixture is uniform; and adding a dispersing agent, a thickening agent, a defoaming agent, a leveling agent and an anti-settling agent, ball-milling for 0.5-6 hours at the speed of 70-1500 revolutions per minute by using a ball mill until the mixture is uniform to obtain a visible light catalytic functional surface coating for the surface of the woodware, packaging the visible light catalytic functional surface coating, and filling nitrogen with the pressure of 0.10-0.13MPa for packaging.
Example 4
A visible light photocatalytic functional surface coating for the surface of a woodware comprises the following components in percentage by weight:
the balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Example 5
A visible light photocatalytic functional surface coating for the surface of a woodware comprises the following components in percentage by weight:
the balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Example 6
A visible light photocatalytic functional surface coating for the surface of a woodware comprises the following components in percentage by weight:
the balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Example 7
A visible light photocatalytic functional surface coating for the surface of a woodware comprises the following components in percentage by weight:
the balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Comparative example 1
The formula and the preparation method of the comparative example 1 are similar to those of the example 1, and the only difference is that: the formulation of comparative example 1 contained no silicon nanoparticles. During preparation, the titanium dioxide quantum dots doped with noble metal ions and water are ball-milled for 0.25 to 1 hour by a ball mill at the speed of 70 to 1500 revolutions per minute until the mixture is uniform, after a suspension is formed, silica sol is added, and the mixture is ball-milled for 0.25 to 1 hour by the ball mill at the speed of 70 to 1500 revolutions per minute until the mixture is uniform; then adding a dispersing agent, a thickening agent, a defoaming agent, a leveling agent and an anti-settling agent, ball-milling for 0.5-6 hours at the speed of 70-1500 revolutions per minute by using a ball mill until the mixture is uniform to obtain a photocatalytic functional surface coating, and finally packaging.
Comparative example 2
The formula and the preparation method of the comparative example 2 are similar to those of the example 1, and the only difference is that: the formulation in comparative example 2 did not contain Au ion doped titanium dioxide quantum dots. During preparation, after the silicon nano particles are added into water for activation, ball milling is carried out for 0.25-1 hour by a ball mill at the speed of 70-1500 r/min until the silicon nano particles are uniform to form a suspension, then silica sol is added into the suspension, and ball milling is carried out for 0.25-1 hour by the ball mill at the speed of 70-1500 r/min until the silicon nano particles are uniform; then adding a dispersing agent, a thickening agent, a defoaming agent, a leveling agent and an anti-settling agent, ball-milling for 0.5-6 hours at the speed of 70-1500 revolutions per minute by using a ball mill until the mixture is uniform to obtain a photocatalytic functional surface coating, and finally packaging.
The paint is used as the surface coating of woodware, has even fineness, does not deteriorate at low temperature, and has no obstacle in coating construction.
The preparation of the paint film sample plate is carried out according to the GB1727 specification, the material is selected from base paper (inert material is required), and the weight is 80g/m2The preparation method generally adopts a spraying method. And (3) measuring the photolysis index, wherein a light source is LED visible light, the illumination intensity is 145 multiplied by 100LUX, and the methyl blue removal rate is performed according to the GB/T30452-2013. The results are shown in Table 1.
TABLE 1 methyl blue removal rate of coatings obtained in examples 1-7 and comparative examples 1-2
| Group of | Methyl blue removal rate (%) |
| Example 1 | 90.9 |
| Example 2 | 89.6 |
| Example 3 | 94.2 |
| Example 4 | 96.3 |
| Example 5 | 90.1 |
| Example 6 | 95.8 |
| Example 7 | 95.1 |
| Comparative example 1 | 66.2 |
| Comparative example 2 | 8.8 |
As can be seen from table 1, the photocatalytic effect of the coatings of examples 1 to 7 of the present invention is significantly improved compared to the photocatalytic functional surface coatings of comparative examples 1 and 2, in which only silicon nanoparticles are added, or only titanium dioxide quantum dots doped with noble metal ions are added. Comparing examples 1-3, it can be seen that adding FeOOH nanoparticles, reducing the particle size of the silicon nanoparticles can further improve the photocatalytic degradation efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The visible light photocatalytic functional top coat for the surface of the woodware is characterized by comprising the following components in percentage by weight:
2. the visible light photocatalytic functional topcoat for woodware surfaces of claim 1, wherein the particle size of the titanium dioxide quantum dots is 2-10 nm.
3. The visible light photocatalytic functional topcoat for woodware surface according to claim 1, characterized in that the noble metal is one of Pt, Au, Pd.
4. The visible light photocatalytic functional topcoat for woodware surface according to claim 1, characterized in that the particle size of the silicon nanoparticles is less than 8 nm.
5. The visible light photocatalytic functional topcoat for woodware surfaces of claim 1, wherein the weight percentage of the FeOOH nanoparticles is 0.02-2%.
6. The visible light photocatalytic functional topcoat for woodware surfaces of claim 1, wherein the particle size of the FeOOH nanoparticles is less than 20 nm.
7. The visible light photocatalytic functional topcoat for woodware surfaces according to claim 1 or 6, wherein the silica sol is an alkaline silica sol, and the particle size is 5 to 100 nm.
8. The visible light photocatalytic functional topcoat for the wood ware surface according to claim 1, wherein the dispersant is a polyethylene glycol octyl phenyl ether dispersant, the thickener is a modified polyurethane thickener, the defoamer is a polyether modified polysiloxane defoamer, and the leveling agent is carboxymethyl cellulose.
9. The visible light photocatalytic functional topcoat for woodware surfaces of claim 1, characterized in that the anti-settling agent is fumed silica.
10. The preparation method of the visible light photocatalytic functional topcoat for the wooden ware surface according to any one of claims 1 to 9, characterized by comprising the following steps:
a) adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions and FeOOH nano particles according to the proportion, and ball-milling uniformly by using a ball mill to form a suspension;
b) adding silica sol into the suspension obtained in the step a), and ball-milling uniformly by using a ball mill; and adding a dispersing agent, a thickening agent, a defoaming agent, a flatting agent and an anti-settling agent, ball-milling uniformly by using a ball mill to obtain a visible light photocatalytic functional surface coating for the surface of the woodware, and packaging.
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