CN105153845B - Coating product and preparation method thereof - Google Patents
Coating product and preparation method thereof Download PDFInfo
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- CN105153845B CN105153845B CN201510657243.7A CN201510657243A CN105153845B CN 105153845 B CN105153845 B CN 105153845B CN 201510657243 A CN201510657243 A CN 201510657243A CN 105153845 B CN105153845 B CN 105153845B
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Abstract
The invention discloses a coating product which comprises a base material and a plurality of layers of coatings, wherein the plurality of layers of coatings cover all or part surface of the base material, and comprises the materials of acrylic resin and metallic oxide spherical particles; the metallic oxide spherical particles are made of copper oxide, zinc oxide, titanium dioxide, aluminum oxide, ferric oxide or zirconium oxide with the particle diameter of 0.2-5.0 [mu]m and the thickness of 10-100 [mu]m; the plurality of layers of coatings consist of the first coating, the second coating, ... and the Nth coating from the bottom surface to the top surface. The invention further discloses a preparation method for the coating product. The uniform coating in the prior art is replaced by the plurality of layers of coatings, so that under the condition of not adding material consumption, the spectral reflectivity of the near-infrared light area is improved, the heating effect of the coating product is reduced, and the performance of the coating product is improved.
Description
Technical field
The invention belongs to coating material field, more particularly, to a kind of coating product and preparation method thereof.
Background technology
Coating material is widely used in building, automobile and other cultures, and tellurian object will be received daily
To substantial amounts of solar radiation.The solar radiation wavelength for reaching earth surface concentrates on 0.3 μm to 2.5 μm in the range of this, specifically
It is divided into ultraviolet range (0.3 μm～0.38 μm), it is seen that light area (0.38 μm～0.78 μm) and near-infrared region (0.78 μm～
2.5μm).Due to a large amount of absorptions to emittance of a large amount of reductions and building, road of city's green areas, so as to generate
Tropical island effect so that intown mean temperature is higher than the temperature of surrounding three to five degrees Celsius.Such radiation absorption increases
The temperature of interior of building is added so as to increased the energy consumption of room air regulation.
In order to improve this situation, some measures for being effectively reduced radiation absorption are proposed out, and comparison is significant
The metal oxide particle (such as titanium dioxide, aluminium oxide, Zinc Oxide etc.) of powder is permeated into into some parents such as resin exactly
In, such coating material can increase the reflectance of near-infrared region as much as possible so as to the heat effect for reducing radiating, while
The reflectance of visible region is reduced so as to the outward appearance softer to human eye is presented.
Research of the Japanese scholars in terms of theoretical and experiment two to copper oxide coating, copper oxide particle are uniform that disperse is being set
In fat parent, the coating for so obtaining not only has good aesthetic compared with conventional material, and heat effect also compares
It is more satisfactory, parameters optimization R of the coating for obtainingoptMaximum be 15.56.(H.Gonome,M.Baneshi,J.Okajima,
A.Komiya,S.Maruyama,Controlling the radiative properties of cool black-color
coatings pigmented with CuO submicron particles,
132 (2014) 90-98. of J.Quant.Spectrosc.Radiant.Transfer), but the coating performance still has into one
Walk improved space.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of coating product and its preparation side
Method, its object is to be increased the reflectance of near-infrared region by the laminated coating on its surface, thus reduces the heat of coating product
Effect.
For achieving the above object, according to one aspect of the present invention, there is provided a kind of coating product, including base material and painting
Layer, the coating are covered in all or part of surface of the base material, and the material of the coating includes acrylic resin and gold
Category oxide particle, the coating is laminated coating, is constituted from bottom to top layer by first coating, second coating to N coatings,
And the volume fraction of wherein metal oxide particle is respectively a1、a2To aN, and 5% >=ai>=0.5%, N are more than or equal to 2
Arbitrary integer, i are 2 to N arbitrary integer；The metal oxide particle be copper oxide, Zinc Oxide, titanium dioxide, aluminium oxide,
Ferrum oxide or zirconium oxide, the metal oxide particle are shaped as spherical or elliposoidal, and particle diameter is 0.2 μm～5.0 μm；It is described
In coating, the volume fraction of metal oxide particle is incremented by successively to top layer from bottom, improves coating product near infrared light
The spectral reflectivity in area, reduces the heat effect of coating product, improves the parameters optimization of coating.
Preferably, the reflectance of the substrate surface is 0～1.0.
Preferably, the gross thickness of the laminated coating is 10 μm～100 μm.
Preferably, first coating, second coating are identical to the thickness of N coatings.
Preferably, the spherical granule of the metal-oxide is copper oxide.
Preferably, 5% >=ai＞ ai-1>=1%.
Preferably, N=2, a2:a1For 4:1～9:1.
It is another aspect of this invention to provide that there is provided a kind of coating for above-mentioned coating product, the material of the coating
Including acrylic resin and metal oxide particle, the metal oxide particle is copper oxide, Zinc Oxide, titanium dioxide, oxygen
Change aluminum, ferrum oxide or zirconium oxide, the metal oxide particle is shaped as spherical or elliposoidal, and particle diameter is 0.2 μm～5.0 μ
M, the coating are made up of to N coating the first coating, the second coating, and the volume fraction of wherein metal oxide particle is respectively
a1、a2To aN, and 5% >=ai＞ ai-1>=0.5%, N are the arbitrary integer more than or equal to 2, and i is 2 to N arbitrary integer.
It is another aspect of this invention to provide that additionally providing a kind of preparation method of above-mentioned coating product, laminated coating is covered
The all or part of surface of base material is placed on, the material of the laminated coating includes acrylic resin and metal oxide particle,
The metal oxide particle is copper oxide, Zinc Oxide, titanium dioxide, aluminium oxide, ferrum oxide or zirconium oxide, metal oxidation
Composition granule is shaped as spherical or elliposoidal, and particle diameter is 0.2 μm～5.0 μm, the laminated coating is applied from bottom to top layer by one
Layer, second coating are constituted to N coatings, and the volume fraction of wherein metal oxide particle is respectively a1、a2To aN, and 5% >=ai
＞ ai-1>=0.5%, N are the arbitrary integer more than or equal to 2, and i is 2 to N arbitrary integer.
By the contemplated above technical scheme of the present invention compared with prior art, have the advantages that：
1st, by the laminated coating that metal oxide particle volume fraction is different, replace uniform coating of the prior art,
Spectral reflectivity of the coating product in near-infrared region is improve, the heat effect of coating product is reduced；
2nd, the coating product is changing in the coating product of the spectral reflectivity and uniform coating of visible region without significant difference
The stimulation to human eye will not be increased while kind heat effect；
3rd, in the case where the mean volume fraction of metal oxide particle is equal, by parameters optimization R of coatingoptImprove
Nearly 30%, so as in the case where material consumption is not increased, improving the performance of coating product, reducing production cost.
Description of the drawings
Fig. 1 is the curve chart of the complex refractivity index with wavelength change of copper oxide particle；
Fig. 2 is present invention coating product schematic diagram；
Fig. 3 is the comparison diagram of the spectral reflectivity of embodiment of the present invention 2-3 and comparative example 1-3；
Fig. 4 is the comparison diagram of the spectral reflectivity of embodiment of the present invention 5-6, comparative example 3 and comparative example 6；
The comparison diagram of the spectral reflectivity of Fig. 5 embodiment of the present invention 4 and comparative example 3-5.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each embodiment
Do not constitute conflict each other can just be mutually combined.
When solar irradiation is mapped in the coating for be covered in substrate surface, it may occur that the physical process such as reflection and scattering.
The performance difference of coating can make above-mentioned physical process produce different results, and the performance of the coating passes through parameters optimization RoptTo comment
Valency：
Wherein I (λ) is the incident radiant intensity of the sun, and ρ (λ) is the spectral reflectivity of coating, and h (λ) is standard luminescent effect
Rate, parameters optimization RoptIt is bigger, then prove that coating performance is better.
When single spherical or ellipsoidal particle even dispersion are in the parent (such as acrylic resin) of nonabsorbable, its scattering
Can be obtained by solving Maxwell equation equation with absorption characteristic, this is based primarily upon incident wavelength λ, metal oxide particle
The complex refractivity index m=n-i κ of diameter d and metal oxide particle.Curve of the complex refractivity index of copper oxide particle with wavelength change
Figure is as shown in Figure 1.
Complex refractivity index change of the copper oxide particle in 0.3 μm～2.5 μ m of wavelength is as shown in Fig. 2 wherein refractive index
And attenuation quotient all shows certain regularity.It is theoretical by Mie, it is possible to use the complex refractivity index of copper oxide particle, meter
Calculation draws the radiation characteristic of copper oxide particle, such as scattering efficiency and absorption efficiency.In the case where the refractive index of base material determines,
Anisotropic scattering phase function can be obtained can also to obtain by Mie theories.
Wherein, scattering efficiency and absorption efficiency can be obtained by below equation：
Here Qsca,λAnd Qabs,λIt is scattering and absorptance respectively, d is particle diameter, fv,calIt is grain volume fraction, NT
It is granule density.
Solar radiation incides the schematic diagram of N shell coating as shown in Fig. 2 wherein, and metal oxide particle is monodispersed.
Sunlight incide the parallel of coating surface and diffusing in penetrate the enough Bird models descriptions of radiation energy (R.E.Bird, C.Riordan,
Simple solar spectral model for direct and diffuse irradiance on horizontal
and tilted planes at the earth's surface for cloudless atmospheres,J Appl
25 (1986) 87-97. of Meteorol Clim), in incident ray and coating N, between substrate and coating 1 due to refractive index not
With direct reflection can occur, reflectance is solved by Fresnel theorem, the scattering efficiency of metal oxide particle between its floating coat
The theoretical solutions of Mie can be led to absorption efficiency.
In order to analyze the radiation transmittance process in coating, by coating as the one-dimensional parallel flat system containing participating medium
System process.Equation of radiative transfer is described in position z, directionAnd the radiant intensity of af at wavelength lambda：
Here I is radiant intensity, and n is the refractive index of parent, c0It is beam spread speed in a vacuum, βλ=κλ+σλIt is
Attenuation quotient, ΦλIt is Scattering Phase Function.Equation (5) integration is obtained：
What the Section 1 on the right side of the equation showed is contribution of the base material to radiant intensity, and what Section 2 was represented is scattering medium
Contribution of scatters, and S is source item.Above-mentioned parameter is substituted into into formula (6), is obtained at an arbitrary position, the radiation under any wavelength
Intensity：
HereWhat is represented is base materialThe energy of transmitting is by base material zwIt is reflected under wavelength XOn direction
Energy fraction,Represent similar implication.
Figure it is seen that solar radiation is incided in coating from top, coating is divided into N deciles, i.e. N in the z-direction
At individual unit, wherein each unit, radiant intensity is divided into 180 deciles again, it is discrete after metal oxide particle at an arbitrary position
Volume fraction be a (z) (for example, a2(0≤the z of (z)=3%<0.5L), a1(z)=1% (0.5L≤z≤L)).
By discrete equation (7), can obtain in unit i1, directionAnd the radiant intensity of af at wavelength lambda
Particle diameter is identical and during identical overall particle fraction, metal oxide particle can have various distribution modes, bag
Include and be uniformly distributed, Gradient distribution and Multi-layers distributing etc., and pass through formula (8) and Gradient distribution, and multilamellar point can be calculated
In the coating of cloth, radiant intensity when wavelength is λ, so as to further calculate its parameters optimization Ropt。
Theoretical basiss according to more than, the invention provides a kind of coating product, including base material and coating, the coating
The all or part of surface of the base material is covered in, the material of the coating includes acrylic resin and metal-oxide
Grain, the coating are laminated coating, are constituted from bottom to top layer by first coating, second coating to N coatings, and wherein metal
The volume fraction of oxide particle is respectively a1、a2To aN, N is the arbitrary integer more than or equal to 2, and i is 2 to N arbitrary integer；
The metal oxide particle is copper oxide, Zinc Oxide, titanium dioxide, aluminium oxide, ferrum oxide or zirconium oxide, metal oxidation
Composition granule is shaped as spherical or elliposoidal, and particle diameter is 0.2 μm～5.0 μm；In the coating, the volume of metal oxide particle
Fraction is incremented by successively to top layer from bottom, so as to improve the parameters optimization of coating, improves coating product in near-infrared region
Spectral reflectivity, reduce coating product heat effect.Here select volume fraction a of metal oxide particlei0.5%～
Between 5%, when grain volume fraction is too small, the effect of coating material is very little, is in close proximity to the spy of pure acrylic resin
Property, the reflectance of its visible region is excessive, affects experience；And when grain volume fraction is excessive, particle occurs bonding
Phenomenon, affects the overall performance of coating.
Coating layer thickness should be controlled within 100 μm, and this is in addition to considering reality processing cost, it is also contemplated that practicality and U.S.
The property seen.When metal oxide particle is with diameter greater than 5 μm, need theory of geometric optics is introduced the meter of the coating parameters optimization
Calculate, be not suitable for the present invention.
The metal oxide particle is preferably copper oxide.The first coating, second coating are preferably phase to N coatings
The coating of stack pile.
As N=2, a2:a1Preferably 4:1～9:1.
Present invention also offers a kind of coating for above-mentioned coating product, it is characterised in that the material bag of the coating
Acrylic resin and the spherical granule of metal-oxide are included, the coating is made up of to N coating the first coating, the second coating, its
The volume fraction of middle metal oxide particle is respectively a1、a2To aN, and 5% >=ai＞ ai-1>=0.5%, N are more than or equal to 2
Arbitrary integer, i are 2 to N arbitrary integer.
The preparation method of the coating is：The quality of the copper oxide particle and acrylic resin needed for coating is calculated,
Then will be dispersion phase copper oxide particle and mixed with resin uniform, homogeneous transparent is thermally formed under 70 DEG C～90 DEG C of temperature conditionss
Colloidal sol.
The coating is sprayed on base material thickness successively that form setting, coating system of the present invention after being dried, is obtained
Product.
Embodiment 1
Base material selects a diameter of 0.57 μm of copper oxide particle from the wall that reflectance is 1.0, metal oxide particle,
Scattering medium selects acrylic resin, and the coating is first coating and second coating, and first coating and second coating are all by oxygen
Change copper granule to constitute with acrylic resin, wherein the volume fraction of copper oxide is respectively 0.5% and 4.5%, and thickness is all 20 μm.
First coating is covered in substrate surface, and second coating is covered in first coating surface.
Using I (λ) and h (λ) parameter in document, and spectral reflectivity ρ (λ), substitution side are obtained by Mie Theoretical Calculation
Journey (1) is obtained parameters optimization Ropt.The R of the coating material for obtainingoptMaximum be 19.80, it is under equal conditions, and existing
In having technology, the uniform coating of copper oxide body fraction is compared, and improves nearly 30%.
Embodiment 2
Repeat embodiment 1, it is 0 that difference is the reflectance of the substrate surface, and metal oxide particle is from a diameter of
0.50 μm of copper oxide particle, the coating are the coating uniformly increased from the volume fraction of bottom to top copper oxide particle,
The volume fraction of the copper oxide particle of coating bottommost is 1%, and the volume fraction of the copper oxide particle of coating top is 4%,
The gross thickness of coating is 50 μm.
Embodiment 3
Repeat embodiment 2, difference is that the coating is made up of first coating and second coating from bottom to top layer, first
In coating, the volume fraction of copper oxide particle is 1%, and in second coating, the volume fraction of copper oxide particle is 4%, described first
The thickness of coating and second coating is all 25 μm.
Embodiment 4
Repeat embodiment 3, it is 2.5% that difference is the volume fraction of copper oxide particle in first coating, in second coating
The volume fraction of copper oxide particle is 5%.
Embodiment 5
Repeat embodiment 3, it is 0.5% that difference is the volume fraction of copper oxide particle in first coating, in second coating
The volume fraction of copper oxide particle is 2.5%.
Embodiment 6
Repeat embodiment 3, it is first coating to the 3rd coating, the wherein volume of copper oxide particle that difference is the coating
Fraction is respectively 0.5%, 2.5% and 5%, and first coating is all 17 μm to the thickness of the 3rd coating.
Comparative example 1
Repeat embodiment 2, it is uniformly to subtract from the volume fraction of bottom to top copper oxide particle that difference is the coating
Few coating, the volume fraction of the copper oxide particle of coating bottommost is 4%, the volume integral of the copper oxide particle of coating top
Number is 1%.
Comparative example 2
Repeat embodiment 3, it is 4% that difference is the volume fraction of copper oxide particle in first coating, oxygen in second coating
The volume fraction for changing copper granule is 1%.
Comparative example 3
Repeat embodiment 3, difference is that the coating is to be from bottom to the volume fraction of top layer copper oxide particle
2.5% uniform coating.
Comparative example 4
Repeat embodiment 3, it is 5% that difference is the volume fraction of copper oxide particle in first coating, oxygen in second coating
The volume fraction for changing copper granule is 2.5%.
Comparative example 5
Repeat embodiment 3 with described same steps, difference is that the volume fraction of copper oxide particle in first coating is
2.5%, in second coating, the volume fraction of copper oxide particle is 0.5%.
Comparative example 6
Repeat embodiment 6 with described same steps, difference be the first coating into the 3rd coating, copper oxide
The volume fraction of grain is respectively 5%, 2.5% and 0.5%.
Interpretation
Fig. 2 is the Spectroscopic analysis results of embodiment 2-3 and comparative example 1-3 under 0.3 μm～2.5 μm of wavelength.Can see
Go out, 0.38 μm～0.78 μm of visible region, compared with comparative example 1-3, its spectral reflectivity does not almost change embodiment 2-3
Become, and 0.78 μm～2.5 μm of near-infrared region, the reflectance of embodiment 2-3 is significantly raised, it was demonstrated that when the cumulative volume of coating
One timing of fraction, metal-oxide upper strata volumetric concentration are larger, have preferable performance, more effectively can reflect when lower floor is less
While the solar radiation of near-infrared region, it is not reduction visible ray and human eye is impacted.
Under the operating mode, coating has more preferably effect, not only reduces stimulation of the light reflection to human eye to a greater degree,
Also reduce building energy consumption simultaneously.
Fig. 3 is the spectrum of embodiment 5, embodiment 6, comparative example 3 and comparative example 6 under 0.3 μm～2.5 μm of wavelength point
Analysis result.As can be seen that 0.38 μm～0.78 μm of visible region, compared with comparative example 3-6, its spectrum is anti-for embodiment 5-6
Penetrate that rate is almost unchanged, and in 0.78 μm～2.5 μm of near-infrared region, embodiment 5 and 3 spectral reflectivity phase of comparative example
Seemingly, embodiment 6 is better than comparative example 3, and comparative example 6 is inferior to comparative example 3.As comparative example 3 can be regarded as first coating and
In two coatings, the volume fraction of copper oxide particle is all 2.5% uniform coating, from embodiment 5 compared with comparative example 3, it was demonstrated that when
When upper strata coating is higher than the volume fraction of copper oxide particle in lower floor coating, even if reducing the volume fraction of lower floor's copper oxide particle
The property of coating is not interfered with, and can now reduces the usage amount of metal oxide particle, reduce production cost yet.And will implement
Example 6, comparative example 6 are compared with comparative example 3, it was demonstrated that when one timing of total volume fraction of copper oxide particle in coating, upper strata coating ratio
When in lower floor's coating, the volume fraction of copper oxide particle is high, the spectral reflectivity of coating is more preferably.
Fig. 4 is the Spectroscopic analysis results of embodiment 4 and comparative example 3-5 under 0.3 μm～2.5 μm of wavelength.Can see
Go out, 0.38 μm～0.78 μm of visible region, embodiment 4 is similar with the spectral reflectivity of comparative example 3-5, and 0.78 μm～
2.5 μm of near-infrared region, comparative example 4 are similar to 3 spectral reflectivity of comparative example, and embodiment 4 is better than comparative example 3, and comparative example 5
It is inferior to comparative example 3.From comparative example 4 compared with comparative example 3, it was demonstrated that the volume of copper oxide particle in upper strata coating is than lower floor coating
When fraction is low, even if the volume fraction for raising lower floor's copper oxide particle does not interfere with the performance of coating yet, and can now increase gold
The usage amount of category oxide particle.From comparative example 5 compared with comparative example 3, it was demonstrated that when the volume of copper oxide particle in lower floor's coating
One timing of fraction, the volume fraction for reducing copper oxide particle in the coating of upper strata can affect the spectral reflectivity of coating.From embodiment 4
Compared with comparative example 3, it was demonstrated that when one timing of volume fraction of copper oxide particle in lower floor's coating, improve copper oxide in the coating of upper strata
The volume fraction of granule can lift the spectral reflectivity of coating.
In sum, double-deck and laminated coating, compared with signal layer coating, can obtain on the premise of production cost is constant
The parameters optimization of get Geng Gao, can not only effectively weaken thorn of the glass curtain wall sunlight reflection of buildings in general to human eye
Swash, and can farthest reflect the solar radiation of near-infrared region, so as to reduce the cooling load of building.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not to
The present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc. are limited, all should be included
Within protection scope of the present invention.
Claims (8)
1. a kind of to coat product, including base material and coating, the coating is covered in all or part of surface of the base material,
The material of the coating includes acrylic resin and metal oxide particle, it is characterised in that the coating is laminated coating, from
Bottom is made up of to N coatings to top layer first coating, second coating, and the wherein volume fraction difference of metal oxide particle
For a1、a2To aN, and 5% >=ai＞ ai-1>=0.5%, i are 2 to N arbitrary integer；The metal oxide particle is oxidation
Copper, Zinc Oxide, titanium dioxide, aluminium oxide, ferrum oxide or zirconium oxide, the metal oxide particle are shaped as spherical or ellipsoid
Shape, particle diameter are 0.2 μm～5.0 μm；In the coating, the volume fraction of metal oxide particle is passed from bottom successively to top layer
Increase, so as to improve spectral reflectivity of the coating in near-infrared region.
2. it is as claimed in claim 1 to coat product, it is characterised in that the reflectance of the substrate surface is 0～1.0.
3. it is as claimed in claim 1 to coat product, it is characterised in that the gross thickness of the laminated coating is 10 μm～100 μm.
4. it is as claimed in claim 1 to coat product, it is characterised in that the thickness of the first coating, second coating to N coatings
Degree is identical.
5. it is as claimed in claim 1 to coat product, it is characterised in that the metal oxide particle is copper oxide.
6. it is as claimed in claim 1 to coat product, it is characterised in that 5% >=ai>=1%.
7. it is as claimed in claim 1 to coat product, it is characterised in that N=2, a2:a1For 4:1～9:1.
8. it is a kind of as described in any one in claim 1-7 coat product preparation method, it is characterised in that by laminated coating
The all or part of surface of base material is covered in, the material of the laminated coating includes acrylic resin and metal-oxide
Grain, the metal oxide particle are copper oxide, Zinc Oxide, titanium dioxide, aluminium oxide, ferrum oxide or zirconium oxide, and its particle diameter is
0.2 μm～5.0 μm, the laminated coating is constituted from bottom to top layer by first coating, second coating to N coatings, wherein gold
The volume fraction of category oxide particle is respectively a1、a2To aN, and 5% >=ai＞ ai-1>=0.5%, N are any more than or equal to 2
Integer, i are 2 to N arbitrary integer.
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