CN104119720A - Red pigment capable of reflecting near infrared radiation - Google Patents

Abstract

The invention discloses a red pigment capable of reflecting near infrared radiation. A preparation method of the red pigment comprises the steps of dissolving soluble slats of Y, La, Ce and Pr into a certain quantity of water according to a certain molar ratio, and adding an excessive precipitant to react for a period of time; after sufficiently reacting, cleaning the product, and drying; mixing a certain quantity of tetrabutyl titanate and the dried product, grinding the mixture, calcining at a high temperature for a period of time, then, grinding and loading a sample. Equipment for producing the pigment capable of reflecting near infrared radiation, provided by the invention, is simple, easy to operate and suitable for large-scale industrial production. In addition, the prepared pigment has the color within the range from light red to brown red and can be used as a functional color master batch to be added into a coating to form a favorable heat insulation coating product.

Description

A kind of red pigment that can reflect near-infrared radiation

Technical field

The present invention relates to a kind of preparation method who reflects near-infrared radiation pigment, the pigment making has pale red to brown red color, for having covering property of the heat coating of reflection near-infrared radiation performance.

Background technology

Buildings or outdoor article, due to for a long time under sun exposure, energy constantly accumulates in by the object coating of radiation, makes its internal temperature have the tendency of rising.Especially in summer, too high indoor and ambient temperature will make people not feel well, and increase cooling electric weight.This just require we have a kind of can reflected solar radiation, reduce the coating that is exposed to the body surface temperature under solar radiation.

Yet initial near-infrared radiation reflective coating, is generally with rutile TiO ₂the vanish system of preparing for the light series pigments of color stuffing.But in fact,, to buildings and outdoor article, we prefer the topcoating of dark or various collocation of colour.For meeting the demand for coloured pigment, such as chromic oxide green (PG-17), chromium iron black or brown (PG-17), chemical constitution is Cu2MgO ₃the dark pigment with reflected infra-red radiation function such as chocolate pigment (JP 2007-204296) be tentatively produced out, and as color stuffing add with coating in, prepare the product with reflective insulation function.Wherein, part is by adding TiO ₂increase the method for preparing pigment of properties of infrared reflection mainly, under more than 1200 ℃ high temperature, calcination oxide raw material is realized.Therefore, this type of infrared reflecting paint, or there is toxicity, or preparation method's more complicated, consume energy more, and the wherein less research of reflected infra-red radiation pigment of red colour system.

Summary of the invention

For above-mentioned deficiency of the prior art, the object of this invention is to provide a kind of can reflected infra-red radiation there is the pale red preparation method to brown red color rare-earth pigment, utilize the red pigment that the method is prepared to there is good infrared radiation reflection, can add to it as color stuffing and in coating, make thermal insulating coating product.

For reaching above object, the present invention takes following technical scheme to be achieved:

A kind of method of preparing red pigment that can reflected infra-red radiation, it is characterized in that, comprise the following steps: the rare earths salt of at room temperature being prepared by certain proportion and precipitant mix, control pH of mixed value in certain limit, precipitin reaction for some time, the precipitation obtaining is cleaned, is dried; The agent of a certain amount of ir radiation reflection enhancement is mixed, ground with desciccate, at high temperature after lower calcining for some time, grind the pigment that can obtain reflected infra-red radiation.Wherein, described raw material is as follows:

Described rare earths salt can be two kinds of mixtures to four kinds of compositions in the soluble salt of Y, La, Ce, Pr; Described precipitation agent is the single or mixture that contains soluble salt hydroxy, preferred ammoniacal liquor in the present invention, and purity is more than technical pure; The agent of described ir radiation reflection enhancement is tetrabutyl titanate.

Described experiment condition is as follows:

Described rare earths salt and precipitant mix method can be that precipitant solution splashes in rare earths salt, described pH value is >=9.0, the described precipitin reaction time is 2～12 hours, and described precipitin reaction is carried out under high-speed stirring, and temperature of reaction keeps 60～100 ℃; Described precipitation is cleaned method therefor for washing or ethanol cleaning; Described precipitation time of drying is 2～12 hours, and reacting drying temperature keeps 60～280 ℃; The agent of described ir radiation reflection enhancement mixes with desciccate, milling time is 2～5 hours, and described process of lapping carries out under wetness conditions; Described high-temperature calcination temperature can be 600～1200 ℃, and calcination time is 2～12 hours.

Product of the present invention adopts Shimadzu UV-3600 type UV, visible light near infrared spectrometer test solid diffuse reflectance spectra; As Fig. 1. as shown in.Adopt the solar spectrum irradiancy normal data of GB/T17683.1-1999 sun power under the different receiving conditions in ground to calculate pigment at 800-2500nm infrared region reflectivity at sunshine.Described calculation formula is

$\mathrm{SR}=\frac{{\∫}_{800}^{2500}R\left(\mathrm{\λ}\right)i\left(\mathrm{\λ}\right)d\left(\mathrm{\λ}\right)}{{\∫}_{800}^{2500}i\left(\mathrm{\λ}\right)d\left(\mathrm{\λ}\right)}$

In formula, the solar radiation reflectivity that SR is sample; Spectral reflectivity (the Wm of sample when R (λ) is wavelength X ^-2); Solar irradiance (the Wm that i (λ) is af at wavelength lambda ^-2nm ^-1).CIE system xy coordinate and L* for product chromaticity coordinates of the present invention, a* and b*, defined by International Commission on Illumination.Concrete grammar is to test solid diffuse reflectance spectra by the desk-top spectrophotometer of X-Rite Color i5, then utilizes software to calculate the chromaticity coordinates value of corresponding product.

Test result and outward appearance show, have the following advantages: employing of the present invention itself has the red lanthanide oxide pigment of certain properties of infrared reflection, and using tetrabutyl titanate as the agent of ir radiation reflection enhancement, thereby avoided the impact of other colored pigment on properties of infrared reflection, resulting heat reflection pigment has good properties of infrared reflection, have pale red to brown red color, can be used for being added in coating, make thermal insulating coating product; Take full advantage of the more rare earth resources of China's content, in product, do not contain high carcinogenic substance, asepsis environment-protecting, the scope of meeting the tendency is wide; In addition, prepared by the present invention can reflected infra-red radiation pigment production device be mainly ball mill and firing electric furnace, equipment investment is few, preparation technology is simple and easy handling, so be applicable to suitability for industrialized production.

Accompanying drawing explanation

Fig. 1 is the spectral reflectivity figure of embodiment 1 gained near-infrared radiation reflection Red pigment.

Fig. 2 is the spectral reflectivity figure of comparative example gained red pigment.

Embodiment

Below in conjunction with specific embodiment, the invention will be further described.Following examples, only for the present invention is described, are not used in and limit the scope of the invention.

The preparation of embodiment 1 near-infrared radiation reflective paint [preparation of infrared reflecting paint 1]

By cerous nitrate, praseodymium nitrate respectively according to mol ratio Ce: Pr=9: 1 ratio weigh to be mixed, and then the powder mixing is progressively added to the water, and stirs, and forms solution.In solution, add ammoniacal liquor, form brown or yellowish brown dirty solution, ammoniacal liquor add-on be take and is more than or equal to 9 as good with PH test paper calibration value; Turbid solution high-speed stirring 2 hours at 80 ℃, at 30 ℃ standing 10 hours.Product is centrifugal, use ethanol or washing repeatedly; Product is dry at 220 ℃.Dried mixture, is ground into powder; Add in molar ratio tetrabutyl titanate 7.5M, under wetness conditions, grind, this time milling time is more than 2 hours, and product be take gel as best.By the calcination 2 hours at 800 ℃ of the mixture gel after mixed grinding, continue to heat up and at 1000 ℃, calcine 4 hours, calcinate grinds and is evenly obtaining near-infrared radiation reflective paint powder.

Adopt Shimadzu UV-3600 type UV, visible light near infrared spectrometer test solid diffuse reflectance spectra, adopt the solar spectrum irradiancy normal data of GB/T17683.1-1999 sun power under the different receiving conditions in ground to calculate pigment at 800-2500nm infrared region reflectivity at sunshine.Wherein, the near infrared spectrum reflectivity mean value that records embodiment 1 pigment sample is 68.6%, and infrared region reflectivity at sunshine is 58.2%.CIE chromaticity coordinates is: x-0.3978, y=0.3504, L*=45.99, a*=16.53, b*=13.38.

The preparation of embodiment 2 near-infrared radiation reflective paint [preparation of infrared reflecting paint 2]

By cerous nitrate, praseodymium nitrate, Yttrium trinitrate respectively according to mol ratio Ce: Pr: Y=8.5: 1: 0.5 ratio weighs mixes, and then the powder mixing is progressively added to the water, and stirs, and forms solution.In solution, add ammoniacal liquor, form brown or yellowish brown dirty solution, ammoniacal liquor add-on be take and is more than or equal to 9 as good with PH test paper calibration value; Turbid solution high-speed stirring 2 hours at 80 ℃, at 30 ℃ standing 10 hours.Product is centrifugal, use ethanol or washing repeatedly; Product is dry at 220 ℃.Dried mixture, is ground into powder; Add in molar ratio tetrabutyl titanate 7.5M, under wetness conditions, grind, this time milling time is more than 2 hours, and product be take gel as best.By the calcination 6 hours at 800 ℃ of the mixture gel after mixed grinding, continue to heat up and at 900 ℃, calcine 1 hour, calcinate grinds and is evenly obtaining near-infrared radiation reflective paint powder.The near infrared spectrum reflectivity mean value that records embodiment 2 pigment sample is 64.9%, and infrared region reflectivity at sunshine is 54.8%.CIE chromaticity coordinates is: x=0.3783, y=0,3496, L*=54.93, a*=13.78, b*=12.41.

The preparation of embodiment 3 near-infrared radiation reflective paint [preparation of infrared reflecting paint 3]

By cerous nitrate, praseodymium nitrate, Yttrium trinitrate, lanthanum nitrate respectively according to mol ratio Ce: Pr: Y: La=8: 1: 0.5: 0.5 ratio weighs mixes, and then the powder mixing is progressively added to the water, and stirs, and forms solution.In solution, add ammoniacal liquor, form brown or yellowish brown dirty solution, ammoniacal liquor add-on be take and is more than or equal to 9 as good with PH test paper calibration value; Turbid solution high-speed stirring 2 hours at 80 ℃, at 30 ℃ standing 10 hours.Product is centrifugal, use ethanol or washing repeatedly; Product is dry at 220 ℃.Dried mixture, is ground into powder; Add in molar ratio tetrabutyl titanate 7.5M, under wetness conditions, grind, this time milling time is more than 2 hours, and product be take gel as best.By the calcination 6 hours at 800 ℃ of the mixture gel after mixed grinding, continue to heat up and at 950 ℃, calcine 5 hours; After it is cooling, be ground into powder, the powder after grinding is arranged to lower secondary clacining 2-6 hour identical, obtain near-infrared radiation reflective paint powder.The near infrared spectrum reflectivity mean value that records embodiment 3 pigment sample is 78.0%, and infrared region reflectivity at sunshine is 71.5%.CIE chromaticity coordinates is: x=0.3894, y=0.3475, L*=47.05, a*=15.59, b*=11.92.

Comparative example

By cerous nitrate, praseodymium nitrate respectively according to mol ratio Ce: Pr=9: 1 ratio weigh to be mixed, and then the powder mixing is progressively added to the water, and stirs, and forms solution.In solution, add ammoniacal liquor, form brown or yellowish brown dirty solution, ammoniacal liquor add-on be take and is more than or equal to 9 as good with PH test paper calibration value; Turbid solution high-speed stirring 2 hours at 80 ℃, at 30 ℃ standing 10 hours.Product is centrifugal, use ethanol or washing repeatedly; Product is dry at 120 ℃.Dried mixture, is ground into powder; By the calcination 1 hour at 800 ℃ of the mixture gel after mixed grinding, continue to heat up and at 1000 ℃, calcine 2 hours, calcinate grinds and is evenly obtaining powder pigment.The near infrared spectrum reflectivity mean value that records embodiment 3 pigment sample is 57.5%, and infrared region reflectivity at sunshine is 36.7%.

At Shimadzu UV-3600 type UV, visible light near infrared spectrometer test solid diffuse reflectance spectra.Embodiment 1 infrared reflecting paint spectral reflectance performance is as Fig. 1. as shown in.And the spectral reflectance performance of employing comparative example as shown in Figure 2.

Contrast two figure, can find out: the red lanthanide pigment that adopts existing technique to prepare, its heat reflectivity major part in near-infrared wavelength section is lower than below 85%, the near-infrared radiation reflective paint (embodiment 1) that adopts the present invention to prepare, owing to only having used, have the infrared reflectance that improves red lanthanide pigment compared with the titanium dioxide of high infrared reflection rate, resulting near-infrared radiation reflective paint has high near-infrared radiation reflecting properties.

Claims (8)

1. can reflect a red pigment for near-infrared radiation, it is characterized in that, the chemical formula of described product can be expressed as (Ce _1-(x+y+z)pr _xla _yy _z) _ati _bo _n, 0.4≤a≤0.7 in wherein said product chemical formula, 0.3≤b≤0.6,0.01≤x≤0.4,0≤y≤0.2,0≤z≤0.2.

2. the red pigment that can reflect near-infrared radiation, it is characterized in that, the preparation method of described product is as follows: according to mole metering ratio of the chemical formula of described pigment, material dissolution, in a certain amount of water, is reacted for some time after adding excessive precipitation agent at a certain temperature; After question response thing precipitation is complete, will precipitate collection, washing and dry; A certain amount of tetrabutyl titanate is mixed, ground with desciccate, after at high temperature lower calcining for some time, grind and obtain powder pigment.

3. can reflect a red pigment for near-infrared radiation, it is characterized in that, described soluble salt is muriate, nitrate and other soluble rare-earth salt.

4. can reflect a red pigment for near-infrared radiation, it is characterized in that, described precipitation agent can be water-soluble alkaline matter that sodium hydroxide, potassium hydroxide, ammoniacal liquor etc. can make rare earth ion be precipitated out.

5. can reflect a red pigment for near-infrared radiation, it is characterized in that, the described precipitin reaction time is 2～12 hours, and temperature of reaction keeps 60～100 ℃.

6. can reflect a red pigment for near-infrared radiation, it is characterized in that, described tetrabutyl titanate mixes with desciccate, grinding product is that gel is yellow to safran material.

7. can reflect a red pigment for near-infrared radiation, it is characterized in that, described high-temperature calcination temperature can be 600～1200 ℃, and calcination time is 2～12 hours.

8. can reflect a red pigment for near-infrared radiation, it is characterized in that, the described powder pigment obtaining has pale red to brown red color.