CN112143491A - Long-afterglow light conversion agent and application thereof - Google Patents

Long-afterglow light conversion agent and application thereof Download PDF

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CN112143491A
CN112143491A CN202011134456.9A CN202011134456A CN112143491A CN 112143491 A CN112143491 A CN 112143491A CN 202011134456 A CN202011134456 A CN 202011134456A CN 112143491 A CN112143491 A CN 112143491A
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long
light conversion
long afterglow
light
film
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谢伟
高玲英
陈航
严惠儒
林水源
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Lingnan Normal University
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Lingnan Normal University
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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7792—Aluminates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
    • A01G13/0268—Mats or sheets, e.g. nets or fabrics
    • A01G13/0275—Films
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Abstract

The invention discloses a long afterglow light conversion agent and application thereof, wherein the chemical composition of the long afterglow light conversion agent is CaxSr3‑ xAl2O5Cl2:Eu2+ y,M3+ zWherein x is more than or equal to 0 and less than or equal to 3 and 0<y≤0.2，0<z is less than or equal to 0.2, and M is one or more of Dy, Nd, Ho and Sm. The long afterglow light conversion film is further prepared by using polyvinyl fluoride as a base resin and a long afterglow light conversion agent together, and the obtained long afterglow light conversion film has good weather resistance and mechanical property and high light transmittance; the film can convert ultraviolet light in sunlight into red orange light, can improve the light energy utilization rate after being introduced into an agricultural film, is beneficial to plant growth, can emit light outwards at night, promotes the plant growth at night, and can be widely applied to agricultural production.

Description

Long-afterglow light conversion agent and application thereof
Technical Field
The invention relates to the technical field of long afterglow materials, in particular to a long afterglow light conversion agent and application thereof.
Background
Illumination is a necessary condition for plant growth and development, the length of illumination time affects the healthy growth of plants, and the too short illumination time can cause the growth speed of plants to be reduced and even stopped. The earth has the conditions of adverse plant growth such as alternate day and night, rainy weather and overhigh latitude, and the like, so that the illumination time of plants is reduced. In order to improve the conditions which are not beneficial to the growth of the plants, the illumination time of the plants can be artificially increased. The long afterglow material is a luminescent material with excellent performance, can absorb energy with a certain range of wavelengths in sunlight in the daytime, can continuously emit light after night, is prepared into a long afterglow light conversion film, is added into a greenhouse film, illuminates plants at night, and is used as an illumination light source in the greenhouse. In addition, when plants are subjected to photosynthesis, ultraviolet light in sunlight can inhibit the growth of the plants, the ultraviolet light part in the sunlight is reduced, the growth of the plants can be promoted, the photosynthesis of red orange light with chlorophyll absorption wavelength of 600-680 nm is strongest, the fruit growth of the plants can be promoted, the light conversion film can convert the ultraviolet light into the red orange light, the light quality in a greenhouse is improved, the light energy utilization rate is improved, the growth of the plants is facilitated, and the production and income increase are promoted, so that the long-afterglow light conversion film can illuminate the plants at night and can convert light.
Chinese patent CN107418565A (published Japanese 2017.12.01) discloses a long afterglow light conversion agent and a preparation method thereof, and a long afterglow light conversion film and a preparation method thereof, wherein SrAl is utilized2O4-3x/2Nx:Eu2+，Re3+(wherein Re3+Is Dy3+、Nd3+、La3 +、Ho3+、Pr3+、Er3+One or a combination of more of rare earth elements) as a long-afterglow light conversion agent and polyethylene as film resin, but the long-afterglow light conversion film still has the problems of poor weather resistance and mechanical property and low light transmittance.
Disclosure of Invention
The invention aims to solve the technical problems of poor chemical stability, poor low-temperature resistance and low light transmittance of the conventional long-afterglow light conversion film, and provides a long-afterglow light conversion agent for further preparing the long-afterglow light conversion film with good weather resistance and mechanical properties and high light transmittance.
It is another object of the present invention to provide a long persistence light converting film.
The invention also provides a preparation method of the long afterglow light conversion film.
The invention also aims to provide application of the long afterglow light conversion film.
The above purpose of the invention is realized by the following technical scheme:
a long-afterglow light-converting agent contains Ca as chemical componentxSr3-xAl2O5Cl2:Eu2+ y,M3+ zWherein x is more than or equal to 0 and less than or equal to 3 and 0<y≤0.2，0<z is less than or equal to 0.2, and M is one or more of Dy, Nd, Ho and Sm.
The long-afterglow light conversion agent selected by the invention is an inorganic material, can convert ultraviolet light in sunlight into red orange light, and has the characteristics of sunlight resistance and high temperature resistance, namely good weather resistance.
The invention protects a long afterglow light conversion film, which is prepared from the long afterglow light conversion agent and polyvinyl fluoride, wherein the mass ratio of the polyvinyl fluoride to the long afterglow light conversion agent is 100: 0.5 to 9.
The polyvinyl fluoride selected by the invention has good mechanical property, contains C-F bonds, has higher bond energy relative to C-H bonds and C-C bonds, is difficult to damage by high temperature, illumination and chemical factors, can be steamed and boiled in strong acid and strong alkali without losing strength, and has very low water vapor, air and organic matter (removing ester and ketone compounds) permeability, so the polyvinyl fluoride has excellent weather resistance. The invention takes polyvinyl fluoride as base resin, which is matched with the long afterglow light conversion agent according to a specific proportion, the long afterglow light conversion agent is coated by the base resin to play a role in water resistance, which is beneficial to prolonging the afterglow time, in addition, the addition amount of the long afterglow light conversion agent is small, the influence on the transmittance is little, the long afterglow light conversion film with high light transmittance and good weather resistance can be obtained, and the invention has better mechanical properties.
Preferably, the mass ratio of the polyvinyl fluoride to the long-afterglow light conversion agent is 100: 2 to 6.
Preferably, the thickness of the long afterglow light conversion film is 20-1000 μm.
More preferably, the thickness of the long afterglow light conversion film is 20-45 μm.
The invention protects the preparation method of the long afterglow light conversion film, which comprises the following steps:
s1, dissolving polyvinyl fluoride in an organic solvent, adding a plasticizer, and dissolving at 80-100 ℃ for 2-5 hours to obtain a polyvinyl fluoride solution;
s2, dissolving the long afterglow light conversion agent in a solvent, and then adding the solution into the polyvinyl fluoride solution obtained in the step S1 to obtain a mixed solution;
and S3, casting the mixed solution obtained in the step S2 into a film, and drying to obtain the long afterglow light conversion film.
Preferably, the plasticizer in step S1 is one or more selected from dioctyl phthalate (DOP), tributyl phosphate, and γ -butyrolactone.
Preferably, the dissolving step S1 further comprises adding an antifoaming agent for 2-5 h.
Preferably, the defoaming agent is one or more of defoaming agent FT-30, defoaming agent XPZ-120 and defoaming agent XPZC-120.
Preferably, the organic solvent in step S1 is one or more of dimethylformamide, dimethylacetamide and hexamethylphosphoramide.
Preferably, the solvent in step S2 is one or more of absolute ethyl alcohol, toluene, and acetone.
Preferably, the drying temperature in the step S3 is 30-70 ℃, and the time is 8-12 h.
The invention also protects the application of the long afterglow light conversion film in agricultural production.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a long afterglow light conversion agent, the chemical composition of which is CaxSr3-xAl2O5Cl2:Eu2+ y,M3+ zWherein x is more than or equal to 0 and less than or equal to 3 and 0<y≤0.2，0<z is less than or equal to 0.2, and M is one or more of Dy, Nd, Ho and Sm. The long afterglow light conversion film is further prepared by using polyvinyl fluoride as a base resin and a long afterglow light conversion agent together, and the obtained long afterglow light conversion film has good weather resistance and mechanical property and high light transmittance; the film can convert ultraviolet light in sunlight into red orange light, can improve the light energy utilization rate after being introduced into an agricultural film, is beneficial to plant growth, can emit light outwards at night, promotes the plant growth at night, and can be widely applied to agricultural production.
Drawings
FIG. 1 shows a long-afterglow light-converting agent Ca of the present invention0.4Sr2.6Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.02FIG. 1(a) is an XRD pattern of the long-afterglow light-converting agent of example 1, FIG. 1(b) is an XRD pattern of the long-afterglow light-converting agent of example 17, and FIG. 1(c) is an XRD pattern of the long-afterglow light-converting agent of example 18.
FIG. 2 is the long-lasting phosphor light-converting agent Ca of example 10.4Sr2.6Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.02A microscopic morphology photograph of (a).
FIG. 3 is a transmission spectrum in the visible light region of the long persistence light-converting film obtained in example 1.
FIG. 4 is an afterglow emission spectrum of the long afterglow converted film obtained in example 1, wherein FIG. 4(a) is the afterglow emission spectrum of the long afterglow converted film of example 1, FIG. 4(b) is the afterglow emission spectrum of the long afterglow converted film of example 17, and FIG. 4(c) is the afterglow emission spectrum of the long afterglow converted film of example 18.
FIG. 5 is a graph showing the elongation at break of the long persistence light-converting films obtained in examples 1 to 2 and 14 to 16.
FIG. 6 is an afterglow luminance decay curve graph of the long afterglow light-converting film obtained in example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The main raw materials used in the examples and comparative examples were:
polyvinyl fluoride (PVF): industrial grade, purchased from shanghai nfurt new materials gmbh;
dimethylformamide (DMF), dimethylacetamide, tributylphosphate: analytically pure, purchased from Beijing chemical plant;
dioctyl phthalate (DOP), hexamethylphosphoramide, γ -butyrolactone: analytically pure, purchased from chemical preparations of national drug group;
defoaming agent: the brands are FT-30, XPZ-120 and XPZC-120 respectively, and are purchased from Nanjing Huaxing defoamer Co.
Example 1
A long-afterglow light-converting agent contains Ca as chemical component0.4Sr2.6Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.02。
A preparation method of a long afterglow light conversion film comprises the following steps:
s1, dissolving: weighing 3g of polyvinyl fluoride powder, placing the polyvinyl fluoride powder in a beaker, adding 80mL of Dimethylformamide (DMF) solvent at 25 ℃, ultrasonically oscillating for 30 minutes, transferring the obtained suspension into a three-neck flask, adding 20mL of dioctyl phthalate (DOP), adding 3mL of defoamer XPZC-120 at the later reaction stage at the temperature of 85 ℃ and at the stirring speed of 100r/min, and stirring for 3 hours to completely dissolve polyvinyl fluoride to obtain a polyvinyl fluoride solution;
s2, mixing: putting 0.09g of long afterglow light conversion agent into absolute ethyl alcohol for ultrasonic dispersion for 30 minutes, slowly dripping the dispersion liquid into polyvinyl fluoride solution, and continuously stirring until the solution is completely and uniformly mixed to obtain mixed solution;
s3, film forming: and pouring the mixed solution into a forming mold for casting to form a film immediately after stirring is stopped, putting the mold into an oven for drying for 10 hours at the temperature of 60 ℃, and removing the film to obtain the transparent long-afterglow light conversion film.
Example 2
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that 1g of polyvinyl fluoride was replaced.
Example 3
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that 2g of polyvinyl fluoride was replaced.
Example 4
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that 4g of polyvinyl fluoride was replaced.
Example 5
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared as in example 1 except that 90mL of Dimethylformamide (DMF) solvent was replaced and 10mL of dioctyl phthalate was replaced.
Example 6
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared as in example 1 except that 70mL of Dimethylformamide (DMF) solvent was replaced and 30mL of dioctyl phthalate was replaced.
Example 7
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared as in example 1 except that dioctyl phthalate was replaced with tributyl phosphate.
Example 8
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared as in example 1 except that dioctyl phthalate was replaced with γ -butyrolactone.
Example 9
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that the temperature in step S1 was changed to 100 ℃.
Example 10
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that the temperature in step S1 was changed to 100 ℃.
Example 11
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that in step S1, the stirring rate was replaced with 300r/min and the stirring was replaced with 2 hours.
Example 12
A long persistence light conversion agent was the same as in example 1.
A long afterglow light converting film is prepared by the same method as in example 1 except that in step S1 the antifoaming agent is replaced with an antifoaming agent FT-30.
Example 13
A long persistence light conversion agent was the same as in example 1.
A long afterglow light converting film is prepared by the same method as in example 1 except that in step S1 the antifoaming agent is replaced with an antifoaming agent XPZ-120.
Example 14
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that in step S1, 0.06g of the long persistence light converting agent was substituted.
Example 15
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that in step S1, 0.12g of the long persistence light converting agent was substituted.
Example 16
A long persistence light conversion agent was the same as in example 1.
A long persistence light converting film was prepared in the same manner as in example 1 except that in step S1, 0.18g of the long persistence light converting agent was substituted.
Example 17
A long-afterglow light-converting agent contains Ca as chemical component1.0Sr2.0Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.02。
A long persistence light conversion film was prepared as in example 1 except that the long persistence light conversion agent was replaced.
Example 18
A long-afterglow light-converting agent contains Ca as chemical component0.4Sr2.6Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.10。
A long persistence light conversion film was prepared as in example 1 except that the long persistence light conversion agent was replaced.
Example 19
A long-afterglow light-converting agent contains Ca as chemical component0.4Sr2.6Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.10。
A long afterglow light converting film is prepared by the same method as in example 1 except that the long afterglow light converting agent is replaced by 30 deg.C and the drying temperature is replaced by 12 hr in step S3.
Example 20
A long-afterglow light-converting agent contains Ca as chemical component0.4Sr2.6Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.10。
A long afterglow light converting film is prepared by the same method as in example 1 except that the long afterglow light converting agent is replaced by 70 deg.C and the drying temperature is replaced by 8 hr in step S3.
Example 21
A long-afterglow light-converting agent is prepared from Sr3Al2O5Cl2:Eu2+ 0.02,Ho3+ 0.10。
A long persistence light conversion film was prepared as in example 1.
Example 22
A long-afterglow light-converting agent contains Ca as chemical component3Al2O5Cl2:Eu2+ 0.02,Nd3+ 0.10。
A long persistence light conversion film was prepared as in example 1.
Comparative example 1
The comparison example replaces the long afterglow light conversion agent with SrAl2O3N2/3:0.02Eu2+，0.02Dy3+. The preparation method of the long afterglow light converting film is the same as that of example 1.
Comparative example 2
The comparative example replaces the mass of the long afterglow light conversion agent with 0.001 g. The preparation method of the long afterglow light converting film is the same as that of example 1.
Comparative example 3
The comparative example replaces the mass of the long afterglow light converting agent with 0.4 g. The preparation method of the long afterglow light converting film is the same as that of example 1.
Comparative example 4
The long persistence light conversion agent of this comparative example was the same as example 1 except that the long persistence light conversion film was prepared by replacing the polyvinyl fluoride with polyethylene.
Performance testing
1. Test method
(1) XRD: the phase structure of the long-afterglow light conversion agent is tested by an X' Pert Pro MPD type X-ray diffractometer, the pipe pressure and the pipe flow are respectively 40kV and 40mA, the scanning speed is 4 DEG/min, the step length is 0.02 DEG, and the measuring angle 2 theta ranges from 10 DEG to 80 deg.
(2) Light transmittance in visible region: and measuring the transmittance of the light conversion film in a visible light region by using a UV3600 type ultraviolet-visible spectrophotometer, wherein the measurement range is 380 nm-780 nm.
(3) Emission spectrum: the FLS1000 type fluorescence spectrometer is used for testing the emission spectrum of the light conversion film, the excitation wavelength is 365nm, and the measurement range is 450 nm-800 nm.
(4) Afterglow luminance decay curve: and measuring the afterglow attenuation curve of the light conversion film by adopting a single photon counting system.
2. Test results
FIGS. 1(a), (b) and (c) are XRD patterns of the products of example 1, example 17 and example 18, respectively. By comparison, the spectra are all consistent with the ICSD card library No.68365 card, which indicates that the long afterglow light conversion agent is successfully prepared and is in an orthorhombic system.
As shown in FIG. 2, the long persistence light conversion agent prepared in example 1 has particle size of about 300-500 nm, and is well dispersed without significant agglomeration.
As is clear from fig. 3, the long afterglow luminance of the light conversion film obtained in example 1 showed about 90% transmittance in red, orange and yellow regions and 85% or more transmittance in blue and green regions. The light transmittance of the long-afterglow light-converting films prepared in the embodiments 2 to 22 can reach more than 85% in a visible light region.
As can be seen from FIG. 4(a), the main emission peak of the long afterglow light-converting film produced by the present invention is at about 620nm, and reddish orange light is obtained.
The elongation at break of the long persistence light conversion films of examples 1-2, 14-16 is shown in FIG. 5, and with the increase of the addition amount of the long persistence light conversion agent, the elongation at break of the long persistence light conversion film is slightly reduced to between 88% and 95%, but still can meet the application requirements, which indicates that the long persistence light conversion film has better mechanical properties.
As shown in FIG. 6, the decay curve of afterglow luminance of the long afterglow light-converting film prepared in example 1 shows that the afterglow time is as long as 480min, and the film can emit light at night to promote the growth of plants at night. The long-afterglow light conversion film can be used in agricultural production, such as preparation of agricultural films, and is used for promoting plants to grow at night.
The long persistence light conversion films prepared in examples 1, 2, 14, 15, and 16 had thicknesses of 42.4 μm, 24.3 μm, 42.1 μm, 42.6 μm, and 43.1. mu.m, respectively.
TABLE 1 test results of examples and comparative examples
Figure BDA0002736209440000081
Figure BDA0002736209440000091
As is clear from the results in Table 1, example 4 was conducted at 200mW/cm2The holding time of the constant elongation at break under the irradiation of strong light is longest and can reach 215 hours, and meanwhile, the lowest temperature for holding the constant elongation at break is also the lowest, and the weather resistance is good. From example 1 and comparative example 1, it can be seen that Ca is the most important factor0.4Sr2.6Al2O5Cl2:Eu2+ 0.02,Dy3+ 0.02Using SrAl2O3N2/3:0.02Eu2+，0.02Dy3+The long persistence light conversion film, which is a long persistence light conversion agent, has a short retention time for a constant elongation at break. Comparative example 2 reduced the amount of the long-afterglow light-converting agent, and although the elongation at break remained constant for a long time, the light-converting effect was lowered due to the very low amount of the light-converting agent, and the practical application value was not achieved. Comparative example 3 increasing the amount of the long afterglow light converting agent results in a significant decrease in the time during which the elongation at break of the resulting long afterglow light converting film is kept constant, while the low temperature resistance is maintainedAlso weakened, showing a significant decrease in weatherability. From example 1 and comparative example 4, it can be seen that the long afterglow light-converting films made using polyvinyl fluoride as the base resin have better weatherability than those made using polyethylene as the base resin.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The long afterglow light converting agent features its chemical composition of CaxSr3-xAl2O5Cl2:Eu2+ y,M3+ zWherein x is more than or equal to 0 and less than or equal to 3 and 0<y≤0.2，0<z is less than or equal to 0.2, and M is one or more of Dy, Nd, Ho and Sm.
2. A long afterglow light conversion film, characterized by comprising the long afterglow light conversion agent as defined in claim 1 and polyvinyl fluoride, wherein the mass ratio of polyvinyl fluoride to long afterglow light conversion agent is 100: 0.5 to 9.
3. The long afterglow light converting film according to claim 2, wherein the mass ratio of said polyvinyl fluoride to said long afterglow light converting agent is 100: 2 to 6.
4. The long afterglow light converting film according to claim 2 or 3, wherein the thickness of said long afterglow light converting film is 20 to 1000 μm.
5. The process for producing a long afterglow light converting film according to any one of claims 2 to 4, comprising the steps of:
s1, dissolving polyvinyl fluoride in an organic solvent, adding a plasticizer, and dissolving at 80-100 ℃ for 2-5 hours to obtain a polyvinyl fluoride solution;
s2, dispersing the long afterglow light conversion agent in a solvent, and then uniformly mixing the long afterglow light conversion agent with the polyvinyl fluoride solution obtained in the step S1 to obtain a mixed solution;
and S3, casting the mixed solution obtained in the step S2 into a film, and drying to obtain the long afterglow light conversion film.
6. The preparation method according to claim 5, wherein the plasticizer in step S1 is one or more selected from dioctyl phthalate, tributyl phosphate, and γ -butyrolactone.
7. The method of claim 5, wherein the dissolving step of step S1 further comprises adding an antifoaming agent.
8. The method according to claim 5, wherein the organic solvent in step S1 is one or more selected from the group consisting of dimethylformamide, dimethylacetamide and hexamethylphosphoramide.
9. The preparation method according to claim 5, wherein the solvent in step S2 is one or more of absolute ethyl alcohol, toluene and acetone.
10. Use of the long persistence light converting film of any one of claims 2 to 4 in agricultural production.
CN202011134456.9A 2020-10-21 2020-10-21 Long-afterglow light conversion agent and application thereof Pending CN112143491A (en)

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Application publication date: 20201229