CN103160276A - Red light conversion agents and preparation method thereof, and enveloped red light conversion agents and preparation method thereof - Google Patents

Red light conversion agents and preparation method thereof, and enveloped red light conversion agents and preparation method thereof Download PDF

Info

Publication number
CN103160276A
CN103160276A CN2012102095596A CN201210209559A CN103160276A CN 103160276 A CN103160276 A CN 103160276A CN 2012102095596 A CN2012102095596 A CN 2012102095596A CN 201210209559 A CN201210209559 A CN 201210209559A CN 103160276 A CN103160276 A CN 103160276A
Authority
CN
China
Prior art keywords
light
converting agent
ruddiness
converting
ruddiness light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2012102095596A
Other languages
Chinese (zh)
Other versions
CN103160276B (en
Inventor
胡广齐
刘晓瑭
方利浮
陈焰
郑明东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FOSHAN ONMILLION NANO MATERIALS Co Ltd
Original Assignee
FOSHAN ONMILLION NANO MATERIALS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FOSHAN ONMILLION NANO MATERIALS Co Ltd filed Critical FOSHAN ONMILLION NANO MATERIALS Co Ltd
Priority to CN201210209559.6A priority Critical patent/CN103160276B/en
Publication of CN103160276A publication Critical patent/CN103160276A/en
Application granted granted Critical
Publication of CN103160276B publication Critical patent/CN103160276B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention discloses red light conversion agents which are characterized in that the composition general formula is Ca1-xMxS:TM, wherein 0<=x<1, M is one or more of Mg, Ba, Sr, Zn, Cd and Hg, and TM is one or more of Sm, Ce, Y, Gd, La, Pr, Eu, Cu and Mn. Compared with the prior art, the resultant temperature of the red light conversion agents are lower, operation is simple, a sample is looser, and cost is greatly lowered. Plant photosynthesis spectral matching can be completed by adjusting and controlling the location of a launch main through changing base material ratio. According to the red light conversion agents, sunlight not only can be converted into light waves, with wavelengths of 380-480 nm and 640-680 nm, which are required in plant photosynthesis, but also can absorb ultraviolet rays with a wavelength of 220-380 nm , and green yellow light with a wavelength of 480-620 nm.

Description

Ruddiness light-converting agent of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof
Technical field
The present invention relates to ruddiness light-converting agent of a kind of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof.
Background technology
Light-converting agent be with in sunlight to the useless ultraviolet ray of photosynthesis of plant, purple light and green glow be converted to can Promoting plant growth Red and blue light.The research of relevant blue light-converting agent report is less, and for the research of red light-converting agent, mainly take rare earth organic complex as main, some document has proposed red light-converting agent the growth of plant is had promoter action.
Yet also there is a lot of problems in the light-converting agent that turns light master batch and light-converting film that can be used for preparing in the market: (1) matching is poor.Especially organic coordination compound light-converting agent, its emission main peak be generally in the 610nm left and right, with absorption spectrum ranges 620 ~ 680nm of plant, larger gap arranged.Therefore (2) preparation cost is high, causes expensively, and market is difficult to accept, and is to hinder at present the biggest obstacle that light-converting agent is used.(3) poor stability.No matter be inorganic light-converting agent or organic coordination compound light-converting agent, under ultraviolet irradiation, all obvious decay can occur for a long time, organic coordination compound also may decompose.(4) fluorescence lifetime is short.Most patents and pertinent literature are not all reported its fluorescence lifetime, and the fluorescence transformation period of indivedual reports also only had about half a year, because update time of plastic sheeting for farm use is 9 ~ 12 months, so can not synchronize with the work-ing life of plastics film.
Summary of the invention
First purpose of the present invention is in order to overcome deficiency of the prior art, a kind of high red light-emitting agent of main peak of launching to be provided.
For realizing above purpose, the present invention is achieved through the following technical solutions:
The ruddiness light-converting agent is characterized in that, its composition general formula is: Ca 1-xM xS:TM;
Wherein, 0≤x<1;
M is one or more in Mg, Ba, Sr, Zn, Cd, Hg;
TM is one or more in Sm, Ce, Y, Gd, La, Pr, Eu, Cu, Mn.
Preferably, described ruddiness light-converting agent emission wavelength is 400-480nm and 640-680nm for emission peak wavelength scope.
Preferably, described red light-converting agent absorbing wavelength scope is 220-380nm and 480-620nm
The ruddiness light-converting agent is characterized in that, its composition general formula is: Ca 1-x-yN xSr yS:Eu;
Wherein, 0≤x<1,0≤y<1, x+y<1;
N is one or more in alkaline-earth metal.
Preferably, described alkaline-earth metal N is one or more in Mg, Ba, Zn, Cd, Hg.
Preferably, also comprise rare earth metal in described ruddiness light-converting agent, its composition general formula is: Ca 1-x-yN xSr yS:Eu, TM; TM is one or more in rare earth metal.
Preferably, described rare earth metal TM is one or more in Sm, Ce, Y, Gd, La, Pr, Cu and Mn.
Preferably, its component also comprises one or both in Cl or Li.
Preferably, its excitation wavelength range is one or both in 220 ~ 350nm and 440 ~ 620nm.
Preferably, described ruddiness light-converting agent emission wavelength ranges is 600 ~ 680nm.
Second purpose of the present invention is to provide a kind of preparation method of ruddiness light-converting agent, it is characterized in that, according to its molecular formula proportioning, the oxide compound and the fusing assistant that take the metallic element in the ruddiness light-converting agent fully grind; Under reducing atmosphere condition, fully reaction, namely obtain product under 600 ℃ ~ 1200 ℃.
Preferably, the oxide compound of the metallic element in the ruddiness light-converting agent comprises CaCO 3, MgO, ZnO, BaCO 3, CdO, HgO, SrCO 3, Eu 2O 3, Sm 2O 3, CeO 2, Gd 2O 3, La 2O 3, CuO, MnO 2, Pr 6O 11And Y 2O 3
Preferably, reaction raw materials also comprises the sulphur powder.
Preferably, described fusing assistant is NaF, CaF 2, BaF 2, Li 2CO 3, K 2CO 3, CaCl 2, KCl, NaCl, NH 4Cl, H 3BO 3In one or more.
Preferably, the weight of described fusing assistant is 0.1 ~ 50% of each metallic element oxide weight sum.Be more preferably, be more preferably, the weight of described fusing assistant is 0.5 ~ 20% of each metallic element oxide weight sum; Most preferably that the weight of fusing assistant is 2 ~ 15% of each metallic element oxide compound and sulphur grain weight amount sum.
Preferably, reducing atmosphere adopts CO, hydrogen or nitrogen hydrogen mixeding gas.
Preferably, reacted 1 ~ 4 hour under 600 ℃ ~ 1200 ℃.
The 3rd purpose of the present invention is to provide a kind of ruddiness light-converting agent of coating, and the ruddiness light-converting agent of coating is characterized in that, the described ruddiness light-converting agent of the arbitrary claim of claim 1-10 is coated with film; Described film is that organic polymer or general formula are MF 2Or MSiO 3Material, M is one or more in Ca, Sr, Ba or Al; The mass ratio of described film and light-converting agent is (0.1 ~ 50): 100.
Preferably, described properties-correcting agent is one or more in resol, aminoresin, Synolac, epoxy resin, acrylic resin, silane coupling agent, titanate coupling agent.
Available resol includes but not limited to versatility resol and modified phenolic resins.Modified phenolic resins includes but not limited to water soluble phenol resin, rosin modified phenolic resin, nylon modified phenolic resin and aniline modified phenolic resins.
Available aminoresin includes but not limited to urea-formaldehyde resin, terpolycyantoamino-formaldehyde resin, aniline formaldehyde resin and water soluble amino resin.
Available Synolac includes but not limited to 300,310,341,342,343-3,343-4,355-5,389-8,3150,3247.
Available epoxy resin includes but not limited to bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy and acrylic acid epoxy resin.
Available acrylic resin includes but not limited to methyl methacrylate, β-dimethyl-aminoethylmethacrylate, poly-n-butyl methacrylate, n-BMA, Octyl methacrylate, methacrylic acid certain herbaceous plants with big flowers ester, phenyl methacrylate and lauryl methacrylate(LMA).
available silane coupling agent includes but not limited to vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethyl silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, anilinomethyl triethoxysilane and anilinomethyl trimethoxy silane.
Available titanate coupling agent includes but not limited to the different capryloyl titanic acid ester of isopropoxy three, isopropoxy three isostearoyl base titanic acid ester, dioleoyl ethylene titanate, three oleoyl isopropyl titanate and tetrabutyl titanates.
Preferably, MF 2Or MSiO 3With the abundant calcination of described ruddiness light-converting agent; Perhaps properties-correcting agent and ruddiness light-converting agent are fully ground.
Preferably, calcination temperature is 200 ℃ ~ 900 ℃.
Preferably, calcination time is 0.5 ~ 4 hour.
Preferably, described MF 2The preparation method is: preparation M salt brine solution, drip the precipitation agent fluorion solution for preparing, and stirred washing, centrifugation 1 ~ 2 hour; Oven dry.
Preferably, described M SiO 3The preparation method is: preparation nitrocalcite or strontium nitrate or nitric acid barium salt or alum liquor, drip the precipitation agent sodium silicate solution, and stirred 0.1-8 hour, separate.
The invention has the beneficial effects as follows: compared with prior art, the synthesis temperature of ruddiness light-converting agent is lower, and is simple to operate, and sample is more open, reduced greatly cost; With the photosynthesis of plant Spectral matching, the position that can regulate and control by changing substrate composition the emission main peak is complementary with it.Ruddiness light-converting agent in the present invention both can be converted into sunlight the ripple of the required 380-480nm of photosynthesis of plant and 640-680nm wavelength, can absorb again 220-380nm ultraviolet ray and the 480-620nm greenish-yellow light harmful to plant.Coating not only effectively improved the ruddiness light-converting agent light-decay characteristic, prevent its oxidation and deliquescence, improved its work-ing life, and can obviously improve its luminous intensity.Due to without H 2The S smell, harmless, preparation be can be widely used in and light master batch and light-converting film turned.The ruddiness light-converting agent is first made master batch be used further to make film, can carry out the ruddiness light-converting agent pre-dispersedly, improve the dispersiveness of ruddiness light-converting agent in film matrix.Dust pollution when reducing execute-in-place.Making master batch, to make the advantage of film be scattered again, and execute-in-place is simple, and stability is high.Light-converting agent is mixed film especially in agricultural film, make film have the effect of light of turning, facilitate the application of light-converting agent.Light-converting film in the present invention and photosynthesis of plant Spectral matching are good.Use light-converting film to apply simultaneously the implantation methods of carbonic acid gas, plant yield-increasing is increased matter play very large effect, disease-free, without insect pest, without chemical pesticide, quality better, raising output etc., successful, have very high economic worth, large-scale promotion prospect is arranged.
Description of drawings
Fig. 1 .CaS:Eu, Cl (CaF 2) the exciting light spectrogram of red light-converting agent;
Fig. 2. the utilizing emitted light spectrogram of (A1, A2) before and after red light-converting agent coats;
Fig. 3. the utilizing emitted light spectrogram of (B1, B2) before and after red light-converting agent coats;
Fig. 4. the utilizing emitted light spectrogram of (C1, C2) before and after red light-converting agent coats;
Fig. 5. the utilizing emitted light spectrogram of (D1, D2) before and after red light-converting agent coats.
Fig. 6 is the light-converting agent luminescent spectrum figure of embodiment 14 and embodiment 15 preparations.
Fig. 7 is the coating ruddiness light-converting agent scanning electron microscope of embodiment 15 preparations.
Fig. 8 is the coating ruddiness light-converting agent scanning electron microscope of embodiment 21 preparations.
Fig. 9 is the ruddiness light-converting agent scanning electron microscope of embodiment 17 preparations.
Figure 10 is the light-converting film of embodiment 21 preparations and absorption and the exciting light spectrogram of common blank film.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail:
Embodiment 1
(1) the ruddiness light-converting agent is synthetic: take respectively 64.5g CaCO by stoichiometric ratio 3, 24.8g sulphur powder, 0.52g Eu 2O 3, 4.6gNH 4Then Cl mixes raw material, fully grinds, cooling gradually in the lower 800 ℃ of roastings of CO reducing atmosphere 2 hours, namely obtains sample (A1), and sample takes on a red color.
A1 forms general formula: CaS:Eu, Cl.
The exciting light spectrogram is seen Fig. 1.Fig. 1 show light-converting agent (A1) can effectively absorb photosynthesis of plant do not absorb or absorb weak UV-light and yellow green light, avoid photosynthetic absorption spectrum, be prepared into the ruddiness that light-converting film can provide the required characteristic wavelength of photosynthesis greatly.
The utilizing emitted light spectrogram is seen Fig. 2.Fig. 2 shows that light-converting agent (A1) can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its spectrum and photosynthesis spectrum are very identical.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 95% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press CaF 2With the ratio of the weight ratio 5:100 of light-converting agent, take the Ca (NO of respective amount 3) 2 4H 20, be made into calcium saline solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with A1, and 500 ℃ of calcinations 1 hour namely obtain being surrounded by CaF 2The sample of film (A2), sample takes on a red color.
A2 forms general formula: CaS:Eu, Cl (CaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Before and after the ruddiness light-converting agent coats, the excitation and emission spectra figure of (A1, A2) as shown in Figure 2.Fig. 2 shows that sample can be the ruddiness of 640nm with UV-light and yellow green light switching emission main peak, and the luminous intensity after coating obviously improves.
Experiment shows, A1 and A2 can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 150kg A1 or A2, Low Density Polyethylene 50kg, linear polyethylene 100kg, polyethylene wax 5kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 1, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 2
(1) the ruddiness light-converting agent is synthetic: take respectively 64.5g CaCO by stoichiometric ratio 3, 24.8 sulphur powder, 0.52g Eu 2O 3, 4.6g Li 2CO 3, raw material is mixed, fully grind, cooling gradually in the lower 850 ℃ of roastings of CO reducing atmosphere 2 hours, namely obtain sample (B1), it is orange red that sample is.
B1 forms general formula: CaS:Eu, Li.
Experiment shows, B1 exciting light spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
The utilizing emitted light spectrogram is seen Fig. 3.Fig. 3 shows that light-converting agent (B1) can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its spectrum and photosynthesis spectrum are very identical.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 95% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press SrF 2With the ratio of the weight ratio 5:100 of light-converting agent, take the Sr (NO of respective amount 3) 2, be made into the strontium salt brine solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with B1, and 600 ℃ of calcinations 1 hour namely obtain being surrounded by SrF 2The sample of film (B2), sample takes on a red color.
B2 forms general formula: CaS:Eu, Li (SrF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Before and after the ruddiness light-converting agent coats, the utilizing emitted light spectrogram of (B1, B2) as shown in Figure 3.Fig. 3 shows that sample can be the ruddiness of 637nm with UV-light and yellow green light switching emission main peak, and the luminous intensity after coating obviously improves.
Experiment shows, B1 and B2 can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 100kgB1 or B2, Low Density Polyethylene 50kg, linear polyethylene 100kg, polyethylene wax 5kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 200kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 2, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 3
(1) the ruddiness light-converting agent is synthetic: take respectively 64.5g CaCO by stoichiometric ratio 3, 24.8 sulphur powder, 0.52g Eu 2O 3, 4.6g CaCl 2, raw material is mixed, fully grind, cooling gradually in the lower 900 ℃ of roastings of CO reducing atmosphere 2 hours, namely obtain sample (C1), sample takes on a red color.
C1 forms general formula: CaS:Eu, Cl.
Experiment shows: C1 exciting light spectrogram is identical with A1, and it also can absorb that the photosynthesis of plant growth is not needed or absorb weak UV-light and yellow green light.
The utilizing emitted light spectrogram is seen Fig. 4.Fig. 4 shows that light-converting agent (C1) can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its spectrum and photosynthesis spectrum are very identical.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 98% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press BaF 2With the ratio of the weight ratio 10:100 of light-converting agent, take the Ba (NO of respective amount 3) 2, be made into the barium salt aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with C1, and 700 ℃ of calcinations 1 hour namely obtain being surrounded by BaF 2The sample of film (C2), sample takes on a red color.
C2 forms general formula: CaS:Eu, Cl (BaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 2.5 times its work-ing life.Can reach several 15 months work-ing life.
Before and after the ruddiness light-converting agent coats, the utilizing emitted light spectrogram of (C1, C2) as shown in Figure 4.Fig. 4 shows that sample can be converted to yellow green light the ruddiness take 635nm as main peak, and the luminous intensity after coating obviously improves.
Experiment shows, C1 and C2 can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 50kg C1 or C2, Low Density Polyethylene 50kg, linear polyethylene 100kg, polyethylene wax 12kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get polyvinyl chloride 1100kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 3, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 4
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 17.5g Sr CO 3, 22.8 sulphur powder, 0.48g Eu 2O 3, 0.10g Sm 2O 3, 4.8g BaF 2, raw material is mixed, fully grind, cooling gradually in the lower 850 ℃ of roastings of CO reducing atmosphere 1.5 hours, namely obtain sample, it is orange red that sample is, and the sample composition general formula is Ca 0.8Sr 0.2S:Eu, Sm.
Experiment showed, that the sample excitation spectrogram is identical with A1, it also can absorb that the photosynthesis of plant growth is not needed or absorb weak UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 633nm, and is very identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 90% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press CaF 2With the ratio of the weight ratio 1:100 of light-converting agent, take the Ca (NO of respective amount 3) 2 4H 20, be made into the calcium aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent, and 500 ℃ of calcinations 1 hour namely obtain being surrounded by CaF 2The sample of film, sample takes on a red color.The sample composition general formula is: Ca 0.8Sr 0.2S:Eu, Sm (CaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 2 times its work-ing life.Can reach several 12 months work-ing life.
Experiment shows, the ruddiness light-converting agent before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 300kg example 4(2) sample, high density polyethylene(HDPE) 250kg, polyoxyethylene glycol 5kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 1200kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 4, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 5
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 8.2g MgO, 26.1 sulphur powder, 0.55g Eu 2O 3, 0.16g Sm 2O 3, 4.3g H 3BO 3, raw material is mixed, fully grind, cooling gradually in the lower 850 ℃ of roastings of CO reducing atmosphere 1.5 hours, namely obtain sample (D1), it is orange red that sample is.
D1 forms general formula: Ca 0.7Mg 0.3S:Eu, Sm.
Experiment shows, D1 exciting light spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
D1 utilizing emitted light spectrogram is seen Fig. 5.Fig. 5 shows that light-converting agent (D1) can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its spectrum and photosynthesis spectrum are very identical.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 96% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press CaF 2With the ratio of the weight ratio 15:100 of light-converting agent, take the Ca (NO of respective amount 3) 2 4H 20, be made into the calcium aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with D1, and 400 ℃ of calcinations 3 hours namely obtain being surrounded by CaF 2The sample of film (D2), sample takes on a red color.
D2 forms general formula: Ca 0.7Mg 0.3S:Eu, Sm (CaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Before and after the ruddiness light-converting agent coats, the utilizing emitted light spectrogram of (D1, D2) as shown in Figure 5.Fig. 5 shows that sample can be converted to yellow green light the ruddiness of 639nm, and the luminous intensity after coating obviously improves.
Experiment shows, D1 and D2 can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 200kg D1 or D2, linear polyethylene 150kg, Zinic stearas 10kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 20kg, the 5kg antioxidant 300 is got light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 5, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 6
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 19.0g MgO, 36.5 sulphur powder, 0.77g Eu 2O 3, 0.18gCeO 2, 6.1gH 3BO 3, raw material is mixed, fully grind, cooling gradually in the lower 850 ℃ of roastings of CO reducing atmosphere 1.5 hours, namely obtain sample, it is orange red that sample is.The sample general formula is: Ca 0.5Mg 0.5S:Eu, Ce.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its spectral emissions main peak is 635nm, and is very identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 98% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press SrF 2With the ratio of the weight ratio 5:100 of light-converting agent, take the Sr (NO of respective amount 3) 2, be made into the strontium salt brine solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of previous step preparation, and 900 ℃ of calcinations 1 hour namely obtain being surrounded by SrF 2The sample of film, sample takes on a red color.The sample general formula is: Ca 0.5Mg 0.5S:Eu, Ce (SrF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 200kg example 6(2) sample, Low Density Polyethylene 50kg, stearic acid pentaerythritol ester 17kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, succinic acid and (4-hydroxyl-2,2, the polymkeric substance of 6,6-tetramethyl--1-piperidine alcohols) 20kg, the 5kg antioxidant 2246, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 6, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 7
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 44.3g MgO, 60.8 sulphur powder, 1.28g Eu 2O 3, 0.31gCeO 2, 3.7g H 3BO 3, raw material is mixed, fully grind, cooling gradually in the lower 850 ℃ of roastings of CO reducing atmosphere 1.5 hours, namely obtain sample, it is orange red that sample is.The sample composition general formula is: Ca 0.3Mg 0.7S:Eu, Ce.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its spectral emissions main peak is 631nm, coincide with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, is about 1 ~ 3 μ m, has narrower particle size distribution range, and being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press BaF 2With the ratio of the weight ratio 8:100 of light-converting agent, take the Ba (NO of respective amount 3) 2, be made into the barium salt aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of (1) step preparation, and 900 ℃ of calcinations 1 hour namely obtain being surrounded by BaF 2The sample of film, sample takes on a red color.The sample composition general formula is: Ca 0.3Mg 0.7S:Eu, Ce (BaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the ruddiness light-converting agent before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 100kg example 7(2) sample, polypropylene 100kg, titanate coupling agent 10kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 7, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 8
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 69.8g Sr CO 3, 36.5 sulphur powder, 0.77g Eu 2O 3, 0.24gCuSO 4, 15.1gBaF 2, raw material is mixed, fully grind, cooling gradually in the lower 1000 ℃ of roastings of nitrogen hydrogen mixeding gas reducing atmosphere 3 hours, namely obtain sample, it is orange red that sample is.The sample composition general formula is: Ca 0.5Sr 0.5S:Eu, Cu.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 630nm, coincide with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 99% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press SrF 2With the ratio of the weight ratio 20:100 of light-converting agent, take the Sr (NO of respective amount 3) 2, be made into the strontium salt brine solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of (1) step preparation, and 650 ℃ of calcinations 2 hours namely obtain being surrounded by SrF 2The sample of film, sample takes on a red color.The sample composition general formula is: Ca 0.5Sr 0.5S:Eu, Cu (SrF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 50kg example 8(2) sample, ethylene-vinyl acetate copolymer 50kg, titanate coupling agent 3kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 8, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 9
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 279.3g Sr CO 3, 91.2 sulphur powder, 1.93g Eu 2O 3, 20.8g KCl mixes raw material, fully grinds, and is cooling gradually in the lower 1150 ℃ of roastings of hydrogen reduction atmosphere 1 hour, namely obtains sample, and it is orange red that sample is.The sample composition general formula is: Ca 0.2Sr 0.8S:Eu, Cl.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 624nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, is about 1 ~ 3 μ m, has narrower particle size distribution range, and being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press BaF 2With the ratio of the weight ratio 4:100 of light-converting agent, take the Ba (NO of respective amount 3) 2, be made into the barium salt aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of (1) step preparation, and 450 ℃ of calcinations 0.5 hour namely obtain being surrounded by BaF 2The sample of film, sample takes on a red color.The sample composition general formula is: Ca 0.2Sr 0.8S:Eu, Cl (BaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 60kg example 9(2) sample, ethylene-vinyl acetate copolymer 50kg, titanate coupling agent 2kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 9, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 10
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 10.0g Sr CO 3, 11.4gMgCO 3, 26.1 sulphur powder, 0.55g Eu 2O 3, 0.12gCuSO 4, 10.0g KCl mixes raw material, fully grinds, and is cooling gradually in the lower 1200 ℃ of roastings of hydrogen reduction atmosphere 3.5 hours, namely obtains sample, and it is orange red that sample is.
The sample composition general formula is: Ca 0.7Mg 0.2Sr 0.1S:Eu, Cu, Cl.
Exciting light spectrogram approximate diagram 1 can absorb that the photosynthesis of plant growth is not needed or absorb weak UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 636nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, 97% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range,, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press CaF 2With the ratio of the weight ratio 2:100 of light-converting agent, take the Ca (NO of respective amount 3) 2 4H 20, be made into the calcium aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of (1) step preparation, and 600 ℃ of calcinations 4 hours namely obtain being surrounded by CaF 2The sample of film, sample takes on a red color.
The sample composition general formula is: Ca 0.7Mg 0.2Sr 0.1S:Eu, Cu, Cl (CaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 50kg example 10(2) sample, high density polyethylene(HDPE) 30kg, vinyl bis-stearamides 3kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 20kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 10, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 11
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 52.4g Sr CO 3, 29.9gMgCO 3, 45.6 sulphur powder, 0.96g Eu 2O 3, 0.26gMnO 2, 27g BaF 2, raw material is mixed, fully grind, cooling gradually in the lower 850 ℃ of roastings of CO reducing atmosphere 3.5 hours, namely obtain sample, it is orange red that sample is.
The sample composition general formula is: Ca 0.4Mg 0.3Sr 0.3S:Eu, Mn.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 632nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, is about 1 ~ 3 μ m, has narrower particle size distribution range,, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press SrF 2With the ratio of the weight ratio 9:100 of light-converting agent, take the Sr (NO of respective amount 3) 2, be made into the strontium salt brine solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of (1) step preparation, and 500 ℃ of calcinations 3.5 hours namely obtain being surrounded by SrF 2The sample of film, sample takes on a red color.
The sample composition general formula is: Ca 0.4Mg 0.3Sr 0.3S:Eu, Mn (SrF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 60kg example 11(2) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 3kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 11, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 12
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 139.7g Sr CO 3, 79.8gMgCO 3, 91.2 sulphur powder, 1.93g Eu 2O 3, 30.0g K 2CO 3, raw material is mixed, fully grind, cooling gradually in the lower 1050 ℃ of roastings of CO reducing atmosphere 4 hours, namely obtain sample, it is orange red that sample is.
The sample composition general formula is: Ca 0.2Mg 0.4Sr 0.4S:Eu.
Experiment shows, sample excitation spectrogram and A1 are approximate, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 632nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 99% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press BaF 2With the ratio of the weight ratio 12:100 of light-converting agent, take the Ba (NO of respective amount 3) 2, be made into the barium salt aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of (1) step preparation, and 650 ℃ of calcinations 1 hour namely obtain being surrounded by BaF 2The sample of film, sample takes on a red color.The sample composition general formula is: Ca 0.2Mg 0.4Sr 0.4S:Eu (BaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 50kg example 12(2) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 3kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 12, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 13
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 139.7g Sr CO 3, 79.8gMgCO 3, 91.2 sulphur powder, 1.93g Eu 2O 3, 0.38gMnO 2, 15.0g K 2CO 3, raw material is mixed, fully grind, cooling gradually in the lower 950 ℃ of roastings of CO reducing atmosphere 1.5 hours, namely obtain sample, it is orange red that sample is.
The sample composition general formula is: Ca 0.5Mg 0.2Ba 0.2Sr 0.1S:Eu, Mn.
Experiment shows, sample excitation spectrogram and A1 are approximate, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 632nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 95% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: press CaF 2With the ratio of the weight ratio 7:100 of light-converting agent, take the Ca (NO of respective amount 3) 2 4H 20, be made into the calcium aqueous solution, then with the precipitation agent NH for preparing 4F solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with the ruddiness light-converting agent of (1) step preparation, and 800 ℃ of calcinations 1 hour namely obtain being surrounded by CaF 2The sample of film, sample takes on a red color.
The sample composition general formula is: Ca 0.5Mg 0.2Ba 0.2Sr 0.1S:Eu, Mn (CaF 2).
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 70kg example 13(2) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 5kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, get light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 13, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 14
Synthesizing of ruddiness light-converting agent: take respectively 64.5g CaCO by stoichiometric ratio 3, 23.5g SrCO 3, 0.27g Eu 2O 3, 0.03gSm 2O 3, 0.15gCuSO 4, 3.5g(NH 4) 2SO 4, then raw material is mixed, fully grind, add the lower 900 ℃ of roastings of sulphur atmosphere reducing atmosphere 2 hours in CO, cooling gradually, namely obtain sample, sample takes on a red color.
The sample general formula is: Ca 0.8Sr 0.2S:Eu, Sm, Cu.Ruddiness light-converting agent luminescent spectrum figure in the present embodiment sees Fig. 6.
Embodiment 15
(1), the ruddiness light-converting agent is synthetic: take respectively 64.5g CaSO by stoichiometric ratio 4, 23.5g SrCO 3, 0.27g Eu 2O 3, 0.03gSm 2O 3, 0.15gCuSO 4, 3.5g(NH 4) 2SO 4, then raw material is mixed, fully grind, add the lower 800 ℃ of roastings of sulphur atmosphere reducing atmosphere 2 hours in CO, cooling gradually, namely obtain sample, sample takes on a red color.
The sample general formula is: Ca 0.8Sr 0.2S:Eu, Sm, Cu.Light-converting agent luminescent spectrum figure in the present embodiment sees Fig. 6.
(2), the preparation of coating ruddiness light-converting agent: press CaSiO 3With the ratio of the weight ratio 5:100 of light-converting agent, take the Ca (NO of respective amount 3) 2 4H 20, be made into the aqueous solution, then with the precipitation agent Na for preparing 2SiO 3Solution is added drop-wise in mentioned solution, stirred 1 hour, and washing, centrifugation, oven dry fully mixes with example 14 light-converting agents, and 400 ℃ of calcinations 1 hour namely obtain being surrounded by CaSiO 3The sample of film, sample takes on a red color.
The sample general formula is: Ca 0.8Sr 0.2S:Eu, Sm, Cu(CaSiO 3).After coating, the Sample Scan Electronic Speculum is seen Fig. 7.As can be seen from the figure, in the middle of film is coated on the ruddiness light-converting agent.
(3) preparation of light-converting agent master batch
Get 40kg example 15(2) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 6kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get metallocene linear polyethylene 200kg, Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 6.5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 3.5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 15, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 16
(1) preparation of the red light-converting agent of coating: the ruddiness light-converting agent that uses embodiment 14 preparations, take light-converting agent 50g, bisphenol A type epoxy resin 55g, β-dimethyl-aminoethylmethacrylate 55g, the vinyl trichloro silane 5g wiring solution-forming of respective amount, again the solution for preparing is added in sand mill, ground 1 hour, washing, centrifugation is dried, and namely obtains being surrounded by the sample of properties-correcting agent.Sample takes on a red color.
(2) preparation of light-converting agent master batch
Get 40kg example 16(1) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 6kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(3) production of light conversion film
Get metallocene linear polyethylene 200kg, Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid is two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg; The 10kg irgasfos 168 is got coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 16, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 17
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 69.8g Sr CO 3, 36.5 sulphur powder, 0.77g Eu 2O 3, 0.24gCuSO 4, 15.1gBaF 2, raw material is mixed, fully grind, cooling gradually in the lower 1000 ℃ of roastings of nitrogen hydrogen mixeding gas reducing atmosphere 3 hours, namely obtain sample, it is orange red that sample is.The sample composition general formula is: Ca 0.5Sr 0.5S:Eu, Cu.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 650nm, coincide with photosynthesis spectrum.
Fig. 9 is the ruddiness light-converting agent scanning electron microscope of embodiment 17 preparations.Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, and 99% above particle diameter is 1 ~ 3 μ m, sees Fig. 9.Have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of the red light-converting agent of coating: in the ratio of the weight ratio 25:100 of light-converting agent and properties-correcting agent, take light-converting agent 50g, acrylic acid epoxy resin 100g, n-BMA 95g, the vinyltrimethoxy silane 5g wiring solution-forming of respective amount, again the solution for preparing is added in sand mill, ground 1 hour, washing, centrifugation is dried, and namely obtains being surrounded by the sample of properties-correcting agent.Sample takes on a red color.
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 100kg example 17(2) sample, linear polyethylene 200kg, polyethylene wax 10kg, maleic anhydride 0.5kg, dicumyl peroxide 0.1kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get metallocene linear polyethylene 200kg, Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 6.5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 3.5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 17, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 18
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 279.3g Sr CO 3, 91.2 sulphur powder, 1.93g Eu 2O 3, 20.8g KCl mixes raw material, fully grinds, and is cooling gradually in the lower 1150 ℃ of roastings of hydrogen reduction atmosphere 1 hour, namely obtains sample, and it is orange red that sample is.The sample composition general formula is: Ca 0.2Sr 0.8S:Eu, Cl.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 654nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, is about 1 ~ 3 μ m, has narrower particle size distribution range, and being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: in the ratio of the weight ratio 35:100 of light-converting agent and properties-correcting agent, take light-converting agent 50g, methyl methacrylate 138g, the γ-glycidyl ether oxygen propyl trimethyl silane 5g wiring solution-forming of respective amount, again the solution for preparing is added in sand mill, ground 1 hour, washing, centrifugation is dried, and namely obtains being surrounded by the sample of properties-correcting agent.Sample takes on a red color.
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 100kg example 18(2) sample,, linear polyethylene 200kg, polyethylene wax 10kg, maleic anhydride 0.5kg, dicumyl peroxide 0.1kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get metallocene linear polyethylene 200kg, Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 6.5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 3.5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 18, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 19
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 10.0g Sr CO 3, 11.4gMgCO 3, 26.1 sulphur powder, 0.55g Eu 2O 3, 0.12gCuSO 4, 10.0g KCl mixes raw material, fully grinds, and is cooling gradually in the lower 1200 ℃ of roastings of hydrogen reduction atmosphere 3.5 hours, namely obtains sample, and it is orange red that sample is.
The sample composition general formula is: Ca 0.7Mg 0.2Sr 0.1S:Eu, Cu, Cl.
Exciting light spectrogram approximate diagram 1 can absorb that the photosynthesis of plant growth is not needed or absorb weak UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 636nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, 97% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range,, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: in the ratio of the weight ratio 50:100 of light-converting agent and properties-correcting agent; take light-converting agent 50g, versatility resol 55g, methacrylic acid certain herbaceous plants with big flowers ester 42g, the different capryloyl titanic acid ester of the isopropoxy three 3g wiring solution-forming of respective amount; again the solution for preparing is added in sand mill; ground 1 hour; washing; centrifugation is dried, and namely obtains being surrounded by the sample of properties-correcting agent.Sample takes on a red color.
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 100kg example 19(2) sample, linear polyethylene 200kg, polyethylene wax 10kg, maleic anhydride 0.5kg, dicumyl peroxide 0.1kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get metallocene linear polyethylene 200kg, Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester 6.5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 3.5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 19, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 20
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 52.4g Sr CO 3, 29.9gMgCO 3, 45.6 sulphur powder, 0.96g Eu 2O 3, 0.26gMnO 2, 27g BaF 2, raw material is mixed, fully grind, cooling gradually in the lower 850 ℃ of roastings of CO reducing atmosphere 3.5 hours, namely obtain sample, it is orange red that sample is.
The sample composition general formula is: Ca 0.4Mg 0.3Sr 0.3S:Eu, Mn.
Experiment shows, the sample excitation spectrogram is identical with A1, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 652nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, in building-up process, meeting release gas, make its median size of final product little, is about 1 ~ 3 μ m, has narrower particle size distribution range,, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: in the ratio of the weight ratio 30:100 of light-converting agent and properties-correcting agent, take light-converting agent 50g, urea-formaldehyde resin 80g, phenyl methacrylate 80g, vinyl three ('beta '-methoxy oxyethyl group) the silane 6.7g wiring solution-forming of respective amount, again the solution for preparing is added in sand mill, ground 1 hour, washing, centrifugation is dried, and namely obtains being surrounded by the sample of properties-correcting agent.Sample takes on a red color.
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 100kg example 20(2) sample,, linear polyethylene 200kg, polyethylene wax 10kg, maleic anhydride 0.5kg, dicumyl peroxide 0.1kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get metallocene linear polyethylene 200kg, Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 6.5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 3.5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 20, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.
Embodiment 21
(1) the ruddiness light-converting agent is synthetic: take respectively 47.5g CaCO by stoichiometric ratio 3, 139.7g Sr CO 3, 79.8gMgCO 3, 91.2 sulphur powder, 1.93g Eu 2O 3, 30.0g K 2CO 3, raw material is mixed, fully grind, cooling gradually in the lower 1050 ℃ of roastings of CO reducing atmosphere 4 hours, namely obtain sample, it is orange red that sample is.
The sample composition general formula is: Ca 0.2Mg 0.4Sr 0.4S:Eu.
Experiment shows, sample excitation spectrogram and A1 are approximate, its also can absorb that the photosynthesis of plant growth is not needed or absorb a little less than UV-light and yellow green light.
This light-converting agent can absorb UV-light and yellow green light and launch the required ruddiness of photosynthesis of plant, and its emmission spectrum main peak is 632nm, and is substantially identical with photosynthesis spectrum.
Because the sulphur powder that is employing carbonate and easily distillation is raw material, can discharge gas in building-up process, make its median size of final product little, 99% above particle diameter is 1 ~ 3 μ m, have narrower particle size distribution range, being conducive to adulterates to be scattered in the PE material is prepared into light-converting film.
(2) preparation of coating ruddiness light-converting agent: in the ratio of the weight ratio 50:100 of light-converting agent and properties-correcting agent, take light-converting agent 50g, Synolac 34150g, poly-n-butyl methacrylate 45g, the vinyltriethoxysilane 5g wiring solution-forming of respective amount, again the solution for preparing is added in sand mill, ground 1 hour, washing, centrifugation is dried, and namely obtains being surrounded by the sample of properties-correcting agent.Sample takes on a red color.After coating, the Sample Scan Electronic Speculum is seen Fig. 8.As can be seen from the figure, in the middle of film is coated on the ruddiness light-converting agent.
After coating, the light decay of ruddiness light-converting agent obviously improves, and is placed in the water rate of decomposition and greatly reduces, and compares not have tunicary ruddiness light-converting agent, is prepared into light-converting film with it, and can extend more than 3 times its work-ing life.Can reach several 18 months work-ing life.
Experiment shows, the sample before and after coating can be all that the exciting light of 220 ~ 350nm or 440 ~ 620nm is converted into the ruddiness that wavelength region is 600 ~ 680nm with wavelength region.
(3) preparation of light-converting agent master batch
Get 100kg example 21(2) sample,, linear polyethylene 200kg, polyethylene wax 10kg, maleic anhydride 0.5kg, dicumyl peroxide 0.1kg sequentially is added to high-speed mixer with above-mentioned materials.After stirring with high-speed mixer, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation is prepared from master batch.
(4) production of light conversion film
Get metallocene linear polyethylene 200kg, Low Density Polyethylene 200kg, linear low density polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 6.5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 3.5kg gets light-converting agent, coating ruddiness light-converting agent or the master batch 30kg of aforementioned prepared example 21, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns; Approximately 165 ℃ of 175 ℃ of inflation film manufacturing machine melt temperatures, die head temperature.Figure 10 is the light-converting film of embodiment 21 preparations and absorption and the exciting light spectrogram of common blank film.Blank film is not for adding the film of ruddiness light-converting agent.
Embodiment 22
Get respectively the light conversion film that the awning film that does not add light-converting agent and the light-converting agent that adds embodiment 18 are made, cover into booth.The awning film of light-converting agent is not added in the use of 1# booth, and the 2# booth is for adding the prepared light conversion film of light-converting agent in example 18, and the 3# booth is the prepared light conversion film of the light-converting agent in use interpolation example 18 and applies carbonic acid gas.3# booth A, B being for adding coating ruddiness light-converting agent and first make master batch and make film again, and 3# booth C is that coating ruddiness light-converting agent is not made master batch but is added directly in film.Each booth specification is that the long 14 meters X of wide 7 meters X are high 3.5 meters.Three booths are planted romaine lettuce simultaneously, and 3# booth 8 carbon dioxides that apply 5 minutes every morning are approximately 0.2% of the interior gas weight of canopy.
The romaine lettuce comparative analysis data of three kinds of greenhouse gardenings are as follows, and every kind of booth is selected three as a reference:
Figure BDA00001800276500311
Embodiment 23
Get respectively the light-converting film that the awning film that does not add light-converting agent and the light-converting agent that adds embodiment 18 are made, cover into booth.The awning film of light-converting agent is not added in the use of 1# booth, and the 2# booth is for adding the prepared light-converting film of light-converting agent in example 18, and the 3# booth is the prepared light-converting film of the light-converting agent master batch in use interpolation example 18 and applies carbonic acid gas.Each booth specification is that the long 14 meters X of wide 7 meters X are high 3.5 meters.Three booths are planted black tea simultaneously, 3# booth 8 carbon dioxides that apply 5 minutes every morning, and the carbonic acid gas applied amount is 1% of the interior gas weight of canopy.
It is as follows that the black tea of plantation is analyzed correlation data:
Pluck for the first time The 1# booth The 2# booth The 3# booth
Output/jin 1.1 1.5 2.6
Biochemical analysis keeps sample/jin 0.4 0.4 0.4
The bright leaf of tea making/jin 0.7 1.0 1.7
Water extraction/% 36.3 36.76 37.26
Tea-polyphenol/% 27.9 27.35 28.92
Amino acid/% 3.58 3.6 3.41
Trimethyl-xanthine/% 3.86 3.87 5.23
Phenol nitrogen ratio 7.79 7.59 8.48
Make dried tea/g 81 112 196
Embodiment 24
Get respectively the light conversion film that the awning film that does not add light-converting agent and the light-converting agent that adds embodiment 21 are made, cover into booth.The awning film of light-converting agent is not added in the use of 1# booth, and the 2# booth is for adding the prepared light-converting film of light-converting agent in example 21, and the 3# booth is the prepared light-converting film of the light-converting agent in use interpolation example 16 and applies carbonic acid gas.Each booth specification is that the long 14 meters X of wide 7 meters X are high 3.5 meters.3# booth A, B being for adding coating ruddiness light-converting agent and first make master batch and make film again, and 3# booth C is that coating ruddiness light-converting agent is not made master batch but is added directly in film.Three booths are planted Japanese Chinese cabbage simultaneously, 3# booth 8 carbon dioxides that apply 5 minutes every morning, and the carbonic acid gas applied amount is 2% of the interior gas weight of canopy.
The Japanese Chinese cabbage comparative analysis data of three greenhouse gardenings are as follows:
Figure BDA00001800276500321
Figure BDA00001800276500331
Embodiment 25
Get respectively the light-converting film that the awning film that does not add light-converting agent and the light-converting agent that adds embodiment 1 are made, cover into booth.The awning film of light-converting agent is not added in the use of 1# booth, and the 2# booth is for adding the prepared light-converting film of light-converting agent in example 1, and the 3# booth is the prepared light-converting film of the light-converting agent in use interpolation example 16 and applies carbonic acid gas.Each booth specification is that the long 14 meters X of wide 7 meters X are high 3.5 meters.3# booth A, B being for adding coating ruddiness light-converting agent and first make master batch and make film again, and 3# booth C is that coating ruddiness light-converting agent is not made master batch but is added directly in film.Three booths are planted leaf mustard simultaneously, 3# booth 8 carbon dioxides that apply 5 minutes every morning, and the carbonic acid gas applied amount is 0.5% of the interior gas weight of canopy.Light-converting film booth and to add carbonic acid gas booth leaf mustard growing state good.
The leaf mustard harvest comparative analysis data of three greenhouse gardenings are as follows:
Figure BDA00001800276500332
Figure BDA00001800276500341
Embodiment 26
Get respectively the light-converting film that the awning film that does not add light-converting agent and the light-converting agent that adds embodiment 10 are made, cover into booth.The awning film of light-converting agent is not added in the use of 1# booth, and the 2# booth is for adding the prepared light-converting film of light-converting agent in example 10, and the 3# booth is the prepared light-converting film of the light-converting agent in use interpolation example 16 and applies carbonic acid gas.3# booth A, B being for adding coating ruddiness light-converting agent and first make master batch and make film again, and 3# booth C is that coating ruddiness light-converting agent is not made master batch but is added directly in film.Each booth specification is that the long 14 meters X of wide 7 meters X are high 3.5 meters.Three booths are planted little tomato simultaneously, 3# booth 8 carbon dioxides that apply 5 minutes every morning, and the carbonic acid gas applied amount is 0.2% of the interior gas weight of canopy.
The little tomato harvest comparative analysis data of three greenhouse gardenings are as follows:
Figure BDA00001800276500351
Embodiment 27
Get respectively the light-converting film that the awning film that does not add light-converting agent and the light-converting agent that adds embodiment 16 are made, cover into booth.The awning film of light-converting agent is not added in the use of 1# booth, and the 2# booth is for adding the prepared light-converting film of light-converting agent in example 16, and the 3# booth is the prepared light-converting film of the light-converting agent in use interpolation example 16 and applies carbonic acid gas.Each booth specification is that the long 14 meters X of wide 7 meters X are high 3.5 meters.3# booth A, B being for adding coating ruddiness light-converting agent and first make master batch and make film again, and 3# booth C is that coating ruddiness light-converting agent is not made master batch but is added directly in film.Three booths are planted potato simultaneously, 3# booth 8 carbon dioxides that apply 5 minutes every morning, and the carbonic acid gas applied amount is 0.2% of the interior gas weight of canopy.
The potato harvest comparative analysis data of three greenhouse gardenings are as follows:
Figure BDA00001800276500361
In the present invention, during granulation, the service temperatures of 130 ℃~200 ℃, being 100~500r/min through rotating speed, twin screw extruder is extruded, air-cooled granulation.Actual temp and rotating speed can be determined according to master batch body material and light-converting agent content, not repeat them here.Granulation also can use existing other agglomeration techniques to realize.
Through evidence, the alkaline-earth metal in above embodiment can adopt other alkaline-earth metal to replace; The rare earth metal that uses in above embodiment can adopt other rare earth metals to replace.
Embodiment in the present invention only is used for that the present invention will be described, does not consist of the restriction to the claim scope, and other substituting of being equal in fact that those skilled in that art can expect are all in protection domain of the present invention.

Claims (24)

1. the ruddiness light-converting agent, is characterized in that, its composition general formula is: Ca 1-xM xS:TM;
Wherein, 0≤x<1;
M is one or more in Mg, Ba, Sr, Zn, Cd, Hg;
TM is one or more in Sm, Ce, Y, Gd, La, Pr, Eu, Cu, Mn.
2. ruddiness light-converting agent according to claim 1, is characterized in that, described ruddiness light-converting agent emission wavelength is 400-480nm and 640-680nm for emission peak wavelength scope.
3. ruddiness light-converting agent according to claim 1, is characterized in that, described ruddiness light-converting agent absorbing wavelength scope is 220-380nm and 480-620nm.
4. the ruddiness light-converting agent, is characterized in that, its composition general formula is: Ca 1-x-yN xSr yS:Eu;
Wherein, 0≤x<1,0≤y<1, x+y<1;
N is one or more in alkaline-earth metal.
5. ruddiness light-converting agent according to claim 4, is characterized in that, described alkaline-earth metal N is one or more in Mg, Ba, Zn, Cd, Hg.
6. ruddiness light-converting agent according to claim 4, is characterized in that, also comprises rare earth metal in described ruddiness light-converting agent, and its composition general formula is: Ca 1-x-yN xSr yS:Eu, TM; TM is one or more in rare earth metal.
7. ruddiness light-converting agent according to claim 6, is characterized in that, described rare earth metal TM is one or more in Sm, Ce, Y, Gd, La, Pr, Cu and Mn.
8. according to claim 4 or 6 described ruddiness light-converting agents, is characterized in that, its component also comprises one or both in Cl or Li.
9. ruddiness light-converting agent according to claim 4, is characterized in that, its excitation wavelength range is one or both in 220 ~ 350nm and 440 ~ 620nm.
10. ruddiness light-converting agent according to claim 4, is characterized in that, described ruddiness light-converting agent emission wavelength ranges is 600 ~ 680nm.
11. the preparation method of the described ruddiness light-converting agent of the arbitrary claim of claim 1-10 is characterized in that, according to its molecular formula proportioning, the oxide compound and the fusing assistant that take the metallic element in the ruddiness light-converting agent fully grind; Under reducing atmosphere condition, fully reaction, namely obtain product under 600 ℃~1200 ℃.
12. the preparation method of ruddiness light-converting agent according to claim 11 is characterized in that, the oxide compound of the metallic element in the ruddiness light-converting agent comprises CaCO 3, MgO, ZnO, BaCO 3, CdO, HgO, SrCO 3, Eu 2O 3, Sm 2O 3, CeO 2, Gd 2O 3, La 2O 3, CuO, MnO 2, Pr 6O 11And Y 2O 3
13. the preparation method of ruddiness light-converting agent according to claim 11 is characterized in that, described fusing assistant is NaF, CaF 2, BaF 2, Li 2CO 3, K 2CO 3, CaCl 2, KCl, NaCl, NH 4Cl, H 3BO 3In one or more.
14. the preparation method of ruddiness light-converting agent according to claim 11 is characterized in that, the weight of described fusing assistant is 0.1 ~ 50% of each metallic element oxide weight sum.
15. the preparation method of ruddiness light-converting agent according to claim 11 is characterized in that, reducing atmosphere adopts CO, hydrogen or nitrogen hydrogen mixeding gas.
16. the preparation method of ruddiness light-converting agent according to claim 11 is characterized in that, reacts 1 ~ 4 hour under 600 ℃~1200 ℃.
17. the preparation method of ruddiness light-converting agent according to claim 11 is characterized in that, reaction raw materials also comprises the sulphur powder.
18. the ruddiness light-converting agent of coating is characterized in that, the described ruddiness light-converting agent of the arbitrary claim of claim 1-10 is coated with film; Described film is that properties-correcting agent or general formula are MF 2Or MSiO 3Material, M is one or more in Ca, Sr, Ba or Al; The mass ratio of described film and light-converting agent is (0.1 ~ 50): 100.
19. the ruddiness light-converting agent of coating according to claim 18 is characterized in that, described properties-correcting agent is one or more in resol, aminoresin, Synolac, epoxy resin, acrylic resin, silane coupling agent, titanate coupling agent.
20. the preparation method of the ruddiness light-converting agent of the described coating of claim 18 is characterized in that MF 2Or MSiO 3With the abundant calcination of described ruddiness light-converting agent; Perhaps properties-correcting agent and ruddiness light-converting agent are fully ground.
21. the preparation method of the ruddiness light-converting agent of coating according to claim 20 is characterized in that, calcination temperature is 200 ℃ ~ 900 ℃.
22. the preparation method of the ruddiness light-converting agent of coating according to claim 20 is characterized in that, calcination time is 0.5 ~ 4 hour.
23. the preparation method of the ruddiness light-converting agent of coating according to claim 20 is characterized in that, described MF 2The preparation method is: preparation M salt brine solution, drip the precipitation agent fluorion solution for preparing, and stirred washing, centrifugation 1 ~ 2 hour; Oven dry.
24. the preparation method of the ruddiness light-converting agent of coating according to claim 20 is characterized in that, described MSiO 3The preparation method is: preparation nitrocalcite or strontium nitrate or nitric acid barium salt or alum liquor, drip the precipitation agent sodium silicate solution, and stirred 0.1-8 hour, separate.
CN201210209559.6A 2012-01-20 2012-06-22 Ruddiness light-converting agent of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof Active CN103160276B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210209559.6A CN103160276B (en) 2012-01-20 2012-06-22 Ruddiness light-converting agent of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201210019469 2012-01-20
CN2012100194690 2012-01-20
CN201210019469.0 2012-01-20
CN201210209559.6A CN103160276B (en) 2012-01-20 2012-06-22 Ruddiness light-converting agent of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103160276A true CN103160276A (en) 2013-06-19
CN103160276B CN103160276B (en) 2015-08-19

Family

ID=48583819

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210209559.6A Active CN103160276B (en) 2012-01-20 2012-06-22 Ruddiness light-converting agent of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103160276B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709678A (en) * 2013-11-29 2014-04-09 佛山安亿纳米材料有限公司 Light conversion film and preparation method thereof
CN105600815A (en) * 2014-11-12 2016-05-25 天津科技大学 Doped nanometer zinc oxide light conversion agent preparation method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317537A (en) * 2001-02-12 2001-10-17 湖南师范大学 Single-base dual-energy light-transforming agent and its preparing prcess and application
CN102212362A (en) * 2010-03-25 2011-10-12 Lg伊诺特有限公司 Phosphor, method of coating the same, and method of manufacturing light emitting apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317537A (en) * 2001-02-12 2001-10-17 湖南师范大学 Single-base dual-energy light-transforming agent and its preparing prcess and application
CN102212362A (en) * 2010-03-25 2011-10-12 Lg伊诺特有限公司 Phosphor, method of coating the same, and method of manufacturing light emitting apparatus

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
M. DANILKIN ET AL: "DIFFERENT Eu-CENTRES IN CaS:Eu,C1", 《RADIATION MEASUREMENTS》 *
NOBORU MIURA: "Color Phosphors for Inorganic Electroluminescent Devices", 《SID SYMPOSIUM DIGEST OF TECHNOLOGY PAPERS》 *
YOSHIYUKI KOJIMA ET AL: "Effect of strontium and lithium ions on afterglow time of red-emitting CaS:Eu2+, Pr3+ phosphor upon visible-light irradiation", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709678A (en) * 2013-11-29 2014-04-09 佛山安亿纳米材料有限公司 Light conversion film and preparation method thereof
CN103709678B (en) * 2013-11-29 2016-01-13 佛山安亿纳米材料有限公司 Light-converting film and preparation method thereof
CN105600815A (en) * 2014-11-12 2016-05-25 天津科技大学 Doped nanometer zinc oxide light conversion agent preparation method
CN105600815B (en) * 2014-11-12 2018-04-20 天津科技大学 A kind of preparation method of doped nano zinc oxide light conversion agent

Also Published As

Publication number Publication date
CN103160276B (en) 2015-08-19

Similar Documents

Publication Publication Date Title
CN103172921B (en) Bifunctional light conversion thin film and preparation method thereof
CN105295188A (en) Nitride red light conversion film and preparation method thereof
CN103160008A (en) Light conversion film and preparation method thereof
CN103709678B (en) Light-converting film and preparation method thereof
CN103160011B (en) Plant cultivation method
CN105713288B (en) One kind turns light conversion farm film and preparation method and application
CN101157854B (en) Oxynitrides luminescent material, preparation method and uses thereof
CN103710022B (en) Light-converting agent and preparation method thereof, turn light master batch and preparation method thereof
CN110157430A (en) One plant growth fluorescent powder and preparation method thereof
CN105385014B (en) A kind of light altering film for agriculture and preparation method and application
CN103160010A (en) Difunctional light conversion master batches and preparation method thereof
CN101117576B (en) Oxynitrides luminescent material and illuminating or exhibiting light source produced thereby
CN1187428C (en) Single-base dual-energy light-transforming agent and its preparing prcess and application
US20130127333A1 (en) Oxynitride luminescent material, preparation method thereof and illumination light source made from such material
CN105482816A (en) Nitride red light conversion master batch and preparation method thereof
CN109874803B (en) Fluorescent powder capable of promoting plant growth and preparation method thereof
CN101280070B (en) Light conversion agent composition and preparation thereof, preparation of light conversion agricultural film
CN101671562A (en) Nitrogen oxides luminescent material and preparation method and application thereof
CN103160009B (en) Turn light master batch and preparation method thereof
CN104087298A (en) Light conversion material and light conversion film, and preparation methods thereof
CN115466620A (en) Sodium europium gallium germanium garnet-based high-efficiency deep red light fluorescent powder and preparation method thereof
CN103160276B (en) Ruddiness light-converting agent of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof
CN103168644B (en) Plant cover cultivation methods
CN102618271B (en) A kind of white light LEDs single-matrix fluorescent material and preparation method thereof
CN103160277B (en) Double-function light conversion agent and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant