CN103160011A - Plant cultivation method - Google Patents
Plant cultivation method Download PDFInfo
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- CN103160011A CN103160011A CN2012103354600A CN201210335460A CN103160011A CN 103160011 A CN103160011 A CN 103160011A CN 2012103354600 A CN2012103354600 A CN 2012103354600A CN 201210335460 A CN201210335460 A CN 201210335460A CN 103160011 A CN103160011 A CN 103160011A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
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Abstract
The invention discloses a plant cultivation method which is characterized in that a double-function optical thin film is utilized to manufacture a greenhouse or a mulching film to form a plant growing space; plants are cultivated in the growing space; the double-function optical thin film comprises a thin film base body, a double-function light conversion agent and an addition agent; the weight of the double-function light conversion agent is 0.01-20% of the weight of the thin film; the weight of the addition agent is 0.1%-10% of the weight of the thin film; the balance is the thin film base body; and a composition general formula of the double-function light conversion agent is Cal-xNxF2:Eu,TM, wherein the x is greater than or equal to 0 and is less than or equal to 1, the N is one kind or more kinds of Ba, Zn, Sr, Mg, Hg, and Fe, and the TM is one kind or more kinds chosen from Sm, Cu, Pr, Tb, Ce, La, Dy, Mn and Ag. The double-function optical thin film can convert ultraviolet light and green light in sunlight into strong blue light and red orange light at the same time, and the strong blue light and the red orange light can promote growth of crops. The plant cultivation method is used for crop production and can remarkably play a role in production increase and quality improvement.
Description
Technical field
The present invention relates to a kind of plant cover cultivation methods.
Background technology
So far, a large amount of research experiments prove, shine in the spectrum of earth surface, be not that all different wave length is all favourable to plant-growth, what really be conducive to photosynthesis of plant has two peaks district: (1) blue light region (400 ~ 500nm), the strongest absorption peak of its Determination of Chlorophyll α is 425nm, chlorophyll β, and xenthophylls and the strongest absorption peak of alpha-carotene are 440nm; (2) blood orange district (600-680nm), wherein 645nm is the strongest absorption peak of chlorophyll β, 660nm is the strongest absorption peak of chlorophyll α.By increasing blue light or the red light irradiation degree to plant, can make crop root flourishing, cauline leaf is luxuriant, and increasing both production and income and quality are superior.
Yet can be for the manufacture of turning the light master batch, and can produce the canopy membrane interaction in the most important material light-converting agent of crop growth, although have made some progress, but focus mostly in monochromatic light-converting agent, such as the ruddiness light-converting agent is mainly the rare earth compounding light-converting agent, also there is a lot of problems in this type of light-converting agent research so far: (1) fluorescence lifetime is short.Seldom there is document can report the fluorescence lifetime of organic coordination compound light-converting agent, even report also only has effect in 3 months, for the production of turning the light master batch, the preparation light-converting film, at the button canopy initial stage, light conversion properties can be relatively good, but very fast its light transition function can descend very soon, causes it not synchronize with the life-span of film.(2) light function singleness.In the light-converting agent of rare earth organic complex, the ultraviolet of only having that can be used at present light-converting film turns red function, seldom has report can be converted to the required blue light of photosynthesis of plant.In addition, on light-use, can only absorb UV-light, and can not absorb green glow, reduce the utilising efficiency to daylight.(3) expensive.The price that it is expensive hinders its application on light-converting film; In addition, seldom see the report of relevant blue light conversion agent, existing bibliographical information can with the green glow in sunlight and UV-light conversion position blue light and blood orange light, make a difficult problem but light-converting agent and polymer are difficult for compatible problem to the practical application of light-converting agent.
Plastic sheeting for farm use market, the world is estimated as 2,000,000 tons at present, and the European market is 500,000 tons, 1,000,000 tons of Chinese markets.Have relative ripe market in Europe and North America, the most of enforcement protection of agricultural ground cultivation, as Hague, Detch, 50% of its arable land is the greenhouse.According to the prediction of the Ministry of Agriculture, 2010, the overlayable canopy membrane area of China was 5,000 ten thousand mu, approximately needed 3,000,000 tons of agricultural films.Plastic sheeting for farm use is the product for agriculture that country widelys popularize, is provided freely to grower's use or government and subsidizes, but the usage quantity less than 30% of present plastic sheeting for farm use.The usage quantity of the plastic greenhouse film of China, although account for the first in the world, the technology content of canopy film is lower, great majority are universal normal film, functional canopy film less than 20%.So, a kind of stable performance, turn optical property significantly, the appearance of long service life, difunctional light-converting film with low cost, will fill up domestic in this blank on the one hand, the assurance of agriculture production is had important practical significance.
The Modern Agriculture crop-planting has used the means such as a large amount of agricultural chemicals, chemical fertilizer, hormone medicine and transgenosis, therefore also a lot of diseases have been brought for the mankind, there is data to show that the possibility of agricultural chemicals and chemical substance cause cancer is very large, hormone medicine and transgenosis also may cause the mankind and grow precocious and some labile factors, and agricultural chemicals and chemical fertilizer have brought destructive strike also for other biology simultaneously.
Existing organic heath food plantation is substantially take common plastic house plastics film with apply the implantation methods such as organic fertilizer as main, and the early investment fund is large, and the process maintenance cost is high, volume increase is general, so existing organic heath food yields poorly, price can't be realized large-scale promotion substantially.
Summary of the invention
First purpose of the present invention is to provide a kind of plant cover cultivation methods that increases output.
For achieving the above object, the present invention is achieved through the following technical solutions:
Plant cover cultivation methods is characterized in that, utilizes difunctional light conversion film to make booth or mulch film, forms a plant-growth space; With plant growing in described growing space; Described difunctional light conversion film comprises film matrix, difunctional light-converting agent and auxiliary agent; The 0.01-20% that described difunctional light-converting agent weight is film weight; Auxiliary agent weight is the 0.1%-10% of film weight; All the other are film matrix; It is Ca that described difunctional light-converting agent forms general formula
1-xN
xF
2: Eu, TM, wherein: 0≤x≤1, N is one or more in Ba, Zn, Sr, Mg, Hg and Fe, TM is selected from one or more in Sm, Cu, Pr, Tb, Ce, La, Dy, Mn and Ag.
Difunctional light-converting agent in the present invention is with alkaline-earth metal fluoride Ca
1-xN
xF
2For matrix, Eu are activator, remaining metal ion is made sensitizing agent.
Preferably, the described difunctional light-converting agent weight 0.1-10% that is film weight.
Preferably, alkaline-earth metal fluoride Ca
1-xN
xF
2Be monobasic alkaline-earth metal fluoride or binary alkaline-earth metal fluoride or polynary alkaline-earth metal fluoride.
Preferably, described auxiliary agent is one or both in photostabilizer and oxidation inhibitor.
Preferably, described film comprises light-converting agent master batch, film matrix and auxiliary agent; Described light-converting agent master batch comprises master batch matrix, difunctional light-converting agent and properties-correcting agent; Described properties-correcting agent weight is the 0.05%-10% of master batch weight; Difunctional light-converting agent weight is the 0.1-90% of master batch weight; In master batch, all the other are the master batch matrix.
Preferably, described master batch matrix and film matrix are same material.
Preferably, described master batch matrix is one or more in Low Density Polyethylene, linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), polypropylene, ethylene-vinyl acetate resin, polyvinyl chloride.
Preferably, the described difunctional light master batch that turns also comprises lubricant, and described lubricant weight is the 0.05-5% that turns light master batch weight.
Preferably, described difunctional turning also comprises one or both in photostabilizer and oxidation inhibitor in the light master batch.
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, described film matrix is one or more in Low Density Polyethylene, linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), polypropylene, ethylene-vinyl acetate resin, polyvinyl chloride.
Preferably, the carbon dioxide amount of discharging is the 0.01%-10% of growing space gas volume total amount.Preferably, the carbon dioxide amount of discharging is the 0.1%-5% of growing space gas gross.
Preferably, described carbonic acid gas continued to discharge into described growing space or intermittently discharge into described growing space.
Preferably, the application time of carbonic acid gas is 6 o'clock to 20 o'clock every day.Preferably, the application time of described carbonic acid gas is 6 o'clock to 16 o'clock every day.Again preferably, the application time of described carbonic acid gas is 6 o'clock to 14 o'clock every day.Again preferably, the application time of described carbonic acid gas is 6 o'clock to 10 o'clock every day.
But described carbonic acid gas is for being applied in the growing space external postpartum in the production space or material or the device of release of carbon dioxide in described growing space again.
Preferably, described plant is farm crop.Described farm crop include but not limited to: (1), food crop include but not limited to paddy rice, corn, beans, potato class, highland barley, broad bean, wheat etc.; (2), cash crop, include but not limited to coffee, pepper, flax, Sunflower Receptacle, tea etc.; (3) vegetable crop includes but not limited to radish, Chinese cabbage, celery, leek, garlic, green onion, Radix Dauci Sativae, snake melon, lotus flower dish, jerusalem artichoke, sword bean, coriander, asparagus lettuce, chrysanthemum, capsicum, cucumber, tomato, romaine lettuce etc.; (4) fruit includes but not limited to pears, green plum, apple, peach, apricot, walnut, plum, cherry, strawberry etc.(5) Chinese medicinal materials includes but not limited to anise, cloves, pseudo-ginseng, rhizoma Gastrodiae, radix polygonati officinalis, Radix Glycyrrhizae, the dried rhizome of rehmannia, gingko, Radix Angelicae Sinensis; (6) flowers include but not limited to rose, Flower of Chu-lan Tree, camellia, Flower of Arabian Jasmine, osmanthus fragrans, orchid, chrysanthemum, money tree etc.
Aforesaid difunctional light conversion film preparation method is for adopting rolling process or extrusion molding production.
Photostabilizer described in the present invention is selected from salol, p-t-butylphenyl salicylate, Resorcinol but benzoic ether, 2,4-dihydroxy benaophenonel, ESCALOL 567, dihydroxyphenyl propane sasapyrin and BP-3-5-sulfonic acid, (2,2,6,6-tetramethyl--4-piperidines) imines, succinic acid and (4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidine alcohols), sebacic acid two-2,2, the mixture of one or more in 6,6-tetramethyl piperidine alcohol ester.Preferably, photostabilizer is the mixture of (2,2,6,6-tetramethyl--4-piperidines) imines and succinic acid and (4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidine alcohols).
Oxidation inhibitor described in the present invention is selected from irgasfos 168, antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant 300, antioxidant 330, antioxidant 3114, oxidation inhibitor 245,2,6-ditertbutylparacresol, 2, one or more in 4,6-tri-butyl-phenol.Irgasfos 168, i.e. three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester; Antioxidant 1010, i.e. four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Antioxidant 1076, i.e. β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid.Preferably, oxidation inhibitor is one or more mixture in three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Preferably, oxidation inhibitor is the 0.01%-10% of film content; Photostabilizer is the 0.05%-5% of film content.
Preferably, described master batch matrix and film matrix are same material.
Preferably, described master batch matrix is one or more in Low Density Polyethylene, linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), polypropylene, ethylene-vinyl acetate resin, polyvinyl chloride.
The difunctional light agglomerate preparation method that turns is characterized in that, with above-mentioned raw material by weight preparation, in 130 ℃～200 ℃, rotating speed is under 100～500r/min condition, prepares through twin screw extruder.The method makes difunctional light-converting agent scattered in organic polymer, and has avoided difunctional light-converting agent the phenomenon of waste to occur in preparation.
The preparation method of aforementioned difunctional light-converting agent, design according to molecular formula, rare earth ion and inorganic salt solution are mixed in molar ratio, form co-precipitation under agitation condition, centrifugation is after washing and drying, under reducing atmosphere, in microwave, high fire reacted 10 ~ 20 minutes or in 800 ℃ ~ 1200 ℃ high-temperature roastings 2 ~ 4 hours, namely obtained product.
Preferably, described reducing atmosphere is the mixture of carbon monoxide or hydrogen and nitrogen.
Preferably, with roasting under throw out and fusing assistant and reducing atmosphere; 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 weight of precipitate.Be more preferably, be more preferably, the weight of described fusing assistant is 0.5 ~ 20% of weight of precipitate; Most preferably that the weight of fusing assistant is 2 ~ 15% of weight of precipitate.
Plant cover cultivation methods in the present invention, the difunctional light-converting film that uses can (300nm ~ 380nm) and green glow (520nm-560nm) convert the strong blue light that can promote crop growth (400nm ~ 500nm) and blood orange light (575nm ~ 630nm), have the effect of light that more takes a turn for the better simultaneously to the UV-light in sunlight.Difunctional light conversion film turn light and farm crop photosynthesis Spectral matching is good, be used for farm crop and produce the effect that can obviously play volume increase, improve quality.Use the inventive method that disease and pest is obviously reduced, have huge economic worth and realistic meaning, can be applicable on a large scale.
Description of drawings
Fig. 1: the SEM figure of the difunctional light-converting agent precursor that embodiment of the present invention 1-18 of the present invention produces.
Fig. 2: the SEM figure of the difunctional light-converting agent that this embodiment of the present invention 1-18 produces.
The difunctional light-converting agent that Fig. 3: embodiment of the present invention 1-18 produces is at the exciting light spectrogram of ultraviolet region.
The difunctional light-converting agent that Fig. 4: embodiment of the present invention 1-18 produces is at the exciting light spectrogram of green Region.
The blue emission spectrogram of the difunctional light-converting agent that Fig. 5: embodiment of the present invention 1-18 produces.
The red emission spectrogram of the difunctional light-converting agent that Fig. 6: embodiment of the present invention 1-18 produces.
Embodiment
Difunctional light-converting agent in the present invention can first be made the difunctional light master batch that turns, and makes difunctional light-converting agent and macromolecular material consistency good, and does not reduce the mechanical property that does not add before light-converting agent; And then make difunctional light conversion film, be used for the plants such as Planting Crops, cash crop.
At first, with difunctional light-converting agent, according to the molecular formula design, take respectively, raw material Rare Earth Ion and inorganic salt solution are mixed in molar ratio, add precipitation agent to form co-precipitation under agitation condition, centrifugation, washing and drying namely get presoma, then under reducing atmosphere, in microwave, high fire reaction 10 ~ 20 minutes or 800 ℃ ~ 1200 ℃ high-temperature roastings are 2 ~ 4 hours, namely obtain the difunctional light-converting agent of stable performance.Secondly; difunctional light-converting agent, properties-correcting agent and master batch body material and/or photostabilizer and/or oxidation inhibitor with above-mentioned production; mix in proportion; be under 100～500r/min condition in 130 ℃～200 ℃ service temperatures and rotating speed, extrude, air-cooled granulation, shear and namely to get the difunctional light master batch that turns through twin screw extruder.When making different goods, the key points for operation of twin screw extruder are also different, the present invention adopts twin screw extruder to make master batch, can make properties-correcting agent and difunctional light-converting agent through forcing machine, be under 100～500r/min condition in 130 ℃～200 ℃ service temperatures and rotating speed, not only can realize effective modification is carried out on the surface of difunctional light-converting agent, and better bring into play the serviceability of twin screw extruder.Difunctional light master batch, film human body and the first auxiliary agent of turning is mixed in proportion, and is that 160-180 ℃ and die head temperature are under 150-175 ℃ of condition in melt temperature, prepares through the inflation film manufacturing machine blown film.
The preparation method of aforementioned difunctional light-converting agent, it is characterized in that, design according to molecular formula, rare earth ion and inorganic salt solution are mixed in molar ratio, form co-precipitation under agitation condition, centrifugation, after washing and drying, under reducing atmosphere, in microwave, high fire reacted 10 ~ 20 minutes or in 800 ℃ ~ 1200 ℃ high-temperature roastings 2 ~ 4 hours, namely obtained product.
Preferably, described reducing atmosphere is the mixture of carbon monoxide or hydrogen and nitrogen.
Preferably, with roasting under throw out and fusing assistant and reducing atmosphere; 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 weight of precipitate.Be more preferably, be more preferably, the weight of described fusing assistant is 0.5 ~ 20% of weight of precipitate; Most preferably that the weight of fusing assistant is 2 ~ 15% of weight of precipitate.
Embodiment 1
(1) the synthetic Ca of difunctional light-converting agent
0.7Ba
0.3F
2: Eu
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (14.8Kg), Ba (NO
3)
2(5Kg), Eu
2O
3(17.00g), NH
4F (11.5Kg), HNO
3(25ml).
A. first use HNO
3Dissolving Eu
2O
3, add Ca (NO
3)
24H
2O and Ba (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.Dry the SEM shape characteristic of rear presoma as shown in Figure 1, its material object is white block.
C. with the throw out after above-mentioned oven dry, through adding 0.5% fusing assistant CaF of weight of precipitate
2Grind, then under CO reducing atmosphere condition, 1200 ℃ of high-temperature roastings 2 hours, cooling gradually, namely obtain sample.The SEM shape characteristic of described sample as shown in Figure 2, its material object is white powder.
(2) turn the production of light master batch
Take the difunctional light-converting agent of 2.4kg; high density polyethylene(HDPE) 20kg; vinyl bis-stearamides 0.4kg, the different capryloyl titanic acid ester of isopropoxy three 0.5kg, bisphenol A type epoxy resin 0.2kg; above-mentioned materials sequentially is added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 200 ℃, extrude through the twin screw extruder that rotating speed is 500r/min; air-cooled granulation is sheared and is prepared from master batch.
(3) 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 aforementioned master batch 30kg, 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 synthetic Ca of difunctional light-converting agent
0.75Zn
0.15F
2: Eu, Ce
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (17.6Kg), Zn (NO
3)
2, Ce
2O
3And MgO (3.2Kg altogether), Eu
2O
3(17.00g), NH
4F (11.5Kg), HNO
3(25ml).
A. first use HNO
3Dissolving Eu
2O
3, Ce
2O
3And MgO, add Ca (NO
3)
24H
2O and Zn (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the CaCl that fluxes of addition agent weight of precipitate 10%
2Grind, then under nitrogen hydrogen mixeding gas reducing atmosphere condition, 800 ℃ high-temperature roasting 4h hour, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the production of light master batch
Take 25.4kg example 2(1) sample; linear polyethylene 20kg; polyethylene wax 0.8kg, isopropoxy three isostearoyl base titanic acid ester 0.4kg, 0.5kg Synolac 342; above-mentioned materials sequentially is added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 130 ℃, extrude through the twin screw extruder that rotating speed is 100r/min; air-cooled granulation is sheared and 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 aforementioned master batch 30kg, 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 synthetic Ca of difunctional light-converting agent
0.65Sr
0.30Fe
0.05F
2: Eu
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (24.5Kg), Sr (NO
3)
2(11.2Kg), Fe
2O
3And Eu
2O
3(31.00g altogether), NH
4F (21.2Kg), HNO
3(30ml).
A. first use HNO
3Dissolving Eu
2O
3, Fe
2O
3And Eu
2O
3, add Ca (NO
3)
24H
2O, Sr (NO
3)
2(11.2Kg) preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 1% advances the capable grinding of NaF, then at H
2With N
2Under mixture reducing atmosphere condition, 950 ℃ of high-temperature roastings 3 hours, cooling gradually, namely obtain sample.
(2) turn the production of light master batch
Take 10kg example 3(1) sample; polyvinyl chloride 30kg; Zinic stearas 0.2kg, stearic acid pentaerythritol ester 0.3kg, polyethylene wax 1.0kg; photostabilizer dihydroxyphenyl propane sasapyrin 5kg; 2.5kg oxidation inhibitor 245; dioleoyl ethylene titanate 1.5kg; urea-formaldehyde resin 1.08kg; above-mentioned materials sequentially is added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 170 ℃, extrude through the twin screw extruder that rotating speed is 250r/min; air-cooled granulation is prepared from master batch.
(3) production of light conversion film
Get polyvinyl chloride 1100kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, aforementioned master batch 30kg mixes and forms 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 synthetic Ca of difunctional light-converting agent
0.75Mg
0.25F
2: Eu, Sm, Pr
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (17.6Kg), Mg (NO
3)
2, Pr
2O
3And Sm
2O
3(3.2Kg altogether), Eu
2O
3(14.00g), NH
4F (17.5Kg), HNO
3(25ml).
A. first use HNO
3Dissolving Eu
2O
3, Pr
2O
3And Sm
2O
3, add Ca (NO
3)
24H
2O, Mg (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant CaCl of addition agent weight of precipitate 0.5%
2Grind, then under CO reducing atmosphere condition, 900 ℃ of high-temperature roastings 3.5 hours, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the production of light master batch
Take 8kg example 4(1) sample; high density polyethylene(HDPE) 20kg; polyethylene wax 1.0kg, dioleoyl ethylene titanate 1.89kg, novolac epoxy 2kg; above-mentioned materials sequentially is added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 170 ℃, extrude through the twin screw extruder that rotating speed is 400r/min; air-cooled granulation is prepared from master batch.
(3) 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 aforementioned master batch 30kg, 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 synthetic Ca of difunctional light-converting agent
0.6Sr
0.25Zn
0.10F
2: Eu, Cu, Dy
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (17.6Kg), Sr (NO
3)
2, ZnO, CuO and Dy
2O
3(5.9Kg altogether), Eu
2O
3(15.00g), NH
4F (18.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, ZnO, CuO and Dy
2O
3, add Ca (NO
3)
24H
2O, Sr (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant K of addition agent weight of precipitate 1.5%
2CO
3Grind, then under CO reducing atmosphere condition, 900 ℃ of high-temperature roastings 4 hours, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the production of light master batch
Take 8kg example 5(1) sample, polypropylene 30kg, polyethylene wax 0.5kg, photostabilizer 2,4-dihydroxy benaophenonel 1.1kg, 1.01kg antioxidant 2246, tetrabutyl titanate 0.8kg, versatility resol 0.2kg, terpolycyantoamino-formaldehyde resin 0.3kg, 0.3kg Synolac 300 sequentially are added to high-speed mixer with above-mentioned materials, after stirring with high-speed mixer, under the operational temperature conditions of 175 ℃, extrude through the twin screw extruder that rotating speed is 350r/min, air-cooled granulation is prepared from master batch.
(3) 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 aforementioned master batch 30kg, 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 synthetic Ca of difunctional light-converting agent
0.6Ba
0.25Fe
0.15F
2: Eu, Mn
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (18.5Kg), Fe (NO
3)
2And MnO (2.4Kg altogether), Ba (NO
3)
2(2.6Kg), Eu
2O
3(16.00g), NH
4F (21.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, MnO, add Ca (NO
3)
24H
2O, Fe (NO
3)
2And Ba (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant BaF of addition agent weight of precipitate 3.6%
2Grind, then at H
2With N
2Under mixture reducing atmosphere condition, 950 ℃ high-temperature roasting 2.5h hour, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 6kg example 6(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 0.6kg, photostabilizer ESCALOL 567 3kg, 1.5kg antioxidant 1010, tetrabutyl titanate 2.19kg, bisphenol f type epoxy resin 0.3, methyl methacrylate 0.2kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 ℃, extrude through the twin screw extruder that rotating speed is 450r/min, air-cooled granulation is prepared from master batch.
(3) production of light conversion film
Get Low Density Polyethylene 200kg, linear low density polyethylene 800kg, succinic acid and (4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidine alcohols) 20kg, the 5kg antioxidant 2246 is got aforementioned master batch 30kg, 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 7
(1) the synthetic Ca of difunctional light-converting agent
0.70Sr
0.20Ba
0.10F
2: Eu, Sm
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (18.5Kg), Sr (NO
3)
2, Sm
2O
3(4.5Kg altogether), Ba (NO
3)
2(1.6Kg), Eu
2O
3(16.00g), NH
4F (21.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, Sm
2O
3, add Ca (NO
3)
24H
2O, Sr (NO
3)
2And Ba (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaCl of addition agent weight of precipitate 5.2% grinds, then at H
2With N
2Under mixture reducing atmosphere condition, in microwave, high fire reacted after 10 minutes, and is cooling gradually, namely obtains sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 6kg example 7(1) sample, Low Density Polyethylene 30kg, polyethylene wax 1.2kg, tetrabutyl titanate 0.3kg, methacrylic acid certain herbaceous plants with big flowers ester 0.5kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 ℃, extrude through the twin screw extruder that rotating speed is 450r/min, air-cooled granulation is prepared from master batch.
(3) 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 aforementioned master batch 30kg, 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 synthetic Ca of difunctional light-converting agent
0.5Sr
0.25Ba
0.25F
2: Eu, La, Tb
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (12.5Kg), Sr (NO
3)
2, La
2O
3And Tb
2O
3(6.5Kg altogether), Ba (NO
3)
2(5.6Kg), Eu
2O
3(16.00g), NH
4F (20.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, La
2O
3And Tb
2O
3, add Ca (NO
3)
24H
2O, Sr (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 2.4% grinds, and then under CO reducing atmosphere condition, in microwave, high fire reacted after 20 minutes, and is cooling gradually, namely obtains sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 7kg example 8(1) sample, linear low density polyethylene 28kg, polyethylene wax 1.4kg, photostabilizer p-t-butylphenyl salicylate 3.5kg, 1.6kg antioxidant 1010, vinyltrimethoxy silane 2.25kg, bisphenol A type epoxy resin 1.2kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 180 ℃, extrude through the twin screw extruder that rotating speed is 350r/min, air-cooled granulation is prepared from master batch.
(3) 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 aforementioned master batch 30kg, 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 synthetic Ca of difunctional light-converting agent
0.70Sr
0.10Ba
0.10Hg
0.10F
2: Eu, Mn
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (28.8Kg), Sr (NO
3)
2, MnO and HgO (5.5Kg altogether), Ba (NO
3)
2(5.4Kg), Eu
2O
3(16.00g), NH
4F (25.6Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, MnO, HgO, add Ca (NO
3)
24H
2O, Sr (NO
3)
2And Ba (NO
3)
2Preparation 0.25mol/L solution A;
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 1.6% grinds, then at H
2With N
2Under mixture reducing atmosphere condition, 1000 ℃ of high-temperature roastings 2 hours, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 10kg example 8(1) sample, high density polyethylene(HDPE) 40kg, polyoxyethylene glycol 0.2kg and aluminate coupling agent 0.8kg, photostabilizer Resorcinol but benzoic ether 5kg, 2.5kg antioxidant 330, tetrabutyl titanate 1.5kg, vinyltriethoxysilane 2.5kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 170 ℃, extrude through the twin screw extruder that rotating speed is 380r/min, air-cooled granulation is prepared into master batch.
(3) 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 aforementioned master batch 30kg, 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 synthetic Ca of difunctional light-converting agent
0.7Ba
0.25Fe
0.05F
2: Eu, Ce
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (14.8Kg), Ba (NO
3)
2, CeO
2And FeO (5Kg altogether), Eu
2O
3(17.00g), NH
4F (11.5Kg), HNO
3(25ml).
A. first use HNO
3Dissolving Eu
2O
3, CeO
2And FeO, add Ca (NO
3)
24H
2O and Ba (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 2.8% grinds, then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, and 1200 ℃ of high-temperature roastings 2 hours, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 2.41kg example 10(1) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 0.4kg, photostabilizer salol 2kg, 1kg antioxidant 330, tetrabutyl titanate 0.5kg, novolac epoxy 0.2kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 130 ℃, extrude through the twin screw extruder that rotating speed is 100r/min, air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take metallocene linear polyethylene 100kg, Low Density Polyethylene 100kg, linear low density polyethylene 300kg, (2,2,6,6-tetramethyl--4-piperidines) imines 1kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 5kg, the 5kg irgasfos 168 takes aforementioned master batch 5.16kg, mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns, 160 ℃ of inflation film manufacturing machine melt temperatures, approximately 175 ℃ of die head temperatures.
Embodiment 11
(1) the synthetic Ca of difunctional light-converting agent
0.85Ba
0.1Fe
0.05F
2: Eu, Ce, Pr
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (17.6Kg), Ba (NO
3)
2, Pr
2O
3And CeO
2(3.2Kg altogether), Eu
2O
3(17.00g), NH
4F (11.5Kg), HNO
3(25ml).
A. first use HNO
3Dissolving Eu
2O
3, Pr
2O
3And CeO
2, add Ca (NO
3)
24H
2O and Ba (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaCl of addition agent weight of precipitate 8% grinds, then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, 1100 ℃ high-temperature roasting 2h hour, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
take 12.7kg example 11(1) sample, high density polyethylene(HDPE) 20kg, Zinic stearas 0.1kg, stearic acid pentaerythritol ester 0.2kg, polyoxyethylene glycol 0.1kg, aluminate coupling agent 0.5kg, photostabilizer ESCALOL 567 2.5kg, oxidation inhibitor 2, 6-ditertbutylparacresol 1.2kg, dioleoyl ethylene titanate 0.4kg, rosin modified phenolic resin 0.2kg, aniline formaldehyde resin 0.3kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 180 ℃, extrude through the twin screw extruder that rotating speed is 300r/min, air-cooled granulation, be prepared from master batch.
(3) production of light-converting film
Take polyvinyl chloride 550kg, (2,2,6,6-tetramethyl--4-piperidines) imines 5kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 6kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3kg, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester 3kg, take the aforesaid light master batch 51kg that turns, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns, 180 ℃ of inflation film manufacturing machine melt temperatures, approximately 150 ℃ of die head temperatures.
Embodiment 12
(1) the synthetic Ca of difunctional light-converting agent
0.6Sr
0.35Mg
0.05F
2: Eu, Mn, La
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (24.5Kg), Sr (NO
3)
2, MnO, La
2O
3And MgO (11.2Kg altogether), Eu
2O
3(31.00g), NH
4F (21.2Kg), HNO
3(30ml).
A. first use HNO
3Dissolving Eu
2O
3, MnO, La
2O
3And MgO, add Ca (NO
3)
24H
2O and Sr (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant KCl of addition agent weight of precipitate 7% grinds, then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, and 1200 ℃ of high-temperature roastings 3 hours, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 10kg example 12(1) sample, polyvinyl chloride 30kg, Zinic stearas 1.5kg, photostabilizer Resorcinol but benzoic ether 5kg, oxidation inhibitor 2,4,6-tri-butyl-phenol 2.5kg, tetrabutyl titanate 1.5kg, bisphenol A type epoxy resin 1.08kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 170 ℃, extrude through the twin screw extruder that rotating speed is 250r/min, air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take Low Density Polyethylene 600kg, (2,2,6,6-tetramethyl--4-piperidines) imines 5kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 5kg, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3kg, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester 3kg takes the aforesaid light master batch 15kg that turns, and mixes to form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
Embodiment 13
(1) the synthetic Ca of difunctional light-converting agent
0.75Sr
0.15Mg
0.05F
2: Eu, Sm, Dy
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (17.6Kg), Sr (NO
3)
2, Sm
2O
3And Dy
2O
3(3.2Kg altogether), Eu
2O
3(14.00g), NH
4F (17.5Kg), HNO
3(25ml).
A. first use HNO
3Dissolving Eu
2O
3, Sm
2O
3And Dy
2O
3, add Ca (NO
3)
24H
2O and Sr (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 6% grinds, and then under reducing atmosphere CO condition, in microwave, high fire reacted after 10 minutes, and is cooling gradually, namely obtains sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 8kg example 13(1) sample, high density polyethylene(HDPE) 20kg, polyoxyethylene glycol 1.0kg; photostabilizer dihydroxyphenyl propane sasapyrin 4kg; 2kg oxidation inhibitor 245, the different capryloyl titanic acid ester of isopropoxy three 1.09kg, bisphenol f type epoxy resin 2.8kg; above-mentioned materials sequentially is added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 170 ℃, extrude through the twin screw extruder that rotating speed is 400r/min; air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take Low Density Polyethylene 100kg, linear low density polyethylene 400kg, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, 2.5kg antioxidant 300, then take the aforesaid light master batch 30kg that turns mixes and forms with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
Embodiment 14
(1) the synthetic Ca of difunctional light-converting agent
0.6Sr
0.35Zn
0.05F
2: Eu, Cu
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (17.6Kg), Sr (NO
3)
2, ZnO and CuO (5.9Kg altogether), Eu
2O
3(15.00g), NH
4F (18.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, ZnO and CuO, add Ca (NO
3)
24H
2O and Sr (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 5% grinds, and then under reducing atmosphere CO condition, in microwave, high fire reacted after 20 minutes, and is cooling gradually, namely obtains sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 3.2kg example 14(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 0.5kg, photostabilizer salol 0.1kg, 0.1kg antioxidant 1010, tetrabutyl titanate 0.8kg, bisphenol A type epoxy resin 0.8kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 175 ℃, extrude through the twin screw extruder that rotating speed is 350r/min, air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take Low Density Polyethylene 100kg, linear low density polyethylene 400kg, succinic acid and (4-hydroxyl-2, the polymkeric substance of 2,6,6-tetramethyl--1-piperidine alcohols) 10kg, 2.5kg antioxidant 2246, then take the aforesaid light master batch 15kg that turns mixes and forms with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
Embodiment 15
(1) the synthetic Ca of difunctional light-converting agent
0.7Sr
0.15Ba
0.1Fe
0.05F
2: Eu
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (18.5Kg), Sr (NO
3)
2, FeO and Ba (NO
3)
2(2.6Kg altogether), Eu
2O
3(16.00g), NH
4F (21.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, FeO, add Ca (NO
3)
24H
2O, Sr (NO
3)
2And Ba (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 5% grinds, then under reducing atmosphere CO condition, 950 ℃ high-temperature roasting 2.5h hour, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 41.38kg example 15(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 0.6kg, photostabilizer dihydroxyphenyl propane sasapyrin 6.48kg, the 3kg antioxidant 1076, tetrabutyl titanate 0.8kg, 0.5kg Synolac 3150, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 ℃, extrude through the twin screw extruder that rotating speed is 450r/min, air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take Low Density Polyethylene 100kg, linear low density polyethylene 400kg, (2,2,6,6-tetramethyl--4-piperidines) imines 5kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 5kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2.5kg, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester 2.5kg, take again the aforesaid light master batch 15kg that turns, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
Embodiment 16
(1) the synthetic Ca of difunctional light-converting agent
0.75Sr
0.15Ba
0.1F
2: Eu
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (18.5Kg), Sr (NO
3)
2(4.5Kg), Ba (NO
3)
2(1.6Kg), Eu
2O
3(16.00g), NH
4F (21.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, add Ca (NO
3)
24H
2O, Sr (NO
3)
2And Ba (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 15% grinds, then under reductibility CO atmospheric condition, and 1000 ℃ of high-temperature roastings 1.5 hours, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 6kg example 7(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 2.17kg, photostabilizer salol 3kg, 1.5kg antioxidant 1010, γ-aminopropyl triethoxysilane 0.3kg, terpolycyantoamino-formaldehyde resin 0.5kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 ℃, extrude through the twin screw extruder that rotating speed is 450r/min, air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take Low Density Polyethylene 100kg, linear low density polyethylene 400kg, (2,2,6,6-tetramethyl--4-piperidines) imines 5kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 5kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2.5kg, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester 2.5kg, take again the aforesaid light master batch 15kg that turns, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
Embodiment 17
(1) the synthetic Ca of difunctional light-converting agent
0.55Sr
0.25Ba
0.2F
2: Eu
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (12.5Kg), Sr
2(NO
3)
3(6.5Kg), Ba (NO
3)
2(5.6Kg), Eu
2O
3(16.00g), NH
4F (20.5Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3, add Ca (NO
3)
24H
2O, Sr
2(NO
3)
3And Ba (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 4% grinds, then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, and 1050 ℃ of high-temperature roastings 1 hour, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 7kg example 17(1) sample, high density polyethylene(HDPE) 28kg, polyethylene wax 1.4kg, photostabilizer p-t-butylphenyl salicylate 3.5kg, 1.6kg antioxidant 1010, vinyl trichloro silane 0.8kg, bisphenol A type epoxy resin 1.22kg, urea-formaldehyde resin 1.0kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 180 ℃, extrude through the twin screw extruder that rotating speed is 350r/min, air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take Low Density Polyethylene 200kg, linear low density polyethylene 800kg, (2,2,6,6-tetramethyl--4-piperidines) imines 20kg, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester 10kg, then take the aforesaid light master batch 30kg that turns mixes and forms with the inflation film manufacturing machine blown film afterwards.Film thickness is 100 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
Embodiment 18
(1) the synthetic Ca of difunctional light-converting agent
0.65Sr
0.17Ba
0.18F
2: Eu, Tb
Take respectively Ca (NO by stoichiometric ratio
3)
24H
2O (28.8Kg), Sr (NO
3)
2, and Tb
2O
3(5.5Kg altogether), Ba (NO
3)
2(5.4Kg), Eu
2O
3(16.00g), NH
4F (25.6Kg), HNO
3(27ml).
A. first use HNO
3Dissolving Eu
2O
3And Tb
2O
3, add Ca (NO
3)
24H
2O, Ba (NO
3)
2, Sr (NO
3)
2Preparation 0.25mol/L solution A.
The NH of preparation 1mol/L
4The F solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues to stir 1 hour centrifugation, 100 ℃ of oven dry.
C. with the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 5% grinds, then under reducing atmosphere CO condition, and 1000 ℃ of high-temperature roastings 2 hours, cooling gradually, namely obtain sample.
Product at the exciting light spectrogram of ultraviolet region as shown in Figure 3, at the exciting light spectrogram of green Region as shown in Figure 4, at the utilizing emitted light spectrogram of blue light region as shown in Figure 5, at the utilizing emitted light spectrogram of red light district as shown in Figure 6.
(2) turn the preparation of light master batch
Take 10kg example 18(1) sample, polypropylene 40kg, polyethylene wax 1kg, photostabilizer salol 5kg, 2.5kg antioxidant 1010, tetrabutyl titanate 1.5kg, Synolac 0.5kg, 1.0kg epoxy resin 310, β-dimethyl-aminoethylmethacrylate 1.0kg, above-mentioned materials sequentially is added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 170 ℃, extrude through the twin screw extruder that rotating speed is 380r/min, air-cooled granulation is prepared from master batch.
(3) production of light-converting film
Take 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, take again the aforesaid light master batch 30kg that turns, mix and form with the inflation film manufacturing machine blown film afterwards.Film thickness is 80 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
The production of the blank canopy film of embodiment 19
Take respectively 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester 5kg, photostabilizer 2kg, antioxidant 1kg mixes and forms with the inflation film manufacturing machine blown film afterwards, wherein, film thickness is 80 microns, 175 ℃ of inflation film manufacturing machine melt temperatures, approximately 165 ℃ of die head temperatures.
The difunctional contrast that turns light canopy film and blank film of embodiment 20 is used
At first carry out three booths and build, each booth specification is the high 14m7m3.5m of being of length and width, then carries out two kinds of canopy films of difunctional light-converting film and blank film and covers, and applies carbon dioxide in the booth of the difunctional light-converting film of one of them use.Wherein the light-converting film canopy is above-mentioned example 1,10 and 15 light-converting film, and blank film is the blank film of above-mentioned example 19.Then according to the photosynthesis spectral signature of crop, the crop of having selected relatively to mate with above-mentioned light-converting film is: the leaf class is milk Chinese cabbage, leaf mustard, Japanese Plantula Brassicae chinensis, romaine lettuce; The melon and fruit class is eggplant, capsicum and fresh kidney beans.Before plantation, in three canopies, soil have carried out abundant mixing, and the weight of fertilising completes equally, and the watering amount of every day is basically identical, does not carry out any pesticide application.Concrete test kind, data logging and comparing result sees attached list 1 and table 2.The difunctional light-converting film of the present invention is applied in data logging such as the following table 1 of leafy vegetable plantation.The difunctional light-converting film of the present invention is applied in data logging such as the following table 2 of leaf melon or fruit type crops plantation.Stimulation ratio in table 1 and table 2 refers to use the output of difunctional light-converting film with respect to the output increment rate of the output of using blank film.
The plantation of table 1 leafy vegetable is contrast table as a result
The plantation of table 2 melon-fruit-like vegetable is contrast table as a result
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 (14)
1. plant cover cultivation methods, is characterized in that, utilizes difunctional light conversion film to make booth or mulch film, forms a plant-growth space; With plant growing in described growing space; Described difunctional light conversion film comprises film matrix, difunctional light-converting agent and auxiliary agent; The 0.01-20% that described difunctional light-converting agent weight is film weight; Auxiliary agent weight is the 0.1%-10% of film weight;
All the other are film matrix; It is Ca that described difunctional light-converting agent forms general formula
1-xN
xF
2: Eu, TM, wherein: 0≤x≤1, N is one or more in Ba, Zn, Sr, Mg, Hg and Fe, TM is selected from one or more in Sm, Cu, Pr, Tb, Ce, La, Dy, Mn and Ag.
2. plant cover cultivation methods according to claim 1, is characterized in that, alkaline-earth metal fluoride Ca
1-xN
xF
2Be monobasic alkaline-earth metal fluoride or binary alkaline-earth metal fluoride or polynary alkaline-earth metal fluoride.
3. plant cover cultivation methods according to claim 1, is characterized in that, described auxiliary agent is one or both in photostabilizer and oxidation inhibitor.
4. plant cover cultivation methods according to claim 1, is characterized in that, described film comprises light-converting agent master batch, film matrix and auxiliary agent; Described light-converting agent master batch comprises master batch matrix, difunctional light-converting agent and properties-correcting agent; Described properties-correcting agent weight is the 0.05%-10% of master batch weight; Difunctional light-converting agent weight is the 0.1-90% of master batch weight; In master batch, all the other are the master batch matrix.
5. plant cover cultivation methods according to claim 4, is characterized in that, described master batch matrix and film matrix are same material.
6. plant cover cultivation methods according to claim 4; it is characterized in that, described master batch matrix is one or more in Low Density Polyethylene, linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), polypropylene, ethylene-vinyl acetate resin, polyvinyl chloride.
7. plant cover cultivation methods according to claim 4, is characterized in that, the described difunctional light master batch that turns also comprises lubricant, and described lubricant weight is the 0.05-5% that turns light master batch weight.
8. plant cover cultivation methods according to claim 4, is characterized in that, described difunctional turning also comprises one or both in photostabilizer and oxidation inhibitor in the light master batch.
9. plant cover cultivation methods according to claim 4, 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.
10. plant cover cultivation methods according to claim 1, it is characterized in that, described film matrix is one or more in Low Density Polyethylene, linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), polypropylene, ethylene-vinyl acetate resin, polyvinyl chloride.
11. plant cover cultivation methods according to claim 1 is characterized in that, in growing process, discharges carbon dioxide in described growing space.
12. plant cover cultivation methods according to claim 11 is characterized in that, the carbon dioxide amount of discharging is the 0.01%-10% of growing space gas volume total amount.
13. plant cover cultivation methods according to claim 11 is characterized in that, the application time of carbonic acid gas is 6 o'clock to 20 o'clock every day.
14. plant cover cultivation methods according to claim 1 is characterized in that, described plant is farm crop.
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Cited By (11)
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| CN103314807A (en) * | 2013-07-05 | 2013-09-25 | 句容市张庙茶场 | Application of light conversion films in greenhouse tea planting |
| CN106941915A (en) * | 2017-03-24 | 2017-07-14 | 滁州恒盛农业科技有限公司 | A kind of method that Muscari botryoides is planted with Bifunctional light conversion thin |
| CN107556613A (en) * | 2017-09-01 | 2018-01-09 | 杭州异客科技有限公司 | A kind of ornamental flower greenhouse gardening method |
| CN107556611A (en) * | 2017-09-01 | 2018-01-09 | 杭州异客科技有限公司 | It is a kind of suitable for conversion film of vegetables greenhouse cultivation and preparation method thereof |
| CN107580919A (en) * | 2017-09-01 | 2018-01-16 | 杭州异客科技有限公司 | A kind of Dendrobium officinale planting device |
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| CN107726251A (en) * | 2017-09-01 | 2018-02-23 | 杭州异客科技有限公司 | A kind of light fixture |
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| CN103314807A (en) * | 2013-07-05 | 2013-09-25 | 句容市张庙茶场 | Application of light conversion films in greenhouse tea planting |
| CN106941915A (en) * | 2017-03-24 | 2017-07-14 | 滁州恒盛农业科技有限公司 | A kind of method that Muscari botryoides is planted with Bifunctional light conversion thin |
| CN107556613A (en) * | 2017-09-01 | 2018-01-09 | 杭州异客科技有限公司 | A kind of ornamental flower greenhouse gardening method |
| CN107556611A (en) * | 2017-09-01 | 2018-01-09 | 杭州异客科技有限公司 | It is a kind of suitable for conversion film of vegetables greenhouse cultivation and preparation method thereof |
| CN107580919A (en) * | 2017-09-01 | 2018-01-16 | 杭州异客科技有限公司 | A kind of Dendrobium officinale planting device |
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| CN107674379A (en) * | 2017-09-01 | 2018-02-09 | 杭州异客科技有限公司 | A kind of LED light bar |
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| CN107726251A (en) * | 2017-09-01 | 2018-02-23 | 杭州异客科技有限公司 | A kind of light fixture |
| CN110962418A (en) * | 2019-11-21 | 2020-04-07 | 徐蕾 | Yield-increasing and high-permeability film, multilayer yield-increasing and high-permeability film and preparation method thereof |
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