CN1442463A - Agricultural long effect antimist film and its preparation method - Google Patents

Agricultural long effect antimist film and its preparation method Download PDF

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Publication number
CN1442463A
CN1442463A CN03117609A CN03117609A CN1442463A CN 1442463 A CN1442463 A CN 1442463A CN 03117609 A CN03117609 A CN 03117609A CN 03117609 A CN03117609 A CN 03117609A CN 1442463 A CN1442463 A CN 1442463A
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film
antifogging film
pva
agricultural long
acting
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CN1219016C (en
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李坤福
徐闻
罗利琴
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Sichuan University
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Sichuan University
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

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  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Protection Of Plants (AREA)

Abstract

A durable antifogging film for agricultural purpose is composed of the basic film layer prepared from polyethyene and its copolymer, the adhesive layer prepared from EVA through alcoholysis to obtain EVOH layer, and the antifogging layer of modified polyvinyl alcohol prepared from polyvinyl alcohol, 3-methylacrylyloxy propyltrimethoxy silane (0.5-30 wt%), catalyst (0.01-10 wt%) and cross-linking agent (0.1-15 wt%). Its preparing process includes sequentially coating said three layers, and ultraviolet radiation for 0.2-5 min.

Description

Agricultural long-acting antifogging film and preparation method thereof
One, technical field
The present invention relates to a kind of agricultural long-acting antifogging film and preparation method thereof.Specifically, the present invention relates to be coated with layer of adhesive on a kind of polyethylene and the multipolymer basement membrane thereof, be coated with the modified polyvinyl alcohol film of one deck anti-fog layer again.
Two, background technology
The effect that agricultural greenhouse is planted in the agriculture production has been well-known.Compare with general open-air plantation, it has high yield, and precocity is managed advantages such as easy, and very big economic benefit and social benefit are arranged.Its abundant raw material of agricultural polyethylene film, handling ease, low price is the maximum kind of current use.But under the high humidity of agricultural polyethylene film in canopy, when outside temperature is lower than the dew point of water vapor, meeting dewfall on the canopy film.Tiny dewdrop makes that illumination level reduces greatly in the canopy, is unfavorable for growth and development of plants, and easily causes water droplet to be dropped in producing disease on the plant.For preventing dewfall, often adopt and in polyethylene, mix antifogging agent or make antifogging film in the method for polyethylene film surface coated antifogging agent.These antifogging agents all are low molecular tensio-active agents, and are poor with poly compatibility, very easily lose with current, cause the antifog property can not be lasting.In order to make antifogging film, adopted in membrane surface and be coated with the method for hydrophilic high molecular material to make long-lasting antifogging film with long-term antifog property.Hydrophilic macromolecule is the macromolecular material that contains volume hydrophilic radical (as carboxyl, hydroxyl, amino, carboxylate group, sulfonic group, sulphonate-base, phosphate etc.) in the molecule.From the source of raw material, antifog property, film-forming properties, film toughness, the transparency, aspects such as manufacturability consider that polyvinyl alcohol (PVA) has outstanding advantage.It has good water-solubility, its aqueous solution can be on many material surfaces coating film forming.But, just because of the wetting ability of polyvinyl alcohol makes its water tolerance deficiency when reality is used; Do not have enough bond strengths with some base material (for example polyolefine material) compound tense in addition, limited it and made the practicality of antifogging film.In addition, the fusing point and the decomposition temperature of polyvinyl alcohol are close, can not be with general working method as extruding blowing (except that the special blow moulding of polyvinyl alcohol), the processing of methods such as injection, and many waters solution coat method, this just brings the aqueous solution to filter, and adds defoamer, softening agent, and problem such as viscosity stabilizer, prescription and technology are comparatively numerous and diverse.In order to overcome above deficiency, many solutions had been proposed once.For example, in the method that proposes, Corona discharge Treatment is carried out on the polyethylene film surface in European patent EP 0770658, its surface tension is reached more than 36 dynes per centimeter, the dried thickness of coating one deck is 0.01～10g/m on this surface then 2Mineral colloid (particle diameter 5～200nm) disperses liquid layers, after the drying again on this mineral colloid layer the dried thickness of coating one deck be 0.01～10g/m 2PVA solution, promptly getting a kind of after the drying is three layers of compound antifogging film of anti-fog layer with PVA.It is said that this antifogging film has good wear resistance and the antifog property behind the high temperature ageing.The interlayer adhesion of this class antifogging film is the basis by physical adhesion power and anchorage effect.In drying regime perhaps suitable bounding force is arranged, but the bounding force under dampness can reduce greatly then, and antifogging film uses under dampness exactly.In addition, unmodified PVA is after pyroprocessing, and degree of crystallinity increases, and the free hydroxyl number reduces, and water-intake rate reduces, and can reduce the antifog property of PVA film again.And, the polyethylene surface after corona treatment, its surface tension can be replied in time, must be coated with PVA as early as possible, is subjected to some restrictions on the technology.Therefore this method also has improved necessity.In world publication PCT/WO 01/17770, in order to improve the water tolerance of PVA, adopted special water tolerance PVA to make raw material, and in PVA coating fluid prescription, used zirconium compounds to make catalyzer.It is crosslinked that the zirconium compounds catalyzer has the PVA of making, and improves the fusible effect between its water tolerance and enhancing and basement membrane.But the zirconium compounds catalyzer must just have effect, this patent under comparatively high temps be to be basement membrane with the polyethylene terephthalate film, uses this catalyzer to be fine.But being used for polyethylene based film then can not use because of its temperature of reaction is too high.
Three, summary of the invention
The objective of the invention is provides a kind of agricultural long-acting antifogging film and preparation method thereof at the deficiencies in the prior art.
A large amount of hydroxyls is arranged in the PVA molecule, and the existence of these hydroxyls makes it have enough wetting abilities, and it can absorb a certain amount of moisture, and water is sprawled from the teeth outwards come and formed the layer of even moisture film, is beneficial to light and sees through.Yet just because of great amount of hydroxy group is arranged, make it very easily produce interaction of hydrogen bond and cause PVA soltion viscosity poor stability, and make hydroxyl can not be exposed to film coated surface, hinder the wetting of moisture and sprawl, do not reach good anti-fog effect at intermolecular and intramolecularly.Therefore must introduce some and hinder the group that hydrogen bonds form in the PVA molecular chain, stable and improve its antifog property with increased viscosity, this is to carry out one of purpose of modification to PVA.Two of modification purpose is to introduce polymerizable double bond on the PVA molecular chain, so that in the photostage of back process, under the effect of light trigger or photosensitizers, make the ethylene/vinyl alcohol copolymer produce chemical bond and connect with PVA and polyethylene, increase the bond strength under the bond strength, particularly hygrometric state.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The agricultural long-acting antifogging film is a three-layer composite structure, wherein one deck is that polyethylene and multipolymer thereof are basement membrane, on basement membrane, be coated with layer of adhesive, be coated with the modified polyvinyl alcohol film of one deck anti-fog layer again, obtain the antifog property of the agricultural long-acting film that interlayer connects with chemical bond through ultraviolet light irradiation.
Polyethylene and multipolymer basement membrane thereof are new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), the multipolymer of linear low density polyethylene and/or ethene and other d-alkene, film thickness 〉=20 μ m can have an amount of protective agent and ultraviolet absorbers in the film.
Tackiness agent is the EVOH that ethylene-vinyl acetate copolymer (EVA) makes through complete alcoholysis, and vinyl acetate content is 14～42% among the EVA, and the melt index of EVA (MI) is 2～400.
The PVA polymerization degree in the modified PVA can be 1000～3000, and alcoholysis degree can be 80～100%.
Properties-correcting agent in the modified PVA is the 3-methyl allyl acyloxypropyl trimethoxysilane, and its consumption is 0.5～30% of a PVA weight.
Catalyzer in the modified PVA solution is aminated compounds R 1R 2R 3N, R 1, R 2, R 3Be respectively H, C 1～C 4At least a in the aliphatic alkyl, as methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, n-propyl amine, di-n-propyl amine, three n-propyl amine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, isobutylamine, diisobutyl amine, tert-butylamine, and/or at least a in the methylethyl amine.
Linking agent in the modified PVA solution is a hydrogen peroxide, Sodium Persulfate, at least a in Potassium Persulphate and/or the ammonium persulphate.
The preparation method of agricultural long-acting antifogging film
(1) add Photoepolymerizationinitiater initiater or photosensitizers in tackiness agent EVOH, consumption is 0.1～10% of an EVOH weight, is made into concentration and is 0.1～20% organic solution.
(2) coating machine of tackiness agent organic solution with any form is applied on polyethylene and the multipolymer basement membrane thereof seasoning or in 60～80 ℃ of warm air dryings of temperature 1～2 hour.
(3) in the PVA aqueous solution, add catalyzer 0.01～10%, properties-correcting agent 0.5～30%, linking agent 0.1～15% is made into concentration 1～10% aqueous solution in the lump, is applied on the binder layer, in 60～80 ℃ of warm air dryings of temperature 1～2 hour.
(4) dried coating is placed wavelength 300～420nm, light intensity 5～20mW/cm 2UV-light under, irradiation 0.2～5 minute obtains the antifogging film of the agricultural long-acting three-decker that interlayer connects with chemical bond.
Photoepolymerizationinitiater initiater or photosensitizers used in the adhesive formula are benzophenone, benzil, benzoin methyl ether, Benzoin ethyl ether, benzoin isobutyl ether, 2, at least a in 2-dimethoxy-2-phenyl methyl phenyl ketone, EAQ and/or the Photoactive titania.
The organic solvent of using in the tackiness agent is a benzene, toluene, at least a in dimethylbenzene and/or the Fatty Alcohol(C12-C14 and C12-C18).
Antifog property and fusible test
1. the test of antifog property: with a 500ml beaker, dress water places 60 ℃ water bath with thermostatic control to from 1 centimetre of rim of a cup.After reaching thermostat temperature, a slice is covered rim of a cup greater than the antifogging film sample of rim of a cup diameter, antifogging film is faced down.After 15 minutes, read the area percent of opaque section, be designated as mist area occupation ratio (%) with visual method.The mean value of 5 samples is got in each test.
2. fusible test: the polyvinyl alcohol face at the antifogging film sample depicts 10 * 10 grids with sharp blade, the about 2 * 2mm of each lattice.Note during portrayal polyethylene based film to be carved and wear.Adhere on the grid that depicts with a slice Pressuresensitive Tape, from an end Pressuresensitive Tape is peeled away by the speed of about 300mm/min with 180 ° of angles then.Read the number of squares that the PVA film is stripped off, be the rate of peeling off (%).The mean value of 5 samples is got in each test.Back sample destruction form peeled off in record simultaneously, and the common damage form has basement membrane/PVA interface peel to destroy, and PVA layer cohesive failure mixes and destroy (having the destruction of above-mentioned two kinds of forms concurrently), and adhesive tape/PVA interface peel destroys.
Four, embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this; present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
With EVOH28 (KE-10 by SUMITOMO CHEMICAL chemical company makes through complete alcoholysis) 2 gram and photosensitizers (1) benzophenone; (2) benzil, (3) benzoin methyl ether, (4) EAQ, (5) 2,2-dimethoxy-2-phenyl methyl phenyl ketone, each 0.06 gram adds benzene 100ml and dissolves in 60 ℃ of water-baths, is mixed with five kinds of binder solutions respectively.With the glass rod is that scraper is applied on the thick commercially available high-pressure polyethylene plastic film for agricultural use of 30 μ m, and drying is 1 hour in 60 ℃ of baking ovens.In a beaker, restrain PVA1799 (Sichuan vinylon plant product) in addition, after the water 150ml heating for dissolving, add 0.1g/ml dimethylamine agueous solution 5ml and 1 gram 3-methyl allyl acyloxypropyl trimethoxysilane 10.Insulated and stirred obtained the modified PVA coating fluid in 18 hours in 30 ℃ of water-baths.With this modified PVA coating fluid separate application to the above-mentioned surface that has been coated with bonding coat, in 60 ℃ of baking ovens dry 2 hours.Dried film is at wavelength 300～420nm, light intensity 8mW/cm 2Down irradiation 60 seconds of ultraviolet lamp, obtain the antifogging film of the agricultural long-acting three-decker that interlayer connects with chemical bond.This film mist area occupation ratio that records and the rate of peeling off are known clearly and are shown in Table 1.
Embodiment 2
Adding 2 gram EVOH 33 (EVA 150 by Du Pont-Mitsui polymer chemistry company makes through complete alcoholysis) and 2 gram EVOH 40 (the EVA 40W by E.I.Du Pont Company makes through complete alcoholysis) and Photoactive titania (the product HR-3 of Zhejiang Zhoushan Tomorrow Nanomaterials Co., Ltd) 0.03 in two beakers respectively restrains, with the dissolving of 70ml toluene and 30ml Virahol and after ultrasonic dispersing, make the bonding coat coating fluid.This binder solution is applied on the thick commercially available high-pressure polyethylene plastic film for agricultural use of 30 μ m, and drying is 1 hour in 60 ℃ of baking ovens.In a beaker, add water 170ml heating for dissolving in addition, add the Di-n-Butyl Amine aqueous solution (0.003g/ml) 15ml with 10 gram PVA1799,3-methyl allyl acyloxypropyl trimethoxysilane 0.5 gram, stirring at room made the modified PVA coating fluid in 24 hours.This modified PVA coating fluid is applied on above-mentioned the filming, and drying is 1.5 hours in 70 ℃ of baking ovens.Dried film is at wavelength 300～420nm, light intensity 10mW/cm 2Down irradiation 60 seconds of ultraviolet lamp, obtain the antifogging film of the agricultural long-acting three-decker that interlayer connects with chemical bond.Record this film mist area occupation ratio and be respectively 3.88% (EVOH 33) and 4.0% (EVOH 40); The rate of peeling off is respectively 38.2% (EVOH 33) and 47.8% (EVOH 40).
Embodiment 3
With 2 gram EVOH, 33,0.07 gram benzils, 86ml dimethylbenzene, the 14ml propyl carbinol is mixed with binder solution, and it is applied on the thick commercially available high-pressure polyethylene plastic film for agricultural use of 30 μ m, and drying is 1 hour in 60 ℃ of baking ovens.With three beakers, add 10 gram PVA1788 respectively, PVA1795 in addition, after PVA1799 and the water 150ml heating for dissolving, each adds diethylamine aqueous solution (0.01g/ml) 5ml, 3-methyl allyl acyloxypropyl trimethoxysilane 0.5 gram, stirring at room obtains the modified PVA coating fluid after 24 hours.It is applied on above-mentioned the filming, and drying is 1 hour in 80 ℃ of baking ovens.Dried film is at wavelength 300～420nm, light intensity 12mW/cm 2(365nm) ultraviolet lamp shone 60 seconds down, obtained the antifogging film of interlayer with the agricultural long-acting three-decker of chemical bond connection.Record this film mist area occupation ratio and be respectively 83% (PVA1788), 13.8% (PVA1795) and 2.0% (PVA1799); The rate of peeling off is respectively 36.4% (PVA1788), and 41.6% (PVA1795) and 50.4% (PVA1799), collapse mode are the PVA cohesive failure.
Embodiment 4
With 2 gram EVOH, 33,0.03 grams 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 90ml toluene, 10ml methyl alcohol is mixed with binder solution, is applied on the thick commercially available high-pressure polyethylene plastic sheeting for farm use of 30 μ m.Drying is 1 hour in 60 ℃ of baking ovens.With two beakers, get 10 gram PVA1799 respectively in addition, 170ml water after the heating for dissolving, adds the thyl methyl amine aqueous solution (0.05087g/ml) 5ml and 3-methyl allyl acyloxypropyl trimethoxysilane, stirring at room 24 hours.Toward the hydrogen peroxide that wherein adds 1.5ml 30% in a glass; In another cup, add Potassium Persulphate 0.15 gram.Stir evenly the back separate application on above-mentioned filming, 80 ℃ of dryings 1 hour.Dry coating is placed wavelength 300～420nm, and the ultraviolet lamp of light intensity 10mW/cm shone 30 seconds down, obtained the antifogging film of the agricultural long-acting three-decker of chemical bond connection.Record this film mist area occupation ratio and be respectively 0.04% (H 2O 2) and 0.28% (Potassium Persulphate); The rate of peeling off is respectively 49% (H 2O 2) and 19.6% (Potassium Persulphate).Collapse mode all is the PVA cohesive failure.
Reference examples 1
PVA1799 and water heating for dissolving are mixed with solution about 5%, and being applied to thickness is on the high-pressure polyethylene plastic sheeting for farm use of 30 μ m, in 80 ℃ of baking ovens dry 1 hour.Gained film AUTOMATIC ZONING.Has no practical value.
Reference examples 2
With 2 gram EVOH 33,70ml toluene, the 30ml Virahol is mixed with the binder layer coating fluid, and being applied to thickness is on the high-pressure polyethylene basement membrane of 30 μ m, and drying is 1 hour in 60 ℃ of baking ovens.In a beaker, restrain PVA1799 in addition with 10, water 162ml, 5ml concentration is the dimethylamine agueous solution of 0.01g/ml, 0.5 gram 3-methyl allyl acyloxypropyl trimethoxysilane, reaction was applied on the film that is coated with bonding coat after 24 hours in 30 ℃ of water-baths, obtained three layers of composite membrane after dry 1 hour in 80 ℃ of baking ovens.It peels off rate is 100%.This film is the automatic shrinkage of PVA layer when antifog property mensuration, strips off.In the PVA layer water soluble of taking off.
The performance of gained antifogging film behind the different photosensitizerss of adding among table 1 EVOH
Photosensitizers Benzophenone Benzil Benzoin methyl ether EAQ 2,2-dimethoxy-2-phenyl methyl phenyl ketone
Mist area occupation ratio (%) ???2.04 ???0.38 ????0.65 ???0.72 ????????0.36
Peel off rate (%) ???90.6 ???96.2 ????97.6 ???98.4 ????????98.4
Collapse mode Mix and destroy Mix and destroy Mix and destroy Mix and destroy Mix and destroy

Claims (10)

1, a kind of agricultural long-acting antifogging film, this film is a three-layer composite structure, wherein one deck is polyethylene and multipolymer basement membrane thereof, it is characterized in that being coated with on the basement membrane layer of adhesive, be coated with one deck modified polyvinyl alcohol anti-fog layer again, obtain the agricultural long-acting antifogging film that interlayer connects with chemical bond through ultraviolet light irradiation.
2, according to the described agricultural long-acting antifogging film of claim 1, it is characterized in that basement membrane is a new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), the multipolymer of linear low density polyethylene and/or ethene and other d-alkene, thickness 〉=20 μ m can have an amount of protective agent and ultraviolet absorbers in the film.
3, according to the described agricultural long-acting antifogging film of claim 1, it is characterized in that tackiness agent is the ethylene-vinyl alcohol copolymer (EVOH) that ethylene-vinyl acetate copolymer (EVA) makes through complete alcoholysis, vinyl acetate content 14～42% among the EVA, and the melt index of EVA (MI) is 2～400.
4, according to the described agricultural long-acting antifogging film of claim 1, the polymerization degree that it is characterized in that the PVA in the modified PVA is 1000～3000, and alcoholysis degree is 80～100%.
5, according to the described agricultural long-acting antifogging film of claim 1, it is characterized in that the properties-correcting agent in the modified PVA is the 3-methyl allyl acyloxypropyl trimethoxysilane, consumption is 0.5～30% of a PVA weight.
6,, it is characterized in that the catalyzer in the modified PVA is aminated compounds R according to the described agricultural long-acting antifogging film of claim 1 1R 2R 3N, R 1, R 2, R 3Be respectively H, C 1～C 4Aliphatic alkyl at least a, its consumption is 0.01～10% of a PVA weight.
7,, it is characterized in that the linking agent in the modified PVA is a hydrogen peroxide, Sodium Persulfate, Potassium Persulphate, and/or at least a in the ammonium persulphate according to the described agricultural long-acting antifogging film of claim 1.
8, according to the preparation method of the described agricultural long-acting antifogging film of claim 1～7, it is characterized in that:
(1) add Photoepolymerizationinitiater initiater or photosensitizers in tackiness agent EVOH, consumption is 0.1～10% of an EVOH weight, is mixed with concentration and is 0.1～20% organic solution,
(2) coating machine of tackiness agent organic solution with any form is applied on the basement membrane, seasoning or in 60～80 ℃ of warm air dryings of temperature 1～2 hour,
(3) in the PVA aqueous solution, add catalyzer 0.01～10% (weight), properties-correcting agent 0.5～30% (weight), linking agent 0.1～15% (weight), be made into the aqueous solution that concentration is 1～10% (weight) in the lump, be coated on the binder layer, in 60～80 ℃ of warm air dryings of temperature 1～2 hour
(4) dried coating is placed wavelength 300～420nm, light intensity is 5～20mW/cm 2UV-light under, irradiation 0.5～5 minute obtains the antifogging film of the agricultural long-acting three-decker that interlayer connects with chemical bond.
9, according to the preparation method of the described agricultural long-acting antifogging film of claim 8, it is characterized in that Photoepolymerizationinitiater initiater or photosensitizers are benzophenone, benzil, benzoin methyl ether, Benzoin ethyl ether, benzoin isobutyl ether, 2, at least a in 2-dimethoxy-2-phenyl methyl phenyl ketone, EAQ and/or the Photoactive titania.
10, according to the preparation method of the described agricultural long-acting antifogging film of claim 8, the organic solvent that it is characterized in that tackiness agent is a benzene, toluene, at least a in dimethylbenzene and/or the fatty alcohol.
CNB031176097A 2003-04-04 2003-04-04 Agricultural long effect antimist film and its preparation method Expired - Fee Related CN1219016C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103190321A (en) * 2013-03-31 2013-07-10 青岛农业大学 Agricultural anti-grass non-woven mulch
CN105017883A (en) * 2014-04-30 2015-11-04 晟通科技集团有限公司 Anti-fog coating and preparing method thereof
CN109180983A (en) * 2018-09-25 2019-01-11 江南大学 A kind of long-acting anti-fog and antifrost film and preparation method thereof
CN114845545A (en) * 2019-12-25 2022-08-02 富士胶片株式会社 Agricultural lighting component and agricultural production box

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103190321A (en) * 2013-03-31 2013-07-10 青岛农业大学 Agricultural anti-grass non-woven mulch
CN103190321B (en) * 2013-03-31 2014-11-05 青岛农业大学 Agricultural anti-grass non-woven mulch
CN105017883A (en) * 2014-04-30 2015-11-04 晟通科技集团有限公司 Anti-fog coating and preparing method thereof
CN109180983A (en) * 2018-09-25 2019-01-11 江南大学 A kind of long-acting anti-fog and antifrost film and preparation method thereof
CN109180983B (en) * 2018-09-25 2021-08-13 江南大学 Long-acting antifogging and antifrosting film and preparation method thereof
CN114845545A (en) * 2019-12-25 2022-08-02 富士胶片株式会社 Agricultural lighting component and agricultural production box
CN114845545B (en) * 2019-12-25 2023-09-22 富士胶片株式会社 Agricultural lighting component and box for agricultural products

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