CN1934207B - Light-blocking agent for agricultural use - Google Patents
Light-blocking agent for agricultural use Download PDFInfo
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- CN1934207B CN1934207B CN2005800086162A CN200580008616A CN1934207B CN 1934207 B CN1934207 B CN 1934207B CN 2005800086162 A CN2005800086162 A CN 2005800086162A CN 200580008616 A CN200580008616 A CN 200580008616A CN 1934207 B CN1934207 B CN 1934207B
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Abstract
Disclosed is a light-blocking agent for agricultural use which is applied to a resin film for agricultural use and forms a light-blocking coating film thereon. Specifically, this light-blocking agent is used for forming an inorganic coating film on an agricultural house or the like for blocking sunlight. The inorganic coating film is formed as a durable light-blocking layer using a resin emulsion as a binder and blending an inorganic matter such as calcium carbonate or titanium oxide thereinto. This light-blocking coating film is resistant to water such as rainwater, and can be easily removed with an alkaline remover if it is no longer necessary.
Description
Technical field
The present invention relates to be applicable to that employed agricultural is with the light-blocking agent for agricultural use of film in greenhouse cultivation or the tunnel cultivation.
Background technology
About the cultivation of greenhouse cultivation or tunnel, for the crop of cultivating in the film booth in agricultural, exist strong excessively as if the solar ray of transmission, can be to dysgenic situation such as burn as deposits yields.Especially; In order to prevent burning of summer crop, be employed in agricultural with covering the method that shading net (thin slice) carries out shading on the booth, perhaps; Through inorganicss such as lime are dispersed in the water, it is sprayed at agricultural with forming the method that the inorganics film carries out shading on the film booth.
But, for example cover in the method for shading net (thin slice) on the film booth in agricultural, have following shortcoming: itself costs an arm and a leg shading net, and can not carry out installation and removal, labor intensive simply.In addition, carry out in the method for shading, have following shortcoming: be difficult on film, be coated with equably shading film, and the film of inorganicss such as lime is washed away easily when rainfall, have to spray repeatedly at film through inorganicss such as formation lime.
Therefore, proposed recently to use atomizer agricultural with film on the spraying coating contain pigment shading with coating (opaque paint), the formation shading is filmed, carry out the method (patent documentation 1) of shading.This agricultural with film on the method for spray coated opaque paint use the white aqueous emulsion paint contain the pigment that is adjusted to particular viscosity, shading is filmed and can be formed on the film well, but the persistence of filming is not enough, and can not easily remove and film.
When not needing this shading to film, must these opaque paints that is coated on the film be removed.But the emulsion coatings that these formation are filmed itself is not to be the prescription blended according to can removing when not required.For example, in the winter time, when needing the seeing through of solar ray in the booth, must use the brute force that comprises tensio-active agent to remove liquid or organic solvent etc. and remove shading and film, perhaps lay new agricultural and use film.
Patent documentation 1: the spy opens the 2002-119148 communique
The problem that invention will solve
In view of the above problems; The objective of the invention is to; A kind of light-blocking agent for agricultural use is provided; It is as being coated on agricultural with the opalizer on the resin film, when through when agricultural is carried out shading with the film that forms the inorganics of white pigment on the booth etc., can form and is not easy to be washed away, make shading to film to have persistence and film in the shading that can use alkaline remover simply to remove when not required by rainwater etc.
Carried out positive research in order to address this problem; As a result, the inventor finds: using resin emulsion as wedding agent, and the inorganics that mixes 2 kinds of different-grain diameters therein forms under the situation of light shield layer; Can obtain that rainwater etc. is had water tolerance; And when not required, can remove the shading that liquid removes simply through alkalescence and film, as covering the inorganic thin film of agricultural with greenhouse film.
In addition; The inventor also finds: use the vinyl chloride-based resin film as the situation of agricultural with greenhouse film under; The acrylic resin that forms at the monomer copolymerization of film surface coating and hydroxyl forms films; Then coating can be used as white pigment inorganics with the aqueous resin emulsion, under the situation of the light-blocking agent for agricultural use formation light shield layer that alkaline remover is removed easily; It is good to obtain in long-time persistence, and can film through the shading that alkaline remover is removed when not required.
The inventor also finds; Use vinyl chloride-based resin film or ethylene series resin film as the situation of agricultural with resin film under; When using the agricultural that in resin film, contains the bulky amine compounds to use resin film; Be coated on shading that the opalizer on the film surface forms film can be in long-time the maintenance persistence, and remove simply can using alkalescence to remove liquid when not required.
The present invention is based on these new solution completion.
Summary of the invention
Therefore; First embodiment of the present invention is a kind of light-blocking agent for agricultural use that contains the shading coating fluid; This shading coating fluid comprises inorganics, resin emulsion, as the water of aqueous solvent; It is characterized in that: the ratio of resinous principle and inorganics; With the solids component ratio count 1: 0.3～1: 15, inorganics uses median size less than the inorganics of 1 μ m and two kinds of inorganicss of the inorganics more than the median size 1 μ m, and median size less than the ratio of the inorganics of 1 μ m and inorganics more than the median size 1 μ m in 1: 0.5～2 scope.
In addition; Second embodiment of the present invention is a kind of light-blocking agent for agricultural use; It is characterized in that: be coated with on the face of opalizer at least one with the vinyl chloride-based resin film of agricultural, the acrylic resin that the monomer copolymerization of coating and hydroxyl forms forms and films, and said light-blocking agent for agricultural use contains organic/inorganic substance and resin emulsion; Be coated on this coated surface and form light shield layer, and use alkaline remover can remove formed light shield layer.
In addition, the 3rd embodiment of the present invention is a kind of light-blocking agent for agricultural use, it is characterized in that: coat contain the bulky amine based compound agricultural with on the resin film, contain organic/inorganic substance and resin emulsion, formed light shield layer can be removed through alkaline remover.
More particularly; The present invention relates to a kind of light-blocking agent for agricultural use; It is characterized in that: agricultural use resin film as the situation of agricultural with the vinyl chloride-based resin film under; The bulky amine based compound that contains 0.05～0.3 weight part, and be under the situation of agricultural with the ethylene series resin film, the bulky amine based compound of 0.05～2 weight part contained.
In the case, more preferably a kind of light-blocking agent for agricultural use is characterized in that: agricultural uses the ethylene series resin film to be multilayered structure, and in the skin that has been coated with opalizer, contains the bulky amine based compound at least.
More particularly; The present invention relates to a kind of light-blocking agent for agricultural use; It is characterized in that: inorganics is to be selected from least a in lime carbonate, titanium oxide, titanium white, talcum, clay, silicon oxide, mica and the permanent white, and preferred inorganics is lime carbonate or titanium oxide.
In addition, more particularly, the present invention relates to a kind of light-blocking agent for agricultural use, it is characterized in that: resin emulsion is that resinous principle is the aqueous resin emulsion of acid value 30～300, and the resin median size is 0.01～0.5 μ m.
In addition, another embodiment of the present invention is the coating process of light-blocking agent for agricultural use, it is characterized in that: be coated with above-mentioned various light-blocking agent for agricultural use, the light shield layer that formation can use alkaline remover to remove.
Utilize the resulting shading of light-blocking agent for agricultural use provided by the invention to film,, can obtain long shaded effect even when meeting with rainfall etc., film and also can not run off.In addition, also has following advantage: when not needing shading to film, needn't lay new agricultural and use resin film, use alkalescence to remove liquid and just can remove simply.
Particularly in first embodiment of the present invention; Water through using two kinds of different inorganicss of resin emulsion, median size and aqueous solvent is as shading coating fluid composition; And with the ratio of resinous principle and inorganics be controlled in solids component than specific scope in; Wherein, particularly, can make resulting shading film and have water tolerance through using the different inorganics of a certain proportion of median size.Therefore, even when meeting with rainfall etc., filming of inorganics also can not be run off, and can obtain long shaded effect.
In addition; In second embodiment of the present invention; Its characteristic especially is: the agricultural as the coating light-blocking agent for agricultural use use the vinyl chloride-based resin film, this agricultural with the vinyl chloride-based resin film on the coating of formation and the acrylic resin that forms of hydroxyl monomer copolymerization as the bottom of opalizer.Utilize this bottom, opalizer can be formed uniformly on this film, and the persistence that formed shading is filmed is good.
In addition; In the 3rd embodiment of the present invention; Its characteristic especially is, uses the resin film that contains the bulky amine based compound to use resin film as the agricultural of coating opalizer, through using described resin film; Make opalizer on this film, be formed uniformly shading and film, formed shading is filmed and is had good persistence.
Preferred forms
Below, the present invention will be described in more detail based on each embodiment.
The inorganics that adds in order to ensure opacifying property that is comprised in the light-blocking agent for agricultural use of each embodiment provided by the invention can be enumerated out lime carbonate, titanium oxide, titanium white, talcum, clay, silicon oxide, mica and permanent white etc.Wherein, especially preferably use lime carbonate or titanium oxide.In addition, also can as required the inorganics more than two kinds be mixed use.
About these inorganicss, in first embodiment of the present invention, two kinds of inorganicss that can median size is different mix use.
Particularly, when the difference of its particle diameter is benchmark with 1 μ m, can be that two kinds of inorganicss combinations more than the 1 μ m are used less than the inorganics of 1 μ m and median size with median size.The peak of median size is about 100 μ m.
Median size less than the inorganics of 1 μ m be coated on resin emulsion as wedding agent agricultural with the situation on the greenhouse film under; Be distributed in the resin emulsion with the subparticle shape; Thereby the firm inorganics of formation is filmed on film, can improve its water tolerance.But, but be difficult to remove when not required.
On the other hand, median size be the above inorganics of 1 μ m be coated on resin emulsion as wedding agent agricultural with the situation on the greenhouse film under, water tolerance is poor.
Therefore, in the present invention, use the two, can keep the balance of water tolerance and removing property through mixing.The inventor's result of study finds, in order to ensure as agricultural with the water tolerance of shading coating fluid and removing property, median size less than the inorganics of 1 μ m and median size be more than the 1 μ m inorganics than in 1: 0.5～2 scope for good.
That is, the ratio of mixture that is the inorganics more than the 1 μ m less than inorganics and the median size of 1 μ m when median size is less than 0.5 the time, and is insufficient with the water tolerance of shading coating fluid as agricultural, but surpassing at 2 o'clock, and water tolerance is abundant, but removing property deficiency.As the different inorganics of these median sizes, can select above-mentioned various inorganics, wherein preferably use lime carbonate or titanium oxide.
On the other hand, in the of the present invention second and the 3rd embodiment, the particle diameter of inorganics is not had special restriction, can be widely used from median size is the inorganics about 100 μ m for the inorganics less than 1 μ m to median size.In addition, when median size be coated on resin emulsion less than the inorganics of 1 μ m as wedding agent agricultural with greenhouse film on the time, be dispersed in the resin with the subparticle shape; Thereby on film, form firm inorganics film; Can improve its water tolerance, but have the shortcoming of removing property difference when not required, still; If there are not the problems referred to above in second embodiment of the present invention and the 3rd embodiment when then using.
In addition; Inorganics more than median size is 1 μ m with the resin emulsion as wedding agent be coated on agricultural with greenhouse film on the time, have the shortcoming of poor water resistance, still; If there are not the problems referred to above in second embodiment of the present invention and the 3rd embodiment when then using.Certainly, in second embodiment and the 3rd embodiment, also can use the opalizer of first embodiment.
In light-blocking agent for agricultural use provided by the invention, the content of this inorganics so long as the amount that can bring into play as the desirable shaded effect of opalizer get final product.When considering that the ratio of resinous principle and inorganics can be 1: 0.3～1: 15 in the solids component ratio under the situation as the dispersiveness in the resin emulsion of wedding agent.That is, when the ratio of mixture of inorganics less than 0.3 the time, be difficult to obtain desirable shaded effect; Surpass 15 even add ratio of mixture in addition, can not obtain better shaded effect, and water tolerance reduces.In addition, when the spraying opalizer, be easy to generate obstruction, so not preferred.
In being applicable to the light-blocking agent for agricultural use of agricultural provided by the present invention with the shading coating fluid of film; As the resin that in the shading coating fluid, is comprised, can use after the shading coating fluid drying that is applied on the film and can form the resin that makes inorganics keep the resin molding of uniform wedding agent.
As this resin, can use acid value is 30～300 resin aqueous emulsion.As such water-dispersed resin; Can select acrylic resin, polyurethane series resin, vinylite, polyester based resin, epoxy for use is resin etc.; Wherein, especially preferably using acid value is that 30～300 water-dispersible acrylic resin, water-dispersible polyurethane are resin.
This acid value is for the polymer system wedding agent, and is relevant with the average number of the free carboxy of every chain, and acid value is big more, just become more easily do not have water tolerance, water-soluble easily.In addition, if the little polymkeric substance of acid value then has the character that is insoluble in water.In the present invention, as resin aqueous emulsion, the use acid value is 30～300 resinous principle, can guarantee water tolerance to a certain degree, and can satisfy the hold-time of necessary shading coated film.
If this acid value is less than 30, filming of formation do not have problems on water tolerance, removes liquid and easily removes and film but aspect removing property, but can not use, so not preferred.In addition, if acid value is for surpassing 300 bigger value, the then water tolerance of resin molding reduction is as should be able in long-time, the performance of the opalizer of covering reducing, so not preferred.
In addition, the median size as the resin of resin emulsion is preferably 0.01～0.5 μ m.When median size during less than 0.01 μ m, can not bring into play function as emulsion, in addition, when surpassing 0.5 μ m, the resin that is coated on the film can run off, so not preferred.
The content of this resin emulsion in the shading coating fluid provided by the present invention is kept in balance with the ratio of mixture of institute blended inorganics, and with respect to the water of 100 weight parts, the resin solid composition that adds 0.1～10 weight part is for well.If less than 0.1 weight part, then the formation of filming on film becomes insufficient, in addition; When surpassing 10 weight parts, the coating operability reduces, and dry time-consuming after the coating; In contrast therefore be that the persistence of filming is not improved accordingly, is uneconomic.
In shading coating fluid of the present invention; Except above-mentioned inorganics; Particularly outside lime carbonate or the titanium oxide, can also further add stiffening agent, sanitas, tackifier, viscosity depressant, dispersion agent, tensio-active agent, oxidation inhibitor, UV light absorber, photostabilizer, alcohols etc. as required.
As the agricultural film of the light-blocking agent for agricultural use that can be suitable for shading coating fluid provided by the present invention, can use any existing goods that are used as agricultural with film.As the material of such film, for example can enumerating out, polyvinyl chloride film, polyester film, acrylic resin film, polyethylene-based film, PP SHEET FOR OPP TAPE, polyurethane film, glass and vinyl acetate are film etc.
Particularly, can enumerate out vinyl chloride copolymers such as polyvinyl chloride homopolymer and vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, VCP, vinylchlorid-isobutylene copolymers, polyvinyl vinylidene chloride, vinylchlorid-phenylethylene-maleic anhydride terpolymer, vinylchlorid-alkyl, naphthenic base or alkyl maleimide multipolymer, vinylchlorid-styrene-acrylonitrile copolymer, vinylchlorid-butadienecopolymer, vinylchlorid-isoprene copolymer, vinylchlorid-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinylchlorid-maleate copolymer, vinylchlorid-alkylmethacrylate polymer, vinyl chloride-acrylonitrile copolymer and vinylchlorid-polyurethane copolymer as constituting the resin of agricultural with the vinyl chloride-based resin film.
In addition, as employed vinyl chloride-based resin, can be the blend goods of following polymers.As such polymkeric substance can enumerate Vilaterm, Vestolen PP 7052, polybutylenes, gather-alpha-olefinic polymer such as 3-methyl butene, multipolymer, acrylonitrile-butadiene-styrene copolymer, methacrylate butadi ene styrene copolymer and the urethane etc. of polyolefine such as ethylene-vinyl acetate copolymer, ethylene-propylene copolymer and their multipolymer, PS, vinyl resin, vinylbenzene and other monomer (for example maleic anhydride, divinyl, vinyl cyanide etc.).
In these vinyl chloride resin compositions, can add various additives such as softening agent, stablizer stablizer, lubricant, anti-adhesive agent, UV light absorber, inhibitor, inorganic filler as required.These additives can be enumerated existing usually as the various additives of the additive of vinyl chloride-based resin film, and its addition is according to the difference of kind and difference, are about 0.001～10 weight part with respect to the vinyl chloride-based resin of 100 weight parts.
For example; In order to give the vinyl chloride-based resin flexibility; Can in vinyl chloride-based resin used in the present invention, add softening agent; As such softening agent; Can use phthalic esters such as dinoctyl phthalate, phthalic acid two-2-(ethyl hexyl) ester, phthalic acid diisononyl esters, phthalic acid dibutyl ester, butyl benzyl phthalate, phthalic acid dilauryl ester, phthalic acid didecyl ester, phthalic acid two (undecyl) ester, phthalic acid two (dodecyl) ester is softening agent, wherein preferably uses phthalic acid di-n-octyl ester (DOP).In addition; As other softening agent, can mix SULPHOSUCCINIC ACID ESTERs such as using tricresyl phosphate (xylyl) ester (TXP), tricresyl phosphate (hydroxytoluene base) ester, tricresyl phosphate (isopropyl phenyl) ester, tricresyl phosphate butyl ester, tricresyl phosphate ethyl ester, phosphate and tricresyl phosphate (ethylphenyl) ester is softening agent.
Use the vinyl chloride-based resin film in order to use above-mentioned vinyl chloride resin composition to make agricultural, can use known method such as at present general rolling process, extrusion process, plavini to process film like.
On the other hand; As constituting the resin of agricultural used in the present invention with the ethylene series resin film, the Vilaterm such as Vilaterm that can use new LDPE (film grade), LLDPE, medium-density polyethylene, high density polyethylene(HDPE), use metalloscene catalyst to be polymerized; Vestolen PP 7052 such as the Vestolen PP 7052 of random polymerization, the Vestolen PP 7052 of block polymerization, isotatic polypropylene, syndiotactic polypropylene; Ethylene series resins such as vinyl copolymer such as ethylene-vinyl acetate, ethylene-acrylic acid, ethylene-acrylate, ethylene-methyl methacrylate, ethylene-methyl acrylate, they can use separately, perhaps use their mixture.
Wherein, preferred for example the use through metalloscene catalyst copolymerization of ethylene and carbonatoms is that the content of the ethene-alpha-olefin copolymer (being commonly referred to metallocene polyethylene) that obtains of 4～10 terminal olefin, high-pressure free radical method new LDPE (film grade) (HP-LDPE), vinyl acetate is the ethylene-vinyl acetate copolymer (EVA) of 1～25 weight % and is the ethene-alpha-olefin copolymer (LLDPE) that 4～20 terminal olefin obtains through Z-type catalyst, chromium oxide catalyst, molybdenum oxide catalyst copolymerization of ethylene and carbonatoms.
Ethylene series resin film of the present invention can be a single layer structure, also can be multilayered structure.Under the situation that is multilayered structure, in the time of at least on being routed to booth, in layer, must mix the bulky amine based compound near the outside that has been coated with opalizer.In addition, in arbitrary layer of multilayered structure, mixing the bulky amine based compound also is fine.
Forming under the situation of this multilayered structure, the kind that constitutes the resin of each layer can be identical, also can be different, but the resin of adjacent layers is to form the high layer of mutual intermiscibility or binding property for well.For example; As outer field ethylene series resin is LLDPE; As the middle layer that is positioned at its underpart (and internal layer); Can use and the intermiscibility of LLDPE new LDPE (film grade) good, by methylacrylic acid, maleic anhydride, acrylic acid any modification, high density polyethylene(HDPE), Vestolen PP 7052, ethylene-vinyl acetate copolymer (EVA) etc., wherein, can use vinyl acetate content is the ethylene-vinyl acetate copolymer (EVA) of 1～25 weight %.
In addition, under the situation of the multilayered structure more than 3 layers,, and add the bulky amine based compound, then any face is laid as the outside and can both be obtained identical effect, so preferred if two outermost layers use the resin of same type.
In addition, in ethylene series resin used in the present invention, only otherwise the infringement target capabilities can contain various additives.For example,, therefore can add lubricant, particularly can add the lubricant of acid amides system because the ethylene series resin film has the tendency poorer than the wearability of vinyl chloride-based resin film.
In addition, can also add various additives such as various stablizers, dripping inhibitor, anti-adhesive agent, UV light absorber, inhibitor, inorganic filler.The combined amount of these additives is according to the difference of its kind and difference is 0.01～10 weight part with respect to 100 weight part ethylene series resins.
In second embodiment provided by the present invention; When the coating light-blocking agent for agricultural use; On the face at least being coated with opalizer of above-mentioned agricultural, film through the acrylic resin formation that coating and hydroxyl monomer copolymerization form with the vinyl chloride-based resin film.This thickness of filming is to be suitable about 0.5～5 μ m.If this is filmed less than 0.5 μ m, then can not improve the persistence that is coated on this light-blocking agent for agricultural use coating on filming, in addition,, can not improve persistence even surpass 5 μ m.
When agricultural with the vinyl chloride-based resin film on this acrylic resin of coating when filming, preferably after forming film, through in same production line, or in other operations, adopt method such as woodburytype to form and film.Also can after be laid on film on the booth, be coated with this acrylic resin and film, film the operability variation but can not easily form uniformly like this.
Be bonded together more firmly in order to make film and to film, can in acrylic resin, add the linking agents such as compound that contain the end group isocyanic ester.
As the hydroxyl monomer that constitute to form acrylic resin above-mentioned bottom, that form with the hydroxyl monomer copolymerization, can enumerate out hydroxy acrylates such as vinylformic acid (methylol) ester, vinylformic acid (2-hydroxyethyl) ester, vinylformic acid (2-hydroxypropyl) ester, vinylformic acid (3-hydroxypropyl) ester, vinylformic acid (2-hydroxybutyl) ester, vinylformic acid (4-hydroxybutyl) ester, vinylformic acid (2-hydroxyl amyl group) ester, vinylformic acid (6-hydroxyl hexyl) ester; Hydroxyl-metacrylates such as methylacrylic acid (methylol) ester, methylacrylic acid (2-hydroxyethyl) ester, methylacrylic acid (2-hydroxypropyl) ester, methylacrylic acid (3-hydroxypropyl) ester, methylacrylic acid (2-hydroxybutyl) ester, methylacrylic acid (4-hydroxybutyl) ester, methylacrylic acid (2-hydroxyl amyl group) ester, methylacrylic acid (6-hydroxyl hexyl) ester.
Can use atomizer etc. to lay coating light-blocking agent for agricultural use of the present invention on the face that acrylic resin films above-mentioned.Usually be the outside to be coated with the face that acrylic resin films, be routed on the booth etc., then, when requiring opacifying property, coating light-blocking agent for agricultural use of the present invention on film surface, formation light shield layer.In the situation that requires opacifying property at the very start, also can be through being coated with in film prodn operation before laying or other the operation, but in the operational phase when laying etc., coming off of light shield layer etc. taken place easily, therefore not preferred.
In addition, the coating light-blocking agent for agricultural use provided by the present invention the 3rd embodiment in agricultural with film in, added the bulky amine based compound.
The addition of bulky amine based compound adds 0.05～0.3 weight part for well for vinyl chloride agricultural is used resin film.If addition, then is formed at the persistence that the shading on the film films less than 0.05 and can not get improving, even and addition surpasses 0.3, can not obtain better effect, on the contrary waste.
In addition, for resin film, the addition of bulky amine based compound is to add 0.05～2 weight part for well for ethylene series agricultural.If addition, then is formed at the persistence that the shading on the film films less than 0.05 and can not get improving, even and addition surpasses 2 weight parts, can not obtain better effect, on the contrary waste.
As bulky amine based compound mentioned above, can enumerate out (2,2,6,6-tetramethyl--4-piperidyl) stearate, (1,2,2; 6,6-pentamethyl--4-piperidyl) stearate, phenylformic acid (2,2,6,6-tetramethyl--4-piperidyl) ester, N-(2,2,6; 6-tetramethyl--4-piperidyl) dodecyl succinimide, 1-[(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy ethyl]-2,2,6,6-tetramethyl--4-piperidyl (3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, two (2,2; 6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1,2; 2,6,6-pentamethyl--4-piperidyl)-2-butyl-2-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) hexa-methylene two amidines, four (2,2,6,6-tetramethyl--4-piperidyl) butylene tetracarboxylic ester, two (2; 2,6,6-tetramethyl--4-piperidyl) two (tridecyl) butane tetracarboxylic acid esters, two (1,2,2,6,6-pentamethyl--4-piperidyl) two (tridecyl) butane tetracarboxylic acid esters, 3; Two { 1,1-dimethyl--2-[three (2,2,6,6-tetramethyl--4-piperidino carbonyl oxygen base) butyl ketonic oxygen base] ethyl }-2,4,8 of 9-; 10-four oxygen spiral shell [5,5] undecanes, 3,9-is two, and { 1,1-dimethyl--2-[three (1,2,2,6; 6-pentamethyl--4-piperidyl oxygen base ketonic oxygen base) butyl ketonic oxygen base] ethyl }-2,4,8,10-four oxygen spiral shell [5,5] undecanes, 1,5,8; 12-four [4, two [N-2,2,6, the 6-tetramethyl--4-piperidyl] butyl of 6-are amino]-1,3; 5-triazine-2-yl]-1,5,8,12-four azepine decane, 1-(2-hydroxyethyl)-2,2,6; 6-tetramethyl--4-piperidines alcohol/Succinic acid dimethylester condenses, uncle's 2-octyl group amino-4,6-two ring s-triazine/N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine/steric hindrance amine compounds such as ethylene dibromide condenses.
Agricultural based on flexible formation used in the present invention is used resin film, can use known method such as now general rolling process, extrusion process, plavini carry out filmization.In addition, the processing conditionss such as temperature when carrying out film, existing agricultural is identical with the situation of resin film with making.In addition, the thickness of film can be about 0.01～0.2mm.As the ethylene series resin film, for example when formation had 3 layers the film of multilayered structure, the thickness of its each layer was preferably skin/middle layer/internal layer=1/3/1 with proportional meter.
Use resin film with respect to agricultural, the glue spread of the opalizer of shading coating fluid of the present invention is preferably 0.1～50g/m with solid component meter
2About.If less than 0.1g/m
2, then can not obtain sufficient shaded effect.In addition, when surpassing 50g/m
2The time, in the coating operating process, produce resin from the problem of agricultural, so not preferred with the film drippage.
Therefore; Comprise inorganics of the present invention and comprise resin emulsion and as the shading coating fluid of the water of aqueous solvent with acid value of 30～300; Through spraying or be coated on agricultural with on the film, form the inorganics that has excellent water-resistance and film, can obtain its shaded effect easily.
On the other hand, when not needing this shading to film, this shading is filmed and needn't be used a large amount of organic solvents, just can remove simply and remove liquid through alkalescence.
Embodiment
The present invention will be described in more detail to pass through embodiment and comparative example below, but the present invention is not limited to these embodiment.
Embodiment 1～8
According to following table 1 described prescription (weight part), obtain shading coating fluid as light-blocking agent for agricultural use of the present invention.Resulting shading coating fluid is sprayed to agricultural with on the ethene greenhouse film, and according to this state of filming of certain benchmark evaluation, the water tolerance of filming and removing property, its result gathers and is shown in Table 1.
[table 1]
* 1: inorganics 1: median size is less than 1 μ m
(ball tail calcium society makes lime carbonate; LUMINOUS (Le ミ Na ス); Median size 0.1 μ m)
* 2: inorganics 2: median size is more than the 1 μ m
(shiraishi calcium society makes lime carbonate; Carbuncle; Median size 2～3 μ m)
* 3: resinous principle A: acrylic resin emulsion; Acid value 60; Solids component 47%; Resin median size 0.09 μ m; Molecular weight is more than 200,000
* 4: resinous principle B: acrylic resin emulsion; Acid value 200; Solids component 32%; Resin median size 0.16 μ m; Molecular weight is more than 200,000
* 5: resinous principle C: acrylic resin emulsion; Acid value 10; Solids component 30%; Resin median size 1 μ m; Molecular weight is more than 200,000
* 6: the state of filming is through following evaluation of measuring.
Coating shading coating fluid forms and films and drying, with finger friction film coated surface, through the state of peeling off that visual observation is filmed, judges according to following benchmark then.
◎: whole no changes.
Zero: some peeling off arranged, but no problem.
: some peeling off arranged.
△: considerable peeling off.
*: all peel off.
* 7: water tolerance is carried out through following mensuration: the shading coating fluid is sprayed at agricultural with on the film and dry; Dipping took out after 12 hours in water then; With finger friction film coated surface,, judge according to following benchmark through the state of peeling off that visual observation is filmed.
◎: whole no changes.
Zero: some peeling off arranged, but no problem.
: some peeling off arranged.
△: considerable peeling off.
*: all peel off.
* 8: removing property is carried out through following mensuration: the shading coating fluid is sprayed at agricultural with on the film and dry; On film, spray then the water contain 100 weight parts, 0.5 weight part sodium hydroxide, 10 weight parts benzylalcohol and 0.2 weight part X 2073 remove liquid; Spray after 5 minutes; Further spray water is then through the visual complexity of filming and coming off according to following benchmark judgement.
◎: all come off.
Zero: have some residual, but no problem.
: small amount of residual.
△: residual in a large number.
*: all do not come off.
Comparative example 1～7
The same with the foregoing description, according to following table 2 described prescriptions (weight part), obtain shading coating fluid as the opalizer of comparative example.Resulting shading coating fluid is sprayed on agricultural with on the ethene greenhouse film, and according to this state of filming of certain benchmark evaluation, the water tolerance of filming and removing property, its result gathers and is shown in Table 2.
[table 2]
* 1～* 8 in the table is identical with table 1.
Result by the foregoing description 1～8 and comparative example 1～7 can know; As the opalizer shading coating fluid of opalizer of the present invention, use resin emulsion as wedding agent, and mix two kinds of different inorganicss of particle diameter therein; Through it being applied to agricultural with on the film; Can obtain good opacifying property, and filming of obtaining of spraying is in good condition, water tolerance and removing property are also all very good.
Embodiment 9～13/ comparative examples 8～10
Following table 3 described priming paints are mixed (weight part), be applied on the Achilles Nonkry (ア キ レ ス ノ Application キ リ-) (vinyl chloride resin film) through woodburytype, drying is 30 seconds under 90 ℃, forms bottom film.
On the other hand, according to following table 3 described prescriptions (weight part), obtain opalizer of the present invention.Resulting opalizer is sprayed on the above-mentioned bottom film, and according to this state of filming of certain benchmark evaluation, the water tolerance of filming and removing property, its result gathers and is shown in Table 3.
[table 3]
* 1: Japanese polyurethane society makes
* 2: acid value 60; Molecular weight is more than 200,000; Solids component is 47% acrylic resin emulsion
* 3: acid value 200; Molecular weight is more than 200,000; Solids component is 32% acrylic resin emulsion
* 4: acid value 400; Molecular weight is more than 200,000; Solids component is 30% acrylic resin emulsion
* 5:, estimate through following test about the persistence that shading is filmed.
Use atomizer that each opalizer is sprayed to equably and be laid on the outdoor above-mentioned film, make it to reach 30% shading.Spraying back about 1 month in outdoor placement is judged the degree that comes off that shading is filmed through visual according to following benchmark.
◎: residual filming more than 80%.
Zero: residual 60%～less than 80% film.
: residual 40%～less than 60% film.
△: residual 10%～less than 40% film.
*: only residual less than 10% film.
* 6: the removing property that shading is filmed is carried out through following mensuration: opalizer is sprayed at agricultural with on the film and dry; Then to the liquid of removing of the X 2073 of the benzylalcohol of the sodium hydroxide that sprays the water comprise 100 weight parts, 0.5 weight part outdoor placement filming after 1 month, 10 weight parts and 0.2 weight part; Spray after 5 minutes; Further spray water is then through the visual complexity of at this moment filming and coming off according to following benchmark judgement.
◎: filming more than 80% comes off.
Zero: 60%～less than 80% film and come off.
: 40%～less than 60% film and come off.
△: 10%～less than 40% film and come off.
*: only have less than 10% film and come off.
* 7: even through atomizers spray shading liquid, shading liquid itself also comes off, and can't judge.
Result by above embodiment 9～13 and comparative example 8～10 can know; Opalizer of the present invention sprays to scatter perhaps and is coated on the vinyl chloride agricultural with on the resin film; Said vinyl chloride agricultural has the bottom of the acrylic resin emulsion that the hydroxyl monomer copolymerization forms with resin film; Form the good inorganics of persistence and film, can in long-time, bring into play its shaded effect (embodiment 9～13).
In contrast; When (comparative example 8 and 9) under the situation of the formed bottom of acrylic resin that does not have on resin film the hydroxyl monomer copolymerization to form in the vinyl chloride agricultural, or be not provided with fully under the situation of bottom (comparative example 10); Can not on film, form shading films; Film even perhaps formed, its persistence is not good with removing property yet.
Embodiment 14～19
Prescription (weight part) according to following table 4 is put down in writing prepares the vinyl chloride agricultural with resin film (thickness 0.1mm) through rolling process.
Use resulting vinyl chloride film; Be laid on agricultural with on the ethene booth; Light-blocking agent for agricultural use of the present invention shown in the spraying table, according to the at this moment formed state of filming of certain benchmark evaluation, the persistence of filming and removing property, its result gathers and is shown in Table 4.
[table 4]
* 1:DS401: fluorine is tensio-active agent (manufacturing of Da Jin (ダ イ キ Application) industrial)
* 2: bulky amine based compound: LA-63 (Asahi Electro-Chemical Co. Ltd's manufacturing)
* 3: acid value 60; Molecular weight is more than 200,000; Solids component is 47% acrylic resin emulsion
* 4: acid value 200; Molecular weight is more than 200,000; Solids component is 32% acrylic resin emulsion
* 5: acid value 400; Molecular weight is more than 200,000; Solids component is 30% acrylic resin emulsion
* 6: about the persistence of shading film, through carrying out same evaluation with embodiment 9～13 identical methods.
*: the removing property that shading is filmed is carried out through following mensuration: opalizer is sprayed at agricultural with also dry on the film; Remove liquid to what the diethylamine that sprays benzylalcohol that pH value by 100 weight parts is 11 ammonia soln, 5 weight parts and 0.2 weight part outdoor placement filming after 1 month mixed then; Place after 5 minutes; Further water flushing is through the visual degree that comes off of filming of judging this moment according to following benchmark.
◎: filming more than 80% comes off.
Zero: 60%～less than 80% film and come off.
: 40%～less than 60% film and come off.
△: 10%～less than 40% film and come off.
*: only have less than 10% film and come off.
Comparative example 11～15
Prescription (weight part) according to following table 5 is put down in writing prepares the vinyl chloride agricultural with resin film (thick 0.1mm) through rolling process.
Use resulting vinyl chloride film; Be laid on agricultural with on the ethene booth; Light-blocking agent for agricultural use of the present invention shown in the spraying table, according to the at this moment formed state of filming of certain benchmark evaluation, the persistence of filming and removing property, its result gathers and is shown in Table 5.
In addition, the note in the table 5 is identical with table 4.
[table 5]
* 8: shading is filmed owing to rainfall comes off, and can't judge.
Result by the foregoing description 14～19 and comparative example 11～15 can know, through the vinyl chloride agricultural that contains the bulky amine based compound with resin film on coating opalizer of the present invention, can access the persistence of good shading film.In contrast, agriculture with resin film for the vinyl chloride of the comparative example that does not contain wedding agent 12, opalizer of the present invention can not be filmed with the surface formation shading of vinyl chloride resin film in agricultural.In addition, can find out that also shading of the present invention films good in when not required removing property.
Embodiment 20～29
According to the prescription (weight part) that following table 6 is put down in writing, has the ethylene series resin film (thickness: 0.1mm of the 3-tier architecture of skin/middle layer/internal layer through the plavini preparation; Layer ratio: skin/middle layer/internal layer=1/3/1).
Use resulting ethylene series film, be laid on agricultural with on the booth, the opalizer of the present invention shown in the spraying table, according to the at this moment formed state of filming of certain benchmark evaluation, the persistence of filming and removing property, its result gathers and is shown in Table 6.
[table 6]
* 1: bulky amine based compound: LA-63 (Asahi Electro-Chemical Co. Ltd's manufacturing)
* 2: acid value 60; Molecular weight is more than 200,000; Solids component is 47% acrylic resin emulsion;
* 3: acid value 200; Molecular weight is more than 200,000; Solids component is 32% acrylic resin emulsion;
* 4: acid value 400; Molecular weight is more than 200,000; Solids component is 30% acrylic resin emulsion;
* 5: the persistence of filming about shading, through carrying out same evaluation with embodiment 9～13 identical methods;
* 6: the removing property that shading is filmed is through carrying out same evaluation with embodiment 14～19 identical methods.
Comparative example 16～18
According to the prescription (weight part) that following table 7 is put down in writing, has the ethylene series resin film (thickness: 0.1mm of the 3-tier architecture of skin/middle layer/internal layer through the plavini preparation; Layer ratio: skin/middle layer/internal layer=1/3/1).
Use resulting ethylene series resin film, be laid on agricultural with on the booth, the opalizer of the present invention shown in the spraying table, according to the at this moment formed state of filming of certain benchmark evaluation, the persistence of filming and removing property, its result gathers and is shown in Table 7.
[table 7]
* 7: shading is filmed after one month owing to rainfall comes off, and is no judge of.
Result by the foregoing description and comparative example can know, through the agricultural that contains the bulky amine based compound with the ethylene series resin film on coating light-blocking agent for agricultural use of the present invention, can access the persistence of good shading film.In contrast, with the ethylene series resin film, opalizer of the present invention can not form shading on the surface of vinyl chloride resin film in agricultural and film for the agricultural of the comparative example that does not contain the bulky amine based compound.Can find out also that in addition shading of the present invention is filmed good in when not required removing property.
Can know in addition: use the ethylene series resin film for the agricultural that comprises the bulky amine based compound; When the wedding agent of light-blocking agent for agricultural use of the present invention is that aqueous resin wedding agent and resinous principle are acid value when surpassing 300 resin emulsion, can not guarantee the persistence that shading is filmed.
Industrial applicability
As stated; Of the present invention employed in the cultivation of greenhouse cultivation or tunnel, be applicable to the light-blocking agent for agricultural use of agricultural with film, when experience rainfall etc. inorganics film can not run off yet, can obtain long shaded effect, shading that persistence is good is filmed even can form.In addition, in the time need not filming, need not to use a large amount of organic solvents, remove liquid through alkalescence and just can remove simply, needn't discard, change covering materials such as booth and tunnel,, also have the advantage of significantly saving funds for agriculture practitioner.
Claims (13)
1. light-blocking agent for agricultural use that contains the shading coating fluid; Described shading coating fluid comprises inorganics, resin emulsion, as the water of aqueous solvent; It is characterized in that: the ratio of resinous principle and inorganics; With the solids component ratio count 1: 0.3～1: 15; Inorganics uses median size less than the inorganics of 1 μ m and two kinds of inorganicss of the inorganics more than the median size 1 μ m, and median size less than the ratio of the inorganics of 1 μ m and inorganics more than the median size 1 μ m in 1: 0.5～2 scope, said resin emulsion is that resinous principle is the aqueous resin emulsion of acid value 30～300; And the resin median size is 0.01～0.5 μ m, and the light shield layer that said opalizer forms can use alkaline remover to remove.
2. light-blocking agent for agricultural use; It is characterized in that: said opalizer comprises inorganics and resin emulsion; Said resin emulsion is that resinous principle is the aqueous resin emulsion of acid value 30～300; And the resin median size is 0.01～0.5 μ m, and said opalizer is to be coated on the opalizer that forms light shield layer on the coated surface, and said coated surface is on vinyl chloride agricultural at least one face with film; The acrylic resin that the monomer copolymerization of coating and hydroxyl forms forms, and formed light shield layer can use alkaline remover to remove on said coated surface.
3. light-blocking agent for agricultural use; It is characterized in that: said opalizer comprises inorganics and resin emulsion; Said resin emulsion is that resinous principle is the aqueous resin emulsion of acid value 30～300; And the resin median size is 0.01～0.5 μ m, and said opalizer is to be coated on the agricultural that comprises the bulky amine based compound with the opalizer that forms light shield layer on the resin film, and formed light shield layer can use alkaline remover to remove on said film.
4. light-blocking agent for agricultural use according to claim 3 is characterized in that: said opalizer is to be coated on the agricultural of the bulky amine based compound that contains 0.05～0.3 weight part with the opalizer that forms light shield layer on the vinyl chloride-based resin film.
5. light-blocking agent for agricultural use according to claim 3 is characterized in that: said opalizer is to be coated on the agricultural of the bulky amine based compound that contains 0.05～2 weight part with the opalizer that forms light shield layer on the ethylene series resin film.
6. light-blocking agent for agricultural use according to claim 5 is characterized in that: said opalizer is to be coated on the opalizer that has multilayered structure and form light shield layer at least in agricultural that skin contains the bulky amine based compound on the ethylene series resin film.
7. according to each described light-blocking agent for agricultural use of claim 1～6, it is characterized in that: inorganics is to be selected from least a in the white pigment of lime carbonate, titanium oxide, titanium white, talcum, clay, silicon oxide, mica, permanent white.
8. according to each described light-blocking agent for agricultural use of claim 1～6, it is characterized in that: inorganics is lime carbonate or titanium oxide.
9. the coating process of a light-blocking agent for agricultural use; It is characterized in that: on vinyl chloride agricultural at least one face with film; The acrylic resin that coating and hydroxyl monomer copolymerization form; Formation is filmed, and coating comprises the inorganics white pigment and resinous principle is that acid value 30～300 and resin median size are the light-blocking agent for agricultural use of the aqueous resin emulsion of 0.01～0.5 μ m on this coated surface then, forms the light shield layer that the alkaline remover of use can be removed.
10. the coating process of a light-blocking agent for agricultural use; It is characterized in that: the vinyl chloride agricultural of the bulky amine based compound that contains 0.05～0.3 weight part with film on; Coating comprises the inorganics white pigment and resinous principle is that acid value 30～300 and resin median size are the light-blocking agent for agricultural use of the aqueous resin emulsion of 0.01～0.5 μ m, forms the light shield layer that uses alkaline remover to remove.
11. the coating process of a light-blocking agent for agricultural use; It is characterized in that: the agricultural of the bulky amine based compound that contains 0.05～2 weight part with the ethylene series resin film on; Coating comprises the inorganics white pigment and resinous principle is that acid value 30～300 and resin median size are the light-blocking agent for agricultural use of the aqueous resin emulsion of 0.01～0.5 μ m, forms the light shield layer that uses alkaline remover to remove.
12. the coating process according to each described light-blocking agent for agricultural use of claim 9～11 is characterized in that: inorganics is to be selected from least a in the white pigment of lime carbonate, titanium oxide, titanium white, talcum, clay, silicon oxide, mica, permanent white.
13. according to the coating process of each described light-blocking agent for agricultural use of claim 9～11, it is characterized in that: inorganics is lime carbonate or titanium oxide.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP073860/2004 | 2004-03-16 | ||
| JP2004073860A JP4632679B2 (en) | 2004-03-16 | 2004-03-16 | Shading coating solution |
| JP209328/2004 | 2004-07-16 | ||
| JP209329/2004 | 2004-07-16 | ||
| JP209327/2004 | 2004-07-16 | ||
| JP2004209329A JP4584642B2 (en) | 2004-07-16 | 2004-07-16 | Agricultural sunscreen |
| JP2004209327A JP4632708B2 (en) | 2004-07-16 | 2004-07-16 | Agricultural sunscreen coating method |
| JP2004209328A JP4632709B2 (en) | 2004-07-16 | 2004-07-16 | Agricultural sunscreen |
| PCT/JP2005/004480 WO2005087885A1 (en) | 2004-03-16 | 2005-03-15 | Light-blocking agent for agricultural use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1934207A CN1934207A (en) | 2007-03-21 |
| CN1934207B true CN1934207B (en) | 2012-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800086162A Active CN1934207B (en) | 2004-03-16 | 2005-03-15 | Light-blocking agent for agricultural use |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4632679B2 (en) |
| CN (1) | CN1934207B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101449795B1 (en) | 2012-02-27 | 2014-10-13 | (주)노루페인트 | Paint composition for vinyl greenhouse and method of manufacturing paint film using the same |
| TR201807389T4 (en) * | 2012-07-23 | 2018-06-21 | Solar Dev Pty Ltd | A method for covering a solar panel. |
| JP6058574B2 (en) * | 2013-11-22 | 2017-01-11 | 能美防災株式会社 | Shielding agent, solar panel surface shading device, and solar panel surface shading method |
| CN104885780A (en) * | 2015-05-04 | 2015-09-09 | 丽水市瑞芝食用菌科技有限公司 | Insulation material capable of reducing temperature in edible fungus greenhouse and matched cultivation process |
| CN107759898B (en) * | 2016-08-18 | 2020-09-25 | 江苏金发科技新材料有限公司 | High-shading-degree polypropylene composite material and preparation method thereof |
| CN107793634A (en) * | 2016-08-29 | 2018-03-13 | 合肥杰事杰新材料股份有限公司 | A kind of light PP alloys with high shading performance and preparation method thereof |
| CN107778648A (en) * | 2016-08-29 | 2018-03-09 | 合肥杰事杰新材料股份有限公司 | A kind of white PP alloys of high light-proofness and preparation method thereof |
| CN111925685A (en) * | 2020-07-30 | 2020-11-13 | 陕西谱润生物科技有限公司 | Plant sun-screening agent and preparation method and application thereof |
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| JP2001224257A (en) * | 2000-02-16 | 2001-08-21 | Mitsubishi Chem Mkv Co | Vinyl chloride-based resin film for agriculture |
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| JPH06126918A (en) * | 1992-10-20 | 1994-05-10 | Toyobo Co Ltd | Translucent lamination layer polyester film |
| JPH09279082A (en) * | 1996-04-11 | 1997-10-28 | Sumitomo Chem Co Ltd | Black coating composition and production of color filter using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3127934B2 (en) * | 1991-12-27 | 2001-01-29 | 住友電気工業株式会社 | How to predict power cable trauma |
| JP2001224257A (en) * | 2000-02-16 | 2001-08-21 | Mitsubishi Chem Mkv Co | Vinyl chloride-based resin film for agriculture |
| JP2001279185A (en) * | 2000-03-31 | 2001-10-10 | Sumitomo Chem Co Ltd | Glass container covering material |
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| JP2003213220A (en) * | 2002-01-22 | 2003-07-30 | Dainippon Ink & Chem Inc | Aqueous flooring coating composition |
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| JP2005263826A (en) | 2005-09-29 |
| CN1934207A (en) | 2007-03-21 |
| JP4632679B2 (en) | 2011-02-16 |
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