CN103535215A - Agricultural-use multilayered film - Google Patents
Agricultural-use multilayered film Download PDFInfo
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- CN103535215A CN103535215A CN201210551833.8A CN201210551833A CN103535215A CN 103535215 A CN103535215 A CN 103535215A CN 201210551833 A CN201210551833 A CN 201210551833A CN 103535215 A CN103535215 A CN 103535215A
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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
This invention provides an agricultural-use multilayered film which can substantially isolate the ultraviolet ray by absorbing the ultraviolet ray in broadband and the capability of absorbing the ultraviolet is not reduced, and thus the influence on environment is small. The agricultural-use multilayered film is characterized in that the thickness of whole agricultural-use multilayered film is smaller than 0.3MM and the gricultural-use multilayered film has more than three layers of polyolefin multilayered film and any of the layers of the polyolefin film take out 3% weight of inorganic compound. At least one atom of Si, Al, Mg,Ca, and Li is selected as a component, and any layer comprises at least more than one triazine ultraviolet light absorber and at least more than one benzotriazole ultraviolet light absorber shown as the following formulation (1). (in the formulation R1 and R2 respectively show hydrogen atom and the carbon number is 1-10 substituted alkyl or non-substituted alkyl , or carbon atom number is 1-10 alkoxy).
Description
[technical field]
The present invention relates to agricultural multilayer film, in the situation that being film material or being processed as sheet material, its UV-preventing is excellent, and its performance also can be maintained the in the situation that of long-term use, and the aspects such as anti-deterioration at Reproduction suppression, control of insect and the inner lining material of disease bacterium or mould are also excellent under canopy indoor environment.
[background technology]
Agricultural is maximizing year by year with canopy chamber, in order to utilize film that canopy chamber is covered to carried out film, sprawls the staff that operation need to be many.On the other hand, agriculture practitioner's number reduces year by year, to aging, develops, annual sprawling in operation, in being difficult to guarantee the situation of staff simultaneously.In view of such situation, for the film of sprawling in canopy chamber, long as far as possible film between the operating period of sprawling till operation easily, is extremely replaced is developed in requirement, in other words, require to develop the long-life having more than 2 years, the high-performance film for agricultural use that process also can keep initial performance for a long time.
In such lining material, the agricultural that the polyolefin-based resins of take is main body is less than ethylene chloride resin by the density of polyolefin-based resins film, thereby light weight, even and if burn, the generation of toxic gas is also less, further, without the bond processing carrying out for connecting, can utilize film blowing that the film of wide cut is provided at low cost, because of these reasons etc., described agricultural is applied energetically with polyolefin-based resins film.
On the other hand, in known oriented film for agricultural use, a small amount of ultra-violet absorber that adds was isolated the method that (カ ッ ト) part is ultraviolet, prevent the UV degradation of film for agricultural use in the past, at present, further produced the ultraviolet ultraviolet barrier film that can isolate whole ultraviolet ranges (200nm～370nm) in fact completely, by Reproduction suppression, the control of insect of the disease bacterium under canopy indoor environment or mould, attempted subtracting agricultural chemicals and cultivate.
At whole film thicknesses, be in the thick following thinner film for agricultural use of 0.3mm, for isolation is ultraviolet completely, need to contain ultra-violet absorber with higher concentration.But, the ultraviolet isolation that these agriculturals cannot the long term maintenance initial stage with ultraviolet barrier film, and mostly be the film that in fact can see through the part in the wave band that can expect ultraviolet screening effect, expectation improves it.
For the ultra-violet absorber being engaged in polyolefin-based resins material, in the past centered by nickel series compounds, but developed in recent years the ultra-violet absorbers such as benzophenone series, BTA system, triazine system, and launched in various uses.
[summary of the invention]
[inventing problem to be solved]
These ultra-violet absorbers have respectively the peculiar absorption bands of its structure, and, according to its structure, molecular weight etc., different from the compatibility of substrate resin.In order to expand the retentivity of ultraviolet absorption territory and raising ultraviolet absorption ability, carry out various trials, but do not obtained having concurrently the film for agricultural use of the two.
And, on the other hand, recently in a part of benzotriazole type ultra-violet absorber (there is BTA skeleton, there is the compound of specified substituent simultaneously) relevant for bioconcentration and virose announcement, it is designated as the first particular chemicals, the first monitors chemical substance etc., thereby the special industrial manufacture for outdoor application, its application becomes problem, requires to develop the goods that do not use these ultra-violet absorbers.
About such environmental influence, clear and definite different according to its degree of the difference of compound substituent kind, but cannot obtain the correlation with structure, be still not clear in the situation of ultra-violet absorber of which kind of structure of concrete use, can suitably as film for agricultural use, use.
Thereby, the object of the present invention is to provide agricultural multilayer film, this agricultural with multilayer film isolate in fact completely the more broadband ultraviolet ray of the degree that can expect ultraviolet screening effect, long-term ultraviolet absorption ability can not reduce, because of the environmental sensitivity index due to using low.
[solving the means of problem]
The inventor conducts in-depth research, found that, following agricultural can solve above-mentioned problem with multilayer film, thereby completed the present invention, this agricultural is characterised in that with multilayer film: in whole layer thicknesses are below 0.3mm and have the random layer of more than at least 3 layers multilayer films, contain and account for all inorganic compounds more than 3 % by weight of layer of film, this inorganic compound contains at least a kind of atom being selected from Si, Al, Mg, Ca, Li as its constituent; And the triazine that this multilayer film contains more than at least one in random layer is that the BTA shown in ultra-violet absorber and the formula more than at least one (1) is ultra-violet absorber; The ultra-violet absorber containing ratio of the per unit volume in the ultra-violet absorber containing ratio > superficial layer of the per unit volume in the layer beyond the superficial layer more preferably.
(in formula, R1, R2 represent replacement that hydrogen atom, carbon number are 1～10 or the alkoxyl that is 1～10 without the alkyl replacing or carbon number independently of one another.)
Find in the present invention, by being that the triazine shown in ultra-violet absorber and formula (2) is ultra-violet absorber at the BTA shown in formula in multilayer film (1) for agricultural, the ultraviolet wavelength region that can isolate the degree that can expect ultraviolet screening effect, and can especially suppress, to the oozing out of resin surface, to obtain good ultraviolet absorption ability retentivity.
In the past, among ultra-violet absorber, BTA system was considered to suitable from the viewpoint of absorbing wavelength etc., and had application more, but these compounds have the shortcoming of easily oozing out.Triazine is that ultra-violet absorber has the character that is difficult for oozing out, but be that ultra-violet absorber is compared with BTA, its absorption bands is offset to short wavelength side, even add in a large number in film for agricultural use, also have part ultraviolet ray and see through, thereby cannot expect sufficient ultraviolet screening effect.Benzophenone series ultra-violet absorber easily oozes out, and wavelength region, also to short wavelength side skew, cannot be used in the film for agricultural use of purposes of expecting ultraviolet screening effect.
In agricultural with in multilayer film, as conventionally add ultra-violet absorber film for agricultural use used in whole layers in the situation that, owing to making the reduction of ultraviolet absorption ability retentivity from oozing out of film superficial layer etc., this point can become problem.The present invention carries out under this background, for the ultra-violet absorber with special provision structure, in the situation that using with multilayer film as agricultural, be surprised to find that it has given play to ultraviolet absorption ability and be difficult for reducing such characteristic, and there is long-term weatherability, this from needn't, can give in addition the important performance as film for agricultural use in the aspect excellences such as anti-deterioration of Reproduction suppression, control of insect and the inner lining material of disease bacterium or mould.Agricultural of the present invention also further has because of the low characteristic of environmental sensitivity index due to using with multilayer film.
[effect of invention]
For agricultural multilayer film of the present invention, ultra-violet absorber is difficult for being exuded to resin surface, thereby its UV-preventing (absorption bands is wide) excellence, and its performance also can be maintained the in the situation that of long-term use, the aspects such as anti-deterioration at Reproduction suppression, control of insect and the inner lining material of disease bacterium or mould under canopy indoor environment are also excellent, and go through long-time after its adaptation of filming, weather resistance can be not impaired yet, can suitably be used as film for agricultural use.And, the in the situation that of being provided with antifog coating on this film, oozing out and suppressed, can not reduce with the adaptation of this base material, thereby preferably.The film that has used polyolefin resin composite of the present invention can for transparent, can be for satin light face, also can be half satin finish face, can be suitably for canopy chamber, tunnel, covering, with, bagging, use etc. the purposes of film for agricultural use (so-called agricultural vinyl chloride (Farming PVC), quantum of agropolymer (Farming Port リ), agricultural vinyl acetate (Farming サ Network PVC), agricultural PO, hard films etc.).In addition, agricultural of the present invention also further has because of the low such effect of environmental sensitivity index due to using with multilayer film.
[accompanying drawing explanation]
Fig. 1 is that the agricultural of embodiment 2 and 3 uses multilayer film in the total light transmittance measurement result (initial stage) of 300nm～700nm.
Fig. 2 be the agricultural of embodiment 2 and 3 with multilayer film the total light transmittance measurement result (outdoor sprawling after 18 months) at 300nm～700nm.
[embodiment]
Below describe the present invention in detail.
Agricultural in the present invention with multilayer film be have at least possess skin, the film of 3 layers of above laminated structure of intermediate layer, internal layer.Herein, so-called skin refers to the floor that becomes outside when spreading in canopy chamber etc., and so-called internal layer refers at the floor that carries out becoming when sprawl canopy chamber inner side, so-called intermediate layer refer to by this skin and internal layer clamping layer.Hereinafter sometimes also skin and internal layer are called to superficial layer altogether.In addition, in not damaging the scope of effect of the present invention, at further laminated resin layer between internal layer and intermediate layer, between skin and intermediate layer; Or skin or intermediate layer, internal layer etc. itself forms by 2 layers and becomes the mode of 4 layers of above multilayer film; These are also contained in the scope of the present application.Intermediate layer in this situation refers to the layer of (beyond superficial layer) beyond outer and internal layer.
Layer thickness ratio for the skin/intermediate layer/internal layer in the present invention is not particularly limited, for example can be with 1/1/1～1/5/1, preferably with 1/2/1 to 1/3/1 layer, recently form.
In addition, in the present invention, said skin, intermediate layer, internal layer mean and in the resin principal component as film for agricultural use performance function, add the layer that resin combination that other compositions form forms.Thereby, can think, it is not to be included in internal layer, outer field concept that the application type antifog coating being coated with thinly in the inner side of internal layer for the object of anti-mist characteristic like that as described later or other form in outer field outside for other objects in the situation that are filmed.
The agricultural of the present application is that the resin, particularly polyolefin-based resins that resin, PET series resin etc. are used as the resin of film for agricultural use all the time can effectively have been given play to effect of the present invention with using polyolefin-based resins, ethlyene dichloride in multilayer film.
As polyolefin-based resins, can enumerate homopolymers, the alpha-olefin of take of alpha-olefin system that be principal component with copolymer heterobifunctional monomer; The copolymers of the polyunsaturated compounds such as alpha-olefin and conjugated diene or non-conjugated diene, acrylic acid, methacrylic acid, vinyl acetate etc. etc., can enumerate such as high density, low-density or LLDPE, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethene-4 methyl 1 pentene copolymer, vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer etc.Among these, from the viewpoint of the transparency, weather resistance and price, the low density polyethylene (LDPE) that preferred density is 0.890～0.935 or ethene-alpha-olefin copolymer and vinyl acetate content are that vinyl-vinyl acetate copolymer below 30 % by weight is as film for agricultural use.
In addition, in the present invention, as at least one composition of polyolefin-based resins, can use the ethene-alpha-olefin copolymer resins that utilizes metallocene catalyst to carry out copolymerization and obtain.
It is the material that is commonly referred to as metallocene PE, is the copolymer of the alpha-olefins such as ethene and 1-butylene, 1-hexene, 4-methyl-1-pentene, octene.
The ethene-alpha-olefin copolymer using as at least one composition in polyolefin-based resins of the present invention preferably demonstrates following physical property.
melt flow rate (MFR) (MFR)
The MFR measuring according to JIS-K7210 demonstrates 0.01g/10 minute～value of 10g/10 minute, be preferably 0.1g/10 minute～5g/10 minute.If this MFR is greater than this scope, when moulding, film crawls and is unstable.In addition, if this MFR is too less than this scope, resin pressure during moulding increases, forming machine has been executed to load, thereby can make output reduce, and must suppress the increase of pressure, lacks practicality.
density
The density of measuring according to JIS-K7112 demonstrates 0.880g/cm
3～0.930g/cm
3, be preferably 0.880g/cm
3～0.920g/cm
3value.If this density is greater than this scope, transparent variation.And, if density is less than this scope, can, because film surfaces of tacky produces adhesion, lack practicality.
molecular weight distribution
The molecular weight distribution (weight-average molecular weight/number-average molecular weight) of trying to achieve by gel permeation chromatography (GPC) demonstrates 1.5～3.5, is preferably 1.5～3.0 value.If this molecular weight distribution is greater than this scope, mechanical strength reduces, not preferred.If this molecular weight distribution is less than this scope, film crawls and unstable during moulding.
In ethane-acetic acid ethyenyl ester copolymer resins used in the present invention, vinyl acetate content be 3 % by weight～25 % by weight scope, be preferably the scope of 5 % by weight～20 % by weight.If vinyl acetate content is less than this scope, resulting film hardening, easily produces fold or lax, and can produce harmful effect to antifog property, thereby lack practicality while sprawling to canopy chamber; In addition, if vinyl acetate content is greater than this scope, the melting point depression of resin, thereby carrying out canopy chamber while sprawling, under the high temperature in summer film occur lax, in wind, touch (ば つ I) thereby and easily break with the friction of canopy cell structure body etc., so shortage practicality.
Agricultural of the present invention is characterised in that with multilayer film, and it contains the BTA shown in following formula (1) is ultra-violet absorber.
(in formula, R1, R2 represent replacement that hydrogen atom, carbon number are 1～10 or the alkoxyl that is 1～10 without the alkyl replacing or carbon number independently of one another.)
As the BTA shown in formula (1), it is the example of ultra-violet absorber, for example can enumerate: 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, (2-[5-chloro-(2H)-BTA-2-yl]-4,6-bis-(tertiary pentyl) phenol), 2-[5-chloro-(2H)-BTA-2-yl]-2-(2 '-hydroxyphenyl)-5-chlorobenzotriazole classes such as 4-methoxyl group-6-(tert-butyl group) phenol.
BTA shown in formula (1) is among ultra-violet absorber, can preferably use maximum absorption wavelength for BTA more than 350nm is at least one in ultra-violet absorber, further can preferably use two kinds.In addition, in the present invention, in the situation that thering is more than 2 absworption peak, in getting peaked wavelength, using the wavelength of long wavelength side more as maximum absorption wavelength.
In the present invention, as the BTA shown in formula (1), be ultra-violet absorber, preferably use the compound with following structure.
2-[5-chloro-(2H)-BTA-2-yl]-4-methyl-6-(tert-butyl group) phenol (" TINUVIN 326 " that Ciba Specialty Chemicals society manufactures) (maximum absorption wavelength 353nm)
(2-[5-chloro-(2H)-BTA-2-yl]-4,6-bis--(tertiary pentyl) phenol) (SHIPRO changes into the SB704CL that Co., Ltd. manufactures) (maximum absorption wavelength 353nm (peak of short wavelength side is 313nm))
(2-[5-chloro-(2H)-BTA-2-yl]-4,6-bis--(tertiary pentyl) phenol) (SHIPRO changes into Co., Ltd. and manufactures SB7021MBCL) (maximum absorption wavelength 371nm (peak of short wavelength side is 309nm))
2,4-di-t-butyl-6-(5-chlorobenzotriazole-2-yl) phenol (" TINUVIN 327 " that Ciba Specialty Chemicals society manufactures) (maximum absorption wavelength 353nm)
In addition, 2 shown in formula (1d), phenol (TINUVIN 327) is noted 4-di-t-butyl-6-(5-chlorobenzotriazole-2-yl) in aquatile, the property of accumulating, thereby from the viewpoint of environmental influence, slightly worry.On the other hand, 2-[5-shown in formula (1a) chloro-(2H)-BTA-2-yl] " TINUVIN 326 " (maximum absorption wavelength 353nm) of manufacturing of-4-methyl-6-(tert-butyl group) phenol, for example Ciba SpecialtyChemicals society be identified that the property accumulated in aquatile is low, harmfulness is also low, can in the such outdoor application of film for agricultural use, suitably use, therefore particularly preferably.But, the benzotriazole type ultra-violet absorber of formula (1a) resistance to exudative low, thereby it can be restricted by addition.
Agricultural in the present invention is characterised in that with multilayer film, and it contains triazine is ultra-violet absorber.The triazine of using in the present invention be ultra-violet absorber for the triaryl triazine shown in following formula (2) be ultra-violet absorber.
Herein, in formula (2), R3～R7 represents the alkyl that hydrogen atom or carbon number are 1～10 independently of one another.More preferably, R3 is that carbon number is 6～10 alkyl, is particularly preferably that carbon number is 6～8 alkyl, and R4～R7 is that hydrogen atom or carbon number are 1～2 alkyl, are particularly preferably hydrogen atom or methyl.
The preparation method that is ultra-violet absorber for the triaryl triazine shown in above-mentioned formula (2) is not particularly limited, and can use commercially available product.Such as enumerating the TINUVIN 1577F of Ciba Specialty Chemicals society manufacture or the UV1164 of SciTech society manufacture etc.
Agricultural of the present invention, with in multilayer film, can be share other ultra-violet absorber in the scope that can not affect desired effect.As the ultra-violet absorber that can share, for example can enumerate: 2,4-dihydroxy benaophenonel, ESCALOL 567,2-hydroxyl-4-octyloxy benzophenone, 5, the 2-hydroxy benzophenone ketones such as 5 '-di-2-ethylhexylphosphine oxide (ESCALOL 567); Phenyl salicytate, resorcinol monobenzoate, 2,4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate, 2,4-bis--tertiary pentyl phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate, cetyl-3, the benzoates such as 5-di-tert-butyl-4-hydroxybenzoic acid ester; 2-ethyl-2 '-ethyoxyl oxanilide (オ キ ザ ニ リ De), 2-ethyoxyl-4 '-dodecyl oxanilide etc. replace oxanilide class; Ethyl-alpha-cyano-β, the cyanoacrylates such as β-diphenylacrylate ester, methyl-2-cyano group-3-methyl-3-(p-methoxyphenyl) acrylate etc.Can enumerate the inorganic oxide system ultra-violet absorbers such as zinc oxide, cerium oxide in addition.These ultra-violet absorbers can be used one or more.
With respect to whole films, agricultural of the present invention is that ultra-violet absorber and triazine are that the content of ultra-violet absorber is less than respectively 2 % by weight with the BTA in multilayer film, is preferably 0.1 % by weight～1.5 % by weight, 0.2 % by weight～1 % by weight more preferably.If content is less than above-mentioned scope, ultraviolet screening effect is low; If exceed above-mentioned scope, in the situation that be applied in the film for agricultural use as general film for agricultural use, exist because of the problems such as albefaction due to oozing out.
For the film for agricultural use that comprises these two kinds of ultra-violet absorbers, preferably in the mode of covering in fact completely more than the ultraviolet amount in 200nm～370nm region, add.
As optimal way of the present invention, by the ultra-violet absorber of the per unit volume in intermediate layer (total of more than two kinds) with respect to the containing ratio (% by weight) of resin combination be made as X, by the ultra-violet absorber containing ratio (% by weight) of the per unit volume in internal layer be made as Y, when the ultra-violet absorber containing ratio (% by weight) of the per unit volume in skin is made as to Z, verified, if X>Y and X>Z, go through and can keep for a long time the effect of ultraviolet absorption ability remarkable.
Particularly when making this layer of formation with two kinds of specific ultra-violet absorbers of the present application, make the situation of same layer formation or with the combination of 2 kinds of other ultra-violet absorbers, make a same layer situation about forming and compare with utilizing separately each ultra-violet absorber, also thering is significant effect.
Herein, Y and Z can for Y=Z, also can be different.And, as particularly preferred mode, can enumerate the situation of Y=Z=0.
Specifically, the containing ratio X as intermediate layer middle-ultraviolet lamp absorbent with respect to resin combination, can enumerate 0.1 % by weight～3.0 % by weight, is preferably 0.15 % by weight～2.0 % by weight, the scope of 0.2 % by weight～1.0 % by weight more preferably.As Y and Z, can enumerate 0 % by weight～2.0 % by weight, be preferably 0 % by weight or be the scope of 0.001 % by weight～0.5 % by weight.
As the further preferred mode of the present invention, can enumerate following agricultural multilayer film, its be have at least possess skin, the agricultural multilayer film of 3 layers of above laminated structure of intermediate layer, internal layer, this agricultural is characterised in that with multilayer film, at outer and internal layer (superficial layer) combined with ultraviolet radiation absorbent and be combined with ultra-violet absorber in intermediate layer not.
Agricultural of the present invention is characterised in that with multilayer film, at whole layer thicknesses, be below 0.3mm and have at least one deck of more than at least 3 layers multilayer films, the inorganic compound that contains 3 % by weight of whole layers that account for film, this inorganic compound contains at least a kind of atom being selected from Si, Al, Mg, Ca, Li as its constituent.As operable inorganic compound, can enumerate for example infrared absorbent (heat preserving agent) or filler.
Infrared absorbent (heat preserving agent) is for having the inorganic particles of infrared ray absorbing ability, and they can use a kind of or be used in combination two or more.For operable inorganic particles, be not particularly limited, for containing, be selected from composition: the inorganic compound of at least a kind of atom in Si, Al, Mg, Ca, Li.For example can enumerate: magnesia, calcium oxide, aluminium oxide, silica, lithium hydroxide, magnesium hydroxide, slaked lime, aluminium hydroxide, magnesium carbonate, calcium carbonate, calcium sulphate, magnesium sulfate, aluminum sulfate, lithium phosphate, calcium phosphate, magnesium silicate, calcium silicates, alumina silicate, calcium aluminate, magnesium aluminate, aluminium oxide silicic acid sodium, aluminium oxide silicic acid potassium, aluminium oxide silicic acid calcium, kaolin, clay, talcum, mica, zeolite, hydrotalcite-based compound, lithium aluminum complex hydroxide, aluminium lithium magnesium compound carbonate compound, aluminium lithium magnesium complex silicate salt compound, magnalium silicon complex hydroxide, magnalium silicon sulfate composite salt compound, magnalium silicon compound carbonate compound, the metal composite hydroxide salt that contains two or more anion etc.They can be for sloughing the material of water of crystallization.
The above-mentioned inorganic particles using as infrared absorbent (heat preserving agent) can be natural goods, can be also composite.And the use of above-mentioned inorganic particles can not be limited to its crystalline texture, crystallization particle diameter etc.
In addition, the above-mentioned inorganic particles using as infrared absorbent (heat preserving agent) also can be used the material that its surface forms through the coatings such as metal organic sulfonate, high fatty acid amide, high-grade aliphatic ester or wax of the higher fatty acid metal salt of the higher fatty acid of stearic acid and so on, oleic acid alkali metal salt and so on, DBSA alkali metal salt and so on.
The above-mentioned inorganic particles using as infrared absorbent (heat preserving agent) can use separately or two or more is used in combination.Its average grain diameter is preferably 0.05 μ m～15 μ m, the scope of 0.1 μ m～10 μ m more preferably.If the average grain diameter of inorganic particles is less than above-mentioned scope, the bad dispersibility in resin, generate concavo-convex point (Block Star, 2 aggregations of inorganic matter) make film degraded appearance, powder when simultaneously mixing with resin disperses, and (powder founds Chi) is violent, treatability is poor.Otherwise, when the average grain diameter of inorganic particles is greater than above-mentioned scope, the transparency poor or in the broken sieve part (ブ レ ー カ ー ス ク リ ー Application portion of extruder) produce mesh obstruction, productivity ratio variation.
In addition, as filler, in order to suppress being clamminess or in order further to improve heat insulating ability, can using such as silica, talcum, aluminium hydroxide, hydrotalcite, calcium sulphate, calcium silicates, slaked lime, magnesium hydroxide, kaolinite clay, mica, aluminium oxide, magnesium carbonate, sodium aluminate, electroconductive zinc oxide, lithium phosphate etc. of film.These fillers can be used a kind, also two or more can be used in combination.
At film all in layer, the consumption of these inorganic compounds is 3 % by weight～30 % by weight, more preferably 3 % by weight～20 % by weight, 3 % by weight～15 % by weight more preferably.If be less than 3 % by weight, cannot give full play of effect of the present invention; When the scope for over 30 % by weight, as the transparency and the bad mechanical strength of film for agricultural use, and unfavorable economically.
In the agricultural that the present invention is used, use in multilayer film, can at least 1 layer of multilayer film, add the hindered amine compound as weather resisting agent.And this hindered amine compound can be used a kind of or be used in combination two or more.For hindered amine compound, all in layer, can contain identical type, this from needn't, for example also can in other layer, contain with containing the HMW type hindered amine compound that is difficult for oozing out in outermost layer (the outdoor face of canopy) hindered amine compound conventionally coordinating as agricultural use at innermost layer.For example, and these HMW hindered amine compounds can be the copoly type with ethene or other monomer (ethene cyclic amino vinyl compound copolymer) or also can be for grafting adduction is in take the type forming on the polymer that polyethylene is representative.In this case, for example also can in same layer, contain ethene cyclic amino vinyl compound copolymer is light stabilizer with the hindered amine conventionally coordinating as agricultural use.
Conventionally the hindered amine coordinating as agricultural use that can use is that light weather resisting agent is preferably and in molecule, at least has more than 2 piperidine ring structure and molecular weight is more than 500 hindered amine compound (hereinafter also referred to as " hindered amine compound that contains piperidine ring ").Herein, the piperidine ring number that contains the hindered amine compound of piperidine ring if above-mentioned is less than 2, can not get sufficient weather resistance; In addition, if molecular weight is less than 500, easily volatilization, cannot obtain long-term weather resistance.In addition, the piperidine ring number of the above-mentioned hindered amine compound that contains piperidine ring is preferably 2～50 and molecular weight and is preferably more than 750.
As the above-mentioned hindered amine compound that contains piperidine ring, for example can enumerate: two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl)-2-butyl-2-(3, 5-di-tert-butyl-4-hydroxyl benzyl) malonate, four (2, 2, 6, 6-tetramethyl-4-piperidyl) butane tetracarboxylic acid esters, four (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) butane tetracarboxylic acid esters, 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, 9-two [1, 1-dimethyl-2-{ three (2, 2, 6, 6-tetramethyl-4-piperidines oxygen base carbonyl oxygen base) butyl carbonyl oxygen base } ethyl]-2, 4, 8, 10-tetra-oxaspiros [5.5] hendecane, 3, 9-two [1, 1-dimethyl-2-{ three (1, 2, 2, 6, 6-pentamethyl-4-piperidines oxygen base carbonyl oxygen base) butyl carbonyl oxygen base } ethyl]-2, 4, 8, 10-tetra-oxaspiros [5.5] hendecane, 1, 5, 8, 12-tetra-[4, 6-is two, and { N-(2, 2, 6, 6-tetramethyl-4-piperidyl) butyl is amino }-1, 3, 5-triazine-2-yl]-1, 5, 8, 12-teteaazacyclododecane, 1-(2-hydroxyethyl)-2, 2, 6, 6-tetramethyl-4-piperidine alcohols/dimethyl succinate condensation product, the tertiary octyl group of 2-amino-4, 6-bis--chloro-s-triazine/N, N '-bis-(2, 2, 6, 6-tetramethyl-4-piperidyl) 1, 6-hexamethylene diamine condensation product, N, N '-bis-(2, 2, 6, 6-tetramethyl-4-piperidyl) 1, 6-hexamethylene diamine/ethylene dibromide condensation product etc.
If exemplify spendable commercially available hindered amine based compound, can enumerate: TINUVIN 770, TINUVIN780, TINUVIN 144, TINUVIN 622LD, TINUVIN NOR 371, CHIMASSORB119FL, CHIMASSORB944 (being manufactured by Ciba-Geigy society above); SANOL LS-765 (Sankyo Co., Ltd's manufacture); MARK LA-63, MARK LA-68, MARK LA-62, MARK LA-67, MARK LA-57, LA-900, LA-81, NO-Alkyl-1 (by ADEKA society, being manufactured above); UV-3346, UV-3529, UV-3581, UV-3853 (by SciTech society, being manufactured above); HOSTAVINN20, HOSTAVINN24, HOSTAVINN30, HOSTAVIN845, HOSTAVIN NOW, Sanduvor PR-31, NYLOSTAB S-EED (being manufactured by ClariantJapan society above); UVINUL5050H (being manufactured by BASF Japan society above) etc.These hindered amine compounds that contain piperidine ring can be used in one or more mode.
As ethene cyclic amino vinyl compound copolymer, can suitably use the copolymer of the cyclic amino vinyl compound (B) shown in ethene (A) and following formula (3).
In formula (3), R3 and R4 represent hydrogen atom or methyl independently of one another, and R5 represents the alkyl that hydrogen atom or carbon number are 1～4, preferably R3 and R4 is respectively methyl, R5 is hydrogen atom.
By using this ethene cyclic amino vinyl compound copolymer, can make long-term weatherability, resistance to exudative excellence, the in the situation that of forming antifog property simultaneously film etc. on base material film, can improve the adaptation of filming.
Vinyl compound (B) shown in formula (3) is known, can utilize known method, such as the method for recording in No. 47-8539, Japanese Patent Publication, Japanese kokai publication sho 48-65180 communique etc., synthesize.
In the present invention, as the commercially available product of spendable above-mentioned ethene cyclic amino vinyl compound copolymer, can enumerate NOVATEC LDXJ100H (Japanese POLYCHEM Co., Ltd. manufacture) etc.
Agricultural of the present invention is with in multilayer film, with respect to whole polyolefin-based resins 100 weight portions in layer of base material film, the content of above-mentioned ethene cyclic amino vinyl compound copolymer is preferably 0.5 weight portion～15 weight portion, 0.5 weight portion～10 weight portion more preferably.If this content is less than above-mentioned scope, weather resistance is poor, thereby not preferred; If surpass above-mentioned scope, not preferred from the viewpoint of economy.
From the viewpoint of cost, above-mentioned ethene cyclic amino vinyl compound copolymer used in the present invention needn't contain in whole layers of base material film, as long as contain at least 1 layer.In the situation that be provided with antifog property on the internal layer of base material film, film, from the viewpoint of improving adaptation that antifog property films, preferably at least in internal layer, contain ethene cyclic amino vinyl compound copolymer.
In addition, in thermoplastic resin film of the present invention, can share the various additives that conventionally use in synthetic resin.As these additives, for example can enumerate: the organic acid salt of metal, basic organic acid salt and high alkalinity organic acid salt; Hydrotalcite compound, epoxide, beta-diketone compound, polyalcohol, halogen oxysalt; The antioxidants such as sulphur system, phenol system and phosphite ester system; Heat stabilizer, lubricant, antistatic additive, colouring agent, anti-blocking agent, antifoggant, bloom inhibitor etc.
As the metal kind that forms organic acid salt, basic organic acid salt and the high alkalinity organic acid salt of above-mentioned metal, can enumerate Li, Na, K, Ca, Ba, Mg, Sr, Zn, Cd, Sn, Cs, Al, organic Sn, as organic acid, can enumerate carboxylic acid, organic phosphor acids or phenol, as this carboxylic acid, for example can enumerate: acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, new decane acid, 2 ethyl hexanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, lauric acid, tridecanoic acid, tetradecylic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxy stearic acid, behenic acid, montanic acid, elaidic acid (acid of エ ラ イ ジ Application), oleic acid, linoleic acid, linolenic acid, TGA, mercaptopropionic acid, octyl group mercaptopropionic acid, benzoic acid, monochloro benzoic acid, p-tert-butyl benzoic acid, dimethyl hydroxyl benzoic acid, 3, 5-di-tert-butyl-4-hydroxybenzoic acid, methyl benzoic acid, mesitylenic acid, ethyl benzoate, isopropyl acid, n-propylbenzene formic acid, acetoxy-benzoic acid, salicylic acid, to monocarboxylic acids such as tertiary octyl group salicylic acids, dicarboxylic acids or their monoesters or the monomer amide compounds such as ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid (acid of メ タ コ Application), itaconic acid, aconitic acid, thio-2 acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), oxygen base phthalic acid, chlorophthalic acid, the diester of the ternarys such as butane tricarboxylic acids, BTCA, benzene-1, trimellitic acid, mellophanic acid, the equal tetracarboxylic acid of benzene or quaternary carboxylic acid or three ester compounds etc., and, as this organic phosphor acids, can enumerate: list or dioctyl phosphoric acid, list or two (dodecyl) phosphoric acid, list or two (octadecyl) phosphoric acid, list or two (nonyl phenyl) phosphoric acid, phosphonic acids nonyl phenylester, phosphonic acids stearyl etc., in addition, as this phenol, can enumerate: phenol, cresols, xylenols, methyl-propyl phenol, methyl-tert octyl phenol, ethyl-phenol, isopropyl-phenol, tert-butyl phenol, normal-butyl phenol, diisobutyl phenol, isopentyl phenol, diamyl phenol, isohesyl phenol, octyl phenol, isooctyl phenol, 2-ethylhexyl phenol, tert-octyl phenol, nonyl phenol, dinonyl phenol, tertiary nonyl phenol, decyl phenol, dodecyl phenol, octadecyl phenol, cyclohexylphenol, phenylphenol phenol, cresols, ethyl-phenol, cyclohexylphenol, nonyl phenol, dodecyl phenol etc.
For above-mentioned antifoggant, be not particularly limited, the known various nonionic of take be surfactant, anion be surfactant, cation be surfactant etc. as polyol partial esters representative, that formed by polyalcohol and higher fatty acid class be that material is suitable.Concrete example as such antifoggant, for example can enumerate: nonionic is surfactant, be surfactant such as sorbitan monostearate, sorbitan list myristinate, sorbitan monopalmitate, sorbitan list behenate, sorbitan and the condensation product of alkylene glycol and the sorbitans such as ester of fatty acid; Glycerine monopalmitate, glyceryl monostearate, glyceryl monolaurate, Sunsoft Q 16D, dipalmitin, glycerol distearate, Sunsoft Q 16D monostearate, triglycerin monostearate, triglycerin distearate or their glycerine such as alkylene oxide adduct are surfactant; The polyethylene glycol such as polyethylene glycol mono stearate, polyethylene glycol monopalmitate, polyalkylene glycol alkyl phenyl ether are surfactant; The trimethylolpropanes such as trimethylolpropane monostearate are in addition surfactant; The pentaerythrite such as pentaerythritol monopalmitate, pentaerythritol monostearate is surfactant; The alkylene oxide adduct of alkylphenol; The condensation product of sorbitan/glycerine and the ester of fatty acid, the condensation product of sorbitan/alkylene glycol and the ester of fatty acid; Diglycerol dioleate NaLS, neopelex, hexadecyltrimethylammonium chloride, dodecyl amine hydrochlorate, lauric acid lauryl acid amides ethyl phosphate, triethyl group cetyl ammonium iodide, the amino diethylamine hydrochloride of oleyl, dodecyl pyridiniujm etc.; Or the material of the isomer that contains them etc.
As above-mentioned bloom inhibitor, can enumerate for example fluorine is surfactant or silicon-type surfactant, as fluorine, be the concrete example of surfactant, for surfactant that the part or all of H of the C bonding of common surfactant and hydrophobic grouping is replaced by F, be in particular the surfactant that contains perfluoroalkyl or perfluorinated alkenyl.Above various additives can be used respectively a kind or two or more to be used in combination.As the fluorochemical with perfluoroalkyl, can enumerate such as anion is that fluorine-containing surfactant, cation are that fluorine-containing surfactant, amphoteric fluorotensides, nonionic are fluorine-containing surfactant, fluorine-containing oligomer etc.
With respect to thermoplastic resin 100 weight portions, the above-mentioned consumption with the fluorochemical of perfluoroalkyl is preferably 0.001 weight portion～10 weight portion, 0.01 weight portion～5 weight portion more preferably.If the consumption of this fluorochemical is less than 0.001 weight portion, almost can not bring into play anti-hazing property effect, even and if over 10 weight portions, effect reaches capacity, thereby not preferred.
As above-mentioned phenol, it is antioxidant, for example can enumerate: 2,6-BHT, 2,6-diphenyl-4-octadecane oxygen base phenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl)-propionic ester, distearyl (3,5-di-tert-butyl-4-hydroxyl benzyl) phosphonate ester, Thiodiglycol two [(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], 1,6-hexa-methylene two [(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] etc.
As above-mentioned sulphur, be antioxidant, can enumerate such as two alkylthio group dipropionate classes such as dilauryl thiodipropionate, two myristins, distearyl esters; And polyalcohol β-alkyl thiol propionic acid ester such as pentaerythrite four (β-dodecyl mercaptopropionic acid ester).
As above-mentioned phosphite ester, it is antioxidant, for example can enumerate: trisnonylphenyl phosphite, three (2,4-di-tert-butyl-phenyl) phosphite ester, three [the 2-tert-butyl group-4-(3-tertiary butyl-4-hydroxy-5-methylbenzene sulfenyl)-5-aminomethyl phenyl] phosphite ester etc.
As above-mentioned colouring agent, can enumerate such as: phthalocyanine blue, phthalocyanine green, hansa yellow, alizarine lake, titanium dioxide, zinc white, ultramarine, permanent bordeaux, quinacridone, carbon black etc.
As anti-blocking agent, can enumerate diatomite, synthetic silica, talcum, mica, zeolite etc.These anti-blocking agents can use separately or two or more is used in combination, and are conventionally preferably the scope of 0.01 % by weight～0.5 % by weight.
Agricultural of the present invention is that combination by containing mentioned component obtains with multilayer film, further can contain as required following any composition that can be included in agricultural use multilayer film of the present invention.So-called composition arbitrarily can be enumerated: other stabilizing agent, resistance to impact improver, crosslinking agent, filler, blowing agent, antistatic additive, nucleator, anti-agent (プ レ ー ト ア ウ ト prevents drug), surface conditioning agent, fire retardant, fluorescer, mould inhibitor, bactericide, matal deactivator, antitack agent, pigment, the processing aid etc. of oozing out.
Agricultural of the present invention is with in multilayer film, in order to coordinate various additives, can weigh respectively needed amount, use known cooperation machine, the mixer all the time such as the cooperation machines such as ribbon blender, Banbury, Henschel mixer, Super Mixer, single screw rod or double screw extruder, roller or mixing roll.For the resin combination so obtaining is become to membranization, can suitably use itself known method, such as using methods such as melt extruding the method for forming (comprising T modulus method, inflation method), calendering processing, roller processing, extrusion molding processing, blow molding, inflation moulding, melting the tape casting, extrusion forming processing, thickener processing, powder moulding.
Thickness about agricultural of the present invention with multilayer film, from the viewpoint of intensity, cost, is preferably the scope of 0.03mm～0.3mm, the scope of 0.05mm～0.2mm more preferably.If be less than this scope, aspect intensity, there will be problem; If exceed this scope, be difficult to moulding.
In the present invention, can join with the innermost layer of polyolefin base material film forms antifog property and films.
As the antifog coating in the present invention, can use the known antifog coating can be used in film for agricultural use.Can preferably use and take antifog coating that colloidal inorganic substance and hydrophily organic compound be principal component or the antifog coating that colloidal inorganic substance and acrylic resin be principal component of take.
As the antifog coating that colloidal inorganic substance and hydrophily organic compound be principal component of take that can use in the present invention, can enumerate the compound shown in No. 63-45432, Japanese Patent Publication, No. 63-45717, Japanese Patent Publication, No. 64-2158, Japanese Patent Publication, No. 3094296th, Japan Patent etc.
In the present invention, also can suitably use and take the antifog property that acrylic resin and inanimate matter colloid solution be principal component and film.
For 1 example preferably using as acrylic resin, can enumerate the hydrophobic acrylic acid as aqueous dispersion polymers or copolymer who obtains is as follows resin: according to common polymerizing condition, for example, under the existence of emulsifier, make at least to add up to the monomer that the alkyl esters by acrylic or methacrylic acid of 60 % by weight forms, or the monomer mixture of the alkyl esters of acrylic or methacrylic acid and alkenyl benzene class and 0～40 % by weight can copolymerization α, β-ethylenically unsaturated monomers carries out emulsion polymerisation in water-medium, obtaining thus the described hydrophobic acrylic acid as aqueous dispersion polymers or copolymer is resin.
In the present invention, to be preferably hydrophobic acrylic acid be resin to acrylic resin used, that is, preferably the monomer mixture of the above-mentioned alkyl esters of acrylic or methacrylic acid or the alkyl esters of acrylic or methacrylic acid and alkenyl benzene class contain be at least 60 % by weight, preferably contain 80 % by weight more than.When lower than 60 % by weight, the resistance to water of filming that forms insufficient, thereby cannot give play to antifog duration performance, not preferred.
It is the resin of 35 ℃～80 ℃ that acrylic resin of the present invention is particularly preferably used glass transition temperature.If glass transition temperature is too low, there is gathering for several times and be easily inhomogeneous dispersity in inanimate matter colloidal solid; Too high in the situation that, be difficult to easily obtain thering is transparent uniform coating.
In the present invention, the formed thickness of filming in the surface of base material film take base material film below 1/10 as benchmark is selected, but and nonessential being limited in this scope.If the thickness of filming is greater than 1/10 of base material film, base material film and overlay film are variant aspect flexibility, thereby the phenomenon of easily filming and peeling off etc. from base material film, and can occur in that the upper generation of filming is chapped and this phenomenon of strength decreased of causing base material film is not preferred.
In addition, base material film with derive from the inadequate situation of the cementability of filming of coating composition, can impose surface treatment to base material film.As the surface of multilayer film of the present invention being imposed to the method for processing, can enumerate the methods such as Corona discharge Treatment, sputter etching processing, sodium processing, blasting treatment.Corona discharge Treatment method is following processing: between needle-like or Knife-edge test electrode and counterelectrode, discharge, insert betwixt sample and process, contain the oxygen-containing functional groups such as aldehyde, acid, alcohol peroxide, ketone, ether at film Surface Creation.Sputter etching is treated to following processing: sample is inserted between the electrode that carries out atmospheric depression glow discharge, utilize the impact of the cation producing by glow discharge on film, to form a large amount of micro crownings.Blasting treatment is following processing: fine sand is blowed and sprayed to face, form from the teeth outwards a large amount of micro concavo-convexes.Among these surface treatments, from the viewpoint of the adaptation with coating layer, workability, safety, cost etc., Corona discharge Treatment is suitable.
Agricultural of the present invention is with multilayer film when reality is used, and the mode that can be canopy chamber or inner side, tunnel according to a side that is provided with antifog coating is sprawled.
The agricultural of the present application so obtaining can be covered the ultraviolet ray of 200nm～370nm in fact completely with multilayer film." cover in fact completely " and mean under the state of untapped film for agricultural use, its light transmittance is below 0～2%.
[embodiment]
Based on embodiment, comparative example, the present invention is further elaborated below, but the present invention only otherwise exceeding its main points is just not limited to following example.
(1) adjustment of laminated film (antifoggant is mediated (Practice り Write body) type, antifog coating application type share)
As 3 layers of inflation shaped device, in used
three layers of die head ((strain) プ ラ work development make), for extruder, the diameter of the extruder of 2 outer internal layers of pipes is
the diameter of the extruder in ((strain) PLAGIKEN manufacture), intermediate layer is
((strain) PLAGIKEN manufacture), make that outer internal layer extruder temperature is that 180 ℃, intermediate layer extruder temperature are that 170 ℃, die head temperature are that 180 ℃～190 ℃, blow-up ratio are 2.0～3.0, extraction speed (drawing the り speed of getting) is 3m/ minute～7m/ minute, thickness is 0.15mm, 3 integrated membranes layer by layer that obtain consisting of composition shown in table 1～table 3.In addition, these films are that the end of pipe is cut and then used carrying out when sprawl canopy chamber, thereby upon deployment, outer tube layer during masking is the internal layer (inner face) of canopy chamber when sprawling.
[cooperation] addition as each table record.
HP-LDPE: side chain shaped polyethylene (MFR:0.8g/10 minute, density 0.922) the Japanese POLYCHEM NOVATEC LD processed " YF30 " that utilizes the manufacture of high-pressure free radical method catalyzer to obtain
Metallocene PE: utilize ethylene-alpha-olefin copolymer (MFR:2g/10 minute, density 0.913) Yu Buwanshan polyethylene Co., Ltd. that metallocene catalyst manufacture obtains to manufacture " 1520F "
EVA1: EVAc (vinyl acetate content 5 % by weight, MFR2g/10 minute)
EVA2: EVAc (vinyl acetate content 15 % by weight, MFR2g/10 minute)
Chimassorb 944:Ciba Specialty Chemicals society manufactures light stabilizer
Ethene cyclic amino ethylenic copolymer: " NOVATECLDXJ100H " MFR=3g/10 minute (190 ℃, JIS-K6760) density=0.931g/cm that Japanese POLYCHEM Co., Ltd. manufactures
3(JIS-K6760) % by mole fusing point=111 ℃, ratio=90 of the isolated cyclic amino vinyl compound existing of cyclic amino vinyl compound content=5.1 % by weight (0.7 % by mole)
Triaryl triazine is that ultra-violet absorber A:R3 is the triaryl triaizine compounds that octyl group, R4～R7 are methyl
BTA is that ultra-violet absorber A:Ciba Specialty Chemicals society manufactures TINUVIN 326 (2-[5-chloro-(2H)-BTA-2-yl]-4-methyl-6-(tert-butyl group) phenol)
BTA is that ultra-violet absorber B:SHIPRO changes into Co., Ltd. and manufactures SB704CL (2-[5-chloro-(2H)-BTA-2-yl]-4,6-bis-(tertiary pentyl) phenol)
BTA is that ultra-violet absorber C:SHIPRO changes into Co., Ltd. and manufactures SB7021MBCL (2-[5-chloro-(2H)-BTA-2-yl]-4,6-bis-(tertiary pentyl) phenol)
BTA is that ultra-violet absorber D:Ciba Specialty Chemicals society manufactures TINUVIN 327 (2,4-di-t-butyl-6-(5-chlorobenzotriazole-2-yl) phenol)
BTA is that ultra-violet absorber E:Ciba Specialty Chemicals society manufactures TINUVIN 320
Benzophenone series ultra-violet absorber A:SciTech society manufactures Cyasorb UV-531
Benzophenone series ultra-violet absorber B:SciTech society manufactures Cyasorb UV-9
(2) surface treatment of film
With discharge voltage 120V, discharge current 4.7A, linear velocity 10m/min, the superficies of resulting tubular film are carried out to Corona discharge Treatment, based on JIS-K6768, measure " wetting index " and confirm.
(3) formation (antifog coating application type) that antifog property is filmed
Antifogging agent composition coordinates for following and coordinates.
Inanimate matter colloid solution (colloidal silica) 4.0
Thermoplastic resin (SANMOL SW-131) 3.0
Crosslinking agent (T.A.Z.M) 0.1
Dispersion medium (water/ethanol=3/1) 93
The combined amount of (notes) inanimate matter colloid solution represents with inanimate matter grain amount, and the combined amount of thermoplastic resin becomes representation in components with polymer solids.
Colloidal silica: produce chemical society daily and manufacture SNOWTEX 30, average grain diameter 15m μ
SANMOL SW-131: Sanyo changes into society and manufactures acrylic emulsion
T.A.Z.M: pharmaceutical worker society manufactures aziridine based compound mutually
Use #5 scraping strip coating machine, above-mentioned antifogging agent composition is coated on respectively to the surface that surface-treated base material film has been carried out in utilization (2).Film after coating is kept 1 minute in the baking oven of 80 ℃, make liquid dispersion medium volatilization, form antifog property and film.The coating thickness of resulting each film is approximately 1 μ m.
This, use to be provided with the type (thickness 150 μ m) that antifog property films and to test, but the type of mediating for antifoggant also obtains same effect.And, even if be the combination beyond this resin used, additive or be the film thickness different from this, only otherwise change its main points, also can obtain same effect.For this each sample used, carrying out following optical characteristics measures.Each determination method in embodiment and comparative example is as follows.
(1) transparency
Utilize spectrophotometer (Hitachi manufactures, U3500 type) to measure the initial stage transparency (the parallel rays transmitance under wavelength 555nm) of film, this value is shown.
(2) UV isolation
(a) initial stage ultraviolet ray transmissivity
Utilize spectrophotometer (Hitachi manufactures, U3500 type) mensuration to utilize the laminated film (after canopy indoor layer side surface formation (coating) antifog property is filmed) that 3 layers of inflation moulding obtain at the total light transmittance of 325nm, this value to be shown.
(b) ultraviolet ray of 200nm～380nm sees through
Utilize the total light transmittance of above-mentioned spectrophotometric determination 200nm～380nm.
(3) ultraviolet absorption ability retentivity
According to airtight mode, in the pipe canopy of building during the laminated film that utilizes 3 layers of inflation moulding to obtain (after the indoor layer of canopy side surface forms (coating) antifog property and film) is spread into farm, Song Ban city, triple county.In late May, 2009～2012 year late May, part film in spreading in above-mentioned pipe canopy is sampled, utilize spectrophotometer (Hitachi manufactures, U3500 type) to measure its ultraviolet absorption ability (total light transmittance under wavelength 325nm).
The transmitance calculating is as stated above classified with following benchmark.
Zero initial stage with sprawl after the difference of total light transmittance be in 10%
* the initial stage with sprawl after the difference of total light transmittance be greater than 10%
(4) environmental influence
The ultra-violet absorber using is examined method etc. based on Japanization and chemical substance is carried out to the rules of control and is existed in specially appointed situation and be recorded as " having ", is recorded as " nothing " without this appointment in the situation that.
[embodiment 1 and comparative example 1～2]
Utilization be used in combination triazine as ultra-violet absorber be ultra-violet absorber and BTA be ultra-violet absorber form with inorganic filler coordinate (embodiment 1) and add triazine be ultra-violet absorber, BTA be any one cooperation forming (comparative example 1,2) of ultra-violet absorber make thickness be 150 μ m, layer than the trilamellar membrane (antifog coating application type) that is 1/3/1, by said method, carry out the evaluation of the transparency, UV isolation, ultraviolet absorption ability retentivity.It the results are shown in table 1.
The evaluation result of polyolefin multilayer film for [table 1] agricultural
By having illustrated in table 1, be that ultra-violet absorber, BTA are that any one comparative example 1,2 of ultra-violet absorber is compared with being added with triazine, using triazine is that ultra-violet absorber and BTA are ultra-violet absorber as the embodiment 1 of ultra-violet absorber excellent aspect the transparency, UV isolation and ultraviolet absorption ability retentivity.
[embodiment 1 and comparative example 3～5]
Utilize to use triazine be ultra-violet absorber and BTA be the cooperation (embodiment 1) that forms as ultra-violet absorber of ultra-violet absorber, add benzophenone series ultra-violet absorber as the cooperation (comparative example 3,4) of ultra-violet absorber, to add triazine be ultra-violet absorber and benzophenone series ultra-violet absorber as the cooperation (comparative example 5) of ultra-violet absorber make thickness be 150 μ m, layer than the trilamellar membrane (antifog coating application type) that is 1/3/1, by said method, carry out the evaluation of the transparency, UV isolation, ultraviolet absorption ability rheological parameters' change with time.It the results are shown in table 2.
The evaluation result of polyolefin multilayer film for [table 2] agricultural
By having illustrated in table 2, be that ultra-violet absorber is compared with the cooperation (comparative example 5) of benzophenone series ultra-violet absorber with only adding the cooperation (comparative example 3～4) of benzophenone series ultra-violet absorber as ultra-violet absorber, being added with triazine, having used triazine is that ultra-violet absorber and BTA are ultra-violet absorber as the embodiment 1 of ultra-violet absorber excellent aspect the transparency, UV isolation and ultraviolet absorption ability retentivity.
[embodiment 2 and 3]
Triazine has been used in utilization be ultra-violet absorber with the BTA shown in formula (1) be in ultra-violet absorber A, B any one as ultra-violet absorber to coordinate (embodiment 2～3) to make thickness be that 150 μ m, layer are than the trilamellar membrane (antifog coating application type) that is 1/3/1.Herein, BTA is that ultra-violet absorber and triazine are that ultra-violet absorber adds respectively 0.92 % by weight, 0.46 % by weight in intermediate layer.
For resulting trilamellar membrane, utilize spectrophotometer (Hitachi manufactures, U3500 type) to measure the initial stage total light transmittance of 300nm～700nm.The results are shown in Fig. 1.
In addition, according to airtight mode, resulting trilamellar membrane (after canopy indoor layer side surface formation (coating) antifog property is filmed) is spread in the pipe canopy of building in liking farm, portion prefecture, county magistrate sea.In late November, 2010～2012 year late May, the part film in spreading in above-mentioned pipe canopy is sampled, and utilizes spectrophotometer (Hitachi manufactures, U3500 type) to measure the total light transmittance of 300nm～700nm.The results are shown in Fig. 2.
From Fig. 1 and 2, using triazine, be that ultra-violet absorber and BTA are ultra-violet absorber A or B as ultra-violet absorber in the situation that, all there is good UV isolation, ultraviolet absorption ability retentivity.
[embodiment 1,4 and comparative example 6]
In the situation that use triazine be the BTA shown in ultra-violet absorber and formula (1) be ultra-violet absorber A or D as ultra-violet absorber (embodiment 1,4) and use triazine be ultra-violet absorber and BTA be ultra-violet absorber E as ultra-violet absorber (comparative example 6), making thickness is 150 μ m, layer than the trilamellar membrane (antifog coating application type) that is 1/3/1.In each embodiment, comparative example, maximum absorption wavelength and the environmental influence of benzotriazole type ultra-violet absorber used are listed in table 3.
The evaluation result of polyolefin multilayer film for [table 3] agricultural
As the above results discloses, known being during film is added in ultra-violet absorber and inorganic filler combination to time by specific benzotriazole type ultra-violet absorber and triazine, can reduce environmental influence, can give wider ultraviolet radiation absorption region and good ultraviolet absorption ability retentivity simultaneously.
For this, there is the multilayer film for agricultural of the long-term retentivity excellence of wider ultraviolet radiation absorption wave band and ultraviolet absorption ability, going through under long canopy indoor environment, the anti-deterioration of Reproduction suppression, control of insect and the inner lining material of its disease bacterium or mould etc. are also excellent, the ultraviolet ray with multilayer film base material worsening reason as agricultural can be absorbed for a long time, thereby membrane lifetime can be extended; And owing to can suppressing to reduce oozing out of reason as the adaptation of filming, thereby can obtain for a long time the good adaptation of filming.
Claims (6)
1. an agricultural multilayer film, it is characterized in that, described agricultural is that whole layer thicknesses are at least 3 layers of above polyolefin multilayer film that have below 0.3mm with multilayer film, the random layer of described polyolefin multilayer film contains inorganic compounds more than 3 % by weight of whole layers that account for film, described inorganic compound contains and is selected from Si, Al, Mg, Ca, at least a kind of atom in Li is as its constituent, and in random layer, containing triazine more than at least one and be ultra-violet absorber is ultra-violet absorber with the BTA as shown in the formula more than (1) represented at least one,
In formula (1), R1, R2 represent replacement that hydrogen atom, carbon number are 1～10 or the alkoxyl that is 1～10 without the alkyl replacing or carbon number independently of one another.
2. agricultural multilayer film as claimed in claim 1, wherein, at least in intermediate layer, containing described BTA is ultra-violet absorber.
3. agricultural multilayer film as claimed in claim 1 or 2, wherein, described BTA is that at least one the maximum absorption wavelength in ultra-violet absorber is more than 350nm.
4. the agricultural multilayer film as described in any one of claim 1～3, is characterized in that, described triazine is that ultra-violet absorber is as shown in the formula shown in (2);
In formula (2), R3～R7 represents the alkyl that hydrogen atom or carbon number are 1～10 independently of one another.
5. the agricultural multilayer film as described in any one of claim 1～4, is characterized in that, the adding conditional of ultra-violet absorber meets following condition:
The ultra-violet absorber containing ratio Y of per unit volume in the ultra-violet absorber containing ratio X> internal layer of per unit volume in intermediate layer, and the ultra-violet absorber containing ratio Z of per unit volume in X> skin.
6. the agricultural multilayer film as described in any one of claim 1～5, is characterized in that, the ultraviolet ray that this agricultural can substantive be covered 200nm～370nm completely with multilayer film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012157639A JP2014018996A (en) | 2012-07-13 | 2012-07-13 | Agricultural multilayer film |
| JP2012-157639 | 2012-07-13 |
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| Publication Number | Publication Date |
|---|---|
| CN103535215A true CN103535215A (en) | 2014-01-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210551833.8A Pending CN103535215A (en) | 2012-07-13 | 2012-12-18 | Agricultural-use multilayered film |
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| Country | Link |
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| JP (1) | JP2014018996A (en) |
| CN (1) | CN103535215A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6365139B2 (en) * | 2014-09-04 | 2018-08-01 | 日本ポリエチレン株式会社 | High radiation resistant film and film product using the same |
| JP6576723B2 (en) * | 2015-07-21 | 2019-09-18 | 住化積水フィルム株式会社 | Agricultural multilayer film |
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