JPH1034841A - Coating material for agriculture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent mechanical characteristics or particularly excellent strength and tear resistance as well as durability by laminating an ethylene tetrafluoride copolymerization resin film and a biaxially oriented polyester film via an adhesive layer. SOLUTION: An ethylene tetrafluoride copolymerization resin film and a biaxially oriented polyester film are laminated via an adhesive layer. A thickness of the resin film is not particularly limited, and its thickness can be set to a suitable range of about l to 50μm. The constituting polyester film is biaxially oriented, the thickness of the film is not particularly limited, and can be set to a suitable range of about 10 to 300μm. A thermally adhesive resin layer is formed of thermoplastic resin, a mixture of them or resin further added with low molecular weight paraffin. The layer is formed of adhesive resin in which when it is heated, it is melted, while when it is cooled, it is solidified.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural covering material.

[0002]

2. Description of the Related Art In recent years, the spread of agricultural houses has been remarkable, and they are widely used for forcing cultivation and suppression cultivation of vegetables, fruits, flowers and the like. The coating materials of these agricultural houses are made of heat-resistant, chemical-resistant,
A biaxially oriented polyester film having excellent mechanical properties and the like is used. Agricultural coatings made of such a biaxially oriented plastic film include, for example,
No. 178049, Japanese Patent Publication No. 59-17735,
Japanese Patent Publication No. 58-38303 is disclosed.

[0003] Furthermore, in order to pursue economical efficiency and labor saving of agricultural houses, even more durable coating materials have been demanded, and such coating materials are the most excellent among plastic films. Application of fluororesin films having excellent weather resistance has been rapidly progressing, and their use has been expanding despite their disadvantages in terms of price compared to other types of coating materials.

[0004] In particular, a tetrafluoroethylene copolymer resin film is superior to a vinylidene difluoride polymer resin film, a monofluoroethylene polymer resin film or the like, among the fluororesin films in terms of optical properties, antifouling properties, mechanical properties and the like. Are well balanced and have many applications. Examples of such agricultural coating materials comprising a tetrafluoroethylene copolymer resin film include, for example, JP-A-5-59202 and JP-A-6-4.
No. 6683 is disclosed.

[0005]

However, in conventional agricultural covering materials made of a biaxially oriented plastic film, the mechanical strength of the film itself is certainly excellent, and its advantages are great. In the case of breakage due to house expansion or hail, etc., because of the low film breakage, film tears were easily propagated, and labor was required for tear measures and tear repair work.

Agricultural coating materials made of a tetrafluoroethylene copolymer resin film have extremely high tear resistance, but on the other hand, have low mechanical strength, so that they have practical properties for house use. It was necessary to thicken the film.

[0007] The present invention solves the above problems,
An object of the present invention is to provide an agricultural covering material having excellent mechanical properties, particularly strength and tear resistance, and also having durability and the like as an agricultural covering material.

[0008]

The agricultural coating material of the present invention for this purpose is obtained by laminating a tetrafluoroethylene copolymer resin film and a biaxially oriented polyester film via an adhesive layer. is there.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a tetrafluoroethylene copolymer resin is a typical one represented by ethylene-tetrafluoroethylene copolymer, hexafluoropropylene-tetrafluoroethylene copolymer, A fluoroalkyl vinyl ether-tetrafluoroethylene copolymer and the like, and a copolymer and a mixture thereof can be used. Mechanical properties, film forming properties,
From the viewpoint of processing suitability and the like, it is preferable to use an ethylene-4fluoroethylene copolymer, and a hexafluoropropylene-4fluoroethylene copolymer. Are particularly preferred. still,
The main component itself occupies 50% by weight or more in the resin component, more preferably 70% by weight or more, and may contain other substances as appropriate. The resin to be added is not particularly limited, and for example, a polyolefin resin, an acrylic resin, or the like can be used. Also, if necessary, the tetrafluoroethylene copolymer resin film may contain appropriate additives in an amount which does not impair the effects of the present invention, such as a heat stabilizer, an oxidation stabilizer, a weather stabilizer, an ultraviolet absorber, and a pigment. ,dye,
Inorganic or organic particles, dispersants, coupling agents, fillers and the like may be blended.

Further, the tetrafluoroethylene copolymer resin film may be used in any of unoriented, uniaxial and biaxial orientations.

The thickness of the tetrafluoroethylene copolymer resin film is not particularly limited, and an appropriate thickness can be set in a range of about 1 to 50 μm. Also, the surface roughness and optical properties of the tetrafluoroethylene copolymer resin film are not particularly limited, but those having a total light transmittance of preferably 70% or more are preferable in terms of transparency in an agricultural house. The above is preferable.

Further, in the present invention, by subjecting the surface of the tetrafluoroethylene copolymer resin film to a surface treatment or an undercoating treatment, the adhesion to the antifouling layer and the adhesive layer, the water resistance and the like are improved. It can be used preferably. As the surface treatment, for example, a corona discharge treatment (in air, in nitrogen, in carbon dioxide, or the like), a plasma treatment (high pressure, low pressure), an alkali metal solution treatment, a high frequency sputter etching treatment, or the like is used. In the case of the surface treatment, the treatment intensity is not particularly limited and may be a desired value. As a guide of the treatment intensity, the surface wetting index of the film measured based on JIS-K-6768 is 35 dyn / cm or more is preferable,
More preferably, it is set to 40 dyn / cm or more.

The polyester in the present invention is a polymer obtained by condensation polymerization of a diol and a dicarboxylic acid. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like. The diols are represented by ethylene glycol, trimethylene glycol, tetramethylene glycol, cyclohexane dimethanol and the like. Specifically, for example, polyethylene terephthalate, polyethylene-p-
Oxybenzoate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and the like are used.

These polyesters may be either homopolyesters or copolyesters. In the case of copolyesters, copolymer components such as diol components such as diethylene glycol, neopentyl glycol and polyalkylene glycol, adipic acid, Sebacic acid,
Dicarboxylic acid components such as phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 5-sodium sulfoisophthalic acid are used.

Further, various additives such as an antioxidant, a heat stabilizer, a lubricant, a pigment, an antistatic agent, and an ultraviolet absorber may be added to the polyester.

Among them, in the present invention, it is more preferable to add an ultraviolet absorber from the viewpoint of the durability of the polyester. As the ultraviolet absorber, for example, benzophenone type,
One or more selected from benzotriazole-based, hindered amine-based and the like can be applied. Particularly preferred are 2,2 ', 4, which have excellent compatibility with polyester.
4'-tetrahydroxy-benzophenone, bis (5
-Benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-methylenebis [4- (1,1,
3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like.

The content of the ultraviolet absorber in the polyester is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight. If the content is out of the above range, sufficient durability cannot be obtained or the properties of the polyester tend to be deteriorated.

In the present invention, it is preferable to use polyethylene terephthalate or polyethylene-2,6-naphthalenedicarboxylate which is excellent in water resistance, chemical resistance, strength and the like as the polyester, since particularly excellent effects can be obtained.

The polyester film constituting the present invention is biaxially oriented, and the thickness of the film is not particularly limited, and an appropriate thickness can be set in a range of about 10 to 300 μm. Also, the surface roughness and optical properties of the biaxially oriented polyester film are not particularly limited, but those having a total light transmittance of preferably 70% or more in terms of transparency in an agricultural house are preferable in terms of characteristics. is there.

Further, in the present invention, by subjecting the surface of the biaxially oriented polyester film to a surface treatment, the adhesion to the drip-proof layer and the adhesive layer, the water resistance, and the like are improved, so that it can be used more preferably. As the surface treatment, for example, a corona discharge treatment (in air, in nitrogen, in carbon dioxide, or the like) is used.

In the present invention, the adhesive layer is not particularly limited, and a general adhesive layer, a heat-adhesive resin layer, a pressure-sensitive adhesive layer, etc. can be applied, and the adhesive layer has excellent adhesion to each substrate. Can be preferably used.

The general adhesive layer referred to in the present invention includes, for example, thermosetting adhesives such as epoxy resin, urea resin, phenol resin, polyisocyanate, and silicone, and various acrylic and methacrylic ester-based adhesives. , Cyanoacrylates, thermoplastic adhesives such as polyamides,
A composite polymer type adhesive such as an epoxy resin / nylon resin type or a rubber / phenol resin type is used.

The thermoadhesive resin layer referred to in the present invention is a resin to which a thermoplastic resin or a mixture thereof, and further a low molecular weight paraffin or the like is added, and which is melted when heated and solidified when cooled. Layers, specifically,
For example, ethylene and ethylene-vinyl acetate copolymer resin, ethylene-acrylate copolymer resin and ionomer resin, polyamide resin, polyester resin, polypropylene resin, polyurethane resin, polyester urethane resin and vinyl chloride resin as copolymers thereof. And a polymethacrylic resin.

The pressure-sensitive adhesive layer in the present invention is not particularly limited, but (1) a polymer such as natural rubber, styrene / butadiene rubber, polyisobutylene, polychloroprene, polyarylate rubber, or polyvinyl ether rubber. (2) Polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl butyral, chlorinated rubber, hydrochloride rubber, polyacrylates and mixtures of high molecular substances such as copolymers thereof with plasticizers, 3) tackifiers such as rosin, rosin ester, coumarone resin, terpene resin, hydrocarbon resin, oil-soluble phenol resin, (4) various additives such as fillers, pigments, antioxidants, stabilizers, etc. Various combinations of 1) to (4) and silicone-based pressure-sensitive adhesives can be used as typical examples.

In the present invention, the thickness of the adhesive layer is not particularly limited and may be a desired value.
m is preferably in the range of 10 to 100 μm in terms of uniform layer formation, processability such as lamination, and adhesion.

The adhesive layer may contain additives such as plasticizers, stabilizers, inorganic or organic lubricants, ultraviolet absorbers, flame retardants and the like, if necessary, in amounts that do not impair the effects of the present invention. Good.

Among them, in the present invention, it is preferable to include an ultraviolet absorber in the adhesive layer from the viewpoint of durability of the adhesive layer. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based and hindered amine-based ones. One or more selected from the above can be applied. Particularly preferred are those having excellent ultraviolet absorbing ability and being uniformly dispersed in the adhesive layer, such as 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, -(2'-hydroxy-5'-t-octylphenol) benzotriazole and the like are used.

The content of the ultraviolet absorbent in the adhesive layer is preferably 0.05 to 30% by weight, and 0.1 to 15% by weight.
Are more preferable. If the content is out of the above range, sufficient durability cannot be obtained or the adhesive strength tends to decrease.

In the present invention, it is particularly preferable to use a heat-adhesive resin layer as the adhesive layer from the viewpoint of the production of the agricultural covering material of the present invention. Is 50% by weight or more in the adhesive layer.

Among the heat-adhesive resins, it is preferable to use polyester resins, polyurethane resins, polyester urethane resins, vinyl chloride resins, polymethacrylic resins and the like in the present invention.

In the present invention, in order to prevent the agricultural covering material of the present invention from deteriorating due to ultraviolet rays, the present invention is further applied to crop cultivation.
It is desirable to provide an ultraviolet absorbing layer when it is preferable to block ultraviolet light.

The ultraviolet absorbing layer is not particularly limited as long as it is a layer having an ultraviolet absorbing ability.
Such an ultraviolet absorbing layer is provided between the tetrafluoroethylene copolymer resin film and the adhesive layer.

In the present invention, as the ultraviolet absorbing layer,
A composition mainly containing a mixture of a general polymer binder and an ultraviolet absorber can be preferably used. The main component refers to one that is 50% by weight or more in the layer.

The polymer binder in the present invention is selected from a thermoplastic resin or a curable resin and is a resin soluble in an organic solvent or the like.
Polyamide, polyesteramide, polyvinyl acetal, polyvinyl chloride, poly (meth) acrylate, polyimide, polyurethane, polycarbonate, polystyrene, polymethylpentene, polyolefin, halogenated polyolefin, alkyd resin, polyamide resin, silicon resin, fluorine resin, etc. Is used.

As the curable resin which is cured by light, heat, oxygen, etc., for example, phenol resin, melamine resin,
In the present invention in which an epoxy resin, a crosslinked silicon resin or the like is used, it is preferable to apply a thermosetting resin from the viewpoint of water resistance, solvent resistance, heat resistance, abrasion resistance, mechanical strength, and the like of the ultraviolet absorbing layer,
Further, those capable of achieving cross-linking by using a cross-linking agent in combination are more preferable.

Further, in the present invention, it is preferable to use a polyester resin, a polyurethane resin or an acrylic copolymer resin among the above-mentioned polymer binders, and it is more preferable to use an acrylic copolymer resin. It is an acid ester copolymer.

As the organic solvent for the polymer binder, for example, alcohols, carboxylate esters, ketones, aliphatic hydrocarbons, alicyclic or aromatic hydrocarbons, and mixtures thereof are used. It is preferable to select one that does not adversely affect the applicability and the like.

The ultraviolet absorber used in the present invention is preferably selected from those which have excellent heat resistance, have good compatibility with the above-mentioned polymer binder, can be uniformly dispersed, have little coloring, and do not adversely affect the resin. .

As the ultraviolet absorber, for example, benzophenone type, benzotriazole type, hindered amine type,
Various adaptations such as oxalic acido are possible,
Specifically, bis (5-benzoyl-4-hydroxy-
2-methoxyphenyl) methane, 2,2'-4,4'-
Tetrahydroxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone,
2,4-di-t-butylphenyl-3 ′, 5′-di-t
-Butyl-4'-hydroxybenzoate, 2-
(3 ′, 5′-Ditertiaryamyl-2′-hydroxyphenyl) benzotriazole, 2 (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2 (2 '-Hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2-ethoxy-2'-ethyloxacacid bisanilide, 2,4-di-t-butylphenyl-
3 ', 5'-di-t-butyl-4'-hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, dimethyl succinate 1- (2
-Hydroxyethyl) -4-hydroxy-2,2,6
6-tetramethylpiperidine polycondensate and the like can be used.

The UV absorber is not particularly limited, and may be used alone or in combination of two or more.

The content of the ultraviolet absorber in the layer is 0.1.
The content is preferably from 01 to 50% by weight, more preferably from 0.1 to 20% by weight. If the content is lower than the above range, it is difficult to obtain a sufficient ultraviolet shielding property, and if the content exceeds the above range, the uniform dispersibility tends to decrease.

In the present invention, the laminated thickness of the ultraviolet absorbing layer is
Although not particularly limited, it is preferably from 0.05 to 50 μm, and more preferably from 0.1 to 20 μm in terms of uniformity of the ultraviolet absorbing layer, adhesion, and the like. Further, if necessary, the ultraviolet absorbing layer may contain various additives such as an antifoaming agent, a coating improver, a thickener, an antistatic agent, and a dye in an amount that does not impair the effects of the present invention. Is also good.

In the present invention, it is particularly preferable to use an ultraviolet-absorbing acrylic resin for the ultraviolet-absorbing layer from the viewpoint of durability and the like. 50% by weight in absorption layer
This refers to the above, and other substances may be added as appropriate. The resin to be added is not particularly limited, and for example, a polyester resin, an acrylic resin, or the like can be used.

In the present invention, the UV-absorbing acrylic resin is, specifically, a reactive benzophenone-based compound having UV-absorbing ability or a reactive benzotriazole-based compound and an acrylic monomer having a polymerizable unsaturated group. Is a copolymer resin.

The reactive benzophenone-based compound or reactive benzotriazole-based compound is a monomer having a copolymerizable unsaturated group in the molecule, and the reactive benzophenone-based compound is, for example, 2
-Hydroxy-4-methacryloxybenzophenone,
2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2-hydroxy-4- (2-methacryloxy) ethoxybenzophenone, 2-hydroxy-4-vinyloxycarbonylmethoxybenzophenone and the like are used. As the reactive benzotriazole-based compound, for example, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-
(2 "-methacryloyloxyethyl) benzotriazole, 2 (2'-hydroxy-5'-methylphenyl)
-5- (2 "-methacryloyloxyethyl) benzotriazole, 2- (2'-hydroxy-5'methacryloxyethylphenyl) -2H-benzotriazole,
2- (2'-hydroxy-5'-methacryloxyethylphenyl) -5-chloro-2H-benzotriazole and the like are used.

The acrylic monomer having a polymerizable unsaturated group is an alkyl acrylate represented by the following chemical formula 1 (R: hydrogen or methyl group, R ′: alkyl group having 1 to 18 carbon atoms), and Alkyl methacrylate, acrylic acid, methacrylic acid, β-hydroxy acrylate, β-hydroxy methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, polyoxyethylene glycol monomethacrylate, polyethylene polytetramethylene ether glycol monomethacrylate, dimethylaminoethyl Methacrylate, diethylaminoethyl methacrylate, acrylamide, methacrylamide, N-methylmethacrylamide, Nn-butoxymethylacrylamide, acid phosphooxyethyl Methacrylate, 3-chloro -
2-acid phosphooxypropyl methacrylate, 3
-Chloro-2-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, methoxypolyethylene glycol monomethacrylate, 3-acrylamide-2-methylpropanesulfonic acid, N-methylolacrylamide, N-methylol Methacrylamide, polyoxyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
At least one selected from dipromneopentyl glycol methacrylate, tetramethylol methane triacrylate and the like is used.

[0047]

Embedded image Among them, the copolymer is preferably an alkyl methacrylate or an alkyl acrylate in terms of its polymerizability, coating film characteristics, and the like, and examples thereof include methyl acrylate and ethyl acrylate. Further, it is preferable to use an acrylic monomer containing a carboxyl group or a methylol group from the viewpoint of adhesion to a substrate.

In terms of the composition of the UV-absorbing acrylic resin, 2-hydroxy-4-methacryloxybenzophenone or 2-hydroxy-4-methacryloxybenzophenone is used as the reactive benzophenone compound.
-Hydroxy-4- (2-methacryloxy) ethoxybenzophenone, as a reactive benzotriazole compound, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole or
Those mainly comprising a combination of-(2'-hydroxy-5'-methacryloxyethylphenyl) -5-chloro-2H-benzotriazole and methyl methacrylate as an acrylic monomer are preferable in terms of characteristics. Also,
When the acrylic monomer is contained in an amount of 20% by weight or more and 80% by weight or less, transparency and coating film characteristics are excellent, so that it is more preferable.

The ultraviolet-absorbing acrylic resin may be used as an aqueous dispersion or an organic solvent. In the case of an organic solvent, for example, alcohol-based, carboxylic ester-based, ketone-based, and aliphatic carbonized solvents may be used as the organic solvent. Hydrogen, alicyclic or aromatic hydrocarbons, and mixtures thereof are used, and those which do not adversely affect the applicability and the like are preferably selected.

In the present invention, in order to further improve the adhesion, solvent resistance, water resistance, scratch resistance, heat resistance and the like of the adhesive layer and the ultraviolet absorbing layer, it is preferable that the layer contains a cross-linking agent. .

The cross-linking agent referred to in the present invention means a cross-linking reaction with a functional group, for example, a hydroxyl group, a carboxyl group, a glycidyl group, an amide group, etc., present in a resin or the like constituting the layer. A cross-linking agent for forming a layer having an original network structure. Representative examples include ureol-based, melamine-based, acrylamide-based, polyamide-based resins, and epoxy compounds, isocyanate compounds, coupling agents, and aziridines. Compounds and the like can be used.

In the present invention, among these, it is preferable to use an isocyanate compound from the viewpoint of adhesion to a support, crosslinkability, and the like.

These crosslinking agents may be used alone or in combination of two or more in some cases. The amount of the cross-linking agent to be added is appropriately selected depending on the type of the cross-linking agent, but is usually preferably 0.01 to 50 parts by weight, more preferably 0.2 to 30 parts by weight, based on 100 parts of the resin solids. It is more preferable to use a crosslinking catalyst together with the crosslinking binder because crosslinking proceeds more. After applying the coating material with the cross-linking agent to the support, heating,
Crosslinking is carried out by ultraviolet rays, electron beams or the like, but usually a method by heating is generally used.

In the present invention, the antifouling layer means a layer having the property of being non-fouling or resistant to fouling and the property of easily removing fouling even if it is fouled. Fluorine-based, silicone-based, wax-based compounds or resins that provide water / oil repellency, and furthermore,
Examples include a layer made of a surfactant, an aqueous resin, and the like and a mixture thereof in which hydrophilicity is imparted to the surface to enhance the antistatic effect and the cleaning effect. However, in the present invention, it is most preferable to apply a layer composed of a composition containing an inorganic hydrophilic colloid substance as a main component, particularly from the viewpoint of antifouling property and durability. The composition as the main component refers to a composition which is 30% by weight or more in the antifouling layer, and may appropriately contain other substances. The substance to be contained is not particularly limited, but in the present invention, especially when a surfactant, a lithium silicate and / or a silane derivative, a polymer resin binder, etc. are contained in the antifouling layer, It is more preferable because the property is improved. In the present invention,
Such an antifouling layer is preferably provided on the outermost layer on the side of the tetrafluoroethylene copolymer resin film.

In the antifouling layer, various additives such as an antifoaming agent, an ultraviolet absorber, a pigment, a dye, a crosslinking agent, an antioxidant, and a coating improver may be added to the antifouling layer in an amount which does not impair the effect of the present invention. Agents and the like may be included. The thickness of the antifouling layer is
Although not particularly limited, it is preferably from 0.01 to 15 μm, more preferably from 0.05 to 5 μm in terms of uniform layer formation, handleability, antifouling property and the like.

When the coating material of the present invention is applied to an agricultural house, water vapor emanating from soil and plants in the house is condensed and adheres as fine water droplets on the inner surface of the coating material. It is preferable to provide a drip-proof layer on the coating material of the present invention since various adverse effects such as deterioration of the toner may occur. In the drip-proof layer, various types of drip-proof agents can be applied. Usually, a material mainly composed of a hydrophilic polymer, a surfactant, colloidal silica, alumina sol, or a mixture thereof is preferably used. obtain. In the present invention, such a drip-proof layer is preferably provided on the outermost layer on the biaxially oriented polyester film side.

Various additives may be added to the drip-proof layer if necessary.
For example, it may contain an antifoaming agent, a pigment, a dye, an antioxidant, a coating improver, and the like. The thickness of the drip-proof layer is
Although not particularly limited, it is preferably from 0.01 to 5 μm, more preferably from 0.05 to 1 μm in terms of drip-proof property and the like.

Next, some examples of the method for producing the agricultural covering material of the present invention will be described, but the present invention is not limited to these examples.

(1) In a film forming process of a tetrafluoroethylene copolymer resin film, each coating solution adjusted to a predetermined amount in advance is applied to the film, and then dried to obtain an antifouling layer.
A base film having an ultraviolet absorbing layer and an adhesive layer is prepared. This is a method in which the base film and the biaxially oriented polyester film are pressure-bonded or heat-bonded with a laminating roll, and heat-treated if necessary.

(2) After winding the tetrafluoroethylene copolymer resin film as a single film, a coating-drying step is provided to produce a base film having an antifouling layer, an ultraviolet absorbing layer and an adhesive layer. . Hereinafter, a method similar to the above (1) is used.

(3) A coating-drying process is provided on the biaxially oriented polyester film to form a drip-proof layer and an adhesive layer. This is a method in which the united resin film is integrated by pressing or heat bonding with a laminating roll.

The coating method is not particularly limited, and an extrusion lamination method, a melt coating method, or the like may be used. However, a gravure coating method, a reverse coating method, a spray coating method, or the like can be used because a thin film can be coated at a high speed. , A kiss coat method, a die coat method, a metaling bar coat method, and the like. It is desirable that the drying conditions of the coating film and the heat bonding under pressure be performed within a range that does not adversely affect the properties of each substrate.

Next, when a thermo-adhesive resin layer is applied as an adhesive layer, the resin pellets are fed to an extruder and melted at a temperature higher than the melting temperature and lower than the temperature at which the resin is decomposed. It is preferable to use a method of forming the solution on the film or a method of uniformly dissolving the resin in an organic solvent to prepare a solution adjusted to a predetermined amount and applying the solution on the film surface.

[0064]

[Method of measuring and evaluating characteristics] The characteristic value of the present invention is as follows.
According to the following evaluation methods and evaluation criteria.

(1) Tensile strength Evaluated according to JIS-C-2318.

(2) Tearing Propagation Resistance The tear propagation resistance was evaluated according to JIS-P-8116.

(3) Drip-proof property The roof of a steel-frame house of about 22 tsubo outdoors is 15
The covering material was spread at an angle of degree, and the drip-proof performance was observed for three months in winter (January to March) under crop cultivation. The criteria were as follows.

：: good △: slightly poor ×: poor

(4) Antifouling Property The degree of dust adhering to the film surface of the steel frame house of the above (3) was compared and observed over time, and evaluated according to the following criteria. The exposure period was six months in winter (October to March).

：: good △: slightly inferior (slightly noticeable dirt) ×: inferior (slightly noticeable dirt)

[0071]

The present invention will be described with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

Example 1 A surface of a 50 μm-thick tetrafluoroethylene copolymer resin film “TOYOFLON” ETFE (manufactured by Toray Industries, Inc.) was subjected to corona discharge treatment, and toluene / methyl ethyl ketone (mixing ratio: 1: 1) as a diluting solvent, and a saturated thermoplastic polyester resin "Vylon" 200 (manufactured by Toyobo Co., Ltd.) and 10 parts by weight of an isocyanate compound "Coronate" HX (Nippon Polyurethane Industry Co., Ltd.) per solid content of the resin. (Manufactured by Co., Ltd.) at a concentration of 20% by weight
Was applied to form an adhesive layer having a thickness of 15 μm. Next, a 50 μm-thick “Lumirror” T60 (manufactured by Toray Industries, Inc.) having a corona discharge treatment on the adhesive surface as a biaxially oriented polyester film was pressure-bonded with a 160 ° C. laminating roll through the adhesive layer. Heat treated at 40 ° C for 40 hours,
An agricultural covering was obtained. As shown in Table 1, the properties of the agricultural covering material were excellent in each property.

Example 2 Based on Example 1, a biaxially oriented polyester film obtained by subjecting the adhesive surface of "Lumirror" Q37 (manufactured by Toray Industries, Inc.) containing a 50 μm-thick ultraviolet absorber to corona discharge treatment. Agricultural coatings were obtained in the same manner as in Example 1, except that was used. As shown in Table 1, the agricultural covering material was excellent in each property.

Example 3 Based on Example 1, toluene / methyl ethyl ketone (mixing ratio: 1: 1) was used as a diluting solvent as an adhesive layer, and a saturated thermoplastic polyester resin “Vylon” 200 (manufactured by Toyobo Co., Ltd.) was added thereto. ) And UV absorber "ADK STAB" LA-
31 (manufactured by Asahi Denka Kogyo KK) at a solid content weight ratio of 90:10
The same as in Example 1 except that after coating a uniform coating material having a concentration of 10% by weight, the coating layer was dried at 120 ° C. for 1 minute to form an adhesive layer containing an ultraviolet absorber having a thickness of 15 μm. Agricultural coatings were obtained by the method. As shown in Table 1, the agricultural covering material was excellent in each property.

Example 4 Based on Example 2, toluene was used as a diluting solvent as an adhesive layer, and the silicone pressure-sensitive adhesive “Trefirm” SD4 was added thereto.
570PSA and crosslinking agent "Catalyst" SRX212
After applying a coating material containing a mixture (100: 0.9) of a concentration of 20% by weight (both manufactured by Toray Dow Corning Silicone Co., Ltd.), the coating layer was dried at 120 ° C. to form an adhesive layer having a thickness of 20 μm. Was formed. Next, the same polyester film as in Example 2 was overlaid on the adhesive layer, and pressure-bonded with a laminating roll to obtain an agricultural covering material. As shown in Table 1, the agricultural covering material was excellent in each property.

Example 5 Based on Example 1, a diluting solvent of toluene / methyl ethyl ketone (mixing ratio: 1: 1) was applied as a coating material on the surface of the corona-discharged fluorine film of Example 1, and this was mixed with an ultraviolet absorbing type. Acrylic resin (ULS-93 manufactured by Ichisha)
5 LH) and a 15 wt% coating material in which isocyanate compound “Coronate” HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was uniformly dissolved at 5 parts by weight per solid content of the resin, and the coating layer was heated at 120 ° C. Dry for 1 minute, thickness 3μm
After the UV absorbing layer was provided, an adhesive layer was formed on the UV absorbing layer by the same method as in Example 1, and thereafter, an agricultural covering material was obtained by the same method as in Example 1. As shown in Table 1, the agricultural covering material was excellent in each property.

Example 6 Corona discharge treatment was applied to both surfaces of the fluororesin film of Example 1, and one surface was treated with methanol as a diluent as a diluting solvent.
To this, colloidal silica (catalyst Kasei Kogyo Co., Ltd. isopropyl alcohol dispersion “OSCAL” (a), β-
Each of (3,4-epoxycyclohexyl) ethyltrimethoxysilane (b) and polyoxyethylene (10 mol) -lauryl ether (c) has a solid content weight ratio of a: b:
The mixture was mixed so that c = 85: 4: 11, and the active ingredient 20 was mixed.
After adjusting to 10% by weight, 10 parts by weight of an acrylic ester-based adhesive “CYBINOL” EK1005 (manufactured by Seiden Chemical Co., Ltd.) and the same amount of water were added to the solid content of the coating material to uniformly disperse. Apply coating material at 100 ° C
To provide a 0.3 μm thick antifouling layer.

Next, based on Example 5, an ultraviolet absorbing layer was formed on the opposite surface where the antifouling layer was provided by the same method as in Example 5.
Hereinafter, an agricultural covering material was obtained in the same manner as in Example 5. Table 1
As shown in Table 2, the agricultural covering material was excellent in each property.

Example 7 Both surfaces of the polyester film of Example 1 were subjected to a corona discharge treatment, and water was used as a drip-proofing agent on one side using water as a diluting solvent, and polyvinyl alcohol "Denkapovar" K-24E was added thereto.
(Manufactured by Denki Kagaku Kogyo Co., Ltd.), colloidal silica “Cataloid” S-30L (manufactured by Catalysis Chemical Industry Co., Ltd.), and nonionic surfactant “Nonion” NS-210 (manufactured by NOF Corporation) The solid content weight ratio is 80: 19.7: 0.3
A coating material having a concentration of 10% by weight and uniformly dispersed in the composition described above is applied, and the coating layer is dried at 120 ° C. for 1 minute to have a thickness of 0.8 μ
m of drip-proof layer was provided.

Next, based on Example 5, an agricultural covering material was obtained in the same manner as in Example 5, using the opposite surface provided with the drip-proof layer. As shown in Table 1, the agricultural covering material was excellent in each property.

Comparative Example 1 The properties of the fluororesin film used in Example 1 are shown in Table 1. As shown in Table 1, it is found that the fluororesin film has low tensile strength.

Comparative Example 2 The properties of the polyester film used in Example 1 are shown in Table 1. As shown in Table 1, the polyester film has a low tear resistance.

[0083]

[Table 1]

[0084]

In the agricultural covering material of the present invention, the following excellent effects are obtained because the tetrafluoroethylene copolymer resin film and the biaxially oriented polyester film are laminated via the adhesive layer. I was able to.

First, the agricultural covering material of the present invention has excellent tensile strength and tear resistance, and is therefore excellent in handleability.

The agricultural house coated with the agricultural covering material of the present invention has excellent antifouling property and drip-proof property, and can maintain the excellent effect as it is. Does not hinder transmission.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B32B 27/36 B32B 27/36

Claims (8)

[Claims] 1. An agricultural covering material comprising a tetrafluoroethylene copolymer resin film and a biaxially oriented polyester film laminated via an adhesive layer. 2. The agricultural covering material according to claim 1, wherein the biaxially oriented polyester film and / or the adhesive layer contains an ultraviolet absorbent. 3. The agricultural covering material according to claim 1, wherein an ultraviolet absorbing layer is provided between the tetrafluoroethylene copolymer resin film and the adhesive layer. 4. The agricultural covering material according to claim 3, wherein the ultraviolet absorbing layer is made of a composition containing an ultraviolet absorbing acrylic resin as a main component. 5. The agricultural covering material according to claim 1, wherein the adhesive layer is composed of a composition containing a thermoadhesive resin as a main component. 6. The agricultural covering material according to claim 1, wherein an antifouling layer is provided on the outermost layer on the side of the tetrafluoroethylene copolymer resin film. 7. The agricultural covering material according to claim 1, wherein a drip-proof layer is provided on the outermost layer on the biaxially oriented polyester film side. 8. The method according to claim 1, wherein the tetrafluoroethylene copolymer resin film is composed of a composition containing an ethylene-4fluoroethylene copolymer resin as a main component. Agricultural coatings.