JPH09322659A - Film for outdoor setup - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film for outdoor setup excellent in transparency and thermal insulation, and useful for e.g. protected horticulture, by providing the surface of a thermoplastic resin film with a layer containing specific inorganic fine particles and by providing the layer and/or the opposite face of the film with a 2nd layer containing hydrophilic inorganic colloid particles. SOLUTION: This film is obtained by providing (A) one side or both sides of a thermoplastic resin film such as of polyethylene terephthalate or fluororesin with layer(s) having heat ray-blocking ability and containing inorganic fine particles such as of tin oxide each <=15μm in average size and by providing the layer(s) and/or the opposite face of the film with (B) a 2nd layer consisting of a composition hydrophilic inorganic colloid particles such as of silica or alumina and a hydrophobic acrylic resin serving as a binder for the colloid particles and having a glass transition temperature of 35-80 deg.C. This film is >=60% in the transmittance of straight-advancing rays with a wavelength of 555nm, being improved in synergistic effect, and markedly improving the ability to protect the space inside agricultural greenhouses from heat rays of sunlight in summer. The amount of the hydrophilic inorganic colloid particles to be incorporated is 0.5-4 in the weight ratio to that of the hydrophobia acrylic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an outdoor stretching film used for covering horticulture facilities.
More specifically, the present invention relates to a film for outdoor expansion having transparency and excellent heat shielding properties.

[0002]

2. Description of the Related Art House covering materials that are generally used in conventional horticulture have the ability to transmit visible light as much as possible for the purpose of improving the heat retention in winter and securing the amount of solar radiation necessary for photosynthesis. Transparent synthetic resin films of polyvinyl chloride, polyolefin, polyethylene terephthalate, etc. are used. These conventional synthetic resin films are intended to improve the cultivability in winter, and the temperature in the house becomes high during the period from early summer to mid-autumn, which makes it difficult to cultivate a facility. Therefore, in the case of perennial flowers that need to go through the summer, use a shading net or a cold gauze as a lining or lining curtain to block solar radiation (including visible light) by about 30 to 80%.
The solar radiation energy that penetrates into the house is reduced, and the rise in the temperature inside the house is suppressed. In the case of flowers, although the cultivation is possible even with a small amount of required light, there is a problem that the plants are prostrate due to shading.

[0003] Cooling in a house is also performed as a countermeasure against high temperature in summer, but cooling by mist is apt to cause diseases due to wet plants, and the working environment deteriorates due to high humidity. Under the high temperature and high humidity environment like Japan, the effect is insufficient, and it is not widely used. On the other hand, cooling by a refrigerator is not often performed in a house where sunlight is poured, since the cooling efficiency is extremely low. On the other hand, regarding the cultivation of fruits and vegetables in summer,
Due to crop physiology and quality, it is almost impossible to block light, so in the southwestern warm areas, there is no cultivation of fruits and vegetables in the summer by facility horticulture, and even in the cool areas of Tohoku and Hokkaido, it is covered with a transparent film in the summer. Then, the temperature inside the house becomes high, and the quality and working environment become problems. Therefore,
There is a demand for a type of coating material that transmits visible light as much as possible and cuts heat rays (that is, near infrared rays) as much as possible.

An infrared reflecting material (a Japanese Patent Publication No. 59-13325) in which a very thin metal layer is vapor-deposited on the surface of a synthetic resin film, an agricultural film using a hologram reflecting near infrared rays and infrared rays in combination with the synthetic resin film ( Japanese Patent Laid-Open No. 7-274738) has been proposed, but the solar radiation energy from the sun is about 50 in the visible light region.
%, The near-infrared region and the infrared region have an energy amount of about 50%. Therefore, if visible light is blocked, the amount of transmitted solar energy can be easily reduced, but there is a problem that the amount of visible light is insufficient. Therefore, it is desirable to positively absorb or reflect (block) light in the near infrared region in the solar energy, and kneading or applying a heat ray absorbent or a heat ray reflector to a synthetic resin film is performed. ing.

[0005]

As a method of kneading particles having a heat ray shielding function, for example, a heat ray reflecting agent such as tungsten hexachloride, cupric sulfide, an aminium-based near-infrared absorbing dye, a metal complex compound or the like is used. The blending of a heat ray absorbent is disclosed in Japanese Patent Publication No. 4-45546, Japanese Patent Publication No. 58-58.
JP-A-56533, JP-B-62-54143,
JP-A-50-51549, JP-B-54-2506
0, Japanese Patent Publication No. 1-114801,
It has been proposed in Japanese Patent Application Laid-Open Nos. 17306, 3-215561, 3-161644, 6-73197, 8-81567, and the like. Further, as a method of applying a heat ray reflector or a heat ray absorber, tin oxide fine particles are dispersed in a binder solution, and the visible light transmittance obtained by forming a film on a transparent substrate is high,
In addition, a heat ray shielding film having excellent heat ray shielding properties (Japanese Unexamined Patent Publication No. 6-26
2717), a near-infrared absorbing film in which an organic near-infrared absorbing layer made of an amino compound and an inorganic near-infrared absorbing layer made of a solid solution of tin oxide and antimony oxide are laminated on a polyethylene terephthalate film.
-100996).

However, in the type that absorbs heat rays (type in which a heat ray absorbent is blended or coated), the base film absorbs the heat rays, and the temperature of the base film rises, and the heat from the base film is lost. There is a problem in that re-radiation occurs, which raises the temperature in the house, which is rather counterproductive. Further, even in the type that reflects heat rays, the heat ray shielding ability has not been sufficient to transmit visible rays as much as possible and to suppress a rise in temperature in summer in an agricultural house.

[0007]

Under these circumstances, the present inventors have further improved the shielding performance of a film that transmits visible light and shields heat rays as an outdoor stretching film. We have been working hard to provide a film for outdoor expansion. As a result, the present inventors have focused on the fact that the layer containing hydrophilic inorganic colloid particles actively takes in moisture in the air, and the latent heat of evaporation of the moisture further enhances the heat shielding effect of the heat ray absorbing material. I confirmed the thing. That is, when the humidity in the house is low, the moisture in the air taken into the surface of the base material evaporates quickly, deprives the latent heat of evaporation, prevents overheating of the base film, and reduces re-radiation of heat rays from the base film. . When the inside of the house is humid, a water film is formed on the film surface, and the water film constantly flows down the surface of the base material to remove heat from the base material film. It is possible to prevent the re-radiation from the base film by reducing the rise of the temperature.

However, the gist of the present invention is to provide a layer (A) containing inorganic fine particles having a heat ray shielding ability on at least one surface of a thermoplastic resin film, and further on the layer and / or the film. The film for outdoor spreading comprises a layer (B) containing hydrophilic inorganic colloid particles on the opposite surface.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a heat ray is a wavelength 2
Means near infrared in the range of 00 to 2600 nm;
Shielding means reflection or absorption. Hereinafter, the present invention will be described in detail. The thermoplastic resin constituting the outdoor stretchable film of the present invention may be a resin generally used for film forming. Specifically, monomers such as vinyl chloride, ethylene, propylene, acrylates, methacrylates, and fluorinated ethylene may be used alone or as a mutual polymer thereof, or at least one of these monomers.
Copolymers of the species with other copolymerizable monomers (eg, vinyl acetate, vinylidene chloride, etc.), fluorine-containing resins, polyesters, polyamides, and the like, or blends of these polymers. Among these, weather resistance, light transmission,
From the viewpoints of economy, strength, etc., vinyl chloride resin (ie,
Preference is given to polyvinyl chloride and its copolymers containing at least 50% by weight of vinyl chloride) and ethylene-based resins (ie polyethylene and its copolymers containing at least 50% by weight of ethylene), most preferably polyethylene terephthalate and It is a fluororesin.

When polyethylene terephthalate is used, the film may be unstretched or biaxially stretched, but preferably biaxially stretched from the viewpoint of film strength. When stretching biaxially, lengthwise,
Those stretched 2.0 to 5.0 times in the horizontal direction are preferable. If the stretching ratio is less than 2.0 times, the strength of the product will not be sufficient, so that it is not preferable. If the stretching ratio exceeds 5.0 times, the strength of the product will be sufficient, but the manufacturing operation is difficult. Is not preferred. The stretching ratio is particularly preferably in the range of 2.5 to 4.0 times in both biaxial directions. The method for producing the biaxially stretched film is not particularly limited and may be any conventionally known method such as sequential or simultaneous biaxial stretching.

The outdoor stretchable film according to the present invention preferably has a thickness of 0.01 to 0.3 mm. The thickness is 0.
If it is less than 01 mm, the strength of the product will not be sufficient, and if it exceeds 0.3 mm, the film will be hard,
It is not preferable because it becomes difficult to handle. These thermoplastic resins include, if necessary, known plasticizers, lubricants, heat stabilizers, metal organic phosphates, anti-fog agents, anti-fog agents, ultraviolet absorbers, Additives such as stabilizers, colorants, stabilizers, and antioxidants can be added in usual amounts.

Examples of the lubricant or heat stabilizer include chelators such as fatty acid-based lubricants, fatty acid amide-based lubricants, ester-based lubricants, polyethylene wax, liquid paraffin, and organic phosphite compounds which are generally used for films for outdoor stretching. Examples include phenols and β-diketone compounds. Specific examples include compounds described in JP-B-62-53543, column 7, lines 1 to 12.

Examples of the ultraviolet absorber include the following. 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-, which is a cyanoacrylate-based ultraviolet absorber
Diphenyl acrylate and the like. 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, which is a benzophenone ultraviolet absorber; 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5
-Sulfonebenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis- (2-methoxy-4 -Hydroxy-5-benzoylphenyl) methane and the like.

2- (2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5), which are benzotriazole ultraviolet absorbers
-Methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methyl Phenyl)
-5-ethylsulfonebenzotriazole, 2- (2 ′
-Hydroxy-5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5 '
-T-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethyl Phenyl) -5-methoxybenzotriazole, 2- (2′-methyl-4′-
Hydroxyphenyl) benzotriazole, 2- (2 ′
-Stearyloxy-3 ', 5'-dimethylphenyl)
-5-methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3'-methyl-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'
-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-Di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-5′-cyclohexylphenyl)
Benzotriazole, 2- (2′-hydroxy-4 ′,
5'-dimethylphenyl) -5-carboxylic acid benzotriazole butyl ester, 2- (2'-hydroxy-
3 ', 5'-dichlorophenyl) benzotriazole,
2- (2'-hydroxy-4 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-dimethylphenyl) -5-ethylsulfonebenzotriazole, 2- (2'-hydroxy-4'-
Octoxyphenyl) benzotriazole, 2- (2 ′
-Hydroxy-5'-methoxyphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5'-
Methylphenyl) -5-carboxylate benzotriazole, 2- (2′-acetoxy-5′-methylphenyl) benzotriazole and the like.

Further, there may be mentioned a number and polymer of these cyanoacrylate, benzophenone and benzotriazole ultraviolet absorbers. Among them, it is desirable to use a benzophenone ultraviolet absorber or a benzotriazole ultraviolet absorber. One or more of these ultraviolet absorbers may be used in combination, and the amount of the ultraviolet absorber used is 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, per 100 parts by weight of the thermoplastic resin.

In the present invention, the inorganic fine particles having a heat ray shielding ability to be formed in the layer (A) may be any particles having an ability to absorb or reflect heat rays. Specifically, Periodic Tables 4A, 5A, 6A Metal oxides, carbides,
Borides and the like, specifically, titanium oxide, a solid solution of tin oxide and antimony oxide, cupric sulfide, tungsten hexachloride, titanium mica (titanium oxide-coated mica), iron oxide-coated mica, and basic lead carbonate , Bismuth oxychloride,
Examples include selenium oxide and zinc oxide. Among them, inorganic oxides are preferred.

The average particle diameter of these inorganic fine particles is 1
Coarse particles exceeding 5 μm are not preferred because surface roughness is reduced, crater-like dents and projections are formed, resulting in poor appearance, irregular reflection on the surface is also remarkable, and visible light transmittance is reduced. Therefore, the average particle diameter of the inorganic fine particles is desirably 15 μm or less. The addition amount of the inorganic fine particles is adjusted so that the film after forming the layer (A) and the layer (B) has a transmittance of 60% or more in a visible light region (typically, a transmittance at 555 nm). However, in consideration of the target crop range, it is more desirable to adjust the blending amount so that the visible light transmittance value is 80% or more.
These inorganic fine particles may be used alone or in combination of several kinds. Further, an anthraquinone derivative, an organic compound such as a phthalocyanine compound, a naphthalocyanine compound, a squarylium compound, a thiourea compound, an immonium compound, or an acetylene compound, or a metal complex such as chromium, cobalt, or copper may be used in combination.

The layer (A) containing inorganic fine particles having a heat ray-shielding ability is prepared by dispersing inorganic fine particles in a liquid dispersion medium together with a binder on the surface of a thermoplastic resin film, and then forcibly drying. Alternatively, it can be formed by naturally drying and volatilizing the liquid dispersion medium. A thermoplastic resin may be used as the binder. Specifically, acrylic resin, vinyl chloride-vinyl acetate resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polyurethane resin, polycarbonate resin, styrene resin, vinyl acetate resin, unsaturated polyester Acrylic resin is particularly preferable.

As a method of forced drying, a hot air drying method,
An infrared radiation method or the like can be adopted. The coating method may be any known method such as a roll coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, and a knife coating method.

When the adhesiveness between the film surface and the layer (A) is not sufficient, it is appropriate to subject the film surface to plasma treatment or corona discharge treatment before applying the layer (A). The surface of the film may be modified by a method such as applying a different anchor agent. In the film for outdoor spreading of the present invention, the layer (B) containing hydrophilic inorganic colloid particles is formed on the layer on which the layer (A) is formed or on the opposite surface of the film on which the layer (A) is formed. That is, when the layer (A) is formed only on one surface of the film, the layer (B) may be formed on the layer (A), on the film surface on which the layer (A) is not formed, or on both. . When the layer (A) is formed on both surfaces of the film, the layer (B) may be formed on at least one surface.

Examples of the hydrophilic inorganic colloidal particles include silica, alumina, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide, barium sulfate, and the like. It is used in the form of an aqueous sol dispersed in a volatile medium. Among them, silica sol and alumina sol are preferable. These may be used alone or in combination. The inorganic colloid sol to be used has a solid average particle diameter of 5 to 10
Those having a range of 0 μm are preferred. Within this range,
Two or more kinds of colloid sols having different average particle diameters may be used in combination. If the average particle diameter exceeds 100 mμ, not only the coating film tends to be white and devitrification but also the heat shielding effect is deteriorated, which is not preferable. If it is less than 5 μm, the stability of the inorganic colloid sol may be lacking.

The layer (B) containing hydrophilic inorganic colloidal particles is preferably a composition containing a hydrophobic acrylic resin having a glass transition temperature of 35 to 80 ° C. as a binder. It is preferable that the amount of the hydrophilic inorganic colloid particles is 0.5 to 4 by weight based on the acrylic resin. That is, when it is less than 0.5, a sufficient heat shielding effect cannot be exhibited. Further, when it exceeds 4, not only the heat-shielding effect does not improve in proportion to the compounding amount, but when the molded product is transparent, the coating film formed after coating becomes cloudy to reduce the light transmittance, However, it is not preferable because the coating film is rough and easily becomes fragile.

As the hydrophobic acrylic resin having a glass transition temperature in the range of 35 to 80 ° C., there are at least 60 (meth) acrylic acid alkyl esters or a mixture of (meth) acrylic acid alkyl esters and alkenylbenzenes. A homopolymer or a copolymer obtained by polymerizing 0% to 40% by weight of an α, β-ethylenically unsaturated monomer copolymerizable with the above is preferable.

The alkyl (meth) acrylates are alkyl esters of acrylic acid or methacrylic acid, and specifically include, for example, methyl acrylate, ethyl acrylate, and n-propyl acrylate. Isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, Methacrylic acid-n-butyl ester, methacrylic acid-2-ethylhexyl ester,
Decyl methacrylate and the like, and in general,
An acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms and / or a methacrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is used.

The alkenylbenzenes include, for example, styrene, α-methylstyrene, vinyltoluene and the like. When a mixture of alkenylbenzenes and (meth) acrylic acid alkyl esters is used, α,
Although it varies depending on the amount of the β-ethylenically unsaturated monomer used, it is usually preferable to use the (meth) acrylic acid alkyl ester in an amount of 10% by weight or more, and occupy in the hydrophobic acrylic resin. Those containing alkenylbenzenes in a range of 70% by weight or less are preferred. Examples of the α, β-ethylenically unsaturated monomer copolymerizable with the above-mentioned (meth) acrylic acid alkyl esters or a mixture thereof with alkenylbenzenes include acrylic acid, methacrylic acid, maleic acid and maleic anhydride. Α, β-ethylenically unsaturated carboxylic acids such as acids, fumaric acid, crotonic acid and itaconic acid: α, β-ethylenically unsaturated sulfonic acids such as ethylenesulfonic acid: 2-acrylamido-2-methylpropanoic acid; α, β-ethylenically unsaturated phosphonic acids: hydroxyl group-containing vinyl monomers such as hydroxyethyl of acrylic acid or methacrylic acid: acrylonitriles: acrylic amides; glycidyl esters of acrylic acid or methacrylic acid. These monomers may be used alone or in combination of two or more, and may be used in the range of 0 to 40% by weight.

The hydrophobic acrylic resin in the present invention is
The glass transition temperature (Tg) thereof is preferably in the range of 35 to 80 ° C. Such Tg can be obtained by selecting the type of monomer used and the amount (blending amount) used. The Tg of the acrylic resin used is 80 ° C.
If it exceeds Tg, it is difficult to obtain a transparent and uniform coating film, and if Tg is less than 35 ° C., the inorganic colloid particles are likely to be agglomerated several times to form a non-uniform dispersion state. Since the adherence to the coated substrate is not sufficient, the inorganic colloidal particles fall off from the substrate surface or flow away over time, impairing the heat shielding performance improving effect, which is not preferable.

The hydrophobic acrylic resin is usually used as an aqueous emulsion. In that case, even if an aqueous emulsion obtained by polymerizing each monomer in an aqueous medium is used as it is, a liquid dispersion medium is further added to this. In addition, it may be diluted, or the polymer produced by the above polymerization may be separately collected and redispersed in a liquid dispersion medium to obtain an aqueous emulsion.

A monovalent electrolyte may be added to the layer (B) in order to improve the wettability of the layer (B). Specific examples include strong electrolytes such as nitric acid, hydroxides and alkali salts of alkali metals and alkaline earth metals, and weak electrolytes such as organic acids and organic bases. Examples of strong electrolytes include inorganic acids such as nitric acid and hydrogen bromide, inorganic hydroxides such as potassium hydroxide, lithium hydroxide and sodium hydroxide, sodium bromide, sodium iodide, potassium bromide, potassium nitrate, and bromide. Inorganic salts such as rubidium, rubidium iodide, cesium bromide, cesium iodide, silver nitrate, ammonium bromide, ammonium iodide, hydrogen chloride, ammonium chloride, sodium chloride, potassium chloride and the like. Specific examples of the weak electrolyte include acetic acid, ammonium acetate, potassium acetate, sodium acetate and the like.

These electrolytes may be used alone or in combination of two or more. The addition amount of these monovalent electrolytes is 0.01 to 100 parts by weight of the hydrophilic inorganic colloid particles.
The amount is 30 parts by weight, preferably 0.01 to 20 parts by weight, particularly preferably 0.01 to 10 parts by weight. If the electrolyte is a liquid, it refers to the weight of 100% active ingredient.

In the layer (B), if necessary, a conventional additive such as a defoaming agent, a plasticizer, a film-forming aid, a thickener, a pigment, a pigment dispersant, a light stabilizer, and an ultraviolet absorber is added. The agents can be mixed.

In the layer (B) of the present invention, a composition containing hydrophilic inorganic colloid particles and a binder is used as a liquid dispersion medium using water or a mixture of water and a hydrophilic or water-miscible solvent. A dispersion liquid is applied to the surface of the thermoplastic resin film or the surface of the layer (A), and the liquid dispersion medium is forcibly dried or naturally dried to vaporize the liquid dispersion medium to form a coating film. Examples of the hydrophilic or water-miscible solvent include monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol: polyhydric alcohols such as ethylene glycol, diethylene glycol, and glycerin: cyclic alcohols such as benzyl alcohol: cellosolve Acetates: ketones and the like. These may be used alone or in combination.

Further, it is preferable to add a crosslinking agent to the dispersion. The acrylic resin is cross-linked by the cross-linking agent, and the water resistance can be improved. Examples of the cross-linking agent include phenol resins, amino resins, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds, and the like, but particularly amine compounds and aziridine compounds. , Epoxy compounds are preferred. As a method of forced drying, a hot air drying method, an infrared radiation method, or the like can be employed.
The heating temperature at the time of forcible drying is determined by the applied composition, but is 50 to 250 ° C., preferably 70 to 250 ° C.
It is in the range of 200 ° C.

As a method of coating, a roll coating method,
Any known method such as dip coating, brush coating, spray coating, bar coating, and knife coating may be used. After the dispersion is applied to the surface of the film, and the liquid dispersion medium is dried and volatilized, the solid adhered amount is usually 0.01 to 10 g / m ² , preferably 0.1 to 10 g / m ² .
It is in the range of 5 g / m ² .

When the adhesiveness between the film surface and the layer (B) is not sufficient, the film surface may be subjected to plasma treatment or corona discharge treatment before applying the dispersion liquid. May be modified.
When the adhesion between the layer (A) and the layer (B) is not sufficient, an anchor coat or the like may be applied on the layer (A) before applying the dispersion. When the film for outdoor stretching according to the present invention is stretched and used, in the case of a film in which the layer (B) is formed on only one side, the film on which the layer (B) is formed is stretched so as to be inside a house or a tunnel. . For the purpose of improving the dust resistance, antifogging property, weather resistance and blocking resistance of the film for outdoor spreading according to the present invention, another resin such as acrylic resin is formed on the surface of the film on which the layer (B) is not formed. A coating layer made of a resin, a fluorine resin, or a polyolefin resin may be provided.

[0035]

The film for outdoor stretching according to the present invention is excellent in transparency and has a remarkable heat shielding effect in an agricultural house in summer due to the synergistic effect of the layer (A) and the layer (B). Therefore, its value as a film for outdoor expansion is extremely large.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the following examples unless it exceeds the gist. Examples 1-11, Comparative Examples 1-6

(1) Preparation of base film (i) Polyethylene terephthalate Polyethylene terephthalate (using o-chlorophenol as a solvent, the intrinsic viscosity measured at 25 ° C. was 0.65).
) Was blended with 100 parts by weight of the ultraviolet absorbers shown in Table 1 in the proportions shown in the same table. After blending each composition with a supermixer for 10 minutes, the mixture is melt-extruded by a conventional method, and stretched at a stretching temperature of 65 ° C in the longitudinal direction and a stretching ratio of 3.5 times, then stretched at a stretching temperature of 65 ° C and a stretching ratio of 3.5 times in the transverse direction. To produce a biaxially oriented film having a thickness of 0.15 mm. The density of this film is 1.37
It was g / cm ³ .

(Ii) Soft vinyl chloride resin film Per 100 parts by weight of polyvinyl chloride (degree of polymerization = 1300), 50 parts by weight of dioctyl phthalate, 5 parts by weight of tricresyl phosphate, and 2 parts by weight of epoxy resin ,
2 parts by weight of Ba-Zn liquid stabilizer, 1 part by weight of Ba-Zn powder stabilizer, 1. sorbitan monopalmitate.
5 parts by weight and 0.1 part by weight of the ultraviolet absorber shown in Table 1 were weighed and mixed by stirring for 10 minutes with a super mixer, and then kneaded on a roll heated to 165 ° C. to obtain L
Width 100 cm, thickness 0.1 by die calender
A 0 mm transparent soft vinyl chloride resin film was produced.

(Iii) Fluororesin film A discharge voltage of 120 V, a discharge current of 4.7 A, and a line speed of 5 to 15 m were formed on one side of an ethylene-tetrafluoroethylene copolymer resin film (Tefzel AS, manufactured by DuPont, thickness: 64 μm). / Min was subjected to corona treatment.

(Iv) Polyolefin-based film As a three-layer inflation molding apparatus, 100
The extruder used was 30 mmφ (manufactured by Pla Giken Co., Ltd.) and two intermediate layers were 40 m.
As a mφ (manufactured by Pla Giken Co., Ltd.), a laminated film having a thickness of 0.15 mm having the following composition was produced at a molding temperature of 160 ° C., a blow ratio of 2.0 and a take-up speed of 5 m / min.

[Outer layer] Raw material resin (EVA (VA component: 5%)) 100 parts by weight Metal phosphate organic phosphate (monooctadecyl zinc phosphate) 0.5 Hindered amine (MARK LA-57) 0.5 UV absorption Agent 0.5 ソ ル sorbitan monostearate 0.5 〃

[Inner layer] Raw material resin (EVA (VA component: 15%)) 100 parts by weight Metal phosphate organic phosphate (monooctadecyl zinc phosphate) 0.5 Hindered amine (MARK LA-57) 0.5 UV absorption Agent 0.5 ソ ル sorbitan monostearate 0.5 ハ イ ド ロ hydrotalcite 15 〃

[0042]

[Table 1] Note) * 1 The parts by weight of the acrylic resin indicates the amount of the polymer solid in the aqueous emulsion, the parts by weight of the inorganic colloid sol indicates the amount of the inorganic particles, and the parts by weight of the crosslinking agent indicates the parts by weight of the solid. * 2 B, F and H used aziridine compounds manufactured by Mutual Yakuko Co., Ltd., and C and D used bisphenol A type epoxy compounds manufactured by Dainichi Ink Chemical Co., Ltd.

(2) Layer (A) (i) Preparation of layer (A) composition Mica titanium, tin oxide and zinc oxide of the types shown in Table 2 were added to an acrylic resin solution (50 parts by weight of methyl methacrylate, butyl). 30 parts by weight of methacrylate and 20 parts by weight of 2-hydroxyethyl methacrylate) (solid content concentration 10 wt%) were compounded in the compounding amounts shown in Table 2 to prepare layers (A) compositions MP. (Ii) Formation of Layer (A) Coating Film One side of each film obtained in (1) (in the case of a fluorine film, on the surface that has been subjected to surface treatment), each of the films obtained in (2)-(i) The composition was applied by a bar coating method so that the coating amount after drying was 6 g / m ² as a solid content.
The mixture was kept in hot air of 1 ° C. for 1 minute to disperse the solvent.

[0044]

[Table 2]

(3) Layer (B) (i) Preparation of acrylic resin A four-necked flask was charged with 2 parts by weight of polyoxyethylene lauryl ether and 80 parts by weight of water and heated to 60 ° C. under a nitrogen gas stream, 0.5 parts by weight of ammonium persulfate was added thereto, and the mixture 1 of each monomer shown in Table 1 was further added.
00 parts by weight were added dropwise over 3 hours. At this time, the reaction temperature was maintained in the range of 60 to 70 ° C., and after the completion of the dropwise addition, the temperature was maintained for 2 hours, followed by cooling to obtain an acrylic resin emulsion. The glass transition temperature of each resin is as shown in Table 1 and is a value calculated by the following formula.

(1 / Tg) = (W1 / Tg1) + (W2
/ Tg2) + ·· + (Wn / Tgn) (wherein Tg: glass transition temperature (K) of the hydrophobic acrylic resin Tg1, Tg2 ·· Tgn: homopolymer of each component 1, 2 ... Glass transition temperature (K) W1, W2 ··· Wn: The weight fraction of each component 1, 2 ···· n is shown.)

(Ii) Preparation of Layer (B) Composition Into the aqueous dispersion of the acrylic resin produced in (3)-(i), the type and amount of inorganic colloid sol and other components shown in Table 1 are added. By blending, various layer (B) compositions were prepared. (Iii) Formation of Layer (B) Coating Film On the surface of the film obtained in (2) on which the layer (A) is formed, various compositions obtained in (3)-(ii) are applied by a bar coating method. , Coating amount after drying is 0.5g / m as solid content
^The solution was coated so as to be ² and kept in hot air at 80 ° C. for 1 minute to disperse the solvent.

(4) Evaluation Various properties of the films obtained in (3)-(iii) were evaluated by the methods described below, and the results are shown in Table 3. (I) Visible light transmittance Total light transmittance at 555 nm was measured using a self-recording spectrophotometer (Hitachi 330 type) using a 60φ integrating sphere. (Ii) Heat ray cutoff ratio Using a self-recording spectrophotometer (Hitachi 330 type), using a 60φ integrating sphere, measure the total light transmittance at 200 to 2600 nm, and obtain the wavelength dependence data of solar radiation energy from the sun. And the ratio of the solar energy blocked by the substrate to the solar energy directly received without the substrate.

(Iii) Ground temperature and temperature in the house The film was spread in a closed pipe house (frontage 5m x depth 10m) with the surface provided with the layer (B) inside the house, and the daytime ground temperature and temperature in the summer were measured. It was measured. The soil temperature was measured by putting sand in the center of the house, blocking the surroundings with a board, setting a thermocouple at a position of 5 cm in depth, and measuring the value at 14:00 when the weather was fine was shown as a value relative to the external value. . (July 1995-8)
(Mon, conducted at a test farm in Mie Prefecture)

(Iv) Summer cultivation Roof type house (width 9m, depth 20m, ridge height 2.5
m, roof slope 30 °), and each film was stretched with the side provided with layer (B) inside the house. Heisei 7 for each house
Tomato (variety Momotaro) was planted from early to mid May,
Harvested from late June to November. The tomatoes in each house were observed from flowering to fruit setting. The evaluation results were as follows.

5 points: The number of flowers is large and the fruit setting is very good. 4 points: The number of flowers is normal and the fruit setting is good. 3 points: The number of flowers is normal, and the fruits are slightly falling. 2 points: Those with a small number of flowers and many fruits falling. 1 point: A flower has skipped (no flowering).

[0052]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 3/36 C08K 3/36 C08L 101/00 LTB C08L 101/00 LTB C09D 133/04 PFZ C09D 133 / 04 PFZ (72) Inventor Atsushi Obayashi 2 Oike, Iwazuka-cho, Nakamura-ku, Nagoya-shi, Aichi Mitsubishi Chemical MKV Co., Ltd. Nagoya Office

Claims (6)

[Claims] 1. A layer (A) containing inorganic fine particles having a heat ray shielding ability is provided on at least one side of a thermoplastic resin film, and a hydrophilic inorganic colloid is further provided on the layer and / or on the opposite side of the film. An outdoor spreading film provided with a layer (B) containing particles. 2. The outdoor stretchable film according to claim 1, wherein the layer (A) comprises an inorganic oxide having an average particle diameter of 15 μm or less as inorganic fine particles and a thermoplastic resin as a binder. 3. The straight light transmittance at 555 nm is 60%.
The film for outdoor stretching according to claim 1 or 2, which is the above. 4. The layer (B) comprises hydrophilic inorganic colloidal particles and a glass transition temperature of 35 to 80 as a binder thereof.
The outdoor spreading film according to any one of claims 1 to 3, which is a composition with a hydrophobic acrylic resin in the range of ° C. 5. The outdoor spreading film according to claim 4, wherein the blending amount of the hydrophilic inorganic colloid particles in the composition is 0.5 or more and 4 or less in weight ratio with respect to the hydrophobic acrylic resin. 6. The outdoor spreading film according to claim 4, wherein the hydrophilic inorganic colloid particles are silica and / or alumina.