JPH08142285A - Agricultural laminated sheet - Google Patents

Abstract

PURPOSE: To provide an agricultural laminated film wherein when it is spread for a house and a tunnel, antifog persitence is excellent, and a characteristic in which an outer surface of the house is difficult to be stained (dust-proofness) is provided. CONSTITUTION: In a structure wherein an inner layer B having X1 (5<X1<40wt.%) content of elastomeric copolymer of olefin resin as main constituent is laminated on an inner surface of an intermediate layer A having the olefin resin as main constituent, and an outer layer B' having X2 (0<X2<X1wt.%) content of the elastomeric copolymer having the olefin resin as main constituent is laminated on an outer surface of the intermediate layer A, at least one kind of anti-fogging agent is contained in at least one layer of the intermediate layer A and the inner layer B.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to agricultural laminated films. More specifically, the present invention relates to an agricultural laminated film which has excellent anti-fogging property when spread on a house or tunnel and has a property (dust-proof property) that the outer surface of the house is not easily soiled.

[0002]

2. Description of the Related Art A large amount of plastic film is used as a covering material for facility horticulture such as agricultural houses and tunnels, and typical ones are polyvinyl chloride film (hereinafter referred to as agricultural product) and polyethylene film (hereinafter referred to as agricultural product). Polyvinyl chloride), ethylene vinyl acetate copolymer film (hereinafter referred to as "agricultural vinyl chloride"), and the like. Among them, agricultural plastics have heat retention, transparency, toughness, anti-fog property, house adhesion and economy. It has excellent properties and is used most often. But,
Agricultural plastics are poor in workability and dust resistance due to the plasticizer contained in the film bleeding out and stickiness on the surface, and recently, various problems such as generating harmful gas at the time of incineration disposal are occurring, An alternative is desired.

On the other hand, although agricultural poly and agricultural vinegar have advantages over agricultural viticula in terms of workability, dust resistance and disposal, they have antifogging durability, transparency, toughness and house adhesion. There was a problem that was inferior. Agricultural poly, which is made of an ethylene polymer, has a problem in imparting antifogging property and antifogging sustainability because it has no polar group. In general, when an agricultural film without anti-fogging property is used as a covering material for a house or tunnel, the water in the soil evaporates and the water content condenses on the inner surface of the film to form water droplets. However, since the film is clouded by the water drops and a part of the sun rays is reflected, the amount of light rays passing through the film is reduced, so that the temperature increasing effect in the house or the tunnel is reduced. In addition, the water droplets condensed on the inner surface of the film fall on the cultivated crops, damaging the shoots and seedlings,
In addition, there are adverse effects such as the occurrence of diseases. Against these adverse effects, a film in which a surfactant having an action of an antifogging agent is kneaded is used, and this antifogging agent prevents evaporated water from staying as a water drop on the film surface, It has the function of spreading water droplets in a film shape and causing them to flow down along the inner surface of the film. In the agricultural film having antifogging property, the kneaded antifogging agent diffuses and leaches from the inside of the film along the surface and is coordinated on the film surface to exert a surface activating effect. However, since the antifogging agent coordinated to the film surface is washed away by water drops during use, it is necessary to always transfer the antifogging agent from the inside of the film toward the surface in order to maintain the antifogging property of the film. . The longer the antifogging effect of the antifogging film,
That is, it is apparent that the more durable the antifogging property is, the more preferable it is in practice. In order to produce such a film having a long anti-fogging effect, generally, a large amount of anti-fogging agent is added at the time of film production, or an anti-fogging agent having a slow migration rate from the inside of the film to the surface after film formation is used. Attempts have been made to make selective use. However, the former, that is, a method of adding a large amount of anti-fogging agent during film production is effective for maintaining anti-fogging, but the amount transferred to the surface immediately after film formation is severe, and transparency due to whitening of the anti-fogging agent There are problems such as deterioration and sticking between films, and it is actually difficult to increase beyond a certain amount, and in the case of the latter method,
An antifogging agent having an antifogging effect and capable of maintaining this antifogging effect for a long period of time has not been actually found.

In view of the above situation, the present invention has an inner layer and an outer layer having an olefin polymer as a main component laminated on the inner and outer surfaces of an intermediate layer having an olefin resin as a main component, and has at least one of the inner layer and the intermediate layer. By providing a specific amount of an elastic copolymer to the inner and outer layers in a structure in which an antifogging agent is added, it is possible to provide an agricultural film that is excellent in antifogging property, antifogging durability, and dustproof property. Made it possible.

[0005]

The present invention has the following constitution. (1) An inner layer B having an olefin resin as a main component and an elastic copolymer content X1 of 5 <X1 ≦ 40% by weight is laminated on the inner surface of an intermediate layer A having an olefin resin as a main component,
The intermediate layer A has a structure in which an outer layer B'having an olefin resin as a main component and an elastic copolymer content X2 of 0≤X2 <X1% by weight is laminated on the outer surface of the intermediate layer A, and the intermediate layer A and An agricultural laminated film in which at least one layer of the inner layer B contains at least one antifogging agent. (2) The agricultural laminate according to the above item 1, wherein the olefin-based resin which is a main component of the inner layer B and the outer layer B ′ is a propylene-based polymer, and the elastic copolymer is a hydrogenated diene-based copolymer. the film. (3) The inorganic filler is 0.5 to 2 in the inner layer B and the outer layer B '.
The agricultural laminated film according to the above-mentioned item 1, which contains 0% by weight. (4) The second aspect, wherein the inorganic filler contains, as a main component, either the hydrotalcites represented by the following general formula (1) or the aluminum-lithium composite hydroxide salt represented by the general formula (2). Laminated film for agriculture. General formula (1) M ²⁺ _1-X Al _X (OH) ₂ (A ⁿ⁻ ) _{X / n} · mH ₂ O (wherein M ²⁺ is 2 selected from the group consisting of magnesium, calcium and zinc) Represents a valent metal ion, A ^n- represents an n-valent anion, _X and m are as follows, 0 < _X <
0.5, 0 ≦ m ≦ 2 is satisfied. ) General formula (2) [Al ₂ Li (OH) ₆ ] _n X · mH ₂ 0 (wherein, X is an inorganic or organic anion,
n is the valence of the anion X, and m is 3 or less. )

Hereinafter, the present invention will be described in detail. The intermediate layer A used in the present invention may be a single layer or a multilayer of two or more layers. In the case of two or more layers, for example, lamination of an antifogging layer and a heat retaining layer, lamination of an antifogging layer, a film strength improving layer and a heat retaining layer, lamination of a different polymer layer and an adhesive layer and the like can be mentioned.

The olefin resin used in the resin layer A is a homopolymer of α-olefin or a copolymer of α-olefin with a different kind of monomer, such as propylene homopolymer or Ethylene, 1-butene, 1
-Pentene, a propylene-based polymer which is a copolymer with 1-hexene, an ethylene homopolymer, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1
-Ethylene-based polymers which are copolymers with octene and vinyl acetate can be mentioned, but ethylene-based polymers are preferred in order to improve flexibility, weather resistance and transparency, and also in terms of price. These resins may be used alone or in combination of two or more.

Of these, an ethylene polymer having a density of 0.88 to 0.935 g / cm ³ is preferably used because it has appropriate flexibility and transparency, but has a melt index of 0.1 g.
/ 10 minutes or less has a problem of workability, and 5g / 10 minutes or more has a decrease in strength, so the melt index is 0.1g / 10 minutes or more and 5g / 10 minutes or less. The thing of is desirable.

Further, an elastic copolymer can be added to the olefin resin. Thereby, it was possible to impart flexibility and improve the durability of the antifogging property. As the elastic copolymer, known elastic copolymers such as ethylene-propylene rubber which is an ethylene-polypropylene elastic copolymer, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile butadiene rubber, polyisoprene rubber, and styrene-isoprene rubber are used. When the main component of the resin layer A is an ethylene-based polymer, it is preferable to use an ethylene-propylene elastic copolymer in order to maintain transparency, and the Mooney viscosity is 20 to 70 ML _{1 + 4.} It is about (100 ° C.) and the propylene unit content is preferably about 20 to 50% by weight. Tendency Mooney viscosity 20 mL 1 + ₄ is reduced film strength (100 ° C.) of less than one, for those exceeding 70ML 1 + ₄ a (100 ° C.) is the inferior film processability, drops internal haze Becomes

Further, the ethylene-vinyl acetate copolymer is used for the purpose of improving flexibility and has a vinyl acetate content of
It is preferably 30% by weight or less and 5% by weight or more, and the melt index is 0.1 g / 10 minutes or more and 5 g / 10 minutes or less. If the vinyl acetate content is 30% by weight or more, the processability will decrease,
If it is less than 5% by weight, the same properties as those of other ethylene-based polymers can be obtained. Also, if the melt index is less than 0.1 g / 10 minutes, the processability will decrease, and
If it is more than a minute, the strength will decrease.

Examples of the olefin resin used in the resin layers B and B'include the propylene polymer and the ethylene polymer as in the case of the intermediate layer A. Among them, the propylene polymer is the outer layers B and B. It was confirmed that the scratch resistance of the surface was improved by using it for 'and the effect of suppressing the decrease in transparency due to the damage was suppressed. As the propylene-based polymer, propylene homopolymer, ethylene, 1-butene, 1
-One or more α selected from pentene, 1-hexene, etc.
Examples thereof include a propylene random copolymer with an -olefin, an ethylene-propylene block copolymer, and the like, but a random copolymer with an α-olefin is preferably used from the viewpoint of improving transparency, flexibility, and heat sealability.

The elastic copolymer used for the resin layers B and B'is an ethylene-polypropylene elastic copolymer such as ethylene-propylene rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyisoprene rubber and styrene. −
Known elastic copolymers such as isoprene rubber can be mentioned. When the olefin resin used for the resin layers B and B ′ is a propylene resin, an ethylene-polypropylene elastic copolymer and a hydrogenated diene copolymer are used. By using a polymer or the like, the flexibility and elastic recovery can be improved without decreasing the transparency, and in particular, the hydrogenated diene-based copolymer can obtain the flexibility and elastic recovery with a small addition amount. It is preferably used because it is easily treated and transparency is improved. These copolymers may be used alone or in combination of two or more.

Hydrogenated diene copolymers are disclosed in JP-A-3-72.
As disclosed in 512, (A)-(consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a vinyl aromatic compound and a conjugated diene random copolymer block (B). B) block copolymer,
Further, if necessary, a (A)-(B)-(C) block copolymer comprising a vinyl aromatic compound and a taper block (C) in which the vinyl aromatic compound among conjugated dienes gradually increases, or a vinyl aromatic compound. Polymer block (A)
(A)-(B)-(A) block copolymer, wherein the weight ratio of vinyl aromatic compound / conjugated diene in all monomers is 5 to 60/95 to 40,
The content of the binding compound of the vinyl aromatic compound in the component (A) and optionally the component (C) is 3 to 50% by weight based on the total amount of the monomers, and the content of the vinyl aromatic compound in the component (A) is The binding content is at least 3% by weight,
The vinyl bond content of the conjugated diene part in the component (B) is 60.
Hydrogenated (hydrogenated) block copolymers exceeding 100% are preferably used. At least 80% of the double bonds in the conjugated diene moiety after hydrogenation are saturated, and those having a number average molecular weight of 50,000 to 600,000 are preferably used.

Further, inner and outer layers containing an olefin polymer as a main component are laminated on the inner and outer surfaces of an intermediate layer containing an olefin resin as a main component, and an antifogging agent is added to at least one of the inner layer and the intermediate layer. In the constitution, the addition amount X1 of the elastic copolymer to the inner layer is preferably 5 to 30% by weight, and the addition amount X2 of the elastic copolymer to the outer layer is preferably less than X1% by weight. If X1 is less than 5%, sufficient antifogging sustainability cannot be obtained, and if it exceeds 30% by weight, the strength of the film decreases and the workability becomes poor due to the adhesion between the films. Further, when X2 is X1 or more, not only effective antifogging sustainability is not obtained, but also the dustproof effect of the outer layer located on the outer surface of the house is deteriorated.

Examples of the antifogging agent used in the present invention include nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants. Among these, ethylene polymers and A nonionic surfactant having a relatively high compatibility with the ethylene-propylene elastic copolymer is preferably used, but a cationic surfactant or anion is used for the purpose of modifying the antifogging property at the initial and low temperatures. A system surfactant and the like are also used in combination. Nonionic surfactants include polyethylene glycol ethers such as polyethylene glycol nonyl phenyl ether and polyethylene glycol stearyl ether, polyethylene glycol stearate, polyethylene glycol carboxylic acid esters such as polyethylene glycol dilaurate, glycerin monostearate and sorbitan. Partial carboxylic acid esters of polyhydric alcohols such as monopalmitate and sorbitan tristearate, polyoxyethylene derivatives of sorbitan monostearate, and partial carboxylic acid esters of polyhydric alcohols such as polyoxyethylene derivative of sorbitan monolaurate Polyoxyethylene derivative, N, N-di- (hydroxyethyl) -laurylamide, N- (2-hydroxypropyl) -stear Amide derivatives such as amides. Examples of cationic surfactants include quaternary ammonium salts such as lauryl trimethyl ammonium chloride, N, N-dimethyl-N- (hydroxyethyl) -3- (stearoamido) -propyl ammonium nitrate, and 2-octadecyl- (hydroxyethyl). ) -2-imidazoline and other imidazoline derivatives, N, N-diethyl- (stearoamido) -methylamine hydrochloride, amines such as polyoxyethylene stearylamine and the like. As the anionic surfactant, sodium lauryl phosphate, phosphates such as polyoxyethylene-sodium lauryl phosphate, sodium lauryl sulfate, sulfates such as sodium salt of sulfated oleic acid, sodium stearylsulfonate, Examples thereof include sulfonates such as dodecylbenzenesulfonic acid triethanolamine salt and dioctylsulfosuccinate sodium salt.

When an antifogging agent is added to the agricultural laminated film of the present invention, it is desirable to add it not only to the inner layer but also to the intermediate layer for the purpose of improving antifogging durability. Although it may be added to the outer layer, stains are likely to adhere due to the bleed-out of the antifogging agent. The amount of the antifogging agent added to the inner layer is preferably in the range of 0.5 to 2% by weight. When it is less than 0.5% by weight, the antifogging property is not sufficiently expressed. Immediately after the film, the antifogging agent is remarkably transferred to the surface, causing problems such as stickiness and deterioration of transparency. The amount of the antifogging agent added to the intermediate layer is 1 to 3% by weight.
When the amount is less than 1% by weight, the antifogging sustainability is not sufficient, and when the amount exceeds 3% by weight, the antifogging agent is remarkably transferred to the surface immediately after the film formation, resulting in stickiness and stickiness. Poor transparency becomes a problem.

In the present invention, the inorganic filler is added to the inner layer B in the range of 0.5 to 20% by weight, and may be added to the outer layer B ', if necessary, from the viewpoint of preventing adhesion between the films. If it is less than 0.5% by weight, it is difficult to obtain the effect of preventing adhesion, and if it exceeds 20% by weight, the transparency of the film is inferior or the physical properties of the film are inferior. Further, if an inorganic filler having infrared absorption around a wavelength of 10 μm is selected, the effect of improving the heat retaining property of the agricultural film can be obtained. Therefore, it is desirable to add it to the inner and outer layers within a range not impairing transparency. The inorganic filler may be added to the layer A.

Examples of the inorganic filler include silicon oxide, magnesium silicate, aluminum silicate, calcium silicate and other silicate compounds, calcium aluminosilicate, sodium aluminosilicate, aluminosilicate compounds such as potassium aluminosilicate, alumina, sodium aluminate and potassium aluminate. , One selected from the group consisting of aluminate compounds such as calcium aluminate, calcium carbonate, hydrotalcites represented by the general formula (1) and lithium-aluminum complex hydroxide salts represented by the general formula (2). The above-mentioned inorganic fillers can be mentioned. General formula (1) M ²⁺ _1-X Al _X (OH) ₂ (A ⁿ⁻ ) _{X / n} · mH ₂ O (wherein M ²⁺ is 2 selected from the group consisting of magnesium, calcium and zinc) Represents a valent metal ion, A ^n- represents an n-valent anion, _X and m are as follows, 0 < _X <
0.5, 0 ≦ m ≦ 2 is satisfied. ) General formula (2) [Al ₂ Li (OH) ₆ ] _n X · mH ₂ 0 (wherein, X is an inorganic or organic anion,
n is the valence of the anion X, and m is 3 or less. )

The transparency of the agricultural laminated film varies depending on the type of the inorganic filler, and the closer the refractive index of the polypropylene resin and the refractive index of the inorganic filler are, the more the transparency is improved. Therefore, the above-mentioned general formula (1) and Hydrotalcites represented by the general formula (2), lithium-aluminum composite hydroxide salt, and the like are preferably used.

In the production of the laminated film according to the present invention, various additives such as a heat retaining agent, an antifog agent, a heat stabilizer, an antioxidant, a hindered amine weather resistance improver, an ultraviolet absorber and a slip agent are added according to a conventional method. Agents may be added.

The agricultural laminated film of the present invention can be produced by known laminating techniques such as coextrusion molding by the inflation method or T-die method, wet lamination, dry lamination, hot melt lamination, extrusion coating lamination, etc. Co-extrusion molding by the inflation method or T-die method, which has excellent properties, is generally used. Further, the effect of exhibiting the antifogging property may be improved by corona discharge treatment or the like after film formation.

The thickness of the agricultural laminated film of the present invention varies depending on the place of use, service life, etc., but is generally 0.05-0.
Those having a size of about 20 mm are preferably used. The thicknesses of the inner layer B and the outer layer B ′ are not particularly limited, and are determined depending on the required antifogging durability, flexibility and the total thickness of the laminated film.

[0023]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The melt flow rate (MFR) shown in Examples and Comparative Examples is a value measured by the method specified in JIS-K-7210. Low temperature anti-fog property (10 ° C method)
Degree, the film sample was fixed to the skylight of a water bath having a skylight with a diameter of 3 inches so that the inner layer surface of the film sample was on the lower side, and the water temperature was kept at 10 ° C and left for 1 day in a constant temperature layer at 0 ° C. A (excellent because it has a uniform water film), B (the water film is slightly uneven, but it can be used), C
Evaluation was made in 3 ranks (dropped and cannot be actually used). Hot water anti-fog persistence (45 ℃), the film sample is fixed so that the inner layer surface of the film sample is on the skylight of a water bath having a 10-degree inclination and a 3-inch diameter skylight,
While keeping the water temperature at 45 ° C, the sample was left in a constant temperature room at 23 ° C, and the period until the antifogging property of the inner surface was maintained was evaluated. The dustproof property was evaluated by sealing and fixing the film sample in a frame of 30 cm in length × 50 cm in width × 30 cm in height in an outdoor field, and measuring the haze value of the film sample on the side of the frame after 3 months.
Regarding transparency, the haze value and total light transmittance of the film were measured using a haze meter in accordance with JIS-K-7105 and used as a measure of transparency. Regarding spreading workability, A (excellent), B (slightly problematic but practical use possible), and C (not practical use possible) are available for the problem of poor workability due to stickiness at the time of expansion to the house. It was evaluated in 3 ranks.

Example 1 Using a 3-layer T-die forming apparatus capable of forming a 3-kind 3-layer film having one 90φ extruder and two 50φ extruders, MF was used.
R (190 ℃, 2.16kgf, A) = 2.0g / 10min, Density ρ = 0.95g / c
m ^3, vinyl acetate content = 15% by weight of ethylene - vinyl acetate copolymer as a main component, sorbitan monostearate
1.0% by weight, polyglycerin monostearate 0.5% by weight, N, N, -bis (2-hydroxyethyl) -alkylamine 0.3% by weight, hydrotalcite compound (trade name; DHT-4A, manufactured by Kyowa Chemical Co., Ltd.) ) 5% by weight, hindered amine weathering agent (trade name: Sanol LS 770 Ciba Geiger Co., Ltd.)
0.2% by weight, phenolic stabilizer (trade name: Irganox 1)
[0101] A resin composition containing 0.1% by weight of Ciba Geiger Co., Ltd. and 0.1% by weight of a phosphorus-based stabilizer (trade name; Irgafos 168 Ciba Geiger Co., Ltd.) was charged into a 90φ extruder to form an intermediate layer A,
MFR (230 ℃, 2.16kgf, A) = 6.0g / 10min, Density ρ = 0.90g /
cm ³ of ethylene, butene as a main component of polypropylene ternary random copolymer and a comonomer, the total bound styrene content = 10 wt%, MFR (230 ℃, 2.16kgf , A) = 3.5g / 10
20% by weight of hydrogenated styrene-butadiene copolymer (trade name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) having a density ρ = 0.89 g / cm ^{3 and} a hydrotalcite compound (inorganic filler) ( Product name: DHT-4A, manufactured by Kyowa Chemical Co., Ltd.
1.0% by weight, sorbitan monostearate 1.0% by weight, polyglycerin monostearate 0.5% by weight, N, N,-
0.3% by weight of bis (2-hydroxyethyl) -alkylamine, hindered amine weathering agent (trade name; Sanol LS770
0.2% by weight, phenolic stabilizer, manufactured by Ciba Geiger Ltd.
50% of the resin composition containing 0.1% by weight (trade name; Irganox 1010 manufactured by Ciba Geigy Co., Ltd.) and 0.1% by weight of a phosphorus stabilizer (trade name: Irgafos 168 manufactured by Ciba Geigy Co., Ltd.)
Put into φ extruder to make inner layer B, and MFR (230 ℃, 2.1
6 kgf, A) = 6.0 g / 10 min, density ρ = 0.90 g / cm ³ ethylene,
Main component is polypropylene ternary random copolymer with butene as comonomer, total bound styrene amount = 10% by weight, MFR (230 ° C, 2.16kgf, A) = 3.5g / 10min, density ρ = 0.
89 g / cm ³ hydrogenated styrene-butadiene copolymer
(Product name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) is 10
Wt%, hydrotalcite compound as inorganic filler
(Brand name: DHT-4A, Kyowa Chemical Co., Ltd.) 1.0% by weight, hindered amine weathering agent (Brand name: Sanol LS 770 Ciba Geiger Co., Ltd.) 0.2% by weight, phenolic stabilizer (Brand name;
Irganox 1010 0.1% by weight of Ciba Geiger Co., Ltd. and 0.1% by weight of a phosphorus-based stabilizer (trade name; Irgafos 168 Ciba Geiger Co., Ltd.) were added to the other 50φ extruder to form the outer layer B. ', Die temperature 200 ° C, extrusion rate 100kg /
Under the condition of hr, the inner layer B (thickness 1) is formed on the inner surface of the intermediate layer A (thickness 70μ).
5 μ), and a three-layer laminated film having a total thickness of 100 μ having a structure in which an outer layer B ′ (thickness 15 μ) was laminated on the outer surface.

Examples 2 to 4 Hydrogenated styrene-butadiene copolymer (trade name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) was used in the inner layer B as 5, 10, 4
0% by weight, hydrogenated styrene-butadiene copolymer in outer layer B '(trade name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.)
Was carried out in the same manner as in Example 1 except that the respective contents were 0, 5, and 20% by weight, respectively.

Examples 5 to 10 Hydrotalcite compounds (trade name: DHT-4A, manufactured by Kyowa Chemical Co., Ltd.) were used as inorganic fillers added to the inner layer B and the outer layer B ', respectively, 0, 0.5, 5.0, 10, 20. Was carried out in the same manner as in Example 1 except that the amount was 30% by weight.

Example 11 Instead of a hydrotalcite compound (trade name; DHT-4A, manufactured by Kyowa Chemical Co., Ltd.) as an inorganic filler to be added to the inner layer B and the outer layer B ', a lithium aluminum complex hydroxide salt (commercial item) Name: Miscaraque, manufactured by Mizusawa Chemical Co., Ltd.) was carried out in the same manner as in Example 1 except that the content was 1.0% by weight.

Example 12 MFR (230 ° C., 2.16 kgf, A) = 6.0 g / 10 min, density ρ = 0.90 g /
cm ³ of ethylene, butene as a main component of polypropylene ternary random copolymer and a comonomer, the total bound styrene content = 10 wt%, MFR (230 ℃, 2.16kgf , A) = 3.5g / 10
20% by weight of hydrogenated styrene-butadiene copolymer (trade name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) having a density ρ = 0.89 g / cm ^{3 and} a hydrotalcite compound (inorganic filler) ( Product name: DHT-4A, manufactured by Kyowa Chemical Co., Ltd.
1.0% by weight, hindered amine weathering agent (trade name: Sanol
LS 770 Ciba Geiger Co., Ltd. 0.2% by weight, phenolic stabilizer (trade name; Irganox 1010 Ciba Geiger Co., Ltd.) 0.1 wt%, phosphorus stabilizer (trade name; Irgafos 168 Ciba Geiger Co., Ltd.) 0.1 wt% % Was carried out in the same manner as in Example 1 except that the resin composition containing 100% was used for the inner layer B.

Example 13 Hydrogenated styrene-butadiene copolymer (trade name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) was used for the inner layer B and the outer layer B '.
Instead of ethylene) -propylene elastic copolymer (Moonie viscosity 24 ML _{1 + 4} (100 ° C), propylene content 26% by weight, density 0.86 g / cm ³ , trade name; EP02P, manufactured by Nippon Synthetic Rubber Co., Ltd. ) Was carried out in the same manner as in Example 1.

Example 14 The intermediate layer A was mainly composed of an ethylene-1-hexene copolymer having MFR (190 ° C., 2.16 kgf, A) = 2.5 g / 10 minutes and a density ρ = 0.92 g / cm ³ . Sorbitan monostearate 1.0% by weight,
Polyglycerin monostearate 0.5% by weight, N, N,
-Bis (2-hydroxyethyl) -alkylamine 0.3
% By weight, hydrotalcite compound (trade name: DHT-4A,
Kyowa Chemical Co., Ltd.) 5% by weight, hindered amine weathering agent
(Product name: Sanol LS 770 manufactured by Ciba Geiger Co., Ltd.) 0.2% by weight, phenolic stabilizer (Product name: Irganox 1010 manufactured by Ciba Geiger Co., Ltd.) 0.1% by weight, phosphorus stabilizer (Product name: Irgafo)
s 168 manufactured by Ciba-Gaige Co., Ltd.). A resin composition containing 0.1% by weight was used, and the same procedure as in Example 1 was performed.

Comparative Example 1 20% by weight of hydrogenated styrene-butadiene copolymer (trade name; DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) was used for the inner layer B, and hydrogenated styrene-butadiene copolymer was used for the outer layer B '. Coalescing
(Product name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) 20
Example 1 was carried out in the same manner as in Example 1 except that the weight% was set.

Comparative Examples 2 to 4 Hydrogenated styrene-butadiene type copolymer (trade name; DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.) was used for the inner layer B at 0, 20, 5
0% by weight, hydrogenated styrene-butadiene copolymer in outer layer B '(trade name: DYNARON 1320P, manufactured by Nippon Synthetic Rubber Co., Ltd.)
Was carried out in the same manner as in Example 1 except that the respective amounts were 10, 30, and 30% by weight, respectively.

Comparative Example 5 The inner layer B had an MFR (190 ° C., 2.16 kgf, A) = 3.0 g / 10 min, a density ρ = 0.95 g / cm ³ , and a vinyl acetate content = 5% by weight of ethylene-vinyl acetate. 1.0 wt% of hydrotalcite compound (trade name; DHT-4A, manufactured by Kyowa Chemical Co., Ltd.) as a main component of polymer and inorganic filler, sorbitan monostearate
1.0 wt%, N, N, -bis (2-hydroxyethyl)
-Alkylamine 0.3% by weight, polyglycerin monostearate 0.5% by weight, hindered amine-based weathering agent (trade name; Sanol LS 770 Ciba-Beige Co., Ltd.) 0.2% by weight, phenolic stabilizer (trade name: Irganox 1010 Ciba-Beige (share) 0.1% by weight, phosphorus-based stabilizer (trade name: Irgafos 1
68 Ciba Geiger Co., Ltd.) 0.1% by weight of the resin composition was used, and MFR (190 ° C., 2.16 kgf, A) = 3.0 g /
10 minutes, density ρ = 0.95 g / cm ³ , vinyl acetate content = 5% by weight
Hydrotalcite compound (trade name; DHT-4
A, 1.0% by weight of Kyowa Chemical Co., Ltd., hindered amine weathering agent (trade name; Sanol LS 770 manufactured by Ciba Geigy Co., Ltd.)
2% by weight, phenolic stabilizer (trade name; manufactured by Irganox 1010 manufactured by Ciba Geigy Ltd.) 0.1% by weight, phosphorus stabilizer (trade name; I)
Example 1 was repeated, except that a resin composition containing 0.1% by weight of rgafos 168 manufactured by Ciba Geiger Co., Ltd. was used.

Comparative Example 6 The inner layer B was mainly composed of an ethylene-1-hexene copolymer having MFR (190 ° C., 2.16 kgf, A) = 2.5 g / 10 minutes and density ρ = 0.92 g / cm ³ Hydrotalcite compound (trade name; DHT-4A, manufactured by Kyowa Chemical Co., Ltd.) as a filler is 1.0% by weight,
Sorbitan monostearate 1.0% by weight, polyglycerin monostearate 0.5% by weight, N, N, -bis (2-
0.3% by weight of hydroxyethyl) -alkylamine, 0.2% by weight of hindered amine weathering agent (trade name; manufactured by Sanol LS 770 Ciba-Gaige Co., Ltd.), phenolic stabilizer (trade name: Ir)
ganox 1010 0.1% by weight, Phosphorus stabilizer (trade name; Irgafos 168, manufactured by Ciba Geiger) 0.1% by weight
The same procedure as in Example 1 was carried out except that the resin composition containing was used. Outer layer B ', MFR (190 ℃, 2.16kgf, A) = 2.5
g / 10 min, density ρ = 0.92 g / cm ³ ethylene-1-hexene copolymer as the main component, hydrotalcite compound (trade name; DHT-4A, Kyowa Chemical Co., Ltd.) as an inorganic filler
1.0% by weight, hindered amine weathering agent (trade name: Sanol
LS 770 Ciba Geiger Co., Ltd. 0.2% by weight, phenolic stabilizer (trade name; Irganox 1010 Ciba Geiger Co., Ltd.) 0.1 wt%, phosphorus stabilizer (trade name; Irgafos 168 Ciba Geiger Co., Ltd.) 0.1 wt% % Was carried out in the same manner as in Example 1 except that the resin composition containing 10% was used.

Comparative Example 7 The procedure of Example 1 was repeated, except that the hydrogenated styrene-butadiene copolymer was not used for the inner layer B and the outer layer B '. The obtained agricultural laminated film had a low-temperature anti-fog property of C, a high-temperature anti-fog durability of 5 days, a total light transmittance of 92%, and a haze value of 6.0.
%, Dustproofness was 14.1%, spreading workability was A, and there was a problem in low temperature antifogging property and antifogging sustainability, and it was not practical.

[0036]

INDUSTRIAL APPLICABILITY The agricultural laminated film of the present invention has at least one of an inner layer and an intermediate layer in which an inner layer and an outer layer having a propylene polymer as a main component are laminated on the inner and outer surfaces of an intermediate layer having a olefin resin as a main component. In the structure in which the antifogging agent is added to the layer, by adding a specific amount of hydrogenated diene-based copolymer to the inner and outer layers, the antifogging sustainability is long and exhibits excellent dust resistance.
Further, since the adhesion trouble between the films is eliminated, it can be suitably used as an agricultural coating material for houses, tunnels and the like.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location B32B 27/20 Z 9349-4F // C08K 3/22 KEC C08L 23/10 LCF

Claims (4)

[Claims] 1. An intermediate layer A containing an olefin resin as a main component.
An inner layer B having an olefin resin as a main component and an elastic copolymer content X1 of 5 <X1 ≤ 40 wt% is laminated on the inner surface of the intermediate layer A, and an elastic layer containing an olefin resin as a main component is provided on the outer surface of the intermediate layer A. A structure in which an outer layer B ′ having a copolymer content X2 of 0 ≦ X2 <X1 wt% is laminated, and an intermediate layer A
And an agricultural laminated film in which at least one layer of the inner layer B contains at least one antifogging agent. 2. The agricultural use according to claim 1, wherein the olefin resin which is a main component of the inner layer B and the outer layer B ′ is a propylene polymer, and the elastic copolymer is a hydrogenated diene copolymer. Laminated film. 3. An inorganic filler is contained in the inner layer B and the outer layer B '.
The agricultural laminated film according to claim 1, which contains 0.5 to 20% by weight. 4. The inorganic filler mainly contains either hydrotalcites represented by the following general formula (1) or aluminum-lithium composite hydroxide salt represented by the following general formula (2). The agricultural laminated film described. General formula (1) M ²⁺ _1-X Al _X (OH) ₂ (A ⁿ⁻ ) _{X / n} · mH ₂ O (wherein M ²⁺ is 2 selected from the group consisting of magnesium, calcium and zinc) Represents a valent metal ion, A ^n- represents an n-valent anion, _X and m are as follows, 0 < _X <
0.5, 0 ≦ m ≦ 2 is satisfied. ) General formula (2) [Al ₂ Li (OH) ₆ ] _n X · mH ₂ 0 (wherein, X is an inorganic or organic anion,
n is the valence of the anion X, and m is 3 or less. )