JP2005186624A - Recovery method for olefin resin laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recovery method for an agricultural olefin resin laminated film which has been difficult to recycle. <P>SOLUTION: The method is employed to recover an olefin resin coating film by putting mixed chips of a chlorinated vinyl film and the olefin resin covering film, conforming to conditions (1) as described hereinafter, into a separation/rinsing tub, by agitating after filling with a separation/rinsing fluid; collecting the supernatant layer after standing, and by filtering and drying. The conditions (1) are as follow. The olefin resin film contains a radiation blocking agent, and has a melt flow rate of 0.1 to 50 g/10min, at least one layer (layer A) comprising an ethylene-α-olefin copolymer (A) with a density of 0.88 to 0.94 g/cm<SP>3</SP>as its principal component, a radiation transmission index of 25 or lower at 23°C, and a density of less than 1 g/cm<SP>3</SP>. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for recovering an olefin-based resin laminated film.

  Conventionally, as agricultural films used for agricultural houses or tunnels in facility horticulture or the like, olefin resin films such as polyethylene films and ethylene-vinyl acetate copolymer films and polyvinyl chloride films are mainly used. Among these, although the olefin resin film is excellent in transparency, it is inferior to the polyvinyl chloride film in terms of heat retention. Therefore, phosphate compounds, silicon oxide, anhydrous aluminosilicates, dehydrated kaolinite, aluminum as described in JP-A-52-105953, JP-B-4-11107, JP-B-57-34871, etc. In general, an olefin-based resin film having improved heat retention by adding an inorganic compound such as silicate, zeolite, hydrotalcite or the like or an organic compound such as acetal resin is used as an agricultural film.

  On the other hand, these used agricultural films are currently being disposed of by recycling, incineration, landfill, etc. In particular, the recycling method is an important method from the viewpoint of global environmental protection in recent years. It is becoming one. The recycling method is a method for recovering and reusing used agricultural films, but olefin resin films and polyvinyl chloride films are usually recovered without distinction and recycled. Sometimes both may mix. However, the quality of the recycled product in which both are mixed is inferior to the quality of both the original olefin resin film and the polyvinyl chloride film, so that there are practical problems such as the limited use of the recycled product. Therefore, in order to obtain a recycled product of better quality, it is necessary to separate the two before recycling.

In general, the recovered film is generally used as a recycled material by the following method (reference: Plastic Age, July special issue, pages 147 to 158, 1994, polymer processing, 40 (12), pages 611 to 621. , 1991).
(1) Fraction collection and foreign matter removal (2) Pretreatment crushing (3) Washing / pulverization / washing (4) Separation (5) Washing / drying (6) Formulation / granulation Water or water / alcohol is used as the cheapest solvent, and in the separation step (4), the polyvinyl chloride film and the olefin resin film are separated by being left in the cleaning solution used in (3). The conventional olefin resin film with improved heat retention as described above is not well separated from the polyvinyl chloride film in this separation step, and therefore it is not easy to recycle and it is difficult to say that the olefin resin film is excellent in recyclability. .

The present invention provides a method for recovering an olefin-based resin laminated film such as an agricultural film that has been difficult to recycle.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, in the present invention, a mixture of a vinyl chloride film piece and an olefin resin-coated film piece satisfying the following condition (1) is put in a separation / washing tank, filled with the separation / washing liquid, stirred, allowed to stand, and supernatant. It is to provide a method for recovering the olefin resin-coated film by recovering, filtering and drying the layer.
Condition (1): Layer mainly composed of an ethylene-α-olefin copolymer (A) having a melt flow rate of 0.1 to 50 g / 10 min and a density of 0.88 to 0.94 g / cm ³ ( Radiant shielding agent-containing olefin-based resin laminated film having at least one layer A), a radiation transmission index at 23 ° C. of 25 or less, and a density of less than 1 g / cm ³

  According to the present invention, it is possible to efficiently separate and collect an olefin-based resin laminated film such as an agricultural film that has been difficult to recycle from a vinyl chloride film.

  Hereinafter, the present invention will be described in detail. In the present invention, the α-olefin of the ethylene-α-olefin copolymer is usually an α-olefin having 3 to 18 carbon atoms, preferably 4 to 12 carbon atoms. Specific examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. These may be used individually by 1 type, or may use 2 or more types together. The content of the α-olefin monomer unit in the ethylene-α-olefin copolymer (the total amount when two or more are used in combination) is usually about 0.5 to 25 mol%, preferably 0.5 to 10 It is mol%, More preferably, it is 1-7 mol%.

The melt flow rate of the ethylene-α-olefin copolymer is 0.1 to 50 g / 10 minutes, preferably 0.3 to 20 g / 10 minutes. If the melt flow rate is too low, the processability when forming a laminated film is inferior, and if it is too large, the strength of the resulting laminated film may be inferior. The density was measured by the provisions of JIS K7112 (1980) (hereinafter, the same) is 0.88~0.94g / cm ^3, preferably 0.90~0.94g / cm ^3, more preferably 0.90 to 0.938 g / cm ³ . In particular, when a layer (A layer) containing an ethylene-α-olefin copolymer as a main component is used as an outer layer as described later, the density is preferably 0.91 to 0.94 g / cm ³ , and more preferably 0.8. 92 to 0.94 g / cm ³ , particularly 0.925 to 0.940 g / cm ³ is preferable. When the inner layer is used, the density is preferably 0.88 to 0.93 g / cm ³ , more preferably 0.88 to 0.92 g / cm ³ , and particularly preferably 0.890 to 0.915 g / cm ³ . The molecular weight distribution (Mw / Mn) determined by GPC is preferably 1.5 to 4 and more preferably 2 to 3.5 from the viewpoint of processability and strength.

The ethylene-α-olefin copolymer used in the present invention is obtained from the viewpoint of the strength of the obtained laminated film, and when the layer A is used as the outermost layer of the laminated film of the present invention as described later, the opening property of the laminated film. From the viewpoint of dust resistance, the composition distribution variation coefficient Cx determined by the following formula (1) is more preferably 0.5 or less, and particularly preferably 0.2 to 0.4.
[Equation 1]
Cx = σ / SCBave. (1)
(However, σ represents the standard deviation of the composition distribution obtained from the elution amount at each temperature and the branching degree of the elution component by the following temperature rise column fractionation method, and SCBave. Per 1000 carbon atoms obtained by the following method. Represents the average number of short chain branches of

  A specific method for obtaining σ and SCBave is as follows. SCBave. Can be determined by measuring an ethylene-α-olefin copolymer by FT-IR, as is usually done by measurement of short chain branching of polyethylene or the like. Here, the short-chain branch is usually a branch having about 1 to 4 carbon atoms. In addition, σ is dissolved in a solvent heated to a predetermined temperature in accordance with a standard method of temperature rising column fractionation method, and placed in a column in a column oven, once the temperature of the oven is lowered, Subsequently, the temperature is raised to a predetermined temperature, and the relative concentration and degree of branching of the eluted components eluted at that temperature are measured by FT-IR connected to the column. Subsequently, the temperature is raised stepwise and raised to the final temperature (the temperature at which all dissolved copolymer is eluted). The relative concentration and branching degree of the respective eluted components obtained are statistically processed, and the standard deviation σ of the composition distribution obtained from the branching degree can be obtained.

  Further, when the A layer is the outermost layer of the laminated film of the present invention, from the viewpoint of the strength, openability and dust resistance of the obtained laminated film, for example, GPC-IR as described in JP-A-08-276542 An ethylene-α-olefin copolymer in which the average value of the number of branches on the high molecular weight side determined by the formula (1) is not less than the average value of the number of branches on the low molecular weight side is also preferably used.

As a method for obtaining an ethylene-α-olefin copolymer having Cx in the above range, for example, ethylene and an α-olefin having 3 to 18 carbon atoms such as transition metal complex catalysts such as palladium and nickel, metallocene catalysts, etc. Examples thereof include a method of polymerizing using a homogeneous catalyst in the presence or absence of a solvent in a gas-solid, liquid-solid or homogeneous liquid phase. The polymerization temperature is usually 30 ° C. to 300 ° C., and the polymerization pressure is normal pressure to 3000 kg / cm ² . For example, so-called metallocene olefin polymerization containing a metallocene catalyst component described in JP-A-6-9724, JP-A-6-136195, JP-A-6-136196, JP-A-6-207057, etc. Produced by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms so that the density of the resulting copolymer is 0.88 to 0.94 g / cm ^{3 in} the presence of a catalyst for use. can do.

In the present invention, the layer A may be a layer composed only of an ethylene-α-olefin copolymer, but for the purpose of improving transparency, the copolymer has a density of 0.94 g / cm ³ or more, It may be a layer made of a resin mixture containing high-density polyethylene preferably 0.945 to 0.955 g / cm ³ . When blending high-density polyethylene, if the melt flow rate of the high-density polyethylene is too low, mixing with the ethylene-α-olefin copolymer is poor, so that so-called fish eyes are generated and the appearance is inferior. Since pinholes are likely to occur in the laminated film, while the strength of the resulting olefin-based resin laminated film is reduced when it is excessive, the melt flow rate of the high-density polyethylene to be contained is usually from 0.1 to 20 g / 10 min. , Preferably 0.3 to 10 g / 10 min. The weight ratio (high density polyethylene / ethylene-α-olefin copolymer) is usually 20/80 or less, preferably in the range of 1/99 to 10/90.

In the high density polyethylene, the value of [g] * defined by the following formula (2) is more preferably 0.2 to 0.8 in terms of the effect of improving transparency, and 0.3 to 0.6. Is more preferable.
[Equation 2]
[G] * = [η] / [η] _l (2)
[Η] represents the intrinsic viscosity of the high-density polyethylene measured with a tetralin solution at 135 ° C., and [η] _l represents a linear high-density molecular weight having the same weight average molecular weight as that of the high-density polyethylene. It is the intrinsic viscosity of polyethylene, and the weight average molecular weight is a value determined by GPC-LALLS method (Gel Permeation Chromatography-Low Angle Laser Light Scattering method). [Η] _l can be obtained by the following equation (3) (see H. Rachapudy, GGSmith, VRRaju, and WWGlassley, J. Polym. Sci., Polym. Phys. Ed., 17, 1211 (1979)).
[Equation 3]
[Η] _l = 4.86 × 10 ⁻⁴ [Mw] ^0.705 (3)
These high-density polyethylenes can be appropriately selected from commercially available products.

In addition, for the purpose of improving the moldability of the laminated film of the present invention, the A layer is an ethylene-α-olefin copolymer, a high-pressure low-density polyethylene that is an ethylene homopolymer by a high-pressure polymerization method, or an ethylene-vinyl acetate copolymer. It may be a layer made of a resin mixture in which an ethylene-polar vinyl monomer copolymer typified by coalescence is blended. When blending high-pressure low-density polyethylene or ethylene-polar vinyl monomer copolymer, these melt flow rates are usually measured under conditions of 190 ° C. and a load of 2.16 kg in accordance with ASTM D 1238-65T. Is 0.1 to 100 g / 10 min, preferably 0.2 to 10 g / 10 min, and more preferably 0.5 to 5 g / 10 min. The density is usually 0.915 to 0.935 g / cm ³ , preferably 0.920 to 0.930 g / cm ³ , more preferably 0.922 to 0.928 g / cm ³ .

Furthermore, the swell ratio of the high pressure method low density polyethylene or ethylene-polar vinyl monomer copolymer is preferably 60% or less, more preferably 50% or less, and particularly preferably 45% or less. The swell ratio is calculated by the following equation (4) by measuring the diameter at a position 5 mm from the end of the strand obtained at the time of measuring the melt flow rate with a micrometer as the diameter (mm) of the sample.
[Equation 4]
Swell ratio (%) = [(L1 / L0) −1] × 100 (4)
L1: Sample diameter (mm)
L0: Orifice diameter (= 2.0955mm)

  When these high-pressure method low-density polyethylene or ethylene-polar vinyl monomer copolymer is blended in the A layer, the blending amount is a weight ratio (high-pressure method low-density polyethylene or ethylene-polar vinyl monomer copolymer / ethylene-α- Olefin copolymer) is 40/60 or less, preferably 5/95 to 30/70, preferably 10/90 to 20/80.

  As the ethylene-polar vinyl monomer copolymer, an ethylene-vinyl acetate copolymer having a vinyl acetate monomer unit content of 2 to 30 mol% is preferable, and a monomer unit content of 2 to 20 mol% is more preferable. 2-10 mol% is more preferable. As the high-pressure method low-density polyethylene, for example, those produced by radical polymerization at 1,000 to 2,000 atm and 200 to 300 ° C. can be used.

  Examples of the resin layer other than the A layer of the olefin resin laminated film of the present invention include an olefin resin layer. Examples of the olefin resin used in the olefin resin layer include homopolymers of α-olefins such as polyethylene and polypropylene, ethylene-propylene copolymers, ethylene-butene-1 copolymers, and ethylene-4-methyl-. An ethylene-α-olefin copolymer such as a 1-pentene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer, the main component of which is an α-olefin Copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, ethylene-polar vinyl monomer copolymers such as ionomer resins A polymer can be mentioned.

  Among these olefin resins, low density polyethylene and copolymers of ethylene and polar vinyl monomers such as ethylene-vinyl acetate copolymers are excellent in transparency and flexibility, and are inexpensive laminated films. Is preferable in that it is obtained. Among the copolymers of ethylene and polar vinyl monomers, ethylene-vinyl acetate copolymers having a vinyl acetate content of 30% by weight or less are excellent in flexibility and can suppress wrinkling when spreading laminated films. Particularly preferred from the viewpoint of excellent heat retention. When an ethylene-polar vinyl monomer copolymer layer is used as the other resin layer, the content of the polar vinyl monomer unit in the olefin-based resin laminated film is preferably 8% by weight or more, preferably 9% by weight or more from the viewpoint of heat retention. Is more preferable. As mentioned above, when the ethylene-polar vinyl monomer copolymer is blended in the A layer, the content of the polar vinyl monomer unit in the olefin-based resin laminated film is the content of the polar vinyl monomer unit in the A layer. Including the amount.

  The olefin resin laminated film of the present invention contains a radiation blocking agent. Radiation rays are emitted as infrared rays in the wavelength range of 2 to 25 μm at night from the ground in a facility such as a house heated by the visible light of the sun during the day. And have the property of absorbing or reflecting this radiation. Examples of the radiation blocking agent include an infrared absorber or an infrared reflector. The infrared reflecting agent is not particularly limited as long as it reflects at least one of the wavelengths in the above wavelength region, and examples thereof include inorganic infrared reflecting agents such as zinc oxide.

  The infrared absorber is not particularly limited as long as it has an infrared absorbing ability superior to that of the olefin resin used in the A layer and the other resin layers, and has an absorption peak at least in any one of the above wavelengths. I just need it. For example, as an inorganic infrared absorber, lithium hydroxide composite hydroxide, composite hydroxide such as hydrotalcite compound, oxide of metal such as magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, titanium oxide, Hydroxides such as lithium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide, carbonates such as magnesium carbonate and calcium carbonate, sulfates such as potassium sulfate, magnesium sulfate, calcium sulfate, zinc sulfate and aluminum sulfate, Phosphate salts such as lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate, zirconium phosphate, oxalate salts such as magnesium oxalate, calcium oxalate, aluminum oxalate, titanium oxalate, sodium aluminate, potassium aluminate, aluminate calcium Examples include aluminates, aluminosilicates such as sodium aluminosilicate, potassium aluminosilicate, calcium aluminosilicate, clay minerals such as kaolin, clay and talc, and other complex oxides, and organic infrared absorption. Examples of the agent include polyacetal, polyvinyl alcohol and derivatives thereof, and ethylene-vinyl alcohol copolymer. These may be used alone or in combination of two or more.

Among these radiation blocking agents, those having a density of 3 g / cm ³ or less are preferable from the viewpoint of recyclability described later, more preferably 2.4 g / cm ³ or less, and infrared absorbers from the viewpoint of economy. Are preferable, and an inorganic infrared absorber is more preferable from the viewpoint of infrared absorbing ability. When the infrared absorber is an inorganic infrared absorber, it is closer to the refractive index of the olefin resin used from the viewpoint of light transmittance, and has absorption performance in a wide wavelength range from the viewpoint of heat retention. For example, hydrotalcite compounds, composite hydroxides such as lithium aluminum composite hydroxide, aluminosilicates and the like can be exemplified as preferred compounds from these viewpoints. In order to improve the dispersibility in the laminated film, the surface treatment of these inorganic infrared absorbers may be performed with a higher fatty acid or an alkali metal salt thereof.

The hydrotalcite compound is a compound represented by the following formula (I)
M ²⁺ _1-x Al _x (OH ⁻ ) ₂ (A ₁ ⁿ⁻ ) _{x / n} · mH ₂ O (I)
( ^Wherein M ²⁺ represents a divalent metal ion selected from the group consisting of magnesium, calcium and zinc, and x and m satisfy 0 <x <0.5, 0 ≦ m ≦ 2, A ₁ ⁿ⁻ represents an n-valent anion, but the n-valent anion is not particularly limited. For example, Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , SO ₄ ²⁻ , CO _{3 ^{2-, SiO 3 2-, HPO 4}} 3-, HBO 4 3-, PO 4 3-, Fe (CN) 6 3-, Fe (CN) 6 4-, CH 3 COO -, C 6 H 4 (OH ) COO ⁻ , (COO) ₂ ²⁻ , anions such as terephthalic acid ions and naphthalenesulfonic acid ions, and polysilicate ions and polyphosphate ions described in JP-A-8-217912. Synthetic hides such as natural hydrotalcite and Alkamizer DHT-4A (trade name, manufactured by Kyowa Chemical Industry) It includes the barrel site.

As the lithium aluminum composite hydroxide, for example, a compound represented by the following general formula (II) described in JP-A-5-179052: Li ⁺ (Al ³⁺ ) ₂ (OH ⁻ ) _6. (A ₂ ⁿ⁻ _{1 / n} · mH ₂ O (II)
(In the formula, m is in the range of 0 ≦ m ≦ 3, and A ₂ ⁿ⁻ represents an n-valent anion, but the n-valent anion is not particularly limited, and examples thereof include the same anions as described above. .).

  Other composite hydroxides include, for example, compounds containing at least one element selected from the group consisting of alkaline earth metals, transition metals, Zn and Si, Li and Al, and having a hydroxyl group ( Hereinafter, it may be referred to as compound (III)). Among alkaline earth metals, magnesium and calcium are preferable. Among transition metals, divalent or trivalent iron, cobalt, nickel, and manganese are preferable, and iron is more preferable. The composition ratio of Al to Li (Al / Li) is a molar ratio, usually 1.5 / 1 to 2.5 / 1, and preferably 1.8 / 1 to 2.5 / 1.

In addition, the molar ratio (a) of (each) element selected from the group consisting of alkaline earth metals, transition metals, Zn and Si is usually 0 <a <1. 5, preferably 0.1 ≦ a ≦ 1.4, more preferably 0.2 ≦ a ≦ 1.2. Examples of the elements or compounds constituting the anionic portion of the compound (III) include, for example, pyrosilicate ions, cyclosilicate ions, isosilicate ions, phyllosilicate ions, polysilicate ions such as tectosilicate ions, carbonate ions, and halogenated ions. Inorganic acids such as ions, sulfate ions, sulfite ions, nitrate ions, nitrite ions, phosphate ions, phosphite ions, hypophosphite ions, aluminate ions, silicate ions, perchlorate ions, borate ions Ions, anionic transition metal complexes such as Fe (CN) ₆ ³⁻ , Fe (CN) ₆ ⁴⁻ , organic acid ions such as acetate ion, benzoate ion, formate ion, terephthalate ion, alkylsulfonate ion, etc. Can be mentioned. Among these compounds, ions such as carbonic acid, halogen, sulfuric acid, phosphoric acid, polyphosphoric acid, silicic acid, polysilicic acid, and perchloric acid are preferable, and ions such as carbonic acid, polyphosphoric acid, silicic acid, and polysilicic acid are more preferable.

Specific examples of the compound (III) include a composite hydroxide containing Al, Li, Mg and Al / Li / Mg = about 2.3 / 1 / 0.28 (molar ratio) (trade name: LMA, Fuji Chemical) Industrial products) and composite hydroxides containing Al, Li, Si and Al / Li / Si = about 2/1 / 1.2 (molar ratio) (trade name Fujirain LS, manufactured by Fuji Chemical Industries) It is done. Further, the following formula (III) described in International Publication No. WO97 / 00828:
[(Li ⁺ _(1-x) M ²⁺ _x ) (Al ³⁺ ) ₂ (OH ⁻ ) ₆ ] ₂ (Si _y 0 _{(2y + 1)} ^2- ) _{(1 + x)} · mH ₂ O (III )
( ^Wherein M ²⁺ is a divalent metal ion, and m, x and y satisfy the conditions 0 ≦ m <5, 0 ≦ x <1, 2 ≦ y ≦ 4), And the following formula (IV) disclosed in JP-A-8-217912:
[(Li ⁺ _(1-x) M ²⁺ _x ) (Al ³⁺ ) ₂ (OH ⁻ ) ₆ ] ₂ (A ₃ ⁿ⁻ ) _{2 (1 + x) / n} · mH ₂ O (IV)
(Wherein M ²⁺ is a divalent metal ion, A ₃ ⁿ⁻ is an n-valent anion, and m, x and n are 0 ≦ m <5, 0.01 ≦ x <1, A compound represented by 1) satisfying the condition of 1 ≦ n ≦ 3 can also be mentioned as a preferred example of the composite hydroxide. Examples of M ²⁺ in formulas (III) and (IV) include Mg ²⁺ , Ca ²⁺ and Zn ²⁺ .

Furthermore, the following formula (V) disclosed in JP-A-9-279131:
mAl ₂ O ₃ · (n / p) M _{2 / p} O · X · kH ₂ 0 (V)
(Wherein, X is a carbonate radical, M is an alkali metal or alkaline earth metal, p is the valence of metal M, m, n and k are 0.3 ≦ m ≦ 1, 0.3 ≦ A basic aluminum carbonate double salt represented by the following conditions: n ≦ 2, 0.5 ≦ k ≦ 4) is also a preferred infrared absorber. X in the above formula (V) is sulfur oxyacid (sulfuric acid, sulfurous acid), nitrogen oxyacid (nitric acid, nitrous acid), hydrochloric acid, chlorine oxyacid (for example, perchloric acid), phosphorus oxyacid ( Phosphoric acid, phosphorous acid, metaphosphoric acid), acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, p-oxybenzoic acid, salicylic acid, A double salt containing an organic anion such as picric acid or toluenesulfonic acid may be used in combination with the basic aluminum carbonate double salt.

When using the said composite hydroxide as an infrared absorber, the average particle diameter is 5 micrometers or less normally, Preferably it is 0.05-3 micrometers, More preferably, it is 0.1-1 micrometer. Moreover, the specific surface area measured by BET method is 1-30 m < ² > / g, Preferably it is 2-20 m < ² > / g. The composite hydroxide may further contain crystal water.

  When the olefin-based resin laminated film of the present invention is used for applications that require more transparency, the refractive index of the radiation blocking agent is preferably close to the olefin-based resin to be used, and the method described in JIS K0062 is used. The measured refractive index is preferably 1.47 to 1.55, more preferably 1.48 to 1.54, and particularly preferably 1.49 to 1.53.

  In order to improve the dispersibility of the radiation blocking agent in the laminated film, the radiation blocking agent may be subjected to a surface treatment with a higher fatty acid or an alkali metal salt of a higher fatty acid.

The radiation blocking agent does not need to be included in all layers of the olefin-based resin laminated film, and may be included in any of the layers, and when the radiation blocking agent is included in two or more layers, the content is Each layer may be the same or different, and may be, for example, an infrared absorber layer or an infrared reflector layer. The content of the radiation blocking agent in the olefin-based resin laminated film is such that the radiation transmission index at 23 ° C. described later of the olefin-based resin laminated film is 25 or less and the density satisfies less than 1 g / cm ^3. There is no particular limitation, and it is appropriately set depending on the infrared absorber or infrared reflector to be used and the layer structure of the laminated film. For example, when the composite hydroxide as described above is used as the infrared absorber, the olefin obtained From the viewpoint of the radiation transmission index and density of the resin-based resin laminated film, the blending amount is about 6 to 13% by weight in the olefin-based resin laminated film.

  In the present invention, the radiation transmission index at 23 ° C. is a measure of heat retention and affects crop viability, and is determined by a measurement method as described later. The smaller the value, the better the heat retention of the film. It shows that it is excellent. The radiation transmission index at 23 ° C. of the olefin-based resin laminated film of the present invention is 25 or less, and when it is larger than 25, the crop growth is inferior to that of the polyvinyl chloride film, which is not preferable. This causes a deterioration in economic efficiency such as heating costs. If the radiation transmission index is 25 or less, the closer to zero, the better. From the viewpoint of crop growth, 20 or less is more preferable, and 15 or less is more preferable.

In the present invention, the density of the olefin-based resin laminated film is one measure of recyclability, and is measured at a temperature of 23 ° C. according to the method of JIS K7112 (1980). less than cm ³ . When the density is 1 or more, separation from the vinyl chloride film collected together is poor and the recyclability is poor. The density is preferably 0.99 or less, more preferably 0.98 or less, and particularly preferably 0.97 or less. In the case where the A layer is an outer layer of the house, attached soil or the like is rarely brought into the separation process, and is more recyclable.

  The polyolefin resin laminated film of the present invention is not particularly limited as long as it has at least one A layer, and usually a layer structure of 3 to 5 layers is often used. The formulation of the agent may be different. In the case of three or more layers, when a book is placed in a facility such as a house, the layer facing the outside of the facility is called the outer layer, the layer facing the inside is called the inner layer, and the other layers are intermediate layers (which have a multilayer structure). In general, it may be referred to. The A layer may be any of these outer layers, intermediate layers, and inner layers, but there is less contact breakage (friction resistance) between the olefin-based resin laminated film and the house band, and the laminated film has an opening property and dustproof property. It is more preferable to use the outermost layer, particularly the outer layer, from the viewpoint of superiority in properties.

  When the A layer is the outermost layer, the A layer may contain a lubricant and / or an antiblocking agent from the viewpoint of the opening property, dust resistance, friction resistance, etc. of the resulting olefin-based resin laminated film. . In particular, when using the above-mentioned ethylene-α-olefin copolymer having Cx of 0.2 to 0.4, by using a lubricant and an anti-blocking agent in combination, the opening property, dustproof property, Friction tearing and the like are further improved.

  A commercially available product can be used as the lubricant, and for example, a fatty acid amide compound having a melting point of 50 to 200 ° C. can be preferably used. Examples of fatty acid amide compounds include saturated fatty acid amides, unsaturated fatty acid amides, bis fatty acid amides, and specific examples include behenic acid amide, stearic acid amide, palmitic acid amide, lauric acid amide, erucic acid amide, and olein. Acid amide, methylene bis stearic acid amide, methylene bis behenic acid amide, methylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide, hexamethylene bis stearic acid amide, Examples include hexamethylene bisbehenic acid amide, hexamethylene bisoleic acid amide, and octamethylene biserucic acid amide.

  When blending a lubricant, the blending amount in the A layer is preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight or more with respect to 100 parts by weight of the ethylene-α-olefin copolymer from the viewpoint of effect. preferable. Moreover, from an economical viewpoint, 1 weight part or less is preferable and 0.5 weight part or less is more preferable.

  As the antiblocking agent, commercially available products can be used. For example, organic fine particles and inorganic fine powders can be used. Examples of the organic fine particles include a crosslinked polymer having a particle size of 0.5 to 20 μm, and those having a refractive index close to that of the A layer are preferable. For example, crosslinked beads such as polyethylene and polymethyl methacrylate are preferably used.

  When these organic fine particles are blended, the blending amount in the A layer is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the ethylene-α-olefin copolymer, and 0.3 parts by weight from the viewpoint of the effect. The above is more preferable, and 1 part by weight or more is particularly preferable. Moreover, 20 weight part or less is preferable from a viewpoint of economical efficiency, 10 weight part or less is more preferable, and 5 weight part or less is especially preferable.

  As an inorganic fine powder, the fine powder of the inorganic type infrared absorber mentioned above can be illustrated, for example, and you may use an infrared absorber and an antiblocking agent together. The blending amount is the same as in the case of the organic fine particles.

  When the olefin-based resin laminated film of the present invention is used in an agricultural facility, the outer layer may be appropriately subjected to dust-proofing treatment, and the inner layer may be appropriately subjected to droplets and fog-proofing treatment.

  The thickness of the olefin-based resin laminated film of the present invention is usually in the range of about 0.02 to 0.3 mm in terms of film strength, film splicing workability and coating workability, and 0.03 to 0.2 mm. The degree is more preferable. When the olefin-based resin laminated film of the present invention has two or more layers having layers other than the A layer, the thickness of the A layer (the total of the thicknesses when the A layer is 2 or more) is usually the thickness of the laminated film. Of about 10 to 90%. About 20 to 80% is preferable from the viewpoint of moldability of the laminated film, and about 30 to 70% is more preferable from the viewpoint of transparency and film strength. In addition, when the polyolefin-based resin laminated film is 3 layers or more, the A layer is the outermost layer, and the infrared layer used as a radiation blocking agent is contained in the intermediate layer in a large amount, about 10 to 40% is preferable. About 15 to 30% is more preferable. In addition, when an olefin resin laminated | multilayer film is two or more layers, the thickness of each layer may not be the same and you may change thickness suitably.

  For the purpose of improving the weather resistance, a commercially available light stabilizer may be contained in the olefin-based resin laminated film, and among the light stabilizers, a hindered amine compound is more preferable. When the light stabilizer is contained, it may be contained in any layer of the olefin-based resin laminated film, and when it is contained in two or more layers, the content thereof may be the same or different in each layer. Examples of the hindered amine compounds include those having the structural formulas described in JP-A-8-73667. Specific examples thereof include trade names Tinuvin 622-LD, Kimasorb 944-LD, Hostavine N30, VP Sanduvor PR-31. Tinuvin 123 and a hindered amine compound-containing stabilizer include compositions described in JP-A-63-286448 (trade names TINUVIN 492, TINUVIN 494, etc., manufactured by Ciba Geigy). These hindered amine compounds may be used alone or in combination of two or more.

  When the hindered amine compound is contained in the olefin resin laminated film, the content is usually 0.02 to 5% by weight, preferably 0, in the entire olefin resin laminated film from the viewpoint of improving weather resistance and suppressing blooming. .1 to 2% by weight, more preferably 0.5 to 2% by weight. Moreover, it is more preferable to use together with the following ultraviolet absorber from a viewpoint of a weather-resistance improvement effect.

  For the same purpose as described above, an ultraviolet absorber may be contained in the olefin-based resin laminated film. When the ultraviolet absorber is contained, it may be contained in any layer of the olefin-based resin laminated film, and when contained in two or more layers, the content thereof may be the same or different in each layer. Examples of such UV absorbers include commercially available UV absorbers, for example, organic UV absorbers such as benzophenone UV absorbers, benzotriazole UV absorbers, benzoate UV absorbers, and cyanoacrylate UV absorbers, and cerium oxide. And inorganic ultraviolet absorbers such as metal oxides such as titanium oxide and the like (trade name Seriguard manufactured by Nippon Inorganic Chemical Industry Co., Ltd.). Moreover, these ultraviolet absorbers may be used independently or may use 2 or more types together.

  When the ultraviolet absorber is contained, the content thereof is usually 0.01 to 3% by weight, preferably 0.05 to 1% by weight in the whole olefin-based resin laminated film from the viewpoint of weather resistance improvement effect and blooming suppression. % Range.

  Moreover, the olefin resin laminated film of the present invention may contain an antifogging agent for the purpose of imparting antifogging properties. When the antifogging agent is blended, the blending amount is usually 0.1 to 4% by weight, preferably 0.5 to 3% by weight, more preferably 1.5 to 5% in the entire olefin-based resin laminated film. 3% by weight, particularly preferably 2.2 to 2.8% by weight, may be contained in any layer of the olefin-based resin laminated film, and when contained in two or more layers, the content is the same for each layer or different. It may be.

  Such antifogging agents include those that are solid at room temperature (23 ° C.) and those that are liquid, and examples of solid antifogging agents include nonionic surfactants such as sorbitan monostearate and sorbitan. Sorbitan fatty acid ester surfactants such as monopalmitate, sorbitan monobehenate, sorbitan monomontanate, glycerol monolaurate, glycerol monopalmitate, glycerol monostearate, diglycerol distearate, triglycerol monostearate, Glycerin fatty acid ester surfactants such as tetraglycerin monomonate, polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate, alkylene oxide adducts of alkylphenols, An ester of the tail / glycerin condensates and organic acids.

  Furthermore, when an antifogging agent that is liquid at room temperature is added to the olefin-based resin laminated film, the phenomenon that the light transmittance is impaired during storage and stretching of the film can be avoided. May be blended. In order to exhibit such an effect, it is preferable to use at least one antifogging agent that is liquid at room temperature.

  Examples of the antifogging agent that is liquid at room temperature include glycerin monooleate, diglycerin monooleate, diglycerin sesquioleate, tetraglycerin monooleate, hexaglycerin monooleate, tetraglycerin trioleate, and hexaglycerin penta. Examples include glycerin fatty acid esters such as oleate, tetraglycerin monolaurate, and hexaglycerin monolaurate, and sorbitan fatty acid esters such as sorbitan monooleate, sorbitan dioleate, and sorbitan monolaurate. When mix | blending a liquid antifogging agent, the compounding quantity is 0.2 to 3 weight% normally in an olefin type resin laminated | multilayer film, Preferably it is the range of 0.5 to 2 weight%.

  Further, from the viewpoint of maintaining the transparency of the olefin-based resin laminated film of the present invention for a long period of time, an antifogging film may be further formed on the surface of at least the inner layer of the laminated film.

  Such anti-fogging coating is, for example, a coating film of inorganic oxide sol typified by colloidal silica or colloidal alumina described in JP-B-49-32668 and JP-B-50-11348, and applications thereof. As described in JP-B-63-45432, JP-B-63-45717, JP-B-64-2158, JP-A-3-207763, etc. Examples thereof include a coating film, a coating film such as a liquid coating film containing a hydrophilic resin as a main component, and a film containing a hydrophilic resin as a main component. Here, examples of the hydrophilic resin include polyvinyl alcohol, polysaccharides, and polyacrylic acid. The method for forming the film may be coating, or a method of forming a film containing a hydrophilic resin as a main component and then laminating the film on the film.

  In the olefin resin laminated film of the present invention, an antifogging agent can be blended for the purpose of imparting antifogging properties. Examples of such anti-fogging agents include fluorine compounds having a perfluoroalkyl group, ω-hydrofluoroalkyl group, etc. (especially fluorine-based surfactants), silicon-based compounds having alkylsiloxane groups, particularly silicon-based surfactants, and the like. Can be mentioned. When blending the antifogging agent, the blending amount is usually in the range of 0.01 to 3% by weight, preferably 0.02 to 1% by weight in the olefin-based resin laminated film. In the case where it is contained in two or more layers, the content thereof may be the same as or different from each other.

  In the olefin-based resin laminated film of the present invention, various stabilizers commonly used other than the above (for example, light stabilizers of nickel compounds, antioxidants, heat stabilizers), antiblocking agents, Additives such as lubricants, antistatic agents, pigments, etc. can be added ("Separation and analysis technology of polymer additives, Tanaka et al., 1987, Japan Science Information Co., Ltd.", "Plastic and rubber additives practical use" Handbook, Goto et al., 1970, “Chemical Industry Co., Ltd.”).

  The olefin-based resin laminated film of the present invention can be blended with a near-infrared shielding agent for the purpose of lowering the temperature inside the house during the hot days. Examples of such near-infrared blocking agents include organic compounds disclosed in JP-A-10-193522 (for example, nitroso compounds and metal complexes thereof, cyanine compounds, squarylium compounds, thiol nickel complex compounds, phthalocyanine compounds). Compounds, triallylmethane compounds, imonium compounds, diimonium compounds, naphthoquinone compounds, anthraquinone compounds, amino compounds, aminium salt compounds) and inorganic compounds (eg carbon black, antimony oxide, indium oxide) Tin oxide, oxides or carbides of metals belonging to Group 4A, 5A or 6A of the periodic table, or carbides, boron compounds). A film containing a near infrared ray blocking agent may be formed on the surface of the laminated film of the present invention. Examples of the method for forming the coating include a method in which a coating liquid containing a near infrared ray blocking agent and a water-soluble resin binder is applied to a laminated film and dried.

  The above various additives may be used alone or in combination of two or more. When various additives are blended, they may be blended in any layer of the olefin-based resin laminated film. When mix | blending above, the quantity may be the same or different for each layer.

  Although the manufacturing method of the olefin resin laminated film of this invention is not specifically limited, For example, it manufactures with the following method. For example, a predetermined amount of radiation blocking agent is added to an ethylene-α-olefin copolymer and / or an olefin resin, and if necessary, an antifogging agent, an antifogging agent, various stabilizers, a lubricant, an antiblocking agent, Each resin composition can be obtained by mixing and kneading various additives such as pigments with an ordinary mixing and kneading machine such as a ribbon blender, a super mixer, a Banbury mixer, a uniaxial or biaxial extruder. The resin composition thus obtained can be used, for example, by a molding method for obtaining an ordinary laminated film such as a T-die film molding method by co-extrusion or an inflation film molding method.

  The olefin-based resin laminated film of the present invention is suitably used for, for example, a facility horticulture house / tunnel. Moreover, also when installing a lining curtain in this facility, the olefin resin laminated film of this invention can be preferably used as a lining curtain. In particular, the olefin-based resin laminated film of the present invention can be suitably used as a substitute for a conventional vinyl chloride film, particularly the vinyl chloride film used in the above-mentioned agricultural applications.

In the present invention, a mixture of a vinyl chloride film piece and an olefin-based resin laminated film piece satisfying the following condition (1) is placed in a separation / washing tank, filled with the separation / washing liquid, stirred, allowed to stand and a supernatant layer. Is recovered, filtered and dried to recover the olefin-based resin laminated film.
Condition (1): Layer mainly composed of an ethylene-α-olefin copolymer (A) having a melt flow rate of 0.1 to 50 g / 10 min and a density of 0.88 to 0.94 g / cm ³ ( A layer of olefin-based resin having a radiation transmission index at 23 ° C. of 25 or less and a density of less than 1 g / cm ^3. The size of the olefin-based resin laminated film piece satisfying (1) is such that it is punched with a JIS No. 1 dumbbell.
The separation / cleaning liquid is a liquid capable of separating and cleaning the vinyl chloride film piece and the olefin-based resin laminated film piece satisfying the above condition (1), and the objective can be sufficiently achieved usually with a 5% aqueous ethanol solution.

  The olefin-based resin laminated film of the present invention has the same heat retention property as one of the most important properties as a cultivation environment, and is equivalent to that of vinyl chloride film. Crop growth (yield) equivalent to or better than vinyl film is achieved. Moreover, since the olefin resin laminated film of the present invention can be easily separated from the polyvinyl chloride film, it is excellent in recyclability. In addition, it has many excellent performances such as workability, cold resistance and price as compared with the polyvinyl chloride film, and is useful as an agricultural film. It is possible to greatly improve the dust-proof property of a vinyl chloride film, which is said to be particularly bad, and it is suitably used as an agricultural film for facilities, horticultural houses, tunnels and the like as an alternative film of a vinyl chloride film.

  The olefin-based resin laminated film of the present invention has an ethylene-α-olefin copolymer layer, so that the mechanical strength is remarkably improved. Especially, when the layer is an outer layer, contact breakage with a house band is remarkably improved. .

  Furthermore, the olefin-based resin laminated film of the present invention can achieve a total light transmittance of 85% or more, in some cases 90% or more, and further 92% or more, and the illuminance on a cloudy day after one month after stretching. It is possible to achieve levels above the vinyl chloride film commonly used in measurements. The HAZE value of the olefin resin laminated film of the present invention is small, and the value obtained by subtracting the HAZE value immediately after film production from the HAZE value after storage for 3 months at room temperature (ΔHAZE value) is within 110% of the HAZE value immediately after production. It is also possible to do. Generally, as for the HAZE value, the smaller the HAZE value is, the higher the transmittance of parallel rays is. However, the higher the transmittance of parallel rays is, the more sunlight is taken into the house and tunnel in the daytime, and the temperature in the house and tunnel. It also has a positive effect on the growth of intense light crops such as solanaceous plants, bell peppers, melons, watermelons, strawberries, etc. Therefore, the olefin resin laminated film of the present invention can be suitably used for cultivation of forced crops.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, the test method in an Example and a comparative example is as follows.

(1) Density The method defined in JIS K7112 (1980) was followed.

(2) Melt flow rate The method specified in JIS K7210 was followed. The load is 2, 16 kg, and the temperature is 190 ° C.

(3) Molecular weight distribution Mw / Mn
GPC: GPC apparatus manufactured by Nippon Waters, Model 150C, Column: TSK GMH-6 manufactured by Tosoh, Solvent: Orthodichlorobenzene (ODCB), Temperature: 135 ° C, Flow rate: 1ml / min, Concentration: 10mg / 10ml Sample injection volume: Measured under conditions of 500 μl. The weight average molecular weight Mw and the number average molecular weight Mn converted from a calibration curve using standard polystyrene were determined, and Mw / Mn was calculated.

(4) Composition distribution coefficient of variation Cx
The measurement was performed using a multifunctional LC manufactured by Tosoh Corporation. The ethylene-α-olefin copolymer was dissolved in an ODCB solvent heated to 140 ° C. and placed in a column filled with sea sand in a column oven, and the oven temperature was lowered to −14 ° C. Subsequently, the temperature was raised to a predetermined temperature set in advance, and the relative concentration and branching degree of the copolymer flowing out during that time were measured by FT-IR connected to a column. The temperature was raised to the set temperature sequentially, and the temperature was raised to the final temperature while obtaining the relative concentration and the branching degree of the copolymer flowing out at each set temperature. A composition distribution curve is obtained from the obtained relative concentration and branching degree, and statistical processing is performed. The standard deviation of the composition distribution was determined. The composition distribution coefficient of variation Cx was obtained from SCBave obtained from FT-IR.

(5) Radiation transmission index Using an infrared spectrophotometer (1640 type FTIR manufactured by PerkinElmer), a radiation transmission index was obtained by the following method and used as a measure of heat retention.

An infrared absorption spectrum (transmission method) of the film (thickness: 100 microns) was measured at a temperature of 23 ° C. within a wave number range of 4000 to 400 cm ⁻¹ to obtain a value of transmittance T (ν)% at a wave number ν. On the other hand, according to the following formula 5 obtained from Planck's law, the black body radiation spectrum intensity e (ν) at a wave number ν at 23 ° C. is calculated. Here, the black body radiation spectrum intensity e (ν) multiplied by the transmittance T (ν) is the radiation transmission intensity f (ν) (Equation 6).

What integrated radiation transmission intensity f (ν) in the range of wave numbers 4000 to 400 cm ⁻¹ and integrated radiation transmission energy F and black body radiation spectrum intensity e (ν) in the range of wave numbers 4000 to 400 cm ^−1. Is defined as a black body radiation energy E as a radiation transmission index G = 100 * F / E. The actual integration was divided into sections with a wave number interval of 2 cm ⁻¹ , and each section was calculated and integrated by trapezoidal approximation. The smaller the radiation transmission index, the better the heat retention of the film.
[Equation 5]
e (ν) = (A / λ ⁵ ) / {exp (B / (λ * T))-1) Equation 5
However, A = 2πhC ² = 3.74 * 10E-6 (W · m ² )
B = hC / k = 0.01439 (m · K)
T (K) is the absolute temperature. λ (cm) is the wavelength (wave number ν is the reciprocal of the wavelength), h is the Planck constant, C is the speed of light, and k is the Boltzmann constant.
[Equation 6]
f (ν) = e (ν) * T (ν) / 100 Equation 6

(6) A fog-proof test film is attached to a 50 x 60 cm acrylic frame with double-sided tape, placed horizontally in a thermostatic bath at 40 ° C placed in a thermostatic chamber at 23 ° C with the test side down. Installed. After the test surface was sufficiently moistened, the amount of fog generated when the ice water was kept in contact with the outside of the film and the time until it disappeared were visually observed and judged according to the following criteria.
: The amount of fog is small and disappears immediately.
: A little fog is generated and it takes time to disappear.
X: The amount of fog generated is very large, and it takes time to disappear.

(7) Anti-fogging test A film is affixed to a 34 x 5 cm acrylic frame with double-sided tape. The test surface is down and placed on a constant temperature water tank placed in an environmental test chamber at a constant temperature. It was installed with an inclination of 15 degrees. At this time, the temperature condition (environmental test chamber / constant water bath) was 3 ° C./20° C. And the state of the water droplet on the film surface was observed, and it determined with the following references | standards.
: The film surface is uniformly wet.
: Some water droplets are attached.
X: Water droplets adhere to the entire surface and are white and cloudy.

(8) Weather resistance test Using a sunshine weather meter (manufactured by Suga Test Instruments), a test piece punched with a JIS No. 1 dumbbell was exposed over time at a black panel temperature of 63 ° C. The test piece exposed with time was subjected to a tensile test using Autograph DSS100 (manufactured by Shimadzu Corporation) to measure the elongation (%), and the elongation was halved relative to the original specimen. The weather resistance test time was determined. The larger the value of this time, the better the weather resistance, and 1000 hours was regarded as the pass level of this test.

(9) Recyclability test Vinyl chloride film (Made by Mitsubishi Chemical MKV, trade name Clean Ace Skin Nine, film thickness 75 μm) and sample film are punched with JIS No. 1 dumbbell, 10 test pieces each at 23 ° C., separation / wash tank (2 In a beaker having a volume of 1 liter), 1500 mL of a separation / washing solution (5% ethanol aqueous solution) was filled, and then stirred with a three-one motor. Thereafter, the mixture was allowed to stand for 1 minute, and the supernatant layer (500 mL) was collected, filtered and dried.
○: The entire sample film is collected.
(Triangle | delta): Some sample films cannot be collect | recovered by mixing with agricultural beans.
X: The sample film cannot be collected.

Examples 1-4
After kneading at 150 ° C. for 5 minutes using a Banbury mixer with the formulation described in Table 1, granulation was performed by a granulator to obtain resin composition pellets of each layer (in the table, the values in parentheses are the values for each layer). Parts by weight based on 100 parts by weight of the resin). Each layer thickness and film thickness were formed by the three-layer inflation film molding machine so that the inner layer composition would be the outer surface of the inflation film tube (the outer layer composition was the inner surface of the inflation tube). . The results are shown in Table 1. The film was excellent in radiation transmission index (heat retention) and recyclability, and particularly excellent in fog prevention, antifogging and weather resistance.

Example 5
Each composition shown in Table 2 was kneaded at 150 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain resin composition pellets of each layer (the values in parentheses in the table are the values in the table). Meaning the same as 1). The film was formed so that each layer thickness and film thickness were as shown in Table 2 by a three-layer inflation film molding machine so that the inner layer composition was the outer surface of the inflation film tube (the outer layer composition was the inner surface of the inflation tube). Thereafter, the following antifogging film was formed. The results are shown in Table 2. The film was excellent in radiation transmission index (heat retention) and recyclability, and particularly excellent in fog prevention, antifogging and weather resistance.

[Formation of anti-fogging film]
Anti-fogging coating: Alumina sol (manufactured by Nissan Chemical Co., Ltd., trade name Alumina sol 520 solid content 20%), colloidal silica (Nissan Chemical Co., Ltd., trade name Snowtex 20 solid content 20%), sodium dodecylbenzenesulfonate (trade name, manufactured by Kao) Neoperex F25) and sodium decanoate (manufactured by Nacalai Tesque) are diluted with water so that the solid component concentrations are 1.6, 0.4, 0.08, and 0.08, respectively. One side of (the film before forming the antifogging film) was subjected to corona treatment, applied to the surface so that the solid content thickness was about 0.11 g / m ^2, and air-dried at room temperature to obtain a film.

Comparative Examples 1 and 2
Each composition shown in Table 2 was kneaded at 150 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain resin composition pellets of each layer (the values in parentheses in the table are the values in the table). Meaning the same as 1). The film was formed so that each layer thickness and film thickness were as shown in Table 2 by a three-layer inflation film molding machine so that the inner layer composition was the outer surface of the inflation film tube (the outer layer composition was the inner surface of the inflation tube). . The results are shown in Table-2.

Example 6
In Example 1, instead of the inner layer resin A1 / A8, a commercially available ethylene-α-olefin copolymer (trade name: Sumikasen E FV201, density: 0.915 g / cm ³ , MI1.5, manufactured by Sumitomo Chemical Co., Ltd.) The same procedure except that a commercially available ethylene-α-olefin copolymer (trade name: Sumikasen E FV202 density 0.925 g / cm ³ , MI 1.7, manufactured by Sumitomo Chemical Co., Ltd.) is used instead of the resin A2 / A8. In addition to being excellent in radiation transmission index (heat retention) and recyclability, it is possible to obtain a film having excellent fog resistance, antifogging properties, and weather resistance.

Example 7
In Example 5, a commercially available ethylene-α-olefin copolymer (trade name: Sumikacene Hiα FW201 density 0.925 g / cm ³ , MI 1.7, manufactured by Sumitomo Chemical Co., Ltd.) was used in the same manner as the inner and outer layer resins. In addition to excellent radiation transmission index (heat retention) and recyclability, it is possible to obtain a film having excellent fog resistance, antifogging properties, and weather resistance.

Example 8
In Example 5, a commercially available ethylene-α-olefin copolymer (trade name: Sumikasen E FV202 Lot. 53281, density: 0.925 g / cm ³ , MI 1.7, manufactured by Sumitomo Chemical Co., Ltd.) was used as the inner and outer layer resin. In the same manner except that no lubricant is used, a film having excellent radiation transmission index (heat retention) and recyclability, as well as excellent fog resistance, antifogging properties, and weather resistance can be obtained.

Example 9
In Example 3, an ethylene-α-olefin copolymer (trade name: Sumikasen E FV402, density 0.915 g / cm ³ , MI4 manufactured by Sumitomo Chemical Co., Ltd.) and low-density polyethylene A8 were used in the inner layer and intermediate layer resins. The blends at a weight ratio of 15 are each made of an ethylene-α-olefin copolymer (trade name: Sumikasen E FV202, density: 0.925 g / cm ³ , MI 1.7, manufactured by Sumitomo Chemical Co., Ltd.) as the outer layer resin. In the same manner as above, a film having excellent radiation transmission index (heat retention) and recyclability, and excellent fog resistance, antifogging properties, and weather resistance can be obtained.

The abbreviations described in Table 1 and Table 2 are as follows.
[List of abbreviations]
A1: Sumitomo Chemical Co., Ltd. Sumikasen E, FV402-0 (hexene content 11.1% by weight)
A2: Sumitomo Chemical Co., Ltd. Sumikasen E, FV403-0 (hexene content 8.6% by weight)
A3: Sumitomo Chemical Co., Ltd. Sumikasen α, FZ202-0 (hexene content 9.4% by weight)
The characteristics of A1 to A3 are as shown in Table 3.

ただし、A1、A2、はメタロセン系触媒を用いて重合したエチレン−ヘキセン共重合体、A3はチーグラー・ナッタ系触媒を用いて重合したエチレン−ヘキセン共重合体である。

A1, A2 are ethylene-hexene copolymers polymerized using a metallocene catalyst, and A3 is an ethylene-hexene copolymer polymerized using a Ziegler-Natta catalyst.

A4: Ethylene-vinyl acetate copolymer (trade name: Evertate H2031 Vinyl acetate content 19% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
A5: Ethylene-vinyl acetate copolymer (trade name: Evertate H2021 vinyl acetate content 15% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
A6: Ethylene-vinyl acetate copolymer (Product name: Evaate D2021 Vinyl acetate content: 10% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
A7: Ethylene-vinyl acetate copolymer (trade name: Evertate D2011, vinyl acetate content 5% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
A8: Low density polyethylene (trade name: Sumikasen F200, density 0.923 g / cm ³ manufactured by Sumitomo Chemical Co., Ltd.)
E1: Product name: Sumilizer BP76 E2 manufactured by Sumitomo Chemical Co., Ltd. E2: Product name: Irgaphos P168 Ciba Geigy E3: Product name: Sumilizer BHT E4 manufactured by Sumitomo Chemical Co., Ltd. E4: Product name: Irganox 1010 F1: Hindered amine compound Kimasorb 944LD Ciba Geigy)
F2: hindered amine compound (trade name: Tinuvin 622LD, manufactured by Ciba Geigy)
F3: hindered amine compound (trade name: Tinuvin 462, manufactured by Ciba Geigy)
F4: hindered amine compound (trade name: Tinuvin 464 manufactured by Ciba Geigy)
F5: hindered amine compound (trade name: Hostabin N30, manufactured by Clariant)
G1: Product name: Sumisorb 130 Sumitomo Chemical Co., Ltd. G2: Product name: Sumisorb 300 Sumitomo Chemical Co., Ltd. H1: Diglycerin sesquioleate H2: Weight ratio of monoglycerin monostearate / diglycerin sesquistearate = 3/7 Mixture H3: sorbitan sesquistearate H4: sorbitan monostearate propylene oxide 1 mol adduct H5: tetraglycerin tristearate I1: fluorinated surfactant (trade name: Unidyne DS403, manufactured by Daikin Industries)
I2: Fluorine compound (trade name: Surflon KC14, manufactured by Asahi Glass)
J1: Hydrotalcite (trade name: DHT4A, manufactured by Kyowa Chemical Industry)
J2: Compound hydroxide (trade name: Fujirain LS, manufactured by Fuji Chemical Industries)
J3: Lithium aluminum composite hydroxide (trade name: Mizukarak Mizusawa Chemical Co., Ltd.)
K1: fatty acid amide compound ethylene bisoleic acid amide K2: fatty acid amide compound erucic acid amide K3: fatty acid amide compound oleic acid amide K4: fatty acid amide compound ethylene bis stearic acid amide

Claims (2)

Put a mixture of vinyl chloride film piece and olefin resin laminated film piece satisfying the following condition (1) into separation / washing tank, fill with separation / washing liquid, stir, let stand and collect and filter supernatant layer -A method of drying and collecting the olefin-based resin laminated film.
Condition (1): Layer mainly composed of an ethylene-α-olefin copolymer (A) having a melt flow rate of 0.1 to 50 g / 10 min and a density of 0.88 to 0.94 g / cm ³ ( Radiant shielding agent-containing olefin-based resin laminated film having at least one layer A), a radiation transmission index at 23 ° C. of 25 or less, and a density of less than 1 g / cm ³ The method according to claim 1, wherein the olefin-based resin laminated film is an agricultural film.