KR100721743B1 - Laminated film - Google Patents

Abstract

The present invention comprises at least one layer (A layer) containing, as a main component, an ethylene-α-olefin copolymer (A) having a melt flow rate of 0.1 to 50 g / 10 minutes and a density of 0.88 to 0.94 g / cm 3. It consists of two or more layers, at least one layer contains a radiation blocker, and is related with the laminated | multilayer film whose radiation transmittance index in 23 degreeC is 25 or less and density is less than 1 g / cm <3>. This laminated film is excellent in heat retention and can be easily separated from a vinyl chloride film, thereby making it easy to recycle.

Description

Laminated Film {LAMINATED FILM}

This invention relates to the laminated | multilayer film which has a layer containing an ethylene-alpha-olefin copolymer as a main component.

Conventionally, agricultural films used in agricultural houses, tunnels, and the like in facility horticulture and the like are mainly olefin resin films such as polyethylene films, ethylene-vinyl acetate copolymer films, and polyvinyl chloride films.

Of these, the olefin resin film is excellent in transparency but inferior to the polyvinyl chloride film in terms of heat retention. Thus, the phosphate compounds, silicon oxides, anhydrous aluminosilicates and dehydrated kaolins disclosed in Japanese Patent Application Laid-Open No. 52-105953, Japanese Patent Application Laid-Open No. 4-11107, and Japanese Patent Application Laid-open No. 57-34871, etc. Increasingly, the use of an olefinic resin film for improving the thermal insulation by adding inorganic compounds such as nitrate, aluminum, silicate, zeolite, hydrotalcite, or organic compounds such as acetal resin has been expanded in recent years. Here, the term "heat insulation" means absorbing and / or reflecting radiation emitted at night from the ground where the sun absorbs solar heat during the day and the temperature rises, thereby adjusting the internal temperature (temperature and geothermal) of the house, tunnel, and the like. It means the performance to maintain.

On the other hand, currently used agricultural films are being disposed of by recycling, incineration, landfill, etc., but recycling has become an important method in terms of protecting the global environment in recent years. Recycling means collecting, reusing and reusing used agricultural films.

It is common to recover without distinguishing an olefin resin film and a polyvinyl chloride film, and there exists a possibility that both may mix when reproducing. However, since the quality of the recycled product in which both are mixed is inferior to that of the original olefin resin film and the polyvinyl chloride film, there is a problem that the use of the recycled product is limited. Therefore, in order to obtain better quality remanufactured products, it is necessary to separate both of them before regeneration.

In general, recovered films are usually remanufactured by the following process (Ref .: Plastic Age, July Interim Extra Care, 147-158 pages, 1994, Polymer Processing, 40 (12), 611-621). Page, 1991, etc.).

① Remove foreign substance

② pretreatment crushing

③ cleaning / grinding / washing

④ Separation

⑤ Cleaning / Drying

⑥ Mixing / Assembling

In washing (3), water which is an inexpensive solvent or a mixed solvent of water / alcohol is usually used. In the separation process of (4), the cleaning liquid obtained in (3) is left to stand and separated into a polyvinyl chloride film and an olefin resin film. However, the conventional olefin resin film with improved heat retention as described above is not easily separated from the polyvinyl chloride film in this separation step, and thus such recycling is not easy. Hereinafter, the ease of recycling of a film is called "recyclability" of a film.

An object of the present invention is to provide an olefin resin film having good heat retention and recycling properties, and furthermore, an olefin having good heat retention and recycling properties, and excellent in anti-fogging property, anti-fogging property, and weather resistance. It is providing a system resin film.

MEANS TO SOLVE THE PROBLEM The present inventors came to this invention as a result of earnestly examining in order to solve the said subject. That is, the present invention provides at least a layer (A layer) containing, as a main component, an ethylene-α-olefin copolymer (A) having a melt flow rate of 0.1 to 50 g / 10 minutes and a density of 0.88 to 0.94 g / cm 3. It consists of two or more layers comprising one layer, at least one layer is a laminated film containing a radiation blocker, and provides a laminated film having a radiation transmittance index of 25 or less and a density of less than 1 g / cm 3 at 23 ° C. In this invention, a "main component" means the component with most content (weight).

 In the present invention, the α-olefin (monomer unit) of the ethylene-α-olefin copolymer (A) 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. An alpha olefin may be used individually by 1 type, or 2 or more types may be used together. Content (the total amount when using 2 or more types together) of the (alpha)-olefin monomer unit in an ethylene-alpha-olefin copolymer (A) is about 0.5-25 mol% normally, Preferably it is about 0.5-10 mol%, More preferably, it is about 1-7 mol%.

The melt flow rate (MFR) of the ethylene-α-olefin copolymer (A) is 0.1 to 50 g / 10 minutes, preferably 0.3 to 20 g / 10 minutes. The said melt flow rate is a value measured on 190 degreeC and the conditions of 2.16 kg of loads based on JISK7210. If the melt flow rate is too low, the processability at the time of manufacturing a laminated film may fall, and when too high, the intensity | strength of the obtained laminated film may fall. The density is usually 0.88 to 0.94 g / cm 3, preferably 0.90 to 0.94 g / cm 3, and more preferably 0.90 to 0.938 g / cm 3. In particular, when the layer (A layer) mainly containing the ethylene-α-olefin copolymer (A) forms the outer layer of the laminated film, the density is preferably 0.91 to 0.94 g / cm 3, and furthermore, 0.92 to 0.94 g / cm 3 In particular, 0.925 to 0.940 g / cm 3 is preferable. In addition, when the A layer forms an inner layer of the laminated film, the density is preferably 0.88 to 0.93 g / cm 3, more preferably 0.88 to 0.92 g / cm 3, particularly preferably 0.890 to 0.915 g / cm 3. The density here is a value measured in accordance with JIS K 7112 (1980). As for molecular weight distribution (Mw / Mn) calculated | required by GPC, 1.5-4 are preferable from a viewpoint of workability and strength, and 2-3.5 are more preferable.

The ethylene-alpha-olefin copolymer (A) used by this invention is the antiblocking property of the said laminated | multilayer film in the case of the viewpoint of the laminated film strength obtained, and A layer forming the outermost layer of the laminated | multilayer film of this invention. From the standpoint of (開口) and dustproofness, the composition distribution variation coefficient Cx obtained by the following formula (1) is more preferably 0.5 or less, and particularly preferably 0.2 to 0.5.

Cx = σ / SCB ave. (One)

(Wherein σ represents the standard deviation of the elution amount of the eluting component at each temperature and the composition distribution determined from the branching degree by the following temperature rise column fractionation method. SCB ave. Average value of the short-chain branch index).

In addition, σ and SCB ave. The specific method of obtaining is as follows.

 SCB ave. Can be calculated | required by ethylene-alpha-olefin copolymer FT-IR spectrum, as is normally done by measurement of short chain branches, such as polyethylene. The short-chain branching here usually means the branch (typically branch having 1 to 4 carbon atoms) having about 1 to 4 carbon atoms. Moreover, (sigma) is calculated | required according to the regular method of a temperature rise column fractionation method. That is, the ethylene-α-olefin copolymer is dissolved in a solvent heated to a predetermined temperature, placed in a column in a column oven, and once the temperature of the oven is lowered, and then raised to a predetermined temperature, the component eluted at that temperature. Relative density and branching degree of are measured by FT-IR connected to column. Subsequently, the temperature is raised step by step to a final temperature (the temperature at which all the dissolved copolymer elutes). The relative concentration and branching degree of each obtained elution component are statistically processed to determine the standard deviation σ of the composition distribution obtained from the branching point.

In addition, when A-layer is the outermost layer of the laminated | multilayer film of this invention, it is GPC-IR as described in Unexamined-Japanese-Patent No. 08-276542 from a viewpoint of the strength, antiblocking property, and dustproofness of a laminated | multilayer film, for example. The ethylene-alpha-olefin copolymer whose average value of the high molecular weight side branch number calculated | required by is more than the average value of the low molecular weight side branch number can also be used preferably.

As a method of obtaining the ethylene-alpha-olefin copolymer which has Cx of the said range, For example, ethylene and the alpha-olefin of C3-C18 are converted into a transition metal complex catalyst (for example, a palladium complex catalyst and nickel). Using a so-called single-site catalyst such as a complex catalyst) and a metallocene catalyst, a method of polymerization in a gas-solid, a liquid-solid, or a uniform liquid phase in the presence or absence of a solvent can be exemplified. Usually, polymerization temperature is 30 degreeC-300 degreeC, and polymerization pressure is normal pressure-3000 kg / cm <2>. For example, the metallocene catalyst component described in Japanese Unexamined Patent Publication No. Hei 6-9724, Japanese Unexamined Patent Publication No. Hei 6-136195, Japanese Unexamined Patent Publication No. Hei 6-136196, Japanese Patent Application Laid-Open No. Hei 6-207057, and the like. In the presence of a so-called metallocene-based olefin polymerization catalyst comprising a ethylene and an α-olefin having 3 to 18 carbon atoms, the copolymer is copolymerized so that the resulting copolymer has a density of 0.88 to 0.94 g / cm 3. It can manufacture.

In the present invention, the layer A may be a layer composed only of the ethylene-α-olefin copolymer (A), but for the purpose of improving transparency, the density is 0.94 g / cm 3 or more, preferably 0.945 to 0.955 g / cm 3. The layer which consists of a mixture of high density polyethylene with a copolymer (A) may be sufficient. When the high density polyethylene is blended, if the melt flow rate is too low, it is difficult to uniformly mix with the copolymer (A), so that so-called fisheye is likely to occur and the appearance is not good, and the laminated film obtained Pinholes are likely to occur in the On the other hand, when the melt flow rate is too high, the strength of the laminated film is lowered. Therefore, the high density polyethylene melt flow rate is usually 0.1 to 20 g / 10 minutes, preferably 0.3 to 10 g / 10 minutes. The weight ratio of the high density polyethylene with respect to an ethylene-alpha-olefin copolymer is 20/80 or less normally, Preferably it is the range of 1/99-10/90.

Regarding the high density polyethylene, from the viewpoint of the transparency improving effect, the value of [g] ^* defined in the following formula (2) is preferably 0.2 to 0.8 in terms of transparency improving effect, and more preferably 0.3 to 0.6.

[g] ^* = [η] / [η] ₁ (2)

([η] shows the intrinsic viscosity of the said high density polyethylene measured by the tetralin solution of 135 degree C. [η] ₁ is the intrinsic viscosity of the linear high density polyethylene which has a weight average molecular weight equivalent to the weight average molecular weight of the said high density polyethylene. ). Here, a weight average molecular weight is the value calculated | required by the GPC-LALLS method (Gel Permeation Chromatography-Low Angle Laser Light Scatterring method). [η] ₁ can be obtained by the following formula (3) (see H. Rachapudy, GG Smith, VRRaju and WW Glassley, J. Polym. Sci., Polym. Phys. Ed., 17, 1211 (1979)). have.

[η] ₁ = 4.86 ^ㅧ 10 ^-4 [Mw] ^0.705 (3)

For the purpose of improving the moldability of the laminated film of the present invention, the layer A is a high pressure low density polyetherene and an ethylene polar vinyl monomer copolymer (ethylene vinyl acetate copolymer, etc.) which is an ethylene homopolymer by a high pressure polymerization method. The layer which consists of a mixture which mix | blended with the ethylene-alpha-olefin copolymer (A) may be sufficient.

When blending a high pressure low density polyethylene or an ethylene-polar vinyl monomer copolymer, these melt flow rates (MFR) are usually 0.1 to 100 g / 10 minutes, preferably 0.2 to 10 g / 10 minutes, more preferably. It is 0.5-5 g / 10min, and a density is normally 0.915-0.935 g / cm <3>, Preferably it is 0.920-0.930 g / cm <3>, More preferably, it is 0.922-00.928 g / cm <3>.

Said MFR is a value measured on 190 degreeC and the conditions of 2.16 kg of loads based on JISK7210.

The swell ratio of the high pressure 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 said swell ratio is computed by following formula (4).

Swell ratio (%) = [(L1 / L0) -1] ㅧ 100 (4)

L1: diameter of the sample (mm)

L0: diameter of the orifice (= 2.0955㎜)

L1 is the diameter (mm) at the position of 5 mm at the tip of the strand obtained at the time of melt flow rate measurement, and is measured in micrometers.

When these high pressure low density polyethylene or ethylene polar vinyl monomer copolymers are blended into the A layer, the weight ratio of the high pressure low density polyethylene or ethylene polar vinyl monomer copolymer to the ethylene alpha -olefin copolymer (A) is 40 /. 60 or less, Preferably it is 5 / 95-30 / 70, Preferably it is 10 / 90-20 / 80.

As an ethylene polar vinyl monomer copolymer, the ethylene vinyl acetate copolymer whose content of a vinyl acetate monomeric unit is 2-30 mol% is preferable. 2-20 mol% is more preferable, and, as for content of a vinyl acetate monomer unit, 2-10 mol% is more preferable. As a high pressure low density polyethylene, what is manufactured by radical polymerization at 1,000-2,000 atmosphere and 200-300 degreeC can be used, for example.

Although materials of layers other than A layer of the laminated | multilayer film of this invention are not specifically limited as long as the objective of this invention is achieved, For example, an olefin resin may be sufficient. As the olefin resin, for example, homopolymers of α-olefins such as polyethylene and polypropylene, ethylene propylene copolymers, ethylene butene-1 copolymers, ethylene 4-methyl-1-pentene copolymers, and ethylene-1 Ethylene-α-olefin copolymers, such as -hexene copolymers and ethylene- 1-octene copolymers, having an α-olefin as a main component, furthermore, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer Ethylene polar vinyl monomer copolymers, such as a copolymer, an ethylene methyl methacrylate copolymer, an ethylene vinyl acetate acetate methyl methacrylate copolymer, and ionoma resin, are mentioned.

Among these olefin resins, ethylene-vinyl vinyl monomer copolymers such as low-density polyethylene and ethylene-vinyl acetate copolymers are preferred because they are excellent in transparency and flexibility and provide a laminated film at low cost. Among the ethylene-polar vinyl monomer copolymers, the ethylene-vinyl acetate copolymer having a vinyl acetate unit content of 30% by weight or less is excellent in flexibility, while the occurrence of wrinkles at the time of extending the laminated film is suppressed, It is especially preferable from a viewpoint of excellent heat retention. When layers other than A-layer are ethylene-polar vinyl monomer copolymer layers, 8 weight% or more is preferable and, as for content of the polar vinyl monomer unit in laminated | multilayer film from a viewpoint of heat retention etc., 9 weight% or more is more preferable. And when mix | blending an ethylene polar vinyl monomer copolymer with A-layer, content of the polar vinyl monomeric unit in a laminated | multilayer film is the quantity containing content of the polar vinyl monomeric unit in A-layer.

The laminated | multilayer film of this invention contains a radiation shielding agent. Radiation is emitted in the daytime, mainly from the ground in a house such as a house warmed by visible light of the sun, etc. as infrared rays at a wavelength of 2 to 25 µm at night, and a radiation shielding agent is a property of absorbing or reflecting this radiation. To have. As a radiation shielding agent, an infrared absorber, an infrared reflector, etc. can be illustrated, for example. The infrared reflector is not particularly limited as long as it reflects infrared rays of at least any wavelength in the wavelength region, and examples thereof include inorganic infrared reflectors such as zinc oxide.

The infrared absorber is not particularly limited as long as the infrared absorbing performance is superior to that of the material of the A layer and the other layer, and may be an absorbing peak at least in any of the wavelength ranges. For example, as an inorganic infrared absorber, complex hydroxides, such as a lithium aluminum complex hydroxide and a hydrotalcite compound, metal oxides, such as magnesium oxide, calcium oxide, aluminum oxide, a silicon oxide, titanium oxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, Carbonates such as hydroxides such as aluminum hydroxide, magnesium carbonate, calcium carbonate and basic aluminum carbonate (e.g., basic aluminum carbonate double salt disclosed in JP-A-9-279131), potassium sulfate, magnesium sulfate, calcium sulfate, zinc sulfate, Phosphates such as sulfates such as aluminum sulfate, lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate and zirconium phosphate (for example, H-type zirconium phosphate described in JP-A-8-67774), magnesium silicate and calcium silicate , Silicates such as aluminum silicate and titanium silicate, eggs such as sodium aluminate, potassium aluminate and calcium aluminate Aluminosilicates, such as a salt of a salt, sodium aluminosilicate, potassium aluminosilicate, and calcium aluminosilicate, clay minerals, such as kaolin, clay, and a tar, complex oxide, etc. are mentioned, As an organic type infrared absorber, Polyacetal, polyvinyl alcohol, its derivatives, ethylene, a vinyl alcohol copolymer, etc. are mentioned, You may use these individually or in combination of 2 or more types.

Among these radiation shielding agents, those having a density of 3 g / cm 3 or less, particularly 2.4 g / cm 3 or less, are preferable from the viewpoint of the recyclability of the laminated film, and an infrared absorber is preferable from the viewpoint of economy, and an inorganic type from the viewpoint of infrared absorption performance. Infrared absorbers are more preferred.

In the case where the infrared absorber is an inorganic infrared absorber, from the viewpoint of light transmittance, the refractive index is preferably closer to the refractive index of the resin material to be used, and it is preferable to have the absorbent performance in a wide wavelength range from the viewpoint of heat retention. From these viewpoints, hydrotalcite compounds, lithium aluminum composite hydroxides, aluminosilicates, basic aluminum carbonate double salts and the like are preferable.

A hydrotalcite compound is a following formula (I):

^{_{M 2+ 1-x A1 3+ x}} (OH -) 2 (A 1 n-) x / n · mH 2 O (Ⅰ)

(Wherein M ²⁺ is a divalent metal ion, A ₁ ⁿ⁻ is an n-valent anion, and x, m and n are 0 <x <0.5, 0 ≦ m ≦ 2, and 1 ≦ n ≦ 3). Satisfactory). As M ²⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ and the like are exemplified. n-valent anion is not particularly limited, for ^{example, Cl -, Br -, I} -, NO 3 -, ClO 4-, S0 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-, terephthalate ion, naphthalene Anions, such as a sulfonic acid ion, and the polysilicate ion and polyphosphate ion of Unexamined-Japanese-Patent No. 8-217912 are mentioned. Specifically, synthetic hydrotalcites such as natural hydrotalcite and alkalizer DHT-4A (trade name, manufactured by Kyowa Chemical Co., Ltd.) may be mentioned.

Furthermore, calcium hydroxide or calcium-aluminum composite hydroxide; You may use CaAl _x (OH) _{2 + 3x together} with a hydrotalcite compound.

As a lithium aluminum composite hydroxide, For example, the following formula (II) disclosed by Unexamined-Japanese-Patent No. 5-179052:

_{^{Li + (A1 3+) 2 (}} OH -) 6 · (A 2 n-) 1 / n · mH 2 O (Ⅱ)

And compounds represented by (wherein A ₂ ^n- is an n-valent anion, m and n satisfy the conditions of 0 ≦ m ≦ 3 and 1 ≦ n ≦ 3). The n-valent anion is not particularly limited, and examples thereof include anion such as A ₁ ^n- in the compound of formula (I).

Examples of the complex hydroxides other than the above two kinds include complex hydroxides containing at least one element selected from the group consisting of alkaline earth metals, transition metals, Zn and Si, Li and Al, and having hydroxyl groups. . Among the alkaline earth metals, magnesium and calcium are preferable. Among the transition metals, divalent or trivalent iron, cobalt, nickel, and manganese are preferable, and iron is particularly preferable. The molar ratio (Al / Li) of Al and Li is usually 1.5 / 1 to 2.5 / 1, preferably 1.8 / 1 to 2.5 / 1.

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 with respect to 1 mol of Li elements, preferably 0.1≤a≤1.4 More preferably 0.2 ≦ a ≦ 1.2. Anionic moieties other than the hydroxyl groups of such composite hydroxides include, for example, polysilicate ions such as pyrosilicate ions, cyclosilicate ions, isosilicate ions, phyllosilicate ions and tectic silicate ions, carbonate ions, halide ions, sulfate ions, Inorganic acid ions such as sulfite ion, nitrate ion, nitrite ion, phosphate ion, phosphite ion, hypophosphite ion, aluminate ion, silicic acid ion, perchlorate ion, boric acid ion, Fe (CN) ₆ ^3- , Fe (CN) ₆ ^{4 And} organic acid ions such as anionic transition metal complexes, acetate ions, benzoic acid ions, formate ions, telephthalic acid ions, and alkylsulfonic acid ions. Among these, carbonate ions, halide ions, sulfate ions, phosphate ions, polyphosphate ions, silicic acid ions, polysilicate ions and perchlorate ions are preferable, and carbonate ions, polyphosphate ions, silicate ions and polysilicate ions are particularly preferred. . Specific examples of such a composite hydroxide include a composite hydroxide containing Al, Li, and Mg, and Al / Li / Mg = about 2.3 / 1 / 0.28 (molar ratio) (trade name LMA, manufactured by Fuji Chemical Co., Ltd.), and And composite hydroxides (trade name Fujilane LS, manufactured by Fuji Chemical Industries, Ltd.) containing Al, Li, and Si and Al / Li / Si = about 2/1 / 1.2 (molar ratio).

Formula (III) disclosed in WO97 / 00828:

[(Li ⁺ _(1-x) M ²⁺ _x ) (Al ³⁺ ) ₂ (OH ⁻ ) ₆ ] ₂ (Si _y O _{(2y + 1)} ^2- ) _{(1 + x)} mH ₂ 0 (III )

(Wherein M ²⁺ is a divalent metal ion and m, x and y satisfy the conditions of 0 ≦ m <5, 0 ≦ x <1, 2 ≦ y ≦ 4), and Japanese Patent Application [Formula IV] disclosed in Japanese Patent Application Laid-Open No. 8-217912:

_{^{[(Li + (1-x}} ) M 2+ x) (Al 3+) 2 (OH -) 6] 2 (A n-) 2 (1 + X) / n · mH 2 0 (Ⅳ)

(Wherein M ²⁺ is a divalent metal ion, A ⁿ⁻ is an n-valent anion, and m, x and n satisfy the condition that 0 ≦ m <5, 0.01 ≦ x <1, 1 ≦ n ≦ 3). Is a preferred example of the complex hydroxide. Examples of M ²⁺ in formulas (III) and (IV) include Mg ²⁺ , Ca ²⁺ , Zn ^2+, and the like.

In addition, the following formula (V) disclosed in Japanese Patent Laid-Open No. 9-279131:

mAl ₂ O ₃ (n / p) M _{2 / p} OX kH ₂ O (Ⅴ)

(Wherein X is a carbonate, M is an alkali metal or an alkaline earth metal, p is a valence of metal M, and m, n and k are 0.3 ≦ m ≦ 1, 0.3 ≦ n ≦ 2, 0.5 ≦ The basic aluminum carbonate double salt represented by k) satisfies the condition of k ≤ 4 is also preferably one of the infrared absorbers. X in the formula (V) as oxyacid (sulfuric acid, sulfurous acid) of sulfuric acid, oxyacid (nitric acid, nitrous acid) of nitrogen, hydrochloric acid, oxyacid of chlorine (for example perchloric acid), oxyacid of phosphorus (phosphoric acid, Complex salts containing inorganic anions such as phosphorous acid and metallinic acid) and organic anions such as acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, telephthalic acid, maleic acid, fumaric acid, succinic acid, p-oxybenzoic acid, salicylic acid, picric acid and toluenesulfonic acid You may use together with the said basic aluminum carbonate double salt.

When using the said composite hydroxide or basic aluminum carbonate double salt 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.

When using the laminated | multilayer film of this invention for the use which requires high transparency, it is preferable that the refractive index of a radiation shielding agent is close to the refractive index of the resin material to be used, and the refractive index measured by the method of JISK0062 is 1.47-1.55. Is preferably, 1.48 to 1.54 is more preferable, and 1.49 to 1.53 is particularly preferable.

In order to improve the dispersibility of a radiation shielding agent in a laminated film, you may surface-treat a radiation blocking agent with a higher fatty acid, the alkali metal salt of a higher fatty acid, etc.

The radiation blocking agent need not be included in the entire layer of the laminated film, but may be included in at least one layer. Moreover, when a radiation shielding agent is contained in two or more layers, the content may be the same or different in each layer. The content of the radiation shielding agent of the laminated film is not particularly limited as long as it satisfies the condition that the radiation transmittance index at 23 ° C. of the laminated film is 25 or less and the density is less than 1 g / cm 3, and the radiation shielding agent and the laminated film to be used are In the case of using the above-mentioned composite hydroxide as a radiation shielding agent, for example, in view of the radiation transmittance index and density of the obtained laminated film, the compounding amount is 6 to 13% by weight in the laminated film. It is enough.

In this invention, the radiation transmittance index of the laminated | multilayer film at 23 degreeC is a measure of the thermal insulation of the said laminated | multilayer film, affects crop growth, is calculated | required by the measuring method mentioned later, The smaller the value, the warmth of a film This is excellent. In this invention, it is preferable that the radiation transmittance index in 23 degreeC of a laminated film is 25 or less. When the laminated film has a radiation transmittance index of 25 or less, the heat insulating property is equal to or superior to that of the polyvinyl chloride film, and when used in a warm house, the heating cost can be reduced, contributing to the improvement of economic efficiency. The radiation transmittance index is preferably 25 or less, closer to zero, more preferably 20 or less, and even more preferably 15 or less.

In this invention, the density of a laminated film is measured at the temperature of 23 degreeC based on the method of JISK7112 (1980), It is preferable that the value is less than 1 g / cm <3>. The density of a laminated film is one of the measures of the recyclability of the laminated film. When the density of the laminated film is less than 1 g / cm 3, separation with the vinyl chloride film recovered together is easy, and the recycling property is excellent. The density of the laminated film is preferably 0.99 or less, more preferably 0.98 or less, and particularly preferably 0.97 or less. When the A layer is the outer layer of the house, soil and the like are less likely to enter together in the separation step, and the recycling property is more excellent.

The laminated | multilayer film of this invention will not be specifically limited in the structure of the layer as long as it has at least one A layer. Usually, the structure of three to five layers is used frequently, and the combination of resin and additive of each layer may differ. In the case of a laminated structure of three or more layers, when the laminated film is transferred to a facility such as a house, a layer facing the outside of the facility is referred to as an outer layer, and a layer facing the inside is called an inner layer, and the other layer is an intermediate layer (may be a multi-layer structure). It is common to call it. The layer A may be any of these outer layers, intermediate layers, and inner layers, but in order to make the laminated film more excellent in friction resistance, antiblocking property, dustproofing, and the like, it is preferable to use the A layer as the outermost layer, particularly the outer layer, of the laminated film. Do.

In the case where the layer A is the outermost layer, a lubricant and / or an antiblocking agent may be blended in the layer A from the viewpoints of anti-locking property, dust resistance, friction resistance, and the like of the laminated film. When using the ethylene-alpha-olefin copolymer whose Cx of 0.2-0.4 mentioned above especially is used, antiblocking property, dustproofness, frictional resistance, etc. of a laminated | multilayer film further improve by using a lubricating agent and an antiblocking agent together.

As the lubricant, for example, a fatty acid amide compound having a melting point of 50 to 200 ° C can be preferably used. Examples of the fatty acid amide compound include saturated fatty acid amides, unsaturated fatty acid amides, bis fatty acid amides, and the like, and specific examples thereof include behenic acid amide, stearic acid amide, palmitic acid amide, lauryl acid amide, and elk acid. Amides, oleic acid amides, methylenepistearic acid amides, methylenebisbehenic acid amides, methylenebisoleic acid amides, ethylenebisstearic acid amides, ethylenebisbehenic acid amides, ethylenebisoleic acid amides, hexamethylenebisstearic acid amides, hexamethylenebisstearic acid amides, Hexamethylene bis oleic acid amide, octamethylene bis errac acid amide, and the like.

When mix | blending a lubricating agent, the compounding quantity with respect to A-layer is preferable 0.01 weight part or more per 100 weight part of ethylene-alpha-olefin copolymers, and 0.03 weight part or more is more 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, for example, organic fine particles and inorganic fine powder can be used. As organic microparticles | fine-particles, the crosslinked polymer of 0.5-20 micrometers of particle diameters can be illustrated, It is preferable that refractive index is close to A layer, For example, crosslinked beads, such as polyethylene and a polymethyl methacrylate, can be used preferably. .

When mix | blending organic microparticles | fine-particles, the compounding quantity in A layer is preferable 0.1 weight part or more per 100 weight part of ethylene-alpha-olefin copolymers, 0.3 weight part or more is more preferable, 1 weight part or more is especially preferable. Do. Moreover, from an economical viewpoint, 20 weight part or less is preferable, 10 weight part or less is more preferable, 5 weight part or less is especially preferable.

As an inorganic fine powder, the fine powder of the inorganic infrared absorber mentioned above can be illustrated, for example, and you may make an infrared absorber and an anti blocking agent also serve. The compounding quantity is the same as that of the said organic fine particle.

When the laminated | multilayer film of this invention is used for agricultural facilities (houses, tunnels, etc.), the dustproof process may be performed for the outer layer, and the oil repellent and the anti-fogging process may be appropriately performed for the inner layer.

The thickness of the laminated film of the present invention is usually in the range of about 0.02 to 0.3 mm, and more preferably about 0.03 to 0.2 mm, in terms of film strength, relay workability of the film, and coating workability.

In addition, when the laminated | multilayer film of this invention is two or more layers which have layers other than A-layer, the thickness of A-layer (when two or more A-layers exist, the sum of the thickness of each A-layer) is normally of a laminated film It is about 10 to 90% of the thickness. About 20 to 80% is preferable at the point of the formation of laminated | multilayer film, and about 30 to 70% is more preferable at the point of transparency, strength, etc. Moreover, when laminated | multilayer film consists of three or more layers, makes A layer an outermost layer, and contains many infrared absorbers used as a radiation shielding agent in an intermediate | middle layer, about 10 to 40% is preferable, and 15 to 30% Degree is more preferable.

And the thickness of each layer of laminated | multilayer film may be same or different.

In order to improve weather resistance, you may mix | blend an optical stabilizer with a laminated | multilayer film, and a hindered amine compound is more preferable among light stabilizers. When mix | blending an optical stabilizer, you may mix | blend in any layer of laminated | multilayer film, and when mix | blending in two or more layers, the quantity may be the same or different each layer. As a hindered amine compound, what has a structural formula of Unexamined-Japanese-Patent No. 8-73667 is mentioned, As a specific example, brand name Tinuvin 622-LD, Kimajan 944-LD, Postavin N30, VPSanduvor PR -31, Tinuvin 123. These hindered amine compounds may be used independently or may use two or more types together. As a hindered amine compound containing stabilizer, the composition (trade name TINUVIN 492, TINUVIN 494 made from Chiba-Geigi Co., Ltd., etc.) of Unexamined-Japanese-Patent No. 63-286448 is illustrated.

In the case where the hindered amine compound is blended into the laminated film, the compounding amount is usually 0.02 to 5% by weight, preferably 0.1 to 2%, in the laminated film as a whole from the viewpoint of improving the weathering resistance effect blooming. %, More preferably, it is the range of 0.5 to 2 weight%. Moreover, it is more preferable to use together with the following ultraviolet absorber from a viewpoint of a weather resistance improvement effect.

You may mix | blend a ultraviolet absorber with a laminated | multilayer film for the above purposes. A ultraviolet absorber may be mix | blended with any layer of laminated | multilayer film, and when mix | blending in two or more layers, the compounding quantity may be the same or different each layer. Examples of such ultraviolet absorbers include organic ultraviolet absorbers such as benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers, and metals such as cerium oxide, titanium oxide, and zinc oxide. Inorganic ultraviolet absorbers, such as an oxide (brand name Serigard Nippon Sangyo Co., Ltd. make), etc. are mentioned. In addition, these ultraviolet absorbers may be used independently or may use 2 or more types together.

When mix | blending a ultraviolet absorber, the compounding quantity is 0.01-3 weight% normally in the whole laminated | multilayer film from a viewpoint of a weather resistance improvement effect and blooming suppression, Preferably it is the range of 0.05-1 weight%.

In addition, you may mix | blend an antifog additive for the laminated | multilayer film of this invention in order to provide antifog property. When mix | blending an antifogging agent, the compounding quantity is 0.1-4 weight% normally in the whole laminated | multilayer film, Preferably it is 0.5-3 weight%, More preferably, it is 1.5-3 weight%, Especially preferably, it is 2.2-2.8 weight% You may mix | blend with any layer of laminated | multilayer film, and when mix | blending in two or more layers, the compounding quantity may be the same or different each layer.

Such antifogging agents include solid and liquid at room temperature (23 ° C.), and nonionic surfactants such as sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate, Glycerin, such as sorbitan fatty acid ester-based surfactants such as sorbitan monomontanate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerol monostearate, and tetraglycerol monomontanate And polyethylene glycol surfactants such as fatty acid ester surfactants, polyethylene glycol monopalmitates and polyethylene glycol monostearates, alkylene oxide adducts of alkylphenols, esters of sorbitan / glycerine condensates with organic acids, and the like. .

Moreover, when a liquid antifog additive is mix | blended with a laminated film at normal temperature, since the deterioration of the light transmittance at the time of film storage and electric field can be avoided, mix | blending of a liquid antifog additive at least 1 type of normal temperature is effective.

As an antifog liquid at normal temperature, for example, glycerin monooleate, diglycerol monooleate, diglycerine sesquioleate, tetraglycerol monooleate, hexaglycerol monooleate, tetraglycerine trioleate, hexaglycerine penta Glycerine fatty acid esters, such as oleate, tetraglycerol monolaurate, and hexaglycerol monolaurate, and sorbitan fatty acid ester, such as sorbitan monooleate, sorbitan dioleate, and sorbitan monolaurate, are mentioned. When mix | blending a liquid antifog, the compounding quantity is 0.2 to 3 weight% normally in a laminated | multilayer film, Preferably it is the range of 0.5 to 2 weight%.

In addition, in order to maintain the transparency of the laminated film of the present invention for a long time, an antifogging film may be further formed on the surface of at least the inner layer of the laminated film.

Such an antifogging film is a coating film of an inorganic oxide sol represented by colloidal silica or colloidal alumina described in, for example, Japanese Patent Publication No. 49-32668, Japanese Patent Publication No. 50-11348, and Japanese Patent Publication. Main components are a coating film of a liquid containing a surfactant as a main component and a hydrophilic resin described in JP-A No. 63-45432, JP-A-63-45717, JP-A-64-2158, JP-A-3-207643, etc. Coating films, such as a coating film of the liquid made into a film, and the film which has a hydrophilic resin as a main component, etc. can be illustrated. Polyvinyl alcohol, polysaccharides, polyacrylic acid, etc. are mentioned here as hydrophilic resin. The method of film formation may be a coating method, or the method of laminating | stacking a film which has hydrophilic resin as a main component after film-forming may be sufficient as it.

A waterproofing agent can be mix | blended with the laminated | multilayer film of this invention for the purpose of providing a weatherproof property. Examples of such a spinning agent include a fluorine compound (particularly a fluorine-based surfactant) having a perfluoroalkyl group, a ω-hydrofluoroalkyl group, and a silicon compound (particularly a silicone-based surfactant) having an alkylsiloxane group. When mix | blending a anti-rust agent, the compounding quantity is 0.01 to 3 weight% normally in an olefin resin laminated film, Preferably it is the range of 0.02 to 1 weight%, You may mix | blend in any layer of a laminated film, and to two or more layers When making it contain, the compounding quantity may be the same or different in each layer.

In the laminated | multilayer film of this invention, various stabilizers (for example, light stabilizer of antioxidant, antioxidant, heat stabilizer of a nickel-type compound), antiblocking agent, a lubricating agent, an antistatic agent, a pigment etc. which are generally used other than the above as needed are needed. Additives can be added ("Technology for Separation and Analysis of Polymer Additives, Tanaka et al., 1987, Nihon Kagakujoho Co., Ltd.," Practical Use Additives for Plastics and Rubber, Goto et al., 1970, See, "Gakugo Oh Teacher."

A near-infrared blocker can be mix | blended with the laminated | multilayer film of this invention for the purpose of the temperature reduction of the inside of a house in the hot day of the day. As such a near-infrared blocking agent, the organic compound (for example, a nitroso compound, its metal complex salt, a cyanine type compound, a squarium type compound, thiol nickel) disclosed by Unexamined-Japanese-Patent No. 10-193522, for example. Complex salt compounds, phthalocyanine compounds, triallyl methane compounds, immonium compounds, dimonium compounds, naphthquinone compounds, anthraquinone compounds, amino compounds, aminium Salt compounds) and inorganic compounds (for example, carbon black, antimony oxide, tin oxide doped with indium oxide, metal oxides or carbides belonging to groups 4A, 5A or 6A of the periodic table, and boron compounds). You may form the film containing a near-infrared blocker on the surface of the laminated | multilayer film of this invention. As a formation method of the said film, the method of apply | coating the coating liquid containing a near-infrared blocker and a water-soluble resin binder to a laminated film, and drying is mentioned, for example.

Said various additives may be used independently, may use two or more types together, and when mix | blending various additives, you may mix | blend in any layer of laminated | multilayer film, and when mix | blending in two or more layers, the quantity is each layer It may be the same or different.

The manufacturing method of the laminated | multilayer film of this invention is not specifically limited, For example, it can manufacture by the method shown next. For example, a predetermined amount of a radiation shielding agent is added to resin materials other than the ethylene α-olefin copolymer (A) and / or the A layer, and antifogging agents, antifoaming agents, various stabilizers, lubricants, antiblocking agents, Various additives, such as a pigment, can be mixed and kneaded with normal mixing and kneading | mixing machines, such as a ribbon blender, a super mixer, Banbury mixer, and a single screw or twin screw extruder, for example, and can obtain each resin composition. The laminated film can be manufactured by the T-die film shaping | molding method by co-extrusion, the inflation film shaping | molding method, etc. using the resin composition obtained in this way.

The laminated | multilayer film of this invention is used suitably for a house tunnel for facility gardening, etc., for example. Moreover, also when installing a built-in curtain in the said facility, the laminated | multilayer film of this invention can be used suitably as a built-in curtain. In particular, the laminated film of the present invention can be suitably used as a substitute for the conventional vinyl chloride film, in particular, the vinyl chloride film used for the above agricultural use.

The laminated film of the present invention is one of the most important properties as a cultivation environment, the insulation is equal to or greater than the vinyl chloride film, and if the crop is grown using a house or a tunnel, the same or more than the conventional vinyl chloride film Viability (harvest) is achieved.

Moreover, since the laminated | multilayer film of this invention is easy to isolate | separate with a polyvinyl chloride film, it is excellent in recycling property. On the other hand, it is excellent in workability, cold resistance, price, etc. compared with a polyvinyl chloride film, and is useful as an agricultural film.

Moreover, since the laminated | multilayer film of this invention is excellent in dustproof property, it is used suitably as a film for house gardening tunnels for facilities, etc. instead of the vinyl chloride film with low dustproofness. Moreover, since the laminated | multilayer film of this invention has an ethylene (alpha)-olefin copolymer layer (A layer), mechanical strength is remarkably outstanding, and the damage by friction is remarkably suppressed especially when this layer is made into an outer layer.

In addition, the laminated film of the present invention can achieve a total light transmittance of 85% or more, in some cases 90% or more, and even 92% or more. In addition, it is possible to achieve the level exceeding the vinyl chloride film generally used in the measurement of the roughness of cloudy days 1 month after the battlefield.

The HAZE value of the laminated | multilayer film of this invention is small, It is also possible that the numerical value (ΔHAZE value) which subtracted the HAZE value immediately after film manufacture from the HAZE value after 3 months storage at normal temperature may be within 110% of the HAZE value immediately after manufacture. In general, the smaller the HAZE value, the higher the transmittance of parallel rays. The higher the permeability of parallel rays, the more sunlight is absorbed in houses and tunnels, thereby raising the temperature and temperature in the houses and tunnels, the better the thermal insulation at night, and the more intensive crops that prefer straight light. For example, it promotes the growth of eggplant plants, bell peppers, melons, watermelons and strawberries. Therefore, the laminated | multilayer film of this invention can be used suitably for the cultivation of an aggressive crop.

Example

Hereinafter, although the Example of this invention is shown, this invention is not limited to this. In addition, the test method in an Example and a comparative example is as follows.

(1) density

The method specified 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 deg.

(3) molecular weight distribution Mw / Mn

GPC: Nippon Waters Co., Ltd. GPC apparatus (150 C type), column: toso manufactured TSK GMH-6, solvent: orthodichlorobenzene (ODCB), temperature: 135 ° C, flow rate: 1 ml / min, concentration : 10 mg / 10ml, sample injection volume: 500 microliters was measured on the conditions. The weight average molecular weight Mw and the number average molecular weight Mn which were converted from the calibration curve using standard polystyrene were calculated | required, and Mw / Mn was computed.

(4) composition distribution variation coefficient Cx

It measured using the multifunctional LC by Toso Corporation. The ethylene-α-olefin copolymer was dissolved in an ODCB solvent heated to 140 ° C, placed in a column packed with sea sand in a column oven, and the temperature of the oven 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 in the meantime were measured by FT-IR connected to the column. Further, the temperature was sequentially raised to the set temperature, and the temperature was raised to the final temperature while obtaining the relative concentration and branching degree of the copolymer which flowed out for each set temperature. The composition distribution curve was calculated from the obtained relative concentration and branching degree, and the standard deviation of the composition distribution was calculated by statistical processing. In addition, SCB ave. The composition distribution variation coefficient Cx was calculated | required from.

(5) radiation transmission index

Using an infrared spectrophotometer (Type 1640 FT-IR manufactured by Perkin Elmer Co., Ltd.), a radiation transmittance index was obtained according to the following method and used as a measure of thermal insulation.

The infrared absorption spectrum (transmission method) of the film (100 micrometers in thickness) was measured in the range of wave number 4000-400 cm <^{-1> at} the temperature of 23 degreeC, and the value of the transmittance | permeability T ((nu)% in wave number (nu) was obtained.

On the other hand, according to the following formula (5) obtained from Planck's law, the blackbody radiation spectral intensity e (v) at the wave number v at 23 ° C is calculated. The product of the black body radiation spectral intensity e (v) multiplied by the transmittance T (v) becomes the radiation transmission intensity f (v) [Equation (6)].

Integrating the radiation transmission intensity f (ν) in the range of wave number 4000 to 400 cm ^-1 and integrating the radiation transmission energy F and the blackbody radiation spectral intensity e (ν) in the range of wave number 4000 to 400 cm ^-1 It is defined as energy E, and the radiation transmittance index G = 100 kHz F / E. The actual integral was divided into intervals of 2 cm ^-1 intervals, and each interval was calculated and integrated by large approximation.

The smaller the radiation transmittance index, the better the heat retention of the film.

e (ν) = (A / λ ⁵ ) / {exp (B / (λ ㅧ T))-1} (5)

[Where, A = 2πhC ² = 3.74 ㅧ 10 E-6 (W · m 2)

    B = hc / k = 0.01439 (mK)

    T (K) is absolute temperature]. λ (cm) is the wavelength (wave number ν is the inverse of the wavelength), h is Planck's constant, C is the luminous flux, and k is the Boltzmann constant.

f (ν) = e (ν) ㅧ T (ν) / 100 (6)

(6) anti-rust test

The film was affixed with a double-sided tape to a frame made of acrylic fabric of 50 cm in width and 60 cm in width, and placed horizontally on a 40 ° C constant temperature bath placed in a 23 ° C constant temperature chamber with the test surface down.

After making the test surface sufficiently moist, the amount of fog generated when the ice water was brought into contact with the outside of the film, the time until disappearing, and the like were visually observed and measured according to the following criteria.

(Circle): The amount of fog generation | occurrence | production is small and disappears immediately.

(Triangle | delta): The amount of generation | occurrence | production of a fog is slightly large, and it takes time to disappear.

X: The amount of generation of fog is very large and it takes time until it disappears.

(7) antifogging test

The film was affixed with a double-sided tape to an acrylic frame having a length of 34 cm x 5 cm, and installed with the test surface down with a 15 degree incline with respect to the horizontal plane on a constant temperature water bath placed in an environmental test chamber with a constant temperature. At this time, the temperature of the environmental test chamber and the constant temperature water bath was 3 ° C and 20 ° C, respectively. The state of the water droplet on the film surface was observed, and it determined by the following reference | standard.

(Circle): The film surface is wet uniformly.

(Triangle | delta): There exists a place where the water droplet adheres partially.

X: Water droplets adhere to the whole and are clouded white.

(8) weather resistance test

The test piece punched with the JIS No. 1 dumbbell was exposed under the condition of a black panel temperature of 63 ° C. using Sunshine Weather Meta (manufactured by Sugashiki). The exposed test piece was subjected to a tensile test using Autograph DSS100 (manufactured by Shimadzu Corporation), and the elongation rate (%) was measured. The time until the elongation rate was half that of the original test piece was determined. It showed that weather resistance was excellent, so that the value of this time was large, and made 1000 hours the pass level of this test.

(9) Recyclability Test

Punch a vinyl chloride film (Mitsubishi MKV brand name Clean Ace QUIRYIN, film thickness 75 μm) and a sample film with JIS No. 1 dumbbells, and each 10 pieces of specimens at 23 ° C., separated and cleaned (2 liter volume Beaker), and the separation and washing solution (5% ethanol aqueous solution) was filled with 1500 mL, followed by stirring with a stirrer (trade name: Three One Motor). Then, it left still for 1 minute and collect | recovered, filtered, and dried the upper layer (500 mL minutes).

(Circle): Whole sample film is collect | recovered.

(Triangle | delta): Some sample films cannot be collect | recovered mixed with a vinyl chloride film.

X: The sample film cannot be recovered.

Examples 1-4

After kneading at 150 DEG C for 5 minutes using a Banbury mixer in the formulations shown in Table 1, granulation was carried out by a granulator to obtain resin composition pellets of each layer (in addition, the numerical values in parentheses in the table are in 100 parts by weight of resin in each layer). Parts by weight). It formed into a film so that each layer thickness and film thickness might be the value shown in Table 1 by the three-layer inflation film molding machine so that an inner layer composition might become the outer surface of an inflation film tube (outer layer composition is an inner surface of an inflation tube).

The result was shown in Table 1, and the film was excellent in radiation transmittance | permeability (thermal insulation), recycling property, and especially excellent in anti-fog property, antifogging property, and weather resistance.

Example 5

After kneading at 150 DEG C for 5 minutes using a Banbury mixer in each of the formulations shown in Table 2, the granulated granules were granulated by a granulator to obtain resin composition pellets for each layer (the numerical values in parentheses in the tables indicate the same meanings as in Table 1). After forming an inner layer composition into the outer surface of an inflation film tube (outer layer composition is an inner surface of an inflation tube), each layer thickness and film thickness are formed into the values shown in Table 2, and the following antifogging film is formed. It was.

The result was shown in Table 2, and the film was excellent in radiation transmittance | permeability (thermal insulation), recycling property, and especially excellent in anti-fog property, antifogging property, and weather resistance.

[Formation of antifogging film]

Anti-fogging film: Alumina sol (manufactured by Nissan Chemical, trade name Alumina sol 520, solid content 20%), colloidal silica (manufactured by Nissan Chemical, trade name Snowtex 20, solid content 20%), sodium dodecylbenzenesulfonate (manufactured by Kao, trade name Neo PEX F25) and sodium decanoate (manufactured by Nakarai Tesque) were diluted with water so as to have a solid component concentration of 1.6, 0.4, 0.08, and 0.08, respectively, to prepare a coating solution, and the one side of the inflation film (film before forming the anti-fogging film). Corona treatment was performed, it apply | coated to the surface so that it might become solid content thickness about 0.11 g / m <^2> , and it dried in the wind at room temperature and obtained the film.

Comparative Examples 1 and 2

After kneading at 150 DEG C for 5 minutes using a Banbury mixer in each of the formulations shown in Table 2, the granulated granules were granulated by a granulator to obtain resin composition pellets for each layer (the numerical values in parentheses in the tables indicate the same meanings as in Table 1). It formed into a film so that each layer thickness and film thickness might become the value shown in Table 2 by the 3-layer inflation film forming machine so that an inner layer composition might be an outer surface of an inflation film tube (outer layer composition is an inner surface of an inflation tube). The results are shown in Table 2.

Example 6

Ethylene-α-olefin copolymer (trade name Sumikacene E FV 201, density 0.915 g / cm ³ , MFR (MI) 1.5, Sumitomo Chemical Co., Ltd.) commercially available in place of inner layer resin A1 / A8 Ethylene-α-olefin copolymer (trade name Sumikasen E FV 202, density 0.925 g / cm 3, MFR 1.7, manufactured by Sumitomo Chemical Co., Ltd.) instead of the outer resin A2 / A8 Except for the use, the film was excellent in radiation transmittance index (thermal insulation) and recycling property in the same manner as in Example 1, and excellent in anti-fogging property, anti-fogging property, and weather resistance.

Example 7

In Example 5, a commercially available ethylene-α-olefin copolymer (trade name Sumikasen Hiα FW 201, density 0.912 g / cm 3, MFR 1.7, manufactured by Sumitomo Chemical Co., Ltd.) was used as the inner and outer layer resins. Except for the excellent radiation transmittance index (heat insulation) and recycling property, the film having excellent anti-fog property, anti-fogging property and weather resistance can be obtained in the same manner as in Example 5.

Example 8

Ethylene-alpha-olefin copolymer commercially available as Example 5 inner and outer layer resin (brand name Sumikasen E FV 202 Lot. 53281, density 0.925 g / cm 3, MFR 1.7, manufactured by Sumitomo Chemical Industries, Ltd.) In the same manner as in Example 5, except that the lubricating agent is used and no lubricating agent is used, a film having excellent radiation resistance, antifogging property, and weather resistance as well as excellent radiation transmittance index (heat insulation) and recycling property can be obtained.

Example 9

In Example 3, an ethylene-α-olefin copolymer (trade name Sumikasen E FV 402, density 0.915 g / cm ³ , MFR 4, manufactured by Sumitomo Chemical Co., Ltd.) and low density polyethylene was used as the inner layer and the intermediate layer resin. What blended A8 in the weight ratio of 85/15 was ethylene-alpha-olefin copolymer (trade name Sumikasen E FV 202, density 0.925 g / cm <3>, MFR 1.7, the Sumitomo Chemical Co., Ltd. product) to outer-layer resin. In the same manner as in Example 3 except that each was used, a film excellent in radiation transmittance index (heat insulation) and recycling property, and excellent in anti-fogging property, anti-fogging property, and weather resistance can be obtained.

Example 1 Example 2 Example 3 Example 4   Outer layer Suzy  A2 A2 / A8 [90/10% by weight] A3 / A8 [90/10% by weight] A3 / A8 [90/10% by weight] Heat stabilizer E1 (0.05) / E2 (0.15) E1 (0.05) / E2 (0.15) E1 (0.05) / E2 (0.15) E1 (0.05) / E2 (0.15) Weathering agent F1 (0.2) / F2 (0.4)  F3 (0.8)  F4 (0.6)  F5 (0.6) UV absorbers  G1 (0.1)  G1 (0.3)  G1 (0.2)  G2 (0.1) Antifog  H1 (0.4) / H2 (0.6)  H1 (0.4) / H8 (0.6)  H1 (0.4) / H4 (0.6)  H1 (0.4) / H5 (0.6) Infrared absorber  J1 (3)  J2 (4)  J2 (5)  J1 (3) Lubricant K1 (0.06) / K2 (0.09) K1 (0.06) / K2 (0.09) K1 (0.06) / K2 (0.09) K1 (0.06) / K2 (0.09) Layer thickness (㎛)  17.5  17.5  20  17.5 Mezzanine Suzy  A4  A4  A5  A4 Heat stabilizer E3 (0.08) / E4 (0.2) E3 (0.08) / E4 (0.2) E3 (0.08) / E4 (0.2) E3 (0.08) / E4 (0.2) Weathering agent F1 (0.2) / F2 (0.4)  F3 (0.8)  F4 (0.6)  F5 (0.6) UV absorbers  G1 (0.1)  none  none  G2 (0.1) Antifog H1 (1.0) / H2 (1.5)  H1 (1.0) / H3 (1.5)  H1 (1.0) / H4 (1.5)  H1 (1.0) / H5 (1.5) Antiseptic  I1 (0.12)  I1 (0.12)  I1 (0.12)  I2 (0.12) Infrared absorber  J3 (11)  J1 (9)  J2 (13)  J3 (11) Lubricant K1 (0.06) / K2 (0.09)  none  none  none Layer thickness (㎛)  65  65  60  65 Inner layer Suzy  A1  A6 A1 / A8 [90/10% by weight] A1 / A8 [90/10% by weight] Heat stabilizer E1 (0.05) / E2 (0.15) E1 (0.05) / E2 (0.15) E1 (0.05) / E2 (0.15) E1 (0.05) / E2 (0.15) Weathering agent F1 (0.2) / F2 (0.4)  F3 (0.8)  F4 (0.6)  F5 (0.6) UV absorbers  G1 (0.1)  none  G1 (0.2)  G2 (0.1) Antifog H1 (1.0) / H2 (1.5)  H1 (1.0) / H3 (1.5) H1 (1.0) / H4 (1.5) H1 (1.0) / H5 (1.5) Antiseptic  I1 (0.1)  I1 (0.1)  I1 (0.1)  I2 (0.1) Infrared absorber  J1 (3)  J2 (3)  J2 (3)  J1 (3) Lubricant K1 (0.02) / K2 (0.03) K3 (0.06) / K4 (0.2) K1 (0.06) / K2 (0.09) K1 (0.06) / K2 (0.09) Layer thickness (㎛) 17.5  17.5  20  17.5 Thickness of entire layer (μm) 100  100 100  100 Radiation Transmittance Index 14 15  13  14 Film weight 0.98 0.97  0.98  0.98 Ministry of Defense ○ ○  ○  ○ Anti-fogging ○ ○  ○  ○ Weather resistance More than 1000  More than 1000  More than 1000  More than 1000 Recyclability ○  ○  ○  ○

Example 5 Comparative Example 1 Comparative Example 2 Outer layer Suzy  A2 / A8 [90/10% by weight]  A3 / A8 [90/10% by weight]  A2 / A8 [90/10% by weight] Heat stabilizer E1 (0.05) / E2 (0.15) E1 (0.05) / E2 (0.15)  none Weathering agent F1 (0.2) / F2 (0.4)  F1 (0.2) / F2 (0.4)  F1 (0.2) UV absorbers  G1 (0.24)  G1 (0.1)  none Antifog  H5 (1.0)  H2 (0.8) / H4 (0.2) H2 (0.8) / H4 (0.2) Infrared absorber  J2 (4)  J1 (5)  J1 (3) Lubricant K1 (0.06) / K2 (0.09) K1 (0.06) / K2 (0.09)  none Layer thickness (㎛)  17.5  25  20  Mezzanine Suzy  A4  A5  A1 Heat stabilizer E3 (0.08) / E4 (0.2) E3 (0.08) / E4 (0.2)  none Weathering agent  F1 (0.2) / F2 (0.4) F1 (0.2) / F2 (0.4)  F1 (0.2) UV absorbers  none  G1 (0.1)  none Antifog  H5 (0.5)  H2 (1.6) / H4 (0.4) H2 (1.6) / H4 (0.4) Antiseptic  none  I1 (0.1)  none Infrared absorber  J2 (13)  J3 (20)  J1 (7) Lubricant  none  K1 (0.06) / K2 (0.09)  none Layer thickness (㎛) 65  50  60 Inner layer   Suzy  A7 A3 / A8 [90/10% by weight] A1 / A8 [90/10% by weight] Heat stabilizer E3 (0.08) / E4 (0.20) E1 (0.05) / E2 (0.15)  none Weathering agent F1 (0.2) / F2 (0.4)  F1 (0.2) / F2 (0.4)  F1 (0.2) UV absorbers  G1 (0.24)  G1 (0.1)  none Antifog  none  H2 (1.6) / H4 (0.4) H1 (1.6) / H4 (0.4) Antiseptic  none  I1 (0.1)  none Infrared absorber  J2 (4)  J1 (5)  none Lubricant K1 (0.02) / K2 (0.03) K1 (0.02) / K2 (0.03)  none Layer thickness (㎛)  17.5  25  20  Thickness of entire layer (μm) 100  100 100 Radiation Transmission Index  11 11 27 Film specific gravity  0.98 1.00 0.94 Ministry of Defense  ○ ○ × Anti-fogging  ○ ○ ○ Weather resistance More than 1000  More than 1000  Less than 1000 Recyclability ○  ×  ○

In addition, the symbol described in the said Table 1 and Table 2 is as follows.

[Abbreviation]

A1: Sumitomo Chemical Co., Ltd. Sumikasen E, FV 402-0 (hexene content 11.1% by weight)

A2: Sumitomo Chemical Co., Ltd. Sumikasen E, FV 403-0 (hexene content 8.6% by weight)

A3: Sumitomo Chemical Co., Ltd. Sumikasen α, FZ 202-0 (hexene content 9.4% by weight)

In addition, the characteristics of A1 to A3 are shown in Table 3.

A1 A2 A3  characteristic  MFR (g / 10 min) 4 4 2  Density (g / cm 3) 0.915 0.920 0.921  Mw / Mn 2.0 2.1 3.7  Cx 0.31 0.36 0.56

However, A1 and 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 (brand name: Evaate H 2031, vinyl acetate content 19 weight%, the Sumitomo Chemical Co., Ltd. make)

A5: Ethylene-vinyl acetate copolymer (brand name: Evaate H 2021, vinyl acetate content 15 weight%, the Sumitomo Chemical Co., Ltd. make)

A6: Ethylene-vinyl acetate copolymer (brand name: Evaate D 2021, vinyl acetate content 10 weight%, the Sumitomo Chemical Co., Ltd. make)

A7: Ethylene-vinyl acetate copolymer (brand name: Evaate D 2011, vinyl acetate content 5 weight%, the Sumitomo Chemical Co., Ltd. make)

A8: low density polyethylene (brand name: Sumikasen F 200, density 0.923 g / cm 3, manufactured by Sumitomo Chemical Co., Ltd.)

E1 Product Name: Sumerizer BP 76, Sumitomo Chemical Co., Ltd.

E2 Product Name: Ilgafoss P 168, manufactured by Chiba

E3 Product Name: Sumerizer BHT, Sumitomo Chemical Co., Ltd.

E4 Product Name: IL KNOX 1010

F1: Hindered Amine Compound (Brand Name: Kimaken 944 LD, manufactured by Chiba-Geigi)

F2: Hindered Amine Compound (Brand Name: Tinuvin 622 LD, manufactured by Chiba-Geigi)

F3: Hindered Amine Compound (Brand Name: Tinuvin 462, manufactured by Chiba-Geigi)

F4: hindered amine compound (trade name: Tinuvin 464, manufactured by Chiba-Geigi)

F5: Hindered Amine Compound (Brand Name: Phostabine N 30, produced by Clariant)

G1 Product Name: Sumitomo 130, Sumitomo Chemical Co., Ltd.

G2 Product Name: Sumitomo 300, Sumitomo Chemical Co., Ltd.

H1: Diglycerin Sesquioleate

H2: Compound having a weight ratio of monoglycerine monostearate / diglycerine sesquistearate = 3/7

H3: Solbitan Seskistearate

H4: 1 mole adduct of sorbitan monostearate propylene oxide

H5: Tetraglycerin Tristearate

I1: fluorine-based surfactant (brand name: Eudine DS 403, manufactured by Daiking Kogyo Co., Ltd.)

I2: fluorine-based compound (brand name: Saffron KC 14, manufactured by Asahigarasu)

J1: Hydrotalcite (trade name: DHT 4A, manufactured by Kyogawa Chemical Co., Ltd.)

J2: Composite Hydroxide (trade name: Fuji Lane LS, manufactured by Fuji Chemical Co., Ltd.)

J3: Lithium Aluminum Composite Hydroxide (trade name: Mizukarak, Mizusawa Chemical Co., Ltd.)

K1: fatty acid amide compound ethylenebisoleic acid amide

K2: fatty acid amide compound elcaic acid amide

K3: fatty acid amide compound oleic acid amide

K4: fatty acid amide compound ethylenebisstearic acid amide.

Claims (13)

At least two layers containing at least one layer (A layer) containing, as a main component, an ethylene-α-olefin copolymer (A) having a melt flow rate of 0.1 to 50 g / 10 minutes and a density of 0.88 to 0.94 g / cm 3. Wherein at least one layer contains a radiation blocker, the radiation transmittance index at 23 ° C. is 25 or less, the density is less than 1 g / cm 3, and the radiation blocker is represented by one of the following formulas (III) to (V): Laminated film which is at least 1 sort (s) chosen from the compound which becomes. [(Li ⁺ _(1-x) M ²⁺ _x ) (Al ³⁺ ) ₂ (OH ⁻ ) ₆ ] ₂ (Si _y O _{(2y + 1)} ^2- ) _{(1 + x)} mH ₂ O (III ) ( ^Wherein M ²⁺ is a divalent metal ion. M, x and y satisfy the conditions of 0 ≦ m <5, 0 ≦ x <1, 2 ≦ y ≦ 4); _{^{[(Li + (1-x}} ) M 2+ x) (Al 3+) 2 (OH -) 6] 2 (A n-) 2 (1 + x) / n · mH 2 O (Ⅳ) ( ^Wherein M ²⁺ is a divalent metal ion and A ⁿ⁻ is an n-valent anion. M, x and n satisfy the condition that 0 ≦ m <5, 0.01 ≦ x <1, 1 ≦ n ≦ 3). ;); mAl ₂ O ₃ (n / p) M _{2 / p} OX kH ₂ O (Ⅴ) (Wherein X is a carbonate, M is an alkali metal or an alkaline earth metal, and p is a valence of metal M. m, n and k are 0.3 ≦ m ≦ 1, 0.3 ≦ n ≦ 2, 0.5 ≤ k ≤ 4 is satisfied.) The laminated | multilayer film of Claim 1 whose composition distribution variation coefficient Cx defined by following formula (1) of an ethylene-alpha-olefin copolymer (A) is 0.5 or less. Cx = σ / SCB ave. (One) (Wherein σ represents the standard deviation of the elution amount of the elution component at each temperature and its compositional distribution determined by the temperature rise column fractionation method, and SCB ave. Represents the average value of the short-chain branch number per 1000 carbon atoms). .) The laminated | multilayer film of Claim 1 whose content of the alpha-olefin monomeric unit in an ethylene-alpha-olefin copolymer (A) is 0.5-10 mol%. The laminated film according to claim 1, wherein the layer A is the outermost layer on at least one side of the laminated film. The laminated film according to claim 2, wherein the composition distribution coefficient of variation Cx is 0.2 to 0.5. The laminated | multilayer film of Claim 4 in which A layer contains 0.01-1 weight part of lubricating agents and 0.1-20 weight part of anti blocking agents with respect to 100 weight part of ethylene-alpha-olefin copolymers (A). The layer A further comprises a high pressure low density polyethylene or an ethylene-polar vinyl monomer copolymer, and the high pressure method low density polyethylene or an ethylene-polar vinyl monomer air. Laminated | multilayer film whose weight ratio with respect to the copolymer (A) of copolymer is 40/60 or less. The laminated film according to claim 1, wherein the radiation blocking agent is a composite hydroxide. The compound according to any one of claims 1, 2 to 4, 6 or 8, which further contains at least one member selected from light stabilizers, ultraviolet absorbers, antifoaming agents, antifogging agents and near infrared rays blocking agents. Laminated film. The laminated | multilayer film of Claim 9 whose content of a light stabilizer, a ultraviolet absorber, an antifog additive, and an antifog additive is 0.02-5 weight%, 0.01-3 weight%, 0.01-3 weight%, and 0.1-4 weight%, respectively. The olefin resin laminated film according to claim 1 or 4, wherein at least one layer other than the A layer is an ethylene-polar vinyl monomer copolymer layer. The laminated | multilayer film of Claim 7 whose content of the polar vinyl monomeric unit in a laminated | multilayer film is 8 weight% or more. The laminated | multilayer film of any one of Claims 1-6 which has an antifogging film further.