KR19990063163A - Film having a resin composition and layers made thereof - Google Patents

Abstract

Disclosed is a film having a resin composition excellent in heat resistance, weather resistance, transparency and processability, and a layer comprising the same, comprising a polyolefin resin, a basic aluminum carbonate salt, and a hindered amine compound. This film is suitable for agriculture.

Description

Film having a resin composition and layers made thereof

The present invention relates to a polyolefin resin composition excellent in heat resistance, weather resistance, transparency and processability, and a use thereof.

In recent years, demand for resins used outdoors, such as automobile materials, building materials, and agricultural materials, has increased dramatically.

As an agricultural material, the agricultural film used for coating | covering facilities, such as a house and a tunnel in facility horticulture, is mentioned. Conventionally, as an agricultural film, a polyvinyl chloride film, a polyolefin resin film (for example, a polyethylene film, an ethylene / vinyl acetate copolymer film), etc. are used universally. Among them, recently, polyolefin-based resin films that are not contaminated well, are light in weight, and are less likely to generate toxic gases upon incineration have been widely used for facility horticulture.

On the other hand, since agricultural films are used outdoors, when the weather resistance of the base resin of the film is not sufficient, physical properties such as elongation retention and tensile strength of the film decrease due to oxidation of the resin, resulting in a decrease in the film. . Then, in order to improve weather resistance, the resin composition which mix | blended various weather resistance imparting agents, such as antioxidant and a ultraviolet absorber, with polyolefin resin was proposed. Among the weathering imparting agents, the hindered amine stabilizer is, for example, disclosed in Japanese Patent Application Laid-Open Nos. 59-86645 and 2-167350, and the addition of a small amount significantly improves the weather resistance of the polyolefin resin and at the same time has an effect. It is preferably used because it is maintained for a long time and the gloss and color tone of the polyolefin resin film are remarkably suppressed.

Japanese Laid-Open Patent Publication No. 56-41254 discloses a thermoplastic resin film containing a hindered amine compound and an inorganic fine powder having a polarity of 10 m 2 / g or more, and Japanese Laid-Open Patent Publication No. 63-175072 discloses a thermoplastic resin, An agricultural film comprising a hindered amine compound and a hydrotalcite compound is disclosed.

However, these films do not sufficiently maintain mechanical properties in an environment exposed to pesticides or acid rain, and furthermore, due to poor thermal stability, they may involve coloration or foaming at the time of processing.

MEANS TO SOLVE THE PROBLEM The present inventors completed this invention as a result of earnestly examining in order to solve such a problem and to develop the polyolefin resin composition excellent in heat resistance and weather resistance.

A first aspect of the present invention provides a resin composition comprising a polyolefin resin, a basic aluminum carbonate salt and a hindered amine compound. This resin composition may further contain a ultraviolet absorber.

Another invention of the present application provides a film having one or more layers of the resin composition. This film may contain an antifogging agent or an antifogging agent, or an antifogging agent and an antifogging agent. In addition, the film of the present invention may have an antifogging film.

Another invention of the present application provides the use of the film of the present invention as an agricultural film.

Another invention of the present application provides the use of the film of the present invention in an agricultural facility.

1 is an X-ray diffraction chart of basic aluminum carbonate salt (SW).

The basic aluminum carbonate salt used in the present invention is composed of one or more kinds of cations other than aluminum ions, carbonate ions, and aluminum ions. Examples of the cation of the aluminum ion include alkali metal ions, alkaline earth metal ions, ammonium ions and transition metal ions. Among them, sodium ions, potassium ions and ammonium ions are preferable. Examples of such basic aluminum carbonate salts include salts described in JP-A-9-279131 and salts exemplified in the following documents (1) and (2). You may use these basic aluminum carbonates 1 type, or 2 or more types. Although the manufacturing method of basic aluminum carbonate is not specifically limited, The method of Unexamined-Japanese-Patent No. 9-279131 is mentioned specifically ,.

The molar ratio (aluminum ions / cationic) of aluminum ions to other cations in the basic aluminum carbonate salt is usually 0.3 / 1 to 2/1, preferably 0.5 / 1 to 1.5 / 1, more preferably 0.9 / 1 to 1.2 / 1

The molar ratio (Al / CO ₃ ) of aluminum ions and carbonate ions is 0.3 / 1 to 2/1, preferably 0.8 / 1 to 1.5 / 1, and more preferably 1/1 to 1.3 / 1.

Specifically, for example, sodium aluminum carbonate (Na ₂ O.Al ₂ O ₃ .2CO ₃ .nH ₂ 0 (n> 0)), potassium aluminum carbonate (K ₂ 0.Al ₂ O ₃ .2CO ₃ .nH ₂ 0 ( n> 0)), and the like. (1) Comprehensive inorganic chemistry vol 2, p. 1045, published in 1973, Pergamon Press Ltd., (2) A comprehensive treatise on inorganic and theoretical chemistry vol 5, p. 358-359, published in 1960, Longman, Green and Co., Ltd.).

The basic aluminum carbonate salt may contain water. The water content is preferably at most 10% by weight, more preferably at most 5% by weight, particularly preferably at most 3% by weight. Water content is measured by the method based on JISK0067 normally. Specifically, the water content is determined by the weight reduction rate during heating at 180 ° C. for 2 hours.

The average particle diameter of basic aluminum carbonate salt is 5 micrometers or less normally, Preferably it is 0.05-3 micrometers, More preferably, it is 0.1-1 micrometer. When using the resin composition of this invention for the use which highly transparency is calculated | required, it is preferable that the refractive index of the basic aluminum carbonate salt is close to the polyolefin resin to be used. Usually, as for the refractive index of the basic aluminum carbonate salt measured by the method of JISK0062, 1.47-1.55 are preferable, 1.48-1.45 are more preferable, 1.49-1.53 are especially preferable.

As for content of basic aluminum carbonate salt of the resin composition of this invention, 0.03-200 weight part is preferable with respect to 100 weight part of polyolefin resin. In addition, when using this resin composition for coating films, such as agricultural facilities, the compounding quantity of a basic aluminum carbonate salt is 35 weight part or less with respect to 100 weight part of polyolefin resin from a viewpoint of transparency and strength of a film, More preferably, Preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less.

In order to improve the dispersibility in a resin composition, basic aluminum carbonate may surface-treat with a dispersing agent. Dispersants include higher fatty acids such as stearic acid, palmitic acid, and lauric acid, metal soaps such as calcium salts, zinc salts, magnesium salts, barium salts and sodium salts of higher fatty acids, phosphate esters, silane coupling agents and aluminum salts. A coupling agent, a zirconium-based coupling agent, a wax, etc. can be illustrated. The method of surface treatment should just be a method in which a dispersing agent adheres uniformly to the surface of basic aluminum carbonate salt. For example, a method of adding a basic aluminum carbonate salt in a suitable solvent to form a slurry, and mixing and stirring this slurry and a dispersant is mentioned.

Examples of the hindered amine compound used in the present invention include those having a structural formula described in JP-A-8-73667, and specifically, trade names TINUVIN 622-LD, CHIMASSORB 944-LD, and TINUVIN 123 (hereinafter, Ciba Specialty Chemicals KK), Hostavin N30, VP Sanduvor PR-31 (hereinafter Clariant KK), Cyasorb UV 3526 (manufactured by Cytec Industries INC.), And the like. As a hindered amine compound containing stabilizer, the composition (brand name TINUVIN 492 and TINUVIN 494; the product made by Ciba Specialty Chimicals K.K.) of Unexamined-Japanese-Patent No. 63-286448 can be illustrated. A hindered amine compound may be used independently or may be used together 2 or more types.

As for content of the hindered amine compound of the resin composition of this invention, 0.02 weight part or more is preferable with respect to 100 weight part of polyolefin resins. In addition, in order to control blooming, 5 weight part or less is preferable, and 0.1-2 weight part is more preferable.

As a polyolefin resin in the resin composition of this invention, For example, homopolymer of alpha-olefins, such as polyethylene and a polypropylene; Ethylene-α-olefin copolymers such as an ethylene-propylene copolymer, an ethylene butene-1 copolymer, an ethylene 4-methyl-1-pentene copolymer, an ethylene hexene copolymer, and an ethylene octene copolymer; Heterogeneous compounds containing α-olefins such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, and ionomer resins as main components And copolymers with monomers. When using the resin composition of this invention for agricultural films, the polyethylene, ethylene-alpha-olefin copolymer, and the ethylene-vinyl acetate copolymer whose content of a vinyl acetate unit are 30 weight% or less from a viewpoint of transparency, weather resistance, price, etc. desirable.

Ethylene and C3-C18 α-olefins are used in the presence or absence of a solvent by using transition metal complex catalysts such as palladium and nickel or so-called single-site catalysts such as metallocene catalysts. The ethylene-α-olefin copolymer obtained by polymerization under a solid, liquid-solid or homogeneous liquid phase can be preferably used. Usually, polymerization temperature is about 30 degreeC-about 300 degreeC, and polymerization pressure is atmospheric pressure-about 3000 kg / cm <^2> . Presence of so-called metallocene-based olefin polymerization catalysts containing metallocene catalyst components described in, for example, Japanese Patent Laid-Open Nos. Hei 6-9724, Hei 6-136195, Hei 6-136196 and Hei 6-207057. Under the present invention, an ethylene-α-olefin copolymer obtained by copolymerizing ethylene with an α-olefin having 3 to 18 carbon atoms can be preferably used.

In order to further improve the weather resistance of the resin composition, the resin composition of the present invention may further contain one or more kinds of ultraviolet absorbers. Examples of such ultraviolet absorbers include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers. When the ultraviolet absorber is contained, the amount thereof is in the range of 0.01 to 3 parts by weight, preferably 0.05 to 1 part by weight based on 100 parts by weight of the polyolefin resin from the viewpoint of the weather resistance improving effect and the blooming control.

The resin composition of this invention is composite hydroxides, such as a lithium aluminum composite hydroxide and a hydrotalcite compound; Metal compounds such as magnesium oxide, calcium oxide, aluminum oxide, silicon oxide and 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; Phosphates such as lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate and zirconium phosphate (for example, H-type zirconium phosphate disclosed in JP-A-8-67774); Silicates such as magnesium silicate, calcium silicate, aluminum silicate and titanium silicate; Aluminates such as sodium aluminate, potassium aluminate and calcium aluminate; Aluminosilicates, such as sodium aluminosilicate, potassium aluminosilicate and calcium aluminosilicate; Clay minerals such as kaolin, clay and talc; You may contain 1 or more types of inorganic compounds, such as another complex oxide.

The hydrotalcite compound is represented by the following formula (I):

^{_{M 2+ 1-x Al 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 satisfy the conditions of 0 <x <0.5, 0 ≦ m ≦ 2, 1 ≦ n ≦ 3) ) Is a compound. Examples of M ²⁺ include Mg ²⁺ , Ca ²⁺ , and Zn ²⁺ . 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-, terephthalate ion and naphthalenesulfonate Anions, such as an ion and the polysilicate ion and polyphosphate ion of Unexamined-Japanese-Patent No. 8-217912 are mentioned. Specifically, for example, synthetic hydrotalcite such as natural hydrotalcite or alkamyza DHT-4A (trade name, manufactured by Kyowa Chemical Co., Ltd.) can be used.

As lithium aluminum composite hydroxide, the following formula (II) described, for example in Unexamined-Japanese-Patent No. 5-179052:

_{^{Li + (Al 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 conditions of 0 ≦ m ≦ 3 and 1 ≦ n ≦ 3). Although it does not specifically limit as an n-valent anion, For example, the same anion as A <_1> ^-in the compound of Formula (I) is mentioned.

Examples of the composite hydroxides other than the two kinds include 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 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 more preferred among them. 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.

Further, the molar ratio (a) of the 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 lithium, preferably 0.1 ≤ a ≤ 1.4, more preferably 0.2 ≦ a ≦ 1.2. Anionic moieties other than the hydroxyl group of such a composite hydroxide include polysilicate ions such as pyrosilicate ions, cyclosilicate ions, isosilicate ions, phyllosilicate ions and techtosilicate ions; Inorganic acid ions such as carbonate ion, halide ion, sulfate ion, sulfite ion, nitrate ion, nitrite ion, phosphate ion, phosphite ion, hypophosphite ion, polyphosphate ion, aluminate ion, silicate ion, perchlorate ion, and borate ion; Anionic transition metal complexes such as Fe (CN) ₆ ^3- and Fe (CN) ₆ ^4- ; Organic acid ions such as acetate ions, benzoate ions, formate ions, terephthalate 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, wherein Al / Li / Mg = about 2.3 / 1 / 0.28 (molar ratio) (trade name: LMA, manufactured by Fuji Chemical Co., Ltd.) And a composite hydroxide (trade name: FUJIRAIN LS, manufactured by Fuji Chemical Industries, Ltd.) containing Al, Li, and Si with Al / Li / Si = about 2/1 / 1.2 (molar ratio).

Formula (III) described in WO 97/00828:

_{^{[(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 and m, x and y satisfy the conditions of 0 ≦ m <5, 0 ≦ x <1, 2 ≦ y ≦ 4), and JP Formula (IV) disclosed in Publication No. 8-217912:

_{^{[(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, A ⁿ⁻ is an n-valent anion, and m, x and n satisfy the conditions of 0 ≦ m <5, 0.01 ≦ x <1, 1 ≦ n ≦ 3) The compound represented by is a preferable example of the composite hydroxide. As M <^2+> in Formula (III) and (IV), Mg <^2+> , Ca <^2+> , Zn <^2+>, etc. are illustrated.

The resin composition of this invention may contain two or more types of infrared absorbers. Examples of such infrared absorbers include organic infrared absorbers such as polyacetal, polyvinyl alcohol and derivatives thereof, and ethylene / vinyl alcohol copolymers.

The resin composition of this invention can contain one or more types of antifouling agents. Examples of the antifoaming agent include fluorine compounds (particularly fluorine surfactants) having perfluoroalkyl groups,? -Hydrofluoroalkyl groups and the like, and silicone compound (particularly silicone surfactants) having alkylsiloxane groups. Specific examples of the fluorine-based surfactant include the trade names Unidyne DS-403, DS-406, DS-401 (all manufactured by Daikin Industries, Co., Ltd.), and the like, and the silicone-based surfactants include the trade name SH-3746 (Toray Dow Corning Silicone Co., Ltd. product) is mentioned.

The resin composition of this invention can contain one or more types of antifog additives. Such antifogging agents are solid and liquid at room temperature.

As an antifogging agent on a solid, Nonionic surfactant, For example, sorbitan fatty acid ester type surfactant, such as sorbitan monostearate, sorbitan monopalmitate, sorbitan monomontanate; Glycerin fatty acid ester-based surfactants such as glycerin monopalmitate, glycerin monostearate, diglycerine distearate, triglycerine monostearate, and tetraglycerin dimontanate; Polyethylene glycol-based surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate; Alkylene oxide adducts of alkylphenols; Esters of sorbitan / glycerine condensates with organic acids; Polyoxyethylene alkylamine compounds, such as polyoxyethylene (2 mol) stearylamine, polyoxyethylene (2 mol) laurylamine, and polyoxyethylene (4 mol) stearylamine, polyoxyethylene (2 mol) stearyl Amine monostearate, polyoxyethylene (2 moles) stearylamine distearate, polyoxyethylene (4 moles) stearylamine monostearate, polyoxyethylene (4 moles) stearylamine distearate, polyoxyethylene Fatty acid ester of polyoxyethylene alkylamine compounds, such as (8 mol) stearylamine monostearate, polyoxyethylene (2 mol) stearylamine monobehenate, and polyoxyethylene (2 mol) laurylamine stearate, poly Amine surfactants, such as fatty acid amide of polyoxyethylene alkylamine compounds, such as oxyethylene (2 mol) stearic acid amide, are mentioned.

As an antifogging agent in a liquid phase, for example, glycerin monooleate, diglycerin monooleate, diglycerine sesquioleate, tetraglycerol monooleate, hexaglycerin monooleate, hexaglycerine trioleate, tetraglycerine trioleate, tetraglycerine Glycerin fatty acid esters such as monolaurate and hexaglycerol monolaurate; Sorbitan fatty acid esters such as sorbitan monooleate and sorbitan dioleate.

The resin composition of the present invention may further contain waxes, antioxidants, antistatic agents, light stabilizers other than hindered amines, lubricants, pigments, and additives.

The resin composition of this invention can be manufactured, for example by the following method. A predetermined amount of basic aluminum carbonate salt, a hindered amine compound, and an additive are mixed and kneaded with a polyolefin resin using a mixing and kneading machine as necessary. As a mixing and kneading machine, conventional apparatuses, such as a ribbon blender, a super mixer, a Banbury mixer, or a single screw or twin screw extruder, can be used, for example. The obtained resin composition can be preferably used for extrusion molding, injection molding and blow molding. In particular, the resin composition of this invention can be used suitably for manufacture of the film which has one or more layers which consist of this resin composition.

The resin composition of this invention may be provided to a shaping | molding process after diluted with polyolefin resin. In this case, the resin composition before dilution is usually called a master batch.

The film of this invention may be a single layer which consists of the resin composition of this invention, and the laminated film which consists of two or more layers which consist of the resin composition of this invention may be sufficient. Moreover, the laminated | multilayer film which consists of one or more layers which consist of the resin composition of this invention, and one or more layers which consist of materials other than the resin composition of this invention may be sufficient. Although the layer structure of laminated | multilayer film is not specifically limited, For example, 2 types of 2 layers, 2 types of 3 layers, 3 types of 3 layers, 3 types of 5 layers, etc. can be illustrated. It is preferable that the layer which consists of a resin composition of this invention is an intermediate | middle layer of the laminated | multilayer film which consists of three or more layers. When the film of this invention is a laminated | multilayer film which has a layer which consists of materials other than the resin composition of this invention, the layer which consists of materials other than the resin composition of this invention usually consists of resin.

The film of this invention can be manufactured by conventional methods, such as extrusion, a coextruder, a melt-coating method, an extrusion lamination method, a dry lamination method, using together the resin composition of this invention and another material as needed.

As resin used for layers other than the layer of the resin composition of this invention, For example, homopolymers of alpha-olefins, such as polyethylene and a polypropylene; Ethylene-alpha-olefin copolymers, such as an ethylene propylene copolymer, an ethylene butene-1 copolymer, an ethylene 4-methyl-1- pentene copolymer, an ethylene hexene copolymer, and an ethylene octene copolymer: ethylene acetic acid Copolymers with different monomers containing α-olefins such as vinyl copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, and ionomer resins Can be mentioned. Of these, when the laminated film of the present invention is used for agricultural use, polyethylene, ethylene-α-olefin copolymers and ethylene-vinyl acetate copolymers having a vinyl acetate unit content of 30% by weight or less are more preferable in terms of transparency, weather resistance and price. desirable. In agriculture, the laminated film whose layer of the resin composition of this invention is an intermediate | middle layer is preferable.

The film of the present invention comprises at least one inorganic compound, such as the same complex hydroxide, metal oxide, hydroxide, carbonate, sulfate, phosphate, silicate, aluminate, aluminosilicate, clay mineral, composite oxide, etc. It may contain. By adding this inorganic compound, the heat retention of a film improves.

Although these inorganic compounds may be contained in any layer in the film of this invention, it is preferable to be contained in the layer of the resin composition of this invention, The quantity is 0.03-150 weight part with respect to 100 weight part of polyolefin resin, 0.03-- 30 weight part is more preferable, and 0.03-15 weight part is especially preferable.

The film of this invention may contain the 1 or more types of infrared absorbers similar to the above.

The film of this invention can contain the 1 or more types of antifog agents similar to the above.

When the film of this invention contains a waterproofing agent, the quantity is preferably 0.01 to 3% by weight of the entire film, more preferably 0.02 to 2% by weight, particularly preferably 0.05 to 0.5% by weight.

The film of this invention can contain the 1 or more types of antifogging agents similar to the above. From the viewpoint of suppressing bleeding to the film surface of the antifogging agent and transparency of the film, it is preferable to use a liquid antifogging agent and a solid antifogging agent together at room temperature. When the film of this invention contains an antifog, 0.1-4 weight% of the whole film is preferable, 1.5-4 weight% is more preferable, 2.2-2.8 weight% is especially preferable.

The film of this invention may have an antifogging film on at least one surface. A film having an antifogging film can maintain its antifogging property for a long time. Such an antifogging film is a coating film of an inorganic oxide sol represented by colloidal silica or alumina sol described in, for example, Japanese Patent Publications Nos. 49-32668 and 50-11348, and Japanese Patent Publications No. 63-45432 and SO63. Coating films of inorganic oxide sol and organic compounds (surfactants, resins, etc.) and hydrophilic resins containing surfactants as main components, such as -45717, SO64-2158, and JP-A-3-207643 The film etc. which have (for example, polyvinyl alcohol, polysaccharide, polyacrylic acid, etc.) as a main component are mentioned. The manufacturing method of these antifogging films may be coated, and after manufacturing an antifogging film, you may laminate | stack this film on laminated | multilayer film. The antifogging film may be a single layer or two or more layers.

The film of the present invention can be produced by conventional molding methods such as calendering, extrusion T die film molding, and inflation film molding. It is preferable that the thickness of a film is 0.01 mm or more from a viewpoint of the strength of a film, and 0.3 mm or less is preferable from a viewpoint of relay workability, coating workability, etc. of a film. More preferably, it is 0.03-0.25 mm.

The said film can be used suitably as an agricultural film, especially the coating film of agricultural facilities, such as a house and a tunnel.

The resin composition obtained by this invention is excellent in heat resistance, weather resistance, and transparency, and is provided in agricultural materials, home appliances, automobile materials, building materials, etc. In particular, the film using this resin composition is remarkably excellent in weather resistance when used as a covering film or a malting film for agricultural house tunnels, and is an effective material for facility horticulture. The film of the present invention is superior in weather resistance to conventional agricultural coating films under conditions such as exposure to light and pesticides. In addition, the resin composition of the present invention is less deteriorated and discolored according to the continuous molding processing conditions, less foaming during molding processing, and excellent molding stability for a long time.

Although the Example of this invention is shown below, this invention is not limited to this.

And the test method in an Example and a comparative example is as follows.

Thermal stability test

A test piece having a thickness of 1 mm was placed in a gear oven under an air atmosphere at 180 ° C., and the coloring degree was visually measured every hour to evaluate the following criteria.

○: almost no pigmentation compared to the initial state

(Triangle | delta): Colored light yellow or light brown compared with an initial state

×: colored yellow or brown compared to the initial state

××: colored dark brown compared to the initial state

Weathering Test (1)

A test piece having a thickness of 1 mm is left for 24 hours under an air blowing temperature of 60 ° C. and a relative humidity of 32% RH using an EYESUPER UV TESTER SUV-W11 (manufactured by Eye Grophics Co., Ltd.). About this test piece, a coloring degree is measured visually and the following reference | standard evaluates.

○: almost no pigmentation compared to the initial state

(Triangle | delta): Colored light yellow or light brown compared with an initial state

×: colored yellow or brown compared to the initial state

××: colored dark brown compared to the initial state

Weathering Test (2)

A 1 mm thick specimen is suspended in a 500 ml glass bottle containing 50 ml of 6% sulfurous acid water, sealed, and left to stand at room temperature for 4 hours. This test piece was left to stand for 24 hours under an air blowing temperature of 60 ° C. and a relative humidity of 32% RH using the I-Super UV Tester SUV-W11. About this test piece, a coloring degree is measured visually and the following reference | standard evaluates.

○: almost no pigmentation compared to the initial state

(Triangle | delta): Colored light yellow or light brown compared with an initial state

×: colored yellow or brown compared to the initial state

××: colored dark brown compared to the initial state

Transparency Measurement

The total light transmittance and the haze are measured using a haze meter (manufactured by Suga Test Instrument Co., Ltd.) in accordance with JIS K 7105. A smaller HAZE value indicates better transparency.

Examples 1-3

Resin, a basic aluminum carbonate salts as shown in Table 1 (composition ratio; Al / Na = 1/1, Al / CO 3 = 1.2 / 1), the hindered amine compound, and other additives using a Banbury mixer 140 ℃, After kneading for 5 minutes, it is granulated by an extruder to obtain pellets. The pellet is molded into a sheet having a thickness of 1 mm by a press molding method, and thermal stability tests and weather resistance tests (1) and (2) are performed. As shown in Table 1, the results were excellent in thermal stability and weather resistance. Details of the basic aluminum carbonate salt used are shown in FIG. 3.

Comparative Examples 1 to 3

The same test as in Examples 1 to 3 was carried out except that hydrotalcite (trade name: DHT-4A; manufactured by Kyowa Chemical Industries, Ltd.) was used instead of the basic aluminum carbonate salt. As shown in Table 1, the thermal stability and heat resistance of the obtained resin composition are inferior to the resin compositions of Examples 1-3. Details of the hydrotalcites used are shown in Table 3.

Examples 4-6

As shown in Table 2, resin, a basic aluminum carbonate salt, and a hindered amine compound are kneaded at 140 DEG C for 5 minutes using a Banbury mixer, and then granulated with an extruder to obtain pellets. The pellet is molded into a sheet having a thickness of 1 mm by a press molding method and subjected to a thermal stability test. The thermal stability of the obtained resin composition is excellent as shown in Table 2.

Comparative Examples 7-9

The same test as in Examples 4 to 6 was carried out except that hydrotalcite (trade name: DHT-4A; manufactured by Kyowa Chemical Industries, Co., Ltd.) was used instead of the basic aluminum carbonate salt. As shown in Table 2, the thermal stability of the obtained resin composition is inferior to the resin compositions of Examples 4-6.

Reference Example 1

Ethylene / vinyl acetate copolymer (trade name: Evatate H2031; manufactured by Sumitomo Chemical Co., Ltd.) 13 parts by weight of basic aluminum carbonate, 8 parts by weight of hindered amine compound A (trade name: TINUVIN 622; manufactured by Ciba Specialty Chemicals KK ) 0.3 parts by weight, hindered amine compound B (trade name: CHIMASSORB 944-LD; manufactured by Ciba Specialty Chemicals KK) 0.3 part by weight, ultraviolet absorber (trade name: Sumisorb 130; manufactured by Sumitono Chemical Co., Ltd.), 0.1 part by weight, Antioxidant (trade name: Irganox 1010; manufactured by Ciba Specialty Calmicals KK) 0.1 parts by weight, monoglycerine monostearate 1.4 parts by weight, diglycerine distearate 0.6 parts by weight, stearic acid amide (active agent) 0.2 parts by weight, fluorine-based surfactant ( Antifoaming agent) (trade name: DS-403; manufactured by Daikin Industries, Co., Ltd.), 0.1 part by weight is added, kneaded for 5 minutes at 150 ° C. using a Banbury mixer, and then granulated by a granulator to pellet pellets of the resin composition. Get Let this resin composition be the resin composition (1). Then, ethylene / vinyl acetate copolymer (trade name: Evatate D 2011; manufactured by Sumitomo Chemical Co., Ltd.) 96.9 parts by weight of hindered amine compound A 0.6 parts by weight, ultraviolet absorber 0.1 parts by weight, antioxidant 0.1 parts by weight, 1.4 parts by weight of monoglycerine monostearate, 0.6 parts by weight of diglycerin distearate, 0.2 parts by weight of stearamide, and 0.1 parts by weight of fluorine-based surfactant were added, and kneaded at 150 DEG C for 5 minutes using a Banbury mixer, By granulation to obtain pellets of the resin composition. Let this resin composition be the resin composition (2). A laminated film having a thickness of 0.1 mm (intermediate layer 0.06 mm) comprising an intermediate layer made of the resin composition (1) and an inner layer and an outer layer made of the resin composition (2) laminated on both sides thereof using an inflation film molding machine using the above two kinds of pellets. , Inner and outer layers each 0.02 mm) can be made. In the production of this laminated film, foaming of the material does not occur. This laminated film is excellent in weather resistance, antifogging property, transparency, etc., and can be used suitably for an agricultural film.

Reference Example 2

Ethylene / vinyl acetate copolymer (trade name: Evatate H2031; manufactured by Sumitomo Chimical Co., Ltd.) 13 parts by weight of basic aluminum carbonate, 0.6 parts by weight of hindered amine compound B, 0.1 part by weight of ultraviolet absorber, oxidation 0.1 weight part of inhibitors and 0.2 weight part of stearic acid amides (lubricant) are added, and it knead | mixes for 140 minutes and 5 minutes using the Banbury mixer, it granulates by a granulator and the pellet of a resin composition is obtained. Let this resin composition be the resin composition (3). Subsequently, ethylene / vinyl acetate copolymer (trade name: Evatate D 2011; manufactured by Sumitomo Chemical Co., Ltd.) 3.0 parts by weight of basic aluminum carbonate, 0.3 parts by weight of hindered amine compound A, and hindered amine 0.3 weight part of compound B and 0.1 weight part of antioxidant are added, it knead | mixes for 5 minutes at 140 degreeC using the Banbury mixer, and granulates with a granulator, and the pellet of a resin composition is obtained. Let this resin composition be the resin composition (4). Further, low-density polyethylene (trade name: Sumikathene F 208-0; manufactured by Sumitomo Chemical Co., Ltd.) 3.0 parts by weight of basic aluminum carbonate, 0.3 parts by weight of hindered amine compound A, 0.3 parts by weight of hindered amine compound B 0.3 0.1 part by weight of UV absorber, 0.1 part by weight of antioxidant, 0.2 part by weight of stearamide, and kneading at 140 DEG C for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain pellets of the resin composition. . Let this resin composition be the resin composition (5). The resin composition laminated | stacked on the other side of the inner layer of the resin composition (4) laminated | stacked on one side of this intermediate | middle layer, and the intermediate | middle layer by the inflation film molding machine using these three types of pellets (5) ) 0.1 mm thick laminated film (middle layer 0.06 mm, inner layer 0.02 mm, outer layer 0.02 mm) can be made. On the surface of the resin composition (4) layer, Snowtex 30, Kayacryl resin H 300, Epichlone 860, water and ethanol were mixed at a weight ratio of 4/3 / 0.1 / 75/25. The antifog coating liquid A may be applied by a bar coater so that the solid content is about 1 g / m ² and dried to obtain a film having an antifogging film. These films are excellent in weather resistance, antifogging property, transparency, etc., and can be used suitably for agricultural films. Snowtex 30 is a trade name of colloidal silica (manufactured by Nissan KK). Kayacryl resin H 300 is a trade name of an acrylic emulsion (manufactured by Nihon Kayaku Industries). Epichlone 860 is a trade name of a bisphenol A type epoxy compound (manufactured by Dainippon Ink).

Reference Example 3

Commercially available ethylene / hexene copolymers in which 85% by weight of the resins in the resin compositions (4) and (5) of Reference Example 2 were polymerized using a metallocene catalyst (trade name: Sumikasen E FV403; density 0.919 g / 10 min. A laminated film can be obtained by the method similar to the reference example 2 except having substituted by MFR: 4g / 10min.). This laminated film is excellent in antiblocking property, weather resistance, and transparency, and can be used suitably for an agricultural film. In addition, a corona treatment is applied to one side of the laminated film, and the antifogging agent coating liquid B prepared as follows is coated on the surface to have a solid content of about 0.1 g / m ² , and when dried at room temperature, the laminated film is also excellent in antifogging property and anti-fogging property. Becomes Anti-fogging coating solution B is alumina sol (manufactured by Nissan Chemical, trade name Alumina sol 520, solid content: 20%), colloidal silica (trade name: Snowtex 20, Nissan Chemical, solid content: 20%), sodium dodecylbenzenesulfonate (trade name) : Neopelex F 25, manufactured by Gao) Sodium decanoate (manufactured by Nakaray Tesque) can be obtained by diluting with water at a weight ratio of 1.6 / 0.4 / 0.08 / 0.08.

Resin composition Thermal stability Weather resistance Resin (part by weight) HALS (part by weight) UVA (part by weight) AO agent (part by weight) TGMS (parts by weight) Inorganic compound (parts by weight) 1 hours 2 hours 3 hours 5 hours (One) (2) Example 1 A1 (100) 0.1 SW (10) ○ ○ ○ ○ to △ ○ ○ Example 2 A1 (100) 0.1 0.1 SW (10) ○ ○ ○ ○ to △ ○ ○ Example 3 A1 (100) 0.1 0.1 2.5 SW (10) ○ ○ ○ ○ to △ ○ ○ Comparative Example 1 A1 (100) 0.1 DHT-4A (10) ○ to △ △ △-× ×× ○ △ Comparative Example 2 A1 (100) 0.1 0.1 DHT-4A (10) △ △ △-× ×× ○ △ Comparative Example 3 A1 (100) 0.1 0.1 2.5 DHT-4A (10) △ △ △-× △-× ○ △ Co., Ltd .: Al: Ethylene / vinyl acetate copolymer (brand name: Evaate H2031; Sumidomo Chemical Co., Ltd. make; vinyl acetate unit content: 19 wt%; MFR: 1.5 g / 10 minutes) HALS: hindered amine System compound (brand name: Chimasov 944-LD; manufactured by Tivas Specialty Chemical Co., Ltd.), UVA: ultraviolet absorber; Trade name: Smithsorb 130; Sumidomo Chemical Co., Ltd. Manufacture and AO agent: Antioxidant; Product name: Irganox 1010: Tiba Specialty Chemical Co., Ltd., TGMS: Tetraglycerin monostearate (trade name: MS-310; manufactured by Sakamoto Yakuching Co., Ltd.), SW: basic aluminum carbonate (composition ratio; Al / Na = 1/1) , Al / CO ₃ = 1.2 / 1 manufactured by Mizusawa Chemical Co., Ltd.), DHT-4A (trade name): hydrotarcite; Kyowa Kagaku Ohyo Manufacturing

Resin composition Thermal stability Resin (part by weight) HALS (part by weight) Inorganic compound (parts by weight) 1 hours 2 hours 3 hours 5 hours Example 4 A2 (100) 0.1 SW (2) ○ ○ to △ ○ to △ ○ to △ Example 5 A2 (100) 0.1 SW (10) ○ ○ to △ ○ to △ ○ to △ Example 6 A2 (100) 0.1 SW (20) ○ ○ to △ ○ to △ ○ to △ Comparative Example 4 A2 (100) 0.1 DHT-4A (2) ○ ○ to △ △ △-× Comparative Example 5 A2 (100) 0.1 DHT-4A (10) ○ ○ to △ △ × Comparative Example 6 A2 (100) 0.1 DHT-4A (20) ○ ○ to △ △ × A2: Low density polyethylene (brand name: Sumakasen F208-0; Sumidomoga Chemical Co., Ltd. make; MFR: 1.5 g / 10 minutes

DHT-4A (Hydrotarsite) SW (basic aluminum carbonate) Chemical composition MgO: 36.5Al ₂ O ₃ : 18.6CO ₂ : 8.3 Moisture, etc .: 36.6 Na ₂ O: 21.0 Al ₂ O ₃ : 36.2CO ₂ : 25.8 Moisture, etc .: 17.0 Moisture (%) 110 ℃, 2 hours 0.7 0.9 Ignition loss (%) 180 ℃, 2 hours 4.2 2.7 Refractive index 1.51 1.51 Average particle size (㎛) 0.28 1.1 (Note) The average particle diameter was measured by using a laser diffraction particle size distribution system by dispersing 1 g of a sample in 50 ml of ethanol.

The polyolefin resin composition of the present invention is excellent in heat resistance, weather resistance, transparency and processability, and a film having a layer made of such a resin composition is suitable for agriculture.

Claims (14)

A resin composition comprising a polyolefin resin, a basic aluminum carbonate salt and a hindered amine compound. The resin composition of Claim 1 whose content of basic aluminum carbonate salt is 0.03-200 weight part with respect to 100 weight part of polyolefin resins. The resin composition of Claim 1 or 2 whose content of a hindered amine compound is 0.02-5 weight part with respect to 100 weight part of polyolefin resins. The resin composition according to any one of claims 1 to 3, wherein the refractive index of the basic aluminum carbonate salt is in the range of 1.48 to 1.53. The resin composition of any one of Claims 1-4 which further contains a ultraviolet absorber. The resin composition of Claim 5 whose content of a ultraviolet absorber is 0.01-3 weight part with respect to 100 weight part of polyolefin resins. The film which has 1 or more layers of layers which consist of the resin composition of any one of Claims 1-6. The film of Claim 7 containing an antifog additive. 8. A film according to claim 7, which contains an antifoaming agent. The film according to claim 8, wherein the amount of the antifogging agent in the film is 0.1 to 4% by weight. The film according to claim 9, wherein the amount of antifoaming agent in the film is 0.01 to 3% by weight. The film as described in any one of Claims 7-11 which has an antifogging film. Use as an agricultural film of the film in any one of Claims 7-12. Use of the film according to any one of claims 7 to 12 in an agricultural facility.