JPH11255974A - Resin composition and film having layer composed thereof - Google Patents

Abstract

(57) [Problem] To provide a polyolefin resin composition having sufficient weather resistance even in an environment exposed to pesticides, acid rain and the like. A resin composition comprising a polyolefin resin, a basic aluminum carbonate salt and a hindered amine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition excellent in heat resistance, weather resistance, transparency and processability, and its use.

[0002]

2. Description of the Related Art In recent years, the demand for resins used outdoors, such as automotive materials, building materials, agricultural materials, etc., has increased dramatically. Agricultural materials include agricultural films used for covering facilities such as houses and tunnels in greenhouse horticulture. Conventionally, as an agricultural film, a polyvinyl chloride film, a polyolefin-based resin film (eg, a polyethylene film, an ethylene / vinyl acetate copolymer film) and the like have been widely used. Among them, recently, polyolefin-based resin films, which are hardly soiled, lightweight, and hardly generate toxic gas during incineration, have been widely used for greenhouse horticulture.

On the other hand, since agricultural films are used outdoors, if the weather resistance of the base resin of the film is not sufficient,
Due to the oxidative degradation reaction of the resin, physical properties such as elongation retention or tensile strength of the film decrease during use, and the film deteriorates. Therefore, in order to improve weather resistance, a resin composition in which various weather resistance imparting agents such as an antioxidant and an ultraviolet absorber are blended with a polyolefin resin has been proposed. Among the weatherability-imparting agents, hindered amine stabilizers are described, for example, in JP-A-59-8 / 1984.
As disclosed in JP-A-6645 and JP-A-2-167350, the addition of a small amount significantly improves the weather resistance of the polyolefin-based resin, maintains its effect for a long time, and improves the gloss of the polyolefin-based resin film. It is preferably used because the change in color tone is significantly suppressed.

JP-A-56-41254 discloses a thermoplastic resin film containing a hindered amine compound and an inorganic fine powder having a surface area of 10 m ² / g or more. Japanese Patent No. 150772 discloses an agricultural film containing a thermoplastic resin, a hindered amine compound and a hydrotalcite compound.

[0005]

However, these films cannot maintain sufficient mechanical properties in an environment exposed to pesticides, acid rain, and the like. In some cases, and the weather resistance is not yet sufficient.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems and to develop a polyolefin resin composition having excellent heat resistance and weather resistance.
The present invention has been completed. That is, the present invention provides a resin composition comprising a polyolefin resin, a basic aluminum carbonate salt and a hindered amine compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The basic aluminum carbonate used in the present invention comprises aluminum ion, carbonate ion and at least one cation other than aluminum ion. Examples of the cation of the aluminum ion include an alkali metal ion, an alkaline earth metal ion, an ammonium ion, and a transition metal ion, and among them, a sodium ion, a potassium ion, and an ammonium ion are preferable. Examples of such a basic aluminum carbonate salt include salts described in JP-A-09-279131 and salts exemplified in the following documents. One or more of these basic aluminum carbonate salts may be used. The method for producing the basic aluminum carbonate salt is not particularly limited, but specific examples thereof are described in JP-A-09-279131.
The method described in Japanese Patent Application Laid-Open Publication No. H10-26095 is cited.

The molar ratio of aluminum ions to other cations in the basic aluminum carbonate salt (aluminum ion / cation) is usually 0.3 / 1 to 2/1, preferably 0.5 / 1 to 1/1. 5/1, more preferably 0.
9/1 to 1.2 / 1. The molar ratio of aluminum ion to carbonate ion (Al / CO ₃ ) is 0.3 /
1 to 2/1, preferably 0.8 / 1 to 1.5 / 1,
More preferably, it is 1/1 to 1.3 / 1.

Specifically, for example, sodium aluminum carbonate (Na ₂ O.Al ₂ O ₃ .2CO ₃ .nH ₂ O (n>
0)), potassium aluminum carbonate (K ₂ O.Al ₂ O ₃
2CO ₃ .nH ₂ O (n> 0)) (refer to literature: literature Comprehensive ino).
rganic chemistry vol 2.104
5 pages Published in 1973 Pergamon Press
Ltd. , Literature Acomprehensivet
reateise on inorganicand t
herochemical chemistry vol
5.358-359, published in 1960 Longm
an, Green and Co Ltd).

[0010] The basic aluminum carbonate salt may include water. The water content is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 3% by weight or less. The water content is usually measured by a method according to JIS K 0067. Specifically, the water content is determined as a weight loss rate during heating at 180 ° C. for 2 hours. The average particle diameter of the basic aluminum carbonate salt is usually 5 μm or less, preferably 0.05 to 3 μm, more preferably,
It is 0.1 to 1 μm. When the resin composition of the present invention is used for applications requiring a high degree of transparency, the refractive index of the basic aluminum carbonate is preferably close to that of the polyolefin resin used. Usually, JIS K00
The refractive index of the basic aluminum carbonate salt measured by the method described in 62 is preferably from 1.47 to 1.55, and more preferably from 1.48 to 1.55.
1.54 is more preferable, and 1.49 to 1.53 is particularly preferable.

The content of the basic aluminum carbonate salt in the resin composition of the present invention is preferably from 0.03 to 200 parts by weight based on 100 parts by weight of the polyolefin resin. When the resin composition is used for a coating film for an agricultural facility or the like, the blending amount of the basic aluminum carbonate is from polyolefin resin 1 in view of transparency and strength of the film.
The amount is preferably 35 parts by weight or less, more preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less based on 00 parts by weight.

The basic aluminum carbonate salt may be subjected to a surface treatment with a dispersant in order to improve dispersibility in the resin composition. As dispersants, stearic acid, palmitic acid, higher fatty acids such as lauric acid, calcium salts of higher fatty acids, zinc salts, magnesium salts, barium salts, metal soaps such as sodium salts, phosphate esters, silane coupling agents, Examples thereof include an aluminum-based coupling agent, a zirconium-based coupling agent, and a wax. The surface treatment method may be any method as long as the dispersant uniformly adheres to the surface of the basic aluminum carbonate salt. For example, there is a method in which a basic aluminum carbonate salt is added to an appropriate solvent to form a slurry, and the slurry and a dispersant are mixed and stirred. The hindered amine compound used in the present invention includes, for example, those having a structural formula described in JP-A-8-73667, and specifically, trade names Tinuvin 622-LD, Chimasorb 944-LD, Tinuvin 123 (Above, manufactured by Ciba Specialty Chemicals), Hostabin N30, VP Sanduvor P
R-31 (all manufactured by Clariant), Sayasorb U
V3526 (manufactured by Scitech) and the like. Hindered amine compound-containing stabilizers are disclosed in
The composition described in 3-286448 (trade name: Tinuvin 492, Tinuvin 494; manufactured by Ciba Specialty Chemicals) is exemplified. The hindered amine compounds may be used alone or in combination of two or more.

The content of the hindered amine compound in the resin composition of the present invention is preferably 0.02 parts by weight or more based on 100 parts by weight of the polyolefin resin. In order to suppress blooming, the content is preferably 5 parts by weight or less,
0.1 to 2 parts by weight is more preferable.

The polyolefin resin in the resin composition of the present invention includes, for example, homopolymers of α-olefins such as polyethylene and polypropylene; ethylene-propylene copolymer, ethylene / butene-1 copolymer, ethylene / 4 -Methyl-1-pentene copolymer, ethylene
Ethylene / α-olefin copolymers such as hexene copolymer and ethylene / octene copolymer; ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate -Methyl methacrylate copolymers and copolymers with different monomers containing α-olefin as a main component such as ionomer resin. When the resin composition of the present invention is used for agricultural films, polyethylene, ethylene-α-
An olefin copolymer, an ethylene / vinyl acetate copolymer having a vinyl acetate unit content of 30% by weight or less has transparency,
It is preferable from the viewpoint of weather resistance, price and the like.

[0015] Ethylene and an α-olefin having 3 to 18 carbon atoms are converted into a gas phase in the presence or absence of a solvent using a so-called single-site catalyst such as a transition metal complex catalyst such as palladium or nickel or a metallocene catalyst. -Solid phase, liquid phase-ethylene-α obtained by polymerization under solid phase or homogeneous liquid phase
-Olefin copolymers are preferably used. Usually, the polymerization temperature is from about 30 ° C. to about 300 ° C., and the polymerization pressure is from atmospheric pressure to about 3,000 kg / cm ² . For example,
JP-A-6-9724, JP-A-6-136195, JP-A-6-136196, JP-A-6-20
Ethylene / α obtained by copolymerizing ethylene with an α-olefin having 3 to 18 carbon atoms in the presence of a so-called metallocene-based olefin polymerization catalyst containing a metallocene catalyst component described in US Pat. -An olefin copolymer can be preferably used in the present invention.

In order to further improve the weather resistance of the resin composition, the resin composition of the present invention may further contain at least one ultraviolet absorber. Examples of such an ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a benzoate-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. When an ultraviolet absorber is included, the amount thereof is determined based on the amount of the polyolefin resin 1 from the viewpoint of improving the weather resistance and suppressing blooming.
It is in the range of 0.01 to 3 parts by weight, preferably 0.05 to 1 part by weight, based on 00 parts by weight.

The resin composition of the present invention includes a composite hydroxide such as a lithium aluminum composite hydroxide and a hydrotalcite compound; and a metal oxide 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; potassium sulfate, magnesium sulfate, calcium sulfate and zinc sulfate;
Sulfates such as aluminum sulfate; lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate, zirconium phosphate (for example, H-type zirconium phosphate disclosed in JP-A-8-67774); magnesium silicate; Silicates such as calcium silicate, aluminum silicate and titanium silicate; aluminates such as sodium aluminate, potassium aluminate and calcium aluminate; aluminos such as sodium aluminosilicate, potassium aluminosilicate and calcium aluminosilicate Silicates;
Clay minerals such as kaolin, clay and talc; and one or more other inorganic compounds such as complex oxides may be contained. The hydrotalcite compound 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 are 0 <x <0.
5, 0 ≦ m ≦ 2, 1 ≦ n ≦ 3. ). As M ²⁺ , Mg ²⁺ , C
a ²⁺ and Zn ²⁺ are exemplified. The n-valent anion is not particularly limited. For example, Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , Cl
O ₄ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ³⁻ , HB
^{_{O 4 3-, PO 4 3-,}} Fe (CN) 6 3-, Fe (CN) 6 4-,
CH ₃ COO ⁻ , C ₆ H ₄ (OH) COO ⁻ , (CO
O) ₂ ^2-, terephthalic acid ion, anion and naphthalene sulfonic acid ion, and a polysilicic acid ions and polyphosphate ions described in JP-A-8-217912. Specifically, for example, natural hydrotalcite or synthetic hydrotalcite such as Alkamizer DHT-4A (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) can be used.

Examples of the lithium aluminum composite hydroxide include, for example, the following formula (II) Li ⁺ (Al ³⁺ ) ₂ (OH ⁻ ) _6. (A ₂ ^{n −} ) ₁ described in JP-A-5-179052. _{/ n} · mH ₂ O (II) (where A ₂ ^n- is an n-valent anion, and m and n
Satisfies the condition of 0 ≦ m ≦ 3, 1 ≦ n ≦ 3). The n-valent anion is not particularly limited. For example, A in the compound of the formula (I)
Anions similar to ₁ ^n- can be mentioned.

The composite hydroxide other than the above two types includes, for example, at least one element selected from the group consisting of alkaline earth metals, transition metals, Zn and Si, and Li and Al. And a compound having a hydroxyl group. Of the alkaline earth metals, magnesium and calcium are preferred. Further, among the transition metals, divalent or trivalent iron, cobalt, nickel, and manganese are preferable, and among them, iron is more preferable. The molar ratio of Al and Li (Al / Li) is usually 1.5 / 1 to 2.5 /
1, preferably 1.8 / 1 to 2.5 / 1.

In addition, alkaline earth metals, transition metals, Zn
The molar ratio (a) of an element selected from the group consisting of Si and Si is usually 0 <a <1.
5, preferably 0.1 ≦ a ≦ 1.4, more preferably 0.2 ≦ a ≦ 1.2. The anion portion other than the hydroxyl group of the composite hydroxide includes, for example, polysilicate ions such as pyrosilicate ion, cyclosilicate ion, isosilicate ion, phyllosilicate ion, and tectosilicate ion; carbonate ion, halide ion, sulfate ion, Sulfite ion, nitrate ion, nitrite ion, phosphate ion,
Inorganic acid ions such as phosphite ion, hypophosphite ion, polyphosphate ion, aluminate ion, silicate ion, perchlorate ion, borate ion; Fe (C
^{_{N) 6 3-, Fe (CN}} ) 6 4- , etc. anionic transition metal complexes; acetate ion, benzoate ion, formate ion, terephthalate ion and organic acid ions such as an alkyl sulfonate ion. Among these, carbonate ions,
Preference is given to halide ions, sulfate ions, phosphate ions, polyphosphate ions, silicate ions, polysilicate ions and perchlorate ions, and particularly preferred are carbonate ions, polyphosphate ions, silicate ions and polysilicate ions.

Specific examples of such a composite hydroxide include Al, Li, Mg, and Al / Li / Mg.
= About 2.3 / 1 / 0.28 (molar ratio), a composite hydroxide (trade name: LMA, manufactured by Fuji Chemical Industry), Al, L
i, containing Si, and Al / Li / Si = about 2/1 /
1.2 (molar ratio) composite hydroxide (trade name: Fujilein LS, manufactured by Fuji Chemical Industry).

The following formula (II) described in WO 97/00828
_{^{I) [(Li + (1}} -x) M 2+ x) (Al 3+) 2 (OH -) 6] 2 (Si y 0 (2y + 1) 2-) (1 + x) · mH 2 O (III) (wherein, M ²⁺ is a divalent metal ion, and m, x, and y satisfy the conditions of 0 ≦ m <5, 0 ≦ x <1, 2 ≦ y ≦ 4) Compound, and JP-A-8-21
No. 7912, the following formula (IV): [(Li ⁺ _(1-x) M ²⁺ _x ) (Al ³⁺ ) ₂ (OH ⁻ ) ₆ ] ₂ (A ⁿ⁻ ) _{2 (1 + x ) / n} · mH ₂ O (IV) (where M ²⁺ is a divalent metal ion, A ⁿ⁻ is an n-valent anion, and m, x and n are 0 ≦ m <5 , 0.
A compound represented by the following formula (01 ≦ x <1, 1 ≦ n ≦ 3) is a preferred example of the composite hydroxide. As M ²⁺ in the formulas (III) and (IV), Mg ²⁺ ,
Ca ²⁺ and Zn ²⁺ are exemplified.

The resin composition of the present invention may contain at least one infrared absorber. Examples of such infrared absorbers include organic infrared absorbers such as polyacetal, polyvinyl alcohol and derivatives thereof, and ethylene / vinyl alcohol copolymer.

The resin composition of the present invention can contain at least one kind of antifog. Examples of the antifog include fluorine compounds having a perfluoroalkyl group, an ω-hydrofluoroalkyl group and the like (especially fluorine surfactants), and silicon compounds having an alkylsiloxane group (especially silicon surfactants) ) And the like.
Specific examples of the fluorine-based surfactant include Unidyne DS-403, DS-406, and DS-401 (all manufactured by Daikin Industries, Ltd.). As the silicon-based surfactant, SH-3746 is a trade name. (Manufactured by Toray Dow Corning Silicon Co., Ltd.).

The resin composition of the present invention can contain at least one kind of antifogging agent. Such anti-fogging agents include those which are solid at room temperature and those which are liquid.

Examples of the solid antifogging agent include nonionic surfactants such as sorbitan fatty acid ester surfactants such as sorbitan monostearate, sorbitan monopalmitate and sorbitan monomontanate; glycerin monopalmitate and glycerin Glycerin fatty acid ester surfactants such as monostearate, diglycerin distearate, triglycerin monostearate, and tetraglycerin dimontanate; polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate Alkylene oxide adducts of alkylphenols; esters of sorbitan / glycerin condensates with organic acids; polyoxyethylene (2 mol) stearylamine, polyoxyethylene (2 mol) la Polyoxyethylene alkylamine compounds such as rilamine, polyoxyethylene (4 mol) stearylamine, polyoxyethylene (2 mol) stearylamine monostearate, polyoxyethylene (2 mol) stearylamine distearate, polyoxyethylene ( 4 mol) stearylamine monostearate, polyoxyethylene (4 mol) stearylamine distearate, polyoxyethylene (8 mol) stearylamine monostearate, polyoxyethylene (2 mol) stearylamine monobehenate, polyoxy Fatty acid esters of polyoxyethylene alkylamine compounds such as ethylene (2 mol) laurylamine stearate;
Examples include amine-based surfactants such as fatty acid amides of polyoxyethylene alkylamine compounds such as polyoxyethylene (2 mol) stearamide.

Examples of the liquid antifogging agent include glycerin monooleate, diglycerin monooleate, diglycerin sesquioleate, tetraglycerin monooleate, hexaglycerin monooleate, hexaglycerin trioleate, and tetraglycerin Glycerin-based fatty acid esters such as trioleate, tetraglycerin monolaurate, hexaglycerin monolaurate;
Sorbitan monooleate, sorbitan dioleate,
And the like.

The resin composition of the present invention further comprises a wax,
It may contain antioxidants, antistatic agents, light stabilizers other than hindered amines, lubricants, pigments, anti-algal agents and the like.

The resin composition of the present invention can be produced, for example, by the following method. A predetermined amount of a basic aluminum carbonate, a hindered amine-based compound and, if necessary, an additive are mixed with a polyolefin-based resin.
Mix and knead using a kneader. As the mixing / kneading machine, for example, a conventional apparatus such as a ribbon blender, a super mixer, a Banbury mixer, or a single or twin screw extruder can be used. The obtained resin composition can be suitably used for extrusion molding, injection molding, blow molding and the like. In particular, the resin composition of the present invention can be preferably used for producing a film having at least one layer composed of the same.

The resin composition of the present invention may be subjected to a molding step after being diluted with a polyolefin resin. In this case, the resin composition before dilution is usually called a master batch.

The film of the present invention may be composed of a single layer composed of the resin composition of the present invention, or may be a laminated film composed of two or more layers composed of the resin composition of the present invention. In addition, a laminated film including one or more layers made of the resin composition of the present invention and one or more layers made of a material other than the resin composition of the present invention may be used. The layer structure of the laminated film is not particularly limited.
Layers, three types of three layers, three types of five layers, and the like. The layer composed of the resin composition of the present invention is preferably an intermediate layer of a laminated film composed of three or more layers. The film of the present invention,
In the case of a laminated film having a layer made of a material other than the resin composition of the present invention, the layer made of a material other than the resin composition of the present invention usually consists of a resin.

The film of the present invention can be prepared by using the resin composition of the present invention and, if necessary, other materials in combination, by conventional methods such as extrusion, coextrusion, melt coating, extrusion lamination, and dry lamination. It can be manufactured by a conventional method.

The resin used in the layers other than the resin composition layer of the present invention includes, for example, α-olefin homopolymers such as polyethylene and polypropylene; ethylene-propylene copolymer, ethylene-butene-1 copolymer. Ethylene / α-olefin copolymers such as polymers, ethylene / 4-methyl-1-pentene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer; ethylene / vinyl acetate copolymer, ethylene Examples include acrylic acid copolymers, ethylene / methyl methacrylate copolymers, ethylene / vinyl acetate / methyl methacrylate copolymers, and copolymers with different monomers containing α-olefin as a main component such as ionomer resins. Among these, when the laminated film of the present invention is used for agricultural purposes, polyethylene, ethylene / α-olefin copolymer, and ethylene / vinyl acetate copolymer having a vinyl acetate unit content of 30% by weight or less are transparent. It is more preferable from the viewpoint of weather resistance and price. For agricultural use, a laminated film in which the layer of the resin composition of the present invention is an intermediate layer is preferred.

The film of the present invention may be formed of the same composite hydroxide, metal oxide, hydroxide, carbonate, sulfate, phosphate, silicate, aluminate, aluminosilicate, It may contain at least one kind of inorganic compound such as clay mineral and composite oxide. The addition of the inorganic compound improves the heat retention of the film.

These inorganic compounds may be contained in any layer of the film of the present invention, but are preferably contained in the layer of the resin composition of the present invention. 0.03 to 150
Part by weight is preferable, 0.03 to 30 parts by weight is more preferable, and 0.03 to 15 parts by weight is particularly preferable. The film of the present invention may be blended with at least one infrared absorber as described above, and may be blended with at least one antifog agent as described above.

When an antifog is incorporated into the film of the present invention, the amount of the antifog is 0.01 to 3% by weight of the whole film.
Is preferable, and 0.02 to 2% by weight is more preferable.
Particularly preferred is 0.5 to 0.5% by weight.

Further, the film of the present invention may contain at least one antifogging agent as described above. From the viewpoint of suppressing the bleeding of the antifogging agent on the film surface and the transparency of the film, it is preferable to use both a liquid antifogging agent and a solid antifogging agent at room temperature. When the film of the present invention contains an antifogging agent, the amount is preferably 0.1 to 4% by weight, more preferably 1.5 to 4% by weight, based on the whole film.
Particularly preferred is 2 to 2.8% by weight.

The film of the present 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 period of time. Such anti-fog coatings are described, for example, in JP-B-49-32.
No. 668, Japanese Patent Publication No. 50-11348, etc., a coating film of an inorganic oxide sol represented by colloidal silica or alumina sol.
No. 432, No. 63-45717, No. 64-2
No. 158, JP-A-3-207643, etc., a coating film of an inorganic oxide sol and an organic compound (surfactant, resin, etc.), a coating film of a liquid containing a surfactant as a main component, hydrophilicity A film containing a resin (for example, polyvinyl alcohol, polysaccharide, polyacrylic acid, etc.) as a main component is given. The method for forming the anti-fogging film may be coating, or after forming the anti-fogging film, the film may be laminated on a laminated film. The antifogging film may be a single layer or two or more layers.

The film of the present invention can be produced by an ordinary molding method such as a calendering method, an extrusion T-die film molding method, and an inflation film molding method. The thickness of the film, from the viewpoint of the strength of the film,
The thickness is preferably 0.01 mm or more, and is preferably 0.3 mm or less from the viewpoints of film splicing workability and coating workability. More preferably, 0.03 to 0.25 mm
It is.

The above film can be suitably used as an agricultural film, particularly as a covering film for agricultural facilities such as a house and a tunnel.

[0041]

The resin composition obtained by the present invention has excellent heat resistance, weather resistance and transparency, and is used for agricultural materials, home electric appliances, automobile materials, building materials and the like. In particular, a film using the resin composition is remarkably excellent in weather resistance when used as a covering film or a mulching film for an agricultural house / tunnel, and is a material effective for greenhouse horticulture. The film of the present invention has better weather resistance than conventional agricultural covering films under conditions such as light and exposure to pesticides. Furthermore, the resin composition of the present invention has less deterioration and discoloration associated therewith even under continuous molding processing conditions,
Low foaming during molding and excellent long-term molding stability.

[0042]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, 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 an air atmosphere at 180 ° C. in a gear oven, and the coloring degree was visually determined every hour, and evaluated according to the following criteria. ：: almost no coloring compared to the initial state △: slightly yellow or light brown compared to the initial state ×: yellow or brown colored compared to the initial state XX: dark brown compared to the initial state Colored

[Weather Resistance Test (1)] A test piece having a thickness of 1 mm was measured using an eye super UV tester SUV-W11 (manufactured by Eye Graphics Co., Ltd.) under the conditions of a blowing temperature of 60 ° C. and a relative humidity of 32% RH. For 24 hours. This test piece was visually evaluated for the degree of coloring, and evaluated according to the following criteria. ：: almost no coloring compared to the initial state △: slightly yellow or light brown compared to the initial state ×: yellow or brown colored compared to the initial state XX: dark brown compared to the initial state Colored

[Weather Resistance Test (2)] A test piece having a thickness of 1 mm was hung and sealed in a 500 mL glass bottle containing 50 mL of 6% sulfurous acid solution, and allowed to stand at room temperature for 4 hours. About this test piece, eye super UV tester SUV-W11
(Eye Graphics Co., Ltd.) and left for 24 hours under the conditions of a blowing temperature of 60 ° C. and a relative humidity of 32% RH. This test piece was visually evaluated for the degree of coloring, and evaluated according to the following criteria. ：: almost no coloring compared to the initial state △: slightly yellow or light brown compared to the initial state ×: yellow or brown colored compared to the initial state XX: dark brown compared to the initial state Colored

[Measurement of Transparency] According to JIS K7105, total light transmittance and HAZE were measured using a haze meter manufactured by Suga Test Instruments. The smaller the value of HAZE, the better the transparency.

Examples 1 to 3 As shown in Table 1, resin, basic aluminum carbonate (constituent ratio: Al / Na = 1/1, Al / CO ₃ = 1.2)
/ 1), a hindered amine compound and other additives were kneaded with a Banbury mixer at 140 ° C for 5 minutes, and then granulated in an extruder to obtain pellets. The pellets were formed into a sheet having a thickness of 1 mm by a press molding method, and the thermal stability test and the weather resistance tests (1) and (2) were performed. As shown in Table 1, the results were excellent in thermal stability and weather resistance. Details of the basic aluminum carbonate used are described in
It is shown in the table.

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

Examples 4 to 6 As shown in Table 2, a resin, a basic aluminum carbonate, and a hindered amine compound were kneaded with a Banbury mixer at 140 ° C. for 5 minutes, and then granulated in an extruder to obtain pellets. . The pellets are 1mm thick by press molding
And a thermal stability test was conducted. The thermal stability of the obtained resin composition was excellent as shown in Table 2.

Comparative Examples 7 to 9 The same tests as in Examples 4 to 6 were carried out except that hydrotalcite (trade name: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) was used instead of the basic aluminum carbonate salt. The thermal stability of the obtained resin composition was inferior to the resin compositions of Examples 4 to 6 as shown in Table 2.

Reference Example 1 Ethylene / vinyl acetate copolymer (trade name: Evatate)
H2031; Sumitomo Chemical Industries, Ltd.) 83.9 parts by weight, basic aluminum carbonate 13 parts by weight, hindered amine compound A (trade name: Tinuvin 622; Ciba Specialty Chemicals) 0.3 part by weight, hindered amine compound B (Trade name: Chimasorb 944-LD; manufactured by Ciba Specialty Chemicals) 0.3 parts by weight, ultraviolet absorber (trade name: Sumisorb 130; manufactured by Sumitomo Chemical Industries) 0.1 part by weight, antioxidant (trade name: Irga) Knox 1010; Ciba Specialty Chemicals)
0.1 parts by weight, monoglycerin monostearate 1.4
Parts by weight, 0.6 parts by weight of diglycerin distearate, 0.2 parts by weight of stearic acid amide (lubricant), fluorine-based surfactant (antifog agent) (trade name: DS-403; manufactured by Daikin Industries) One part by weight is added, and the mixture is kneaded at 150 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain pellets of the resin composition. This resin composition is referred to as a resin composition. Next, an ethylene / vinyl acetate copolymer (trade name: Evatate D2011; manufactured by Sumitomo Chemical Co., Ltd.) 9
To 6.9 parts by weight, 0.6 parts by weight of the hindered amine compound A, 0.1 part by weight of an ultraviolet absorber, 0.1 part by weight of an antioxidant, 1.4 parts by weight of monoglycerin monostearate,
0.6 parts by weight of diglycerin distearate, 0.2 parts by weight of stearic acid amide, and 0.1 parts by weight of a fluorosurfactant are added, and the mixture is kneaded at 150 ° C. for 5 minutes using a Banbury mixer, and then granulated. Granulate to obtain pellets of the resin composition. This resin composition is referred to as a resin composition. Using an inflation film molding machine using the above two types of pellets, a 0.1 mm-thick laminated film (intermediate layer 0) composed of an intermediate layer made of a resin composition and an inner layer and an outer layer made of the resin composition laminated on both sides thereof .06
mm, 0.02 mm each of the inner and outer layers). In the production of this laminated film, no foaming of the material occurs. This laminated film has excellent weather resistance, anti-fog properties, transparency, etc.
It can be suitably used as an agricultural film.

Reference Example 2 Ethylene / vinyl acetate copolymer (trade name: Evatate H)
2031; 86 parts by weight of Sumitomo Chemical 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, 0.1 part by weight of antioxidant, stearic acid Amide (lubricant) 0.2
Parts by weight, using a Banbury mixer at 140 ° C,
After kneading for 5 minutes, the mixture is granulated by a granulator to obtain pellets of the resin composition. This resin composition is referred to as a resin composition. Next, 96.3 parts by weight of an ethylene / vinyl acetate copolymer (trade name: Evatate D2011; manufactured by Sumitomo Chemical Co., Ltd.), 3.0 parts by weight of a basic aluminum carbonate salt, 0.3 parts by weight of a hindered amine compound A, and hindered amine 0.3 parts by weight of the compound B and 0.1 parts by weight of the antioxidant are added, and the mixture is kneaded at 140 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain pellets of the resin composition. This resin composition is referred to as a resin composition. Further, to 96 parts by weight of low-density polyethylene (trade name: Sumikacene F208-0; manufactured by Sumitomo Chemical Industries), 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 Parts, 0.1 parts by weight of an ultraviolet absorber, 0.1 parts by weight of an antioxidant, and 0.2 parts by weight of stearamide, and kneaded at 140 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator. Granulate to obtain pellets of the resin composition. This resin composition is referred to as a resin composition. Using an inflation film molding machine using these three types of pellets, an intermediate layer made of a resin composition, an inner layer of the resin composition laminated on one surface of the intermediate layer, and laminated on the other surface of the intermediate layer 0.1 mm-thick laminated film (intermediate layer 0.06 mm, inner layer 0.02 mm, outer layer 0.0
2 mm). On the surface of the layer of the resin composition, Snowtex 30, Kayacryl Resin H300, Epicron 860, water and ethanol were added to 4/3 / 0.1 / 7.
The antifogging agent coating solution A mixed at a weight ratio of 5/25 is applied with a bar coater so that the solid content becomes 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 and the like, and can be suitably used as agricultural films. Snowtex 30 is a trade name of colloidal silica manufactured by Nissan Chemical Industries. Kayaacryl resin H300 is a trade name of an acrylic emulsion manufactured by Nippon Kayaku Kogyo. Epicron 860 is a trade name of a bisphenol A type epoxy compound manufactured by Dainippon Ink and Chemicals.

Reference Example 3 A commercially available ethylene / hexene copolymer (trade name: Sumikacene EFV403; density: 0.919 g) obtained by polymerizing 85% by weight of the resin in the resin composition of Reference Example 2 using a metallocene catalyst / 10 min (MFR: 4 g / 10 min) except that the laminated film can be obtained in the same manner as in Reference Example 2. This laminated film is excellent in antiblocking properties, weather resistance, transparency and the like, and can be suitably used as an agricultural film. Further, one side of the laminated film is subjected to a corona treatment, and an antifogging agent coating solution B prepared as described below is applied thereon so as to have a solid content of about 0.1 g / m ² and dried at room temperature. Then, a laminated film excellent in anti-fogging property and anti-fog property is obtained. The anti-fogging coating solution B includes alumina sol (trade name: alumina sol 520, solid content 20%, manufactured by Nissan Chemical Co., Ltd.), colloidal silica (trade name: Snowtex 20, manufactured by Nissan Chemical; solid content: 20)
%), Sodium dodecylbenzenesulfonate (trade name: Neoperex F25; manufactured by Kao), and sodium decanoate (manufactured by Nacalai Tesque) at 1.6 / 0.4 / 0.0.
It is obtained by dilution with water at a weight ratio of 8 / 0.08.

[0054]

[Table 1] (Note) A1: Ethylene / vinyl acetate copolymer (trade name: Evatate H2031; manufactured by Sumitomo Chemical Co., Ltd .; vinyl acetate unit content: 19 wt%; MFR: 1.5 g / 10 min) HALS; hindered amine compound (trade name) UVA: UV absorber; Trade name: Sumisorb 130;
Sumitomo Chemical AO agent: Antioxidant; Trade name: Irganox 101
0; Ciba Specialty Chemicals TGMS: Tetraglycerin monostearate (trade name: MS-310; Sakamoto Yakuhin) SW: Basic aluminum carbonate (constituent ratio: Al / Na)
= 1/1, Al / CO ₃ = 1.2 / 1; manufactured by Mizusawa Chemical Industries) DHT-4A (trade name): Hydrotalcite; manufactured by Kyowa Chemical Industry

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[Table 2] (Note) A2: Low-density polyethylene (trade name: Sumikasen F2)
08-0; manufactured by Sumitomo Chemical Co., Ltd .; MFR: 1.5 g / 10
Minutes)

[0056]

[Table 3] (Note) The average particle size was measured by dispersing 1 g of a sample in 50 ml of ethanol and using a laser diffraction type particle size distribution meter.

[Brief description of the drawings]

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

Claims (14)

[Claims] 1. A resin composition comprising a polyolefin resin, a basic aluminum carbonate and a hindered amine compound. 2. The content of the basic aluminum carbonate is 0.03 to 200 parts by weight per 100 parts by weight of the polyolefin resin.
The resin composition according to claim 1, which is in parts by weight. 3. The resin composition according to claim 1, wherein the content of the hindered amine compound is 0.02 to 5 parts by weight based on 100 parts by weight of the polyolefin resin. 4. A basic aluminum carbonate having a refractive index of 1.
4. A method according to claim 1, wherein the value is in the range of 48 to 1.53.
Item 10. The resin composition according to item 8. 5. The method according to claim 1, further comprising an ultraviolet absorber.
The resin composition according to any one of the above. 6. The resin composition according to claim 5, wherein the content of the ultraviolet absorber is 0.01 to 3 parts by weight based on 100 parts by weight of the polyolefin resin. 7. A film having at least one layer comprising the resin composition according to claim 1. 8. The film according to claim 7, which comprises an antifogging agent. 9. The film according to claim 7, which comprises an antifog. 10. The film according to claim 8, wherein the amount of the antifogging agent in the film is 0.1 to 4% by weight. 11. The amount of the antifog in the film is 0.01 to 3
The film according to claim 9, which is in weight%. 12. The film according to claim 7, which has an antifogging film. 13. Use of the film according to any one of claims 7 to 12 as an agricultural film. 14. Use of the film according to any one of claims 7 to 12 in an agricultural facility.