JPH09235420A - Polyolefin resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin composition having excellent weather resistance and its use. SOLUTION: This composition comprises 100 pts.wt. polyolefin resin, 0.03-60 pts.wt. compound hydroxide having at least one element selected from the group consisting of alkaline earth metals, transition metals, Zn and Si, Li, and Al and 0.02-5 pts.wt. hindered amine compound. Films made from this composition are used for, e.g. greenhouse horticulture or agriculture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin resin composition having excellent weather resistance and its use.

[0002]

2. Description of the Related Art In recent years, the demand for resins used for molded articles used outdoors such as automobile materials, building materials, and agricultural materials has increased dramatically. As an example of the molded product used outdoors, there is an agricultural coating film used for coating a house, a tunnel, etc. in facility gardening. Conventionally, a polyvinyl chloride film, a polyethylene film which is a polyolefin resin film, an ethylene-vinyl acetate copolymer film, etc. have been used as an agricultural coating film. Generally, these are commonly called agricultural crops, agricultural plastics, and agricultural crisps, and are widely used for institutional horticulture.

However, when exposed to sunlight in the presence of oxygen, the polyolefin resin undergoes an oxidative deterioration reaction, so that the physical properties such as the elongation retention rate or tensile strength of the polyolefin resin film deteriorate and the agricultural coating The film did not have sufficient weather resistance. Therefore, a polyolefin resin composition is known in which various weather resistance-imparting agents such as an antioxidant and an ultraviolet absorber are blended with a polyolefin resin for improving weather resistance. Among them, hindered amine-based stabilizers significantly improve the weather resistance of polyolefin-based resins with a small amount of addition and bring about the effect for a long period of time, or significantly suppress changes in gloss and color tone due to deterioration of polyolefin-based resin moldings. Therefore, it is often used (for example, JP-A-59-86645 and JP-A-2-167350). In addition, Japanese Unexamined Patent Publication No.
Japanese Unexamined Patent Publication No. 6-41254 discloses a thermoplastic resin film containing a hindered amine compound and a polar inorganic fine powder having a surface area of 10 cm ² / g or more and having improved weather resistance.

[0004]

However, in the above-mentioned conventional techniques, the weather resistance under the environment exposed to pesticides and acid rain, that is, the mechanical resistance under the environment exposed to pesticides and acid rain. It was hard to say that the effect of suppressing the deterioration of physical properties was sufficient.

[0005]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention is based on 100 parts by weight of polyolefin resin, alkaline earth metal, transition metal,
It is characterized by containing 0.03 to 150 parts by weight of a composite hydroxide containing at least one element selected from the group consisting of Zn and Si and Li and Al, and 0.02 to 5 parts by weight of a hindered amine compound. The present invention provides a polyolefin resin composition and its use.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The composite hydroxide used in the present invention is an alkaline earth metal,
Contains at least one element selected from the group consisting of transition metals, Zn and Si, and Li and Al,
And it is a compound having a hydroxyl group. Among the alkaline earth metals, magnesium and calcium are preferable. Also,
Among the transition metals, divalent or trivalent iron, cobalt,
Nickel and manganese are preferable, and iron is more preferable. In the composite hydroxide, the composition ratio of Al and Li (Al / L
i) is a molar ratio and is usually 1.5 / 1 to 2.5 / 1, preferably 1.8 / 1 to 2.5 / 1. Also,
The molar ratio (a) of (each) element selected from the group consisting of alkaline earth metals, transition metals, Zn and Si is L
Usually, 0 <a <1.5 with respect to 1 mol of the i element,
Preferably 0.1 ≦ a ≦ 1.4, and more preferably 0.
2 ≦ a ≦ 1.2. The complex hydroxide is usually one in which a cationic part and an anionic part are ionically bonded. The cationic portion includes at least Li and Al. Examples of the element or compound constituting the anionic portion include, for example, pyrosilicate ion, cyclosilicate ion, isosilicate ion, phyllosilicate ion, polysilicate ion such as tectosilicate ion, carbonate ion, halide ion, sulfate ion, Inorganic acid ions such as sulfite ion, nitrate ion, nitrite ion, phosphate ion, phosphite ion, hypophosphite ion, aluminate ion, silicate ion, perchlorate ion and borate ion, Fe
Examples thereof include anionic transition metal complexes such as (CN) ₆ ³⁻ and Fe (CN) ₆ ⁴⁻ , organic acid ions such as acetate ion, benzoate ion, formate ion, terephthalate ion and alkylsulfonate ion. Among these compounds,
Carbonic acid, halogen, sulfuric acid, phosphoric acid, polyphosphoric acid, silicic acid,
Ions such as polysilicic acid and perchloric acid are preferable, and ions such as carbonic acid, polyphosphoric acid, silicic acid and polysilicic acid are more preferable. As a specific example of the composite hydroxide, a composite hydroxide containing Al, Li and Mg and having Al / Li / Mg = about 2.3 / 1 / 0.28 (molar ratio) (trade name LMA, Fuji Chemical Industry Co., Ltd. Manufactured), Al, Li,
An example is a composite hydroxide containing Si and having Al / Li / Si = about 2/1 / 1.2 (molar ratio) (trade name: Fujirain LS, manufactured by Fuji Chemical Industry).

The average particle size of the composite hydroxide is usually 5 μm.
m or less, preferably 0.05 to 3 μm, and more preferably 0.1 to 1 μm. The specific surface area measured by the BET method is 1 to 30 m ² / g, preferably 2 to 10 m
² / g. When the polyolefin resin composition of the present invention is used for a film application requiring transparency, the refractive index of the composite hydroxide is preferably close to that of the polyolefin resin used. Usually JIS K0062
The refractive index of the composite hydroxide measured by the method described is 1.4.
7 to 1.55, preferably 1.48 to 1.54, and more preferably 1.49 to 1.53. The composite hydroxide may further contain water of crystallization. The compounding amount of the composite hydroxide is 0.03 to 150 parts by weight in the polyolefin resin composition from the viewpoint of the weather resistance improving effect. When the resin composition is used for an agricultural coating film, the compounding amount of the composite hydroxide is preferably 35 parts by weight or less, more preferably 20 parts by weight or less, from the viewpoint of transparency and strength of the obtained film. It is particularly preferably 13 parts by weight or less. Further, the composite hydroxide may be preliminarily subjected to a firing treatment for the purpose of preventing foaming during molding. Examples of the firing treatment include a method of treating at a high temperature in an inert gas atmosphere.

The composite hydroxide may be surface-treated with a dispersant in order to improve the dispersibility in the polyolefin resin composition or in the film. As the dispersant, higher fatty acids such as stearic acid, palmitic acid, and lauric acid, higher fatty acid calcium salts, metal soaps such as zinc salts, magnesium salts, barium salts, and sodium salts, various phosphate esters, silane coupling agents, Examples include aluminum-based coupling agents, zirconium-based coupling agents, and various waxes. The surface treatment method may be a method in which the dispersant is uniformly attached to the surface of the composite hydroxide. For example, the composite hydroxide is slurried in a suitable solvent, and the slurry and the dispersant are mixed. Examples include a method of mixing and stirring.

The hindered amine compound used in the present invention is preferably a 2,2,6,6-tetraalkylpiperidine derivative having a molecular weight of 250 or more and having a substituent at the 4-position, and the substituent at the 4-position. Examples thereof include a carboxylic acid residue, an alkoxy group and an alkylamino group. An alkyl group may be substituted at the N-position. As specific examples, compounds represented by the following formulas (1) to (23) and stabilizers containing hindered amine compounds described in JP-A-63-286448 (trade name TI
NUVIN 492, TINUVIN 494, manufactured by Ciba Geigy) can be exemplified.

[0010]

[0011]

[0012]

The amount of the hindered amine compound used in the present invention is 0.02 parts by weight or more based on 100 parts by weight of the polyolefin resin from the viewpoint of the effect of improving weather resistance, and from the viewpoint of suppressing the blooming phenomenon,
5 parts by weight or less. Preferably it is 0.1 to 2 parts by weight. Further, these hindered amine compounds may be used alone or in combination of two or more kinds.

Examples of the polyolefin resin used in the present invention include homopolymers of α-olefins such as polyethylene and polypropylene, or ethylene-propylene copolymers, ethylene-butene-1 copolymers and ethylene. Ethylene-α-olefin copolymers such as 4-methyl-1-pentene copolymer and ethylene-hexene copolymer, and, for example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene- Α of methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, ionomer resin, etc.
-A copolymer with a different type of monomer containing olefin as a main component. When the polyolefin resin composition of the present invention is used for an agricultural coating film, the content of polyethylene, ethylene-α-olefin copolymer and vinyl acetate is 3
An ethylene-vinyl acetate copolymer of 0% by weight or less is more preferable in view of transparency, weather resistance and cost.

In the present invention, an ultraviolet absorber may be used in combination in order to obtain a more excellent weather resistance improving effect. Examples of the UV absorber include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, benzoate-based UV absorbers, and cyanoacrylate-based UV absorbers. For example, compounds represented by the following formulas (24) to (32) may be mentioned.

[0016]

When an ultraviolet absorber is used in combination, it is usually 0.01 to 3 with respect to 100 parts by weight of the polyolefin resin.
Parts by weight, preferably 0.05 to 1 part by weight. These ultraviolet absorbers may be used alone or in combination of two or more kinds.

In the present invention, other inorganic compounds may be added. Examples of other inorganic compounds include oxides, hydroxides, carbonates, sulfates, phosphates, and silicates of metals such as lithium, sodium, potassium, magnesium, calcium, zinc, aluminum, silicon, and titanium. , aluminates, aluminosilicates, also the following general formula _{(I) M 1-x Al} 3+ x (OH -) 2 (A 1 n-) x / n · mH 2 O (I) ( wherein, M Represents a divalent metal ion selected from the group consisting of Mg ²⁺ , Ca ²⁺ + and Zn ²⁺ , A ₁ ^n- represents an n-valent anion, and x represents a condition: 0 <x <0.5. , M satisfies the condition: 0 <m <2, and n is an integer of 1 to 4) (for example, JP-A-60-104141, JP-A-63-104141). 149
(See Japanese Patent Application Laid-Open No. 147, JP-A-8-217912)
Further, the following general formula (II) Li ⁺ (Al ³⁺ ) ₂ (OH) ₆ · (A ₂ ^n- ) _{1 / n} · mH ₂ O (II) described in JP-A-5-179052 (wherein A ₂ ^n- represents an n-valent anion, but does not contain an alkaline earth metal, a transition metal, Zn or Si, n is 1 to 4
, And m is a numerical value that satisfies the condition of 0 ≦ m ≦ 3. ) And a lithium aluminum composite hydroxide. The blending amount of these inorganic compounds is usually
0.03 per 100 parts by weight of polyolefin resin
To 150 parts by weight, preferably 0.03 to 30 parts by weight, more preferably 0.03 to 10 parts by weight.

Various kinds of antifog agents can be added to the polyolefin resin composition of the present invention for the purpose of imparting antifog properties. Examples of the anti-fog agent include fluorine compounds having a perfluoroalkyl group, ω-hydrofluoroalkyl group and the like (especially fluorine-based surfactant), and silicon compounds having an alkylsiloxane group (especially silicon-based surfactant). ) And the like. Specific examples of the fluorinated surfactant include trade names Unidyne DS-403 and D.
S-406, DS-401 (both made by Daikin Industries)
Examples of the silicone surfactant include trade name SH-3746 (manufactured by Toray Dow Corning Silicon Co., Ltd.). The amount of the fog-preventing agent is generally 0.01 to 4 with respect to 100 parts by weight of the polyolefin resin.
Parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.1 to 1 part by weight.

The polyolefin resin composition of the present invention may contain various antifogging agents for the purpose of imparting antifogging properties. Such antifogging agents include those that are solid and those that are liquid at room temperature. As the solid antifogging agent, a nonionic surfactant, for example, sorbitan monostearate,
Sorbitan fatty acid ester-based surfactants such as sorbitan monopalmitate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate,
Glycerin fatty acid ester-based surfactants such as diglycerin distearate, triglycerin monostearate,
Examples thereof include polyethylene glycol-based surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate, alkylene oxide adducts of alkylphenols, and esters of sorbitan / glycerin condensates with organic acids. As, for example, glycerin monooleate, diglycerin monooleate,
Glycerin fatty acid esters such as diglycerin sesquioleate, tetraglycerin monooleate, hexaglycerin monooleate, hexaglycerin pentaoleate, tetraglycerin trioleate, tetraglycerin monolaurate, hexaglycerin monolaurate, etc. Examples thereof include sorbitan fatty acid esters such as sorbitan monooleate, sorbitan dioleate and sorbitan trioleate. From the viewpoint of the effect of suppressing bleed-out of the antifogging agent on the film surface during storage of the film and the transparency of the film, it is preferable to use a liquid antifogging agent and a solid antifogging agent together at room temperature. . Generally, the amount of the antifogging agent is 10
0.5 to 3 parts by weight, preferably 1.
5 to 3 parts by weight, more preferably 2.2 to 2.8 parts by weight. The polyolefin-based resin composition of the present invention further comprises a wax, an antioxidant, an antistatic agent, and
A weathering agent other than a hindered amine-based light stabilizer such as a light stabilizer, a lubricant, and a pigment may be added. These may be used alone or in combination of two or more.

The polyolefin resin composition of the present invention comprises:
For example, it can be manufactured by the following method. Polyolefin resin with a specified amount of complex hydroxide and hinder
The doamine-based compound and, if necessary, various additives are mixed and kneaded by an ordinary mixing / kneading machine such as a ribbon blender, a super mixer, a Banbury mixer, or a single-screw or twin-screw extruder. The polyolefin resin composition thus obtained can be suitably used for an extrusion molded product, an injection molded product, a blow molded product and the like. In particular, it can be suitably used for an agricultural coating film as described below.

The agricultural coating film of the present invention can be produced from the above polyolefin resin composition. The agricultural coating film can be produced by, for example, a calendering method, an extrusion T-die film forming method, or an inflation film forming method. Etc. can be carried out by a usual molding method. The thickness of the agricultural coating film of the present invention is preferably 0.01 mm or more from the viewpoint of the strength of the film, and is preferably 0.3 mm or less from the standpoint of film intermediate workability and coating workability. More preferably, 0.03-0.25 mm
It is.

For the purpose of maintaining the transparency of the agricultural coating film in the present invention for a long period of time, in addition to the above-mentioned polyolefin resin composition containing an antifogging agent which is liquid at room temperature, An antifogging film may be formed on at least one surface. The surface on which the antifogging film is formed is preferably the side facing the inside of the facility when the agricultural coating film is spread on a horticultural facility such as a house or a tunnel.
Such an antifogging film is, for example, Japanese Patent Publication No. 49-3266.
No. 8, Japanese Patent Publication No. 50-11348, etc., coating films of inorganic oxide sols represented by colloidal silica and alumina sol, and their applications, such as Japanese Patent Publication Nos. 63-45432 and 63-4571.
7, JP-B-64-2158, JP-A-3-20764
No. 3, 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, a hydrophilic resin (for example, polyvinyl alcohol, Polysaccharides, polyacrylic acid, etc.) as a main component. The method for forming the anti-fogging film may be coating, or after forming the anti-fogging film, it may be laminated on the agricultural coating film. The antifogging coating may be a single layer or two or more layers.

The film of the present invention may have at least one layer comprising the above polyolefin resin composition,
In the case of a laminated film having a layer other than the layer made of the polyolefin resin composition, the other layer is usually a layer made of a resin (hereinafter, may be abbreviated as other resin layer).
In the case of a laminated film, the layer constitution is 2 types 2 layers, 2 types 3
Layers, 3 types of 3 layers, etc. can be illustrated. Of these layer configurations, 3
It is preferable to use a layer made of the above-mentioned polyolefin-based resin composition as an intermediate layer in a laminated film of layers or more. The laminated film can be produced by using the above polyolefin resin composition by a coextrusion method, a melt coating method, an extrusion lamination method, a dry lamination method, or the like. As the resin used in the other resin layer, for example, a homopolymer of α-olefin such as polyethylene or polypropylene, or, for example, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4- Ethylene-α-olefin copolymers such as methyl-1-pentene copolymer and ethylene-hexene copolymer, and, for example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer Examples thereof include a polymer, an ethylene-vinyl acetate-methyl methacrylate copolymer, and a copolymer with a different monomer having an α-olefin as a main component such as an ionomer resin. Among these, when the polyolefin resin composition of the present invention is used for an agricultural coating film, polyethylene, an ethylene-α-olefin copolymer, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less. Is more preferable in view of transparency, weather resistance and price.
When the adhesive force between the other resin layer and the layer made of the above polyolefin resin composition is not sufficient, it is preferable to separately provide an adhesive resin layer between the two. The adhesive resin may be any one that does not cause delamination at a practical stage, and an unsaturated carboxylic acid or an anhydride thereof is used as an olefin polymer (for example, polyethylene, polypropylene,
Examples thereof include modified olefin-based polymers containing a carboxyl group obtained by chemically (for example, addition reaction or graft reaction) bonding to a polyolefin such as polybutene or a polymer mainly composed of olefins. Specifically, 1 selected from maleic anhydride graft modified polyethylene, maleic anhydride graft modified polypropylene, maleic anhydride graft modified ethylene-ethyl acrylate copolymer, maleic anhydride graft modified ethylene vinyl acetate copolymer, and ionomer resin. The species or mixtures of the two are mentioned as suitable.

[0025]

EFFECT OF THE INVENTION The polyolefin resin composition obtained by the present invention has excellent weather resistance and is used for agricultural materials, home electric appliances, automobile materials, construction materials and the like. Among them, the agricultural coating film using the resin composition, an agricultural house,
It is used as a material for tunnels, mulching films, etc., which has remarkably excellent weather resistance during expansion and is an effective material for horticulture in facilities. The agricultural coating film of the present invention is light,
Under conditions such as pesticide exposure, it has better weather resistance than conventional agricultural coating films. Furthermore, the polyolefin-based resin composition of the present invention has little deterioration and discoloration accompanying it even under continuous molding processing conditions, has less foaming during molding processing, and is excellent in molding processing stability for a long time.

[0026]

EXAMPLES Examples of the present invention will be shown 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. [Weather resistance test] A lime sulfur mixture (calcium polysulfide 2
After being immersed in a 7.5% aqueous solution of Hokuko Kagaku Kogyo for 24 hours,
It was washed and dried. This test piece was exposed with time in a sunshine weather o-meter (manufactured by Suga Test Instruments Co., Ltd.) under the condition of a black panel temperature of 63 ° C. Tensile test was performed on the aged test piece using Autograph DSS100 (manufactured by Shimadzu Corp.) to obtain an elongation rate (%).
Was measured, and the weather resistance test time (hereinafter, weather resistance half-life) when the elongation became half the elongation of the original test piece.
Called). The greater the value of this time, the better the weather resistance. The elongation rate was calculated by the following formula. Elongation rate (%) = [marker distance at break (mm)-
Mark distance before tensile test (mm)] ÷ Mark distance before tensile test (mm) x 100 [Haze measurement] Based on JISK7105, using a haze meter manufactured by Suga Test Instruments, total light transmittance and HA.
ZE was measured.

Example 1 Ethylene-vinyl acetate copolymer (vinyl acetate content: 15% by weight, density: 0.94 g
/ Cm ³ , MFR: 1.1 g / 10 min), 8.0% by weight of composite hydroxide M (trade name LMA manufactured by Fuji Chemical Co., Ltd.), hindered amine compound A (trade name Tinuvin 62).
0.6% by weight (2-LD manufactured by Ciba-Geigy) was added to make 100% by weight as a whole. 100 parts by weight of the obtained resin composition was mixed with antioxidant H (trade name Irganox 1010).
0.1 parts by weight of Ciba Geigy), 1.4 parts by weight of monoglycerin monostearate as an antifogging agent, 0.6 parts by weight of diglycerin distearate, and 0.2 parts by weight of stearic acid amide as a lubricant are added to a Banbury mixer. The mixture was kneaded at 130 ° C. for 5 minutes and granulated with a granulator to obtain a composition pellet. This is referred to as a resin composition. Next, ethylene-vinyl acetate copolymer (trade name: Evatate D2
011 (manufactured by Sumitomo Chemical Co., Ltd.), hindered amine compound A 0.6% by weight, antioxidant H 0.1% by weight, monoglycerin monostearate 1.4% by weight, diglycerin distearate 0.6% by weight, stearin 0.2% by weight of acid amide was added to make 100% by weight in total, and after kneading at 130 ° C. for 5 minutes using a Banbury mixer, granulation was performed by a granulator to obtain a composition pellet. This is referred to as a resin composition. A film having a film thickness of 0.1 mm (intermediate layer 0.06 m is formed by using an inflation film molding machine with the resin composition as an intermediate layer and the resin composition as both outer layers.
m, both outer layers 0.02 mm) were prepared and a weather resistance test was conducted. The results were excellent as shown in Table 1.

(Example 2) A film was prepared in the same manner as in Example 1 except that 0.1 part by weight of each of the resin composition and the ultraviolet absorber U (trade name Sumisorb 130 manufactured by Sumitomo Chemical Co., Ltd.) was added. Then, a weather resistance test was conducted. The results were excellent as shown in Table 1.

(Example 3) 0.1 part by weight of each UV absorber U was added to the resin composition and further mixed with the resin composition so that the content of the composite hydroxide M was 2.0% by weight. A film was prepared and a weather resistance test was performed in the same manner as in Example 1 except for the above. The results were excellent as shown in Table 1.

(Example 4) In the resin composition, instead of the composite hydroxide M, the composite hydroxide L (trade name, Fujirain LS, manufactured by Fuji Chemical Co., Ltd.) was blended so as to have a content of 8.0% by weight. A film was prepared and a weather resistance test was performed in the same manner as in Example 1 except for the above. The results were excellent as shown in Table 1.

(Comparative Example 1) In the resin composition, silicon oxide S (trade name: Snowmark SP-10, manufactured by Venusmatic) was used in place of the composite hydroxide M except that the content was 10% by weight. A film was prepared and a weather resistance test was conducted in the same manner as in Example 1. The results were inferior as shown in Table 1.

Example 5 Ethylene-vinyl acetate copolymer (vinyl acetate content: 15% by weight, density: 0.94 g
/ Cm ³ , MFR: 1.1 g / 10 min), composite hydroxide M 8.0 wt%, hindered amine compound A
0.3% by weight, hindered amine compound B (trade name, Kimasorb 944-LD, manufactured by Ciba Geigy) 0.3% by weight
Was added to make the total 100% by weight. 100 parts by weight of the obtained resin composition, 0.1 part by weight of an ultraviolet absorber U, 0.1 part by weight of an antioxidant H, 1.4 parts by weight of monoglycerin monostearate as an antifogging agent, and 0.1 part of diglycerin distearate. 6 parts by weight, 0.2 part by weight of stearic acid amide as a lubricant, fluorine-based surfactant F as an antifog agent (trade name D
(S-403 manufactured by Daikin Industries, Ltd.) 0.1 part by weight was added, the mixture was kneaded at 130 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain a composition pellet. This is referred to as a resin composition. Next, ethylene-vinyl acetate copolymer (trade name: Evatate D2011, manufactured by Sumitomo Chemical Co., Ltd.)
In addition, hindered amine compound A 0.6% by weight, ultraviolet absorber U 0.1% by weight, antioxidant H 0.1% by weight, monoglycerin monostearate 1.4% by weight, diglycerin distearate 0.6% by weight , 0.2% by weight of stearic acid amide and 0.1% by weight of fluorosurfactant F were added to make 100% by weight, and the mixture was kneaded at 130 ° C. for 5 minutes using a Banbury mixer and then granulated by a granulator. , A composition pellet was obtained. This is referred to as a resin composition. The resin composition was used as an intermediate layer, and the resin composition was used as both outer layers, and the film thickness was 0.
1 mm film (middle layer 0.06 mm, both outer layers 0.0
2 mm) was prepared and a weather resistance test was conducted. The result is first
It was excellent as shown in the table.

(Example 6) A film was prepared in the same manner as in Example 5 except that the composite hydroxide M was added to the resin composition so that the content thereof was 2.0% by weight. Was done. The results were excellent as shown in Table 1.

Example 7 In the resin composition, the composite hydroxide M was replaced by 2.
A film was prepared and a weather resistance test was performed in the same manner as in Example 5 except that 0% by weight and 10% by weight of silicon oxide S were blended. The results were excellent as shown in Table 1.

Example 8 In the resin composition, the composite hydroxide L was replaced by 2.
A film was prepared and a weather resistance test was performed in the same manner as in Example 5 except that 0% by weight and 10% by weight of silicon oxide S were blended. The results were excellent as shown in Table 1.

(Comparative Example 2) A film was prepared in the same manner as in Example 5 except that silicon oxide S was added in an amount of 10% by weight in place of the compound hydroxide M8.0% by weight in the resin compound. It was prepared and a weather resistance test was conducted. The results were inferior as shown in Table 1.

Example 9 Ethylene-vinyl acetate copolymer (vinyl acetate content: 15% by weight, density: 0.94 g
/ Cm ³ , MFR 1.1 g / 10 min), 8.0 wt% of complex hydroxide M and 0.6 wt% of hindered amine compound B were added to make 100 wt% in total. 100 parts by weight of the obtained resin composition, 0.1 part by weight of an ultraviolet absorber U, 0.1 part by weight of an antioxidant H, 1.4 parts by weight of monoglycerin monostearate as an antifogging agent, and 0.1 part of diglycerin distearate. Add 6 parts by weight and 0.2 parts by weight of stearic acid amide as a lubricant, and add 13 parts by using a Banbury mixer.
After kneading at 0 ° C. for 5 minutes, the mixture was granulated with a granulator to obtain composition pellets. This is referred to as a resin composition. Next, ethylene-vinyl acetate copolymer (trade name: Evatate D201
1 Sumitomo Chemical Co., Ltd.) hindered amine compound A
0.30% by weight, hindered amine compound B 0.30
% By weight, UV absorber U 0.1% by weight, antioxidant I
0.1% by weight, monoglycerin monostearate 1.4
% By weight, 0.6% by weight of diglycerin distearate and 0.2% by weight of stearic acid amide are added to make a total of 10%.
0% by weight, using a Banbury mixer, 130 ℃,
After kneading for 5 minutes, granulation was performed by a granulator to obtain a composition pellet. This is referred to as a resin composition. A film having a film thickness of 0.1 mm (intermediate layer 0.06 mm, both outer layers 0.02 mm) was prepared by an inflation film molding machine using the resin composition as an intermediate layer and the resin composition as both outer layers, and a weather resistance test was conducted. . The results were excellent as shown in Table 1.

Example 10 Example 9 was repeated except that the compound hydroxide was mixed in the resin compound in an amount of 8.0 wt% instead of the compound hydroxide M 8.0 wt%. Similarly, a film was prepared and a weather resistance test was conducted. The results were excellent as shown in Table 1.

(Comparative Example 3) In the same manner as in Example 9 except that in the resin compound, silicon oxide S was added in an amount of 10% by weight instead of 8.0% by weight of the composite hydroxide M. A film was prepared and a weather resistance test was conducted. The results were inferior as shown in Table 1.

Example 11 To an ethylene-vinyl acetate copolymer (trade name: Evatate D2011 manufactured by Sumitomo Chemical Co., Ltd.), 8.0% by weight of a composite hydroxide M and 0.6% by weight of a hindered amine compound A were added, and the whole was added. 100% by weight
And 0.1 part by weight of antioxidant H, 1.4 parts by weight of monoglycerin monostearate as an antifogging agent, 0.6 part by weight of diglycerin distearate, and stearic acid amide as a lubricant to 100 parts by weight of the obtained resin composition. Add 0.2 parts by weight, and use a Banbury mixer at 130 ° C for 5
After kneading for a minute, granulated pellets were prepared with a granulator. A film having a film thickness of 0.075 mm was produced from the pellets by an inflation film molding machine, and a weather resistance test was conducted. The results were excellent as shown in Table 2.

(Example 12) Further, the ultraviolet absorber U0.
A film was prepared in the same manner as in Example 11 except that 1% by weight was blended, and a weather resistance test was conducted. The results were excellent as shown in Table 2.

(Example 13) In the same manner as in Example 12 except that the compound hydroxide M was mixed in an amount of 8.0% by weight instead of the compound hydroxide M 8.0% by weight. A film was prepared and a weather resistance test was conducted. The results were excellent as shown in Table 2.

Comparative Example 4 8.0% by weight of composite hydroxide M
Instead of the above, a film was prepared in the same manner as in Example 11 except that silicon oxide S was blended so as to have a content of 10% by weight, and a weather resistance test was conducted. The results were inferior as shown in Table 2.

Example 14 Ethylene-vinyl acetate copolymer (trade name: Evatate D2011, manufactured by Sumitomo Chemical Co., Ltd.) was added with 8.0% by weight of a complex hydroxide M, 0.3% by weight of a hindered amine compound A, and a hindered amine compound. 0.3% by weight of B was added to make 100% by weight as a whole.
To 100 parts by weight of the obtained resin composition, an ultraviolet absorber U0.
1 part by weight, 0.1 part by weight of antioxidant H, 1.4 parts by weight of monoglycerin monostearate as an antifogging agent, 0.6 part by weight of diglycerin distearate, and 0.2 parts by weight of stearic acid amide as a lubricant. In addition, the total amount was 100 parts by weight, and the film thickness was 0.0 in the same manner as in Example 11.
A 75 mm film was prepared and a weather resistance test was conducted.
The results were excellent as shown in Table 2.

(Example 15) Instead of 8.0% by weight of the composite hydroxide M, 2.0% by weight of the composite hydroxide M and S of silicon oxide were used.
A film was prepared in the same manner as in Example 14 except that 10% by weight was blended, and a weather resistance test was conducted. The results were excellent as shown in Table 2.

(Comparative Example 5) 8.0% by weight of composite hydroxide M
Instead of the above, a film was prepared and a weather resistance test was conducted in the same manner as in Example 14 except that silicon oxide S was blended so as to have a content of 10% by weight. The results were inferior as shown in Table 2.

Example 16 To an ethylene-vinyl acetate copolymer (trade name: Evatate D2011 manufactured by Sumitomo Chemical Co., Ltd.), 8.0% by weight of a complex hydroxide M and 0.6% by weight of a hindered amine compound B were added, and the whole was added. It was 100 parts by weight. 100 parts by weight of the obtained resin composition, 0.1 part by weight of an ultraviolet absorber U, 0.1 part by weight of an antioxidant H, 1.4 parts by weight of monoglycerin monostearate as an antifogging agent,
Diglycerin distearate (0.6 parts by weight) and stearic acid amide (0.2 parts by weight) as a lubricant were added, and a film having a film thickness of 0.075 μm was produced in the same manner as in Example 11, and a weather resistance test was performed. The results were excellent as shown in Table 2.

(Example 17) A film was prepared in the same manner as in Example 16 except that the compound hydroxide L was blended in an amount of 8.0% by weight instead of the compound hydroxide M 8.0% by weight. Was prepared and a weather resistance test was conducted. The results were excellent as shown in Table 2.

Comparative Example 6 8.0% by weight of composite hydroxide M
Instead of the above, a film was prepared in the same manner as in Example 16 except that silicon oxide S was blended so as to have a content of 10% by weight, and a weather resistance test was conducted. The results were inferior as shown in Table 2.

(Example 18) Ethylene-vinyl acetate copolymer (trade name: Evatate H2031 manufactured by Sumitomo Chemical Co., Ltd.)
10% by weight of the composite hydroxide L and 0.6% by weight of the hindered amine compound B were added to 100% by weight. UV absorber U was added to 100 parts by weight of the obtained resin composition.
0.1 parts by weight, 0.1 parts by weight of antioxidant H, and 0.2 parts by weight of stearic acid amide as a lubricant were added, and the mixture was kneaded at 130 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator. A product pellet was obtained. This is referred to as a resin composition. Next, ethylene-vinyl acetate copolymer (trade name
Evatate D2011 manufactured by Sumitomo Chemical Co., Ltd.) with complex hydroxide L3.0% by weight hindered amine compound A0.30
% By weight, hindered amine compound B 0.30% by weight,
UV absorber U 0.1% by weight, antioxidant I 0.1% by weight, and stearic acid amide 0.2% by weight were added to make 100% by weight as a whole.
After kneading at 0 ° C for 5 minutes, the mixture was granulated by a granulator to obtain a composition pellet. This is referred to as a resin composition. Furthermore, low-density polyethylene (trade name Sumikasen F208-0 manufactured by Sumitomo Chemical Co., Ltd.) is mixed with composite hydroxide L3.0% by weight hindered amine compound A0.30% by weight, hindered amine compound B0.30% by weight, and ultraviolet absorber U0.1. % By weight, antioxidant I 0.1% by weight, diglycerin distearate 0.6% by weight, stearic acid amide 0.2% by weight
Was added to make 100% by weight as a whole, and the mixture was kneaded at 130 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain a composition pellet. This is referred to as a resin composition. A film having a film thickness of 0.1 mm (intermediate layer 0.06 mm, using a resin composition as an intermediate layer and a resin composition as both outer layers by an inflation film molding machine).
Both outer layers (0.02 mm) were prepared, and the antifogging agent coating liquid A (Snowtex 30 / Kayacryl resin H300 / Epiclon 860 / water / ethanol = 4/3 / 0.1 / 75/25) was formed on the surface of the resin composition. (Mixed in weight ratio)
With a bar coater to a solid content of about 1 g / m ^2.
It was dried to obtain a film. When a weather resistance test was conducted, the weather resistance was excellent, with a half-life of 1,000 hours or more.
Further, when this film was spread on a house, the anti-fogging property was also good. (Product name Snowtex 30: Nissan Chemical Industries colloidal silica Product name Kayacryl resin H300: Nippon Kayaku Kogyo Acrylic Emulsion Product name Epicron 860: Dainippon Ink and Chemicals bisphenol A type epoxy compound)

[Table 1]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/32 B32B 27/32 Z C08J 5/18 CES C08J 5/18 CES C08K 3/22 C08K 3 / 22 5/13 KER 5/13 KER 5/3435 KFB 5/3435 KFB (72) Inventor Aki Kudo 2-10-1 Tsukahara, Takatsuki City, Osaka Prefecture Sumitomo Chemical Co., Ltd.

Claims (8)

[Claims] 1. At least one element selected from the group consisting of alkaline earth metals, transition metals, Zn and Si and Li based on 100 parts by weight of a polyolefin resin.
A polyolefin resin composition comprising 0.03 to 150 parts by weight of a composite hydroxide containing Al and 0.02 to 5 parts by weight of a hindered amine compound. 2. The polyolefin resin composition according to claim 1, wherein the content of the composite hydroxide is 0.03 to 30 parts by weight. 3. The polyolefin resin composition according to claim 1, wherein the content of the composite hydroxide is 0.03 to 13 parts by weight. 4. The polyolefin resin composition according to claim 1, which further comprises 0.01 to 3 parts by weight of an ultraviolet absorber. 5. A laminated film having at least one layer composed of the polyolefin resin composition according to claim 1. 6. Use of the polyolefin resin composition according to any one of claims 1 to 4 for institutional horticulture. 7. Use of the laminated film according to claim 5 as an agricultural film. 8. The use according to claim 7, wherein the agricultural film is an agricultural covering film.