JP2001089610A - Polyolefin resin composition, its film and agricultural film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably and continuously form a polyolefin film having excellent weather resistance, anti-blocking property and / or slip property, and improved yellowing resistance to heat and ultraviolet rays. Provided are a resin composition, a film obtained by molding the same, and an agricultural film. SOLUTION: (A) 100 parts by weight of a polyolefin-based resin and (B) a hydrotalcite-based compound in an amount of 0.01 to 100 parts by weight.
1.0 parts by weight, (C) 0.01 to 1.0 parts by weight of a metal salt of Group II of the Periodic Table of higher fatty acids, (D) 0.02 to 1.0 parts by weight of a hindered amine light stabilizer, and ( E) A polyolefin-based composition comprising 0.05 to 3.0 parts by weight of at least one antiblocking agent selected from aluminosilicate and silica and / or 0.01 to 0.3 part by weight of (F) a higher fatty acid amide. Resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyolefin-based resin composition, a film thereof and an agricultural film, and more particularly, to an excellent weather resistance, an anti-blocking property and / or a slip property, and a heat or heat resistance. Polyolefin-based film with improved yellowing resistance to ultraviolet light,
The present invention relates to a polyolefin-based resin composition that can be continuously and stably formed, a film thereof, and an agricultural film using the film.

[0002]

2. Description of the Related Art Polyolefin films are used in a wide range of applications, such as food packaging, textile packaging, pharmaceutical packaging, fertilizer packaging, miscellaneous goods packaging, and other agricultural and architectural coatings. ing. Such a polyolefin-based film is blended with an anti-blocking agent such as silica, talc, zeolite or the like, or an additive such as a lubricant in order to improve handling workability.

Further, in order to improve the thermal stability during the molding process of the polyolefin resin or the heat aging resistance, a phosphorus-based, sulfur-based, or phenol-based heat stabilizer is generally added to the polyolefin. I have. However, when these heat stabilizers are used in combination with an anti-blocking agent and / or a lubricant, there is a problem that a molded article or the like is yellowed by heat or ultraviolet rays.

Further, a hindered amine light stabilizer is often blended in a film requiring weather resistance such as an agricultural coating material. In this case, the problem that the molded product turns yellow has become more remarkable. Therefore, it has become clear that a conventional polyolefin-based film cannot obtain a polyolefin-based film that sufficiently satisfies anti-blocking properties and / or slip properties and weather resistance without causing yellowing. Is coming.

[0005] Polyolefin resins, particularly polyolefin resins produced using a Ziegler-type catalyst, contain halides (residual chlorine) originating from the catalyst used. Therefore, if the polyolefin-based resin is molded as it is, hydrogen halide may be generated at the time of molding, and the molding machine may be corroded. further,
The polyolefin-based film containing a halide may cause an undesirable situation such as yellowing with the passage of time.

[0006] Residual chlorine in the polyolefin-based resin is likely to adversely affect the effect of the hindered amine-based light stabilizer, that is, the weather resistance of the polyolefin-based film. Therefore, a residual chlorine scavenger is usually added to the polyolefin-based resin for the purpose of preventing adverse effects due to residual chlorine.

[0007] Higher fatty acid metal salts and the like are known as residual chlorine scavengers. However, higher fatty acid metal salts do not always have a sufficient effect of supplementing chlorine. Therefore, in order to obtain a sufficient effect of supplementing chlorine, it is necessary to add a large amount of a higher fatty acid metal salt to the polyolefin-based resin, which causes a problem that the physical properties of the polyolefin-based resin are impaired.

As another residual chlorine scavenger, a hydrotalcite-based compound is disclosed in JP-A-52-49258.
An aluminum / magnesium composite hydroxide is disclosed in Japanese Patent Publication No. 28102/1988. Hydrotalcite-based compounds and aluminum / magnesium composite hydroxides have a higher chlorine-trapping effect than metal salts of higher fatty acids. However, when a hydrotalcite-based compound or a polyolefin-based resin to which an aluminum / magnesium composite hydroxide is added in such an amount that a sufficient chlorine-trapping effect can be obtained, adhesion of an adhesive substance to a die lip when forming into a film is not possible. And melt fracture occur, and it is difficult to perform stable continuous molding.

As described above, a polyolefin resin composition which has excellent weather resistance, maintains anti-blocking properties and / or slip properties, and is capable of stably and continuously forming a polyolefin film having improved yellowing resistance to heat and ultraviolet rays. Things have not yet been found.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to stabilize a polyolefin film having excellent weather resistance, anti-blocking properties and / or slip properties, and improved yellowing resistance to heat and ultraviolet rays. To provide a polyolefin-based resin composition and an agricultural film having excellent weather resistance, excellent anti-blocking properties and / or slip properties, and improved yellowing resistance to heat and ultraviolet rays. It is in.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a polyolefin resin composition having the above-mentioned preferable properties. As a result, the polyolefin resin has a hindered amine light stabilizer and an antioxidant. When a blocking agent and / or a lubricant is added, the hydrotalcite-based compound and the higher fatty acid metal salt are simultaneously added, so that the molding stability of the polyolefin-based resin composition is not reduced and the yellowing of the polyolefin-based film is reduced. It has been found that the anti-blocking property and / or the slip property can be maintained while suppressing, and the weather resistance of the polyolefin-based film is remarkably improved as compared with the case where the hydrotalcite-based compound or the higher fatty acid metal salt is blended alone. Thus, the present invention has been completed.

That is, the polyolefin resin composition of the present invention comprises (A) 100 parts by weight of a polyolefin resin and (B) a hydrotalcite compound in an amount of 0.01 to 1.
0 parts by weight, (C) 0.01 to 1.0 parts by weight of a metal salt of Group II of the Periodic Table of higher fatty acids, (D) 0.02 to 1.0 parts by weight of a hindered amine light stabilizer, and (E) It is characterized in that 0.05 to 3.0 parts by weight of at least one antiblocking agent selected from aluminosilicate and silica and / or 0.01 to 0.3 parts by weight of (F) higher fatty acid amide are blended.

The molecular weight of the hindered amine light stabilizer (D) is preferably in the range of 700 to 4,000. The hindered amine light stabilizer (D) is preferably a hindered amine light stabilizer in which a hydrogen atom is not bonded to an N atom constituting an amine. Further, it is desirable that the polyolefin resin (A) is a linear low-density polyethylene.

Further, the film of the present invention is characterized by comprising a resin material containing the polyolefin resin composition of the present invention as a main component. Further, the agricultural film of the present invention is characterized by comprising the film of the present invention or a multilayer film of the film of the present invention and another polyolefin film.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, (A) a polyolefin resin (hereinafter, referred to as “polyolefin resin”).
Examples of (A) component) include homopolymers of ethylene such as linear low-density polyethylene, high-pressure low-density polyethylene, and high-density polyethylene, or copolymers of ethylene and α-olefins having 3 to 12 carbon atoms. Polymer: polypropylene, propylene-ethylene copolymer, polybutene
1, poly 4-methylpentene-1 and the like. These polyolefin resins may be used alone or in combination of two or more. Among them, linear low-density polyethylene is preferably used in terms of transparency, weather resistance, and the like.

As the linear low-density polyethylene, ethylene and preferably at least one of 0.2 to 20 mol%, more preferably 1 to 10 mol%, of an α-olefin having 3 to 12 carbon atoms, Examples thereof include those copolymerized in a liquid phase or a gas phase. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, and 4-methyl-1 -Hexene, 4,4-dimethyl-1-pentene and the like can be used. Among such linear low-density polyethylenes, the density is particularly 0.900 to 0.960 g / cm.
³ , preferably in the range of 0.910 to 0.940 g / cm ³ and a melt index (MI) of 0.1 to
50 g / 10 min, preferably 0.5 to 20 g / 10 min,
Those having a range of 0.5 to 10 g / 10 minutes are more preferable from the viewpoints of transparency, weather resistance and cost.

(B) Hydrotalcite in the present invention
The compound (hereinafter, referred to as component (B)) is magnesium
And aluminum hydrated basic carbonate. (B) component
May be a natural product or a synthetic product. Natural products
Is Mg₆Al_Two(OH)₁₆CO _Three・ 4H_TwoO indicated
It is a compound. As a synthetic product, the ratio between Mg and Al is different.
Examples, for example, those represented by the following formula
You. Mg_FourAl_Two(OH)₁₂CO_Three・ 3H_TwoO, Mg_FiveAl_Two(OH)₁₄CO_Three・ 4H_TwoO, Mg_TenAl_Two(OH)_{twenty two}(CO_Three)_Two・ 4H_TwoO, Mg_4.5Al_Two(OH)₁₃CO_Three・ 3.5H_TwoO These hydrotalcite compounds can be used alone
Or two or more of them may be used in combination.

The amount of the component (B) is 100 parts (A).
It is in the range of 0.01 to 1.0 part by weight, preferably 0.02 to 0.2 part by weight, based on part by weight.
If the amount of the component (B) is less than 0.01 part by weight, the polyolefin film will have insufficient weather resistance and yellowing resistance. On the other hand, if it exceeds 1.0 part by weight, a problem occurs in molding stability.

The (C) higher fatty acid group II metal salt of the periodic table (hereinafter referred to as "component (C)") in the present invention includes:
For example, calcium stearate, zinc stearate,
Examples include magnesium stearate and calcium palmitate. These higher fatty acid metal salts may be used alone or in combination of two or more.

The amount of the component (C) is 100
It is in the range of 0.01 to 1.0 part by weight, preferably 0.02 to 0.3 part by weight, based on part by weight.
If the amount of the component (C) is less than 0.01 part by weight, stable continuous molding of the polyolefin film becomes difficult.
On the other hand, if it exceeds 1.0 part by weight, undesired phenomena such as a decrease in transparency of the polyolefin-based film and poor dispersion are likely to occur. In the present invention, the combined use of the hydrotalcite-based compound (B) and the component (C) dramatically improves the weather resistance of the resulting film.

As the hindered amine light stabilizer (D) in the present invention, various compounds usually compounded in polyolefin resins can be used. Specific examples include the following hindered amine light stabilizers. However, the component (D) of the present invention is not limited to the following specific examples.

The component (D) includes, for example, a condensate of 1,2,3,4-butanecarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, polymethyl Propyl-3-oxy- [4 (2,2,6,6-tetramethyl) piperidyl] siloxane, dibutylamine • 1,3,5-triazine • N, N′-bis (2,2,6,6, -Tetramethyl-4-piperidyl) -1,6-hexamethylenediamine · N- (2,2,6,6, -tetramethyl-4-piperidyl) butylamine polycondensate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,
3,4-butanetetracarboxylate, poly [｛6- (1,1,3,
3-tetramethylbutyl) amino) -1,3,5-triazine-2,4-
Diyl {(2,2,6,6-tetramethyl-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-piperidyl) imino}], 1- [2- [3- (3 , 5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate,

Dimethyl succinate and 4-hydroxy 2,2,6,6-
Condensation product of tetramethyl-1-piperidineethanol, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,
2,3,4-butanetetracarboxylate, bis [1,2,2,6,6
-Pentamethyl-4-piperidyl] sebacate, 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine, poly [6-
Morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene
[(2,2,6,6-tetramethyl-4-piperidyl) imino)}], N,
N'-bis (3-aminopropyl) ethylenediamine and 2,4-
Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -chloro-1,3-5-triazine condensate, 1,1 ′
-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazion),

Condensate of 1,2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanetetracarboxylic acid And 1,2,2,6,
6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,
5] Undecane) Condensation product with diethanol, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl -3,9- (2,4,
Condensate with 8,10-tetraoxaspiro [5,5] undecane) diethanol, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5 ] Decan-2,4-dione, 1,6-bis (2,2,6,6, -tetramethyl-4-piperidylamino) hexane and 2,4-dihalo-6-morpholino-1,3,5- Polycondensate with triazine, poly {[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine-2,4-diyl] [2- (2, 2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene- [4- (2,2,6,6, -tetramethyl-4-
Piperidyl) imino]｝, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-
And polycondensates with dibromoethane. These hindered amine light stabilizers may be used alone,
Two or more kinds may be used in combination.

The amount of the component (D) is 100
It is in the range of 0.02 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight, based on part by weight.
If the amount of the component (D) is less than 0.02 parts by weight, the weather resistance of the film is not sufficient. On the other hand, if it exceeds 1.0 part by weight, bleed out to the film surface becomes large,
The transparency of the film is deteriorated, and the weather resistance effect is not improved for the amount, which is rather economically disadvantageous.

The component (D) has a molecular weight of 700
Those having a range of -4000 are more preferred. Molecular weight 70
If it is less than 0, the component (D) tends to bleed out, so that the transparency is lowered and the weather resistance is also lowered. On the other hand, if the molecular weight exceeds 4,000, dispersibility in the polyolefin-based resin becomes poor, and transparency is lowered, which is not preferable. Further, among the components (D) having a molecular weight in the range of 700 to 4000, a hindered amine compound in which a hydrogen atom is not bonded to an N atom constituting an amine is more preferably used from the viewpoint of less yellowing.

The (E) anti-blocking agent (hereinafter referred to as component (E)) in the present invention is at least one selected from aluminosilicate and silica. These can also be used in combination. Many of the antiblocking agents other than aluminosilicate and silica, for example, talc and diatomaceous earth are not preferable because they easily cause yellowing.

As the aluminosilicate in the present invention, any of natural products and synthetic products can be used. As these compounds, those subjected to ion exchange treatment, acid treatment, heat treatment and the like can also be used. They may be crystalline or amorphous. As a method for obtaining a typical amorphous aluminosilicate, for example,
No. 1-38666, Japanese Patent Publication No. 5-42367,
JP-B 5-69865, JP-B 6-17217, JP-A-64-36631, JP-A-64-3
No. 6632 and JP-A-63-256512. Suitable commercially available amorphous aluminosilicate compounds include "trade names: Shilton AM series, Shilton AMT series, Shilton JC series, and AMT-silica series" manufactured by Mizusawa Chemical Industry Co., Ltd. Can be used.

The amount of the component (E) is 100
It is 0.05 to 3.0 parts by weight, preferably 0.1 to 2.0 parts by weight, based on parts by weight. When the amount of the component (E) is less than 0.05 part by weight, the anti-blocking property is poor. On the other hand, if it exceeds 3.0 parts by weight, the effect of improving the optical properties is inferior, which is not preferable. In the conventional polyolefin-based resin composition, when the hindered amine light stabilizer of the component (D) and the component (E) are used in combination, the resulting film is yellowed. Therefore, these components cannot be used in combination. In the present invention, the yellowing of the film is suppressed by further using the hydrotalcite-based compound as the component (B), and the components (D) and (E) can be used together. .

The (F) higher fatty acid amide (hereinafter referred to as the (F) component) in the present invention is a lubricant. As the component (F), for example, erucic acid amide, stearic acid amide, palmitic acid amide, oleic acid amide, behenic acid amide, N-stearylbutyric acid amide, N-stearylcaprylic acid amide, N-stearyllauric acid amide,
N-stearylstearic acid amide, N-stearylbehenic acid amide, N-oleyl oleic acid amide, N-
Oleyl behenic acid amide, N-butyl erucic acid amide, N-octyl erucic acid amide, N-lauryl eric acid amide, ethylene bisoleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic amide and the like.

The amount of the component (F) is 100 parts (A).
It is 0.01 to 0.3 parts by weight, preferably 0.05 to 0.2 parts by weight, based on parts by weight. If the blending amount of the component (F) is less than 0.01 part by weight, no slip property is imparted,
If the amount exceeds 0.3 parts by weight, transparency is significantly impaired due to whitening of bleed on the film surface, which is not preferable. In the conventional polyolefin-based resin composition, when the hindered amine light stabilizer of the component (D) and the component (F) are used in combination, the resulting film is yellowed, and thus these components cannot be used in combination. According to the present invention, yellowing of the film is suppressed by further using a hydrotalcite-based compound as the component (B).
The component and the component (F) can be used in combination.

The polyolefin resin composition of the present invention contains various additives usually used in polyolefin resins, such as antioxidants, ultraviolet absorbers, lubricants other than those described above, antistatic agents, antifogging agents. , A nucleating agent, a coloring agent, a clarifying agent, a metal deactivator, a radical generator, and the like can be added as long as the object of the present invention is not impaired.

As the antioxidant, phenol-based and phosphorus-based antioxidants can be preferably mentioned, and the combination thereof is particularly preferable. Specific examples of phenolic antioxidants include, for example, 2,6-di-t-butyl-4.
-Methylphenol, tocopherol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t-butyl-
4-ethylphenol, 2,6-di-t-butyl-4-methoxyphenol, octadecyl-3- (4'-hydroxy-3 ', 5'-di-
t-butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-oxamidobis [ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate], 2,2'-ethylidenebis (4,6-
Di-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis ( 2-t-butyl-5-methylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol),

N, N'-hexamethylenebis (3,5-di-t-
Butyl-4-hydroxyhydrocinnamate), hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamate, 1,1,3-tris (2-methyl-4-hydroxy-
5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,
6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane,
Bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butanoic acid] glycol ester, 1,4-benzenedicarboxylic acid bis [2- (1,1-dimethylethyl) -6- [ [3- (1,1-
(Dimethylethyl) -2-hydroxy-5-methylphenyl] methyl] -4-methylphenyl] ester, tris (3,5-di-
t-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) Ethyl] -4,6-di-t-pentylphenyl acrylate, 2-t-butyl-6- (3'-t-
Butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 3,9-bis [2- {3- (3-t-butyl-4
-Hydroxy-5-methylphenyl) propionyloxy}-
1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,
5] Undecane and the like.

Specific examples of the phosphorus antioxidant include, for example, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, bis (2,6-di-t-butyl-4-methylphenoxy) ) Diphosphospiroundecane, bis (stearyl) diphosphospiroundecan, cyclic netopentanetetraylbis (nonylphenylphosphite), bis (nonylphenylphenoxy) diphosphospiroundecane, 3,4,5,6- Dibenzo-1,2-oxaphosphane-2-oxide, tris (2,4-di-t-butylphenyl)
Phosphite, 2,4,6-tri-t-butylphenyl-2-butyl
-2-ethyl-1,3-propanediol phosphite, 2,2'-
Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methyl-phenyl] ethyl phosphite, bis (2,4-diphenyl -t-butylphenoxy) diphosphospiroundecan, trilauryltrithiophosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite 5-t-butylphenyl)
Butane, 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite,

4,4'-isopropylidenediphenolalkyl (C12-C15) phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) -di-tridecyl phosphite, diphenylisodecyl Phosphite, diphenyl mono (tridecyl) phosphite, tris- (mono and di mixed nonylphenyl) phosphite, phenyl-bisphenol A pentaerythritol diphosphite,
Di (laurylthio) pentaerythritol diphosphite, tetrakis (2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) -4,4'-biphenylene
-Di-phosphonite, tetrakis [2,6-di-t-butyl
-4- (2,4'-di-t-butylphenyloxycarbonyl) -phenyl] -4,4'-biphenylene-di-phosphonite),
Tricetyl trithiophosphite, di-t-butylphenyl-m-cresylphosphonite and condensate of biphenyl, cyclic butylethylpropanediol-2,4,6
-Tri-butylphenylphosphite, tris- [2- (2,4,
8,10-tetrabutyl-5,7-dioxa-6-phospho-dibenzo-
(a, c {cyclohepten-6-yl-oxy) ethyl] amine, calcium bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) calcium, 3,9-bis {2,4-bis (1 -
Methyl-1-phenylethyl) phenoxy {-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane.

Examples of the ultraviolet absorber include salicylate, benzophenone, triazole and anilide oxalates.

The polyolefin resin composition of the present invention comprises:
The component (A), the component (B), the component (C), the component (D), the component (E) and / or the component (F), and various additives used as desired are melt-kneaded in a conventional manner. Can be prepared. This melt kneading,
For example, it can be performed using a Henschel mixer, a single or twin screw extruder, a Banbury mixer, a roll, or the like.

The film of the present invention is a film made of a resin material containing the polyolefin resin composition of the present invention as a main component. The resin material containing the polyolefin-based resin composition of the present invention as a main component is a resin composition obtained by appropriately blending a polyolefin-based resin that can be used as the component (A). Polyolefin resin composition + LDPE, EVA, LLDPE, HDPE (LDPE: branched low-density polyethylene, EVA:
Blend compositions with ethylene-vinyl acetate copolymer, LLDPE: linear low density polyethylene, HDPE: high density polyethylene) and the like. By using the polyolefin-based resin composition of the present invention as a resin material containing 50% by weight or more, these resin materials have excellent weather resistance, molding stability, and chlorine resistance, and can be used for agricultural films and food packaging films. First, it is suitably used for various applications.

The resin material containing the polyolefin resin composition of the present invention thus prepared as a main component can be prepared by a method conventionally used for producing a polyolefin film, for example, a casting method, a calendering method, A film can be formed by an extrusion method such as a T-die method or an inflation method.

The agricultural film of the present invention is a film comprising the film of the present invention and a multilayer film of the film of the present invention and another polyolefin film. As a specific example of the multilayer film, the composition of the present invention (LLDP
E) / film layer comprising EVA film layer, composition of the present invention (LLDPE) + LDPE /
EVA film layer, film layer composed of composition of the present invention (LLDPE) / EVA film layer / film layer composed of composition of the present invention (LLDPE), film layer composed of composition of the present invention (LLDPE) + LDPE / EVA
Film layer / film layer composed of the composition of the present invention (LLDPE), film layer composed of the composition of the present invention (LLDPE) + LDPE / EVA film layer / film layer composed of the composition of the present invention (LLDPE) + LDPE, and the like. Can be Here, the composition of the present invention (LLDPE) is
The polyolefin resin composition of the present invention using LLDPE as the component (A).

[0042]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Examples 1 to 10 and Comparative Examples 1 to 1
0] 1) Preparation of resin composition Ethylene and 1-butene are copolymerized by a gas phase method using a Ziegler catalyst, the density is 0.950 g / cm ³ , and the melt index (MI) is 0.2 g / 10 min. (Polyethylene (A) component) was obtained. This powder 10
0 parts by weight of the additives shown in Table 1 were blended according to the blending ratio shown in Table 1, and these were kneaded to obtain a resin composition.

The additives used in this example are as follows. (B) Component (hydrotalcite-based compound) DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) (C) Component (Group II metal salt of higher fatty acid in the periodic table) Calcium stearate (D) Component (hindered amine-based light) Stabilizer) H-1: bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate (trade name: TINUVIN 770, manufactured by Ciba Specialty Chemicals) H-2: poly [Ｈ6- (1,1,3,3-tetramethylbutyl) amino) -1,3,5-triazine-2,4 -Diyl (2,2,6,6-tetramethyl-piperidyl) imino hexamethylene (2,2,6,6
-Tetramethyl-piperidyl) imino}] (trade name: CHI
H-3: Condensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (trade name: TINUVIN 622LD, manufactured by Ciba Specialty Chemicals) H-4) N, N'-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -Chloro-1,3-5-triazine condensate (trade name: CHIMASSORB 119, manufactured by Ciba Specialty Chemicals) H-5: tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2 , 3,4-butanetetracarboxylate (trade name: ADK STAB LA-52, manufactured by Asahi Denka Kogyo Co., Ltd.)

Component (E) (anti-blocking agent) T-1: amorphous aluminosilicate (manufactured by Mizusawa Chemical Co., trade name: Shilton JC-30) T-2: silica (manufactured by Mizusawa Chemical Co., trade name: Shilton AM)
T-30) T-3: talc (antioxidant) Antioxidant 1: octadecyl-3- (4'-hydroxy-3 ', 5'
-Di-t-butylphenyl) propionate (trade name: I
RGANOX 1076, manufactured by Ciba Specialty Chemicals) Antioxidant 2: Tris (2,4-di-t-butylphenyl) phosphite (trade name: IRGAFOS 168, manufactured by Ciba Specialty Chemicals)

2) Molding stability test Film inflation molding was carried out using the resin compositions shown in Table 1, and the molding stability was examined. Extrusion was performed using a 50 mmφ extruder (150 mmφ die) under the conditions of an extrusion rate of 35 kg / hr and a thickness of 100 μm and a width of 45 μm.
A 0 mm tubular film was obtained. Molding stability was comprehensively determined from melt fracture during molding, fluctuation of bubbles, and the degree of surging, and the thickness unevenness of the formed film. Table 1 shows the results. Table 1
The symbols shown in the column of molding stability represent the following. ：: Melt fracture, bubble fluctuation and surging were hardly observed, and the thickness unevenness of the formed film was less than 10%. Δ: Melt fracture, fluctuation of bubbles, and surging are sometimes observed. Alternatively, the thickness unevenness of the film is 10% or more.

3) Weather Resistance Test A film formed under the above conditions was subjected to an accelerated weather resistance test using a Sunshine Weatherometer manufactured by Suga Test Instruments Co., Ltd. Then, as a criterion for judging weather resistance, the time required for the elongation percentage of the film to drop to 50% immediately after molding by a tensile test was measured, and the results are shown in Table 1. The test conditions are shown below. (1) Black panel temperature: 63 ° C (2) Water spray / dry cycle: 18 minutes / 120
Minutes (3) Humidity in testing machine: 60% RH (4) Tensile test: According to ASTM D882

4) Yellowing degree (Δb value) test This shows the change in yellowness (b value) before and after the tests in a gear oven test and an ultraviolet irradiation test.
The measurement was performed using a test piece having a thickness of 5 mm which was compression molded at 00 ° C. The change in the degree of yellowing was calculated by measuring the degree of yellowing using an SM color computer manufactured by Suga Test Instruments Co., Ltd. Table 2 shows the results. The conditions of the gear oven test and the ultraviolet irradiation test are as follows. (1) Gear oven test: The test piece was left for 200 hours in a dark place at a temperature of 80 ° C. and a humidity of 70%, and the yellowness was measured. As a gear oven,
The experiment was performed using a GPS23 type oven manufactured by Tabai Seisakusho Co., Ltd. (2) UV irradiation test: The above test piece was left for 40 hours under the same conditions as shown in 3) Weather resistance test, and the yellowness was measured.

[0049]

[Table 1]

[Summary of Examples 1 to 10 and Comparative Examples 1 to 10] The results of Examples 1 to 10 and Comparative Examples 1 to 10 are summarized as follows. According to the results in Table 1, Example 1
The films molded using the resin compositions of Comparative Examples 1 to 10 exhibited better weather resistance and yellowing resistance than the films molded using the resin compositions of Comparative Examples 1 to 10.

On the other hand, hydrotalcite DHT-4A,
That is, the resin composition of the comparative example in which the hydrotalcite-based compound was not blended, that is, comparative examples 1, 3, and 5
Nos. And 7 have no problem in terms of molding stability, but the weather resistance of the resulting film is not sufficient, and the object of the present invention cannot be achieved. It is also clear that the result of the gear oven test is inferior to any of the examples in the change of the yellowing degree.

The resin compositions of Comparative Examples not containing calcium stearate, that is, the metal salt of Group II of the Periodic Table of higher fatty acids, ie, Comparative Examples 2, 4, and 6
And 8 are not sufficient in terms of molding stability, and are further inferior to the examples in terms of the weather resistance of the obtained film, so that the object of the present invention cannot be achieved. In Comparative Examples 9 and 10 using talc as an anti-blocking agent, the change in the degree of yellowing was large, and the object of the present invention could not be achieved.

Examples 11 to 20 and Comparative Examples 11 to
20] A resin composition was obtained in the same manner as in Example 1 except that the component (F) was used in place of the component (E) and the additives shown in Table 2 were blended in accordance with the blend ratios in Table 2, and various tests were performed. Was done. Table 2 shows the results. (F) component (higher fatty acid amide) S-1: stearic acid amide S-2: erucic acid amide

[0054]

[Table 2]

[Examples 11 to 20 and Comparative Examples 11 to 20]
Summary] The results of the examples and comparative examples in Table 2 are summarized as follows. According to the results in Table 2, Examples 11 to
The films molded using the resin compositions of Nos. 20 and 20 exhibited better weather resistance and yellowing resistance than the films molded using the resin compositions of Comparative Examples 11-20.

On the other hand, hydrotalcite DHT-4A,
That is, the resin composition of the comparative example in which the hydrotalcite-based compound was not blended, that is, the comparative example 11, 1
Nos. 3, 15, 17 and 19 have no problem in terms of molding stability, but the obtained film has insufficient weather resistance and cannot achieve the object of the present invention. It is also clear that the result of the gear oven test is inferior to any of the examples in the change of the yellowing degree.

In addition, the resin composition of Comparative Example not containing calcium stearate, that is, the metal salt of Group II of the Periodic Table of higher fatty acids, ie, Comparative Examples 12 and 1,
Nos. 4, 16, 18 and 20 are not sufficient in terms of molding stability, and are further inferior to the examples in terms of the weather resistance of the resulting film, failing to achieve the object of the present invention.

[0058]

As described above, the polyolefin resin composition of the present invention comprises (A) a polyolefin resin 1
The hydrotalcite-based compound (B) was added in an amount of 00 parts by weight.
01-1.0 parts by weight, (C) Periodic Table II of higher fatty acids
Group metal salt 0.01 to 1.0 part by weight, (D) hindered amine light stabilizer 0.02 to 1.0 part by weight, and (E)
Since at least one kind of anti-blocking agent selected from aluminosilicate and silica is mixed at 0.05 to 3.0 parts by weight and / or (F) 0.01 to 0.3 parts by weight of higher fatty acid amide, It is possible to continuously and stably obtain a polyolefin film having excellent weather resistance, anti-blocking properties and / or slip properties, and improved yellowing resistance to heat and ultraviolet rays.

When the molecular weight of the hindered amine light stabilizer (D) is in the range of 700 to 4000, a film having further improved weather resistance and transparency can be obtained. When the hindered amine light stabilizer (D) is a hindered amine light stabilizer in which a hydrogen atom is not bonded to an N atom constituting an amine, a film with further improved yellowing resistance can be obtained. When the polyolefin resin (A) is a linear low-density polyethylene, a film having better transparency, weather resistance and the like can be obtained.

Further, since the film of the present invention is made of a resin material containing the polyolefin resin composition of the present invention as a main component, it has excellent weather resistance, maintains anti-blocking properties and / or slip properties, and has heat and heat resistance. Improved yellowing resistance to ultraviolet light. Further, since the agricultural film of the present invention is composed of the film of the present invention or a multilayer film of the film of the present invention and another polyolefin film, the film has excellent weather resistance, anti-blocking properties and / or slip properties are maintained, In addition, yellowing resistance to heat and ultraviolet rays is improved.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08K 3/34 C08K 3/34 5/17 5/17 F term (reference) 4F071 AA15 AA16 AA18 AA19 AA20 AA21 AA59 AB26 AC09 AC12 AH01 AH04 BC01 4F100 AA20H AC10H AH02H AH03H AK03A AK03B AK63A AL05A BA02 CA07 CA17 GB01 JK15 JL09 JL09A JL14 4J002 BB031 BB051 BB121 BB151 BB171 CF202 CM012 CM022 CP09 EU0 019 EGDE0 DJ0 EG010

Claims (6)

[Claims] (1) A hydrotalcite-based compound (B) is used in an amount of 0.01 to 100 parts by weight of a polyolefin-based resin (A).
1.0 parts by weight, (C) 0.01 to 1.0 parts by weight of a metal salt of Group II of the Periodic Table of higher fatty acids, (D) 0.02 to 1.0 parts by weight of a hindered amine light stabilizer, and ( E) 0.05 to 3.0 parts by weight of at least one antiblocking agent selected from aluminosilicate and silica and / or 0.01 to 0.3 part by weight of (F) higher fatty acid amide. Polyolefin resin composition. 2. The polyolefin resin composition according to claim 1, wherein the molecular weight of the hindered amine light stabilizer (D) is in the range of 700 to 4000. 3. The polyolefin resin according to claim 2, wherein the hindered amine light stabilizer (D) is a hindered amine light stabilizer in which a hydrogen atom is not bonded to an N atom constituting an amine. Composition. 4. The polyolefin resin composition according to claim 1, wherein the polyolefin resin (A) is a linear low-density polyethylene. 5. A film comprising a resin material containing the polyolefin resin composition according to claim 1 as a main component. 6. An agricultural film comprising the film according to claim 5, or a multilayer film of the film according to claim 5 and another polyolefin film.