JP2001089609A - Polyolefin based resin composition, its film and agricultural film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyolefin based resin compositions capable of stably effecting continuous molding of polyolefin based films having excellent weatherability and chlorine resistance, and films and agricultural films obtained by molding these compositions. SOLUTION: Polyolefin based resin compositions comprise (A) 100 pts.wt. polyolefin based resin, (B) 0.01-1.0 pt.wt. hydrotalcite based compound, (C) 0.01-1.0 pt.wt. salt of a group II metal in the periodic table with a higher fatty acid, and (D) 0.02-1.0 pt.wt. hindered amine light stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyolefin resin composition, a film thereof, and an agricultural film. More specifically, the present invention relates to a method for producing a polyolefin film having excellent weather resistance and chlorine resistance continuously and stably. The present invention relates to a polyolefin resin composition that can be molded, a film thereof, and an agricultural film using the film.

[0002]

2. Description of the Related Art Conventionally, polyolefin films such as polyethylene film and polypropylene film have been used for packaging of articles such as food packaging, textile packaging, pharmaceutical packaging, miscellaneous goods packaging, agricultural films, architectural films, and household use. Widely used for applications such as wrap.

[0003] In recent years, for the purpose of increasing the marketability and productivity by semi-forcing or suppressing cultivation of agricultural products, polyolefin-based materials such as agricultural vinyl chloride films, polyethylene films, and ethylene-vinyl acetate copolymer films have been developed. BACKGROUND ART So-called house cultivation and tunnel cultivation for cultivating agricultural crops under a covering with an agricultural film such as a film are actively performed. Above all, polyolefin-based films do not contain plasticizers in the film, and because they are chemically stable, their light transmittance hardly changes even when used for a long period of time. In recent years, it has been widely used.

[0004] Since these agricultural films are used under sunlight, a polyolefin film used for agricultural films is required to have weather resistance. However, the polyolefin resin used as a raw material of the polyolefin film alone has insufficient weather resistance.

As a polyolefin resin having improved weather resistance, a polyolefin resin composition to which an ultraviolet absorber or a hindered amine light stabilizer is added has been proposed. In particular, the polyolefin resin composition used for thin agricultural films has a large effect of improving weather resistance,
A hindered amine-based light stabilizer with a small addition amount and a low cost is mainly used. However, in long-term use, the durability of the weathering effect was not yet sufficient.

[0006] Polyolefin resins, especially 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.

[0007] 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. Furthermore, agricultural films often come in contact with chlorine during pesticides or chlorine fumigation. Therefore, a residual chlorine scavenger is usually added to the polyolefin resin for the purpose of preventing the adverse effect of chlorine.

As the residual chlorine scavenger, higher fatty acid metal salts and the like are known. 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 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. Furthermore, inflation molding has the disadvantages that phenomena such as bubble fluctuation and surging are likely to occur, and that the film thickness tends to be uneven.

As described above, a polyolefin-based resin composition capable of stably and continuously forming a polyolefin-based film having excellent weather resistance and chlorine resistance has not been found yet.

[0011] On the other hand, polyolefin resins have high chargeability, and thus polyolefin films formed therefrom have problems such as adhesion of dust and mist droplets. In order to prevent this, various kinds of general antistatic agents or antifogging agents are often added to the polyolefin resin.

However, like an agricultural film,
When a hindered amine-based light stabilizer is compounded, there is a problem that the film turns yellow. Therefore, it is difficult for the conventional polyolefin-based resin composition to sufficiently satisfy the antistatic property and the weather resistance without causing yellowing.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin-based resin composition capable of stably and continuously forming a polyolefin-based film having excellent weather resistance and chlorine resistance.
An object of the present invention is to provide a polyolefin film and an agricultural film having excellent weather resistance and chlorine resistance. Further, an object of the present invention is to provide a polyolefin-based film resin composition which is excellent in weather resistance and antistatic properties, and has improved yellowing resistance, and which can be continuously and continuously formed into a polyolefin-based film resin composition, weather resistance and antistatic properties. An object of the present invention is to provide a polyolefin film and an agricultural film which are excellent and have improved yellowing resistance.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a polyolefin-based resin composition having the above-mentioned preferable properties. As a result, a hindered amine-based light stabilizer is added to the polyolefin-based resin. When the hydrotalcite-based compound or the higher fatty acid metal salt is compounded alone without lowering the molding stability of the polyolefin-based resin composition by simultaneously mixing the hydrotalcite-based compound and the higher fatty acid metal salt The present inventors have found that the weather resistance and the chlorine resistance of the polyolefin-based film can be remarkably improved as compared with the above, and have completed the present invention.

In addition, the present inventors have found that when a hindered amine light stabilizer and an antistatic agent are added to a polyolefin resin, a hydrotalcite compound and a higher fatty acid metal salt are simultaneously added to the polyolefin resin composition. The weatherability of polyolefin-based films is significantly lower than when hydrotalcite-based compounds or metal salts of higher fatty acids are used alone, without lowering the molding stability of the product and suppressing yellowing of the polyolefin-based films. And found that the chlorine resistance can be improved, and completed the present invention.

That is, the polyolefin-based resin composition of the present invention comprises (B) a hydrotalcite-based compound in an amount of 0.01 to 1.
0 parts by weight, (C) 0.01 to 1.0 part by weight of a metal salt of Group II of the periodic table of higher fatty acid, and (D) 0.02 to 1.0 part by weight of a hindered amine light stabilizer. It is characterized by. Further, the polyolefin-based resin composition of the present invention is further characterized in that 0.05 to 2.0 parts by weight of (E) a polyoxyethylene alkylamine-based compound is further blended as an antistatic agent.

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.

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.

[0019]

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 at least one kind of an α-olefin having 3 to 12 carbon atoms of preferably 0.2 to 20 mol%, more preferably 1 to 10 mol%, 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.
When the blending amount of the component (B) is less than 0.01 part by weight, the weather resistance and the chlorine resistance of the polyolefin film become insufficient, and the polyoxyethylene alkylamine compound (E) described below is used as an antistatic agent. When blended in the polyolefin resin composition, the yellowing resistance of the film becomes insufficient. 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 parts.
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 component (B) of the hydrotalcite compound and the component (C) dramatically improves the weather resistance and chlorine resistance of the resulting film.

As the hindered amine light stabilizer (D) in the present invention, various compounds usually used in agricultural films can be used. Specific examples include the following hindered amine light stabilizers. However, (D) of the present invention
The components are 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 parts (A)
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 chlorine resistance.

In the present invention, the (E) polyoxyethylene alkylamine compound (hereinafter, referred to as component (E)) to be blended as an antistatic agent includes, for example, N, N-
Bis (2-hydroxyethyl) stearylamine, N, N
-Bis (2-hydroxyesyl) laurylamine, N, N
-Bis (4-hydroxybutyl) stearylamine, N,
N-bis (4-hydroxybutyl) laurylamine, N, N
-Bis (6-hydroxyhexyl) stearylamine,
Polyoxyethylene alkylamine compounds such as N, N-bis (6-hydroxyhexyl) laurylamine,
Fatty acid ester compounds of these polyoxyethylene alkylamine compounds, and mixtures thereof.

The amount of the component (E) is 100 parts (A).
It is in the range of 0.05 to 2.0 parts by weight, preferably 0.1 to 1.0 part by weight, based on parts by weight.
When the amount of the component (E) is less than 0.05 parts by weight, the antistatic effect of the film is not sufficient. On the other hand, if it exceeds 2.0 parts by weight, problems such as bleeding on the film surface tend to occur. 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. .

In addition to the component (E), other nonionic antistatic agents such as fatty acid esters of glycerin, higher alcohols and alkyldiethanolamides can be used in combination. The combined use of other nonionic antistatic agents may increase the antistatic effect of the film.

The polyolefin resin composition of the present invention contains various additives usually used in polyolefin resins, such as antioxidants, ultraviolet absorbers, lubricants, antistatic agents other than those described above, and 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, a phenol-based or phosphorus-based antioxidant can be preferably mentioned, and a 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-hydroxybenzyl phosphite 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 salicylates, benzophenones, triazoles, and anilide oxalates.
For example, stearic acid amide, palmitic acid amide, oleic acid amide, erucic acid amide and the like can be mentioned.

The polyolefin resin composition of the present invention comprises:
It can be prepared by melt-kneading the components (A), (B), (C), (D), (E) and various additives used as desired according to a conventional method. . This melt-kneading can be performed using, for example, a Henschel mixer, a single-screw or twin-screw extruder, a Banbury mixer, a roll, or the like.

The film of the present invention is a film comprising 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-based resin composition of the present invention thus prepared as a main component can be produced by a method conventionally used for producing a polyolefin-based 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).

[0044]

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 0.922 g / cm ³ , and the melt index (MI) is 1.0 g / 10 min. Was obtained as a powder of a linear low-density polyethylene (component (A)). The additives shown in Table 1 were blended with 100 parts by weight of this powder 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.)

(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) Antioxidant 3: tetrakis (2 , 4-di-t-butylphenyl)-
4,4'-biphenylenediphosphonite (trade name: Sand)
stab P-EPQ, manufactured by Clariant Japan)

2) Molding stability test Film inflation molding was performed 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) Chlorine resistance test A chlorine-based insecticide (trade name: chlorate, manufactured by Showa Denko KK) was applied to the above film, and the same test as in 3) was performed. The time required to decrease to 50% was measured, and the results are shown in Table 1. here,
The chlorine resistance is the time required for the elongation of the film to fall to 50% immediately after molding when the chlorine-based insecticide is applied, and the time when the chlorine-based insecticide is applied and the application of the chlorine-based insecticide. Judgment was made based on two types of differences from the time when no operation was performed.

[0051]

[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 than the films molded using the resin compositions of Comparative Examples 1 to 10. Further, Examples 1 to
The film molded using the resin composition of No. 10 had a longer time until the elongation of the film decreased to 50% immediately after molding than the films molded using the resin compositions of Comparative Examples 1 to 10. It was long and showed excellent chlorine resistance.

Further, Example 7 using a hindered amine compound having a molecular weight in the range of 700 to 4000 and having no hydrogen atom bonded to the N atom constituting the amine,
8, 9, and 10 show a small difference between the time required for elongation of the film when the chlorine-based insecticide is applied to decrease to 50% immediately after molding and that when no application is made, and in terms of chlorine resistance. It turns out that it is better.

On the other hand, hydrotalcite DHT-4A,
That is, the resin composition of the comparative example containing no hydrotalcite-based compound has no problem in terms of molding stability, but the obtained film has insufficient weather resistance and chlorine resistance. Also, calcium stearate,
The resin composition of Comparative Example in which the Group II metal salt of the higher fatty acid is not blended is not sufficient in terms of molding stability, and also in terms of weather resistance and chlorine resistance, as compared with Examples. Somewhat inferior.

Examples 11 to 20 and Comparative Examples 11 to
20] 1) Preparation of resin composition Ethylene and 1-butene were copolymerized by a gas phase method using a Ziegler catalyst, the density was 0.922 g / cm ³ , and the melt index (MI) was 1.0 g / 10 min. Was obtained as a powder of linear low density polyethylene. This powder 100
The additives shown in Table 2 were blended in parts by weight according to the blending ratios in Table 2, and these were kneaded to obtain a resin composition. Also,
As the component (E), N, N-bis (2-hydroxyethyl) stearylamine was used.

In the same manner as in Example 1, 2) a molding stability test and 3) a weather resistance test were performed. Table 2 shows the results. 5) Yellowing frequency (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.

[0057]

[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
3, 15, 17, and 19 have no problem in terms of molding stability, but the weather resistance of the obtained 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 composition of Comparative Example not containing calcium stearate, that is, the metal salt of Group II of the Periodic Table of higher fatty acids, that is, 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 obtained film, so that the object of the present invention cannot be achieved.

[0061]

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
It is excellent in weather resistance and chlorine resistance because it contains 0.01 to 1.0 parts by weight of a group III metal salt and 0.02 to 1.0 parts by weight of a hindered amine light stabilizer (D). A polyolefin-based film can be obtained continuously and stably. Further, if the polyolefin resin composition of the present invention further contains 0.05 to 2.0 parts by weight of (E) a polyoxyethylene alkylamine compound as an antistatic agent, weather resistance and antistatic properties are obtained. And a polyolefin film having improved yellowing resistance can be continuously and stably obtained.

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. Further, the (D) hindered amine light stabilizer comprises:
A hindered amine-based light stabilizer in which a hydrogen atom is not bonded to an N atom constituting an amine can provide a film having further improved chlorine resistance. When the polyolefin resin (A) is a linear low-density polyethylene, a film having better transparency, weather resistance and the like can be obtained.

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 and chlorine resistance. In addition, the agricultural film of the present invention is excellent in weather resistance and chlorine resistance since it is composed of the film of the present invention or a multilayer film of the film of the present invention and another polyolefin film. When (E) a polyoxyethylene alkylamine-based compound is blended as an antistatic agent, a film and an agricultural film having excellent weatherability and antistatic properties and improved yellowing resistance are obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08K 5/17 C08K 5/17 F term (reference) 4F071 AA14 AA15 AA18 AA19 AB32 AC09 AC12 AC19 AF02 AF38 AF57 AH01 AH04 BC01 4F100 AC10H AH02H AH03H AK03A AK03B AK63 AK63A AK65 AL05A BA02 CA05 CA07 CA22 GB01 JA06A JA13A JL08A JL09 4J002 BB031 BB051 BB121 BB151 BB171 CB003 CF202 CM012 CM022 CP092 DE146 DE286 EG037 EG0FE EU088 EG037 EG048

Claims (7)

[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 part by weight, (C) 0.01 to 1.0 part by weight of a metal salt of Group II of the periodic table of higher fatty acids, and (D) 0.02 to 1.0 part by weight of a hindered amine light stabilizer. A polyolefin-based resin composition, comprising: 2. A polyoxyethylene alkylamine compound (E) as an antistatic agent in an amount of from 0.05 to 2.0.
The polyolefin resin composition according to claim 1, wherein the polyolefin resin composition is blended in parts by weight. 3. 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. 4. The polyolefin resin according to claim 3, 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. 5. The polyolefin resin composition according to claim 1, wherein the polyolefin resin (A) is a linear low-density polyethylene. 6. A film comprising a resin material containing the polyolefin resin composition according to claim 1 as a main component. 7. An agricultural film comprising the film according to claim 6, or a multilayer film of the film according to claim 6 and another polyolefin film.