JP2001089611A - 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 which excel in heat aging resistance and weatherability and, simultaneously, have improved yellowing resistance against heat and ultraviolet rays, 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, (D) 0.02-1.0 pt.wt. hindered amine light stabilizer, and (D) 0.01-1.0 pt.wt. specific phenolic antioxidant such as 3,9-bis[2- 3-(3-tert-butyl-4-hydroxy-5- methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5 ,5]undecane.

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 a polyolefin resin composition having excellent heat aging resistance and weather resistance and improved yellowing resistance to heat and ultraviolet rays. The present invention relates to a polyolefin-based resin composition capable of continuously and stably forming a polyolefin-based film or a polyolefin-based film further provided with an antistatic property, a film thereof, and an agricultural film using the film.

[0002]

2. Description of the Related Art Polyolefin resins have excellent mechanical properties and are very useful as molded articles, films, fibers and the like. However, in order to improve the thermal stability during molding or heat aging resistance of the polyolefin resin, a heat stabilizer (antioxidant) such as a phosphorus, sulfur or phenol compound is added to the polyolefin resin. , There is a problem that the molded product etc. is yellowed by heat and ultraviolet rays

[0003] Further, hindered amine light stabilizers are often blended in films requiring weather resistance, such as agricultural coating materials. In this case, the problem that the molded product turns yellow has become more remarkable. Therefore, it has become clear that a conventional polyolefin film cannot be mixed with various additives without causing yellowing, so that a polyolefin-based film sufficiently satisfying the heat aging resistance and the weather resistance cannot be obtained.

[0004] Polyolefin-based resins, particularly polyolefin-based resins produced using a Ziegler-type catalyst, contain halides (residual chlorine) originating from the used catalyst. 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.

[0005] 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.

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-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 is excellent in heat aging resistance and weather resistance and which can continuously and continuously form a polyolefin film having improved yellowing resistance to heat and ultraviolet rays has not been found yet. is the current situation.

[0009] 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.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin-based film which is excellent in heat aging resistance and weather resistance and has improved yellowing resistance to heat and ultraviolet rays, or a polyolefin further provided with antistatic properties. An object of the present invention is to provide a polyolefin-based resin composition capable of stably and continuously forming a system film, a film thereof, and an agricultural film using the film.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a polyolefin resin composition having the above-mentioned preferable properties. As a result, a hindered amine light stabilizer and an antioxidant were added to the polyolefin resin. By adding a hydrotalcite-based compound and a higher fatty acid metal salt at the same time when the agent is added, heat resistance can be maintained without deteriorating the molding stability of the polyolefin-based resin composition and suppressing yellowing of the polyolefin-based film. It has been found that the aging property can be maintained, 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, and the present invention has been completed.

That is, the polyolefin-based resin composition of the present invention comprises (A) 100 parts by weight of a polyolefin-based resin and (B) a hydrotalcite-based 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) The following (E
-1) to 0.01 to 1.0 parts by weight of at least one selected from phenolic antioxidants (E-5). (E-1) 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, (E-2) 1,3,5-trimethyl-2, 4,6-Tris (3,5-
Di-t-butyl-4-hydroxybenzyl) benzene, (E
-3) (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, (E-4) (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, (E-5) ) 1,3,
5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

The polyolefin resin composition of the present invention may further contain 0.05 to 2.0 parts by weight of (F) a polyoxyethylene alkylamine compound as an antistatic agent. The molecular weight of the hindered amine light stabilizer (D) is preferably in the range of 700 to 4000. 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-based 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.

[0016]

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 the (C) component) 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-based light stabilizer (hereinafter, referred to as the component (D)) in the present invention, various compounds usually blended with a polyolefin-based resin 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 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 less yellowing.

In the present invention, (E) a phenolic antioxidant (hereinafter referred to as a component (E)) includes the following (E-1)
To (E-5). These phenolic antioxidants may be used in combination. (E-1) 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, (E-2) 1,3,5-trimethyl-2, 4,6-Tris (3,5-
Di-t-butyl-4-hydroxybenzyl) benzene, (E
-3) (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, (E-4) (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, (E-5) ) 1,3,
5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

The amount of the component (E) is 100
It is 0.01 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight based on part by weight. When the amount of the component (E) is less than 0.01 part by weight, the antioxidant effect (heat aging resistance) is obtained.
Is inferior. On the other hand, if it exceeds 1.0 part by weight, it is not preferable in terms of improvement of yellowing resistance, and it is not economical when comparing the effect of antioxidation and the cost. 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, although yellowing is less than that of the phenolic antioxidant other than the component (E), the yellowing is still low. The effect is not enough. In the present invention, yellowing of the film is suppressed by further using the hydrotalcite-based compound as the component (B), and the effect of using the components (D) and (E) in combination is further increased. I have.

In the present invention, examples of the (F) polyoxyethylene alkylamine compound (hereinafter, referred to as component (F)) blended as an antistatic agent include, 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 (F) 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 (F) is less than 0.05 part 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, even if the hindered amine light stabilizer of the component (D) and the component (F) are used in combination, the effect is still insufficient. In the present invention, yellowing of the film is suppressed by further using the hydrotalcite-based compound as the component (B), and the effect of using the component (D) and the component (F) together is further increased. I have.

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.

In the polyolefin resin composition of the present invention, various additives usually used for the polyolefin resin, for example, an antioxidant other than those described above, an ultraviolet absorber, a lubricant, an antistatic agent other than the above, An anti-fogging agent, a nucleating agent, a coloring agent, a clarifying agent, a metal deactivator, a radical generator and the like can be added within a range that does not impair the object of the present invention.

As the antioxidant other than the above, a phosphorus-based antioxidant can be preferably mentioned, and the combination with the phenol-based antioxidant is particularly preferable.
Specific examples of phosphorus antioxidants include, for example, 3,5-di-t-
Butyl-4-hydroxybenzyl phosphite diethyl ester, bis (2,6-di-t-butyl-4-methylphenoxy) diphosphospiroundecan, bis (stearyl) diphosphospiroundecan, cyclic netopentantetraylbis (Nonylphenylphosphite), bis (nonylphenylphenoxy) diphosphospiroundecan,
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-di-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:
The component (A), the component (B), the component (C), the component (D), and the component (E) are melt-kneaded with the component (F) and other various additives used as desired according to a conventional method. Can be prepared. 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).

[0041]

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) (phenolic antioxidant) The phenolic antioxidant of (E-1) to (E-5), and AO-6: octadecyl-3- (4'-hydroxy-3 ') , 5'-di-
t-butylphenyl) propionate (trade name: IRG)
ANOX 1076, manufactured by Ciba Specialty Chemicals) AO-7: 2,6-di-t-butyl-4-methylphenol (phosphorous antioxidant) Tris (2,4-di-t-butylphenyl) phosphite ( Product 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.

[0048]

[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 addition, (E-1) to (E-
The resin compositions containing phenolic antioxidants other than 5), that is, Comparative Examples 9 and 10, have good molding stability and weather resistance, but have a large change in yellowing degree and cannot achieve the object of the present invention.

Examples 11 to 20 and Comparative Examples 11 to
20] Further, as an antistatic agent of the component (F), N, N-
A resin composition was obtained and subjected to various tests in the same manner as in Example 1 except that bis (2-hydroxyethyl) stearylamine was used and the additives shown in Table 2 were blended in accordance with the blending ratios in Table 2. Table 2 shows the results.

[0053]

[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, and 17 have no problem in terms of molding stability,
The weather resistance of the obtained film is not sufficient, and the object of the present invention cannot be achieved. Also, in the change of the yellowing frequency,
It is clear that the gear oven test results are inferior to any of the examples.

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, and 18 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. Also, (E-
The resin compositions containing phenolic antioxidants other than 1) to (E-5), that is, Comparative Examples 19 and 20, have good molding stability and weather resistance, but have a large change in yellowing degree, and the present invention Cannot achieve the purpose of

[0057]

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 it is obtained by mixing 0.01 to 1.0 part by weight of at least one selected from the phenolic antioxidants of (E-1) to (E-5), heat aging resistance and weather resistance And a polyolefin film having improved yellowing resistance to heat and ultraviolet rays can be continuously and stably obtained.

Further, (F) a polyoxyethylene alkylamine-based compound as an antistatic agent.
When 0 parts by weight is added, the resulting film can be provided with antistatic properties while suppressing yellowing 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. Also,
When the polyolefin-based resin (A) is a linear low-density polyethylene, a film having better transparency and weather resistance 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 heat aging resistance and weather resistance, and has improved yellowing resistance to heat and ultraviolet rays. You. 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, it is excellent in heat aging resistance and weather resistance, and yellowing resistance to heat and ultraviolet rays. Is improved.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/159 C08K 5/159 5/16 5/16 5/17 5/17 5/3492 5/3492 C08L 23/06 C08L 23/06 F term (reference) 4F071 AA14 AB21 AC09 AC11 AC12 AC19 AE05 AE16 AH01 BB02 BB04 BB05 BC01 4J002 BB031 BB121 BB171 DE286 EF057 EL129 EN100 EU088 EU199 FD048 FD079 FD100 GA01

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 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 resin composition comprising 0.01 to 1.0 parts by weight of at least one selected from the following phenolic antioxidants (E-1) to (E-5). (E-1) 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, (E-2) 1,3,5-trimethyl-2, 4,6-Tris (3,5-
Di-t-butyl-4-hydroxybenzyl) benzene, (E
-3) (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, (E-4) (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, (E-5) ) 1,3,
5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 2. A polyoxyethylene alkylamine compound (F) of 0.05 to 2.0 as an antistatic agent.
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.