JP3256816B2 - Polyolefin resin composition and film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition and a film formed therefrom, and more particularly to a polyolefin resin containing a specific phosphorus compound, hydrotalcites, an antiblocking agent, a lubricant or a surfactant. A composition obtained by adding at least one or more or a color stability, a heat stability, a corrosion resistance, an anti-blocking property, an antistatic obtained by adding a phenolic antioxidant and / or a thioether antioxidant. The present invention relates to polyolefin compositions and films having improved properties, anti-fog properties and the like.

[0002]

2. Description of the Related Art Recently, in order to reduce the cost of plastic films, higher molding speeds and thinner products have been attempted. In order to cope with these, the film forming temperature tends to be set higher than before. In addition, linear low-density polyethylene has strength even when it is thin, and has excellent heat sealing properties, so that it has been used as a sealant film instead of branched low-density polyethylene, and the range of applications in which it is used has been widened. However, the linear low-density polyethylene has a high viscosity during processing, so that it must be molded at a lower temperature than the branched low-density polyethylene. The problem in this case is
Continuous operation becomes impossible due to thermal deterioration of the resin, poor appearance due to generation of fish eyes, blocking occurs because the film is wound without being sufficiently cooled, and lubricants and antistatic agents are caused because the film is thinned. And the effect of an antifogging agent or the like may not be sufficiently exhibited.

For this reason, various antioxidants have been widely used for the purpose of preventing thermal deterioration during molding. Conventionally, these additives, especially polyolefins containing phenolic antioxidants, have a long effect. It has the disadvantage of turning yellow when stored for a period of time. Further, a method of adding a phosphorus-containing compound such as phosphite has been proposed in order to prevent deterioration during high-temperature processing. (For example, Japanese Patent Publication No. 62-4418). However, phosphorus compounds having good antioxidant performance are not yet satisfactory, such as having a disadvantage that they are easily absorbed by moisture and are difficult to handle, and are liable to cause corrosion of metals. Various oxides are used to prevent blocking, but those having a large blocking effect deteriorate the transparency of the film, and addition of zeolite is known as an oxide whose transparency is relatively maintained. (For example, Japanese Patent Application Laid-Open No. 61-101543) has a drawback such as generation of eye oil during processing due to its hygroscopicity.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to prevent yellowing during long-term storage due to the chemical action of light, oxygen and the like, deterioration during heating at high speed and high temperature processing and generation of grease, and prevent metal corrosion. It is an object of the present invention to provide a polyolefin composition in which the film has a reduced amount and to provide a film having less blocking and good opening properties.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following general formulas (I), (II) and (II)
By adding one or more of the phosphorus compounds represented by I) or (IV) and the hydrotalcites and one or more of an anti-blocking property, a lubricant and a surfactant, heat resistance is increased. It has been found that a polyolefin resin composition which is extremely excellent in properties, prevention of yellowing during long-term storage, prevention of metal corrosion, blocking of a processing path, prevention of grease, and the like can be obtained.

That is, one aspect of the present invention is to provide a polyolefin resin comprising (A) one or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV): A polyolefin resin composition comprising B) hydrotalcites and (C) an antiblocking agent:

Formula (I):

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General formula (II):

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General formula (III):

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General formula (IV):

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[0011] [is wherein R1, R2, R3 and R4 hydrogen, alkyl, aryl, alkylaryl, or arylalkyl group, _{M 1} and _{M 5} is hydrogen, periodic table group Ia alkali metals, Group IIa alkaline earth a metal or a group IIb zinc genus metals, _{M 2} and _{M 3} hydrogen or a group Ia alkali metal and _{M 4} represents a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t
Represents the valence of M ₁ and M ₅ , respectively. w is 1 or 0
It is. The present invention relates to (2) a polyolefin resin comprising: (A) one or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV); A polyolefin resin composition comprising: ()) a hydrotalcite and (D1) a lubricant.

General formula (I):

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General formula (II):

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General formula (III):

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Formula (IV):

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[0016] [is wherein R1, R2, R3 and R4 hydrogen, alkyl, aryl, alkylaryl, or arylalkyl group, _{M 1} and _{M 5} is hydrogen, periodic table group Ia alkali metals, Group IIa alkaline earth a metal or a group IIb zinc genus metals, _{M 2} and _{M 3} hydrogen or a group Ia alkali metal and _{M 4} represents a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t
Represents a valence of each of _{1, M 5} is. w is 1 or 0. And 3) a polyolefin resin comprising: (A) one or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV); ) Hydrotalcites A polyolefin resin composition containing (C) an antiblocking agent and (D2) a surfactant.

General formula (I):

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General formula (II):

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Formula (III):

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Formula (IV):

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[0021] [is wherein R1, R2, R3 and R4 hydrogen, alkyl, aryl, alkylaryl, or arylalkyl group, _{M 1} and _{M 5} is hydrogen, periodic table group Ia alkali metals, Group IIa alkaline earth a metal or a group IIb zinc genus metals, _{M 2} and _{M 3} hydrogen or a group Ia alkali metal and _{M 4} represents a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t
Represents the valence of M ₁ and M ₅ , respectively. w is 1 or 0
It is. In the present invention, the polyolefin resin comprises (A) one or two or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV) and (B) ) Hydrotalcites 1 selected from the group consisting of (C) antiblocking agents and (D) lubricants and surfactants
A polyolefin resin composition comprising at least one compound.

Formula (I):

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Formula (II):

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General formula (III):

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Formula (IV):

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[0026] [is wherein R1, R2, R3 and R4 hydrogen, alkyl, aryl, alkylaryl, or arylalkyl group, _{M 1} and _{M 5} is hydrogen, periodic table group Ia alkali metals, Group IIa alkaline earth a metal or a group IIb zinc genus metals, _{M 2} and _{M 3} hydrogen or a group Ia alkali metal and _{M 4} represents a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t
Represents the valence of M ₁ and M ₅ , respectively. w is 1 or 0
It is. ].

The present invention will be described more specifically. The polyolefin of the present invention includes ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene-1, 1
-Homopolymers or interpolymers of α-olefins such as octene, ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers, ethylene-unsaturated carboxylic acids or derivatives thereof copolymers or mixtures thereof Etc., which can be obtained by using an appropriate catalyst such as a Ziegler-based catalyst, a chromium-based catalyst, a metallocene-based (Kamminsky-based) catalyst, but is polymerized by a Ziegler-based highly active catalyst and has not undergone a catalyst removal step. It shows a remarkable effect when polyolefin is used.

In the present invention, the Ziegler-based highly active catalyst comprises a solid catalyst component containing at least magnesium and titanium and an organoaluminum compound. Examples of the solid catalyst component include: metal magnesium; magnesium hydroxide; magnesium oxide; magnesium salts such as magnesium chloride; silicon, aluminum, calcium; double salts and double oxides containing an element selected from magnesium carbonate and a magnesium atom; Carbonates, chlorides,
Or a hydroxide or the like; or an inorganic solid compound containing an oxidized compound, a sulfur-containing compound, an aromatic hydrocarbon,
Examples thereof include those in which a titanium compound is supported by a known method on an inorganic solid compound containing magnesium, such as a material treated or reacted with a halogen-containing substance.

Examples of the oxygen-containing compound include water; organic oxygen-containing compounds such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, polysiloxanes and acid amides; and inorganic compounds such as metal alkoxides and metal oxychlorides. An oxygen-containing compound can be exemplified.

Examples of the sulfur-containing compound include organic compounds such as thiol and thioether, and sulfur-containing compounds, and inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide and sulfuric acid. Examples of the aromatic hydrocarbon include various monocyclic and polycyclic and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. Examples of the halogen-containing substance include compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides. On the other hand, examples of the titanium compound to be supported on the inorganic solid compound containing magnesium include titanium halides, alkoxy halides, alkoxides, and halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and as the tetravalent titanium compound, specifically, a general formula Ti (OR) _n X _4-n (where R is 1 carbon atom) -20 represents an alkyl group, an aryl group or an aralkyl group, X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4).
Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium,
Trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium , Monobutoxytrichlorotitanium, dibutoxydichlorotitanium,
Monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, tetraphenoxytitanium and the like can be mentioned. As the trivalent titanium compound, a trihalide obtained by reducing a titanium tetrahalide such as titanium tetrachloride or titanium tetrabromide with hydrogen, aluminum, titanium or an organometallic compound of a metal of Groups I to III of the periodic table. Titanium is mentioned. The general formula Ti (OR) _n X
_4-n (where R represents an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and m is an integer of 0 ≦ m ≦ 4) A trivalent titanium compound obtained by reducing a halogenated alkoxytitanium with an organometallic compound of a metal in Groups I to III of the periodic table may be used.

Of these titanium compounds, tetravalent titanium compounds are particularly preferred. Examples of other catalyst systems include:
As a solid catalyst component, a reaction product of an organic magnesium such as a so-called Grignard compound and a titanium compound can be used.

As another example of the catalyst system, a solid substance obtained by contacting an inorganic oxide such as SiO ₂ or Al ₂ O ₃ as a solid catalyst component with the above-mentioned solid catalyst containing at least magnesium and titanium is used. It can also be used.

Specific examples of the organoaluminum compound to be combined with the solid catalyst component described above include the general formulas R ₃ Al, R ₂ Alx, RAlX ₂ , R ₂ AlOR, R
Al (OR) X and an organoaluminum compound of R ₃ Al ₂ X ₃ (where R represents an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, (May be different), and include, for example, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof.

The amount of the organoaluminum compound used is not particularly limited, but is usually 0.1 to 1, based on the titanium compound.
It can be used 000 mol times. The polymerization reaction is carried out in the same manner as in the usual polymerization reaction of olefins using a Ziegler-type catalyst. That is, all reactions are carried out in a gas phase or in a liquid phase using the monomer itself as a solvent, with substantially no oxygen, water, or the like. The olefin polymerization reaction is carried out at a temperature of 20 to 300 ° C., preferably 4 ° C.
0 to 200 ° C, pressure is from normal pressure to 70 kg / cm
² G, preferably 2 kg / cm ² G to 60 kg / c
m ² G. The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst. However, it can be effectively controlled by adding hydrogen to the polymerization system. Of course, a multi-stage polymerization reaction of two or more stages with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any trouble.

The polyolefin polymerized by the above-mentioned catalyst is clearly distinguished from a polyolefin obtained by using a conventional vanadium-based solid catalyst component as a solid catalyst component. Both are identical monomers constituting the copolymer, and even density are the same, T _n by DSC has higher polyolefins of the present invention. Also C ₆
The insoluble content of the copolymer of the present invention is 10% by weight or more, while the use of a vanadium-containing catalyst results in the absence or extremely small amount of the insoluble content.

As an example of the organic phosphite compound represented by the general formula (I) in the present invention, the phosphorus compound represented by the general formula (I) is more specifically exemplified.

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A more specific example of the phosphorus compound represented by the general formula (II) is as follows:

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A more specific example of the phosphorus compound represented by the general formula (III) is:

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A more specific example of the phosphorus compound represented by the general formula (IV) is:

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The composition of the above components used in the present invention is as follows:
0.005 to 5 based on 100 parts by weight of polyolefin
Parts by weight, preferably 0.01 to 2 parts by weight.

The hydrotalcites used in the present invention are double salt compounds represented by the following formula.

(M ²⁺ ) _1−x Al _x (OH) ₂ (A ⁿ⁻ ) _{x / n} · mH ₂ O (where 0 <x ≦ 0.5, m: real number M ²⁺ : Mg, Ca or Zn , ^{a n-:} Although both used natural products and synthetic products as n-valent anion) this compound, particularly M2 + is ^{Mg, a n-is} _CO ^{3 2-} is a synthetic desirable. The compounding composition of the above components used in the present invention is 0.00.0 parts by weight based on 100 parts by weight of polyolefin.
It is 1 to 1 part by weight, preferably 0.02 to 0.08 part by weight. By adding this component, the antioxidant performance is significantly improved more synergistically than by adding the phosphorus compound alone.

In the present invention, blocking during high-speed molding can be prevented by adding an anti-blocking agent. Examples of the anti-blocking agent include silicon oxide, zeolite, talc, and metal carbonate. Among them, amorphous zeolite has an excellent balance between blocking property and transparency.

As the silicon oxide, raw diatomaceous earth is pulverized and classified, and then calcined, or synthetic silica produced by neutralizing sodium silicate with an acid, and produced by producing and treating acid clay. Amorphous silica, fumed silica produced by combustion hydrolysis of silicon halide, and the like. The blocking effect and the transparency of the film differ depending on the particle shape and the particle system. Diatomaceous earth silica in which the jagged surface of the surface generated at the time of pulverization remains has a large blocking effect, but conversely the transparency is deteriorated. Synthetic silica having a nearly spherical shape can maintain transparency, but tends to cause blocking. The larger the particle size, the greater the blocking effect, but the lower the transparency.
From the balance between the transparency and the blocking, the silica is nearly spherical and has a particle size of 10 μm or less, preferably 2 μm or less.
の も の 6 μm is preferably used. The compounding amount is 0.05 to 2.
0 parts by weight, preferably 0.1 to 1.0 parts by weight.

As the zeolite, any zeolite-based anti-blocking agent such as a crystalline aluminosilicate salt having a zeolite structure can be used. However, there are no defects such as foaming at the time of extrusion molding and adhesion of grease to a die. Amorphous zeolite is particularly preferable because a film having good antiblocking properties and transparency can be obtained.

This amorphous zeolite is obtained by pre-treating ordinary crystalline zeolite and then dehydrating by heating. The amorphous zeolite is substantially amorphous without a crystal peak by X-ray diffraction. , Which exist as particles having a constant morphology.

The crystalline zeolite as the raw material is A type, X type,
Any of P-type and Y-type may be used, and the acid used may be an inorganic acid,
Organic acids may be used, but hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like are used. The acid is added to the aqueous slurry of the crystalline zeolite, but it is desirable to neutralize it under the condition that the final pH becomes 7.0 to 3.0. If the pH is higher than this range, the alkali in the zeolite will not be sufficiently removed, resulting in insufficient amorphous zeolite, which will cause the transparency of the film to deteriorate. If the pH is lower than this range, the alumina component in the zeolite is eluted and the cubic shape of the particles cannot be maintained, and the blocking effect becomes insufficient. This amorphous zeolite is filtered, washed with water, dried or calcined to obtain an amorphous zeolite.

Examples of other amorphous zeolites include those obtained by ion-exchanging a P-type zeolite with a divalent metal represented by Group II of the periodic table and then firing. By ion-exchanging Na contained in the P-type zeolite with Ca, Mg, Zn, etc., it becomes easy to be easily amorphized, and the hygroscopicity is further reduced. Therefore, the grease and foaming during extrusion are reduced. Further, since the compound is modified to be weakly alkaline, the hue of the compounded polyolefin is stabilized. Further, since the zeolite has a refractive index closer to that of polyolefin as an effect of substitution with a divalent metal, the transparency of the film is maintained. The ion exchange treatment is carried out by agitating a divalent metal salt aqueous solution, for example, a chloride or nitrate aqueous solution and a P-type zeolite in an aqueous slurry state, or by bringing the zeolite into contact with the metal salt aqueous solution in a fixed bed or a fluidized bed. Done. The contact temperature is suitably from 30 ° C. to 70 ° C., and the higher the temperature, the shorter the processing time. The processing time is 0.5 to 3 hours. The exchanged zeolite after the treatment is subjected to solid-liquid separation, washed with water, dried, and then calcined. As the calcination temperature, a temperature at which the exchanged zeolite is substantially non-crystallized is selected, and generally, the calcination is performed at 200 to 700 ° C. The particle size of these amorphous zeolites is 10 μm or less, preferably 1 to 5 μm.
μm is preferably used. The compounding amount is 0.05 to 2 parts by weight, preferably 0.1 to 1.0 part by weight, based on the polyolefin.

The talc used in the present invention is obtained by pulverizing and classifying natural talc. Silicon oxide has a high hardness, so if the compounding amount is large, the film may be finely scratched and white spots may occur, resulting in poor transparency. However, talc is soft and has lubricity, so that a blocking effect is obtained. And transparency is maintained. Particle size is 10 μm or less,
Desirably, those having a thickness of 2 to 5 μm are preferably used. The compounding amount is 0.05 to 3 parts by weight, preferably 0.1 to 1.0 part by weight, based on the polyolefin.

The calcium carbonate used in the present invention is a so-called heavy calcium carbonate obtained by pulverizing and classifying limestone, or limestone is roughly crushed and calcined to produce quicklime, and then hydrated to produce lime milk. Further, light calcium carbonate obtained by reacting with carbon dioxide gas generated from a firing furnace is used. In order to improve compatibility with polyolefin,
Surface-treated with fatty acids, metal soaps, silane coupling agents, titanate coupling agents, and the like may be used.
Calcium carbonate slightly degrades surface haze, but has a large blocking effect, so that the amount of calcium carbonate can be reduced, and thus the influence on haze can be suppressed to a small extent. In addition, there is a feature that white spots are hardly generated. Finer particle size is desirable, 5μm
Hereinafter, those having a thickness of 0.05 to 3 μm are preferably used. The blended amount is based on the polyolefin,
It is used in an amount of 0.05 to 3 parts by weight, preferably 0.1 to 1.0 part by weight.

In the present invention, lubricity can be imparted to the film by adding a lubricant. Examples of the lubricant include fatty acids, fatty acid esters, fatty acid metal salts, and fatty acid amides, with fatty acid amide being particularly preferred. In the present invention, since the lubricant has an effect as an acid capture, the generation of rust is also improved. As fatty acid amides, higher fatty acid amides having 8 to 22 carbon atoms,
Examples thereof include ethylene bis fatty acid amides having 16 or 18 carbon atoms, stearyl erucamide, and oleyl palmito amide. The selection of these lubricants is selected according to the molding temperature of the polyolefin, and those having a low molding temperature are selected from amides having a low melting point, and those having a high molding temperature are selected from saturated fatty acid amides having a high melting point. For example, oleic acid amide, linear low density polyethylene, and erucic acid amide and behenic acid amide are preferably used as low-density polyethylene and polypropylene. The compounding amount is 0.02 to 1 part by weight, preferably 0.03 to 0.5 part by weight with respect to the polyolefin.
Used in parts by weight. When the amount is less than 0.02 parts by weight, the lubricating effect is insufficient and the mouth opening is insufficient. When the amount is more than 1 part by weight, the amide is more likely to be blocked by bleeding.

In the present invention, a metal salt of a fatty acid, a metal salt of a hydroxy fatty acid, and a fatty acid are preferably used in combination. For example, a metal salt of a fatty acid, a metal salt of a hydroxy fatty acid and a fatty acid are exemplified by lauric acid, myristic acid and myristine. Salts of fatty acids such as acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid with salts of metals such as lithium, sodium, magnesium, calcium, and zinc are exemplified, and calcium stearate is particularly desirable.
Also, mixtures of these metal salts and fatty acids are used to improve color stability. Examples of the fatty acids include the above-mentioned fatty acids, and a mixture of stearic acid and calcium stearate is most preferably used. The composition of the above components used in the present invention is 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyolefin. In the present invention, an antistatic property and an antifogging property can be imparted to the polyolefin film by adding a surfactant.

As the surfactant, a nonionic surfactant is preferably used. Specific examples thereof include glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, and the like. Polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, trimethylolpropane fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, N, N bis (2-hydroxyethyl)
Alkylamine, N, N bis (2-hydroxyethyl)
Examples thereof include an alkyl amide, a condensate of a fatty acid and diethanolamine, and the like. As the anionic surfactant,
Examples thereof include an alkyl sulfonate, sodium dicyclohexyl sulfosuccinate, and polyoxyethylene alkyl phosphate. As the cationic surfactant,
Examples thereof include alkyl betaine, alkyl imidazoline, and alkyl alanine. These surfactants are used in an amount of 0.03 to 1 part by weight, preferably 0.1 to 0.5 part by weight, based on the polyolefin. It is used in an amount of 0.03 to 1 part by weight, preferably 0.1 to 0.5 part by weight.
If the amount is less than 0.03 parts by weight, the effect is insufficient. If the amount is more than 1 part by weight, the opening property of the film is deteriorated due to excessive surface bleeding. In the present invention, it is desirable to use in combination with the above antiblocking agent, lubricant and surfactant.

In the present invention, the heat stability can be improved by adding a phenolic antioxidant and / or a thioether antioxidant in addition to the antiblocking agent, the lubricant and the surfactant. desirable. Specific examples of phenolic antioxidants include
2,6-tert-butyl-4-methylphenol, 2-tert-
Butyl-4-methoxy-phenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-ethylidene-bis (2,4-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 1,
3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, tris (4-tert-butyl-2,6-dimethyl-3-)
(Hydroxybenzyl) isocyanurate, tetrakis-
[Methylene-3- (3'-5'-di-tert-butyl)-
4'-hydroxy-phenyl) propionate] methane, 3,9-bis [1,1-di-methyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} Ethyl] -2,4,8,1
0-tetraoxaspiro [5,5] undecane, 4,
4'-thio-bis- (3-methyl-6-tert-butylphenol) and the like. These antioxidants are 0.01 to
0.15 parts by weight is added and used.

The thioether antioxidants include dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, dimyristyl-
3,3'-thiodipropionate, pentaerythritol
Examples thereof include ru-tetrakis- (β-lauryl-thiopropionate) and 2-mercapto-5-methylbenzimidazole. These antioxidants are used in an amount of 0.01 to 0.1.
15 parts by weight are used.

The weatherability of the composition of the present invention can be improved by adding a light stabilizer such as an ultraviolet absorber and a hindered amine compound. Specific examples of the ultraviolet absorbent include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
-Hydroxy-4-octoxybenzophenone, 5,
2-hydroxybenzophenones such as 5'-methylenebis (2-hydroxy-4-methoxybenzophenone),
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-third
Octylphenyl) benzotriazole, 2- (2-hydroxy-3 ', 5'-ditertiarybutylphenyl) -5
Chlorobenzotriazole, 2- (2'-hydroxy-
3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis (4-
Benzotriazoles such as tertiary octyl-6-benzotriazole) phenol, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3'-5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl Benzoates such as -3-5-di-tert-butyl-4-hydroxybenzoate are exemplified.

As hindered amine light stabilizers, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butane tetracarboxylate, bis (1,2,2,6,
6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, 1- (2-hydroxyethyl) -2,2,6,6-
Polycondensate of tetramethyl-4-piperidinol and diethyl succinate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane and 2,4-dichloro-6-tert-octyl And polycondensates of amino-s-triazine.

If necessary, the composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metal soap, an acid absorbent, a pigment,
Fillers, plasticizers, epoxy compounds, foaming agents, antistatic agents, flame retardants, lubricants, processing aids, polar group-containing polyolefins, and the like can be included.

The film of the present invention can be formed by any conventionally known method. For general-purpose applications such as garbage bags, shopping bags, standard bags, and cleaning bags, air-cooling or water-cooling inflation molding methods are used. It is preferably used. In the case of molding LLDPE, it is desirable to use a screw exclusively for LLDPE which suppresses heat generation, instead of a commonly used full flight screw because of high viscosity during processing. LL molded at high temperature in this way
In the case of DPE or polypropylene molded by a water cooling method, the composition of the present invention is preferably used because heat resistance is required and blocking is likely to occur. In the case of forming a raw material for lamination or a wide film, a cast film forming method using a T-die is preferably used. In this case, the composition of the present invention in which not only blocking but also a metal roll and a film adhere during molding and become difficult to peel off, and a lubricant as the component (d) is also preferably used.

[0060]

Examples and Comparative Examples Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited by these. In addition, the measurement of the property in an Example and a comparative example was based on the following method.

(Sample) Polyolefin resin The same as described in Example 1 of JP-A-55-52309.
Using a solid catalyst obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride and a catalyst comprising triethylaluminum, ethylene and 1-butene were converted to 1-butene in an autoclave gas phase. -Bute
The ethylene / ethylene molar ratio to 0.13 and the total hydrogen pressure to 20%.
The copolymer was adjusted and copolymerized to obtain an ethylene / 1-butene copolymer.

The ethylene / α-olefin copolymer had a 1-butene content of 4 mol% and a density of 0.922 g / cm
³ , MFR was 2 g / 10 min.

(Initial hue) After adding various additives to the polyolefin resin, a 2 mm-thick press sheet was prepared, and its yellowness (according to JIS K7103) was measured to obtain an initial hue.

(Color Stability) In a composition containing a phenolic antioxidant, there is a practical problem that the pellets or the molded product are yellowed by long-term storage. In Examples in which a phenolic antioxidant was used in combination, an accelerated test was performed to estimate the degree of yellowing during long-term storage. That is,
After exposing a 2 mm-thick press sheet made of the prepared composition to a constant-temperature and constant-humidity bath at a temperature of 80 ° C. and a relative humidity of 90% for 2 weeks, yellowing (according to JIS K7103) was measured.

(Thermal Stability) As a measure of the thermal stability at the time of melt-kneading the composition, a change corresponding to a change in viscosity during kneading was measured. That is, the prepared composition was subjected to a temperature of 210 ° C. and a temperature of 40 ° C. using Labo Plastomill manufactured by Toyo Seiki Co.
Kneading at pm, measuring the time (minutes) until the steady torque value shows a sudden increase change for polyethylene, and measuring the reduction rate (%) of the torque value after kneading for 20 minutes for polypropylene did. This is defined as the degree of thermal deterioration.

(Corrosion Resistance) A phosphorus compound was placed in a Petri dish, and a Zemclip was left on the powder to obtain a temperature of 30%.
The sample was exposed to a constant temperature and humidity chamber at 90 ° C. and a relative humidity of 90%, and the time until rust was generated was measured.

(Film forming) Using a 50 mm LLDPE film forming machine, a die having a diameter of 100 mm and a lip gap of 2 mm was attached, and a thickness of 3 mm was formed under the following forming conditions.
A 0 μm film was formed. Molding temperature C1 C2 C3 C4 D (° C.) 200 200 200 200 200 Blow ratio: 1.9 Take-off speed: 20 m / min.

(Evaluation of Film Forming) The optical properties, blocking strength, lubricity and antistatic performance of the film were evaluated by the following methods. Optical properties: Haze measurement by ASTM D1003 Blocking strength: Two films are superimposed, and the temperature is 60 ° C.
Was left in an oven for 5 hours to forcibly block, and then the peeling strength by sliding was measured at a tensile strength of 500 mm / min. Lubricity: The coefficient of static friction between the film surfaces was measured. Antistatic performance: Surface resistivity was measured.

[0069]

Examples 1 to 13 and Comparative Examples 1 to 4 The above-mentioned polyolefin-free powder was dry-blended with various additives and then kneaded with an extruder to form pellets. The additives used in the examples and comparative examples are shown below. Component (a): As a phosphorus compound of the general formula (I), exemplified compound No. 6, No. 6 as general formula (II). 7, No. 7 as general formula (III). 12. N as the general formula (IV)
o. 17 (c) component: c-1: amorphous zeolite (Silton JC-30 manufactured by Mizusawa Chemical) c-2: diatomaceous earth (Superfloss manufactured by John Manville) c-3: talc (Micron White 5000 manufactured by Hayashi Kasei)
s) c-4: calcium carbonate (d) component: d-1: amide erucate d-2: amide behenate d-3: amide stearic acid d-4: N, N-bis (2-hydroxyethyl) stearyl Amine (e) component: e-1: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate e-2: dilaurylthiodipropionate Other phosphorus compound: p-1: Bis (2,4, -di-t-butylphenyl) pentaerythritol diphosphite Other blocking agent: m-1: crystalline zeolite

Examples 1 to 4 show examples in which the phosphorus compound of the present invention was added as the component (a). Comparative Examples 1 to 3
Shows an example in which another phosphorus compound p-1 was added. The compounds of Examples have significantly improved antioxidant performance and no rust as compared with Comparative Examples. Also, the initial hue is not yellowish.

Examples 1 and 5 to 7 show examples in which the antiblocking agent of the present invention was added as the component (c).
Comparative Example 2 shows an example containing no component (c), and Comparative Example 3 shows an example in which crystalline zeolite as another anti-blocking agent was added as the component (c). In Comparative Example 2 containing no component (c), the film was severely blocked and did not open at all. In Comparative Example 3, in which zeolite containing 24% water was blended as an equilibrium component, eye grease was generated during extrusion, and continuous operation could not be performed. Further, the transparency was excellent, but blocking occurred. In the examples, there is little eye oil and no blocking.

Examples 8 to 10 show examples in which a lubricant or a surfactant was blended as the component (d). Example 8 has less blocking, and Examples 9 and 10 containing a surfactant have smaller surface resistivity than Comparative Example 1 and have an antistatic effect.

Examples 11 to 13 show examples in which another antioxidant was further added as a component (e) to the phosphorus compound of the present invention. Comparative Example 4 shows an example in which only the component (e-1) was added. Even when the total amount of the antioxidant is the same, the antioxidant performance is synergistically improved by using the phosphorus compound and another antioxidant in combination. In Comparative Example 4, the hue changes to yellow with the passage of time and cannot be used practically.
The compositions of the examples are also stable in color.

[0074]

[Effect] By blending the above-mentioned phosphorus compound, hydrotalcite, anti-blocking agent and lubricant or surfactant with polyolefin, it has excellent heat resistance, corrosion resistance, anti-blocking performance, etc. It is possible to obtain a polyolefin resin composition and a film which does not generate and which does not yellow over time.

[0075]

[Table 1]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 5/13 C08K 5/13 5/36 5/36 5/52 5/52 (72) Inventor Fumio Sato Small in Yashio, Saitama 460 (56) References JP-A-3-181533 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23/36

Claims (10)

(57) [Claims] 1. A polyolefin resin comprising: (A) one or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV) and (B) hydrotalcites And (C) a polyolefin resin composition comprising a blocking inhibitor. General formula (I): General formula (II): General formula (III): General formula (IV): Wherein R1, R2, R3 and R4 are hydrogen, alkyl,
An aryl, alkylaryl or arylalkyl group, M ₁ and M ₅ are hydrogen, a group Ia alkali metal, a group IIa alkaline earth metal or a group IIb zinc group metal of the periodic table, M ₂ and M ₃ are hydrogen or the group Ia alkali metals and _{M 4} shows a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t represent the valencies of M ₁ and M ₅ respectively. w is 1 or 0. ] 2. A polyolefin resin comprising: (A) one or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV) and (B) hydrotalcites And (D1) a polyolefin resin composition containing a lubricant. General formula (I): General formula (II): General formula (III): General formula (IV): Wherein R1, R2, R3 and R4 are hydrogen, alkyl,
An aryl, alkylaryl or arylalkyl group, M ₁ and M ₅ are hydrogen, a group Ia alkali metal, a group IIa alkaline earth metal or a group IIb zinc group metal of the periodic table, M ₂ and M ₃ are hydrogen or the group Ia alkali metals and _{M 4} shows a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t represent the valencies of M ₁ and M ₅ respectively. w is 1 or 0. ] 3. A polyolefin resin comprising: (A) one or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV) and (B) hydrotalcites A polyolefin resin composition comprising (C) an antiblocking agent and (D2) a surfactant. General formula (I): General formula (II): General formula (III): General formula (IV): Wherein R1, R2, R3 and R4 are hydrogen, alkyl,
An aryl, alkylaryl or arylalkyl group, M ₁ and M ₅ are hydrogen, a group Ia alkali metal, a group IIa alkaline earth metal or a group IIb zinc group metal of the periodic table, M ₂ and M ₃ are hydrogen or the group Ia alkali metals and _{M 4} shows a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t represent the valencies of M ₁ and M ₅ respectively. w is 1 or 0. ] 4. A polyolefin resin comprising: (A) one or more phosphorus compounds represented by the following general formulas (I), (II), (III) or (IV) and (B) hydrotalcites 1 selected from the group consisting of (C) an antiblocking agent and (D) a lubricant and a surfactant.
A polyolefin resin composition comprising at least one compound. General formula (I): General formula (II): General formula (III): General formula (IV): Wherein R1, R2, R3 and R4 are hydrogen, alkyl,
An aryl, alkylaryl or arylalkyl group, M ₁ and M ₅ are hydrogen, a group Ia alkali metal, a group IIa alkaline earth metal or a group IIb zinc group metal of the periodic table, M ₂ and M ₃ are hydrogen or the group Ia alkali metals and _{M 4} shows a group IIa alkaline earth metals or the group IIb zinc genus metals. s and t represent the valencies of M ₁ and M ₅ respectively. w is 1 or 0. ] 5. The polyolefin resin composition according to claim 1, further comprising (E) a hindered phenol antioxidant and / or a thioether antioxidant. 6. The polyolefin resin composition according to claim 1, wherein the polyolefin resin is polymerized using a highly active Ziegler-based resin and has not been subjected to a deashing step. 7. The method according to claim 1, wherein the antiblocking agent is silicon oxide,
Zeolite claim 1 or one or more antiblocking agents selected from the group consisting of talc and carbonates
The polyolefin resin composition according to any one of items 3 to 6 . 8. The polyolefin resin according to claim 2 , wherein the lubricant is at least one lubricant selected from the group consisting of metal salts of fatty acids, metal salts of hydroxy fatty acids, and higher fatty acid amides. Composition. 9. The polyolefin resin composition according to claim 3 , wherein the surfactant is a nonionic surfactant. 10. A film formed using the resin composition according to claim 1. Description: