JP2002194152A - Plyolefin resin composition having dirt resistance for its processing machine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin composition in which thermal stability in processing, dirt resistance for its processing machine, corrosion resistance and color tone are excellent, a molded article and a film which consist of the resin composition. SOLUTION: The polyolefin resin composition consists of (A) a 100 pts.wt. polyolefin resin, (B) a 0.001-0.2 pts.wt. neutralizing agent, (C) a 0.01-1.0 pts.wt. phosphates shown in general formula (I). In this composition, (B) the neutralizing agent is preferably inorganic, and the inorganic neutralizing agent is more preferably at least one component selected from hydrotalcite, and an oxide or a hydroxide of an alkali earth metal.

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 molded article and a film made of the resin composition. More specifically, the present invention relates to a polyolefin-based resin composition excellent in thermal stability during processing, stain resistance of a processing machine, corrosion resistance, and color tone, and a molded article and a film made of the resin composition.

[0002]

2. Description of the Related Art Polyolefin resins have good moldability.
Because of its excellent appearance, mechanical properties, chemical resistance, packaging suitability, etc., it is widely used in the fields of packaging materials such as food and fiber, containers, medical applications, containers, home appliances, automotive interior and exterior products, etc. . Generally, a polyolefin-based resin is usually heated, melted and kneaded using an extruder or the like in a temperature range of 180 ° C. to 300 ° C. to form a pellet, and further molded into various products according to the intended use. However, because the thermal stability of the polyolefin resin during processing is not sufficient, the resin is affected by the shearing force of the extruder used for processing, high-temperature heat, and residual catalyst such as halogens and transition metals remaining in the resin. May be decomposed and product characteristics may not be sufficiently obtained. Furthermore, metal parts such as an extruder, a molding machine, a molding die, and a cooling roll used for processing may be corroded or rusted due to the halogen-containing catalyst residue.

[0003] In order to solve the above problems, a method for improving the thermal stability during processing of a polyolefin-based resin to prevent the decomposition of the resin, and for preventing corrosion and rusting of a metal part of an extruder used for processing. Conventionally, a method of adding a neutralizing agent and various antioxidants to a polyolefin resin has been known. For example, JP-A-52-49258 discloses that
Hydrotalcites as a neutralizer and Irganox from Ciba Geigy as an antioxidant are added to polypropylene.
A polyolefin composition excellent in rust resistance and yellowing resistance, in which 1010 and 2,6-di-tert-butyl-4-methylphenol are blended, is described.

Further, the latest technology of polymer additives (CMC Corporation, Chapter 11, pages 250 to 254, 19)
1998) describes a phosphorus-based antioxidant, which suppresses the deterioration of the polymer during processing and at the same time suppresses the coloring of the polymer during heating and light irradiation, and is used in combination with a phenolic antioxidant. Is common, and
It is described that the water resistance is poor and a derivative formed by hydrolysis causes rust of a molding machine.

As described above, even if a polyolefin-based resin composition obtained by blending a polyolefin-based resin with at least one neutralizing agent and at least one conventionally known antioxidant is used, heat stability during processing can be improved. However, it has not been possible to satisfy all of the prevention of corrosion and rusting of the processing machine and the color tone of the polyolefin-based resin composition, and further improvement has been desired for these.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin resin composition which is excellent in thermal stability during processing, stain resistance, corrosion resistance and color tone of a processing machine, and a molding comprising the resin composition. To provide body and film.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the present invention can solve the above-mentioned problems, and have completed the present invention. That is, the present invention provides a polyolefin resin (A) 100 parts by weight, a neutralizing agent (B)
0.001 to 0.2 parts by weight, the following general formula (I) (Wherein R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, and R ³ represents a hydrogen atom or 1 carbon atom.
To 8 alkyl groups. X is a sulfur atom or -CH
An R ⁶ -group (R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms),
n is 0 or 1. A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ⁷ ) m- group (R ⁷ represents an alkylene group having 1 to 8 carbon atoms, and * represents a portion bonding to an oxygen atom; Represents 0 or 1.). Y and Z are
One of them represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The present invention relates to a polyolefin-based resin composition comprising 0.01 to 1.0 parts by weight of a phosphite (C) represented by the formula (1), a molded article and a film comprising the resin composition. Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin resin (A) used in the present invention is a polyethylene resin, a polypropylene resin, or another olefin resin,
These polyolefin resins may be used alone or in combination of two or more.

Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, linear low-density polyethylene which is a copolymer of ethylene and α-olefin, and elastomer.

The polypropylene resin is a polymer or a copolymer obtained by polymerizing a monomer containing propylene as a main component. Examples thereof include a homopolymer of propylene, a propylene-ethylene random copolymer, and propylene-α. An olefin random copolymer, a propylene-ethylene-α-olefin random copolymer, a propylene homopolymer component or a copolymer component obtained by polymerizing a monomer mainly composed of propylene, and propylene and ethylene and / or α. A polypropylene-based copolymer comprising an olefin copolymer component;

The other olefin-based resin is a polymer or a copolymer obtained by polymerizing a monomer having an olefin other than ethylene and propylene as a main component,
For example, a homopolymer of an α-olefin and the like can be mentioned.

The α-olefin is not particularly limited, but is preferably an α-olefin having 4 to 12 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- Examples thereof include pentene, 1-octene, 1-decene, and more preferably 1-butene and 1-butene.
Hexene, 1-octene.

The high-density polyethylene is an ethylene homopolymer having a density obtained by polymerizing ethylene exceeding 0.935 g / cm ³ , and the low-density polyethylene is a polymer having a density obtained by polymerizing ethylene having a density of 0.1 g / cm ³ . It is an ethylene homopolymer of 935 g / cm ³ or less. Linear low-density polyethylene, which is a copolymer of ethylene and α-olefin, refers to ethylene and α-olefin having a density exceeding 0.88 g / cm ^3.
It is a copolymer of olefin, and the elastomer is a copolymer of ethylene and α-olefin having a density of 0.88 g / cm ³ or less.

The linear low-density polyethylene or elastomer which is a copolymer of ethylene and α-olefin includes, for example, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene Copolymer, ethylene-4-methyl-1-pentene copolymer,
Examples thereof include an ethylene-1-octene copolymer and an ethylene-1-decene copolymer.

Examples of the propylene-α-olefin random copolymer include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, a propylene-1-octene random copolymer and the like. .

Examples of the propylene-ethylene-α-olefin copolymer include, for example, propylene-ethylene-1-
Butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer and the like.

The main component of a propylene homopolymer component or a copolymer component obtained by polymerizing a monomer mainly composed of propylene, and a copolymer component of propylene and ethylene and / or an α-olefin are mainly used in a polypropylene copolymer. Examples of the copolymer component obtained by polymerizing a monomer composed of propylene include a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, and the like. Examples of the copolymer component of propylene with ethylene and / or α-olefin include propylene-ethylene copolymer component, propylene-ethylene-1-butene copolymer component, and propylene-ethylene-1-hexene copolymer. Coalescence component, propylene-ethylene-1-octene copolymer component, propylene Len-1-butene copolymer component, propylene-1-hexene copolymer component, propylene-1
-Octene copolymer component. The content of ethylene and / or α-olefin in the copolymer component of propylene and ethylene and / or α-olefin is not particularly limited, but is usually 0.01 to 70% by weight.

Examples of the propylene homopolymer component or a copolymer component obtained by polymerizing a monomer mainly composed of propylene, and a polypropylene copolymer composed of a copolymer component of propylene and ethylene and / or an α-olefin include: For example, (propylene)-(propylene-ethylene) copolymer, (propylene)-(propylene-ethylene-1-butene) copolymer, (propylene)-(propylene-ethylene-1-hexene) copolymer, (Propylene)-(propylene-1-butene) copolymer, (propylene)-(propylene-1-hexene) copolymer,
(Propylene-ethylene)-(propylene-ethylene)
Copolymer, (propylene-ethylene)-(propylene-
(Ethylene-1-butene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-hexene) copolymer, (propylene-ethylene)-(propylene-1-
(Butene) copolymer, (propylene-ethylene)-(propylene-1-hexene) copolymer, (propylene-1-
(Butene)-(propylene-ethylene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-)
(Butene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-hexene) copolymer, (propylene-1-butene)-(propylene-1-butene) copolymer, (propylene-1) -Butene)-(propylene-
1-hexene) copolymer and the like.

The polyolefin resin (A) used in the present invention is preferably a linear low-density polyethylene which is a copolymer of ethylene and an α-olefin, a propylene homopolymer, or a propylene-α-olefin random copolymer. A polypropylene-based copolymer composed of a copolymer component obtained by polymerizing a propylene homopolymer component or a monomer mainly composed of propylene, and a copolymer component of propylene and ethylene and / or an α-olefin. . More preferably, a polypropylene copolymer comprising a propylene homopolymer component or a copolymer component obtained by polymerizing a monomer mainly composed of propylene, and a copolymer component of propylene and ethylene and / or an α-olefin It is.

The method for producing the polyolefin resin (A) used in the present invention is not particularly limited, and it can be produced by a known polymerization method using a known polymerization catalyst. Examples of the polymerization catalyst include, for example, a Ziegler-type catalyst containing a titanium component and a halogen component as a main component, a Ziegler-Natta type catalyst, and a catalyst system comprising a transition metal compound of Group IV of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane. Or a catalyst system comprising an organoaluminum compound and a compound which reacts therewith with a transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl ring to form an ionic complex.

Examples of the polymerization method of the polyolefin resin (A) include a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method using no solvent, and a gas phase polymerization method. A polymerization method in which two or more of these are combined, for example, a liquid-gas phase polymerization method and the like can be mentioned.
These polymerization methods may be a batch type or a continuous type. Preferably, it is a continuous gas phase polymerization method.

The method of polymerizing the polyolefin resin (A) may be a method of polymerizing in one step or a method of polymerizing in two or more steps. Particularly, production of a polypropylene-based copolymer composed of a propylene homopolymer component or a copolymer component obtained by polymerizing a monomer mainly composed of propylene, and a copolymer component of propylene and ethylene and / or an α-olefin. As the method, preferably, a step of producing a propylene homopolymer component or a copolymer component obtained by polymerizing a monomer mainly composed of propylene, and a step of producing a copolymer component of propylene and ethylene and / or an α-olefin. This is a multi-stage manufacturing method including two or more stages.

In the production of the polyolefin resin (A), a step of decalcifying the catalyst residue remaining during the polymerization after the polymerization of the polyolefin resin (A) may or may not be used. In order to remove the residual solvent contained in the polyolefin resin (A) and the ultra-low molecular weight oligomer produced as a by-product during the polymerization, the polyolefin resin (A) is optionally replaced with the resin (A). Drying may be performed at a temperature lower than the melting temperature. As a drying method,
For example, JP-A-55-75410, Japanese Patent No. 256
No. 5753, and the like.

The total weight of the residue resulting from the polymerization catalyst contained in the polyolefin resin (A) used in the present invention is:
There is no particular limitation, but preferably 1000 pp in atom conversion.
m, and the halogen contained in the polyolefin-based resin (A) is not limited, but is preferably less than 100 ppm. Usually, the metal component in the residue caused by the polymerization catalyst is measured by an ICP emission method, and the halogen is measured by using ion chromatography. In particular, the content of the metal component is preferably less than 10 ppm of a metal atom (titanium, zirconium, hafnium) of Group IV of the periodic table,
Less than 20 ppm of magnesium, 500 of aluminum
ppm, more preferably 5 ppm or less of Group IV metal atoms, 10 ppm or less of magnesium, and 200 ppm of aluminum. More preferably, 5 ppm or less of Group IV metal atoms and 5 ppm or less of magnesium. , Aluminum is 100 ppm or less. The halogen content is preferably 5
0 ppm or less, more preferably 20 ppm or less.

The melt index (MI) of the polyolefin resin (A) used in the present invention, measured at a load of 2.16 kg, is not particularly limited, and is arbitrarily determined according to the processing method and application. However, from the viewpoint of moldability, it is usually preferably 0.01 to 300 g / 10 min, more preferably 0.1 to 200 g / 10 min, and still more preferably 0.1 to 100 g / 10 min. is there.

The neutralizing agent used in the present invention includes an organic neutralizing agent and an inorganic neutralizing agent. Examples of the organic neutralizing agent include metal salts of higher fatty acids (metal soaps). Examples of the inorganic neutralizing agent include hydrotalcite, alkaline earth metal oxides and hydroxides, and the like. Preferred are inorganic neutralizers, and more preferred are oxides or hydroxides of hydrotalcite and alkaline earth metals. These neutralizing agents may be used alone or in combination of at least two or more.

The metal salts of higher fatty acids (metal soaps) are higher fatty acids such as lauric acid, ricinoleic acid, palmitic acid and stearic acid and metal salts of groups I and II of the periodic table. , Mg, Li, Z
n and Ba.

Hydrotalcite is defined by the following general formula (I)
It is an anion-exchangeable layered compound represented by I). [M²⁺ _1-XM³⁺ _X(OH)_Two]^{X +}[A^n- _{X / n}・ MH_TwoO]^X- Formula (II) [M²⁺ _1-XM³⁺ _X(OH)_Two]^{X +}Is the basic layer, [A^n-
_{X / n}・ MH_TwoO]^X-Is an intermediate layer. M²⁺Is Mg²⁺, M
n²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn ²⁺Etc. 2
Is a valent metal cation;³⁺Is Al³⁺, Fe³⁺, Cr
³⁺, Co³⁺, In³⁺And the like. A^n-
Is OH^-, F^-, Cl^-, Br^-, NO^3-, CO_Three ^2-, S
O_Four ^2-, Fe (CN)₆ ^3-, CH_ThreeCOO^-, Oxalate ion
N-valent anions such as salicate ions,
Is a positive integer. X is 0 <X ≦ 0.33, and m
Is a positive number. The above hydrotalcite is a natural mineral
Or a synthetic product, and its crystal structure
Used regardless of the structure, crystal particle size, water content, surface treatment, etc.
Can be

Of the hydrotalcites represented by the above general formula, preferred is a hydrotalcite represented by the following formula (III). Mg _Y Al ₂ (OH) _{2 Y + 4} CO ₃ .mH ₂ O Formula (III) (where Y is Y ≧ 4 and m is a positive number.)

More preferably, M ^{2+ of the} general formula (III)
Is composed of any one of Mg ²⁺ and Zn ²⁺ or two kinds of divalent metal cations, and particularly preferred is the following hydrotalcite. _{Mg 4.5 Al 2 (OH) 13} CO 3 · 3H 2 O Mg 4.5 Al 2 (OH) 13 (CO 3) 0.8 · O 0.2 Mg 4 Al 2 (OH) 12 CO 3 · 3H 2 O Mg 5 Al 2 (OH ₁₄ CO ₃ .4H ₂ O Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O (natural mineral) Zn ₄ Al ₂ (OH) ₁₂ CO ₃ .mH ₂ O (m is 0 to 4) Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ · mH ₂ O (m is 0 to
4)

The oxide or hydroxide of an alkaline earth metal is an oxide or hydroxide of a metal atom belonging to Group II of the periodic table, for example, calcium oxide, magnesium oxide,
Examples include calcium hydroxide and magnesium hydroxide. Preferably it is calcium hydroxide.

The neutralizing agent used in the present invention is not particularly limited, but a powdery one is preferably used because of its excellent dispersibility. The average particle size is not particularly limited, but is preferably 50 μm or less, more preferably 10 μm or less, and still more preferably 5 μm.
It is as follows.

The amount of the neutralizing agent used in the present invention is 0.001 to 100 parts by weight of the polyolefin resin.
０．２0.2 parts by weight. Preferably, 0.001-0.
1 part by weight, more preferably 0.005 to 0.05
Parts by weight.

If the amount of the neutralizing agent is less than 0.001 part by weight, the catalyst residue may not be sufficiently deactivated, and the corrosiveness (prevention of rust generation) of the processing machine may be insufficient. , 0.2
If the amount exceeds the weight part, discoloration of the molded article and decomposition of the stabilizer may occur, and it is not economical.

The phosphites (C) used in the present invention are represented by the following general formula (I) (Wherein R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, and R ³ represents a hydrogen atom or 1 carbon atom.
To 8 alkyl groups. X is a sulfur atom or -CH
An R ⁶ -group (R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms),
n is 0 or 1. A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ⁷ ) m- group (R ⁷ represents an alkylene group having 1 to 8 carbon atoms, and * represents a portion bonding to an oxygen atom; Represents 0 or 1.). Y and Z are
One of them represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ).

In the phosphites (C) represented by the general formula (I), the substituents R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl having 1 to 8 carbon atoms. Group,
Cycloalkyl group having 5 to 8 carbon atoms, 6 to 6 carbon atoms
12 alkylcycloalkyl groups, having 7 to 12 carbon atoms
Represents an aralkyl group or a phenyl group.

Here, representative examples of the alkyl group having 1 to 8 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec- A butyl group, a t-butyl group, a t-pentyl group, an i-octyl group, a t-octyl group, a 2-ethylhexyl group and the like are exemplified. As a typical example of a cycloalkyl group having 5 to 8 carbon atoms, for example, cyclopentyl Group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Representative examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl -4
-I-propylcyclohexyl group and the like. Representative examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group and an α, α-dimethylbenzyl group.

R ¹ , R ² and R ⁴ are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkylcycloalkyl group having 6 to 12 carbon atoms. Among them, R ¹ and R ⁴ are more preferably a t-alkyl group such as a t-butyl group, a t-pentyl group, a t-octyl group, a cyclohexyl group, and a 1-methylcyclohexyl group.

R ² is more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl,
An alkyl group having 1 to 5 carbon atoms such as a t-pentyl group, and more preferably a methyl group, a t-butyl group, and a t-pentyl group.

R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, more preferably a hydrogen atom, a methyl group,
Alkyl groups having 1 to 5 carbon atoms such as ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and t-pentyl group. .

The substituent R ³ is a hydrogen atom or a group having 1 carbon atom.
Represents an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above. It is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

The substituent X, when n is 0, indicates that two groups having a phenoxy group skeleton are directly bonded, and when n is 1, when it is 1, a sulfur atom or a carbon atom having 1 carbon atom.
Represents a methylene group which may be substituted by an alkyl group having from 8 to 8 or a cycloalkyl group having from 5 to 8 carbon atoms.
Here, examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms which are substituted on the methylene group include the same alkyl groups and cycloalkyl groups as described above. As the substituent X, n is preferably 0
Wherein two groups having a phenoxy group skeleton are directly bonded, or n is 1, and a methylene group or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group , I-butyl group, t-butyl group and the like.

The substituent A is an alkylene group having 2 to 8 carbon atoms or a * -CO (R ⁷ ) m- group (where R ⁷ is
In the alkylene group of 8, * indicates that the moiety is bonded to an oxygen atom, and m is 0 or 1. ).

Here, typical examples of the alkylene group having 2 to 8 carbon atoms include ethylene group, propylene group,
Examples thereof include a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a 2,2-dimethyl-1,3-propylene group, and a propylene group is preferable. Further, * in the * -COR ⁷ -group indicates that the carbonyl group is a part bonded to the oxygen atom of the phosphite group. Representative examples of the alkylene group having 1 to 8 carbon atoms in R ⁷ include, for example, methylene group, ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl- 1,3
-Propylene groups and the like. * -CO (R ⁷⁾ m-
The group is preferably a * -CO- group in which m is 0, or a * -CO- group in which m is 1 and R ⁷ is ethylene.
(CH ₂ CH ₂ ) — group.

One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents

Here, examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above, and examples of the alkoxy group having 1 to 8 carbon atoms include, for example, the alkyl moiety having the above-described alkyl group having 1 to 8 carbon atoms. Examples of the aralkyloxy group having 7 to 12 carbon atoms include an aralkyloxy group having the same alkyl as the aralkyloxy group having 7 to 12 carbon atoms. .

The compounding amount of the phosphites (C) used in the present invention is 100 polyolefin resin (A).
It is 0.01 to 1.0 part by weight based on part by weight. Preferably it is 0.01 to 0.5 part by weight, more preferably 0.05 to 0.3 part by weight. If the phosphite (C) is less than 0.01 part by weight, the processing stability may be insufficient. If it exceeds 1.0 part by weight, the appearance and processing of the molded article such as hue may be insufficient. Machine contamination may be insufficient.

The polyolefin resin composition of the present invention may contain other additives as long as the object of the present invention is not impaired. Other additives include, for example, phenolic antioxidants, sulfuric antioxidants, ultraviolet absorbers, light stabilizers, hydroxylamine (processing stabilizer), plasticizers,
Flame retardants, nucleating agents, metal deactivators, antistatic agents, pigments,
Anti-blocking agent, surfactant, processing aid, foaming agent, emulsifier, brightener, and 9,10-dihydro-
A coloring improver such as 9-oxa-10-phosphophenanthrene-10-oxide; and US Pat. No. 4,325,853.
No. 4,338,244, 5,175,312,
5,216,053, 5,252,643, 4,3
16,611, German Patent DE-A-4,31
No. 6,622, DE-A-4,316,876, EP-A-589,839, EP-A-
Co-stabilizers such as benzofurans and indolines described in JP-A-591,102 and the like. These other additives may be blended simultaneously with the neutralizing agent (B) and the phosphites (C) used in the present invention, or may be blended separately.

As other additives, particularly, phenolic antioxidants, sulfur antioxidants, ultraviolet absorbers, light stabilizers, metal deactivators, and nucleating agents are often used.

Examples of the phenolic antioxidants include the following. Tetrakis [methylene-3
(3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 3,9-bis [2- {3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4
8,10-tetraoxaspiro [5.5] undecane,
1,3,5-tris 2 [3 (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy] ethyl isocyanate, 1,3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-)
4-hydroxybenzyl) isocyanurate, 1,3
5-tris (4-t-butyl-3-hydroxy-2,6
-Dimethylbenzyl) isocyanurate,

Pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], triethylene glycol-N-bis-3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], 2,2-thiobis-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate],

2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-
Bis- (4-ethyl-6-t-butylphenol),
2,2′-methylene-bis- (4,6-di-t-butylphenol), 2,2′-ethylidene-bis- (4,6
-Di-t-butylphenol) (Cheminox 112)
9), 2,2'-butylidene-bis- (4-methyl-6
-T-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2-t-
Butyl-6- (3-tert-butyl-2-hydroxy-5-
Methylbenzyl) -4-methylphenyl acrylate,
2,4-di-t-amyl-6- (1- (3,5-di-t
-Amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, tocopherols and the like.

Examples of the sulfur-based antioxidants include the following. Dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate;
Lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate) and the like.

Examples of the ultraviolet absorber include the following. (1) Examples of salicylate derivatives Phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-
Di-tert-butyl-4'-hydroxybenzoate, 4-
t-octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl 3 ', 5'-di-t-butyl-
4'-hydroxybenzoate, octadecyl 3 ',
5'-di-t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl
3 ', 5'-di-t-butyl-4'-hydroxybenzoate and mixtures thereof and the like.

(2) Examples of 2-hydroxybenzophenone derivatives 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2,2'-dihydroxy-
4-methoxybenzophenone, bis (5-benzoyl-
4-hydroxy-2-methoxyphenyl) methane, 2,
2 ', 4,4'-tetrahydroxybenzophenone and mixtures thereof.

(3) 2- (2'-hydroxyphenyl)
Examples of benzotriazole 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'
-Hydroxyphenyl) benzotriazole, 2-
(5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-
Octylphenyl) benzotriazole, 2- (3-t
-Butyl-2-hydroxy-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (3'-s-butyl-2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, −
(3 ′, 5′-di-t-amyl-2′-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-
3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-[(3′-t-
Butyl-2'-hydroxyphenyl) -5 '-(2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-5'
-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxyphenyl] -5-chlorobenzotriazole,

2- [3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-t
-Butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole, 2-
[3'-t-butyl-2'-hydroxy-5- (2-octyloxycarbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl-2'-hydroxy-5 '-[2- ( 2-ethylhexyloxy) carbonylethyl] phenyl] benzotriazole, 2- [2-
Hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole , 2-
(3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- [3'-t-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl] benzo A mixture of triazoles,

2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3
-Tetramethylbutyl) phenol, 2,2'-methylenebis [4-t-butyl-6- (2H-benzotriazol-2-yl) phenol], poly (3-11) (ethylene glycol) and 2- [3 '-T-butyl-2'-
Hydroxy-5 '-(2-methoxycarbonylethyl)
Phenyl] benzotriazole, poly (3-
11) (Ethylene glycol) and methyl 3- [3-
Condensation product with (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate, 2-ethylhexyl 3- [3-t-butyl-5
-(5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-t-butyl-5- (5-chloro-2H
-Benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2)
-Yl) -4-hydroxyphenyl] propionate,
3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof.

Examples of the light stabilizer include the following. (1) Examples of hindered amine light stabilizers Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1, 2,
2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-
2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) 2- (3,5-di-t-butyl-4-)
Hydroxybenzyl) -2-butylmalonate, bis (1-acyl-2,2,6,6-tetramethyl-4
-Piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate,

Bis (1,2,2,6,6-pentamethyl-4-piperidyl) decandioate, 2,2,6,6
-Tetramethyl-4-piperidyl methacrylate, 4
-[3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,
6-tetramethyl-4-piperidyl) amino-N-
(2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1, 2, 2, 6,
6-pentamethyl-4-piperidyl) 1,2,3,4
-Butanetetracarboxylate, a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol;

Mixed ester of 1,2,3,4-butanetetrabonic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol;
2,3,4-butanetetracarboxylic acid and 1,2,2
6,6-pentamethyl-4-piperidinol and 3,
9-bis (2-hydroxy-1,1-dimethylethyl)
Mixed esterified product with -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-
Mixed esterified product of 4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dimethyl succinate and 1 Polycondensate with-(2-hydroxyethyl) -4-hydroxy-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)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-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 '
A polycondensate of bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane;

N, N ', 4,7-tetrakis [4,6-
Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10- Diamine, N, N ', 4-tris [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazine- 2-yl] -4,7-diazadecane-1,10-diamine,
N, N ', 4,7-tetrakis [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-
Piperidyl) amino) -1,3,5-triazine-2-
Yl] -4,7-diazadecane-1,10-diamine,
N, N ', 4-tris [4,6-bis (N-butyl-N
-(1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl]-
4,7-diazadecane-1,10-diamine and mixtures thereof and the like.

(2) Examples of acrylate light stabilizers Ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano- β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-
Methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline and mixtures thereof and the like.

(3) Examples of nickel-based light stabilizers Nickel complex of 2,2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, monoalkyl ester Nickel salts, ketoxime nickel complexes and mixtures thereof.

(4) Examples of oxamide light stabilizers: 4,4'-dioctyloxyoxanilide, 2,2'-
Diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butylanilide, 2,2'-didodecyloxy-5,5'-di-t-butylanilide, 2
-Ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-t-butyl-2'-ethoxyanilide,
-Ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide and mixtures thereof.

(5) 2- (2-hydroxyphenyl)-
Examples of 1,3,5-triazine-based light stabilizers 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-
(Hydroxy-4-octyloxyphenyl) -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3 , 5-Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-
Methylphenyl) -1,3,5-triazine, 2- (2
-Hydroxy-4-dodecyloxyphenyl) -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Such as triazines and mixtures thereof.

Examples of the metal deactivator include the following. N, N′-diphenyloxamide, N-salicyral-N′-salicyloylhydrazine,
N, N'-bis (salicyloyl) hydrazine, N, N '
-Bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene)
Oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide,
N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide and mixtures thereof.

Examples of the nucleating agent include the following. Sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate,
[Phosphate-2,2'-methylenebis (4,6-di-t-
Butylphenyl)] dihydroxyaluminum, bis [2,2′-methylenebis (phosphate) (4,6-di-t-phosphate)
Butylphenyl)] hydroxyaluminum, tris [2,2′-methylenebis (4,6-di-t-phosphate) phosphate
Butylphenyl)] aluminum, sodium bis (4-t-butylphenyl) phosphate, metal salts of benzoic acid such as sodium benzoate, pt-butyl aluminum benzoate, 1,3: 2,4-bis (o-benzylidene) ) Sorbitol, 1,3: 2,4-bis (o-methylbenzylidene) sorbitol, 1,3: 2,4-bis (o-ethylbenzylidene) sorbitol, 1,3-o
-3,4-dimethylbenzylidene-2,4-o-benzylidene sorbitol, 1,3-o-benzylidene-2,
4-o-3,4-dimethylbenzylidene sorbitol,
1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol, 1,3-op-chlorobenzylidene-2,4-o-3,4-dimethylbenzylidene sorbitol, 1,3- o-3,4-dimethylbenzylidene-2,4-op-chlorobenzylidene sorbitol,
1,3: 2,4-bis (op-chlorobenzylidene)
Sorbitol and mixtures thereof, rosin alkali metal salts, alkaline earth metal salts, specifically lithium, sodium, potassium, calcium salts of rosin,
Compounds such as magnesium salts and aluminum salts.

The polyolefin-based resin composition of the present invention may contain other resins than the polyolefin-based resin used in the present invention, if necessary, as long as the object of the present invention is not impaired. Examples thereof include petroleum resin, styrene-based copolymer rubber obtained by hydrogenating styrene-butadiene-styrene copolymer and styrene-isoprene-styrene copolymer, and other elastomers.

The polyolefin resin composition of the present invention comprises:
A polyolefin-based resin (A), a neutralizing agent (B), and a phosphite (C) are blended, and the mixture is mixed with, for example, a melt extruder or a Banbury mixer in the presence or absence of an organic peroxide. The melt flow rate can be adjusted by a method of melt-kneading in the presence.

The molded article and the film of the present invention are obtained by using the polyolefin resin composition of the present invention by various molding methods. Examples of the method for producing the molded article of the present invention include, for example, injection molding, press molding, vacuum molding, foam molding, extrusion molding, and the like, which are usually used industrially, and according to the purpose. And the same type of polyolefin resin, and a molding method of laminating with another resin. Further, the shape, size, and the like of the molded body are not particularly limited.

Examples of the use of the molded article of the present invention include, for example,
Examples include automotive materials, home electric materials, building materials, various liquid bottles, containers, sheets, films, and the like. Automotive materials include, for example, interior materials such as instrument panels and exterior materials such as bumpers, and home electric appliance materials include, for example, washing machines and vacuum cleaners.

The method for producing the film of the present invention is not particularly limited, and is a method generally used industrially. Examples of the method include an extrusion molding method such as a T-die film forming method and a tubular film forming method. And a T-die film forming method capable of forming a film at a high speed using a large film forming machine. The processing temperature of the film of the present invention is not particularly limited.
80-350 ° C.

The thickness of the film of the present invention is not particularly limited, but is preferably from 10 to 500 μm, and more preferably from 10 to 150 μm.

The film of the present invention may be a laminated film obtained by using the polyolefin resin composition of the present invention as at least one layer. As other layers,
Although not particularly limited, for example, polyethylene film,
Examples include a polypropylene biaxially stretched film, an unstretched and stretched nylon film, a stretched polyethyl terephthalate film, a polyolefin-based resin of the same type, or other resins or aluminum stays. The method for producing the laminated film is not particularly limited, and examples thereof include a dry lamination method and an extrusion lamination method.

The use of the film of the present invention is not particularly limited, and examples thereof include packaging bags for foods, fibers, miscellaneous goods, etc., wrapping films for confectionery, liquid foods, etc., and packaging materials for retort foods, etc. No.

[0078]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to the examples. The polyolefin resin and additives used are shown below. (1) Polyolefin-based resin (component A) It was produced by a gas-phase polymerization method using a catalyst according to the method described in Example 5 of Japanese Patent No. 2950168 under conditions such that a polyolefin-based resin having the following physical properties was obtained. (1-1) PP-1: propylene- (ethylene-propylene) copolymer MI: 0.5 g / 10 min (230 ° C.) Content of Ti, Mg, Al and Cl contained in resin;
Ti: less than 1 ppm, Mg: 6 ppm, Al: 33 pp
m, Cl: 11 ppm (1-2) PP-2: propylene- (ethylene-propylene) copolymer MI: 3.0 g / 10 min (230 ° C.) Content of Ti, Mg, Al and Cl contained in resin ;
Ti: less than 1 ppm, Mg: 5 ppm, Al: 27 pp
m, Cl: 14 ppm (1-3) PP-3: homopolypropylene MI: 0.5 g / 10 min (230 ° C.) Content of Ti, Mg, Al and Cl contained in the resin;
Ti: less than 1 ppm, Mg: 5 ppm, Al: 30 pp
m, Cl: 5 ppm

(2) Neutralizing agent (component B) (2-1) Hydrotalcite DHT4C (manufactured by Kyowa Chemical Industry Co., Ltd.) Chemical formula: Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) _0.8 · O _0.2 Heat loss (% by weight), which is the amount of water loss at temperature: 100 ° C: 0.6% by weight, 200 ° C: 1.2% by weight, 300 ° C: 5.1% by weight (2-2) Hydrotalcite ZHT4D (Manufactured by Kyowa Chemical Industry Co., Ltd.) Chemical formula: Zn ₄ Al ₂ (OH) ₁₂ CO ₃ .mH ₂ O (m is 0
４4) Heat loss (% by weight), which is the amount of water loss at 100 ° C .; 0.2% by weight (2-3) Calcium hydroxide TP-2B (manufactured by Kyodo Yakuhin Co., Ltd.) Chemical formula: Ca (OH) ₂ (2-4) Magnesium hydroxide (chemical formula: Mg (OH)
₂ ) (2-5) Magnesium oxide (chemical formula: MgO) (2-6) Zinc oxide (chemical formula: ZnO)

(3) Phosphites (component C) 2,4,8,10-tetra-t-butyl-6- [3-
(3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphepin (CAS No. 203255-8)
1-6, Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.),
The structure is represented by the formula (Formula 1). (1)

(AO-1): pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-)
Hydroxyphenyl) propionate] (IRGANO
X1010: Ciba Specialty Chemicals Co., Ltd. (AO-2): 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1, 1-dimethylethyl] -2,4
8,10-Tetraoxaspiro [5.5] undecane (Sumilyzer GA80: manufactured by Sumitomo Chemical Co., Ltd.) (AO-3): Tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS168:
Ciba Specialty Chemicals (made)

The measured value of each item in the examples was determined by the following method. (1) Thermal stability test (high-temperature repetitive kneading test) Using a single-screw extruder having an inner diameter of 40 mm, the pellets prepared by melt-kneading once at a set temperature of 250 ° C. are subjected to a single-screw extruder having an inner diameter of 20 mm. At a set temperature of 300 ° C., and a heat stability test was carried out by further repeating the heat-melt kneading twice. The melt index of the once-kneaded pellets and the twice-kneaded pellets was measured, and it was determined that the smaller the MI change, the better the thermal stability. The melt index (MI: g / 10 minutes) was measured at 230 ° C. under a load of 2.16 kg according to JIS K7210. Also, the yellow index (YI) of the pellet was measured,
The smaller the YI change, the better the hue stability.

(2) Processing Machine Contamination Test (Roll Contamination) Using a single screw extruder having an inner diameter of 20 mm, the resin was heated and melted at a set temperature of 300 ° C., and the molten resin was extruded from a T-die. This was cooled and solidified with a cooling roll (made of SUS) at 30 ° C., and processed into a film having a width of about 10 cm and a thickness of 50 μm. This was continuously extruded for about 10 minutes (equivalent to 200 g of resin) and then subjected to extrusion processing in which cooling and solidification were repeated. Thereafter, dirt adhering to the cooling roll was wiped off with a black cloth for about 1 minute while rotating the roll. The degree of contamination was determined by visually observing the degree of adhesion of the white powdery adhering matter to the black cloth in five stages. XX: Extremely dirty. X: Stained. ▲: Slightly dirty. Δ: Slightly soiled. ：: No stain.

(3) Corrosion Test (a) Preparation of Iron Plate for Corrosion Test Iron plate having a thickness of 2 mm (material: SS-41, dimensions: 30 × 6)
0 mm) was polished with sandpaper to finish the surface to a mirror-like state. (The iron plate was stored in a desiccator filled with silica gel.) (B) Hot press molding Next, this iron plate was subjected to hot press molding in a mold (dimensions: 20 × 25).
mm, thickness 3 mm) and hot pressed at a temperature of 280 ° C. and a pressure of 100 kg / cm ² G for 10 minutes. After the hot press, the pressure is released and immediately cooled by a water-cooled press (30 ° C.). This hot press molding was repeated five times using the same iron plate with the same contact surface with the polyolefin resin.

(C) Condition Adjustment (Aging) After hot press molding, the iron plate was released for 24 hours in a test tank maintained at 30 ° C. and 80% relative humidity.

(D) Judgment of Corrosion (Rusting) The corrosion state of the iron plate surface was visually compared with a corrosion standard plate (5 levels), and the degree of corrosion was ranked. The ranking of the degree of corrosion was as follows, and the rank of 2 or less was a level having no practical problem.

(4) Judgment of End Face Color Using a single screw extruder having an inner diameter of 20 mm, the resin was heated and melted at a set temperature of 300 ° C., and the molten resin was extruded from a T die. This was cooled and solidified with a cooling roll (made of SUS) at 30 ° C., and processed into a film having a width of about 10 cm and a thickness of 50 μm. While the film was wound, the color of the end face of the film was visually observed and judged in five steps. XX: extremely yellow, X: yellow, ▲: slightly yellow, Δ: slightly yellow, ○: white

Example 1 0.01 parts by weight of hydrotalcite (DHT4C) was added to 100 parts by weight of polypropylene (propylene-ethylene block copolymer: PP-1), and phosphorous acid represented by the formula (1) was used. 0.2 part by weight of the ester compound is blended,
Premixed with a Henschel mixer. This mixture was heated and melt-kneaded with a 40 mmφ single screw extruder at a set temperature of 250 ° C. and a rotation speed of 50 rpm to form pellets. The MI of the pellet was 0.51 g / 10 minutes, and the pellet YI value was -0.2. When a thermal stability test was performed using the pellets, the MI after kneading once and twice was 0.75 and 1.03 (g / 10 minutes), respectively. The pellets have YI values of 3.1, respectively.
7.4. The degree of roll dirt was determined to be 1, and no dirt was confirmed. When a corrosion test was performed on the pellets, no corrosion (rust) was observed. The results are shown in Tables 1 and 2.

Example 2 The same procedure as in Example 1 was carried out except that the amount of the phosphite compound represented by the formula (Formula 1) used in Example 1 was changed to 0.1 part by weight. Was. The results are shown in Tables 1 and 2.

Comparative Examples 1-5 Except that the phosphite compound represented by the formula (Formula 1) used in Example 1 and the compounding amount thereof were changed to the antioxidants and compounding amounts shown in Table 1, It carried out similarly to the method of Example 1. The results are shown in Tables 1 and 2.

Comparative Examples 6 and 7 The procedure of Example 1 was repeated, except that the neutralizing agent used in Example 1 was not used and the antioxidant was used in the amount shown in Table 1. Was. The results are shown in Tables 1 and 2.

[0092]

[Table 1] Component A: PP-1 was used.

[0093]

[Table 2]

Example 3 The procedure of Example 1 was repeated except that the polypropylene PP-1 used in Example 1 was changed to polypropylene PP-2. The results are shown in Tables 3 and 4.

Examples 4 to 8 The same procedures as in Example 3 were carried out except that the neutralizing agent used in Example 3 and the compounding amount thereof were changed to the neutralizing agents and compounding amounts shown in Table 3. Was. The results are shown in Tables 3 and 4.

Comparative Examples 8 and 9 The phosphite compound represented by the formula (Chemical Formula 1) used in Example 3 and the compounding amount thereof were changed to the antioxidants and compounding amounts shown in Table 3, and Example 3 was carried out in the same manner as in Example 3, except that the neutralizing agent used in Example 3 was changed to the neutralizing agent shown in Table 3 and the amount thereof. Table 3 shows the results.
The results are shown in Table 4.

[0097]

[Table 3] Component A: PP-2 was used.

[0098]

[Table 4]

Example 9 The polypropylene PP-1 used in Example 1 was changed to polypropylene PP-3, and the blending amount of the phosphite compound represented by the formula (Formula 1) was changed to 0.01 part by weight. Except for the above, the procedure was the same as in Example 1. The results are shown in Tables 5 and 6.

Comparative Example 10 The procedure of Example 9 was repeated, except that the phosphite compound of the formula (Formula 1) used in Example 9 was changed to AO-1. The results are shown in Tables 5 and 6.

[0101]

[Table 5] Component A: PP-3 was used.

[0102]

[Table 6]

Examples 1 to 9 satisfying the requirements of the present invention include:
It can be seen that they are excellent in thermal stability during processing, stain resistance, corrosion resistance and color tone of the processing machine. On the contrary,
Comparative Example 1, which did not use phosphites, which is a requirement of the present invention, was insufficient in color tone and stain resistance of a processing machine,
Comparative Example 2 was insufficient in heat stability during processing, color tone, and stain resistance of the processing machine. Comparative Example 3 was insufficient in color tone and stain resistance of the processing machine. Comparative Example 4 was Comparative Example 5 was insufficient in heat stability and color tone during processing, and Comparative Example 6 was insufficient in color tone and stain resistance of the processing machine, and did not use a neutralizing agent, which is a requirement of the present invention. , The corrosion resistance of the processing machine is insufficient,
Comparative Example 7, in which the neutralizing agent and the phosphites required for the present invention were not used, had insufficient color tone, stain resistance of a processing machine, and corrosion resistance, and the phosphorous acid required for the present invention was not used. It can be seen that Comparative Examples 8, 9 and 10 in which no acid esters were used had insufficient heat stability during processing, color tone, and stain resistance of the processing machine.

[0104]

According to the present invention, there are provided a polyolefin resin composition excellent in thermal stability during processing, stain resistance of a processing machine, corrosion resistance and color tone, and a molded article and a film made of the resin composition. be able to.

Continued on the front page F-term (reference) 4F071 AA15X AA20 AA20X AA75X AA76X AB18 AB21 AC15 AE05 AE22 AF02 AF34 AF45 AF53 BA01 BB06 BB07 BC01 4J002 BB031 BB121 BB151 BB171 BB181 BP031 DE077 DE087 FD 207 FD 066066

Claims (6)

[Claims] 1. A polyolefin resin (A) (100 parts by weight), a neutralizing agent (B) (0.001 to 0.2 parts by weight), and the following general formula (I) (Wherein R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, and R ³ represents a hydrogen atom or 1 carbon atom.
To 8 alkyl groups. X is a sulfur atom or -CH
An R ⁶ -group (R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms),
n is 0 or 1. A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ⁷ ) m- group (R ⁷ represents an alkylene group having 1 to 8 carbon atoms, and * represents a portion bonding to an oxygen atom; Represents 0 or 1.). Y and Z are
One of them represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A) a phosphite (C) represented by the formula (1), which comprises 0.01 to 1.0 part by weight. 2. The polyolefin resin composition according to claim 1, wherein the neutralizing agent (B) is an inorganic neutralizing agent. 3. The polyolefin resin composition according to claim 2, wherein the inorganic neutralizing agent is at least one selected from hydrotalcite, oxides or hydroxides of alkaline earth metals. 4. The polyolefin resin (A),
The total weight of the residue resulting from the polymerization catalyst is 100
The polyolefin resin composition according to claim 1, wherein the content is 0 ppm or less and the content of halogen is 100 ppm or less. 5. A molded article comprising the polyolefin resin composition according to claim 1. 6. A film comprising the polyolefin resin composition according to claim 1.