JPH07330963A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To improve the transparency, rigidity, etc., of a molding by incorporating specific amounts of a specific cyclic phosphorus compound and a halogen- trapping agent into a polyolefin containing a magnesium halide compound as a catalyst residue. CONSTITUTION:Crystalline polyolefin in an amount of 100 pts.wt. containing a magnesium halide compound as a catalyst residue is mixed with 0.001-1 pt.wt. cyclic phosphorus compound represented by the formula (wherein R1 is a 1-4C alkylidene and Ar1 and Ar2 each is an alkylarylene, cycloalkylarylene, arylarylene, or aralkylarylene) [e.g. 2,2'-methylenebis(4,6-di-t-butylphenyl) phosphite] and 0.001-1 pt.wt. halogen-trapping agent (e.g. calcium stearate) to obtain the objective composition having a significantly improved transparency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polyolefin composition capable of obtaining a molded article excellent in transparency, rigidity and heat resistance, or tensile elongation. More specifically, a crystalline polyolefin composition containing a crystalline polyolefin containing a magnesium halide compound as a catalyst residue, a specific cyclic phosphorus compound and a halogen scavenger each having a specific amount of excellent transparency, and a crystalline polyolefin composition, crystals Crystalline polyolefin composition, which can be obtained as a molded article excellent in rigidity and heat resistance consisting of a specific polyolefin, a specific cyclic phosphorus compound and a specific sodium salt, respectively, or a crystal having a specific isotactic pentad fraction Propylene homopolymer or crystalline ethylene-propylene block copolymer, cyclic phosphorus compound with specific structure, specific magnesium compound and fluorophosphite compound with specific structure Crystals that give molded products -Related polyolefin composition.

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties.
It is used to manufacture various molded products such as hollow molded products, films, sheets and fibers. However, while the crystalline polyolefin has excellent mechanical properties, it has a drawback in that its use is limited because its transparency is poor due to the high crystallinity of the crystalline polyolefin.
In addition, depending on various specific uses, the mechanical properties may not be sufficient, and there is a problem that expansion of the specific uses is limited. In particular, the rigidity surface such as rigidity and heat resistance rigidity (hereinafter, “rigid surface means rigidity and heat resistance rigidity”) is inferior to polyesters such as polystyrene, ABS resin, polyethylene terephthalate and polybutylene terephthalate. The use of crystalline polyolefin has a drawback that it may be limited in specific applications.

Therefore, various nucleating agents have heretofore been used for the purpose of improving the transparency or rigidity of crystalline polyolefin. Further, for the purpose of improving the rigidity of the crystalline propylene polymer, JP-A-58-104905, JP-A-58-104906, and JP-A-58-104907 relating to applications of the same applicant as the present application Publication and JP-A-59-22913
In each of the publications, a crystalline propylene homopolymer having a specific isotactic pentad fraction is proposed. On the other hand, depending on the specific use of the crystalline propylene polymer, the impact resistance may not be sufficient,
There is a drawback in that it is difficult to use for a molded product that receives a mechanical shock or a molded product that is used at a low temperature. Generally, the rigidity and impact resistance of a plastic material are incompatible with each other, and it is often extremely difficult to improve and improve the former and the latter at the same time. For specific applications of the crystalline propylene polymer and further for expanding demand, it is required to further improve not only the above-mentioned impact resistance but also the rigidity. By improving these physical properties, it becomes possible to use the crystalline propylene polymer in the application fields where other general-purpose resins such as high-impact polystyrene (HIPS) resin or ABS resin are used.
Regarding the improvement of the impact resistance of the crystalline propylene polymer,
Several suggestions have been made. In particular, the method of block copolymerizing propylene with ethylene is well known. The obtained crystalline ethylene-propylene block copolymer has a remarkable improvement in low temperature impact resistance as compared with the crystalline propylene homopolymer, but has a drawback that the rigidity is lowered. Therefore, for the purpose of improving the rigidity of the crystalline ethylene-propylene block copolymer, it has a specific isotactic pentad fraction in JP-A-58-201816 relating to the application of the same applicant as the present application. Crystalline ethylene-propylene block copolymers have been proposed.

On the other hand, JP-A-4-89838 discloses that a polypropylene polymer is allowed to coexist with water and a polycyclic arylene phosphite-based processing stabilizer, and a vent type extruder is used to remove the volatile components while pushing. A method for producing a polypropylene polymer composition having an improved hue is described. Further, the publication describes that a heat stabilizer, an ultraviolet absorber, a slip agent and an antistatic agent, which are usually used in the production of polyolefin, can be used in combination. In addition, JP-A-5-
78527 discloses conventional additives for stabilized polyolefins containing alkylidene-bis (substituted aryl) acid phosphites, such as UV absorbers and photoprotectors, metal deactivators, other phosphites, peroxides. Degradants, nucleating agents, plasticizers, lubricants, emulsifiers, fillers, carbon black, kaolin, talc, glass fibers, pigments, optical polishes, flame retardants, antistatic agents, and other antioxidants. It is stated that an agent can be included. Further, in JP-A-6-41159, a wide range of organic phosphorus compounds including alkylidene-bis (alkylaryl) acid phosphite, which is useful as a stabilizer for organic polymers, for example, a stabilizer for polycarbonates, is used as a metal. A method for stabilizing organophosphorus compounds by adding an acid scavenger selected from carboxylates, oxides and carbonates is described.

On the other hand, in the polymerization of crystalline polyolefin, if a halogen-containing magnesium compound is used as a catalyst carrier, a transition metal (for example, titanium) which is the main component of the catalyst.
When a catalyst having a polymer yield per unit of no carrier (for example, a system in which titanium tetrachloride-aluminum chloride mixture activated by reduction of titanium tetrachloride with metallic aluminum and further activated by grinding is combined with diethylaluminum monochloride) is used As a new generation catalyst that does not require catalyst removal (deashing) or amorphous polymer extraction (de-APO) processes because it is several hundred times to several thousand times higher than the above and the crystallinity of the produced polymer is high. It is in the spotlight.
Representative examples of such new type catalysts include JP-A-47-9342 and JP-A-50-126590. However, such a supported catalyst has a high polymer yield per transition metal, which is the main component of the catalyst, but has a low polymer yield per catalyst carrier corresponding to a low transition metal supported concentration, and therefore does not undergo deashing. The crystalline polyolefin is adversely affected by the residual catalyst carrier. That is, since the amount of the transition metal component supported on the catalyst carrier is 1% or less to 10% (weight) at most per solid catalyst component, the polymer yield per catalyst carrier (magnesium compound) should be about several thousand to tens of thousands. Therefore, if deashing is not performed, the residual magnesium compound (usually a magnesium halide compound) may cause deterioration of the quality of the product polymer. In particular, if a magnesium halide compound remains as a catalyst residue in the crystalline polyolefin, the magnesium halide compound (eg, magnesium chloride) is thermally decomposed to generate an acidic substance such as hydrogen halide when the crystalline polyolefin is melt-processed. However, the thermal stability, odor, hue, corrosiveness, weather resistance, etc. of the product polymer tend to deteriorate.

[0006]

However, a molded article obtained from a composition comprising a crystalline polyolefin in which a magnesium halide compound remains as a catalyst residue and an alkylidene-bis (substituted aryl) acid phosphite as a nucleating agent. Has the drawback that the transparency of is hardly improved. JP-A-4-89838 describes that a polypropylene polymer is coexisted with water and a polycyclic arylene phosphite processing stabilizer and extruded. However, although the publication describes that the polycyclic arylene phosphite-based processing stabilizer is partially hydrolyzed by entrainment of water to lower the effective concentration, the polycyclic arylene phosphite-based processing stabilizer is stable. There is no description of a clear chemical composition of a hydrolyzate produced from the agent, and as the hydrolyzate, a polycyclic arylene acid phosphite, an aminotriazine compound or hydroxylamine as a heat stabilizer, and a fatty acid metal salt or a fat as a slip agent. Composition using a polypropylene-based polymer containing a halogenated magnesium compound as a catalyst residue as a polypropylene-based polymer in combination with an aliphatic phosphate metal salt or an aliphatic amide or an antistatic agent, an aliphatic amine or an aliphatic amide What is the improvement of the transparency of molded products obtained from Mounting nor suggested.
Further, in the above-mentioned JP-A-5-78527, alkylidene-bis (alkylaryl) acid phosphite, a hindered amine-based compound as a photoprotective agent, an aminotriazine-based compound as a metal deactivator, and an aliphatic polynuclear agent as a nucleating agent are disclosed. Carboxylic acid metal salt, alicyclic carboxylic acid metal salt, aromatic carboxylic acid metal salt or aromatic phosphoric acid metal salt, fatty acid metal salt, aliphatic phosphoric acid metal salt or aliphatic amide as lubricant, metal oxidation as filler Substance, metal hydroxide or carbonate metal salt, metal hydroxide as flame retardant, aliphatic amine or aliphatic amide as antistatic agent, or hydroxylamine as other antioxidant, combined with catalyst residue as polyolefin. The transparency of molded articles obtained from a composition using a crystalline polyolefin containing a magnesium halide compound. Thereby improving sexual also no suggestion according any. Further, although Japanese Patent Laid-Open No. 6-41159 describes the use of an organic phosphorus compound as the only organic polymer in polycarbonates, alkylidene-bis (alkylaryl) acid phosphite and a metal are used as the organic phosphorus compound. In combination with an acid scavenger selected from carboxylic acid salts, oxides and carbonates of
There is no description or suggestion of improving the transparency of a molded article obtained from a composition using a crystalline polyolefin containing a magnesium halide compound as a catalyst residue as an organic polymer.

On the other hand, the rigidity of the molded product obtained from the composition obtained by mixing the crystalline polyolefin with various conventionally known nucleating agents has been improved to some extent, but still not satisfactory. JP-A-4-89838 describes that a polypropylene polymer is coexisted with water and a polycyclic arylene phosphite processing stabilizer and extruded. However, although the publication describes that the polycyclic arylene phosphite-based processing stabilizer is partially hydrolyzed by entrainment of water to lower the effective concentration, the polycyclic arylene phosphite-based processing stabilizer is stable. There is no description of a clear chemical composition of the hydrolyzate produced from the agent, and it is not possible to improve the rigidity of the molded article obtained from the polypropylene-based polymer composition in which the hydrolyzate and a specific sodium salt are used in combination. , There is no description or suggestion. Further, JP-A-5-78527 discloses improving the rigidity of a molded product obtained from a crystalline polyolefin composition in which an alkylidene-bis (alkylaryl) acid phosphite is used in combination with a specific sodium salt as a lubricant. There is no description or suggestion. Further, the above-mentioned JP-A-6-
Although 41159 describes that an organic phosphorus compound is the only organic polymer used in polycarbonates, alkylidene-bis (alkylaryl) acid phosphite is used as the organic phosphorus compound and a specific sodium salt is used as the acid scavenger. There is no description or suggestion of improving the rigidity of the molded product obtained from the crystalline polyolefin composition in which and are used together.

On the other hand, the specific ones proposed in the above-mentioned JP-A-58-104905, JP-A-58-104906, JP-A-58-104907 and JP-A-59-22913. A crystalline propylene homopolymer having an isotactic pentad fraction or a crystalline ethylene-propylene block copolymer having a specific isotactic pentad fraction proposed in JP-A-58-201816 is The rigidity is considerably improved, but the tensile elongation is remarkably reduced. JP-A-4-89838 describes that a polypropylene polymer is coexisted with water and a polycyclic arylene phosphite processing stabilizer and extruded. However, in the publication, the polycyclic arylene phosphite-based processing stabilizer is accompanied by water,
Although it is described that a part of them is hydrolyzed to lower the effective concentration, there is no description of a definite chemical composition of a hydrolyzate produced from a polycyclic arylene phosphite-based processing stabilizer, and as the hydrolyzate, Polypropylene using a polycyclic arylene acid phosphite, a fatty acid magnesium or aliphatic magnesium phosphate as a slip agent and a fluorophosphite compound as a heat stabilizer in combination, and having a specific isotactic pentad fraction as a polypropylene polymer There is no description or suggestion of improving the tensile elongation of the molded article obtained from the composition using the polymer. Further, in the above-mentioned JP-A-5-78527, alkylidene-bis (alkylaryl) acid phosphite and alkylidene-bis (substituted aryl) fluorophosphite as other phosphite and fatty acid magnesium and aliphatic magnesium phosphate as lubricants are disclosed. , Magnesium oxide as a filler,
In combination with a magnesium compound selected from magnesium hydroxide and magnesium carbonate, the tensile elongation of a molded product obtained from a composition using a crystalline propylene polymer having a specific isotactic pentad fraction as a polyolefin There is no description or suggestion of improvement. Further, although JP-A-6-41159 describes the use of an organic phosphorus compound as the only organic polymer in polycarbonates, alkylidene-bis (alkylaryl) acid phosphite and alkylidene are used as the organic phosphorus compound. -A combination of bis (alkylaryl) fluorophosphite and a magnesium compound selected from magnesium carboxylates, oxides and carbonates as an acid scavenger to give a specific isotactic pentad fraction as an organic polymer. There is no description or suggestion of improving the tensile elongation of the molded article obtained from the composition using the crystalline propylene polymer.

The present inventor has found that a crystalline polyolefin having a magnesium halide compound remaining as a catalyst residue and an alkylidene-bis (substituted aryl) as a nucleating agent.
A composition that solves the above-mentioned problems relating to a composition comprising acid phosphite, that is, a crystalline polyolefin composition with improved transparency, the above-mentioned problems with respect to a crystalline polyolefin composition, that is, a molded article with improved rigidity. The above-mentioned problems regarding the crystalline polyolefin composition to be given, or the crystalline propylene polymer having a specific isotactic pentad fraction, that is, to obtain a crystalline polyolefin composition which gives a molded article having improved tensile elongation, Researched. As a result, the present inventors have found that a crystalline polyolefin composition containing a magnesium halide compound as a catalyst residue, a crystalline polyolefin composition containing a specific amount of a specific cyclic phosphorus compound and a specific amount of a halogen scavenger are molded products with improved transparency. (1st invention of the present application), a crystalline polyolefin composition comprising a crystalline polyolefin, a specific cyclic phosphorus compound, and a specific sodium salt in specific amounts, respectively, gives a molded article with improved rigidity. Composition (second invention of the present application), or crystalline propylene homopolymer or crystalline ethylene-propylene block copolymer having a specific isotactic pentad fraction, cyclic phosphorus compound having a specific structure, specific Of Fluorophosphite with Specific Structure and Magnesium Compound It was found that the crystalline polyolefin composition consisting of a specific amount of each compound is a composition that gives a molded article with improved tensile elongation (the third invention of the present application), and the present invention was completed based on this finding. As is clear from the above description, the object of the present invention is the transparency of the molded product when it is formed,
It is an object of the present invention to provide a crystalline polyolefin composition having an improved rigid surface or tensile elongation.

[0010]

The present invention has the following constitution. (1) To 100 parts by weight of a crystalline polyolefin containing a magnesium halide compound as a catalyst residue, 0.005 parts of a cyclic phosphorus compound represented by the following chemical formula 5 (hereinafter referred to as compound A)
A crystalline polyolefin composition containing 1 to 1 part by weight and 0.001 to 1 part by weight of a halogen scavenger (hereinafter referred to as compound B).

[Chemical 5] (In the formula, R ₁ represents an alkylidene group having 1 to 4 carbon atoms, and Ar ₁ and Ar ₂ represent an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.) (2) Compound B Are fatty acid metal salts, alkanoyl lactic acid metal salts, aliphatic hydroxy acid metal salts, hydrotalcites, lithium aluminum complex hydroxide salts, metal oxides, metal hydroxides, carbonate metal salts, aliphatic phosphate metal salts ,
2. The crystalline polyolefin composition according to the above item 1, which is an epoxy compound, an aliphatic amine, an aliphatic amide, a hindered amine compound, an aminotriazine compound, or a mixture of two or more thereof. (3) Compound A 0.001 in 100 parts by weight of crystalline polyolefin
~ 1 part by weight and one or two selected from the following ~
A crystalline polyolefin composition containing 0.001 to 1 part by weight of one or more compounds (hereinafter referred to as compound C). Aliphatic sodium monocarboxylic acid Sodium aliphatic hydroxyacid having 2 to 6 carbon atoms Sodium alkanoyl lactate

(4) Fraction of isotactic pentad (P)
And melt flow rate (MFR: load at 230 ° C 21.
0.001 to 1 part by weight of compound A to 100 parts by weight of a crystalline propylene homopolymer having a relationship of 1.00 ≧ P ≧ 0.015 log MFR + 0.955 with respect to the amount of molten resin discharged for 10 minutes when 18N is added) 0.001 to 1 of 1 or 2 or more magnesium compounds selected from (hereinafter referred to as compound D)
A crystalline polyolefin composition containing 1 part by weight and 0.001 to 1 part by weight of a fluorophosphite compound (hereinafter, referred to as compound E) represented by Chemical Formula 8 below. Fatty Acid Magnesium Aliphatic Magnesium Phosphate Magnesium Oxide Magnesium Carbonate Magnesium Carbonate Magnesium Salt of Cyclic Phosphorus Compound Represented by Chemical Formula 6 Magnesium Phosphinate Compound represented by Chemical Formula 7

[Chemical 6]

[Chemical 7]

[Chemical 8] (In the formula, Ar _{3 to} Ar ₆ represent an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group, and R ₂
Represents a direct bond, an alkylidene group having 1 to 4 carbon atoms or a sulfur atom, and Ar ₇ and Ar ₈ represent an alkylarylene group or a cycloalkylarylene group, respectively.) (5) Isotactic pentad of crystalline propylene homopolymer The first stage polymer having a relationship between the fraction (P) and the melt flow rate (MFR) of 1.00 ≧ P ≧ 0.015 log MFR + 0.955 is 70 to 95% by weight of the total amount of polymer, and then the total amount of polymer is 30 to 5% by weight of ethylene or ethylene and propylene are polymerized in one or more steps to obtain 100 parts by weight of a crystalline ethylene-propylene block copolymer having an ethylene content of 3 to 20% by weight based on the total amount of the polymer. , Compound A 0.001
˜1 part by weight, compound D 0.001˜1 part by weight and compound E
A crystalline polyolefin composition containing 0.001 to 1 part by weight.

The crystalline polyolefin used in the first invention of the present application contains a magnesium halide compound as a catalyst residue, and is obtained, for example, by polymerization in the presence of a Ziegler type complex catalyst using a halogen-containing magnesium compound as a catalyst carrier. A crystalline polyolefin obtained according to the present invention, which has not been subjected to a catalyst residue removal step or has been obtained through an incomplete catalyst residue removal step. The details will be described below. The Ziegler-type complex catalyst using a halogen-containing magnesium compound as a catalyst support is a Ziegler-type complex catalyst, that is, a transition metal compound of Groups 4 to 8 of the periodic table and an organometallic compound of a metal of Groups 1 to 3 of the periodic table. In the complex catalyst produced by the combination of the above, the former transition metal compound is supported on the halogen-containing magnesium compound. Here, "to be a catalyst carrier" or "to be supported" means not only when the transition metal compound is physically present on the halogen-containing magnesium compound, but also when both are physically, physicochemically or chemically. It does not exclude the case where the halogen-containing magnesium compound performs any catalytic action, including the case where the halogen-containing magnesium compound interacts or bonds.

Typical examples of the transition metal used in the Ziegler type complex catalyst include titanium and vanadium. These are used in their highest valence or reduced state, halides,
It can be used in the form of a compound such as oxyhalide, alkoxide, and alkoxyhalide which is most preferable in terms of catalytic performance for individual metals. These transition metal compounds include titanium tetrachloride, titanium trichloride,
Titanium dichloride, tetrabutoxy titanium, tributoxy titanium monochloride, dibutoxy titanium dichloride,
Vanadium tetrachloride, vanadium oxymonochloride,
Vanadium trichloride and the like can be exemplified, and these can be used alone or in combination of two or more kinds. Typical of the organometallic compounds are alkylaluminum compounds, particularly trialkylaluminum, dialkylaluminum monohalides, alkylaluminum dihalides, alkylaluminum sesquihalides, dialkylaluminum monohydrides, alkylaluminum dihydrides (wherein these compounds are alkyl The group is preferably C _{1 to} C ₈ and the halogen is preferably chlorine, bromine or iodine).
Specifically, for example, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-i-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, tri-n-hexyl aluminum, tri-n. Examples thereof include octyl aluminum, tri-2-ethylhexyl aluminum, diethyl aluminum monochloride, diethyl aluminum monoiodide, ethyl aluminum dichloride, ethyl aluminum sesquichloride and diethyl aluminum monohydride.

Preferred halogen-containing magnesium compounds as the catalyst carrier include magnesium dihalide,
Oxymagnesium halogenide, oxymagnesium halogenide treated with alkylaluminum dihalogenide (for example, ethylaluminum dichloride) and part of which was converted to magnesium dihalide, magnesium dihalide treated with various electron donor compounds Examples thereof include those complexed with each other. On the other hand,
Halogen-free magnesium compounds as catalyst carriers (eg magnesium hydroxide, magnesium oxide)
In a crystalline polyolefin obtained using a halogen-containing organometallic compound,
Those containing a magnesium halide compound as a catalyst residue are also included in the crystalline polyolefin of the first invention of the present application, and the effects of the first invention of the present application can be obtained. In order to support the transition metal catalyst component on the halogen-containing magnesium compound carrier, a method of co-milling both with a ball mill or the like, when the former is in a liquid state (itself in a liquid state, or a solvent such as hydrocarbon, halogen It can be carried out by a method of dispersing the latter in a solution of a modified hydrocarbon or the like, or a method of dissolving the both in a suitable common solvent, or any other known or available method. For the purpose of improving the catalyst performance, various electron donating compounds can be combined with any catalyst component at any stage of the catalyst production by any method. As a typical example, (1)
As shown in JP-A-48-16986, N, N, N ',
N'-tetramethylethylenediamine was reacted with titanium tetrachloride to prepare a 1: 1 molecular compound in advance, and this was ground in a mill with anhydrous magnesium chloride (A), triethylaluminum and ethyl benzoate. A method of obtaining a catalyst for propylene polymerization by combining with a product (B) obtained by reacting in advance, (2) As shown in JP-A-50-126590, anhydrous magnesium chloride and ethyl benzoate are placed in a ball mill. Co-grinding with, and then suspending the pulverized product in titanium tetrachloride to support titanium tetrachloride on magnesium chloride, treating it with hexane to wash off unsupported titanium tetrachloride to obtain a solid catalyst component. Is prepared and is combined with triethylaluminum to obtain a propylene polymerization catalyst.

The method for polymerizing the crystalline polyolefin used in the first invention of the present application is optional, such as suspension polymerization in a solvent, suspension polymerization in a liquefied monomer, and dilution under conditions where the monomer exists in a gaseous state. There is a gas phase polymerization method which is performed without using it, and others. The "catalyst residue removal step" referred to in the first invention of the present application is a reaction with a catalyst such as alcohols and water in order to positively remove the catalyst residue contained in the crystalline polyolefin obtained by the polymerization. And treating this crystalline polyolefin with a compound that inactivates or solubilizes it,
Then, it means a step of removing the inactivated or solubilized catalyst by physical means such as filtration, drying and centrifugation.
Therefore, in the step of separating the produced polymer from the dispersion medium (solvent or liquefied monomer) in the suspension polymerization, even if removal of the dispersion medium-dissolved catalyst may be performed, the catalyst residue removal step referred to in the first invention of the present application. Does not apply to Also, in order to deactivate the catalyst after polymerization, a small amount of catalyst poison such as ether, alcohol, ketone, ester, and water is added to the produced polymer, or the produced polymer suspension is treated with steam or nitrogen to remove the dispersion medium. The step of treating with such a gas does not correspond to the step of removing the catalyst residue in the first invention of the present application.

The crystalline polyolefin used in the first invention of the present application is a crystalline polyolefin containing a magnesium halide compound as a catalyst residue, such as ethylene,
Crystalline homopolymers of α-olefins such as propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, crystalline or low levels of these two or more α-olefins Crystalline random copolymer or crystalline block copolymer, copolymer of α-olefin and vinyl acetate or acrylic ester described above, saponified product of the copolymer, and α-olefin and unsaturated silane compound A copolymer of these α-olefins and an unsaturated carboxylic acid or an anhydride thereof, a reaction product of the copolymer and a metal ion compound, a crystalline homopolymer of the above α-olefin, A modified polyolefin obtained by modifying a crystalline or low-crystalline random copolymer or a crystalline block copolymer with an unsaturated carboxylic acid or a derivative thereof, a crystalline homopolymer of the above α-olefin. Coalescence, it is possible to exemplify a silane-modified polyolefin obtained by modifying a crystalline or low crystalline random copolymer or a crystalline block copolymer with an unsaturated silane compound, not to mention the single use of these crystalline polyolefins, It is also possible to use a mixture of two or more crystalline polyolefins.

Further, various synthetic rubbers (eg, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene 3) are added to the crystalline polyolefin containing a magnesium halide compound as the catalyst residue.
Original copolymer, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-
Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-
Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, ethylene-ethylene-
Butylene-ethylene block copolymer, ethylene-propylene-butylene-ethylene block copolymer, etc.) or thermoplastic synthetic resin (for example, atactic polystyrene, syndiotactic polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-)
Styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, hydrogenated C) ₅ series petroleum resin, C
_9- based petroleum resin, hydrogenated C _9- based petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉ copolymerized petroleum resin, acid-modified C _9- based petroleum resin, etc., DCPD resin (eg cyclo Pentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene-C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymer petroleum resin, cyclopentadiene-C ₉ copolymer petroleum resin, hydrogenated cyclopentadiene- C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, etc., having a softening point of 80 to 200 ° C. Can also be used. A crystalline propylene homopolymer containing a magnesium halide compound as a catalyst residue, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, which is a crystalline ethylene-propylene random copolymer, a crystalline propylene- Butene-1 random copolymer, crystalline ethylene-propylene-butene-1 terpolymer, crystalline propylene-hexene-butene-1 terpolymer, and mixtures of two or more thereof are particularly preferably used. .

The crystalline polyolefin used in the second invention of the present application is ethylene, propylene, butene-1, pentene-1,
Crystalline homopolymer of α-olefin such as 4-methyl-pentene-1, hexene-1, octene-1, crystalline or low crystalline random copolymer or crystalline block of two or more α-olefins Copolymers, copolymers of the above α-olefins with vinyl acetate or acrylic acid ester, saponified products of the copolymers, copolymers of these α-olefins with unsaturated silane compounds, and these α-olefins Copolymers with unsaturated carboxylic acids or their anhydrides, reaction products of the copolymers with metal ion compounds, crystalline homopolymers of the above α-olefins, crystalline or low crystalline random copolymers Alternatively, a modified polyolefin obtained by modifying a crystalline block copolymer with an unsaturated carboxylic acid or a derivative thereof, a crystalline homopolymer of the above α-olefin, a crystalline or low crystalline run Examples thereof include silane-modified polyolefins obtained by modifying a copolymer or crystalline block copolymer with an unsaturated silane compound. These crystalline polyolefins can be used alone or two or more crystalline polyolefins can be used. It can also be used as a mixture.

Further, various synthetic rubbers (for example, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, polybutadiene, polyisoprene, polychloroprene) are added to the above-mentioned crystalline polyolefin. , Chlorinated polyethylene, chlorinated polypropylene, fluoro rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene
-Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene
-Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, ethylene-ethylene
-Butylene-ethylene block copolymer, ethylene-propylene-butylene-ethylene block copolymer, etc.) or thermoplastic synthetic resin (for example, atactic polystyrene, syndiotactic polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-)
Styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, hydrogenated C) ₅ series petroleum resin, C
_9- based petroleum resin, hydrogenated C _9- based petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉ copolymerized petroleum resin, acid-modified C _9- based petroleum resin, etc., DCPD resin (eg cyclo Pentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene-C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymer petroleum resin, cyclopentadiene-C ₉ copolymer petroleum resin, hydrogenated cyclopentadiene- C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, etc., having a softening point of 80 to 200 ° C. Can also be used. Crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer,
Crystalline propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-1 terpolymer, crystalline propylene-hexene-butene-1 terpolymer and a mixture of two or more thereof. Particularly preferably used.

The crystalline propylene homopolymer used in the third invention of the present application has a relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of 1.00 ≧ P ≧ 0.015.
It is a crystalline propylene homopolymer satisfying log MFR + 0.955 (hereinafter abbreviated as HCPP (H)). Such HCPP (H) can be produced, for example, by the production method described in JP-A-58-104907, which is related to the application of the same applicant as the present application. That is, the organoaluminum compound (i) (for example, triethylaluminum,
A solid product obtained by reacting a reaction product (v) of titanium aluminum chloride (eg, diethyl aluminum monochloride) or an organoaluminum compound (i) with an electron donor (eg, diisoamyl ether, ethylene glycol monomethyl ether) with titanium tetrachloride. The solid product (iii) obtained by further reacting (ii) with an electron donor and an electron acceptor (for example, anhydrous aluminum chloride, titanium tetrachloride, vanadium tetrachloride) is treated with an organoaluminum compound (i) and an aromatic compound. Group carboxylic acid ester (iv) (for example, ethyl benzoate,
p-methyl toluate, ethyl p-toluate, 2-ethylhexyl p-toluate, etc.), and the molar ratio iv / i of the aromatic carboxylic acid ester (iv) and the solid product (iii).
It can be obtained by polymerizing propylene in one or more steps in the presence of a catalyst having ii = 0.1 to 10.0 (hereinafter abbreviated as catalyst (MC)). Further, a highly active and highly stereoregular catalyst composition (hereinafter referred to as catalyst (HAC) in which a highly active catalyst composition containing a titanium halide catalyst component supported on magnesium halide and an organoaluminum catalyst component is combined with an electron donor catalyst component. It is also possible to obtain (preferably deashing-free process) by polymerizing propylene in one or more steps in the presence of ().

The crystalline ethylene-propylene block copolymer used in the third invention of the present application has a relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of the crystalline propylene homopolymer. 1.00 ≧ P ≧ 0.015
The first-stage polymer with log MFR + 0.955 is the total polymer amount.
70-95% by weight, then 30-5% by weight of the total polymer
Ethylene or ethylene and propylene are polymerized in one or more steps, and the ethylene content is 3-20% of the total polymer amount.
It is a crystalline ethylene-propylene block copolymer (hereinafter, abbreviated as HCPP (B)) in a weight percentage. HCP
In the first stage polymerization, P (B) is the amount of the total polymer (excluding the polymer soluble in the polymerization solvent).
70-95 wt% propylene is polymerized. Then, after the second step, ethylene or ethylene and propylene are polymerized in one or more steps. After the second step, 30 to 5% by weight of the total amount of the above-mentioned polymer, ethylene or ethylene and propylene are polymerized in one or more steps.
However, the ethylene content in the finally obtained polymer (excluding the soluble polymer eluted in the polymerization solvent) must be within the range of 3 to 20% by weight based on the total amount of the polymer. Therefore, if only 70% by weight of propylene is polymerized in the first stage, the amount of ethylene copolymerized in the second stage is limited to 20% by weight or less. For the remaining 10 to 27% by weight, propylene or other α-olefins other than ethylene must be block-copolymerized. However, when 80% by weight of propylene is polymerized in the first stage, only 20% by weight of ethylene can be polymerized in the second stage. As described above, in the second stage, ethylene alone or ethylene and propylene or other α may be used within the limits of the stage in which ethylene can be polymerized and the ethylene content in the whole polymer. -The block copolymerization can be carried out in a single stage or in multiple stages by mixing with an olefin. Such HCPP (B) is disclosed in, for example, Japanese Patent Application Laid-Open No. 58-2018 related to an application of the same applicant as the present application.
It can be manufactured by the manufacturing method described in JP-A-16. That is, in the presence of the catalyst (MC),
70 to 95% by weight of propylene are polymerized, and then 30 to 5% by weight of the total amount of ethylene or ethylene and propylene are polymerized in one or more steps to obtain an ethylene content of 3 to 20%.
It can be obtained by copolymerizing so that the amount of the compound becomes% by weight. Also, in the presence of a catalyst (HAC),
70 to 95% by weight of propylene are polymerized, and then 30 to 5% by weight of the total amount of ethylene or ethylene and propylene are polymerized in one or more steps to obtain an ethylene content of 3 to 20%.
It can also be obtained by copolymerization so that the weight% is obtained (preferably a deashing-free process). The above-mentioned one stage means one segment of continuous or temporary supply of these monomers.

Here, the isotactic pentad fraction
(P) means Macromolecules, Volume 6, Issue 6, November
December, pp. 925-926 (1973) [Macromolecules, Vol.
6, No. 6, November-December, 925-926 (197
3)], that is, the isotactic fraction in the pentad unit in the propylene-based polymer molecular chain, which is measured using ¹³ C-NMR. In other words, the fraction means the fraction of propylene monomer units in which five propylene monomer units are continuously isotactically bonded. The attribution of the peak of the spectrum in the measurement using the above ¹³ C-NMR is determined by Macromolecules, Volume 8, No. 5, September to October, pages 687 to 689 (1975
Year) [Macromolecules, Vol. 8, No. 5, September
-October, 687-689 (1975)]. Incidentally, the measurement by ¹³ C-NMR in the examples described later was carried out by using an FT-NMR 270 MHz device, and by integrating measurement 27,000 times, the signal detection limit was improved to 0.001 in terms of isotactic pentad fraction. It was HC above
The requirement for the relational expression between the isotactic pentad fraction (P) and the melt flow rate (MFR) in PP (H) and HCPP (B) is generally that the fraction P of the crystalline propylene homopolymer having a low MFR is P Therefore, as a crystalline propylene homopolymer to be used, the lower limit of P corresponding to its MFR is limited. Since P is a fraction, 1.00 is the upper limit, and M is
FR is usually 0.05 to 100 g / 10 minutes. Also, MFR is J
According to IS K 7210, measured at 230 ℃, load 21.18N,
The ethylene content is measured by infrared absorption spectroscopy.

The HCPP (H) used in the third invention of the present application
Alternatively, HCPP (B) is an ordinary crystalline propylene-based compound having an isotactic pentad fraction (P) outside the range of HCPP (H) or HCPP (B) within a range that does not impair the effects of the third invention of the present application. Polymer, that is, crystalline propylene homopolymer, propylene containing 70% by weight or more of propylene component and ethylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, etc. α- Low crystalline or crystalline random copolymers or crystalline block copolymers with one or more olefins, copolymers of propylene and vinyl acetate or acrylate, or saponified products of the copolymers, A copolymer of propylene and an unsaturated silane compound, a copolymer of propylene and an unsaturated carboxylic acid or an anhydride thereof, or a copolymer of the copolymer and a metal ion compound Reaction products, or modified propylene-based polymers obtained by modifying crystalline propylene-based polymers with unsaturated carboxylic acids or their derivatives, silane-modified propylene-based polymers obtained by modifying crystalline propylene-based polymers with unsaturated silane compounds, etc. It is also possible to mix and use various synthetic rubbers (for example, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated rubber). Polypropylene, styrene-butadiene rubber, acrylonitrile-
Butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, ethylene- (Ethylene-butylene-ethylene block copolymer, ethylene-propylene-butylene-ethylene block copolymer, etc.)

Alternatively, a thermoplastic synthetic resin (for example, ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, amorphous ethylene-cyclic alkene copolymer ( For example, amorphous ethylene-tetracyclododecene copolymer), polybutene, polyolefin excluding crystalline propylene-based polymers such as poly-4-methylpentene-1, atactic polystyrene, syndiotactic polystyrene, styrene-acrylonitrile. Copolymer, acrylonitrile-butadiene-styrene copolymer, methacryl-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate , Polyvinyl chloride, fluorocarbon resins, petroleum resins (e.g. C ₅ petroleum resins, hydrogenated C ₅
Petroleum resin, C ₉ petroleum resin, hydrogenated C ₉ petroleum resin, C _5-
C ₉ copolymer petroleum resin, hydrogenated C ₅ -C ₉ copolymer petroleum resin, acid-modified C ₉ petroleum resin, etc., DCPD resin (for example, cyclopentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene- C ₅ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymerized petroleum resin, cyclopentadiene-C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene
-C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, etc. with a softening point of 80 to 200 ° C.)
It is also possible to mix and use.

The compound A used in the present invention is 2,
2'-methylene-bis (4-methyl-6-t-butylphenyl) acid phosphite, 2,2'-methylene-bis (4-ethyl)
-6-t-Butylphenyl) acid phosphite, 2,2'-
Methylene-bis (4-methyl-6-nonylphenyl) acid phosphite, 2,2'-methylene-bis (4,6-dinonylphenyl) acid phosphite, 2,2'-methylene-bis (4-methyl) -6-Cyclohexylphenyl) acid phosphite, 2,2'-methylene-bis {4-methyl-6- (1'-methylcyclohexyl) phenyl} acid phosphite, 2,2'-i-propylidene-bis (4 -Nonylphenyl) acid phosphite, 2,2'-butylidene-bis (4,6-dimethylphenyl) acid phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) acid phosphite Fight, 2,2'-methylene-bis (4,6-di-t-amylphenyl) acid phosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4-ethyl-6-t-butylphenyl) Cid phosphite, 2,2'-ethylidene-bis (4-s-butyl-6-t-butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) Acid phosphite, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphite, 2,2'-methylene-bis (4-methyl-6-t-octylphenyl) acid phosphite Fight, 2,2'-methylene-bis (4,6-diphenylphenyl) acid phosphite,
2,2'-methylene-bis (4,6-dibenzylphenyl) acid phosphite, 2,2'-ethylidene-bis (4-methyl-6)
-α-methylbenzylphenyl) fluorophosphite, 2,2'-i-propylidene-bis (4,6-dibenzylphenyl) acid phosphite, 2,2'-butylidene-bis {4-methyl-6- ( 1'-methylcyclohexyl) phenyl}
Acid phosphite and 2,2'-methylene-bis (4,
Examples thereof include 6-dimethylphenyl) acid phosphite, and 2,2′-methylene-bis (4,6-di-t-butylphenyl) acid phosphite is particularly preferable. These compounds A are prepared, for example, by reacting phosphorus trichloride with 2,2'-alkylidene bisphenol and then hydrolyzing it with water, or by reacting with 2,2'-alkylidene-bis (substituted aryl).
It can be obtained by hydrolyzing phosphite. Not to mention the single use of these compound A 2
It is also possible to use one or more compounds A together. The compound A
The content ratio of crystalline polyolefin, crystalline polyolefin, or HCPP (H) or HCPP containing a magnesium halide compound as a catalyst residue is
(B) 0.001 to 1 part by weight, preferably 0.
It is from 01 to 0.5 parts by weight. If the content is less than 0.001 part by weight, the effect of improving transparency, rigidity and heat resistance, or tensile elongation will not be sufficiently exerted, and if it exceeds 1 part by weight, transparency, rigidity and Not only is it impractical because the effect of improving heat resistance rigidity or tensile elongation cannot be expected, it is also uneconomical.

The compound B used in the present invention includes fatty acid metal salts (eg, acetic acid, propionic acid, butyric acid, valeric acid, α-methylbutyric acid, hexanoic acid, sorbic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid). , Decanoic acid, caproreic acid, undecanoic acid, undecylenic acid, lauric acid, linderic acid, myristic acid, fizeteric acid, myristoleic acid, palmitic acid, palmitoleic acid, hiragoic acid, stearic acid, petroselinic acid, oleic acid, elaidic acid, Asclepic acid, vaccenic acid, linoleic acid, α-eleostearic acid, β-eleostearic acid,
Punicic acid, linolenic acid, γ-linolenic acid, moloctic acid,
Stearidonic acid, stearolic acid, arachidic acid, gadoleic acid, gondoinic acid, arachidonic acid, behenic acid, cetoleic acid, erucic acid, brassic acid, iwasic acid, lignoceric acid, ceracoleic acid, nisinic acid, serotic acid, ximenoic acid, montan Acids, metal salts of fatty acids such as melissic acid, lumecic acid), metal salts of alkanoyl lactic acid (for example, metal salts of alkanoyl lactic acid such as dodecanoyl lactic acid, tetradecanoyl lactic acid and octadecanoyl lactic acid),
Aliphatic hydroxy acid metal salts (eg glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, tartronic acid, glyceric acid, malic acid, tartaric acid, mesotartaric acid, grape acid, citric acid, 2-hydroxytetradecanoic acid, iprolic acid) , 2-hydroxyhexadecanoic acid, yarapinoleic acid, uniperic acid, ambretoleic acid, aleuritic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid , Metal salts of aliphatic hydroxy acids such as camlorenic acid, licanoic acid, ferronic acid and cerebronic acid), alicyclic carboxylic acid metal salts (naphthenic acid metal salt), aromatic carboxylic acid metal salts (eg benzoic acid, pt- Metal salts of aromatic carboxylic acids such as butylbenzoic acid), alicyclic hydroxy Aroma such as metal salt (hydroxynaphthenic acid metal salt), aromatic hydroxy acid metal salt (eg salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid) Hydroxy acid metal salts), amino acid metal salts,

Hydrotalcites, basic aluminum lithium hydroxycarbonate hydrate and basic aluminum lithium hydroxy.
Lithium-aluminum complex hydroxide salts such as sulfate and hydrate, metal oxides, metal hydroxides, metal carbonates, metal phosphates, metal aliphatic phosphates (eg (mono, dimixed) hexyl phosphate, (mono , Dimixed) octyl phosphate, (mono, dimixed) 2-
Ethylhexyl phosphate, (mono, dimixed) decyl phosphate, (mono, dimixed) lauryl phosphate, (mono, dimixed) myristyl phosphate, (mono, dimixed) palmityl phosphate, (mono, dimixed) stearyl phosphate, (mono, Dimixed) oleyl phosphate, (mono, dimixed) linole phosphate, (mono,
Dimixed) linoleyl phosphate, (mono, dimixed) docosylphosphate, (mono, dimixed) erucylphosphate, (mono, dimixed) tetracosylphosphate,
(Mono, dimixed) hexacosyl phosphate, (mono,
Dimixed) metal salts of aliphatic phosphoric acid such as octacosyl phosphate), aromatic metal salts of phosphoric acid (eg bis (p-
t-Butylphenyl) phosphoric acid, mono (pt-butylphenyl) phosphoric acid, 2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphoric acid, 2,2'-methylene-bis ( 4,6-di-t-amylphenyl) phosphoric acid, 2,2'-ethylidene-bis (4,6-di-t
-Butylphenyl) phosphoric acid, 2,2'-ethylidene-bis (4,6
-Di-t-amylphenyl) phosphoric acid and other aromatic phosphoric acid salts), tribasic lead sulfate, hydrazone, alkenes, cyclic esters, organometallic compounds, benzhydrol, epoxy compounds (eg epichlorohydrin and bisphenol A) Condensation product with, 2-methyl epichlorohydrin with bisphenol A, triglycidyl isocyanurate, epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, etc.), hydroxylamine,

Aliphatic amines (eg octylamine,
Laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, cocoamine,
Tallow amine, soy amine, N, N-dicocoamine, N,
N-ditaromine, N, N-disoyamine, N-lauryl
-N, N-dimethylamine, N-myristyl-N, N-dimethylamine, N-palmityl-N, N-dimethylamine, N-
Stearyl-N, N-dimethylamine, N-coco-N, N-dimethylamine, N-tallow-N, N-dimethylamine, N-
Soy-N, N-dimethylamine, N-methyl-N, N-ditaromine, N-methyl-N, N-dicocoamine, N-oleyl-1,3-diaminopropane, N-tallow-1,3-diaminopropane , Hexamethylenediamine, N-lauryl-N, N,
N-trimethylammonium chloride, N-palmityl
-N, N, N-trimethylammonium chloride, N-stearyl-N, N, N-trimethylammonium chloride, N-docosyl-N, N, N-trimethylammonium chloride, N-coco-N, N, N-trimethyl Ammonium chloride, N-tallow-N, N, N-trimethylammonium chloride, N-soy-N, N, N-trimethylammonium chloride, N, N, N-triethyl-N-benzylammonium chloride, N-lauryl-N , N-dimethyl
-N-benzylammonium chloride, N-myristyl-
N, N-dimethyl-N-benzylammonium chloride,
N-stearyl-N, N-dimethyl-N-benzylammonium chloride, N-coco-N, N-dimethyl-N-benzylammonium chloride, N, N-dioleyl-N, N-dimethylammonium chloride, N, N- Dicoco-N, N-dimethylammonium chloride, N, N-ditarou-N, N
-Dimethylammonium chloride, N, N-disoy-N,
N-dimethylammonium chloride, N, N-bis (2-
Hydroxyethyl) -N-lauryl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-
Stearyl-N-methylammonium chloride, N, N-
Bis (2-hydroxyethyl) -N-oleyl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-coco-N-methylammonium chloride, N,
N-bis (polyoxyethylene) -N-lauryl-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-stearyl-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-Oleyl
-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-coco-N-methylammonium chloride,

N, N-bis (2-hydroxyethyl) laurylaminobetaine, N, N-bis (2-hydroxyethyl)
Tridecylaminobetaine, N, N-bis (2-hydroxyethyl) myristylaminobetaine, N, N-bis (2-hydroxyethyl) pentadecylaminobetaine, N, N-
Bis (2-hydroxyethyl) palmitylaminobetaine, N, N-bis (2-hydroxyethyl) stearylaminobetaine, N, N-bis (2-hydroxyethyl) oleylaminobetaine, N, N-bis (2- Hydroxyethyl)
Docosylaminobetaine, N, N-bis (2-hydroxyethyl) octacosylaminobetaine, N, N-bis (2-hydroxyethyl) cocoaminobetaine, N, N-bis (2-
Hydroxyethyl) tallow aminobetaine, hexamethylenetetramine, triethanolamine, triisopropanolamine, N- (2-hydroxyethyl) laurylamine, N- (2-hydroxyethyl) tridecylamine, N- (2-hydroxyethyl) Myristylamine, N-
(2-Hydroxyethyl) pentadecylamine, N- (2-
Hydroxyethyl) palmitylamine, N- (2-hydroxyethyl) stearylamine, N- (2-hydroxyethyl) oleylamine, N- (2-hydroxyethyl) docosylamine, N- (2-hydroxyethyl) octacosylamine, N- (2-hydroxyethyl) cocoamine, N-
(2-Hydroxyethyl) tallow amine, N-methyl-N-
(2-hydroxyethyl) laurylamine, N-methyl-N
-(2-hydroxyethyl) tridecylamine, N-methyl
-N- (2-hydroxyethyl) myristylamine, N-methyl-N- (2-hydroxyethyl) pentadecylamine,
N-methyl-N- (2-hydroxyethyl) palmitylamine, N-methyl-N- (2-hydroxyethyl) stearylamine, N-methyl-N- (2-hydroxyethyl) oleylamine, N-methyl-N -(2-hydroxyethyl) docosylamine, N-methyl-N- (2-hydroxyethyl) octacosylamine, N-methyl-N- (2-hydroxyethyl) cocoamine, N-methyl-N- (2-hydroxyethyl) ) Taro amine,

N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-hydroxyethyl) tridecylamine, N, N-bis (2-hydroxyethyl) myristylamine, N, N- Bis (2-hydroxyethyl) pentadecylamine, N, N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl) stearylamine, N, N-bis (2-hydroxyethyl) ) Oleylamine, N, N-bis (2-hydroxyethyl) docosylamine, N, N-bis (2-hydroxyethyl) octacosylamine, N, N-bis (2-hydroxyethyl) cocoamine, N, N-bis ( N, N-bis (2-hydroxyethyl) aliphatic amines such as 2-hydroxyethyl) tallow amine,
Mono- or diesters of N, N-bis (2-hydroxyethyl) aliphatic amine with lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid and the like, polyoxyethylene lauryl amino Ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene cocoamino ether, polyoxyethylene tallow amino ether, N, N, N ', N'-tetra (2-hydroxyethyl) -1, 3-diaminopropane, N,
N, N ', N'-tetra (2-hydroxyethyl) -1,6-diaminohexane, N-lauryl-N, N', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-stearyl
-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-coco-N, N', N'-tris (2-hydroxyethyl) -1,3-diaminopropane , N-Taro-N,
N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N, N-dicoco-N', N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N, N-Zitarou-N ',
N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N-coco-N, N ', N'-tris (2-hydroxyethyl) -1,6-diaminohexane, N-tallow-N , N ', N'-tris (2-hydroxyethyl) -1,6-diaminohexane,
N, N-dicoco-N ', N'-bis (2-hydroxyethyl) -1,
6-diaminohexane and N, N-ditallow-N ', N'-bis (2-hydroxyethyl) -1,6-diaminohexane etc.),

Aliphatic amides (eg oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, montanic acid amide, N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N -Oleyl stearic acid amide,
N-stearyl erucic acid amide, N-oleyl palmitic acid amide, N, N'-methylene-bis-lauric acid amide,
N, N'-methylene-bis-myristic acid amide, N, N'-methylene-bis-palmitic acid amide, N, N'-methylene-bis-palmitoleic acid amide, N, N'-methylene-bis-stearoamide, N, N'-methylene-bis-12-hydroxystearic acid amide, N, N'-methylene-bis-oleic acid amide, N, N'-methylene-bis-behenic acid amide, N,
N'-methylene-bis-erucic acid amide, N, N'-methylene-
Bis-montanic acid amide, N, N'-ethylene-bis-lauric acid amide, N, N'-ethylene-bis-myristic acid amide, N, N'-ethylene-bis-palmitic acid amide, N,
N'-ethylene-bis-palmitoleic acid amide, N, N'-
Ethylene-bis-stearoamide, N, N'-ethylene-bis
-12-hydroxystearic acid amide, N, N'-ethylene-
Bis-oleic acid amide, N, N'-ethylene-bis-behenic acid amide, N, N'-ethylene-bis-erucic acid amide, N,
N'-ethylene-bis-montanic acid amide, N, N'-hexamethylene-bis-stearoamide, N, N'-hexamethylene-bis-oleic acid amide, N, N'-hexamethylene-bis-behenic acid amide , N, N'-Distearyl oxalic acid amide, N, N'-Dioleyl succinic acid amide, N, N'-Distearyl succinic acid amide, N, N'-Dioleyl succinic acid amide, N, N'- Distearyl adipic amide, N, N'-
Dioleyl adipic acid amide, N, N'-distearyl sebacic acid amide, N, N'-dioleyl sebacic acid amide, N, N-bis (2-hydroxyethyl) lauryl amide, N, N-bis (2- Hydroxyethyl) tridecylamide, N, N-bis (2-hydroxyethyl) myristylamide, N, N-bis (2-hydroxyethyl) pentadecylamide, N, N-bis (2-hydroxyethyl) palmitylamide , N, N-bis (2-hydroxyethyl) stearylamide, N, N-bis (2-hydroxyethyl) oleylamide, N, N-bis (2-hydroxyethyl) docosylamide, N, N-bis (2- Hydroxyethyl) octacosylamide, N, N-bis (2-hydroxyethyl) cocoamide,
N, N-bis (2-hydroxyethyl) tallow amide, polyoxyethylene lauryl amide ether, polyoxyethylene stearyl amide ether, polyoxyethylene oleyl amide ether, polyoxyethylene cocoamide ether, polyoxyethylene tallow amide ether, etc.),

Hindered amine compounds (eg 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-
4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-t-butyl-2-butenyl)- 4-hydroxy-2,2,6,
6-tetramethylpiperidine, 4-stearoyloxy-2,
2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 1-benzyl-2,
2,6,6-tetramethyl-4-piperidyl malate, bis (2,
2,6,6-Tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4- Piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) fumarate, bis (1,2,3, 6-tetramethyl-2,6
-Diethyl-4-piperidyl) sebacate, bis (1-allyl
-2,2,6,6-Tetramethyl-4-piperidyl) phthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,1 '-(1,2-ethanediyl) Bis (3,3,5,5-tetramethylpiperazinone), 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino-N- (2,2,6, 6-Tetramethyl-4-piperidyl) propionamide, 2-methyl-2-
(1,2,2,6,6-pentamethyl-4-piperidyl) imino-N-
(1,2,2,6,6-pentamethyl-4-piperidyl) propionamide, 1-propargyl-4-β-cyanoethyloxy-2,2,
6,6-tetramethylpiperidine, 1-acetyl-2,2,6,6-tetramethyl-4-piperidyl-acetate, trimellitic acid
-Tris (2,2,6,6-tetramethyl-4-piperidyl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6 , 6-pentamethyl-4-
Piperidyl) dibutyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) dibenzyl-malonate, bis (1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl ) Dibenzyl-malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate ,

Bis (2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3-dicarboxylate, bis (1,2,2,6,6 -Pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3
-Dicarboxylate, bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.5]
Undecane-3,3-dicarboxylate, 1,3-bis [2,2'-
[Bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-dioxacyclohexane-5,5-dicarboxylate]],
Bis (2,2,6,6-tetramethyl-4-piperidyl) -2- [1-methylethyl] -1,3-dioxacyclohexane-5,5-dicarboxylate]], 1,2-bis [2,2 '-[Bis (2,2,6,6-
Tetramethyl-4-piperidyl) -2-methyl-1,3-dioxacyclohexane-5,5-dicarboxylate]], bis (2,2,6,6-tetramethyl-4-piperidyl) -2- [2- (3,5-
Di-t-butyl-4-hydroxyphenyl)] ethyl-2-methyl-1,3-dioxacyclohexane-5,5-dicarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl ) -1,5-
Dioxaspiro [5.11] heptadecane-3,3-dicarboxylate, hexane-1 ', 6'-bis-4-carbamoyloxy
-1-n-butyl-2,2,6,6-tetramethylpiperidine), toluene-2 ', 4'-bis (4-carbamoyloxy-1-n-butyl-
2,2,6,6-tetramethylpiperidine), dimethyl-bis (2,2,6,6-tetramethylpiperidine-4-oxy) -silane, phenyl-tris (2,2,6,6-tetramethyl Piperidine-4-oxy) -silane, tris (1-propyl-2,2,6,6-)
Tetramethyl-4-piperidyl) -phosphite, tris (1-propyl-2,2,6,6-tetramethyl-4-piperidyl)-
Phosphate, phenyl- [bis (1,2,2,6,6-pentamethyl-4-piperidyl)]-phosphonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2 , 3,4-Butane tetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) 1,2,3,4-butanetetracarbonamide,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)
1,2,3,4-butanetetracarbonamide,

2-dibutylamino-4,6-bis (9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.
5] -3-Undecylmethoxy) -s-triazine, 2-dibutylamino-4,6-bis (9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] -3-Undecylmethoxy) -s-triazine, tetrakis (9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.
5] -3-Undecylmethyl) -1,2,3,4-butanetetracarboxylate, tetrakis (9-aza-3-ethyl-8,8,9,1
0,10-Pentamethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) -1,2,3,4-butanetetracarboxylate, tridecyl tris (2,2,6,6-tetramethyl- 4-piperidyl) 1,2,3,4-butane tetracarboxylate, tridecyl tris (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, Di (tridecyl) bis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, di (tridecyl) bis (1,2,2,6, 6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 2,2,4,4-
Tetramethyl-7-oxa-3,20-diazadisspiro [5,1,11,
2] HENEICOSAN-21-ON, 3,9-bis [1,1-dimethyl-
2- {Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,
4,8,10-Tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butyl Carbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane, poly (2,2,6,6-tetramethyl-4-piperidyl acrylate), poly (1,2,2,6,6-pentamethyl-4)
-Piperidyl acrylate), poly (2,2,6,6-tetramethyl-4-piperidyl methacrylate), poly (1,2,2,6,6
-Pentamethyl-4-piperidyl methacrylate), poly [[bis (2,2,6,6-tetramethyl-4-piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (1,2,2,6, 6-pentamethyl-4-piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (2,2,2
6,6-Tetramethyl-4-piperidyl) itaconate] [vinyl octyl ether]], poly [[bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) itaconate] [vinyl octyl ether]], dimethyl succinate-2- (4-
Hydroxy-2,2,6,6-tetramethylpiperidyl) ethanol condensate,

Poly [hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [ethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[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- (diethylimino)-
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-[(2-ethylhexyl) 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]], 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]], poly [[6- (Cyclohexylimino) -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-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- (butoxyimino) -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-[(1,1,3,3-tetramethylbutyl))
Oxy] -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 [oxy [6-[(1-piperidyl) -1,3,5] -
Triazine-2,4-diyloxy-1,2-ethanediyl]
[(2,2,6,6-tetramethyl-3-oxo-1,4-piperidyl)
-1,2-ethanediyl] [(3,3,5,5-tetramethyl-2-oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [oxy [6-[(1,1 , 3,3-Tetramethylbutyl) imino]-
1,3,5-Triazine-2,4-diyloxy-1,2-ethanediyl] [(2,2,6,6-tetramethyl-3-oxo-1,4-piperidyl) -1,2-ethanediyl] [(3,3,5,5-tetramethyl-2-
Oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [[6-[(ethylacetyl) 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]], poly [[6-[(2,2,6,6-
Tetramethyl-4-piperidyl) butylimino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2 , 6,6-Tetramethyl-4-piperidyl) imino]],

1,6,11-tris [{4,6-bis (N-butyl-
N- (2,2,6,6-tetramethyl-4-piperidyl) amino)-
1,3,5-Triazin-2-yl} amino] undecane, 1,6,1
1-tris [{4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazine
-2-yl} amino] undecane, 1,6,11-tris [{4,6-
Bis (N-octyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl} amino]
Undecane, 1,6,11-Tris [{4,6-bis (N-octyl
-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl} amino] undecane,
1,5,8,12-Tetrakis [4,6-bis (N- (2,2,6,6-tetramethyl-4-piperidyl) -butylamino) -1,3,5-triazin-2-yl ] -1,5,8,12-Tetraazadodecane, 1,5,8,1
2-Tetrakis [4,6-bis (N- (1,2,2,6,6-pentamethyl-4-piperidyl) -butylamino) -1,3,5-triazine-
2-yl] -1,5,8,12-tetraazadodecane etc.),

Aminotriazine compounds (eg 2,4,
6-triamino-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5
-Triazine, 1,4-bis (3,5-diamino-2,4,6-triazinyl) butane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane etc.) and the like. Also,
Examples of the metal include lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, aluminum and the like, and the above-mentioned metal salts include not only a normal salt but also various basic salts. In particular, fatty acid metal salts, alkanoyl lactic acid metal salts, aliphatic hydroxy acid metal salts, hydrotalcites, lithium aluminum complex hydroxide salts, metal oxides, metal hydroxides, carbonate metal salts, aliphatic phosphate metal salts, Epoxy compounds, aliphatic amines, aliphatic amides, hindered amine compounds, aminotriazine compounds and mixtures of two or more of these are preferred. These compounds B may be used alone or in combination of two or more kinds. The content ratio of the compound B is 0.001 to 1 part by weight, preferably 100 parts by weight of the crystalline polyolefin containing a magnesium halide compound as a catalyst residue.
0.01 to 0.5 parts by weight. If the content is less than 0.001 part by weight, the transparency improving effect is not sufficiently exerted, and if it exceeds 1 part by weight, further transparency improving effect cannot be expected and it is not practical. It is also uneconomical.

The compound C used in the present invention is sodium acetate, sodium propionate, sodium butyrate, sodium valerate, sodium α-methylbutyrate, sodium hexanoate, sodium sorbate, sodium octanoate, sodium 2-ethylhexanoate. , Sodium nonanoate, sodium decanoate, sodium caproate, sodium undecanoate, sodium undecylenate, sodium laurate, sodium linderate, sodium myristate, sodium fizeterate, sodium myristoleate, sodium palmitate, sodium palmitoleate, Sodium hiragoate, sodium stearate, sodium petroselinate, sodium oleate, sodium elaidate,
Sodium asclepinate, sodium vaccenate, sodium linoleate, sodium α-eleostearate, sodium β-eleostearate, sodium punicate, sodium linolenate, sodium γ-linolenate, sodium moloctate, sodium stearidate, Sodium stearate, sodium arachidate, sodium gadoleate, sodium gondoinate, sodium arachidonate, sodium behenate, sodium selenate, sodium erucate, sodium brassidate, sodium iwasate, sodium lignocerate, sodium ceracolate, herring Sodium acid salt, sodium cerotate, sodium ximenate, sodium montanate, sodium melicinate, sodium lumecitrate,

Sodium 2-hydroxytetradecanoate,
Sodium iprolate, Sodium 2-hydroxyhexadecanoate, Sodium yarapinoleate, Sodium uniperate, Sodium ambretolate, Sodium aleurite, Sodium 2-hydroxyoctadecanoate, Sodium 12-hydroxyoctadecanoate, 18-
Sodium hydroxyoctadecanoate, sodium 9,10-dihydroxyoctadecanoate, sodium ricinoleate, sodium camlorenate, sodium licanoate, sodium ferronate, sodium cerebronate,

Sodium glycolate, sodium lactate, sodium hydroacrylate, sodium α-oxybutyrate, sodium tartronate, sodium glycerate, sodium malate, sodium tartrate, sodium meso-tartrate, sodium grate, sodium citrate, dodecanoyl lactic acid Sodium, sodium tetradecanoyl lactate and sodium octadecanoyl lactate can be exemplified,

Particularly preferred is sodium stearate.
These compounds C may be used alone or in combination of two or more kinds. The content ratio of the compound C is 0.0 with respect to 100 parts by weight of the crystalline polyolefin.
The amount is 01 to 1 part by weight, preferably 0.01 to 0.5 part by weight. 0.0
If the content is less than 01 parts by weight, the effect of improving the rigidity cannot be fully exerted, and if it exceeds 1 part by weight, it is not practical because the effect of improving the rigidity cannot be expected further. It is also uneconomical.

As the compound D used in the present invention, magnesium acetate, magnesium propionate, n-magnesium butyrate, i-magnesium butyrate, n-magnesium valerate, i-magnesium valerate, n-magnesium hexanoate, n- Magnesium octoate, magnesium 2-ethylhexanoate, magnesium decanoate, magnesium laurate, magnesium myristate, magnesium myristoleate, magnesium palmitate, magnesium palmitoleate, magnesium stearate, magnesium oleate, magnesium linoleate, linolenic acid Magnesium, magnesium arachiate, magnesium behenate, magnesium erucate, magnesium lignocerate, magnesium serotenate, magnesium montanate, melicinate Gnesium, magnesium 12-hydroxyoctadecanoate, magnesium ricinoleate, magnesium cerebronate, (mono, dimixed) magnesium hexyl phosphate, (mono, dimixed) magnesium octyl phosphate, (mono, dimixed) magnesium 2-ethylhexyl phosphate, (mono , Dimixed) magnesium decyl phosphate, (mono, dimixed) magnesium lauryl phosphate, (mono, dimixed) magnesium myristyl phosphate, (mono, dimixed) magnesium palmityl phosphate, (mono,
Dimixed) magnesium stearyl phosphate, (mono, dimixed) oleyl magnesium phosphate, (mono, dimixed) magnesium linoleate, (mono, dimixed) magnesium linoleyl phosphate, (mono, dimixed) magnesium docosylphosphate, (mono, dimixed) erucillin Magnesium acid, magnesium (mono, dimixed) tetracosyl phosphate,
(Mono, dimixed) magnesium hexacosylphosphate, (mono, dimixed) magnesium octacosylphosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate,

10-hydroxy-9,10-dihydro-9-oxa-1
0-phosphaphenanthrene-10-oxide, 1-methyl
-10-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphafe Nanthrene-10-oxide, 6-methyl-10-hydroxy-9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 7-methyl-10-hydroxy-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 8-methyl-10-hydroxy-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 6,8-dimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8- Trimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospha phenanthrene-10-oxide, 2-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide, 6-ethyl-10-hydroxy-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-oxide, 8-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-diethyl-10-hydroxy-9,10-dihydro -9-
Oxa-10-phosphaphenanthrene-10-oxide,
2,6,8-Triethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-
i-Propyl-10-hydroxy-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 6-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-i-propyl-1
0-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-i-propyl-10
-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-i-propyl-
10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,

2-s-butyl-10-hydroxy-9,10-dihydro
-9-oxa-10-phosphaphenanthrene-10-oxide, 6-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8 -s-
Butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1,8-di-s-butyl-10-hydroxy-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-s-
Butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-butyl-1
0-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide, 8-t-butyl-10-hydroxy-9,1
0-dihydro-9-oxa-10-phosphaphenanthrene-10
-Oxide, 1,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-di-t-butyl-10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,7-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, 2,8-di-t-butyl-10-hydroxy-9,10-dihydro-
9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide,
2,6,8-Tri-t-butyl-10-hydroxy-9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide,
2-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 6-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-amyl-10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide,

2,6,8-tri-t-amyl-10-hydroxy-9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 2-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-octyl-10-hydroxy-9,10-dihydro- 9-
Oxa-10-phosphaphenanthrene-10-oxide,
8-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 6,8-di-
t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 2,6,8-tri-t-octyl-10-hydroxy-9,10-dihydro-9-oxa
-10-phosphaphenanthrene-10-oxide, 2-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 6-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
Phosphaphenanthrene-10-oxide, 8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-cyclohexyl-10- Hydroxy-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 2,6,8-tri-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-
Phenyl-10-hydroxy-9,10-dihydro-9-oxa-10-
Phosphaphenanthrene-10-oxide, 2-benzyl
-10-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphafe Nanthrene-10-oxide, 8-benzyl-10-hydroxy-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-Oxide, 6,8-di-benzyl-10-hydroxy-9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 2,6,8-tri-benzyl-10-hydroxy-9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 2- (α-methylbenzyl) -10-hydroxy-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-oxide,

6- (α-methylbenzyl) -10-hydroxy-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-Oxide, 8- (α-methylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di (α-methylbenzyl) )-
10-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri (α-methylbenzyl) -10-hydroxy-9,10-dihydro- 9-oxa
10-phosphaphenanthrene-10-oxide, 2,6-di (α, α-dimethylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 6-t-butyl-8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-methyl-10-hydroxy- 9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 6-cyclohexyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-t-butyl-10- Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- (α-methylbenzyl)-
8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 6-t-butyl-8-cyclohexyl-10-hydroxy-9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide,
6-benzyl-8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-benzyl-10-hydroxy-9, Ten
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 6-cyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-di-t-butyl-8-benzyl- 1
0-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2,6-dicyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa- Magnesium salts of cyclic phosphorus compounds such as 10-phosphaphenanthrene-10-oxide,

Magnesium-bis (1'-hydroxy-2,2'-
Biphenylenephosphinate), magnesium-bis (5-methyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (6-methyl-1'-hydroxy-2,2'-biphenylenephos) Finate), magnesium-bis (1'-hydroxy-4'-methyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-5'-methyl-2,2'-biphenylenephos) Finate), magnesium-bis (1'-hydroxy-6'-methyl-
2,2'-biphenylene phosphinate), magnesium-
Bis (1'-hydroxy-4 ', 6'-dimethyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4', 6'-
Trimethyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (5-ethyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy) -4'-ethyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-6'-ethyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy) -4 ', 6'-diethyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4', 6'-triethyl-1'-hydroxy-2,2'-
Biphenylene phosphinate), magnesium-bis (5-i-propyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-
4'-i-propyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-6'-i-propyl-2,2'-biphenylenephosphinate), magnesium-bis (1 '-Hydroxy-4', 6'-di-i-propyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4 ', 6'-tri-i-propyl-1'-hydroxy- 2,2'-biphenylene phosphinate), magnesium-bis (5-s
-Butyl-1'-hydroxy-2,2'-biphenylenephosphinate),

Magnesium-bis (1'-hydroxy-4'-s-
Butyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-6'-s-butyl-2,2'-biphenylenephosphinate), magnesium-bis (6,6'-
Di-s-butyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (5,4 ', 6'-tri-s-butyl-1'-hydroxy-2,2'- Biphenylene phosphinate), magnesium-bis (5-t-butyl-1'-hydroxy-
2,2'-biphenylene phosphinate), magnesium-
Bis (1'-hydroxy-4'-t-butyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-6'-t-butyl-2,2'-biphenylenephosphinate ), Magnesium-bis (5,6'-di-t-butyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (5,4'-di-t-butyl-1 '-Hydroxy-2,2'-
Biphenylene phosphinate), magnesium-bis (5,5'-di-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (6,4'-di-t-
Butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-
t-Butyl-2,2'-biphenylenephosphinate), magnesium-bis (5,4 ', 6'-tri-t-butyl-1'-hydroxy
-2,2'-biphenylene phosphinate), magnesium
-Bis (5-t-amyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-t-amyl-2,2'-biphenylene phosphinate ), Magnesium-bis (1'-hydroxy-6'-t-amyl
-2,2'-biphenylene phosphinate), magnesium
-Bis (1'-hydroxy-4 ', 6'-di-t-amyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4',
6'-tri-t-amyl-1'-hydroxy-2,2'-biphenylenephosphinate),

Magnesium-bis (5-t-octyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-t-octyl-2,2'- Biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'-t-octyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy)
-4 ', 6'-di-t-octyl-2,2'-biphenylenephosphinate), magnesium-bis (5,4', 6'-tri-t-octyl
-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-cyclohexyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy- 4'-cyclohexyl-2,2'-
Biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'-cyclohexyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-cyclohexyl- 2,2'-biphenylenephosphinate), magnesium-bis (5,4 ', 6'-tri-cyclohexyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (1'- Hydroxy-4'-
Phenyl-2,2'-biphenylenephosphinate), magnesium-bis (5-benzyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (1'-
Hydroxy-4'-benzyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-6'-benzyl-2,2'-biphenylenephosphinate), magnesium-bis (1'- Hydroxy-4 ', 6'-di-benzyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4', 6'-tri-benzyl-1'-hydroxy-2,2'-biphenylene Phosphinate), magnesium-bis [5-
(Α-Methylbenzyl) -1′-hydroxy-2,2′-biphenylenephosphinate], magnesium-bis [1′-hydroxy-4 ′-(α-methylbenzyl) -2,2′-biphenylenephosphine Nate],

Magnesium-bis [1'-hydroxy-6'-
(Α-Methylbenzyl) -2,2'-biphenylenephosphinate], magnesium-bis [1'-hydroxy-4 ', 6'-
Di (α-methylbenzyl) -2,2'-biphenylene phosphinate], magnesium-bis [5,4 ', 6'-tri (α-methylbenzyl) -1'-hydroxy-2,2'-biphenylene Phosphinate], magnesium-bis [5,4'-di (α, α-
Dimethylbenzyl) -1'-hydroxy-2,2'-biphenylenephosphinate], magnesium-bis (1'-hydroxy-4'-t-butyl-6'-methyl-2,2'-biphenylenephosphinate ), Magnesium-bis (1'-hydroxy-4'-benzyl-6'-methyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-cyclohexyl-6'-t -Butyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-benzyl
-6'-t-butyl-2,2'-biphenylenephosphinate),
Magnesium-bis [1'-hydroxy-4 '-(α-methylbenzyl) -6'-t-butyl-2,2'-biphenylenephosphinate], magnesium-bis (1'-hydroxy-4'-t -Butyl-6'-cyclohexyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-benzyl-6'-cyclohexyl-2,2'-biphenylenephosphinate), magnesium -Bis (1'-hydroxy-4'-t-butyl-6'-benzyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-cyclohexyl-6'-benzyl- 2,2'-biphenylene phosphinate), magnesium-bis (5,4'-di-t-butyl-6'-benzyl-1'-hydroxy-2,2'-biphenylene phosphinate) and magnesium-bis (5,4'-dicyclohexyl
-6'-benzyl-1'-hydroxy-2,2'-biphenylenephosphinate) and the like,

In particular, magnesium 2-ethylhexanoate, magnesium laurate, magnesium myristate, magnesium palmitate, magnesium stearate,
Magnesium oleate, magnesium behenate, magnesium erucate, magnesium montanate, magnesium 12-hydroxyoctadecanoate, magnesium (mono, dimixed) stearyl phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, 10-hydroxy-9,10 The magnesium salt of -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and magnesium-bis (1'-hydroxy-2,2'-biphenylenephosphinate) are preferred. These compounds D may be used alone or in combination of two or more kinds. The content ratio of the compound D is 0.001 to 1 part by weight based on 100 parts by weight of HCPP (H) or HCPP (B),
It is preferably 0.01 to 0.5 parts by weight. When the content is less than 0.001 part by weight, the effect of improving tensile elongation is not sufficiently exerted, and the compound D excluding magnesium oxide, magnesium hydroxide and magnesium carbonate may exceed 1 part by weight, The effect of improving the tensile elongation cannot be expected and is not practical, and it is uneconomical. When the amount of magnesium oxide, magnesium hydroxide and magnesium carbonate exceeds 1 part by weight, the effect of improving the tensile elongation cannot be achieved.

The compound E used in the present invention is 2,
2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-bis (4 -t-Amyl-6-methylphenyl) fluorophosphite, 2,2'-bis (4-s
-Eicosylphenyl) fluorophosphite, 2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-ethyl-6-t
-Butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-nonylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-dinonylphenyl) fluorophosphite , 2,2'-methylene-bis (4-
Methyl-6-cyclohexylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6- (1'-methylcyclohexyl) phenyl) fluorophosphite,
2,2'-i-Propylidene-bis (4-nonylphenyl) fluorophosphite, 2,2'-butylidene-bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-methylene-
Bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) fluorophosphite, 2,2'-ethylidene-bis ( 4-Methyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4-ethyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4- s-Butyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4, 6-di-t-amylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-t-octylphenyl) fluorophosphite, 2,2'-butylidene-bis (4-methyl- 6- (1'-methylcyclohexyl) phenyl)
Fluorophosphite, 2,2'-methylene-bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-thio-
Bis (4-t-octylphenyl) fluorophosphite, 2,2'-thio-bis (4,6-di-s-amylphenyl) fluorophosphite, 2,2'-thio-bis (4,6- Di-i-octylphenyl) fluorophosphite, 2,2'-thio-bis (5-t-butylphenyl) fluorophosphite, 2,
2'-thio-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-methyl-6-α-methylbenzylphenyl) fluorophosphite, 2,2 '
-Thio-bis (3-methyl-4,6-di-t-butylphenyl) fluorophosphite and 2,2'-thio-bis (4-t-amylphenyl) fluorophosphite can be exemplified,

Particularly 2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-
Methyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl)
Fluorophosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) fluorophosphite,
2,2'-Ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite and 2,2'-thio-bis (4-methyl
-6-t-Butylphenyl) fluorophosphite is preferred. These compounds E may be used alone or in combination of two or more kinds. The content ratio of the compound E is HCPP (H) or HCPP (B) 100.
0.001 to 1 part by weight, preferably 0.01 to 0.5 with respect to parts by weight
Parts by weight. If the content is less than 0.001 part by weight, the effect of improving tensile elongation is not sufficiently exerted, and if it exceeds 1 part by weight, a further effect of improving tensile elongation cannot be expected and it is not practical. It is also uneconomical.

In the composition of the first invention of the present application, various additives usually added to crystalline polyolefins such as antioxidants such as phenol type, thioether type, phosphorus type (excluding compound A), Light stabilizer (excluding compound B), heavy metal deactivator (copper damage inhibitor; excluding compound B), clarifying agent (excluding compound A and compound B), nucleating agent ( However, compound A and compound B are excluded), lubricant (however, compound B is excluded), antistatic agent (however, compound B is excluded), antifogging agent, antiblocking agent, drop-free agent, peroxide, etc. Radical generator, flame retardant (excluding compound B), flame retardant aid, pigment, organic or inorganic antibacterial agent, inorganic filler (for example, talc, mica, clay, wollastonite, zeolite, kaolin, Tontonite, perlite, diatomaceous earth, asbestos, silicon dioxide, titanium dioxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal fiber, etc. ), A coupling agent (for example, a silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, etc.) surface-treated inorganic or organic filler (for example, wood powder, pulp) , Waste paper, synthetic fiber, natural fiber, etc.) can be used together within a range not impairing the object of the present invention.

In the composition of the second invention of the present application, various additives which are usually added to crystalline polyolefins, for example, antioxidants such as phenol-based, thioether-based, phosphorus-based (except compound A), Light stabilizer, heavy metal deactivator (copper damage inhibitor), clarifying agent (excluding compound A), nucleating agent (excluding compound A), lubricant, antistatic agent, antifogging agent, Antiblocking agent, non-dropping agent, radical generator such as peroxide, flame retardant, flame retardant aid, pigment, halogen scavenger (excluding compound C), dispersant or neutralizer for metallic soaps Agents (excluding compound C), organic or inorganic antibacterial agents, inorganic fillers (eg talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos) Calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, hydrotalcite, basic aluminum lithium hydroxy carbonate carbonate hydrate, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, calcium oxide, zinc sulfide, sulfuric acid Barium, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal fiber), coupling agent (for example, silane-based, titanate-based, boron-based, aluminate-based) , Zircoaluminate-based) and inorganic fillers or organic fillers (eg, wood powder, pulp, waste paper, synthetic fibers, natural fibers, etc.) surface-treated with a surface treatment agent such as To use together Door can be.

In the composition of the third invention of the present application, various additives which are usually added to the crystalline propylene polymer, such as phenol-based, thioether-based and phosphorus-based antioxidants (provided that compound A and compound are used). Except E), light stabilizer, heavy metal deactivator (copper damage inhibitor), clarifier, β
Crystal nucleating agent, lubricant (excluding compound D), antistatic agent, antifogging agent, antiblocking agent, non-dripping agent, flame retardant (excluding compound D), flame retardant aid, pigment, halogen Scavenger (excluding compound D), dispersant or neutralizing agent for metal soaps (excluding compound D), organic or inorganic antibacterial agent, inorganic filler (eg talc, mica, Clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, aluminum hydroxide, hydrotalcite, basic aluminum lithium hydroxy carbonate carbonate hydrate, silicon dioxide, titanium dioxide, oxidation Zinc, calcium oxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate Surface treatment agents such as glass fibers, potassium titanate, carbon fibers, carbon black, graphite and metal fibers), coupling agents (eg silane, titanate, boron, aluminate, zircoaluminate, etc.) The surface-treated inorganic or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used together within the range not impairing the object of the present invention.

The composition of the first invention of the present application comprises, for example, the above-mentioned compound A and compound B in a crystalline polyolefin containing a magnesium halide compound as a catalyst residue, and each of the above-mentioned various additives usually added to the crystalline polyolefin. A predetermined amount of the composition of the second invention of the present application is obtained, for example, by adding the compound A to the crystalline polyolefin.
And a predetermined amount of each of the above-mentioned various additives which are usually added to the crystalline polyolefin, and the composition of the third invention of the present application is, for example, HCPP (H) or HCPP (B). D and compound E and predetermined amounts of the above-mentioned various additives which are usually added to the crystalline propylene polymer are mixed using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, or a Banbury mixer. It can be obtained by mixing and pelletizing by a conventional single-screw extruder, twin-screw extruder, Brabender or roll at a melt-kneading temperature of 150 ° C to 300 ° C, preferably 180 ° C to 270 ° C. The composition obtained is an injection molding method,
Various molding methods such as an extrusion molding method and a blow molding method are used to manufacture a desired molded article.

Further, the composition of the present invention is used for various post-treatments, for example, sterilization by radiation for medical use or food packaging, or surface properties such as paintability and printability. In order to improve the above, it can be used for applications such as low temperature plasma treatment and corona discharge treatment after molding.

[0059]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. 1) Transparency: length 50 mm, width 25 using the obtained pellets
A test piece having a thickness of 1 mm and a thickness of 1 mm was prepared by an injection molding method, and the haze was measured using the test piece (based on ASTM D-1003-61) for evaluation. A highly transparent material has a small haze value. 2) Rigidity: evaluated by a bending test. That is, a test piece having a length of 100 mm, a width of 10 mm and a thickness of 4 mm was prepared by using the obtained pellet by an injection molding method, and the flexural modulus was measured by using the test piece (according to JIS K 7203) to obtain rigidity. Was evaluated. A material having a high rigidity means a material having a large flexural modulus. 3) Heat resistance rigidity: Evaluated by a deflection temperature under load test. That is, using the obtained pellets length 130 mm, width 13 mm,
A test piece having a thickness of 6.5 mm was prepared by an injection molding method, and the heat distortion temperature was measured using the test piece (according to JIS K 7207;
0.451 MPa) to evaluate the heat resistance rigidity. A material having high heat resistance and rigidity means a material having a high heat distortion temperature. 4) Impact resistance: evaluated by the Izod impact test. That is, using the obtained pellets length 63.5 mm, width 13 mm,
A 3.5 mm-thick test piece (having a notch) was prepared by an injection molding method, and the test piece was used to measure the Izod impact strength at 23 ° C. (according to JIS K 7110) to evaluate the impact resistance. A material having excellent impact resistance means a material having a high Izod impact strength. 5) Tensile elongation: evaluated by a tensile test. That is, a JIS No. 1 test piece with a length of 175 mm, a width of 10 mm, and a thickness of 3.3 mm was prepared by using the obtained pellets by an injection molding method, and the tensile elongation was measured using the test piece (based on JIS K 7113). did. A material having an excellent tensile elongation means a material having a large tensile elongation.

Production Examples 1 to 3 (Method for producing HCPP (H) used in Examples 79 to 105 and Comparative Examples 22 to 51) (1) Preparation of catalyst n-hexane 600 ml, diethylaluminum monochloride (DEAC) 0.50 mol , 1.20 mol of diisoamyl ether were mixed at 25 ° C. for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (v) (diisoamyl ether / DEAC molar ratio).
2.4) was obtained. Titanium tetrachloride 4.0 in a reactor purged with nitrogen
Add the mole and heat to 35 ° C, and add the above reaction product solution (v) to it.
After dripping the entire amount of the above in 180 minutes, keep it at the same temperature for 30 minutes, raise the temperature to 75 ℃ and react for another 1 hour, then room temperature (20 ℃)
The mixture was cooled to 4, the supernatant was removed, 4,000 ml of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain 190 g of a solid product (ii). The total amount of this solid product (ii) was suspended in 3,000 ml of n-hexane at 20 ° C.
Then, 160 g of diisoamyl ether and 350 g of titanium tetrachloride were added at room temperature for about 1 minute and reacted at 65 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, 4,000 ml of n-hexane was added, the mixture was stirred for 10 minutes, allowed to stand, and the procedure of removing the supernatant was repeated 5 times. It was dried under reduced pressure to obtain a solid product (iii). (2) Preparation of pre-activated catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 20 l with nitrogen gas, 15 l of n-hexane, 42 g of diethylaluminum monochloride, and 30 g of the solid product (iii) were stirred at room temperature. Then, add 15 Nl of hydrogen, and add propylene partial pressure of 0.588 MPa.
For 5 minutes, unreacted propylene, hydrogen and n-hexane were removed under reduced pressure to obtain pre-activated catalyst (vi) in the form of powder (82.0 g reaction of propylene per 1 g of solid product (iii)).

(3) Polymerization of propylene 100 l of dried n-hexane was placed in a stainless steel polymerization vessel with an internal volume of 250 l, which was replaced with nitrogen gas, and equipped with a turbine type stirring blade.
Then 10 g of diethylaluminum monochloride, 10 g of the preactivated catalyst (vi) and 11.0 g of methyl p-toluate.
Was added, and hydrogen was further added to 100 Nl in Production Example 1 and 2 in Production Example 2.
00Nl and Production Example 3 were each added with 410Nl. Then, after the temperature inside the vessel was raised to 70 ° C., propylene was supplied into the vessel and the pressure inside the vessel was increased to 1.079 MPa. And the temperature is 70
After continuing the polymerization for 4 hours while maintaining the temperature at 1.07 MPa and the pressure at 1.079 MPa, 25 l of methanol was supplied and the temperature was raised to 80 ° C.
After 30 minutes, add another 20% by weight aqueous sodium hydroxide solution to 10%.
After adding 0 g and stirring for 20 minutes and adding 50 l of pure water, residual propylene was discharged. After extracting the water layer, 50 l
Pure water was added and the mixture was stirred and washed with water for 10 minutes, the aqueous layer was withdrawn, the HCPP (H) -n-hexane slurry was withdrawn, the slurry was filtered, and the filtered material was dried to obtain white HCPP (H).
A powder was obtained. The obtained HCPP (H) was used to determine the above-mentioned melt flow rate (MFR) and isotactic pentad fraction (P). The results of these analyzes are shown in Table 1. The HCPP (H) obtained in Production Examples 1 to 3
Are respectively referred to as HCPP (H)-[1] and HCPP (H)-
[2] and HCPP (H)-[3].

Production Examples 4 to 6 (Examples of production of HCPP (B) used in Examples 106 to 132 and Comparative Examples 52 to 81) (1) Preparation of catalyst n-hexane 600 ml, diethylaluminum monochloride (DEAC) 0.50 mol , 1.20 mol of diisoamyl ether were mixed at 25 ° C. for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (v) (diisoamyl ether / DEAC molar ratio).
2.4) was obtained. Titanium tetrachloride 4.0 in a reactor purged with nitrogen
Add the mole and heat to 35 ° C, and add the above reaction product solution (v) to it.
After dripping the entire amount of the above in 180 minutes, keep it at the same temperature for 30 minutes, raise the temperature to 75 ℃ and react for another 1 hour, then room temperature (20 ℃)
The mixture was cooled to 4, the supernatant was removed, 4,000 ml of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain 190 g of a solid product (ii). The total amount of this solid product (ii) was suspended in 3,000 ml of n-hexane at 20 ° C.
Then, 160 g of diisoamyl ether and 350 g of titanium tetrachloride were added at room temperature for about 1 minute and reacted at 65 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, 4,000 ml of n-hexane was added, the mixture was stirred for 10 minutes, allowed to stand, and the procedure of removing the supernatant was repeated 5 times. It was dried under reduced pressure to obtain a solid product (iii). (2) Preparation of pre-activated catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 20 l with nitrogen gas, 15 l of n-hexane, 42 g of diethylaluminum monochloride, and 30 g of the solid product (iii) were stirred at room temperature. Then, add 15 Nl of hydrogen, and add propylene partial pressure of 0.588 MPa.
For 5 minutes, unreacted propylene, hydrogen and n-hexane were removed under reduced pressure to obtain pre-activated catalyst (vi) in the form of powder (82.0 g reaction of propylene per 1 g of solid product (iii)).

(3) Polymerization method Dry n-hexane 250 l was placed in a stainless steel polymerization vessel equipped with a turbine type stirring blade and having an internal volume of 400 l, which was replaced with nitrogen gas.
Then 10 g of diethylaluminum monochloride, 10 g of the preactivated catalyst (vi) and 11.0 g of methyl p-toluate.
Was further added, and hydrogen was added so that the concentration in the gas phase gas was 6 mol% in Production Example 4, 8 mol% in Production Example 5 and 10 mol% in Production Example 6, respectively. Then the temperature inside the vessel
After the temperature was raised to 70 ° C., propylene was supplied into the vessel to raise the pressure in the vessel to 1.079 MPa. And the temperature is 70 ℃ and the pressure is 1.
After continuing the polymerization for 4 hours while maintaining at 079 MPa, the supply of propylene was stopped, unreacted propylene was discharged, a part of the slurry in the polymerization vessel was collected, filtered, washed and dried to obtain white HCPP ( H) powder was obtained. The obtained HCPP
(H) was used to determine the melt flow rate (MFR) and the isotactic pentad fraction (P) described above. The results of these analyzes are shown in Table 2. After releasing unreacted propylene, the inside of the polymerization vessel was maintained at a temperature of 60 ° C. and a pressure of 0.108 MPa, and the supply ratio of ethylene as the second stage polymerization raw material was maintained at 33% by weight in Production Examples 4 to 6, respectively. Then, ethylene and propylene were continuously fed for 2 hours so that the total supply amount of ethylene was 2.4 kg in Production Example 4, 5.4 kg in Production Example 5 and 8.8 kg in Production Example 6, respectively. After the polymerization for 2 hours, the supply of ethylene and propylene was stopped, and unreacted ethylene and propylene were discharged. Then, 25 l of methanol was supplied into the polymerization vessel, and the temperature was raised to 75 ° C. After 30 minutes, 100 g of a 20% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred for 20 minutes. After adding 100 l of pure water, residual propylene was discharged. After extracting the water layer, a further 100 l
Pure water was added and the mixture was stirred and washed with water for 10 minutes, the aqueous layer was extracted, the HCPP (B) -n-hexane slurry was extracted, the slurry was filtered, and the filtered product was dried to give white HCPP (B).
A powder was obtained. The obtained HCPP (B) was used to determine the above-mentioned melt flow rate (MFR) and each ethylene content. The results of these analyzes are shown in Table 2. In addition, HCPP (B) obtained in Production Examples 4 to 6 is
PP (B)-[1], HCPP (B)-[2] and HCPP
(B)-[3] is abbreviated.

Examples 1 to 17 and Comparative Examples 1 to 2 100 parts by weight of powdered crystalline propylene homopolymer having an MFR of 6.0 g / 10 min (a magnesium chloride content of 40 ppm) as a crystalline polyolefin, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) acid phosphite, 2,2'-methylene-bis (4,
6-di-t-butylphenyl) acid phosphite or 2,2'-methylene-bis (4,6-dinonylphenyl) acid phosphite, lithium acetate, calcium stearate, zinc montanate, octadecanoyl as compound B Calcium lactate, basic 12-hydroxy octadecanoate magnesium, lithium glycolate, calcium lactate, zinc tartrate, sodium citrate, basic magnesium aluminum hydroxy carbonate carbonate hydrate or basic aluminum lithium hydroxy carbonate carbonate hydrate A predetermined amount of each of the rate and other additives was put into a Henschel mixer (trade name) at the content ratios shown in Table 3 below, and the mixture was stirred and mixed for 3 minutes, and then melted at 200 ° C. in a twin-screw extruder with a diameter of 30 mm. The mixture was kneaded and pelletized. In addition, as Comparative Examples 1 and 2, MF
Unstabilized powdery crystalline propylene homopolymer with R of 6.0 g / 10 min (magnesium chloride content 40 ppm) 100
A predetermined amount of each of the additives shown in Table 3 described later was mixed in parts by weight, and the mixture was subjected to melt-kneading treatment in accordance with Examples 1 to 17 to obtain pellets. A test piece used for evaluation of transparency was prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the obtained test piece, the transparency was evaluated by the above test method. The results are shown in Table 3.

Examples 18 to 34, Comparative Examples 3 to 4 Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 4.0% by weight, chloride Magnesium content 54ppm) 100 parts by weight of 2,2'-as compound A
Ethylidene-bis (4-methyl-6-t-butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4,6-di-t
-Butylphenyl) acid phosphite or 2,
2'-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphite, zinc oxide, magnesium hydroxide, calcium carbonate, (mono, dimixed) calcium stearyl phosphate, (mono, dimixed) stearyl phosphorus as compound B Zinc acid, sodium-2,2'-methylene
-Bis (4,6-di-t-butylphenyl) phosphate, epoxidized soybean oil, hexamethylenetetramine, triisopropanolamine, N, N-bis (2-hydroxyethyl) cocoamine or N, N-bis (2 -Hydroxyethyl) tallow amine and other additives in the prescribed amounts shown in Table 4 below in a Henschel mixer (trade name), and the mixture was stirred and mixed for 3 minutes.
Was melt-kneaded at 200 ° C. with a twin-screw extruder to produce pellets. Further, as Comparative Examples 3 to 4, 100 parts by weight of powdery crystalline ethylene-propylene random copolymer (ethylene content 4.0% by weight, magnesium chloride content 54 ppm) which is not stabilized and has an MFR of 7.0 g / 10 min will be described later. Predetermined amounts of the additives shown in Table 4 above were mixed and melt-kneaded according to Examples 18 to 34 to obtain pellets. The test piece used for the evaluation of transparency is obtained pellet resin temperature 250 ℃,
It was prepared by injection molding at a mold temperature of 50 ° C. Using the obtained test piece, the transparency was evaluated by the above test method. The results are shown in Table 4.

Examples 35 to 51, Comparative Examples 5 to 6 As crystalline polyolefin, MFR 6.0 g / 10 minutes, unstabilized powdery crystalline propylene homopolymer (magnesium chloride content 15 ppm) 15% by weight, MFR 7 .0g / 10
Unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer (ethylene content 4.0% by weight, butene-1 content 4.5% by weight, magnesium chloride content 95 ppm) 80% by weight and MI (load at 190 ℃ 21.1
Discharge rate of molten resin for 10 minutes when 8N is added) 5.0g / 1
Unstabilized powdered Ziegler-Natta high density ethylene-propylene copolymer for 0 minutes (density 0.950 g / c
2,3'-methylene-bis (4,6-diphenylphenyl) acid phosphine as compound A in a total of 100 parts by weight consisting of m ³ , methyl branch 3.0 / 1000 carbon, magnesium chloride content 20 ppm) 5% by weight Phyto, 2,2'-i-propylidene-bis (4,6-dibenzylphenyl) acid phosphite or 2,2'-butylidene-bis (4-methyl-6- (1'-methylcyclohexyl) phenyl) acid Phosphite, octadecanoic acid 2-[(2-hydroxyethyl) octadecylamino] ethyl ester (octadecylimino) diethylene distearate as compound B, oleic acid amide, erucic acid amide, N, N′-ethylene-bis-stearamide, N, N-bis (2-hydroxyethyl) cocoamide, 2,4,6-triamino-1,3,5-triazine, bis (2,
2,6,6-Tetramethyl-4-piperidyl) sebacate, 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]], 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]] or 1,5,8,12-tetrakis [4,6- Screw (N-
(1,2,2,6,6-Pentamethyl-4-piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane and other additions Henschel Mixer (trade name) with a prescribed amount of each of the agents at the compounding ratios shown in Table 5 below.
After being stirred and mixed for 3 minutes, the mixture was melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 5 and 6, MFR was stabilized at 6.0 g / 10 min, powdery crystalline propylene homopolymer (magnesium chloride content: 15 ppm) of 15% by weight, MFR was stabilized at 7.0 g / 10 min. Not powdery crystalline ethylene-propylene-
Butene-1 terpolymer (ethylene content 4.0% by weight, butene-1 content 4.5% by weight, magnesium chloride content 95 pp
m) 80 wt% and MI 5.0 g / 10 min unstabilized powdered Ziegler-Natta high density ethylene-propylene copolymer (density 0.950 g / cm ³ , methyl branch 3.0 /
1000 carbon, magnesium chloride content 20 ppm) 5 wt% and a total of 100 parts by weight of each of the predetermined amounts of the additives shown in Table 5 below, and melt-kneading according to Examples 35-51. To obtain pellets. The test piece used for the evaluation of transparency was obtained by pelletizing the pellets at a resin temperature of 250 ° C and a mold temperature of 5
Prepared by injection molding at 0 ° C. Using the obtained test piece, the transparency was evaluated by the above test method. The results are shown in Table 5.

Examples 52 to 60, Comparative Examples 7 to 11 As crystalline polyolefin, 100 parts by weight of powdered crystalline propylene homopolymer having an MFR of 6.0 g / 10 min, and 2,2 'as Compound A were added. -Methylene-bis (4-methyl)
-6-t-Butylphenyl) acid phosphite, 2,2'-
Methylene-bis (4,6-di-t-butylphenyl) acid phosphite or 2,2'-methylene-bis (4,6-dinonylphenyl) acid phosphite, sodium acetate as compound C, sodium stearate or Predetermined amounts of sodium montanate and other additives were added to the Henschel mixer (trade name) at the content ratios shown in Table 6 below, and the mixture was stirred and mixed for 3 minutes.
Was melt-kneaded at 200 ° C. with a twin-screw extruder to produce pellets. Further, as Comparative Examples 7 to 11, powdery crystalline propylene homopolymers having unstabilized MFR of 6.0 g / 10 min.
A predetermined amount of each of the additives shown in Table 6 described below was added to 0 part by weight, and melt-kneaded according to Examples 52 to 60 to obtain pellets. The test pieces used for the evaluation of rigidity and heat resistance were obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50.
Prepared by injection molding at ° C. Using the obtained test piece, the rigidity and the heat resistance rigidity were evaluated by the above-mentioned test methods. The results are shown in Table 6.

Examples 61 to 69, Comparative Examples 12 to 16 As crystalline polyolefin, MFR 4.0 g / 10 min, unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) 100 In parts by weight,
As compound A, 2,2'-ethylidene-bis (4-methyl-6-t-
Butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) acid phosphite or 2,2'-ethylidene-bis (4,6-di-t-
Amylphenyl) acid phosphite, compound C as sodium 12-hydroxyoctadecanoate, sodium glycolate or sodium lactate, and other additives in predetermined amounts in Henschel mixer (trade name) at the content ratios shown in Table 7 below. The mixture was put in, mixed for 3 minutes with stirring, and then melt-kneaded at 200 ° C. in a twin-screw extruder having a diameter of 30 mm to pelletize. As Comparative Examples 12 to 16, M
Unstabilized powdery crystalline ethylene-propylene block copolymer with an FR of 4.0 g / 10 min (ethylene content
(8.5 wt%) 100 parts by weight of each of the predetermined amounts of the additives shown in Table 7 described below were mixed and melt-kneaded according to Examples 61 to 69 to obtain pellets. Test pieces used for evaluation of rigidity, heat resistance and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Table 7.

Examples 70 to 78, Comparative Examples 17 to 21 As crystalline polyolefin, MFR 7.0 g / 10 min unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 90 %, And a total of 100 parts by weight of unstabilized powdered Ziegler-Natta high density ethylene homopolymer of 10% by weight and MI 15.0 g / 10 min, 2,2'-methylene as compound A
-Bis (4,6-diphenylphenyl) acid phosphite, 2,2'-i-propylidene-bis (4,6-dibenzylphenyl) acid phosphite or 2,2'-butylidene-bis (4-methyl- 6- (1'-methylcyclohexyl) phenyl) acid phosphite, compound C as sodium tartrate, sodium citrate or sodium octadecanoyl lactate, and other additives in predetermined amounts at the content ratios shown in Table 8 below. Put in a Henschel mixer (trade name), stir and mix for 3 minutes, then calibrate 30
The mixture was melt-kneaded at 200 ° C. in a twin screw extruder of mm to pelletize. Further, as Comparative Examples 17 to 21, 90% by weight of powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) having an MFR of 7.0 g / 10 min and an MI of 15.0 g / 10 min. The non-stabilized powdered Ziegler-Natta high-density ethylene homopolymer (10% by weight) was added to 100 parts by weight in total, and each of the additives shown in Table 8 below was added in a predetermined amount. Melt-kneading was performed according to 78 to obtain pellets. Test pieces used for evaluation of rigidity and heat resistance rigidity were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the obtained test piece, the rigidity and the heat resistance rigidity were evaluated by the above-mentioned test methods. The results are shown in Table 8.

Examples 79 to 87, Comparative Examples 22 to 31 MF produced in Production Example 1 as a crystalline propylene polymer
R2.5g / 10min unstabilized powdered HCPP (H)
-[1] 100 parts by weight, as compound A, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) acid phosphite, 2,2'-methylene-bis (4,6-di) -t-butylphenyl) acid phosphite or 2,2'-methylene-bis (4,6-dinonylphenyl) acid phosphite,
Compound D as magnesium acetate, (mono, dimixed) 2-ethylhexyl magnesium phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, 10-
Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide magnesium salt or magnesium-bis (1'-hydroxy-2,2'-biphenylenephosphinate), as compound E 2,2'-bis (4,6-
The predetermined amounts of di-t-butylphenyl) fluorophosphite or 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) fluorophosphite and other additives are shown in Table 9 below. Put in the Henschel mixer (trade name) with the content ratio of
A twin screw extruder having a diameter of 30 mm was melt-kneaded at 200 ° C. to form pellets. Further, as Comparative Examples 22 to 31, MFR is 2.5 g /
10 minutes unstabilized powdered HCPP (H)-[1] 10
A predetermined amount of each of the additives shown in Table 9 described below was mixed with 0 parts by weight, and melt-kneaded according to Examples 79 to 87 to obtain pellets. Test pieces used for evaluation of tensile elongation were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 9.

Examples 88 to 96, Comparative Examples 32 to 41 MF produced in Production Example 2 as a crystalline propylene polymer
R10.6g / 10min unstabilized powdered HCPP
To 100 parts by weight of (H)-[2], 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) acid phosphite as compound A, 2,2'-ethylidene-bis (4, 6-di-t-butylphenyl) acid phosphite or 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphite, magnesium stearate as compound D, (mono, dimixed) stearyl Magnesium phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, 2,6,8-tri-t-butyl-10-hydroxy-9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Magnesium salt of oxide or magnesium-bis (5,4 ', 6'-tri-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), 2,2'-methylene-bis as compound E (4,6-di-t-butylphenyl) fluorophosphite or 2,2'-ethylidene-bis (4-methyl-6)
-t-Butylphenyl) fluorophosphite and other additives were added to Henschel Mixer (trade name) in the proportions shown in Table 10 below, and mixed for 3 minutes with stirring. It was melt-kneaded at 200 ° C. in an extruder and pelletized. Further, as Comparative Examples 32 to 41, unstabilized powdered H having an MFR of 10.6 g / 10 min.
100 parts by weight of CPP (H)-[2] was mixed with predetermined amounts of the additives shown in Table 10 described below, and melt-kneaded according to Examples 88 to 96 to obtain pellets. Test pieces used for evaluation of tensile elongation were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 10.

Examples 97-105, Comparative Examples 42-51 MF produced in Production Example 3 as crystalline propylene polymer
R3 4.0g / 10min unstabilized powdered HCPP
100 parts by weight of (H)-[3], 2,2'-methylene as compound A
-Bis (4,6-diphenylphenyl) acid phosphite, 2,2'-i-propylidene-bis (4,6-dibenzylphenyl) acid phosphite or 2,2'-butylidene-bis (4-methyl- 6- (1'-Methylcyclohexyl) phenyl) acid phosphite, magnesium oleate as compound D, magnesium (mono, dimixed) stearyl phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, 2-cyclohexyl-10-hydroxy- 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide magnesium salt or magnesium-bis (5-cyclohexyl-1'-hydroxy-2,
2'-biphenylene phosphinate), as compound E
2,2'-Ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite or 2,2'-thio-bis (4-methyl-6-t-butylphenyl) fluorophosphite and other A predetermined amount of each additive was put in a Henschel mixer (trade name) at the content ratios shown in Table 11 below, stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a twin-screw extruder with a diameter of 30 mm. Pelletized. Comparative Examples 42-51
As an example, 100 parts by weight of unstabilized powdered HCPP (H)-[3] having an MFR of 34.0 g / 10 min was added with a predetermined amount of each of the additives shown in Table 11 described below, and Examples 97 to 105 Melt-kneading treatment was carried out according to to obtain pellets. The test piece used for evaluation of tensile elongation was obtained by pelletizing the obtained pellets at a resin temperature of 250.
It was prepared by injection molding at a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 11.

Examples 106 to 114, Comparative Examples 52 to 61 MF produced in Production Example 4 as a crystalline propylene polymer
R8.5g / 10min unstabilized powdered HCPP (B)
-[1] (ethylene content 4.2% by weight) 100 parts by weight, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) acid phosphite as compound A, 2,2'-methylene -Bis (4,6-di-t-butylphenyl) acid phosphite or 2,2'-methylene-bis (4,6-dinonylphenyl) acid phosphite, compound D magnesium behenate, (mono, dimixed ) Magnesium stearyl phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, 6-phenyl-10-hydroxy-9,1
0-dihydro-9-oxa-10-phosphaphenanthrene-10
-Magnesium salt of oxide or magnesium-bis (1'-hydroxy-4'-phenyl-2,2'-biphenylene phosphinate), 2,2'-bis (4,6-di- as compound E
t-butylphenyl) fluorophosphite or 2,
2'-methylene-bis (4-methyl-6-t-butylphenyl) fluorophosphite and other additives were added to the Henschel mixer (trade name) at the respective prescribed amounts shown in Table 12 below, After stirring and mixing for 3 minutes, caliber 30
The mixture was melt-kneaded at 200 ° C. in a twin screw extruder of mm to pelletize. In addition, as Comparative Examples 52 to 61, 100 parts by weight of powdered HCPP (B)-[1] (ethylene content 4.2% by weight) having an MFR of 8.5 g / 10 minutes and not stabilized was added to Table 12 described later. A predetermined amount of each of the agents was mixed and melt-kneaded according to Examples 106 to 114 to obtain pellets. The test piece used for evaluation of tensile elongation was obtained by pelletizing the obtained pellets at a resin temperature of 250.
It was prepared by injection molding at a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 12.

Examples 115-123, Comparative Examples 62-71 MF prepared in Preparation Example 5 as crystalline propylene polymer
R9.0g / 10min unstabilized powdered HCPP (B)
-[2] (Ethylene content 8.5% by weight) 100 parts by weight, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) acid phosphite as compound A, 2,2'-ethylidene -Bis (4,6-di-t-butylphenyl) acid phosphite or 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphite, magnesium montanate as compound D, ( Mono, dimixed) magnesium stearyl phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium 2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Salt or magnesium-bis (5-benzyl-1'-hydroxy-2,2'-biphenylenephosphinate), compound E is 2,2'-methylene-bis (4,6-di-t-butylphenyl) fluoro Fossfu Ito or 2,2'-ethylidene - bis (4-methyl-6
-T-Butylphenyl) fluorophosphite and other additives were added to Henschel mixer (trade name) in the proportions shown in Table 13 below, and the mixture was stirred and mixed for 3 minutes. It was melt-kneaded at 200 ° C. in an extruder and pelletized. Further, as Comparative Examples 62 to 71, powdered HC having an MFR of 9.0 g / 10 minutes and not stabilized
100 parts by weight of PP (B)-[2] (ethylene content 8.5% by weight) was mixed with predetermined amounts of the additives shown in Table 13 below, and melt-kneaded according to Examples 115 to 123. To obtain pellets. Test pieces used for evaluation of tensile elongation were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 13.

Examples 124 to 132, Comparative Examples 72 to 81 MF produced in Production Example 6 as a crystalline propylene polymer
R7.7g / 10min unstabilized powdered HCPP (B)
-[3] (Ethylene content 12.1% by weight) 100 parts by weight, as compound A, 2,2'-methylene-bis (4,6-diphenylphenyl) acid phosphite, 2,2'-i-propylidene-
Bis (4,6-dibenzylphenyl) acid phosphite or 2,2'-butylidene-bis (4-methyl-6- (1'-methylcyclohexyl) phenyl) acid phosphite, 12-hydroxyoctadecanoic acid as compound D Magnesium, (mono, dimixed) stearyl magnesium phosphate, magnesium oxide, magnesium hydroxide,
Magnesium carbonate, magnesium salt of 6- (α-methylbenzyl) -8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or magnesium-bis [1'-Hydroxy-4 '-(α-methylbenzyl) -6'-t-butyl-2,2'-biphenylenephosphinate], 2,2'-ethylidene-bis (4,6- as compound E The prescribed amounts of di-t-butylphenyl) fluorophosphite or 2,2'-thio-bis (4-methyl-6-t-butylphenyl) fluorophosphite and other additives are shown in Table 14 below. Put in the Henschel mixer (trade name) with the content ratio of
A twin screw extruder having a diameter of 30 mm was melt-kneaded at 200 ° C. to form pellets. Further, as Comparative Examples 72 to 81, MFR is 7.7 g /
10 minutes unstabilized powdered HCPP (B)-[3]
(Ethylene content 12.1% by weight)
Prescribed amounts of each of the additives described in
Melt-kneading processing according to No. 132 to obtain pellets. Test pieces used for evaluation of tensile elongation were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 14.

The compounds and additives relating to the present invention shown in Tables 3 to 14 are as follows. Compound A [1]: 2,2'-methylene-bis (4-methyl-6-t-
Butylphenyl) acid phosphite compound A [2]: 2,2'-methylene-bis (4,6-di-t-butylphenyl) acid phosphite compound A [3]: 2,2'-methylene-bis ( 4,6-Dinonylphenyl) acid phosphite Compound A [4]: 2,2'-ethylidene-bis (4-methyl-6-t
-Butylphenyl) acid phosphite compound A [5]: 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) acid phosphite compound A [6]: 2,2'-ethylidene-bis (4,6-Di-t-amylphenyl) acid phosphite compound A [7]: 2,2'-methylene-bis (4,6-diphenylphenyl) acid phosphite compound A [8]: 2,2 ' -i-Propylidene-bis (4,6-dibenzylphenyl) acid phosphite Compound A [9]: 2,2'-butylidene-bis (4-methyl-6-
(1'-Methylcyclohexyl) phenyl) acid phosphite

Compound B [1]: Lithium acetate Compound B [2]: Calcium stearate Compound B [3]: Zinc montanate Compound B [4]: Calcium octadecanoyl lactate Compound B [5]: Basic 12-hydroxy Magnesium octadecanoate (0.44 MgO ・ C ₁₇ H ₃₄ (OH) COOM
g _1/2 ) Compound B [6]: Lithium glycolate Compound B [7]: Calcium lactate Compound B [8]: Zinc tartrate Compound B [9]: Sodium citrate Compound B [10]: Basic magnesium aluminum・
Hydroxy carbonate hydrate (Mg _4.5 Al ₂
(OH) ₁₃ CO ₃ · 3.5H ₂ O) [Kyowa Chemical Industry Co., Ltd. DHT
-4A] Compound B [11]: Basic aluminum lithium hydroxycarbonate hydrate (Al ₄ Li ₂ (OH)
₁₂ CO ₃ · 1.6H ₂ O) Compound B [12]: Zinc oxide Compound B [13]: Magnesium hydroxide Compound B [14]: Calcium carbonate Compound B [15]: (Mono, dimixed) calcium stearyl phosphate Compound B [ 16]: (mono, dimixed) zinc stearyl phosphate Compound B [17]: Sodium-2,2'-methylene-bis (4,6
-Di-t-butylphenyl) phosphate Compound B [18]: Epoxidized soybean oil Compound B [19]: Hexamethylenetetramine Compound B [20]: Triisopropanolamine Compound B [21]: N, N-bis ( 2-Hydroxyethyl) cocoamine Compound B [22]: N, N-bis (2-hydroxyethyl) tallowamine Compound B [23]: Octadecanoic acid 2-[(2-hydroxyethyl) octadecylamino] ethyl ester Compound B [24 ]: (Octadecylimino) diethylene distearate Compound B [25]: Oleic acid amide Compound B [26]: Erucamide amide Compound B [27]: N, N′-ethylene-bis-stearoamide Compound B [28]: N, N-bis (2-hydroxyethyl) cocoamide compound B [29]: 2,4,6-triamino-1,3,5-triazine compound B [30]: bis (2,2,6,6-tetra Methyl -4-piperidyl) sebacate compound B [31]: 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]] Compound B [32]: poly [[ 6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidyl) imino]] compound B [33]: 1,5,8,12-tetrakis [4,6-bis (N-
(1,2,2,6,6-Pentamethyl-4-piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane

Compound C [1]: Sodium acetate Compound C [2]: Sodium stearate Compound C [3]: Sodium montanate Compound C [4]: Sodium 12-hydroxyoctadecanoate Compound C [5]: Sodium glycolate Compound C [6]: Sodium lactate Compound C [7]: Sodium tartrate Compound C [8]: Sodium citrate Compound C [9]: Sodium octadecanoyl lactate

Compound D [1]: Magnesium acetate Compound D [2]: Magnesium stearate Compound D [3]: Magnesium oleate Compound D [4]: Magnesium behenate Compound D [5]: Magnesium montanate Compound D [ 6]: Magnesium 12-hydroxyoctadecanoate Compound D [7]: (Mono, dimixed) 2-ethylhexyl magnesium phosphate Compound D [8]: (Mono, dimixed) magnesium stearyl phosphate Compound D [9]: Magnesium oxide compound D [10]: Magnesium hydroxide Compound D [11]: Magnesium carbonate Compound D [12]: 10-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide magnesium salt Compound D [13]: 2,6,8-tri-t-butyl-10-hydroxy-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-Oxide magnesium salt Compound D [14]: 2-cyclohexyl-10-hydroxy-9,1
0-dihydro-9-oxa-10-phosphaphenanthrene-10
-Magnesium salt of oxide Compound D [15]: 6-phenyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-Magnesium salt of oxide Compound D [16]: 2 -Benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide magnesium salt Compound D [17]: 6- (α-methylbenzyl) -8-t- Butyl
-10-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide magnesium salt Compound D [18]: Magnesium-bis (1'-hydroxy-
2,2'-biphenylene phosphinate) Compound D [19]: magnesium-bis (5,4 ', 6'-tri-t-
Butyl-1'-hydroxy-2,2'-biphenylenephosphinate) Compound D [20]: Magnesium-bis (5-cyclohexyl-1'-hydroxy-2,2'-biphenylenephosphinate) Compound D [21 ]: Magnesium-bis (1'-hydroxy-
4'-phenyl-2,2'-biphenylene phosphinate) Compound D [22]: magnesium-bis (5-benzyl-1'-
Hydroxy-2,2'-biphenylene phosphinate) Compound D [23]: Magnesium-bis [1'-hydroxy-
4 '-(α-methylbenzyl) -6'-t-butyl-2,2'-biphenylenephosphinate]

Compound E [1]: 2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite Compound E [2]: 2,2'-methylene-bis (4-methyl-6) -t-
Butylphenyl) fluorophosphite compound E [3]: 2,2'-methylene-bis (4,6-di-t-butylphenyl) fluorophosphite compound E [4]: 2,2'-ethylidene-bis ( 4-methyl-6-t
-Butylphenyl) fluorophosphite compound E [5]: 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite compound E [6]: 2,2'-thio-bis (4-Methyl-6-t-butylphenyl) fluorophosphite lithium salt 1: lithium stearate lithium salt 2: basic aluminum lithium hydroxycarbonate hydrate (Al ₄ Li ₂ (OH) ₁₂
CO ₃・ 1.6H ₂ O)

Phenolic antioxidant 1: 2,6-di-t-butyl-p-cresol Phenolic antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: tris (3,5-di-t-butyl-
4-Hydroxybenzyl) isocyanurate Phenolic antioxidant 4: 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene phenolic antioxidant 5: n-octadecyl-β- (4'-
Hydroxy-3 ′, 5′-di-t-butylphenyl) propionate Phenol-based antioxidant 6: Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate Phosphorus-based antioxidant 1 : Bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 2: Tris (2,4-di-t-butylphenyl) phosphite phosphorus oxidation Antioxidant 3: Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite Phosphorus antioxidant 4: Bis [2,2'-ethylidene-bis (4,
6-Di-t-amylphenyl)]-3,9-bis (1,1-dimethyl-2)
-Hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite phosphorus antioxidant 5: tetrakis (2,4-di-t-butylphenyl) -4,4'- Biphenylene-The-Phosphonite

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

[Table 9]

[0091]

[Table 10]

[0092]

[Table 11]

[0093]

[Table 12]

[0094]

[Table 13]

[0095]

[Table 14]

In the examples and comparative examples shown in Table 3, the content of magnesium chloride as crystalline polyolefin is 40 ppm.
This is the case of using the crystalline propylene homopolymer. As can be seen from Table 3, Examples 1 to 17 contain Compound A and Compound B relating to the first invention of the present application,
Comparison between Examples 1 to 17 and Comparative Example 1 (one containing neither compound A nor compound B) shows that Examples 1 to 17 have remarkably excellent transparency. In addition, compound A
Comparative Example 2 and Examples 1 to 17 containing
In comparison with Comparative Example 1, Comparative Example 2 is improved in transparency by the inclusion of Compound A, but is still not sufficiently satisfactory. It can be seen that 1 to 17 have remarkably improved transparency. Therefore, the comparative examples which do not simultaneously satisfy the specific amounts of the three components of the crystalline polyolefin containing the magnesium halide compound as the catalyst residue, the compound A and the compound B according to the first invention of the present application are the first invention of the present application. It is clear that the above effect is not achieved. That is, it can be said that the transparency obtained in the first invention of the present application is a unique effect that can be seen only when compound A and compound B are contained in a crystalline polyolefin containing a magnesium halide compound as a catalyst residue.

Tables 4 to 5 show crystalline ethylene-propylene random copolymers having a magnesium chloride content of 54 ppm, crystalline propylene homopolymers having a magnesium chloride content of 15 ppm, and magnesium chloride contents of 95 ppm, respectively, as crystalline polyolefins. Crystalline ethylene-propylene-
Butene-1 terpolymer and magnesium chloride content 2
A mixture of 0 ppm Ziegler-Natta high-density ethylene-propylene copolymer was used, and the same effects as those described above were confirmed.

The examples and comparative examples shown in Table 6 are the cases where a crystalline propylene homopolymer was used as the crystalline polyolefin. As can be seen from Table 6, Examples 52 to
No. 60 contains the compound A and the compound C according to the second invention of the present application, and comparing Examples 52 to 60 and Comparative Example 7 (no compound A and compound B), It can be seen that Examples 52 to 60 have remarkably excellent rigidity. Further, comparing Comparative Example 8 containing only the compound A with Examples 52 to 60, the effect of improving the rigidity of Comparative Example 8 can be recognized to some extent as compared with Comparative Example 7, but it is still sufficient. I'm not satisfied. Similarly, Comparative Example 9 containing only Compound B and Examples 52-60
It can be seen that the effect of improving the rigidity of Comparative Example 9 is almost negligible. Further, comparing Comparative Examples 10 to 11 in which Compound B is replaced with Lithium Salts 1 to 2 in Examples 52 to 60 and Examples 52 to 60, the effect of improving the rigid surface of Comparative Examples 10 to 11 is Comparative Example. It is about the same as 8 and it can be seen that even if the lithium salts 1 and 2 are used in combination with the compound A, almost no effect of improving the rigidity is observed. Therefore, it is apparent that the comparative examples that do not simultaneously satisfy the inclusion of the two components of the compound A and the compound C according to the second invention of the present application do not exhibit the effect of the second invention of the present application. That is, it can be said that the rigid surface obtained by the second invention of the present application is a unique effect that can be seen only when compound A and compound C are contained in the crystalline polyolefin.

Tables 7 to 8 use a mixture of a crystalline ethylene-propylene block copolymer, a crystalline ethylene-propylene random copolymer and a high-density ethylene homopolymer as the crystalline polyolefin. The effects similar to those described above were confirmed for these as well. In addition, in each of the examples of the composition of the second invention of the present application in Table 7, the inclusion of the compound A and the compound C did not show a decrease in the impact resistance due to the improvement of the rigidity surface, which is different from the comparative examples. However, it was confirmed that the impact resistance was not inferior.

The examples and comparative examples shown in Table 9 are the cases where HCPP (H)-[1] was used as the crystalline propylene polymer. As can be seen from Table 9, Examples 79 to 87 contain Compound A, Compound D and Compound E according to the third invention of the present application, and Examples 79 to 87 and Comparative Example 22
By comparing with (compounds containing no compound A, compound D and compound E), it is found that Examples 79 to 87 have remarkably excellent tensile elongation. Comparing Comparative Examples 23 to 27 and Examples 79 to 87 containing Compound A, Compound D or Compound E respectively, the tensile elongations of Comparative Examples 23 to 27 are almost the same as those of Comparative Example 22. It turns out that there is no improvement. In addition, Comparative Examples 28 to 30 and Example 79 each containing two components of Compound A, Compound D or Compound E.
~ 87, the tensile elongations of Comparative Examples 28 to 30 are about the same as those of Comparative Example 22, and two components of Compound A, Compound D to Compound E according to the third invention of the present application are respectively compared. It can be seen that the tensile elongation is hardly improved even when used together. Furthermore, in Examples 79 to 87, compound D [9]
Comparing Comparative Example 31 containing [11] in excess of the content ratio of the third invention of the present application and Examples 79 to 87, Comparative Example 31 also contains Compound A, Compound D and Compound E. Nevertheless, it can be seen that the effect of improving the tensile elongation is hardly recognized. Therefore, the compound A according to the third invention of the present application,
It is clear that the comparative examples that do not satisfy the specific amounts of the three components of the compound D and the compound E at the same time do not exhibit the effect of the third invention of the present application. That is, it can be said that the tensile elongation obtained in the third invention of the present application is a unique effect that can be seen only when the compound A, the compound D, and the compound E are contained in specific amounts in the HCPP (H).

Tables 10 to 14 show HCPP (H)-[2] and HCPP (H)-as crystalline propylene polymers, respectively.
[3], HCPP (B)-[1], HCPP (B)-[2], HC
PP (B)-[3] was used, and the same effects as above were confirmed for these.

[0102]

The crystalline polyolefin composition of the first invention of the present application is greatly improved in transparency. The composition of the second invention of the present application (1) is extremely excellent in the rigidity of the molded product when it is formed into a molded product. (2) Not only can it contribute to resource saving by reducing the wall thickness of the molded product, but it also contributes to improving productivity by increasing the molding speed per unit time because the cooling speed during molding is also faster. it can. The composition of the third invention of the present application is remarkably excellent in the tensile elongation of the molded product when the molded product is formed by using HCPP (H) or HCPP (B).

Claims (5)

[Claims] 1. To 100 parts by weight of a crystalline polyolefin containing a magnesium halide compound as a catalyst residue,
0.001 to 1 part by weight of a cyclic phosphorus compound represented by the following chemical formula 1 (hereinafter referred to as compound A) and a halogen scavenger (hereinafter referred to as
A crystalline polyolefin composition containing 0.001 to 1 part by weight of Compound B). [Chemical 1] (In the formula, R ₁ represents an alkylidene group having 1 to 4 carbon atoms, and Ar ₁ and Ar ₂ represent an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.) 2. The compound B is a fatty acid metal salt, alkanoyl lactic acid metal salt, aliphatic hydroxy acid metal salt, hydrotalcites, lithium aluminum complex hydroxide salt, metal oxide, metal hydroxide, metal carbonate salt. , Aliphatic metal phosphates, epoxy compounds, aliphatic amines, aliphatic amides,
The crystalline polyolefin composition according to claim 1, which is a hindered amine compound, an aminotriazine compound, or a mixture of two or more thereof. 3. One or more compounds selected from 0.001 to 1 part by weight of compound A and 100 parts by weight of crystalline polyolefin (hereinafter referred to as compound C) per 100 parts by weight of crystalline polyolefin.
A crystalline polyolefin composition containing 0.001 to 1 part by weight. Aliphatic sodium monocarboxylic acid Sodium aliphatic hydroxyacid having 2 to 6 carbon atoms Sodium alkanoyl lactate 4. Isotactic pentad fraction (P) and melt flow rate (MFR: load at 230 ° C. 21.18)
0.001 to 1 part by weight of compound A to 100 parts by weight of a crystalline propylene homopolymer having a relationship of 1.00 ≧ P ≧ 0.015 log MFR + 0.955 with respect to the amount of molten resin discharged for 10 minutes when N is added. 0.001 to 1 part by weight of one or more magnesium compounds selected from (hereinafter referred to as compound D) and 0.001 to 1 part by weight of a fluorophosphite compound represented by the following chemical formula 4 (hereinafter referred to as compound E) A crystalline polyolefin composition containing: Fatty Acid Magnesium Aliphatic Magnesium Phosphate Magnesium Oxide Magnesium Hydroxide Magnesium Carbonate Magnesium Salt of Cyclic Phosphorus Compound Represented by Chemical Formula 2 Magnesium Phosphinate Compound represented by Chemical Formula 3 [Chemical 3] [Chemical 4] (In the formula, Ar _{3 to} Ar ₆ represent an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group, and R ₂
Represents a direct bond, an alkylidene group having 1 to 4 carbon atoms or a sulfur atom, and Ar ₇ and Ar ₈ represent an alkylarylene group or a cycloalkylarylene group, respectively. ) 5. An isotactic pentad fraction (P) and a melt flow rate (M) of a crystalline propylene homopolymer.
FR) has a relationship of 1.00 ≧ P ≧ 0.015 log MFR + 0.955 with 70 to 95% by weight of the total amount of polymer, followed by 30 to 5% by weight of the total amount of ethylene or ethylene. 100 parts by weight of a crystalline ethylene-propylene block copolymer obtained by polymerizing propylene and propylene in one or more steps and having an ethylene content of 3 to 20% by weight based on the total amount of the polymer.
A crystalline polyolefin composition containing 0.001 to 1 part by weight of compound A, 0.001 to 1 part by weight of compound D and 0.001 to 1 part by weight of compound E.