JPH03181533A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition giving molded products having excellent rigid surfaces, capable of being thinned and having high resource saving and productivity by compounding a fluorophosphite compound, an aliphatic monocarboxylic acid metal salt, etc., with a crystalline polyolefin in a specific ratio. CONSTITUTION:The objective composition comprises (A) 100 pts.wt. of a crystalline polyolefin, (B) 0.001-1 pt.wt. of a fluorophosphite compound of the formula (R is 1-4C alkylidene or sulfur; Ar1 and Ar2 are alkylarylene or cycloalkylarylene; Ar3 and Ar4 are arylene, alkylarylene, etc.; M is lithium, sodium, etc.; n is 0 or 1; m is the valency of M), (C) 0.001-1 pt.wt. of one kinds or more of compounds selected from aliphatic monocarboxylic acid salts (metal is potassium, strontium or barium), hydroxymonocarboxylic acid metal salts, etc., and (D) 0.01-1 pt.wt. of an aliphatic amine.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a crystalline polyolefin composition from which a molded article having excellent rigidity and heat-resistant rigidity can be obtained. More specifically, it relates to a crystalline polyolefin composition that is obtained by blending a fluorophosphite compound having a specific structure, a specific metal compound, and an aliphatic amine with a crystalline polyolefin, and from which a molded article with excellent rigidity and heat resistance can be obtained. . [Prior Art] Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties, so they can be used for injection molded products, blow molded products, films, sheets, etc. It is used to manufacture various molded products such as male molds. However, depending on various specific uses, one mechanical property may not be sufficient, and there is a problem in that the expansion of specific uses is limited. In particular, it is inferior to polyesters such as polystyrene, ABS resin, polyethylene terephthalate, and polybutylene ethylene phthalate in terms of rigidity such as rigidity and heat-resistant rigidity (hereinafter, rigidity means rigidity and heat-resistant rigidity). However, there are disadvantages in that the applications for which crystalline polyolefins can be used are limited. For this reason, various nucleating agents have been used for the purpose of improving the rigidity of crystalline polyolefins. Furthermore, JP-A-63-227594 discloses a composition in which an aromatic fluorophosphorus compound is blended as an antioxidant into a crystalline polyolefin, and a lubricant such as calcium stearate, a nucleating reagent, or a filler is added to the composition. It is disclosed that they can be used together. [Invention tries to solve it! [l1M] However, although the rigidity of molded products obtained from compositions containing crystalline polyolefin and various conventionally known nucleating agents has been improved to some extent, it is still not fully satisfactory. JP-A No. 63-227594, which discloses a composition containing an aromatic fluoroline compound, includes (1) potassium stearate, strontium stearate, or barium stearate as a lubricant; ■ Using an aliphatic dicarboxylic acid alkali metal salt, an aromatic carboxylic acid alkali metal salt, or an aromatic carboxylic acid aluminum and an aliphatic amine together as a nucleating reagent, or ■
By using magnesium hydroxide, aluminum hydroxide, magnesium oxide, magnesium carbonate or calcium carbonate and an aliphatic amine as a filler,
There is no mention of improving the rigidity of a molded article obtained from a crystalline polyolefin composition, nor is there any description suggesting that the combination improves the rigidity. The inventors of the present invention have conducted extensive research in order to obtain a crystalline polyolefin composition that can provide a molded article with improved rigidity, ie, the above-mentioned problems regarding crystalline polyolefin compositions. As a result, the present inventor found that a specific one for crystalline polyolefins.
! It has been discovered that a crystalline polyolefin composition containing a fluorophosphite compound having a fluorophore structure, a specific metal compound, and an aliphatic amine in specific amounts is a composition that provides a molded article with improved rigidity, The present invention was completed based on this knowledge. As is clear from the above description, an object of the present invention is to provide a crystalline polyolefin composition which, when formed into a molded article, has improved rigidity. [Means for Solving the Problems] The present invention has the following configuration. (1) 100 layers of crystalline polyolefin! :For the department,
A fluorophosphite compound represented by the following general formula [■] (hereinafter referred to as compound A) and one or more compounds selected from the following ■ to 0 (hereinafter referred to as compound B) are each A crystalline polyolefin composition containing 0.01 to 1 part by weight of an aliphatic amine (hereinafter referred to as compound C). ■Aliphatic monocarboxylic acid metal salts (However, the metal represents potassium, strontium, or barium.) ■Hydroxy higher fatty acid metal salts (However, the metal represents potassium, strontium, or barium.) ■Aliphatic polycarboxylic acid metal salts (However, metal refers to lithium, sodium, potassium, strontium, or barium.) ■Metal salt of aliphatic hydroxy acid having 2 to 6 carbon atoms (However, metal refers to lithium, sodium, potassium, magnesium, strontium, or barium.) ) ■Aromatic carboxylic acid metal salt (however, the metal is lithium,
(represents sodium, strontium, barium or aluminum) ■Glutamic acid metal salt (however, the metal represents lithium, sodium, potassium, strontium or barium) ■Aliphatic phosphate metal salt (however, the metal represents sodium, potassium, calcium) , indicates strontium or barium) ■Metal of a cyclic phosphorus compound represented by the following general formula [11] (however, the metal indicates lithium, sodium, potassium or barium) ■Metal hydroxide (however, the metal indicates (Indicates magnesium or aluminum) [Phase] Magnesium oxide ■ Metal carbonate (However, ) indicates calcium. ■ Hydrotalcite metal is magnesium) (However, in the formula, R is an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar) and Ar2 are alkylarylene groups or cycloalkylarylene groups, Ar3 and Ar are arylene groups, alkylarylene groups, cycloalkylarylene groups, arylarylene groups, or aralkylarylene groups, M is lithium, sodium , potassium or barium, n is ○ or 1
, m indicates the valence of M, respectively) (2) Compound A and Compound B are each 0.001-1 part by weight, and Compound C is 0.01-1 part by weight, relative to 100 parts by weight of the crystalline polyolefin. 1. A crystalline polyolefin composition comprising 0.01 to 25 parts by weight of an inorganic filler (excluding magnesium hydroxide, aluminum hydroxide, magnesium oxide, magnesium carbonate, and calcium carbonate). (3) As a crystalline polyolefin, isotactic pentad fraction (P) and melt flow rate (MFR;
10 when applying a load of 2.16 kg at 230°C
Discharge amount of molten resin per minute) is 1.00≧P≧0
．． 015 The crystalline polyolefin composition according to item (1) or item (2) above, which uses a crystalline propylene homopolymer having a Q ogM F R+ of 0.955. (4) As a crystalline polyolefin, the relationship between the isotactic pentad fraction (P) and melt flow rate (M F R”) of propylene homopolymer is 1.00≧P
≧O, OI5 Q ogM F R+ 0.955 of the first stage polymer accounts for 70 to 95 of the total polymer amount! %, and then 30 to 5% by weight of the total polymer amount of ethylene or ethylene and propylene are polymerized in one or more steps, and the ethylene content is 3 to 20 weight% of the total polymer amount.Crystalline ethylene - The crystalline polyolefin composition according to item (1) or item (2) above, which uses a propylene block copolymer. The crystalline polyolefin used in the present invention is a crystalline homopolymer of α-olefin such as ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1, etc. A crystalline or low-crystalline random copolymer or crystalline block copolymer of more than one species of α-olefin, a copolymer of the above-mentioned α-olefin and vinyl acetate or acrylic ester,
Saponified products of said copolymers, copolymers of these α-olefins and unsaturated silane compounds, copolymers of these α-olefins and unsaturated carboxylic acids or their anhydrides, said copolymers and metal ion compounds. reaction product with α-
Crystalline homopolymers of olefins, modified polyolefins obtained by modifying crystalline or low-crystalline random copolymers, or crystalline block copolymers with unsaturated carboxylic acids or derivatives thereof, and crystalline 11 polymers of the above-mentioned α-olefins. Examples include silane-modified polyolefins obtained by modifying a combined 1M quality or low-crystalline random copolymer or a crystalline block copolymer with an unsaturated silane compound.
Of course, these crystalline polyolefins can be used alone, but two or more types of crystalline polyolefins can also be used in combination. Furthermore, in addition to the above-mentioned crystalline polyolefin, various synthetic rubbers (e.g., amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, 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 polymers, styrene-propylene-butylene-styrene block copolymers, etc.) or thermoplastic synthetic resins (e.g. polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyamides, polyethylene terephthalate, polybutylene terephthalate, polycarbonates) , polyvinyl chloride, fluororesin, etc.) can also be used in combination. A crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of propylene residue, a crystalline ethylene/propylene random copolymer,
Particularly preferred are crystalline propylene-butene-1 random copolymers, crystalline ethylene-propylene-butene-13-element copolymers, crystalline propylene-hexene-butene-13-element copolymers, and mixtures of two or more of these. used. In particular, the crystalline polyolefin used in the present invention has a relationship between isotactic pentad fraction (P) and melt flow rate (MFR) of 1.00≧P≧0.0.
15 A crystalline propylene homopolymer (hereinafter referred to as H (PP(H)) that satisfies Q og M F R 10.955, or isotactic pentad content 1 (P) of a propylene homopolymer Melt flow rate (M
The relationship with F R) is 1,00≧P≧0.015 Q o
The first stage polymer having a zM F R+ of 0.955 is 70 to 95% by weight of the total polymer amount, and then ethylene or ethylene and propylene is polymerized in one or more stages in an amount of 30 to 5% by weight of the total polymer amount. The use of a crystalline ethylene-propylene block copolymer (hereinafter abbreviated as PP(B)) having an ethylene content of 3 to 20% by weight based on the total amount of the polymer is advantageous in that the resulting crystal This is preferable because the properties of the polyolefin composition are further improved.Such H (PP(H)) can be produced by the production method described in Japanese Patent Application Laid-Open No. 104907/1983, which is filed by the same applicant as the present application. It can be manufactured by:
Organoaluminum compound (I) (e.g. triethylaluminum, diethylaluminum monochloride, etc.)
Or organoaluminum compound (1) and electron donor (
The solid product (II) obtained by reacting the reaction product (V) with titanium tetrachloride (for example, diisoamyl ether, ethylene glycol monomethyl ether, etc.) is further added with an electron donor and an electron acceptor (for example, anhydrous aluminum chloride). , titanium tetrachloride, vanadium tetrachloride, etc.) is reacted with organoaluminum compound (1) and aromatic carboxylic acid ester (■
) (e.g. ethyl benzoate, P-)methyl ruylate,
P-ethyl toluate, P-toluyl W11-2-ethylhexyl, etc.), the molar ratio of the aromatic carboxylic acid ester (IV) and the solid product (m) ■/III
=O, i~10.0 catalyst (hereinafter referred to as catalyst (MC)
It is abbreviated as ) in the presence of propylene in one or more stages. Also, H(P
In the first stage of polymerization, P(B) polymerizes propylene in an amount of 70 to 95% by weight of the total polymer amount (excluding polymers soluble in the polymerization solvent). Then, after the second stage every other day, ethylene or ethylene and propylene are polymerized in one or more stages. Every other day after the second stage, 30 to 5% by weight of the total polymer amount of ethylene or ethylene and propylene are polymerized in one or more stages. However, the ethylene content in the finally obtained polymer (excluding the soluble polymer dissolved in the polymerization solvent) must be within the range of 3 to 20% by weight of the total polymer amount. Therefore, if only propylene is polymerized at 70% by weight of the total polymer in the first stage, the amount of ethylene block copolymerized in the second stage is limited to 20% by weight or less. In this case, the remaining 10 to 27 t% by weight must be block copolymerized with propylene or with propylene and other α-olefins other than ethylene. However, if 80% by weight of propylene is polymerized in the first stage, only 20% by weight of ethylene can be polymerized in the 122nd stage. Within the limits of the ethylene content in the polymer, block copolymerization of ethylene alone or with ethylene and propylene or other α-olefins can be carried out in one step or in multiple steps in the second step. It can be performed. Such H(P
P(B) can be manufactured by the manufacturing method described in Japanese Patent Application Laid-Open No. 58-201.816, filed by the same applicant as the present application. That is, the catalyst (MC)
70 to 95% by weight of the total polymer amount of propylene is polymerized in the presence of 30 to 5% of the total polymer amount of ethylene or ethylene and propylene in one or more steps to reduce the ethylene content to 3. It can be obtained by copolymerizing so that the amount becomes 20% by weight. One stage as mentioned above means one section of continuous or temporary feeding of these monomers. Here, the isotactic bentande fraction (P) is
Macromolecules, Volume 6, Issue 6, November-December,
pp. 925-926 (1973) [Mac
romol, ecules. Vol.6. Na6. November-De
It is the isotactic fraction in pentand units in a propylene polymer molecular chain measured using the method published in J. Chem., 925-926 (1973)], that is, 13 cm NMR. In other words, the fraction means the fraction of propylene monomer units in which five propylene monomer units are consecutively bonded isotactically. The determination of the attribution of the spectrum peak in the measurement using 13C-NMR described above is based on macromolecules,
Volume 8, No. 5, September to October, pp. 687 to 689 (1
975) [Macromolecules, V
ol, 8. &5゜S epte+wber-○ct
Ober, 687-689 (1975)], by the way, I30-
For NMR measurement, an FT-NMR 270MHz device was used, and after 27,000 cumulative measurements, the signal detection limit was determined to be 0.00 in terms of isotactic pentad fraction.
I improved it to 1. The requirements for the above relational expression between isotactic pentad fraction (P) and melt flow rate (M, FR) in H(P P (H) and H(PP(B)) generally apply to crystalline propylene with low MFR. Since the fraction P of the homopolymer decreases, it is a constitutional requirement to limit the lower limit of P corresponding to the MFR of the crystalline propylene homopolymer to be used. Since P is a fraction, the upper limit is 1.00,
MFR is usually 0.05 to 100 g/10 minutes. Further, MFR is measured according to JISK 7210 at 230° C. under a load of 2.16 kg, and ethylene content is measured by infrared absorption spectroscopy. Furthermore, as the crystalline polyolefin used in the present invention, a highly active catalyst composition containing a titanium halide catalyst residue supported on magnesium halide and an organoaluminium catalyst component, particularly an electron donor catalyst component is further added to the highly active catalyst composition. The use of an undeashed crystalline propylene polymer obtained by polymerization in the presence of a combined highly active and highly stereoregular catalyst composition further improves the rigidity of the resulting crystalline polyolefin composition. Therefore, it is preferable. Compound A used in the present invention is 2,2'-bis(
4,8-di-t-butylphenyl)fluorophosphite, 2,2'-bis(4-methyl-et-butylphenyl)fluorophosphite, 2,2'-bis(4-t-butylphenyl) 6-methylphenyl)fluorophosphite, 221-bis(4-s-eicosylphenyl)fluorophosphite, 2,2'-methylene-bis(4-methyl-6-savetylphenyl)fluorophosphite, 2 .2'-methylene-bis(4-ethyl-6-t-butylphenyl)fluorophosphite,
2.2'-methylene-bis(4-methyl-6-nonylphenyl)fluorophosphite 1-, 2.2'-methylene-bis(4,6-dinonylphenyl)fluorophosphite, 212'-methylene- Bis(4-methyl-
6-cyclohexylphenyl)fluorophosphite, 2,2'-methylene-bis(4-methyl-6-(1'
-methylcyclohexyl)phenyl)fluorophosphite, 2.2'-3-propylidene-bis(4-nonylphenyl)fluorophosphite, 2.2'-butylidene-bis(4,6-dimethylphenyl)fluorophosphite, 2 .2'-methylene-bis(4,6
- dibutylphenyl) 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-phthyl-B-t-butylphenyl)fluorophosphite, 2,2I-ethylidene-bis(4,
6-di-t-butylphenyl) fluorophosphite, 2,2+ methylene-bis(4-methyl-6-t-octylphenyl) fluorophosphite, 2,2'-
Butylidene-bis(4-methyl-6-(1ξmethylcyclohexyl)phenyl)fluorophosphite, 2,
2'-methylene bis(4,6-dimethylphenyl)fluorophosphite, 2,2'-thio-bis(4
-octylphenyl)fluorophosphite, 2
, 2'-thio-bis(4,6-diS-amylphenyl)fluorophosphite, 2,2'-thio-bis(4
, 6-di-i-octylphenyl)fluorophosphite, 2,2ξthio-bis(5-di-octylphenyl)
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-7-butylphenyl)fluorophosphite and 2°2′-thio-bis(4-t- Examples include amyl phenyl) fluorophosphite, particularly 2,21-bis(
4,6-di-t-butylphenyl)fluorophosphite, 2,2'-methylene-bis(4-methyl-8-t
-butylphenyl)fluorophosphite, 2.
2'-methylene-his(4,6-di-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 are preferred; these compounds A are described in JP-A-63-227594. It can be obtained by the described production method. That is, according to the reaction formula below, bisphenol, which is a raw material phenol for compound A, is reacted with phosphorus trichloride or phosphorus tribromide to produce diarylene monohalophosphite (diarylene monochlorophosphite or diawarene monobromorph osphite). ) and the resulting diarylene monohalophosphite is treated with a fluorinating reagent (e.g. HF, LiF, NaF, KF,
RbF, CsF, 5bFa, SbF5. AgF,
HgF2. CoF3, SF. Compound A can be obtained by reacting (etc.). (However, in formula 5, R is an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar and Ar2 are an alkylarylene group or a cycloalkylarylene group, X is chlorine or bromine, YF is a fluorinating reagent, and n is 0 or 1 respectively) Also, the above-mentioned Japanese Patent Application Laid-Open No. 63-2275
It can also be obtained by the manufacturing method described in JP-A-1-135789, which is an improved method of the manufacturing method described in No. 94. That is, when reacting the above-mentioned diarylene monohalophosphite with a fluorinating reagent, a hydrogen halide of a pyridine type compound (e.g., pyridine acid salt, pyridine hydrobromide, pyridine fluoride) is used as a fluorination reaction accelerator. Compound A can also be obtained by reacting in the presence of hydroxide, picoline salt, quinoline hydrochloride, nicotinic acid hydrochloride, 2-aminopyridine salt *salt, 2-phenylpyridine hydrochloride, etc.) . It is natural to use the compound A alone, but it is also possible to use two or more kinds of the compound A in combination. The blending ratio of the compound A is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on the amount of crystalline polyolefin 1001[C]. If the amount is less than o or ooi parts by weight, the effect of improving the rigidity will not be sufficiently exhibited, and although it is possible to exceed the amount of the royal setting, it is not practical because no further improvement in the rigidity can be expected. It is also uneconomical. Compound B used in the present invention includes acetic acid 1. Propionic acid, butyric acid, valeric acid, α-methylbutyric acid, hexanoic acid, sorbic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, caproleic acid, undecanoic acid, undecanoic acid, lauric acid, Linderic acid, myristic acid Acid, puizeteric acid, myristoleic acid, balmitic acid, palmitoleic acid, hiratic acid, stearic acid, petroselic acid, oleic acid, elaidic acid, azelaic acid, vaccenic acid, linoleic acid, α-eleostearic acid, β-eleoacid Stearic acid, punicic acid, lylunic acid, γ-lylunic acid, moroctic acid, stearidonic acid, stearolic acid, arachidic acid, gadoleic acid, bondoic acid, arachidonic acid, behenic acid, cetoleic acid, erucic acid, brassic acid, sardine acid , potassium salts of aliphatic monocarboxylic acids, such as lignoceric acid, ceracoleic acid, nisic acid, cerotic acid, ximenic acid, montanic acid, melisic acid and lumecic acid,
Strontium and barium salts, 2-hydroxytetradecanoic acid, ibrolic acid, 2-hydroxyhexadecanoic acid, yarapinoleic acid, unipelic acid, ampletolic acid, alluritic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18- Hydroxyoctadecanoic acid, 9°10-dihydroxydioctadecanoic acid, ricinoleic acid. Potassium, strontium and barium salts of hydroxy higher fatty acids such as camrolenic acid, lycanic acid, ferronic acid and cerebronic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, Lithium, sodium, potassium, strontium and barium salts of aliphatic polycarboxylic acids such as sebacic acid, 1,2,3-propanetricarboxylic acid and 1,2,3,4-butanetetracarboxylic acid, glycolic acid, Lactic acid, hydroacrylic acid, α-
Oxybutyric acid, tartronic acid, glyceric acid, malic acid,
Lithium salts, sodium salts, potassium salts, magnesium salts, strontium salts and barium salts of l111 aliphatic hydroxy acids having 2 to 6 carbon atoms such as tartaric acid, tartaric acid, grape acid and citric acid, benzoic acid, 0 to toluic acid , -toluic acid, P-toluic acid. pt-butylbenzoic acid, 0-methoxybenzoic acid, V-methoxybenzoic acid, anisic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellidic acid, pyromellitic acid, salicylic acid and 3,5-di-monobutyl Lithium, sodium, strontium, barium and aluminum salts of aromatic carboxylic acids such as 4-hydroxybenzoic acid, monolithium glutamate, monosodium glutamate, monopotassium glutamate, strontium glutamate, barium glutamate, (
Mono, Simituxt) hexyl phosphate, (Mono, Simituxt) octyl phosphate, (Mono, Simituxt)
2-Ethylhexyl phosphate, (mono, Simituxt)
Decyl phosphate, (mono, Simituxt) lauryl phosphate, (Mono, Simituxt) myristyl phosphate. (mono, simituxt) palmityl phosphate, (mono,
Simituxt) stearyl phosphoric acid, (mono, Simituxt) oleyl phosphoric acid, (mono, Simituxt) linole phosphoric acid, (mono, Simituxt) linole phosphoric acid, (mono, Simituxt) tocosyl phosphoric acid,
(Mono, Simituxt) erucyl phosphate, (Mono, Simituxt) tetracosyl phosphate, (Mono, Simituxt) hexacosyl phosphate and (Mono, Simituxt)
Sodium, potassium, calcium, strontium and barium salts of aliphatic phosphoric acids such as oftacosyl phosphate, lO-hydroxy-9,10-dihydro-
9-oxa-10-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-1°-phosphaphenanthrene-10-oxide, 6-methyl-1
0-hydroxy-9,10-dihydro-9-oxa 1
〇-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-phospufugphenanthrene-1
0-oxide, 2-ethyl-10-hydroxy-9,
10-dihydro9-oxa-10-phosphughphenanthrene-10-oxide, 6-ethyl-10-hydroxy-9,10-dihydro9-oxa-10-phosphughphenanthrene-10-oxide, 8- Ethyl-1
0-hydroxy-9,10-dihydro-9-oxa-1
0-phosphaphenanthrene-10-oxide, 6
,8-diethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospufugphenanthrene-1
0-oxide, 2,6.8-triethyl-IO-hydroxy-9,10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide, 2-1-
Propyl-10-hydroxy-9,10-dihydro-9
-Oxa-10 Phosfugphenanthrene-10-oxide, 6-i-propyl-10-hydroxy-9,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-i-propyl-10
-t nitroxy-9,10-dihydro -9-, t xa-10-7 osphenthrene-10-oxide, 6,8-j-probyl-10-hydroxy-9
, 10-dihydro-9-oxa.10-poosphaphenanthrene-10-oxide. 2.8.8-Treamy propyl-10-hydroxy-9,1o-dihydro-9-oxa-10-phosphabenanthrene-10-oxide, 2-s-butyl-
1o-hydroxy-9,1o-dihydro-9-oxa-
10-phosphaphenanthrene-lO-oxide,
6-5-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phthasphaphenanthrene-1
0-oxide, 8-s-butyl-10-hydroxy-
9,10-dihydro-9-oxa-10-phosphaphenanthrene-io-oxide, 1,8-di-S-butyl-1o-hydroxy-9,10-dihydro-9-oxa-10-phospha Fetinthrene-10-oxide, 2,6.8-tri-S-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphughphenanthrene-10-oxide, 2-t-butyl -10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-phthyl-10-hydroxy-9,10-dihydro-g-oxa-10-phosphaphenan Threne-10-oxide, 8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospufugphenanthrene-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-G L-
Butyl-10-hydroxy-9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide, 2,8-di-t-butyl-10-hydroxy.
9.10-dihydro-9-oxa-IO-phosphaphephenanthrene-10-oxide, 6,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10 phosphaphe Nanthrene] O-oxide, 2,6.8-) So-t-butyl-10-hydroxy-9,1o-dihydro-9-oxa-10-phospufugphenanthrene-10-oxide, 2-t- 7 Mil-10-Human O'f C9.10-C? Nidro9-oxer10-phosphaphenanthrene-10-
oxide, 6-t-amyl-1o-hydroxy-9,
1o-dihydro-9-oxa-]O-phosphofugphenanthrene-10-oxide, 8-t-amyl-10-
Hydroxy-9,1o-dihydro-9-oxa-10-
Phosphugh phenanthrene-10-oxide, 6.8
-Z-Shi-A-ξ-1o-Hydroxy-9,1゜-dihydro-9-oxa-10-Phosfugphenanthrene-
10-oxide, 2,6.8-tri-L-amylu 1
0-hydroxy-9,10-dihydro-9-oxa-1
0-phospufugphenanthrene-10-oxide, 2
-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphofugphenanthrene-1
0-oxide, 6-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphofugphenanthrene-10-oxide, 8-t-octyl-10-hydroxy-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-1O-oxide, 6,8-dihydrof) Lt-10-human O#-cy9,10-dihydro-9-oxa-10-phospha Phenanthrene-10 oxide, 2,6.8-tri-t-octyl-10-hydroxy-9゜10-dihydro-9-oxa-10 phosphofugphenanthrene-10
-oxide, 2-cyclohexyl-10-hydroxy-9,1o-dihydro-9-oxa-10-phosphofugphenanthrene-10-oxide, 6-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa -10-Phosfugphenanthrene-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-tricyclohexyl/lO-hydroxy-9,10-dihydro-9-oxa-10-phosphafinanthrene-]O-oxide, 8-phenyl-10-hydroxy-9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-1
0 oxide, 6-benzyl-10-hydroxy-9
, 10-dihydro-9-oxa-10-phospufugphenanthrene-10-oxide, 8-benzyl-104
Nitroxy-9,10-dihydro-9-oxa-10-
Phosphugh phenanthrene-10-oxide, 6,8
-di-benzyl-1O-hydroxy-9,1o-dihydro-9-oxa-10-phosphaphenanthrene 1
0-oxide, 2,6.8-tribenzyl-10-
Hydroxy-9,1o-dihydro-9-oxa-10-
Phosphugu phenanthrene-10-oxide, 2-(
α-methylbenzyl)-10.hydroxy-9,IO
-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-(α-methylbenzyl)
-10-hydroxy-9,1o-dihydro-9-oxa-10-phosphofugphenanthrene-10-oxide, 8-(α-methylbenzyl)-10-hydroxy-9
, 1o-dihydro-9-oxa-10-phosphfugphenanthrene-10-oxide, 6,8-di(α-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-phos Puffer phenanthrene-10
-oxide, 2,6.8-tri(α-methylbenzyl)-10-hydroxy-9,1o-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,IO
-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-methyl-
10-hydroxy-9,10-dihydro-9-oxa-
1O-phosphafluorene-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-1O-phosphaphenanthrene-10-oxide, 6-(α-methylbenzyl)-8(
-butyl-10-hydroxy-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-cyclohexyl-10
-hydroxy-9,to-dihydro-9-oxa-10
-Phosphafluorene-10-oxide, 8-
Benzyl-8-cyclohexyl-10-hydroxy-9
, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-
Benzyl-10-hydroxy-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-8 benzyl-10-
Hydroxy-9,10-dihydro-9-oxa-1O-
Phosphenthrene 10-oxide, 2,6
-di-t-butyl-8-benzyl-1O-hydroxy-
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2,6-dicyclohexyl-8-benzyl-10-hydroxy-9,1
lithium, sodium, potassium and barium salts of cyclic phosphorus compounds such as 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
Examples include magnesium hydroxide, aluminum hydroxide, magnesium oxide, magnesium carbonate, calcium carbonate, and hydrotalcite, particularly potassium stearate, strontium stearate, barium stearate, potassium 12-hydroxyoctadecanoate,
- Strontium hydroxyoctadecanoate, barium 12-hydroxyoctadecanoate, lithium adipate, sodium adipate, potassium adipate, strontium adipate, barium adipate, lithium lactate, sodium lactate, potassium lactate, magnesium lactate, strontium lactate, barium lactate , lithium citrate, sodium citrate, potassium citrate, magnesium citrate, strontium citrate, barium citrate, lithium benzoate, sodium benzoate, strontium benzoate, barium benzoate, p-t-butyl aluminum benzoate, Monolithium glutamate, monosodium glutamate, monopotassium glutamate, strontium glutamate, barium glutamate, (mono, simituxt) sodium stearyl phosphate, (mono, simituxt) potassium stearyl phosphate, (mono, simituxt) stearyl Calcium phosphate, Strontium stearyl phosphate (mono, diyotxt), Barium stearyl phosphate (mono, diyotxt), 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-1
Lithium salt of 0-oxide, 10-hydroxy-9,
Sodium salt of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, potassium salt of 10-hydroxy-9,1O-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , 10-hydroxy-9,10-dihydro-9-
Barium salt of oxa-10-phosphaphenanthrene-10-oxide. Magnesium hydroxide, aluminum hydroxide, magnesium oxide, magnesium carbonate, calcium carbonate and hydrotalcite are preferred. These compounds B can be used alone, but two or more types of compounds B can also be used in combination. The blending ratio of the compound B is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the crystalline polyolefin. If the amount is less than 0.001 part by weight, the effect of improving the rigidity will not be sufficiently exhibited, and although it is possible to add more than 1 part by weight, it is not practical because no further improvement in the rigidity can be expected. It is also uneconomical. Compound C used in the present invention includes octylamine,
laurylamine, myristylamine, valmitylamine, stearylamine, oleylamine, cocoaamine, tallowamine, soyamine, N,N-dicocoamine, N,
N-citaroamine, N,N-diamine, 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-citaroamine, N-methyl-N, N-dicokoamine, N-oleyl-1,3-diaminopropane, N-tallow-1,3-diaminopropane, hexamethylenediamine, N-lauryl-N,N,N -) dimethylammonium chloride, N-palmityl N, N, N-
) dimethylammonium chloride, N-stearyl-
N,N,N-trimethylammonium chloride,
N-tocosyl-N,N,N-trimethylammonium chloride. N-coco N,N,Nl-dimethylammonium chloride, N-tallow-N,N,N-)dimethylammonium chloride, N-soy-N,N,N-)dimethylammonium chloride, N,N,N-)diethyl -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-dicoko N,N-dimethylammonium chloride, N,N-citaro-N,N-dimethylammonium chloride, N,N-shisoy 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(polyoxy ethylene)-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- Screw (2
-Hydroxyethyl)pentadecylaminobetaine, N
, N-bis(2-hydroxyethyl) pallylaminobetaine, N,N-bis(2-hydroxyethyl)stearylaminobetaine, N,N-bis(2-hydroxyethyl)oleylaminobetaine, N,N -Bis(2-
hydroxyethyl) tocosylaminobetaine, N, N-
Bis(2-hydroxyethyl)octacosylaminobetaine, N,N-bis(2-hydroxyethyl)cocoaminobetaine, N,N-bis(2-hydroxyethyl)tallowaminobetaine, hexamethylenetetra-rich, tri Ethanolamine, triisopropanolamine, N-
(2-hydroxyethyl)laurylamine, N.(2-
hydroxyethyl) tridecyl apine, N-(2-hydroxyethyl) myristylamine, N-(2-hydroxyethyl) bentadecylapine, N-(2-hydroxyethyl)pal-ξthylamine, N-(2-hydroxyethyl) stearylamine , N-(2-hydroxyethyl)
Oleylamine, N-(2-hydroxyethyl)tocodylamine, N-(2-hydroxyethyl)oftacosylamine, N-(2-hydroxyethyl)cocoamine, N.(2-hydroxyethyl)tallowamatane, N-methyl- N-(2-hydroxyethyl)laurylamine,
N-Methyl-N-(2-hydroxyethyl)tridecylamine, N-methyl-N-(2-hydroxyethyl)-based listylamine, N-methyl-N-(2-hydroxyethyl)pentadecylamine, N-methyl -N-(2-hydroxyethyl)valmitylamine, N-methyl-N-
(2-hydroxyethyl)stearylamine, N-methyl-N-(2-hydroxyethyl)oleylamine, N
-Methyl-N-(2-hydroxyethyl)tocodylamine, N-methyl-N-(2-hydroxyethyl)oftacosylamine, N-methyl-N-(2-hydroxyethyl)cocoamine, N-methyl-N(2-hydroxyethyl)cocoamine, -hydroxyethyl) tallowamine, N, N-bis(2-hydroxyethyl) laurylamine, N, N-bis(2-hydroxyethyl) tridecylamine, N, N-bis(2-hydroxyethyl) myristylabine, N , N-bis(2-
hydroxyethyl)pentadecylamine, N,N-bis(2-hydroxyethyl)valmitylamine, N,N-
Bis(2-hydroxyethyl)stearylamine, N
, N-bis(2-hydroxyethyl)oleylamine, N,N-bis(2-hydroxyethyl)tocodylamine, N,N-bis(2-hydroxyethyl)oftacosylamine, N,N-bis(2-hydroxyethyl) ) Cocoamine, N,N-bis(2-hydroxyethyl) aliphatic amines such as N,N-bis(2-hydroxyethyl)tallowamine, UN,N-bis(2-hydroxyethyl)aliphatic amines and lauric acid, Mono- or diesters with Fw fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, poly oxyethylene cocoaminoether, polyoxyethylene cocoaminoether,
N,N,N',N'-tetra(2-hydroxyethyl)-1,3-diaminopropane, N,N
, N', N'-tetra(2-hydroxyethyl)
-1,6-diaξhexane, N-lauryl-N, N
', N' tris(2-hydroxyethyl) -1,
3-Sia [noproban, N-stearyl-N, N', N
'-) Lis(2-hydroxyethyl)-1,3-diaminopropane, N-CocoIJ, N',N'-tris(2-hydroxyethyl)-1,,3-diaminopropane, N-Tallow N, N', N'-tris(2-
hydroxyethyl)-1,3-diaminopropane. N,N-dicoko N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane, N,N-citaro-N'N'-bis(2-hydroxyethyl)-1,
3-diaminopropane, N-coco N,N',N''-tris(2-hydroxyethyl)-1,,6-dia-based hexane, N-tallow-NNr, Nl-tris(
2-hydroxyethyl)-1,6-cyamitsuhexane, N,N-dicoko N', N'-bis(2-hydroxyethyl)-1,,6-cyamitsuhexane and N,N-citaro-N' , N'-bis(2-hydroxyethyl)-1,6-cyamitzhexane, etc., and N,N-bis(2-hydroxyethyl) aliphatic amine is particularly preferred. It is natural to use these compounds C alone, but it is also possible to use two or more kinds of compounds C in combination. The blending ratio of the compound C is 100% of the crystalline polyolefin.
0.01 to 1 part by weight, preferably 0.0 part by weight
The amount is 5 to 0.5 parts by weight and 1 part by weight. If the amount is less than 0.01 part by weight, the effect of improving the rigidity will not be sufficiently exhibited, and although it is possible to exceed 1 part of FFI, it is not practical as it cannot expect any further improvement in the rigidity. It is also uneconomical. In the composition of the present invention, it is preferable to use an inorganic filler (excluding compound B) in combination, since the effect of improving the rigidity is synergistically exhibited.
Inorganic fillers include talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, silicon dioxide, titanium dioxide, zinc oxide, zinc sulfide, barium sulfate, calcium silicate, and aluminum silicate. Surfaces such as titanium, glass fibers, potassium titanate, carbon fibers, carbon blanks, graphite and metal fibers, and camping agents (such as silanes, titanates, borons, aluminates, zircoaluminates, etc.) Examples of the inorganic fillers surface-treated with a treatment agent include talc, which is particularly preferred.These inorganic fillers can be used alone, but two or more types of inorganic fillers can also be used in combination. The blending ratio of the inorganic filler is 0.01 to 25 parts by weight, preferably 0.1 parts by weight, per 100 parts by weight of the crystalline polyolefin.
~20 parts by weight, more preferably 1 to 15 parts by weight. In the composition of the present invention, by using a phenolic antioxidant in combination, thermal oxidative deterioration properties can be improved. Examples of phenolic antioxidants include 2,6-di-L-butyl-P-cresol, 2-L-butyl-4,
6-Situtylphenol, 2,6-di-t-butyl-4
-ethylphenol, 2,6-di-butyl-4.n
-butylphenol, 2,6-di-butyl-4-n
-butylphenol, 2,6-di-cyclopentyl-4
-Methylphenol, 2-(α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4.6-tricyclohexylphenol, 2,6-dimethylphenol Monobutyl-4-methoxymethylphenol, n-octadecyl=
β-(4'-hydroxy-3'.5'-disavetylphenyl)propionate,
2.6-di-butyl-4-methoxyphenol, 2
．． 5-di-t-butylhydroquinone, 2,5-di-L
-amylhydroquinone, 2,2'-thio-bis(6-
t-butyl-4-methylphenol), 2,2'-thio-bis(4-octylphenol), 2,2'-thio-
Bis(6-thi-butyl-3-methylphenol), 4.
4'-thio-bis(6-t-butyl-2-methylphenol), 4,4'-thio-bis(6-t-butyl-3-
methylphenol), 4,4'-thio-bis (2
, 6-di-t-butylphenol), 2,2'-methylene-bis(6-t-butyl-4-methylphenol),
2,2'-methylene-bis(6-t-butyl-4-ethylphenol), 2,2'-methylene-bis[4-methyl-6-(α-methylcyclohexyl)-phenol]
, 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6
-nonyl-4-methylphenol), 2,2'-methylene-bis[8-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis[6-(α,α
-dimethylbenzyl)-4-nonylphenol]. 2.2'-methylene-bis(4,6-di-butylphenol), 2.2'-ethylidene-bis(4,6-di-t-butylphenol), 2,2'-ethylidene-bis(6-t-butylphenol) -butyl-4-3-butylphenol), 4
．． 4'-methylene-bis(2,6-di-t-butylphenol), 4,4'-methylene-bis(6-butyl-2-methylphenol), 4,4'-butylidene-bis(6-t-butylphenol) -butyl-2-methylphenol), 4.4
'-Butylidene-bis(6-L-butyl-3-methylphenol), 4,4'-butylidene-bis(2,6-di-butylphenol), 4,4'-butylidene-bis(3,6- Butylphenol), 1.1
-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di(3-t-butyl-5
-methyl-2-hydroxybenzyl)-4-methylphenol, calcium-bis[〇-ethyl-(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, 2-t-butyl-6- (3-t-butyl-2-
Hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-t-butyl-6-[3-t-butyl-2-hydroxy-5-methyl(α-methylbenzyl)]-]4-methylphenylacrylate 2,4-di-butyl-6-[3,5-di-butyl-2-hydroxy(α-methylbenzyl)]phenylacrylate, tocopherol, 2,6-diphenyl-4-octadecyloxyphenol, 2, 4-bis(n-octylthio) -6-(4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4.6-
) Lis(2'-hydroxy-4'-octoxyphenyl)-1,3,5-)riazine, 2,4,6-tris[
3-(3',5'-di-t-butyl-4'-bitroxyphenyl)ethyl]-1,3,5-triazine, 2,4
．． 6-tris(3'.5'-di-butyl-4'-hydroxybenzylthio)-1,3,5-triazine, 1,3.5-)
3',5'-di-t-butyl-4'-hydroxybenzylacetyl)hexahydro-1,3,5-triazine,
1,1.3-) Lis(5-t-butyl-4-hydroxy-2-methylphenyl)-butane, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl) ) propionate], 1.6
-hexanethiolubis[3-(3,5-di-L-butyl-4-hydroxyphenyl)propionate, N
N I-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]-hexamethylenediamine, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl Ester, 2,2-thio-diethylenebis[:3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, bis[3,3-bis(4″-hydroxy-3′- t-butylphenyl)butyric acintocoethylene glycol ester, bisC3,3-bis(4'-hydroxy-31
-Methyl-5'-t-butylphenyl)butyric acintocoethylene glycol ester, bis[3,3-bis(4'-hydroxy-3'.5'-di-butylphenyl)butyric acintocoethylene glycol Ester, bis[3,3-bis(4
'-Hydroxy-3'-t-butylphenyl)butyrin acid] -2,2-bis(hydroxyethoxyphenyl)propane ester, bis[3,3-bis(4'
-Hydroxy-3'-methyl-5'-t-butylphenyl)butyrin acid] -2,2-bis(hydroxyethoxyphenyl)propane ester, bis[3,3
-bis(4'-hydroxy-3',5'-di-butylphenyl)butyrin acid] -2,2-bis(
Hydroxyethoxyphenyl)propane ester, bis[2-(3'-t-phthyl-2'-hydroxy 51-
methylbenzyl)-6-t-butyl-4-methylphenyl]terephthalate, 3,9-his(3,5-di-t
-butyl-4-hydroxyphenyl) -2,4,8,
], ]0-tetraoxaspiro5.5] undecane, 3.9-bis[1,1-dimethyl-2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl] -
2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-(β
-(3-savetyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl]-2.4,8,1
．． 0-Tetraoxaspiro[5,5-oundecane, 3.
9-bis[1,1-dimethyl-2-(β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5 ,5-oundecane, 3,9-bis[1,1-dimethyl-2-(β-(3゜5-diphenyl-4-hydroxyphenyl)propionyloxy)ethyl] -2,
4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis[l,1-dimethyl=2-(β-(3
,5-dicyclohexyl-4-hydroxyphenyl)propionyloxy)ethyl] -2,4,8゜10-tetraoxaspiro[5,5] undecane, l, 3゜5
-trimethyl-2,4,6-tris(3,5-di-butyl-4-hydroxybenzyl)benzene, tris(
3,5-di-t-butyl-4-hydroxybenzyl)in cyanurate, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)in cyanurate,
Tris[3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2,2-pisC4-(2-(3-methyl-5-t
-butyl-4-hydroxyphenylpropionyloxy)ethoxy]phenylcopropane, 2,2-bis[4-
(2-(3,5-di-t-butyl-4-hydroxyphenylpropionyloxy)ethoxy]phenyl]propane, tetrakis[methylene-3-(3'-methyl-5'
-t-butyl-4'-hydroxyphenyl)propionate comethane and tetrakis[methylene-3-(3'
, 5'-di-t-butyl-41-hydroxyphenyl)
Examples include propionate comethane. It is natural to use these phenolic antioxidants alone, but it is also possible to use two or more types of phenolic antioxidants in combination. The blending ratio of the phenolic antioxidant is 0.01 to 1 part by weight, preferably 0.5 part by weight of O,OS, per 100 parts by weight of the crystalline polyolefin. In the composition of the present invention, resistance to thermal oxidative deterioration can be improved by using a thioether antioxidant. Examples of thioether antioxidants include dilaurylthiodipropionate, ditridecylthiodipropionate, di-listylthiodipropionate, dicetylthiodipropionate, and distearylthiodipropionate. Dilaurylthiodibutyrate, ditridecylthiodibutyrate, dimyristylthiodibutyrate, dicetylthiodibutyrate, distearylthiodibutyrate, laurylstearylthiodipropionate, laurylstearylthiodibutyrate. Pentaerythritol-β-laurylthiodipropionate, Pentaerythritol-tetrakis (3-octylthiopropionate), Pentaerythritol-tetrakis (3-nonylthiopropionate), Pentaerythritol-tetrakis (3-decylthiopropionate) pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-tridecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate) (3
-balmitylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), pentaerythritol-tetrakis (4-octylthiobutyrate), pentaerythritol-tetrakis (4-nonylthiobutyrate), pentaerythritol-tetrakis (4-nonylthiobutyrate), Erythritol-tetrakis (4-decylthiobutyrate), Pentaerythritol-tetrakis (4-laurylthiobutyrate), Pentaerythritol-tetrakis (4-tridecylthiobutyrate), Pentaerythritol-tetrakis (4-myristylthiobutyrate) ) Pentaerythritol-tetrakis (4-palmitylthiobutyrate)
, pentaerythritol-tetrakis (4-stearylthiobutyrate), pentaerythritol-tetrakis (3-octylthiobutyrate), pentaerythritol-tetrakis (3-nonylthiobutyrate), pentaerythritol-tetrakis (3-decylthiobutyrate) butyrate), pentaerythritol-tetrakis (3-laurylthiobutyrate), pentaerythritol-tetrakis (3-tridecylthiobutyrate), pentaerythritol-tetrakis (3-myristylthiobutyrate)
, pentaerythritol-tetrakis (3-balmitylthiobutyrate), pentaerythritol-tetrakis (3-stearylthiobutyrate), tetrakis[3-
(2-(octyloxycarbonyl)ethylthio)propionyloxymethylcomethane, tetrakis[3-(2
-(nonyloxycarbonyl)ethylthio)propionyloxymethylcomethane, tetrakis[3-(2-(decyloxycarbonyl)ethylthio)propionyloxymethylcomethane, tetrakis[3-(2-(dodecyloxycarbonyl)ethylthio)propionyloxy] Methylcomethane, TetrakisC3-(2-(tridecyloxycarbonyl)ethylthio)propionyloxymethylcomethane, Tetrakis[3-(2-(tetradecyloxycarbonyl)ethylthio)propionyloxymethylcomethane, Tetrakis[3-( 2-(hexadecyloxycarbonyl)ethylthio)propionyloxymethylcomethane, tetrakis[3-(2-(octadecyloxycarbonyl)ethylthio)propionyloxymethylcomethane, 1,3.5-tris[3-(2-( Octyloxycarbonyl)ethylthio)propionylcohexahydro-1,3,5-1-riazine, 1.3.5
-) Lis[3-(2-(nonyloxycarbonyl)ethylthio)probionylcohexahydro-1,3,5-
Triazine, 1,3.5-tris[3-(2-(,decyloxycarbonyl)ethylthio)propionyl]hexahydro-1,3,5-triazine, 1,3.5-tris[3-(2-( dodecyloxycarbonyl)ethylthio)propionylcohexahydro-1,3,5-)riazine, 1.3.5-tris(3-(2-()lysyloxycarbonyl)ethylthio)propionyl]hexahydro-1,3 ,5-triazine, 1,3.51
Lis[3-(2-(tetradecyloxycarbonyl)ethylthio)propionyl]hexahydro-1,3,5-
) riazine, 1,3.5- ) lis[3-(2-(hexadecyloxycarbonyl)ethylthio)propionylcohexahydro-1,3,5-triazine, 1,3.5
-tris[3-(2-(octadecyloxycarbonyl)ethylthio)propionylcohexahydro-1,3,
5-) riazine, 2,4.6-tris[3-(2-(
octyloxycarbonyl)ethylthio)probionylco-1,3,5-triazine, 2,4.6-)lis[
3-(2-(nonyloxycarbonyl)ethylthio)propionyl]-1,3,5-triazine, 2,4.6-
Tris[3-(2-(decyloxycarbonyl)ethylthio)probionyl-1.3.5-triazine,2
,4.6-)Lis[3-(2-(dodecyloxycarbonyl)ethylthio)propionyl]-L3,5-triazine,2,4.6-)Lis(3-(2-()
lysosyloxycarbonyl)ethylthio)propionyl]-1,3,5-triazine, 2,4,6-tris[3
-<2- (tetradecyloxycarbonyl)ethylthio)propionyl]-1,3,5-triazine, 2,4
．． 6- Tris[3-(2-(hexadecyloxycarbonyl)ethylthio)propionyl] -1,3,5-
Triazine, 2,4.6- ) Lis[3-(2-(octadecyloxycarbonyl)ethylthio)propionyl]-1,3,5-triazine, Tris[:3- (2-
(Octyloxycarbonyl)ethylthio)propionyl coisocyanurate, Tris[3-(2-(nonyloxycarbonyl)ethylthio)propionylcoisocyanurate, Tris[3-(2-(decyloxycarbonyl)ethylthio)probionylcoisocyanurate] , Tris[:3-(2-(dodecyloxycarbonyl)ethylthio)propionyl coin cyanurate, Tris[
3-(2-(hlysosyloxycarbonyl)ethylthio)propionyl coin cyanurate, tris[3-(2
-(tetradecyloxycarbonyl)ethylthio)propionyl coisocyanurate, tris[3-(2-(hexadecyloxycarbonyl)ethylthio)propionylcoin cyanurate, tris[3-(2-(octadecyloxycarbonyl)ethylthio)propionylcoin] Cyanurate, Tris[3-(2-(octyloxycarbonyl)ethylthio)propionyloxyethylcoisocyanurate, Tris[3-(2-(nonyloxycarbonyl)ethylthio)probionyloxyethylcoisocyanurate, Tris[3- (2-(decyloxycarbonyl)ethylthio)propionyloxyethyl]
Isocyanurate, Tris[3-<2- (dodecyloxycarbonyl)ethylthio)probionyloxyethylcoisocyanurate, Tris[3-(2-()lysosyloxycarbonyl)ethylthio)propionyloxyethylcoisocyanurate, TrisC3 -<2- (tetradecyloxycarbonyl)ethylthio)propionyloxyethyl]isocyanurate, tris[3-<2
-(hexadecyloxycarbonyl)ethylthio)propionyloxyethyl]isocyanurate, tris[3
-(2-(octadecyloxycarbonyl)ethylthio)propionyloxyethyl]isocyanurate, bis(4-t-amyl phenyl) sulfide, dilauryl disulfide, diξlistyl disulfide, distearyl disulfide, 3,9-bis(2 -laurylthioethyl) -2,4,8,10-tetraoxaspiro[5,5
]Undecane, 3,9-bis(2-main listylthioethyl)-2,4,8,10-tetraoxaspiroC5,
5] Undecane, 3,9-bis(2-stearylthioethyl)-2,4,8,10-tetraoxaspiro[5
,5-oundecane, 3,9-bis(2-laurylthiopropyl)-2,4,8,10-tetraoxaspiro[5
,5] undecane, 3.9-bis(2-myristylthiopropyl) -2,4,8゜10-tetraoxaspiro[5,5 undecane, 3,9-bis(2-stearylthiopropyl) -2, 4,8,10-tetraoxaspiro(5,51 undecane, 3,9-bis[ ], ]1-
dimethyl-2-3-laurylthiopropionyloxy)
ethyl]-2.4. lt, 10-tetraoxaspiro[
5,5-oundecane, 3,9-bis[1,1-dimethyl-2-(3-myristylthiopropionyloxy)ethyl-2.4,8.10-tetraoxaspiro[5,5
] Undecane, 3,9-bis[1,1-dimethyl-2
-(3-stearylthiopropionyloxy)ethyl)
-2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1,1-dimethyl-2-(3
-Laurylthiobutyroyloxy)ethylco2.4,
8.10-tetraoxaspiro[:5.5]undecane, 3,9-bis[1,1-dimethyl-2-(3-myristylthiobutyroyloxy)ethyl] -2,4,8,
10-tetraoxaspiro[5,5]undecane, 3
．． 9-bis[1,]-]dimethyl-2-3-stearylthiobutyroyloxy)ethyl2.4,8.10-
Tetraoxaspiro[5,5]undecane, 3-(laurylthio)propionyl 7mide, 3-(myristylthio)propionylamide, 3-(stearylthio)propionylamide, N,N'-methylene-bis(3-laurylthio) propionyl)amide, N,N″-methylene-
Bis(3-myristylthiopropionyl)amide, N
, N'-methylene-bis(3-stearylthiopropionyl)amide, N,N'-ethylene-bis(3-laurylthiopropionyl)amide, N,N'-ethylene-bis(3-myristylthiopropionyl)amide, N, N
'-ethylene-bis(3-stearylthiopropionyl)amide, N,N'-bis(3-laurylthiopropionyl)hydrazide, N,N'-bis(3-myristylthiopropionyl)hydrazide, N,N'-bis (
3-stearylthiopropionyl) hydrazide, thioethylene glycol-bis(β-aminocrotonate),
Examples include bis[2-methyl-4-(3-alkylthiopropionyloxy)-5-butylphenyl]sulfide and poly[114-bis(hydroxymethyl)cyclohexane-thiodipropionate]. These thioether antioxidants can be used alone, but two or more thioether antioxidants can also be used in combination. The blending ratio of the thioether antioxidant is
0.0 for 100 parts by weight of crystalline polyolefin
The amount is 1 to 1 part by weight, preferably 0.05 to 0.5 part by weight. In the composition of the present invention, by using a phosphorous antioxidant (excluding Compound A) in combination, it is possible to improve heat oxidative deterioration resistance, 1 weather (light) resistance, and color resistance. can. Phosphorous antioxidants include distearyl pentaerythritol diphosphite and diphenyl.
Pentaerythritol-shifuosphite, bis(nonylphenyl)pentaerythritol-shifuosphite, canacyl-2,6-di-L-butyl-4-methylphenylphosphite, canacyl-2,4,6-tri-monobutylphenyl phosphite, α-naphthylcathyl phosphite, 2.2'-methylenebis(4-
Methyl-6-t-butylphenyl)-2-naphthylphosphite, 4.4'';'Tylidene bis(3-methyl-at-butylphenyl-di-tridecylphosphite), 1,1.3 -) Lis(2-methyl-4-di-
tridecylphosphite-5-sheepylphenyl)
Butane, trilauryltrithiophosphite, tricetyltrithiophosphite, di(laurylthio)pentaerythritol siphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-1
0-oxide, 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-1
0-oxy)te, triphnylphosphite, tris(nonylphenyl)phosphite, tris(2,4
-di-nonylphenyl) phosphite, tris(mono, dinonylphenyl) phosphite, tris(2,4
-di-t-butylphenyl) phosphite, tris(
2,6-di-butyl-4-methylphenyl)phosphite, bis(2,4-di-butylphenyl)pentaerythritol-siphosphite, bis(2,6-di-butyl-4-methylphenyl)phosphite,
-di-tert-butyl-4-methylphenyl)pentaerythritol-shiphosphite, bis(2,6-di-butyl-4-s-butylphenyl)pentaerythritol-shiphosphite, bis(2,4,6- ) sort t-
butylphenyl) pentaerythritol-shiphosphite, bis(2,6-di-butyl-4-n-octadecyloxycarbonylethyl-phenyl)pentaerythritol-shiphosphite, bis[2,6-di-butyl-4- (2',4''-di-savetylphenyloxycarbonyl)-phenyl]pentaerythritol-siphosphite, bis(2,8-di-butyl-4-n-hexadecyloxycarbonyl-phenyl)
Pentaerythritol-siphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-diphosphonite, tetrakis(2,
6-dibutyl-4-methylphenyl) -4,4'
-Biphenylene diphosphonite, Tetrakis (2,6-sheet t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) -4,4'-biphenylene diphosphonite 2 Tetrakis [2,6-
Di-butyl-4-(2'. 4'-di-butylphenyloxycarbonyl)-phenyl]-4,4'-biphenylene-diphosphonite, tetrakis(2,6-di-butyl-4 -n-
hexadecyloxycarbonyl-phenyl) -4,4
'-biphenylene diphosphonite, tetrakis(214-di-t-butylphenyl)-3,9-bis(Ill-dimethyl-2-hydroxyethyl)-2,4
,8,No-tetraoxaspiro[5,5]undecane-siphosphite, tetrakis(2,6-di-L-butyl-4-methylphenyl)-3,9-bis(1,1
-dimethyl-2-hydroxyethyl) -2,4,8,
10-tetraoxaspiro[5,5]undecane-siphosphite, tetrakis(2,6-di-butyl-
4-n-octadecyloxycarbonylethyl-phenyl)-3,9-bis(1,l-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[
5,5] undecane-shiphousphite, tetrakis [
2,6-di-butyl-4-(2',4'-di-savetylphenyloxycarbonyl)-phenyl-3
．． 9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5
] undecane-siphousphite, tetrakis (2,6
-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl)-3,9-bis(1,1-dimethyl-
2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-siphosphite,
Bis[2,2'-methylene-bis(4-methyl-6-t
-butylphenyl)]-]4.4'-biphenylene-diphosphonite bis[2,2'-methylene-bis(4,6-di-L-butylphenyl)]-]4.4
'-Biphenylenziphosphonite bis[2,2
'-ethylidene-bis(4-methyl-6-t.butylphenyl)] -]4.4'-biphenylene-diphosphonite bisC2,2'-ethylidene-bis(4゜6-t.butylphenyl) butylphenyl) -4,4'-biphenylene diphosphonite, bis[2,2'-methylene-bis(4-methyl-6-t-butylphenyl)
-3,9-bis(],]1-dimethyl-2-hydroxyethyl-2,4,8,10-tetraoxaspiro[
5,5] undecane-siphosphite, bis[2,2
'-methylene-bis(4,6-di-t-butylphenyl)]-]3,9-bisl,agemethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5 ] undecane-siphousphite, bis[
2゜2'-ethylidene bis(4-methyl-8-t-butylphenyl)co3,9-bis(1,1-dimethyl-
2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5-oundecan-diphosphite,
Bis[2,2'-ethylidene-bis (4,6-di

[
-butylphenyl) ] -]3.9-bis1,1-di
Methyl-2-hydroxyethyl) -2,4,8,10
-tetraoxaspiro[5,5]undecane-sihuo
Sphite, 2,2'-bis(4,6-di-butyl)
phenyl)octylphosphite, 2,2'-bis(
4,6-di-butylphenyl)nonylphosphite
2,2'-bis(4,6-di-L-butylphenyl)
) lauryl phosphite, 2,2'-bis(4,6-
di[-butylphenyl)tridecyl phosphite,
2,2'-His(4,6-di-t-butylphenyl)mi
Listyl phosphite, 2,2'-bis(4,6-di
-butylphenyl) stearyl phosphite, 2
,2'-bis(4,6-di-t-butylphenyl)
(2,4-di-t-butylphenyl)phosphite,
2,2'-bis(4,6-di-t-butylphenyl) (
2,6-di-butyl-4-methylphenyl)phos
phyto, 2,2'-bis(4,6-di-t-buty)
(2,4,6-)so-t-butylphenyl
〉phosphite, 2,2'-bis(4,6-bis)
butylphenyl) (2,6-di-t-butyl-4-
n-octadecyloxycarbonylethyl-phenyl)
Phosphite, 2,2'-bis(4゜6-di-t-b)
tylphenyl) [2,6-di-butyl-4-(
2',4'-di-t-butylphenyloxycarbonyl
)-phenylkothosphite, 2,2'-bis(4,
6-di-t-butylphenyl) (2,6-di-t-
Butyl-4-n-hexadecyloxycarbonyl-phene
phosphite, 2,2'-methylene-bis(4
-Methyl-6-t-butylphenyl)octylphosph
2,2'-methylene-bis(4-methyl-6-
t-butylphenyl) nonyl phosphite, 2.2'
-methylene-bis(4-methyl-6-t-butylphenyl
) lauryl phosphite, 2,2'-methylene-bi
(4-methyl-6-t-butylphenyl)tridecyl
phosphite, 2,2' methylenebis(4-methyl
-6-t-butylphenyl) myristyl phosphite
, 2,2'-methylene-bis(4-methyl-6-t
-butylphenyl)stearylphosphite, 2.2
'-Methylene-bis(4-methyl-6-t-butylphenylene)
(2,4-di-t-butylphenyl)phos
phyto, 2,2'-methylene-bis(4-methyl-6
-t-butylphenyl”) (2,6-dibutylphenyl)
(4-methylphenyl)phosphite, 2.2'-
methylene-bis(4-methyl-6-t-butylphenyl
) (2,4,8-tri-t-butylphenyl)pho
Sphite, 2.2+ methylene-bis(4-methyl-
6-t-butylphenyl) (2,6-di-t-butylphenyl)
-40-octadecyloxycarbonylethyl-phene
phosphite, 2,21-methylene-bis(4
-methyl f3-t-butylphenyl) [2,6-
di-L-butyl-4-(2',4'-di-t-butyl
(phenyloxycarbonyl)-phenylcottosphite
, 2,2'-methylene-bis(4-methyl-6-t-butylene)
Tylphenyl> (2,6-di-L-butyl-4-n
-hexadecyloxycarbonyl-phenyl)phosph
2,2'-methylene-bis(4,6-di-t-
butylphenyl) octyl phosphite, 2.2'-
Methylene-bis(4,6-di-t-butylphenyl)no
Nylphosphite, 2,21-methylene-bis(4゜
6-di-t-butylphenyl〉lauryl phosphite
, 2,2'-methylene-bis(4,6-di-butyl)
phenyl) tridecyl phosphite, 2,2'-methy
Ren-bis(4,6-csavetylphenyl)milis
Tylphosphite, 2,2'-methylene-bis(4,
6-di-t-butylphenyl) stearyl phosphite
2,2'-methylene-bis(4,6-di-L-
butylphenyl) (2,4-di-7-butylphenyl)
) phosphite, 2,2'-methylene-bis(4,
6-di-t-butylphenyl) (2,6-di-t-
Butyl-4-methylphenyl) phosphite, 2゜2
'-methylene-bis(4,6-di-t-butylphenyl
)(2,4,6-tri-butylphenyl)phosph
2,2'-methylene-bis(4,6-di-bis)
butylphenyl) (2,6-di-t-butyl-4-n-
octadecyloxycarbonylethyl-phenyl)pho
Sphite, 2,2'-methylene-bis(4,6-di
(1-butylphenyl) [2゜6-di-t-butyl-
4.(2',4'-di-t-butylphenyloxycal
(bonyl)-phenylcottosphite, 2,2'-methy
Len-bis(4,6-di-t-butylphenyl)(2,
6-di-butyl-4-n-hexadecyloxycal
(bonyl-phenyl)phosphite, 2,2'-e
tylidene-bis(4-methyl-6-t-butylphenyl
) Octyl phosphite, 2,2'-ethylidene-bi
(4-methyl・6-t-butylphenyl)nonylphos
Sphite, 2,2'-ethylidene-bis(4-methyl
-6-t-butylphenyl) lauryl phosphite,
2.2'-ethylidene-bis(4-methyl-6-t-butylene)
tylphenyl) tridecyl phosphite, 2,2'-
Ethylidene-bis(4-methyl-6-t-butylphenylate)
) myristyl phosphite, 2,2+ ethylidene
-bis(4-methyl-6-t=nibutylphenylstea)
Lylphosphite, 2,2'-ethylidene-bis(4
-methyl-8-h-butylphenyl) (2,4-di
-t-butylphenyl)phosphite, 2,2'-ethyl
tylidene-bis(4-methyl-6-t-butylphenyl
) (2,6-di-t-butyl-4-methylphenyl
) phosphite, 2. Z'-ethylidene-bis(4-
Methyl-6-t-butylphenyl) (2,4,6-
tri-t-butylphenyl) phosphite, 2.
2'-ethylidene-bis(4-methyl-6-t-butyl
phenyl) (2,6-di-t-butyl-4-n-o
tadecyloxycarbonylethyl-phenyl)phos
phyto, 2,2'-ethylidene-bis(4-methyl-
8-t,-butylphenyl) [2,8-di-t-butylphenyl)
Chil-4-(2',4'-di-t-butylphenyloxy
cyclocarbonyl)-phenylcottosphite, 2,2'
-ethylidene-bis(4-methyl-6-t-butylphenylene)
(2,6-di-t-butyl-4-n-hexadecy)
(oxycarbonyl-phenyl) phosphite,
2.2'-ethylidene-bis(4,6-di-t-butyl
phenyl)octylphosphite, 2,2'-ethyl
Den-bis(4,6-t-butylphenyl)nonyl
Phosphite, 2゜2'-ethylidene-bis(4,8
-di-t-butylbuenyl) lauryl phosphite,
2.22-ethylidene-bis(4,6-di-t-butyl
phenyl) tridecyl phosphite, 2.2'-
ethylidene-bis(4,6-di-t-butylphenyl)
Myristyl phosphite, 2,2'-ethylidene-bi
(4,6-di-t-butylphenyl)stearylpho
sphite, 2,2'-ethylidene-bis(4°6-di
-t-butylphenyl) (2,4-di-t-butyl
phenyl) phosphite, 2,2'-ethylidene-bi
(4,6-di-t-butylphenyl) (2,6-
di-t-butyl-4-methylphenyl) phosphite
, 2,2'-ethylidene-bis(4,6-seehye petite)
(2,4,8-tri-t-butylphenyl)
phosphite, 2,21'ethylidene-bis(
4,6-di-butylbuenyl) (2,6-di-t-
Butyl-Ln-octadecyloxycarbonylethyl-
phenyl) phosphite, 2,2'-ethylidene
-bis(4,6-di-t-butylphenyl) [2゜
6-di-butyl-4- (2', 4'-di-t-butyl
tylphenyloxycarbonyl)
22 + ethylidene-bis(4,6-dit)
-butylphenyl) (2,6-di-t-butyl 4-n
-hexadecyloxycarbonyl-phenyl)phosph
2.21-thio-bis(4-methyl-6-t,
-butylphenyl)octylphosphite, 2,2'
-thio-bis(4-methyl-6-t-butylphenyl)
Nonylphosphite, 2,2'-thiobis(4-
Methyl-6-t-butylphenyl) lauryl phospha
2,2'-thio-bis(4-methyl-6-t-butyl)
tylphenyl) tridecyl phosphite, 2,2'-
Thio-bis(4-methyl-6-t-butylphenyl)mi
Listyl phosphite, 2,2'-thio-bis(4-
Methyl-6-t-butylphenyl)stearylphosph
2,2'-thio-bis(4-methyl-6-t-
butylphenyl) (2,4-di-t-butylphenyl)
) phosphite, 2,2'-thio-bis(4-methy
(6-t-butylphenyl) (2,6-t-butylphenyl)
(4-methylphenyl)phosphite, 2.2'-
Thio-bis(4-methyl-6-L-butylphenyl)
(2,4,6-tri-1-butylphenyl)phosph
2,2″・thio-bis(4-methyl-6-t-
butylphenyl) (2,6-di-t-butyl-4-
n-octadecyloxycarbonylethyl-phenyl)
Phosphite, 2,2'-thio-bis(4-methyl-
6-t-butylphenyl) [2,8-di-t-butyl-
4-(2',4'-di-t-butylphenyloxycal
(bonyl)-phenylcottosphite and 2,2'-
Thio-bis(4-methyl-6-t-butylphenyl)
(2,6-di-butyl-4-n-hexadecyl)
Examples include (xycarbonyl-phenyl) phosphite, etc.
can. The use of these phosphorus antioxidants alone is of no use.
In addition, it is also possible to use two or more types of phosphorus antioxidants together.
Wear. The blending ratio of the phosphorus antioxidant is
0.01 to 1 part by weight per 100 parts by weight of refin, preferably
Preferably, it is 0.05 to 0.5 parts by weight. In the composition of the present invention, a light stabilizer may be used in combination.
Therefore, weather resistance (light) resistance can be improved. photostable
As agents, 2,4-dihydroxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone, 2-hydro
xy-4-methoxybenzophenone-5 sulfoninc
Acindo, 2-hydroxy-4-n-octoxybenzo
Phenone, 2-hydroxy-4-n-dodisiloxyben
Zophenone, 2-hydroxy-4-benzyloxybenzo
Phenone, bis(5-benzoyl-4-hydroxy 2
-methoxyphenyl)methane, 2,2'-dihydroxy
-4-methoxybenzophenone, 2,2'-dihydroxy
C-4,4'-dimethoxybenzophenone, 2.2
', 4,4'-tetrahydroxybenzophenone and
2-hydroxy-4-methoxy-2' carboxyben
Benzophenone ultraviolet absorbers such as Zophenone, 2-
(2'-hydroxy-5'-methylphenyl)benzoto
Riazole, 2-[2'-hydroxy-3',5''-bi
(α,α・dimethylbenzyl)phenyl]benzotri
Azole, 2-(2'-hydroxy-3',5'-di-
t-butylphenyl)benzotriazole, 2-(2'
-Hydroxy-3'-t-butyl-5'-methylphenylene
)-5-chlorobenzotriazole, 2-(2'-hydroxy
droxy-3',5'-disavetylphenyl)-5
-chlorobenzotriazole, 2-(2″-hydroxy
-3″5 Tozy-amylphenyl)benzotriazo
2-(2'-hydroxy-5'-L-octyl
phenyl)benzotriazole, 2,2'-methylene-
Bis(4-(1,1,3,3-tetramethylbutyl)-
6-(2N-benzotriazol-2-yl)phenol
], methyl-343-t-butyl-5-(2H-ben
Zotriazol-2-yl)-4-hydroxyphenyl
] Propionate-polyethylene glycol condensate
and 2-(2-hydroxyphenyl)benzotriazo
benzotriazole-based UV-absorbing materials such as alcohol copolymers, etc.
Absorbent, N,N'-diethyloxaline acindobis
-anilide, 2-ethoxy-2'-ethyloxalic
Acid-bisanilide, 2-ethoxy-5-butylene
Thyl-2'-ethyloxalinefanrad-bis-ani
Lido and 2-ethoxy-5-t-butyl-2'-ethyl
le・4′・t-butyloxaline acindobisur
Oxalink acid anilide-based UV absorbers such as nilide
Agent Ia, N-(4-ethoxycarbonylphenyl)-N
'・Methyl-N'-phenylformamidine, N-(
4-ethoxycarbonylphenyl)-N'-ethyl N'
-phenylformamidine, N-(4-ethoxylic
(bonylphenyl)-N'-ethoxyl-N'-phenyl
Formamidine and N-(4-ethoxycarbonyl
phenyl)-N', N'-diphenylformamidine
Formamidine-based UV absorbers such as
scz, z'-thio-bis(4-t-octylferule)
)], nickel-bis[0-t-butyl-(3,5
-di-butyl-4-hydroxybenzyl) fuosuf
ionate], nickel-bis[〇-ethyl-(3,5-
Butyl-4-hydroxybenzyl
], 2,2'-thio-bis(4-thio-octylph)
eruleto)-butylamino-nickel (n), 2.2
'-Thio-bis(4-t-octylferrate)-cy
Chlohexylamino-nickel (n), 2,2'-thio
-bis(4-L-octylferulate)-diethanol
Ruaminoninkel (II), 2,2'-thio-bis(
4-t-octylferulate)-phenyl-jetano
-amino-nickel(II), 2,2'-thio-bis
(4-t-octylferulate)/i-octylamine
nornickel (II), 2,2'-thio-bis(4
-t-octylferulate)-octylamino-ni
Kel(n), 2,2'-thio-bis(4-L-octyl
ferulate)-cyclohexyl-jetanol-amino
-nickel CI+> and nickel dibutyl dithiocal
Nickel-based quencher such as bamate, 2°4-G
tylphenyl-3',5'-di-t-butyl-4''-h
Droxybenzoate, 2,6-di-butylphenylate
Ru 3',5'-di-t-butyl-4'-hydroxybeta
nzoate and n-hexadecyl-3,5-di-t-
Hydroxy such as butyl-4-hydroxybenzoate
Benzoate light stabilizer, 4-hydroxy-2,2,6
, 8-tetramethylpiperidine, 1-allyl-4-hydro
Roxy-2,2,6,6-tetramethylpiperidine, 1
-benzyl-4-hydroxy-2,2,6,6-tetra
Methylpiperidine, 1-(4-t-butyl-2-butenyl)
)-4-hydroxy-2,2,6,6-tetramethyl
Piperidine, 4-stearoyloxy-2,2,6,6
-tetramethylpiperidine, 4-methacryloyloxy
-1,2,2,6,6-pentamethylpiperidine, 1-
Benzyl-2,2,6,6-tetramethyl-4-piperi
Jill Marate. Bis(2,2,8,6-tetramethyl-4-piperidyl
) adipate, bis(2,2,6,6-tetramethyl-
4-piperidyl) sebacate, bis(2,2,8,6-
Tetramethyl-4-piperidyl) fumarate, bis(1
,2,3,8-tetramethyl-2,6-danityl-4-
Piperidyl〉7)〈Kate, bis(]-]aryruu2.
2,6,6-titramethyl-4piperidyl) phthalate
, bis(1,2,2,6,8-pentamethyl-4-pipe
lysyl) sebacate, 1.1'-(1,2-ethane
diyl)bis(3,3,5,5-tetramethylpiperazi)
non), 2-methyl-2-(2,2,6,6-titrame
thyl-4piperidyl)imino-N-(2,2,6,6-
Chitramethy J-ray 1-piperidyl) propionamide
, 2-methyl-2(1,2,2,6,6-bentamethyl
-4-piperidyl)imino-N-(1,2,2,6,6
-bentamethyl-4-piperidyl)propionamide,
1-propargyl-4-β-cyanoethyloxy-2,2
, 6,6-tetramethylpiperidine, 1-acetyl-2
,2,8,6-tetramethyl-4-piperidyl-acetate
trimellitic acid-tris(2,2,6,6-tetris)
tramethyl-4-piperidyl) ester, 1-acrylo
yl-4-benzyloxy-2,2,6,6-tetrame
Tilpiperidine, bis(1,2,2,8,6-bentameth)
Thiru-4-piperidyl)dibutylmalonate, bis(1
,2,2,6,8-pentamethyl-4-piperidyl)di
Benzyl-malonate, bis(1,2,3,6-tetra
Methyl-2,6-dinityl-4-piperidyl)dibenzi
Ru-malonate, bis(i, z, z, 6.6-benthamet
-2-(3,5-Piperidyl) -2-(3,5-Piperidyl)
(4-hydroxybenzyl) 4-n-butyl malo
nate, bis(2,2,6,6-tetramethyl-4-pi
peridyl)-1,5-dioxaspiro[5,51 unde
Can-3,3-dicarboxylate, bis(1,2,2
,6,8-pentamethyl-4-piperidyl)-1,5-
Dioxaspiro [5゜57 undecane-3,3-dical
Boxylate, bis(1-acetyl-2,2,6,8.
Tetramethyl-4-piperidyl)-1+5-dioxas
Pyro[5,5]undecane-3,3-dicarboxylate
t, 1,3-bis[2,2'-[bis(2,2,6,6
-tetramethyl-4-piperidyl) -1,3-dioxy
sacyclohexane-5,5-dicarboxylate],
Bis(2,2,6,8-tetramethyl-4-piperidyl
) -2-[1-methylethyl] -1,3-dioxa
Cyclohexane-5゜5-dicarboxylate coco, 1
,2-bis[2,2'-[bis(2,2,6,8-tet
lamethyl 4-piperidyl)-2-methyl-1,3-di
Oxacyclohexane-5,5-dicarboxylate co
], bis(2,2,6,6-tetramethyl-4-piperi
-2-[2-(3,5-di-t-butyl-4
-hydroxyphenyl)]]ethyl-2-methyl-1,
3-Dioxacyclohexane 5,5-dicarboxylene
bis(2,2,8,6-tetramethyl-4-piperi)
-1,5-dioxaspiro[5,11]hepta
Decane-3,3-dicarboxylate, hexane-1'
, 8'-bis・4-carbamoyloxy・1-n-buty
(2,2,6,6-tetramethylpiperidine), tolu-2,2,6,6-tetramethylpiperidine)
En-2',4'-bis(4-carbamoyloxy-1
,-n-butyl 2,2,6,6-tetramethylpiperi
dimethyl-bis(2,2,8,6-tetramethylene), dimethyl-bis(2,2,8,6-tetramethyl
lupiperidine-4-oxy)-silane, phenyl-tri
(2,2,6,6-tetramethylpiperidin-4-o)
xy)-silane, tris(1-propyl-2,2,6,
6-titramethyl-4-piperidyl)-phosphite
, tris(1-propyl-2,2,8,6-tetramethy)
-4-piperidyl)-phosphate, phenyl-[
Bis(1,2,2,6,8-pentamethyl-4-piperi
Zyl)]-Fphosphatetetrakis(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-Butanetetracarboxylate, tetrakis (
2,2,8,6-tetramethyl-4-piperidyl) 1
, 2,3,4-butanetetracarbonamide, tetraki
(1,2,2,6,8-pentamethyl-4-piperid
) 1,2,3.4 butanetetracarbonamide, 2
-dibutylamino-4,6-bis(9-aza-3-ethyl
Ru-8,8,10,10-tetramethyl-1,5-dio
xaspiro[5,5-3-undecylmethoxy)-S
-) riazine, 2-dibutylamino-4,6-bis(9
-aza-3-ethyl-8,8,9,10,10-benta
methyl-], 5-dioxaspiro[:5.5]-3-U
(decylmethoxy)-S-) riazine, tetrakis(9
-aza-3-ethyl-8,8,10,10-tetramethy
Ru-1,5-dioxaspiro[5,5]-3-unde
silmethyl)-1,2,3,4-butanetetracarbo
xylate, tetrakis (9-aza-3-ethyl-8,
8,9,10,10-pentamethyl-1,5-dioxa
spiro[5,5)-3-undecylmethyl)-1,
2,3,4-butanetetracarboxylate, tridecyl
Le Tris(2,2,6,6-tetramethyl-4-pipe
Lysyl) 1,2,3,4-butanetetracarboxylate
tridecyl tris(1,,2,2,6,6-beta)
4-piperidyl)i,2,3,4-butane
Tetracarboxylate, di(tridecyl) bis(2
, 2,6,6-tetramethyl-4-piperidyl) 1.
．． 2,3,4-butanetetracarboxylate, di(t)
bis(1,2,2,6,6-bentamethyl)
-4-piperidyl) 1,2,3,4-butanetetraka
Ruboxylate, 2,2,4,4-tetramethyl-
7-oxa-3,20-diazadispiro[5,1,H,
2] Heneicosan-21-one, 3.9-bis[1,
1-dimethyl-2-(tris(2゜2.6.6-tetra
Methyl-4-piperidyloxycarbonyl)butylcar
(bonyloxy)ethyl] -2,4,8゜10-tetra
Oxaspiro[:5.5]undecane, 3,9-bis[
1,1-dimethyl-2-(tris(1,2,2,6,6
-bentamethyl-4-piperidyloxycarbonyl)butylene
thylcarbonyloxy)ethyl]-2.4,8.10-
Tetraoxaspiro [5,5 undecane, Bot (2,
2,6,6-tetramethyl-4-piperidyl acrylate
), poly(1,2,2,6,6-bentamethyl-4
-piperidyl acrylate), poly(2,2,6,6
-tetramethyl-4-piperidyl methacrylate), poly
Li(1,2,2,6,6-bentamethyl-4-piperidi
methacrylate), poly[[bis(2,2,6,6-
Tetramethyl-4-piperidyl) itaconateco
Nylbutyl ether coco, poly[[bis(1,2,2,
6,6-pentamethyl-4-piperidyl) itaconate
][vinyl butyl ether]], polymouth [bis(2,2
,6,6-tetramethyl-4-piperidyl) itakone
] [Vinyl octyl ether coco, poly[[bis(
], ]2,2,6,6-bentamethyl-4piperidyl)
Itaconetoko [vinyl octyl ether coco dimethi]
Rusuccinate-2-(4-hydroxy-2,2°6.
6-tetramethylbiperidyl) ethanol condensate, poly
[Hexamethylene [(2,2,6,8-tetramethyl,
4-piperidyl)imino]], poly[ethylene [(2,
2,6,6-tetramethyl-4-piperidyl)imino]
hexamethylene [(2,2,6,6-tetramethyl-4
-piperidyl)iminoco], poly[[1,3,5-)ri
Azine-2,4-diylco [(2,2,8,8-tet)
lamethyl-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)iminoco-1,3,5-)ria
di-2,4-diyl] [(2,2,6,6-tet
lamethyl-4-piperidyl)imino]hexamethylene[
(2,2,6,6-titramethyl-4-piperidyl)i
Minokoko, poly[[6-[(1,1,3,3-tetramethane)
(Tylbutyl)imino]-1,3,5-triazine-2
,4-diyl] [(2,2,6,6-titramethyl
-4-piperidyl)imino]hexamethylene[(2,2
,6,6-tetramethyl-4-piperidyl)iminococo
. PolyC[6-(cyclohexylimino)-1,3,5
-triazine-2,4-diylco [(2,2,6,6
-tetramethyl-4-piperidyl)iminocohexamethylene
Ren[(2,2゜6.6-tetramethyl-4-piperid
imino]], poly[[6-morpholino-1,3,
S-triazine-2,4-diyl]((2,2,6,6
-tetramethyl-4-piperidyl)imino]hexamethylene
Ren[(2,2,6,6-tetramethyl-4-piperid
) iminococo, poly[[6-(butoxyimino) −
1,3,5-triazine-2,4-diyl] [(2,
2,[11,6-tetramethyl-4-piperidyl)imie
]hexamethylene[(2,2,6,6-tetramethyl
-4-piperidyl)iminoco], poly[[6-[(1,
1,3,3-tetramethylbutyl)oxy] -1,3
,5-1 riazine-2,4-diyl] [(2,2,
6,6-tetramethyl-4-piperidyl)imino]hex
Sameethylene [(2,2,6,6-tetramethyl-4-pi
peridyl) iminoco], poly[oxy[8-1, (1-
piperidyl) -1,3,5-triazine-2゜4-di
yloxy-1,2-ethanediyl] [(2,2,
8,6-tetramethyl-3-oxo-1,4-piperidi
-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-tetramethy
(3-oxo-1,4-piperidyl)-1,,2-e
Tandiylco [(3,3,S,5-tetramethyl-2
-oxo-1,4-piperidyl)-1,,2-ethanedi
Ilcoco, poly[[6-[(ethyl acetyl)iminoco]
-1,3,5-)Ryazine-2,4-diylco[(2
,2,8,6-tetramethyl-4-piperidyl)imino
]Hexamethylene [(2,2,6,8-tetramethyl-
4-piperidyl) i main] co, poly[[6-[(2,2
,6,6-titramethyl-4-piperidyl)butylimide
]-L3,5-)riazine-2,4-diyl] [
(Z, 2.fi. 6-tetramethyl-4-piperidyl)iminocohexame
tyrene [(2,2,6,8-tetramethyl-4-piperi
1,5,8.12-tetrakis [4
,6-bis(N-(2,2,6,6-tetramethyl-4
-piperidyl)-butylamino)-1,3,5-)ri
azin-2-yl] -1,5,8,12゜tetraaza
Dodecane and 1,5,8.12-tetrakis[4,6
-bis(N-(1,2,2,6,6-bentamethyl-4
-piperidyl)-butylamino)-1,3,5-)ri
Azin-2-ylco-1,5,8.12-tetraazade
Examples include hindered amine light stabilizers such as decane.
Wear. There are two types of light stabilizers, although it is impossible to use them alone.
The above light stabilizers can also be used in combination. of the light stabilizer
The blending ratio is based on 100 parts by weight of crystalline polyolefin.
0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight
It is a quantity part. In the composition of the present invention, a heavy metal deactivator may be used in combination.
Heavy metal resistance can be improved by
Heavy metal deactivators include benzotriazole, 2,4
．． 6-tria main no 1,3.5-triazine, 3,9-
Bis(2-(3,5-diamino-2,4,6-)reaza
phenyl)ethyl] -2,4,8,10-tetraoxy
Suspiro[5,5]undecane, ethylenediamine-te
Traacetic acid, ethylenediamine-tetraacetic acid
Alkali metals (Li, Na,
K) Salt, N,N'-disalicylidene-ethylenethia
hmm. N,N'-disalicylidene-1,2-propylene diamide
N, N, N''-disalicylidene-N'-methyldi
Propylene triamine, 3-salicilyl acetate no 1.
2.4-triazole, decamethylene dicarboxylic
Quacid-bis(N'-salicyloylhydrazide),
Nickel bis(1-phenyl-3-methyl-4-deca
Phil 5-virazolate>, 2-ethoxy-2'-et
Tyloxanilide, 5-t-butyl-2-ethoxy-2
'-ethyloxanilide, N,N-diethyl-N',
N'-diphenyloxamide, N,N'-diethyl-
N,N'-diphenyl oxamide, oxalic acid
Dobis (benzylidene hydrazide), thiodiprobio
Nincacidubis (benzylidene hydrazide),
Softalin acid bis(2-phenoxyprobio)
nylhydrazide), bis(salicyloylhydrazine),
N-salicylidene-N'-salicyloylhydrazone, N
N I-bis[3-(3,5-di-sabtyl-4-hi)
Droxyphenyl)propionyl]hydrazine, Tris
[2-tert-butyl-4-thio(2'-methyl 4'-hyperoxygenate)
Droxy-5'-L-butylphenyl)-5-methylphenyl
phenyl]phosphite, bis[2-t-butyl-4-
Thio(2'-methyl-4'-hydroxy-5'-t-butyl
tylphenyl)-5-methylphenyltwopentaerys
Littor-siphosphite, tetrakis[2-t-bu
thyl-4-thio(2'-methyl-4'-hydroxy-5
'-t-butylphenyl)-5-methylphenyl]-1
,6-hexamethylene-bis(N-hydroxyethyl-
N-methylsemicarbazide)-siphosphite, tet
Lakis[2-t-butyl-4-thio(2'-methyl-4
'-Hydroxy-5'-t-butylphenyl)-5-methane
Tylphenylco-1,10-decamethylene-dicarbo
Xylic acid hydroxyethyl carbonyl
hydrazidodiphosphite, tetrakis[2・L-
Butyl-4-thio(2'-methyl-41-hydroxy-
5'・t-butylphenyl)-5-methylphenyl]
-1゜10-decamethylene-dicarboxylic acid
dodgy salicylyl hydrazi dodge phosphite
, tetrakis[2-t-butyl-4-thio(2'-methy
-4'-hydroxy-5'-t-butylphenyl)-
5-methylphenyl]-di(hydroxyethylcarbony)
) Hydrazide-shiphosphite, tetrakis[2-
t-Butyl-4-thio(2'-methyl-4'-hydroxy
C-5'-t-butylphenyl)-5-methylphenyl
]-N,N'-bis(hydroxyethyl)oxamide-
Siphosphite and N,N'-bis[2-(3-(
3,5-dibutyl-4-hydroxyphenyl)
Examples include ropionyloxy]ethyl]oxamide.
Ru. Use of these heavy metal deactivators alone is controversial.
, two or more types of heavy metal deactivators can also be used together.
. The blending ratio of the heavy metal deactivator is
0.01 to 1 part by weight per 100 parts by weight of fin, preferably
The amount is preferably 0.05 to 0.5 parts by weight. In the M acid product of the present invention, as a crystalline polyolefin,
Compositions using crystalline propylene polymers, i.e.
Combining a radical generator with a crystalline propylene polymer composition
Molding processability can be improved by
. As a radical generator, benzoyl peroxide,
t-butyl peracetate, t-butyl peracetate
, butylperoxyisopropyl carbonate, 2
,5-di-methyl-2,5-di(benzoylperoxy)
) hexane, 2,5-di-methyl-2,5-di(benzo
ylperoxy)hexyne-3, t-butyl t-jeeper
Adipate, t-butylperoxy-3,5,5-)
Methyl hexanoate, methyl m=thyl ketone peroxide
Side, cyclohexanone peroxide, G-shibu
chill peroxide, dicumyl peroxide, 2,
5-di-methyl-2,5-di(t-butylperoxy)
Hexane, 2,5-di-methyl-2,5-di(L-butylene)
luperoxy)hexyne-3,1,3-bis(t-butylene)
(L-peroxyisopropyl)benzene, L-ButylCu
Milperoxide, 1,1-bis(t-butylperoxide)
xy) -3,3,5-trimethylcyclohexane, 1
．． 1-bis(butylperoxy)cyclohexane,
2,2-bis(L-butylperoxy)butane, P-methane
tanthane hydroperoxide, di-isopropylben
Zen hydroperoxide, cumene hydroperoxide
oxide, t-butyl hydroperoxide, P-sa
Imen hydroperoxide, 1,1,3,3-tet
-methylbutyl hydroperoxide, 2,5-di
-Methyl-2,5-di(hydroperoxy)hexane
, trimethylsilyl-cumyl peroxide, 2.5
-di-methyl-2,5-bis(trimethylsilylpero)
xy)hexane, 2,5-di-methyl-2,5-bis(
trimethylsilylperoxy)hexyne-3 and 1.
3-bis(trimethylsilylperoxyisoprobyl)
Examples include benzene. These radical generators
It is a matter of course that it should be used in Germany, but it should be noted that the combination of two or more radical generators
It can also be used. The blending ratio of the radical generator is:
0.0 per 100 parts by weight of crystalline propylene polymer
01-0.5 parts by weight, preferably 0.01-0.2 parts by weight
Department. Furthermore, the composition of the present invention typically contains crystalline polyol.
Various additives added to refin, such as clarifying agents,
Nucleating agent (excluding compound B), lubricant, qF! Electric protection
Antifogging agent (excluding compound B and compound C), antifogging agent
agents, anti-blocking agents, non-drop agents, flame retardants (however,
(excluding compound B), flame retardant aids, pigments, halogen scavengers (
However, excluding compound B and compound C), metal soaps
Dispersants or neutralizing agents such as (excluding compound B)
) or organic fillers (e.g. wood flour, pulp, waste paper, synthetic materials, natural fibers, etc.) without impairing the purpose of the invention.
Can be used together within a certain range. The composition of the present invention contains the above-mentioned compound in a crystalline polyolefin.
A, Compound B and Compound C and normally crystalline polio
Each of the above-mentioned various additives added to the refin
Mix the amount using a normal mixing device such as a Henschel mixer (product
), Super Mixer, Ribbon Blender, Pan Bali
Mix using a mixer, etc., and use a regular single-screw extruder or twin-screw extruder.
With an extruder, Brabender or roll, etc., melt mixing temperature
degree 150℃~300℃, preferably 180℃~270℃
It can be obtained by melt kneading and pelletizing with
. The resulting composition can be processed by injection molding, extrusion molding, or blow molding.
Used to manufacture desired molded products using various molding methods such as
be done. [Function] In the present invention, compound/substance A, compound B and compound C
The mechanism of action itself is what kind of effect the combined use of
Although it is not clear, it is assumed that the mechanism of action is as follows.
It will be done. In other words, compound B has a higher metal ion content than compound A.
act as a electron donor, and the electronegativity in the molecule of compound A
The largest element, fluorine atom, and the metal ion of compound B
by forming coordinate bonds or ionic bonds between
hand. It acts as a nucleating agent to improve the rigidity, and further improves the rigidity of compound C.
The cation is in some form between compound A and compound B.
By forming coordinate bonds or ionic bonds with
It is thought that this contributes synergistically to the improvement of rigidity. [Examples] The present invention will be specifically explained below using Examples and Comparative Examples.
However, the present invention is not limited to this.
stomach. The evaluation method used in the examples and comparative examples is as follows.
According to 1) Rigidity: Evaluated by bending test. i.e. obtained
Using a beret, length 1. OOnn, width 1.0mm,
A test piece with a gage of 4 m was made by injection molding.
Measuring the flexural modulus using a specimen (JIS K 7
Rigidity was evaluated based on 203). High rigidity
The material has a large flexural modulus. 2) Heat-resistant rigidity: Evaluated by load deflection temperature test. vinegar
That is, using the obtained pellet, the length is 130 m, the medium is 13
Tm, a test piece with a thickness of 6.5++m was made by injection molding.
The heat distortion temperature was measured using the test piece (JISK7
Compliant with 207; 4.6kgf/c+a2 load'! i)
The heat resistance stiffness was evaluated by High heat resistant and rigid material
refers to a material with a high heat deformation temperature. 3) Impact resistance: Evaluated by Izod impact test. vinegar
That is, using the obtained pellet, the length is 63.5 m and the width is 1.
Injection molding of 3m long and 3.5m thick test piece (with non-chip)
method, and the test piece was used to test the eye temperature at 23°C.
Measuring impact strength (according to Tl5K7110)
The impact resistance was evaluated by: Materials with excellent impact resistance are materials with high Izotsu impact strength.
say something Production Examples 1 to 3 (Examples 1 to 55 and Comparative Examples 1 to 55)
H used (method for producing PP(H)) (1) Catalyst tlgl n-hexane 600-, diethylaluminium monochrome
Lido (D E A C) 0.50 mol, diisoamyl ester
Mix 1.20 mol of ether at 25°C for 5 minutes and hold for 5 minutes.
The reaction product solution (V) (diisoamyl ether) is
A molar ratio of TE/DEAC of 2.4) was obtained. replaced with nitrogen
4.0 mol of titanium tetrachloride was placed in a reactor and heated to 35°C.
Heat and add the entire amount of the reaction product solution (V) to this for 180 minutes.
After dripping at , keep at the same temperature for 30 minutes and raise the temperature to 75℃.
The mixture was allowed to react for an additional 1 hour, then cooled to room temperature (20°C).
Remove the supernatant, add 4,000 ml of n-hexane, and decant.
Repeat the process of removing the supernatant liquid four times to remove the solid
190 g of a product (If) was obtained. This solid product (I
The entire amount of I) was added to n-hexane3. suspended in OOOmQ
160 g of diisoamyl ether and four
Add 350g of titanium chloride at room temperature for about 1 minute at 65°C.
After 1 hour of reaction, cool to room temperature and
After removing the clear liquid by decantation, 4. OO
Add OmQ n-hexane, stir for 10 minutes, and let stand.
After repeating the process of removing the supernatant 5 times, dry under reduced pressure.
to obtain a solid product (m) (2) Preparation of preactivated catalyst
After replacing with nitrogen gas, n-hexane l5 (1, di
42 g of ethylaluminum monochloride, solid product (
After adding 30g of nr) at room temperature, add 15NQ of hydrogen.
and reacted for 5 minutes at a propylene partial pressure of 5 kg/cm2G.
to reduce unreacted propylene, hydrogen and n-hexane.
It was removed under pressure to obtain a preactivated catalyst (Vl) in the form of powder (
82.0 g of propylene per Ig of solid product (Iff)
Response). (3) Polymerization of propylene Turbine type stirring with an internal volume of 250 Q replaced with nitrogen gas
Dry n-hexane in a stainless steel polymerization vessel with vanes.
100R then diethylaluminum monochloride 10
g, the preactivated catalyst (VI) 10 and P-)
Example of preparing hydrogen by adding 11.0g of methyl ylate
1 is 10011112. Production example 2 is 200 series and production
Example 3 added 410-each. Next, check the temperature inside the vessel.
After raising the temperature to 70°C, feed propylene into the vessel, and
The pressure was increased to 10 kg/cm2G. and set the temperature to 7
4 hours while maintaining pressure at 0°C and 10 to ζ/c12G.
After continuing the polymerization, methanol was supplied at 250 ml, and the temperature was increased to 80 ml.
The temperature was raised to ℃. After 30 minutes, add 20% by weight of sodium hydroxide.
Add 100g of thorium aqueous solution, stir for 20 minutes, and add 5g of pure water.
After adding 0Ω, the remaining propylene was discharged. water layer
After taking it out, add 50Q pure water and stir for 10 minutes.
Wash with water, extract the aqueous layer, and mix roughly with H(PP(H)-n
- Remove the hexane slurry, filter the slurry and
i1! The filtrate was dried to obtain white H (PP(H) powder).
. The obtained H (PP(H) is the above-mentioned melt flow rate)
(M F R> and isotactic pentad minutes
It was used to determine the ratio (P). These analysis results are ff
It is shown in Table 1. In addition, H (P P (H) obtained in Production Examples 1 to 3)
, H(PP(H)-[Iko, H(PP(H)
) - [11 and H (P P (H) - [abbreviated as 11
Write down. Production Example 4 (Examples 56-77 and Comparative Examples 56-77)
The crystalline propylene homopolymer used (hereinafter referred to as PP(H)
It is abbreviated as ) Manufacturing example) Turbine type stirring with an internal volume of 250 Q replaced with nitrogen gas
Dry n-hexane in a stainless steel polymerization vessel with vanes.
100Q then diethylaluminum monochloride 10
g. Grinding activity by reducing titanium tetrachloride with metal aluminum
40 g of commercially available catalyst (type AA) and P-) Louis
Methyl phosphate 22.0. and then add 20ON of hydrogen.
I2 was added. Then, after raising the temperature inside the vessel to 70℃,
Supply propylene into the vessel and increase the pressure inside the vessel to 10 kg/c.
The pressure was increased to m2G. Then the temperature is 70℃ and the pressure is 10k.
(After continuing polymerization for 4 hours while maintaining 7 cm2G,
250 ml of nol was fed and the temperature was raised to 80°C. After 30 minutes, add another 20% by weight aqueous sodium hydroxide solution.
100, stirred for 20 minutes, and added 50Q of pure water.
Then, the remaining propylene was discharged. After extracting the water layer
Add 50ff of pure water and wash with water for 10 minutes.
Pull out the layer and roughly coat it with PP(H)-n-hexane slurry.
The slurry is filtered, and the filtrate is dried.
A white PP(H) powder was obtained. The obtained PP(H) is
The melt flow rate (MFR) and each iso
It was used to determine the tactical pentad fraction (P). Check out these analysis results! It is shown in Table 1. Production Examples 5-7 (Examples 78-121 and Comparative Examples 78-
H used in 121 (Production example of PP (B)) (1) Catalyst
Preparation n-hexane 800+d, diethyl aluminum monochrome
Loride (DEAC) 0.50 mol, diisoamyl
Mix 1.20 mol of ether at 25℃ for 1 minute and then mix for 5 minutes.
The reaction product liquid (■) (diisoamyl ether) was reacted at the same temperature.
A molar ratio of ether/DEAC of 2.4) was obtained. Nitrogen replacement
4.0 mol of titanium tetrachloride was placed in a reactor and heated to 35°C.
Heat and add the entire amount of the reaction product solution (V) to this for 180 minutes.
After dropping the mixture, it was kept at the same temperature for 30 minutes and then raised to 75℃.
React for another 1 hour at warm temperature, then cool to room temperature (20℃)
4. Remove the supernatant and add n-hexane. OOOm(add
Repeat the process of removing the supernatant liquid by decantation 4 times.
, solid product (ff) 190. I got it. This solid product
The total amount of (IT) was suspended in 3,000-hexane.
160g of diisoamyl ether at 20℃
Titanium tetrachloride 350. Add 65 for about 1 minute at room temperature.
After one reaction was completed at °C for 1 hour, it was cooled to room temperature.
, after removing the supernatant by decantation, 4.
Add n-hexane of 0001d, stir for 10 minutes, and let stand.
After repeating the procedure 5 times to remove the supernatant liquid, remove the supernatant liquid under reduced pressure.
After drying, a solid product (nl) was obtained. (2) Preparation of preactivated catalyst A stainless steel reactor with inclined blades with an internal volume of 20Q was heated with nitrogen gas.
After replacing with gas, n-hexane 15Q, diethyl acetate
Luminium monochloride 42g, solid product (m) 30
After adding 15g of hydrogen at room temperature, add 15% of hydrogen and add propylene.
React for 5 minutes at a partial pressure of 5 kg/cm2G, and remove unreacted polymer.
Lopyrene, hydrogen and n-hexane were removed under reduced pressure and
Pre-activated catalyst (Vl) was obtained in the form of powder (solid product (m
) 82.0 g of propylene per Ig reaction). (3) Polymerization method Turbine type stirring blade with internal volume of 400Q replaced with nitrogen gas
Dry n-hexane 2 in a stainless steel polymerization vessel with roots.
50Q then 10g of diethylaluminum monochloride
, the preactivated catalyst (■HOg and P-toluic acid
11.0g of methyl was charged, and hydrogen was added in the gas phase.
Production example 5 had a concentration of 6 mol%, production example 6 had a concentration of 8 mol%, and
In Production Example 7, each was added so as to maintain 10 mol%. Next, after raising the temperature inside the vessel to 70℃, propylene was added to the vessel.
The pressure inside the vessel was increased to 10kg/cn2G.
did. Then, the temperature is 70℃ and the pressure is 10kg/cm2G.
After continuing polymerization for 4 hours while maintaining
stop, release unreacted propylene, and drain the reactor.
Collect some of the rally and get 1! ! Wash, wash and vL dry
to obtain white H(PP(H) powder.
(H) is the aforementioned melt flow rate (MFR>) and
Used to determine the isotactic pentad fraction (P).
Ta. The results of these analyzes are shown in Table 2. After releasing unreacted propylene, the inside of the polymerization vessel was heated to 60°C.
Maintain the pressure at 0.1 kg/cm2G and remove the polymerization source at the south exit of the second stage.
The feed ratio of ethylene was maintained at 33% by weight.
The total amount of ethylene supplied was 2.4 k in Production Example 5.
g, Preparation Example 6 to 5.4, and Preparation Example 7 to s, a
Ethylene and propylene are mixed at 2 o'clock so that k=, respectively.
It was supplied continuously for a period of time. After 2 hours of polymerization, ethylene and polymer
Stop the supply of lopylene and remove any unreacted ethylene and propylene.
Released pyrene. Then, add 25 methanol into the polymerization vessel.
9 and the temperature was raised to 75°C. 30 minutes later, more
Add 100g of 20t% sodium hydroxide aqueous solution
After stirring for 20 minutes and adding 100 Q of pure water, remove the remaining plastic.
Lopyrene was excreted. After extracting the water layer, add 1 more
Add 00Q pure water, stir and wash for 10 minutes, then remove the water layer.
and further H(P P (B)-n-hexane slurry
The slurry is filtered, and the filtrate is dried.
A white H(PP(B) powder was obtained.The obtained H(PP(B)
B) is the melt flow rate (MFR) and each
It was used to determine the tyrene content. These analysis results
It is shown in Table 2. In addition, H(PP(B) obtained in Production Examples 5 to 7 is referred to below as
H(PP(B)-[1 piece, H(PP(B)-[
■] and H(PP(B)-[II[ko and I]8;
Ru. Production Example 8 (Examples 122-143 and Comparative Examples 122-
Crystalline ethylene-propylene block used in 143
Example of ¥B production of polymer (hereinafter abbreviated as PP(B)) Turbine type stirring blade with internal volume of 400Q replaced with nitrogen gas
Dried n-hexane in a rooted stainless steel git mixer
250Q then diethylaluminium monochloride lo
g. Grinding activity by reducing titanium tetrachloride with metallic aluminum
The commercially available catalyst (type AA) 30 and P-toluyl
Methyl acid 11. Prepare OK and further hydrogen in gas phase
It was added to maintain a concentration of 8 mol%. Then inside the vessel
After raising the temperature to 70°C, supply propylene into the vessel,
The pressure inside the vessel was increased to 10 to 4/cm2G. and
Maintain the temperature at 70℃ and the pressure at 10k (/cm2G).
After continuing polymerization for 4 hours, the supply of propylene was stopped,
Unreacted propylene is released and part of the slurry in the polymerization vessel is
A sample is collected, filtered, washed and dried to produce a white crystalline product.
A ropyrene homopolymer powder was obtained. The obtained polymer is as described above.
Melt flow rate (MFR) and isotak of
It was used to determine the tic pentad fraction (P). this
The results of their analysis are shown in Table 2. After releasing unreacted propylene, the inside of the double polymerization vessel was heated to 60°C.
Maintain the pressure at 0.1kg/c112G and reduce the weight at the south exit of the second stage.
The supply ratio of ethylene as a synthesis raw material is 33% ffi%.
The total amount of ethylene supplied is 5.4 kg.
Ethylene and propylene were continuously supplied for 2 hours.
. After 2 hours of polymerization, the supply of ethylene and propylene was stopped.
The reaction was stopped and unreacted ethylene and propylene were released. Next, 259 methanol was supplied into the polymerization vessel, and the temperature was lowered to 7.
The temperature was raised to 5°C. After 30 minutes, further 20% hydroxylation
Add 100g of sodium aqueous solution, stir for 20 minutes, and add IA
After adding Al2O2Q, the remaining propylene was discharged.
. After extracting the water layer, add another 1000 ml of pure water.
Stir for 10 minutes, wash with water, extract the aqueous layer, and then add P
(B) - Take out the n-hexane slurry and slurry
, and dry the filtrate to obtain white PP(B) powder.
Obtained. The obtained PPCB) has the above-mentioned melt flow rate.
<MFR) and each ethylene content.
. The results of these analyzes are shown in Table 2. Example work~11. Comparative Examples 1 to 11 M produced in W4 Preparation Example 1 as crystalline polyolefin
FR2,5c/10 minutes unstabilized powder
To 1100 parts by weight of H(PP(H)-[I, compound A and
2,2'-bis(4,6-di-butylphenyl)
) Fluorophosphite, 2,2'-methylene-bis
(4,6-di-butylphenyl)fluorophosphate
2,2'-ethylidene-bis(4,8-
di-t-butylphenyl) fluorophosphite,
As compound B, potassium acetate, potassium stearate, 2
-strontium ethylhexanoate or stearin
Strontium acid, laurylamine as compound C, N
, N-dicocoamine, N,N-bis(2-hydroxyethyl)
chill) cocoamine or N,N-bis(2-hydroxy
ethyl) tallowamine and other additives
Henschelmi's quantitative determination was made using the blending ratios listed in Table 3 below.
After stirring and mixing for 3 minutes,
Melt-kneaded at 200℃ using a twin-screw extruder with a diameter of 30mm.
It was pelletized. In addition, as Comparative Examples 1 to 11, MFR is
2.5 g/10 min of unstabilized powdered H (PP
(H)-[:+ 1100 parts by weight as listed in Table 3 below
A predetermined amount of each of the additives was blended, and in Examples 1 to 1.
A pellet was obtained by melt-kneading in accordance with the above-mentioned rules. The test pieces used for evaluation of stiffness and heat-resistant stiffness were obtained
Injection molding of pellets at wood temperature 250℃ and mold temperature 50℃
Prepared by shape. Using the obtained test piece, the stiffness and
and heat resistance rigidity were evaluated. These results are shown in Table 3.
did. Examples 12-22. Comparative Examples 12-22 MF produced in Production Example 2 as crystalline polyolefin
R10,8g/10 minutes unstabilized powder
H(P P (H)-[■ 1100 parts by weight, compound A
as 2,2'-bis(4-s-eicosylphenyl)
Fluorophosphite, 2,2'-methylene-bis(
4,6-di-butylphenyl) fluorophosphat
or 2,2'-ethylidene-bis(4,6-di
-L-butylphenyl) fluorophosphite, compound
Barium stearate, barium montanate as substance B
, potassium 12-hydroxyoctadecanoate or 2
-strontium hydroxytetradecanoate, compound C
as N-stearyl-N,N-dimethylamine, hex
Sameethylene diamine, N,N-bis(2-hydroxyethyl)
chill) cocoamine or N,N-bis(2-hydroxy
ethyl) tallowamine and other additives
Henschelmi's quantitative determination was made using the blending ratios listed in Table 4 below.
After stirring and mixing for 3 minutes,
Melt-kneaded at 200℃ using a twin-screw extruder with a diameter of 30m5.
It was pelletized. In addition, as Comparative Examples 12 to 22, M,
Unstabilized flour with F R of 10-ag/10 minutes
Terminal H (PP(H)-[11 pieces, 100 ml [described later in the section]
Blend the prescribed amounts of each of the additives listed in Table jI4,
A pellet is obtained by melt-kneading according to Examples 12 to 22.
I got it. The test pieces used for evaluation of stiffness and heat-resistant stiffness were obtained
The pellet is injection molded at a resin temperature of 250℃ and a mold temperature of 50℃.
Prepared by shape. Using the obtained test piece, the stiffness and
and heat resistance rigidity were evaluated. These results are shown in Table 4.
did. Examples 23-33, Comparative Examples 23-33 MF produced in Production Example 3 as crystalline polyolefin
R34°Ox/10 min unstabilized powder H
(To 100 parts by weight of PP(H)-[Iff], compound A and
and 2,2'-methylene-bis(4-methyl-6-t-
butylphenyl)fluorophosphite, 2,2'-
Methylene-bis(4,6-di-t-butylphenyl)phenyl
Fluorophosphite or 2,2'-ethylidene-
Bis(4,6-di-t-butylphenyl)fluorophore
sphite, barium ricinoleate as compound B,
Lithium oxalate, sodium succinate or adipine
potassium acid, N-crow-1,3-dia as compound C
Minopropane, hexamethylenetetramine, N, N-bi
(2-hydroxyethyl)cocoamine or N,N
-bis(2-hydroxyethyl)tallowamine and others
The predetermined amounts of each of the additives listed in Table 5 below are used.
Add the mixture to a Henschel mixer (product name) and mix for 3 minutes.
After stirring and mixing, a twin-screw extruder with a diameter of 30 nm was used to
The mixture was melt-kneaded at ℃ and pelletized. Also, comparative example 2
3 to 33, the MFR is stabilized at 34.0 g/10 minutes.
Powdered H(P P (H)-[I[I]1
Add each of the additives listed in Table 15 below to 100 parts by weight.
Blend a certain amount and melt and cross-wire according to Examples 23 to 33.
The pellets were obtained by processing. The test pieces used for evaluation of stiffness and heat-resistant stiffness were obtained
Pellets are injected at a resin temperature of 250°C and a mold temperature of 50°C.
Prepared by molding. Using the obtained test piece, the stiffness and
and heat resistance rigidity were evaluated. These results are shown in Table 5.
did. Examples 34-44, Comparative Examples 34-44 MF produced in Production Example 1 as crystalline polyolefin
R2,5g/10min unstabilized powder H
(PP(H)-[+]11.2% by weight M F R7,
0g/10 minutes of unstabilized powdered crystalline ethylamide
Ren-propylene random copolymer (ethylene content 2
．． 5 wt%) 83 wt% and MI (at 190°C
for 10 minutes when a load of 2, ], 6 kg is applied.
Discharge amount of molten resin) 5.0g/10 minutes stabilized
Powdered Ziegler-Natsuta high-density ethylene alone
Polymer (1 degree 0.9634/c++”) 5% by weight
2,2' as compound A to a total of 100 parts by weight consisting of
-methylene-bis(4,6-di-L-butylphenyl)
Fluorophosphite, 2,2'-methylene-bis(
4,6-dithnylphenyl) fluorophosphite
or 2,2'-ethylidene-bis(4,6-di-t-
butylphenyl) fluorophosphite, compound B and
Strontium sebacate, 1,2,3,4-buta
Barium tetracarboxylate, lithium glycolate also
or sodium lactate, N-tocosyl- as compound C
N,N,N-trimethylammonium chloride,
N,N,N-triethyl-N-benzylammonium
Muchloride, N,N-bis(2-hydroxyethyl)
Cocoamine or N,N-bis(2-hydroxyethyl
) the prescribed amounts of each of tallowamine and other additives.
Henschel mixer at the mixing ratio listed in Table 6 below.
(product name), stir and mix for 3 minutes, and then
The mixture was kneaded at 200℃ using a mm twin-screw extruder.
Pelleted. In addition, as Comparative Examples 34 to 44, MFR is
2.5 g/10 min of unstabilized powdered H (PP
(H)-[1j12% by weight, MFR is 1-Ox/10
unstabilized powdered crystalline ethylene-propylene
Ren random copolymer (ethylene containing ff12.5 weight
%) 83 wt% and MI 5-(h/10 min stable
Powdered Ziegler-Natsuta high-density etching
Ren homopolymer (density 0.963g/c lo3) 5% by weight
Additions listed in Table 6 below to a total of 100 parts by weight consisting of
A predetermined amount of each additive was blended, and the mixture was prepared according to Examples 34 to 44.
Accordingly, pellets were obtained by melt-kneading treatment. The test pieces used to evaluate stiffness, heat-resistant stiffness, and impact resistance are
, the obtained pellets were heated at a resin temperature of 250°C and a mold temperature of 50°C.
It was molded by injection molding at 11°C. Using the obtained test piece, the stiffness and resistance were determined by the test method described above.
Thermal rigidity and @ impact resistance were evaluated. These results are shown in Table 6. Examples 45-55, Comparative Examples 45-55 MF produced in Production Example 1 as crystalline polyolefin
R2,5g/10min unstabilized powder H
(PP(H)-[1160% by weight, M F R7,0g
/ 10 minutes unstabilized powdered crystalline ethylene
- Propylene random copolymer (ethylene containing ji 4
．． Ot ffi%) 10% by weight, M F R1.0g/
Unstabilized powdered crystalline ethylene for 10 minutes -
Propylene-butene-13-element copolymer (ethylene content
Contains 4.0% by weight of butene-1! 4.5% by weight) 10wt
% and stabilized to M I 5.0 for 710 min.
Powdered Ziegler-Natsuta high-density ethylene-pro
Pyrene copolymer (density 0.950g/cm',
3.0 chill branches/1000 carbons) 20% by weight
A total of 100 parts by weight of 2,2'-
Methylene-bis(4,6-di-t-butylphenyl)phenyl
Fluorophosphite, 2,2'-ethylidene-bis(
4-Methyl-6-t-butylphenyl)fluorophos
Phite or 2,2'-ethylidene-bis(4,6
-di-t-butylphenyl) fluorophosphite,
Potassium malate, magnesium tartrate as compound B
, strontium grapeate or barium citrate,
N,N-bis(2-hydroxyethyl) as compound C
-N-oleyl-N-methylammonium chloride,
N,N-bis(2-hydroxyethyl)stearylamide
Novetaine, triisopropanolamine or N,
N-bis(2-hydroxyethyl)cocoamine and others
The prescribed amounts of each of the additives are described below! The arrangement listed in Table 7
Add the mixture to a Henschel mixer (product name) and mix for 3 minutes.
After stirring and mixing, a twin-screw extruder with a diameter of 30 mm was used to
The mixture was melted and kneaded at ℃ to form pellets. Also, comparative example 4
5-55, MFR is stabilized at 2.5g/10min.
Powdered F((P P (H)-[I roller 0 weight
%, MFR 7,0g710min unstabilized powder
Terminal crystalline ethylene-propylene random copolymer (e.g.
Tyrene content: 4.0% by weight) 10% by weight, MFR: 7
．． 0 g/10 minutes of unstabilized powder crystalline e.g.
ethylene-propylene-butene-13 copolymer (ethylene
ffi content: 4.0% by weight, butene-1 content: 4.5
% by weight) 10% by weight, stabilization of MI to 5.0/10 minutes
Powdered Ziegler-Natsuta high-density ethylene
-propylene copolymer (density 0.950g/a11
3. 3.0 methyl branches/1000 carbons) 20% by weight
Additions listed in Table 7 below to a total of 100 parts by weight consisting of
A predetermined amount of each additive was blended, and the mixture was prepared according to Examples 45 to 55.
Accordingly, pellets were obtained by melt-kneading treatment. The test pieces used to evaluate stiffness, heat-resistant stiffness, and impact resistance are
, the obtained pellets were heated at a resin temperature of 250°C and a mold temperature of 50°C.
Prepared by injection molding at °C. Using the obtained test piece, the stiffness and resistance were determined by the test method described above.
Thermal stiffness and impact resistance were evaluated. These results are shown in Table 7. Examples 56-66, Comparative Examples 56-66 MF produced in Production Example 4 as crystalline polyolefin
R9.8g/10 minutes unstabilized powder P
2,2' as compound A to 100 parts by weight of P (H)
-methylene-bis(4,6-di-butylphenyl)
Fluorophosphite, 2,2'-ethylidene-
Bis(4,6-di-1-butylpheny/L/)fluoro
Phosphite or 2,2'-butylidene-bis(
4-Methyl-8-(1'-methylcyclohexyl)phene
fluorophosphite, tereph as compound B
Lithium tarate, lithium pyromellitate 5 Sodium benzoate
Thorium or P-) Sodium Ruylate, Compound C
as triisopropazuramine, N,N-bis(2
-hydroxyethyl)cocoamine, N,N-bis(2-
hydroxyethyl) tallowa≧n or octadecane
Acid 2-[(2-hydroxyethyl)octadedylayono
Each prescribed amount of coethyl ester and other additives
Henschel mixer at the blending ratios listed in I [Table 8] below.
- (product name) and stirred and mixed for 3 minutes, then 1 caliber 3
Melt and knead the pellets at 200°C using a 0am 21 extruder.
It became a let. In addition, as Comparative Examples 56 to 66, Production Example 4
The manufactured MFR is not stabilized at 9°8g/10min.
To 100 parts by weight of powdery P P (H) was added as shown in Table 8 below.
Predetermined amounts of each of the described additives were blended, and Examples 56-
Pellets were obtained by melt mixing in accordance with 66. The test pieces used to evaluate stiffness and heat resistance stiffness are as follows. The obtained pellets were heated at a resin temperature of 250°C and a mold temperature of 50°C.
It was manufactured by injection molding. Using the obtained test piece, the stiffness and
and heat resistance rigidity were evaluated. These results are shown in Table 8.
did. Examples 67-77, Comparative Examples 67-77 MF produced in Production Example 4 as crystalline polyolefin
R9.8g/10 minutes unstabilized powder P
2,21 as compound A to 100 parts by weight of P (H)
-methylene-bis(4,8-di-t-butylphenyl)
Fluorophosphite, 2,2'-ethylidene-bis
(4,6-di-t-butylphenyl)fluorophosph
or 2,2'-thio-bis(4-methyl-6
-t-butylphenyl)fluorophosphite, compound
Strontium naphthoate and strontium phthalate as substance B.
barium salicylate or 3.5-di-t
-Barium-butyl-4-hydroxybenzoate, compound C
2-[(2-hydroxyethyl) octadecanoate as
Octadecylaminocoethyl ester, (octadecylaminocoethyl ester)
lumino) diethylene distearate, polyoxyethyl
Renlaurylaminoether or polyoxyethylene
stearyl amino ether and other additives.
Mix the specified amount with the mixing ratio listed in Table 9 below.
After stirring and mixing for 3 minutes,
Melt kneading at 200℃ using a twin-screw extruder with a diameter of 30nvn.
Processed and pelletized. Also, as comparative examples 67 to 77
The MFR produced in Production Example 4 was stable at 9.8 g/10 minutes.
Powdered P P (J() 1.00 parts by weight)
Add the prescribed amounts of each of the additives listed in Table 9 below to
Then, it was melted and cross-wired according to Examples 67 to 771.
Got a let. The test pieces used for evaluation of stiffness and heat-resistant stiffness were obtained
Inject the pellets at a wood temperature of 250°C and a mold temperature of 50°C.
Manufactured by tM by molding. Using the obtained test piece, the stiffness and
Thermal stiffness was evaluated. These results are shown in Table 9.
did. Examples 78-88, Comparative Examples 78-88 M remaining in W4 in Production Example 5 as crystalline polyolefin
FR8,51: / Stabilized for 10 minutes (\none)
Powdered H(PP(B)-[Ico(ethylene content 4.2
weight%) 100 weight ffi + kp, 2 as compound A
,2'-methylene-bis(4,6-di-butylphenylene)
fluorophosphite, 2,2'-ethylidene
-bis(4,6-cseptylphenyl)fluorophore
Phosphite or 2,2'-thio-bis(4-methy)
(6-α-methylbenzylphenyl)fluorophos
pt-butyl benzoate as compound B.
aluminum, aluminum anisate, monolithic glutamic acid
tium or monosodium glutamate, compound C
Polyoxyethylene lauryl amino ether, poly
Lyoxyethylene stearyl amino ether, N
, N , N'N'-thitra(2-hydroxyethyl)
-1,3-Shea Chestnut Nobroban or N-Tallow N
, N', N'-tris(2-hydroxyethyl)
- that of 1,3-diaminopropane and other additives
Mix the prescribed amounts of each at the mixing ratios listed in Table 10 below.
Place in shell mixer (product name) and mix for 3 minutes.
Later, at 200°C using a twin screw extruder with a diameter of 30III11.
The mixture was melted and mixed into pellets. Also, Comparative Examples 78-8
8, the MFR is stabilized at 8-5g/10min.
Powdered H(P P (B)-[11 (ethylene-containing)
Amount: 4.2%) 100 parts by weight as listed in Table 10 below
Mix the prescribed amounts of each of the additives. Melt-kneaded pellets according to Examples 78 to 88
I got it. The test pieces used to evaluate stiffness, heat-resistant stiffness, and impact resistance are
, the resulting pellets were heated to a resin temperature of 250' C1 mold temperature.
Prepared by injection molding at 50°C. Using the obtained test piece, the stiffness, i
Thermal stiffness and impact resistance were evaluated. These results are shown in Table 10. Examples 89-99, Comparative Examples 89-99 MF produced in Production Example 6 as crystalline polyolefin
R9, Og/10 minutes unstabilized powder H
(PPCB) - [n (ethylene content 8.5% by weight)
2,2'-bis(4,
6-di-butylphenyl) fluorophosphite
, 2.2″-methylene-bis(4,6-di-t-butyl
phenyl)fluorophosphite or 2,2'-
Ethylidene-his (4,6-di-hyphthylphenyl)
Fluorophosphite, glutamic acid as compound B
Monopotassium, strontium glutamate, glutami
Barium phosphate or (mono, simituxt) 2-ethyl
Sodium hexyl phosphate, polyoxychloride as compound C
Thiethylene stearyl amino ether, N, N,
N', N'-tetra(2-hydroxyethyl
)-1,3-diaminopropane, N・Tallow N, N
',N'-tris(2-hydroquinethyl)-1
,3-diaminopropane or N,N-dicokoN
',N'-bis(2- and droxyethyl)-i,a-
the respective prescribed amounts of diaminohexane and other additives.
Henschel mixer at the blending ratio listed in Table 111 below.
- (product name), stir for 3 minutes, then add 1 caliber 3
Melt-kneaded at 200℃ using a 0m 2I211 extruder.
It was pelletized. In addition, as comparative examples 89 to 99, MFR
is 9.0 g/10 minutes of unstabilized powdered Hc
pp(B)-[nl (ethylene content 8.5% by weight) 1
00 parts by weight of each of the additives listed in Table 11 below
Blend the specified amount and melt-knead according to Examples 89 to 99.
Processed to obtain pellets. The test pieces used to evaluate stiffness, heat-resistant stiffness, and impact resistance are
, the obtained pellets were heated to a resin temperature of 250°C, a mold temperature of 5.
It was manufactured by injection molding at 0°C. Using the obtained test piece, the stiffness and resistance were determined by the test method described above.
Thermal stiffness and impact resistance were evaluated. These results are shown in Table 11. Examples 100-110. Comparative Examples 100-110 Crystalline Po
M F R7 manufactured as Lyolefin in Production Example 7,
7g/10 min unstabilized l,% powdered H(P
P(B)-4I [I (ethylene containing fi12.1 weight
%) 100 parts by weight, 2.2'-methylene as compound A
-bis(4-methyl-6-t-butylphenyl)fluor
Orophosphite, 2,2'-methylene-bis(4,
6-di-t-butylphenyl)fluorophosphite
or 2,2' ethylidene-bis(4,6-di-bis)
butylphenyl) fluorophosphite, compound B and
(Mono. Simituxt) Potassium lauryl phosphate, (Mono. Simituxt) Calcium stearyl phosphate, (Mono.
, Simituxt) Strontium Tocosyl Phosphate or
Barium Oftacosyl Phosphate
, as compound C, N,N-bis(2-hydroxyethyl
) Cocoamine, N,N-bis(2-hydroxyethyl)
Tallowamine, octadecanoic acid 2-[(2-hydroxy
ethyl)octadecylamino]ethyl ester or
(octadecyl imino) diethylene distearate and
The prescribed amounts of each of the additives and other additives are listed in Table 12 below.
Put it in the Henschel mixer (product name) at the mixing ratio,
After stirring and mixing for 3 minutes, 2
The mixture was melt-kneaded and pelletized at 00°C. Compare again
As examples 100 to 110, the MFR is 7.7g/10 minutes.
Undefined powdered H (PP(B)-[ml (E)
100 parts by weight (tyrene content: 12.1% by weight) of the following
Blend the prescribed amounts of each of the additives listed in Table 12 and carry out
Examples 100 to 110? Melt and knead the pellets based on
I got it. The test pieces used to evaluate stiffness, heat-resistant stiffness, and impact resistance are
, the obtained pellets were heated at a resin temperature of 250°C and a mold temperature of 50°C.
TM manufactured by injection molding at ℃. Using the obtained test piece, the stiffness and resistance were determined by the test method described above.
Thermal stiffness and impact resistance were evaluated. These results are shown in Table 12. Examples 111-121. Comparative Examples 111-121 Crystalline Po
M F R9 produced in Production Example 6 as lyolefin,
0 g/10 min of unstabilized powdered H(PP(
B)-[1] (ethylene content 8.5% by weight) 100wt
2,2'-methylene-bis(4
,6-di-t-butylphenyl)fluorophosphite
2,2'-methylene-bis(4,6-ditunyl)
phenyl)fluorophosphite or 2,2'-
ethylidene-bis(4,6-di-t-butylphenyl)
Fluorophosphite, 2,6.8- as compound B
) So-t-butyl-10-hydroxy-9,1,0-
Dihydro-9-oxa-10 phosphaphenanthrene
-10-oxide lithium salt, 10-hydroxy
C-9,10-dihydro-9-oxa10-phospha
Sodium salt of phenanthrene-10-oxide, 2
-cyclohexyl-10-hydroxy-9,10-dihydrogen
Dro-9-oxa-10-phosphaenanthrene-
Sodium salt of 10-oxide or 6-phenyl
・10-hydroxy-9,10-dihydro-9-oxa
-10-phosphaphenanthrene-10-oxide
Potassium salt of N,N-bis(2-hydro) as compound C
Roxyethyl) Cocoamine, N, N, N', N
'-tetra(2-hydroxyethyl)-1,3-dia
Minopropane, N-tallow, N, N', N'4 squirrel (2
-Hydroxyethyl)-],,]3-diaminopropa
or N,N-zicoco-N'N'-bis(2-hi
(Droxyethyl)-1,6-cyamitzhexane and
The prescribed amounts of each of the other additives are listed in Table 31113 below.
Add to the Henschel mixer (product name) using the listed mixing ratio.
After stirring and mixing for 3 minutes, a twin-screw presser with a diameter of 30 an
It was melted and cross-wired at 200°C to form a pellet. Also
Comparative Examples 111 to 121 have an MFR of 9.0 g/10 minutes
Unstabilized powdered H (PP(B)-[11]
(Ethylene content 8.5% by weight) 100 parts by weight (described later)
Blend a predetermined amount of each of the additives listed in Table 13,
Pellets were prepared by melt-kneading according to Examples 111 to 121.
I got a cut. The test pieces used to evaluate stiffness, heat-resistant stiffness, and impact resistance are
, the obtained pellets were heated at a wood temperature of 250°C and a mold temperature of 50°C.
Prepared by injection molding at °C. Using the obtained test piece, the stiffness and resistance were determined by the test method described above.
Thermal stiffness and impact resistance were evaluated. These results are shown in Table 13. Examples 122-132. Comparative Examples 122-132 Crystalline Po
M F R8 produced in Production Example 8 as lyolefin,
1+;/10 min unstabilized powdered PP (B
) (ethylene content 8.3% by weight) to 100 parts by weight,
As compound A, 2,2'-methylene-bis(4,6-di
-1-butylphenyl)fluorophosphite, 2.
2'-ethylidene-bis(4-methyl-6-t-butyl
phenyl)fluorophosphite or 2,2'-
ethylidene-bis(4,6-di-t-butylphenyl)
Fluorophosphite, 2-benzyl as compound B
-10-hydroxy-9,]O~dihydro-9-oxa
-10-7 Osph Afeffenance Lane-10-Oxide
Barium salt of 6-(α-methylbenzyl)-a-t
-butyl-10-hydroxy-9,10-dihydro-9
-oxa-10-phosphaphenanthrene-10-o
Oxide barium salt, magnesium hydroxide or water
Aluminum oxide, N,N-bis(2-
hydroxyethyl) tallowamine, N, N, N'
, N'-tetra(2-hydroxyethyl)-1,3-
Diaminopropane, N-tallow-N, N', N'-tri
(2-hydroxyethyl)-1,3-diaminopropylene
Bread or N, N-Jikoko N'N'-bis (2-H)
droxyethyl) -1,8-diaminohexane and
The prescribed amounts of each of the other additives are listed in Table 14 below.
Add to Henschel mixer (product name) at the blending ratio and mix 3
After stirring and mixing for a minute, use a twin-screw extruder with a diameter of 30 rIn.
5 which was melted and mixed at 200℃ and made into pellets
MFR manufactured in Manufacturing Example 8 as Comparative Examples 122 to 132
is 8.1 g/10 min of unstabilized powdered PP (
B) (Ethylene content 8.3% by weight) 100 parts by weight
Add the prescribed amounts of each of the additives listed in Table 14 above to 6 parts.
and melt-kneaded according to Examples 122 to 132.
Obtained pellets. Tests used to evaluate stiffness, heat-resistant stiffness, and GIII resistance
For the pieces, the obtained pellets were heated at a resin temperature of 250°C and a mold temperature of
Ti was manufactured by injection molding at 50°C. Using the obtained test piece, the stiffness and resistance were determined by the test method described above.
Thermal stiffness and impact resistance were evaluated. These results are shown in Table 14. Examples 133-143, Comparative Examples 133-143 Crystalline po
M F R8 produced in Production Example 8 as lyolefin,
1 g/10 min of unstabilized powdered PP(B) (
To 100 parts by weight (ethylene content: 8.3% by weight), compound
A is 2,2'-methylene-bis(4,6-di-bis-
butylphenyl)fluorophosphite, 2.2'-
ethylidene-bis(4,6-di-t-butylphenyl)
Fluorophosphite or 2,2'-thio-bis
(4-methyl-6-t-butylphenyl)fluorophore
sphite, magnesium oxide as compound B, magnesium carbonate
Gnesium, calcium carbonate or hydrotalcium
and compound C as octadecanoic acid 2-[(2-hydro
xyethyl) octadecylaminocoethyl ester, N
, N, N', N'-tetra(2-hydro
(oxyethyl)-1,3-diaminopropane, N-talo
Wu N, N', N'-) Lis(2-hydroxyethyl)
-1,3-diaminopropane or N,N-dicoko
N'N'-bis(2-hydroxyethyl) -1,6-
the respective prescribed amounts of diaminohexane and other additives.
Henschel mixer at the blending ratio listed in Table 15 below.
- (product name), stir and mix for 3 minutes, then
Pellets are melt mixed at 200℃ using a 0+n twin-screw extruder.
It became a let. In addition, production examples as Comparative Examples 133 to 143
The MFR produced in 8 was stabilized at 8.1 g/10 min.
powdered PPCB) (ethylene content 8.3 wt.
%') Additions listed in Table 15 below to 100 parts of Ti
A predetermined amount of each agent was blended, and Examples 133 to 143 were prepared.
Pellets were obtained by melt cross-fertilization in accordance with the standards. Test piece used for evaluation of stiffness, heat-resistant stiffness, and #J impact property
The obtained pellets were heated at a ma temperature of 250°C and a mold temperature of 5.
Prepared by injection molding at 0°C. Using the obtained test piece, the stiffness and resistance were determined by the test method described above.
Thermal stiffness and IWA properties were evaluated. These results are shown in Table 15. Alternative compounds of the present invention shown in Tables 3 to 15
and additives are as follows. Compound A[I]: 2,2″-bis(4,6-di-butyl)
tylphenyl) fluorophosphite compound A [II]: 2,2'-bis(4-8-ethyl)
icosylphenyl) fluorophosphite compound A [ll1l]: 2,2'-methylene-bi
(4-methyl-6-t-butylphenyl)fluorophore
Phosphite compound A [1”/]: 2,2'-methane
tyrene-bis(4,6-di-butylphenyl)fluor
Orophosphite compound A [Vconi 2,2'-methy
Ren-bis(4,6-ditunylphenyl)fluorophore
Sphite compound A [VI]: 2,2'-ethyl
Den-bis(4-methyl-6-t-butylphenyl)phenyl
Fluorophosphite compound A [■coni 2,2'-ethylidene-bis(4,
6-di-1-butylphenyl) fluorophosphite
Compound A [■]: 2,2'-butylidene-bis(4
-Methyl-6-(1'-methylcyclohexyl)phenylene
) fluorophosphite compound A, [IXconi 2,2'-thio-bis(4-meth
(6-tert-butylphenyl) fluorophosphite
Compound A [X]: 2,2'-thio-bis(4-
Methyl-6-α-methylbenzylphenyl)fluorophenyl
Phosphite compound B [:I]: Potassium acetate compound B [11]: Potassium stearate compound
B [lI+]: 2-ethylhexanoic acid strontide
Compound B []V] Strontium nistearate
Compound B [V]: Barium stearate compound B
[VI]: Barium montanate compound B [■Koni 12
-Hydroxyoctadecanoic acid potassium compound B [■ Conitrontium compound B [廄]: Compound B EX]: Compound B [XI Coni compound BCXnl: Compound BCXIIrCX Compound B [XIV]: Acid barium compound B [XV Coni compound B [XVI ] Compound BCX ■ CX Compound B [X ■ Compound B [X] Potassium malate: Magnesium tartrate Strontium vitrate Barium citrate: Lithium terephthalate Lithium pyromellitate Sodium dibenzoate P-) Sodium 2-hydroxytetradecanoate Barium suricinolate Lithium oxalate Sodium succinate Potassium adipate Strontium sebacate 1.2,3.4-butanetetracarboxylic compound B [XX
V]: Strontium naphthoate compound B [χXVII
: Strontium phthalate compound B [XX■ Konisari
Barium thylate compound B [XX■ Coni-3,5-di-t-
Barium butyl-4-hydroxybenzoate compound B [Xχ仄]: Al p-t-butylbenzoate
aluminum compound B [XXX]: aluminum anisate compound B
[XXX[, Gluta-based monolithium compound B [
XXX] I Coni Monosodium Glutamate Compound B
[XXX Ro: Monopotassium glutamate compound B [XX
XrV]: Strontium glutamate compound B[X
XXV]: Barium glutamate compound BCXXX■
: (Mono, Simituxt) 2-ethylhexyl phosphate
Sodium compound B [XχX■: (mono, simituxt) lauri
Potassium ruphosphate compound B
Calcium lyluphosphate compound B [XXX addition: (mono, simituxt) tocosyl
Strontium phosphate compound B [XL Koni (mono, Simituxt) Offtaco
Barium silphosphate compound B [XLI]: 2,6.8-) Lee L
-butyl-10-hydroxy-9,10-dihydro-9
-oxa-10-phosphaphenanthrene-10-o
Oxide lithium salt compound B [χLn]: 10-
Hydroxy-9,10-dihydro-9-oxa-10-
Phosphaenanthrene-10-Oxide Natori
um salt compound B [χLm]: 2-cyclohexyl-10-
Hydroxy-9,10-dihydro-9-oxa-1O-
Phosphaphenanthrene-10-oxide
Um salt compound B [XLrV]: 6-phenyl-1
0-hydroxy-9゜10-dihydro-9-oxa-1
0-phosphaphenanthrene-10-oxide
Lium salt compound B [XLV coni-2-benzyl-10-
Hydroxy-9゜10-dihydro-9-oxa-10-
Fuosfahu Enanthren-10-Oxide Variu
Mu salt compound B [:XLVI]: 6- (a-mef
rubendi/l/) -8-t-butyl-10-hydro
Oxy-9,10-dihydro-9-oxa-10-phos
Faphenanthrene-10-oxide barium salt compound BCXL■]: Magnesium hydroxide compound B [χ
L■]: Aluminum hydroxide compound B[XL]X]: Acid
Magnesium carbonate compound B [L]: Magnesium carbonate
Compound B [j]: Calcium carbonate compound B [Lnl: Hydrotalcite (M, gt5A
Q2 (OH> +3C○3・3.5H20) [Kyowa Chemical Industry
DHT-4A co-compound C [1:]: Laurylamine compound C [II
:] : ]N,N-dicocoamine compound CI:III
]: N-stearyl-N,N-dimethylamine compound C[]V]: Hexamethylenediamine compound C
[■Coni N-crow-1,3-diaminopropane compound C[V[]: Hexamethylenetetramine compound
C[■]: N-tocosyl-N,N,N-trimethyl
Ammonium chloride compound C [■]: N, N, N-) diethyl-N-beta
Ammonium chloride compound C [IX]: N,N-bis(2-hydroxy
ethyl)-N-oleyl-N-methylammonium chloro
Ride compound COX coni N,N-bis(2-hydroxyethyl
) Stearylaminobetaine compound C [XI] : ) Lysopropanolamine
Compound C[XIr1: N,N-bis(2-hydroxy
ethyl) cocoa refreshment compound C [Xml: N,N-bis(2-hydroxy
ethyl) tallowamine compound C[XTV]: octadecanoic acid 2-[:(2-hyperoxychloride)
Droxyethyl) octadecyl aminoconityl ester compound! 'l! IC[X■Koni (Octadecylimino)
Diethylene distearate compound C [X■]: Polyoxyethylene lauryl amine
Noether compound C[X■]: Polyoxyethylene stearyl aminoether compound CCX■]: N, N, N″N +-tetra(
2-hydroxyethyl)-1,,3-diaminopropane
Compound C[XIK]: N-tallow N, N',
N'-)lis(2-hydroxyethyl) 4.3-di
Aminopropane compound C[XX]: N,N-zicoco
-N',N'-bis(2-hydroxyethyl)-
1,6-diamithexane inorganic filler 1: Talc (average
Particle size 2-3μ) Inorganic filler 2: Silicon dioxide (average particle size
1.8μ) Inorganic filler 3: Barium sulfate (average particle size 0.
4-0.6 μ) Phenolic antioxidant 1: 2,6-di-t-butyl-
P-cresol phenolic antioxidant 2: Tetrakis [methylene-3
-(3',5'-di-t-butyl-4'-hydroxyph)
phenyl) propionate comethane phenolic antioxidant 3: t, 3. s-trimethy
2.4.8- ) Lis(3,5-di-t-butyl-
4-Hydroxybenzyl)benzenephenolic antioxidant 4: Tris(3,5-di-t)
-butyl-4-hydroxybenzyl)isocyanurate
Phenolic antioxidant 5: n-octadecyl-β (4
'-Hydroxy-3',5'-di-t-butylphenyl
) Propionate phenolic antioxidant 6: Tris (4-t-butyl
-3-hydroxy-2,6-cymethylbenzyl)isocy
Anurate phenolic antioxidant 7: 3,9-bis[1,1-di
Methyl-2-(β-(3-t,-butyl-4-hydroxy)
C-5-methylphenyl)propionyloxy)ethyl
]・2,4,8.10-tetraoxaspiro[5,5]
Undecanephenolic antioxidant 8:2,2-bis[4-[2-
(3,5-di-butyl-4-hydroxyphenylp)
Ropionyloxy)ethoxy]phenylcopropanphe
Nord antioxidant 9: Bis[2-(3″-7-butylene)
-21-hydroxy-5'-methylbenzyl)-6
-t-butyl-4-methylphenylcoterephthalate
Phenolic antioxidant 10: Bis[3,3-His(4
'-Hydroxy-3'-t-butylphenyl) butyritz
Quacid coethylene glycol ester phenolic
Antioxidant 11: 2,2″-ethylidene-bis(4,
6-di-t-butylphenol) phenolic antioxidant
Agent 12: 2-t-butyl-6-(3-t-butyl-2
-hydroxy-5-methylbenzyl)-4 methylphene
Nyl acrylate phenolic antioxidant 13: Tocopherol thioacetate
Tel-based antioxidant 1: Dimyristylthiodiprobione
Tothioether antioxidant 2-distearylthiodipro
Pionate thioether antioxidant 3: Pentaerythritol
Tetrakis(3-laurylthiopropionate) Phosphorous antioxidant 1: Bis(2,4-disabtyl)
phenyl)-pentaerythritol-siphosphi)
・ Phosphorous antioxidant 2: Bis(2,6-di-butyl)
4-methylphenyl)-pentaerythritol-shifuo
Sphite phosphorus antioxidant 3: Bis(2,4,61)
tylphenyl) pentaerythritol-Sifosphi
Thorin-based antioxidant 4: Tetrakis (2,4-G)
tylphenyl) -4,4'-biphenylene dipho
Sulfonitroin antioxidant 5: Tris (2,4-di-butylene)
phosphite phosphorus antioxidant 6: 2,2'-methylene-bis(4,
6-di-t-butylphenyl) octyl phosphite
Light stabilizer 1: 2-hydroxy-4-n-octoxyben
Zophenone light stabilizer 2: 2-(2'-hydroxy-3'-L-butylene
-5'-methylphenyl)-5-chlorobenzotria
sol light stabilizer 322,4-di-butylphenyl-3',
5'-di-L-butyl-4'-hydromodibenzoate
Light stabilizer 4: bis(2,2,6,6-tetramethyl-
4-piperidyl) sebacate light stabilizer 5: Tetrakis(2,2,8,6-tetramethy
1,2,3,4-butanetetra
Carboxylate light stabilizer 6: 3,9-bis[1,1-dimethyl-2-(
Tris(1,,2,2,6,6-bentamethyl-4-pi
peridyloxycarbonyl)butylcarbonyloxy)
ethyl]2,4,8, ], ]O-tetraoxy
Suspiro5.5]undecane light stabilizer 7: poly[[6-[(1,1,3,3-tetra
Methylbutyl)iminoco-1,3,5-)riazine-2
,4-diylco ((2,2,6,6-tetramethyl-
4-piperidyl)iminocohexamethylene [(2,2,
6,6-tetramethyl-4-piperidyl)iminococo light stabilizer 8: poly[[6-morpholino-1,3,5-
) riazine-2,4-diylco [(2,2,6,6-
Tetramethyl-4-piperidyl)imino]hexamethylene
[(2,2,8,6-tetramethyl-4-piperidyl
) 15733 Heavy metal deactivator 1: N,N'-bis[2
-(3-(3,5-di-t-butyl-4-hydroxyphenyl)
phenyl)propionyloxy]ethyl]oxamide heavy metal deactivator 2: tris[2-t-butyl-4-
Thio(2'-methyl-4'-hydroxy-5'-t-butyl
(tylphenyl)-5-methylphenylcottosphite
Heavy metal deactivator 37 N,N'-bis[3-(3,5
-di-butyl-4-hydroxyphenyl)propioni
]hydrazine heavy metal deactivator 4:3-salicyloyl amino-1,2
,4-triazole heavy metal deactivator 5: decamethylene dicarboxylink
Acid-bis(N″-salisilylhydrazide) Radical generator 1: 2,5-di-methyl-2,5-di(
t-butylperoxy)hexane radical generator 2: 1,3-bis(t-butylperoxy)
Cisoprobil) Benzene Clarifying Agent 1: 1,3,2,4-dibenzylidene sorbitol
Clearing agent 2: 1,3,2,4-di(P-methylbenzyl)
Sorbitol Clarifying agent 3: 1, 3, 2, 4-di(P-ethyl benzyl)
Sorbitol clarifying agent 4: 1,3-P-chlorobenzylidene-2,4
-P-methylbenzylidene sorbitol Antistatic agent: glyceryl monostearate lubricant 1 niole
Inic acid amide lubricant 2: Erucic acid amide lubricant 3: N,N'-ethylene-bis-stearoamide E
PR: Non-quality ethylene-propylene random copolymer (
Mooney viscosity MLl+4 (100°C) 63, propylene
Contains ff123% by weight: JSR77 made by Japan Gosho Rubber
961) EPDM: Amorphous ethylene-propylene-ethylene
Lubornane random copolymer (Mooney viscosity ML1+4
(100℃)82. Propylene content 26% iodine
Value 15.0; Japan Synthetic Rubber I JSREP57P
) Nucleating agent dibenzoic acid lubricant 1 calcium nystearate lubricant 2 zinc nystearate aromatic amine: 4.4'-bis(α,α-dimethylbenzyl)-diphenylamine Examples and comparisons given in Table 3 An example is crystalline polyolefin
When using crystalline propylene homopolymer as the fin
It is. As can be seen from the jIa table, Examples 1 to 11 were
Compound A, compound B and compound C related to the present invention
Examples 1 to 11 and Comparative Example 1 (compound
When compared with the product containing only Product A), Example
It can be seen that samples No. 1 to No. 11 are significantly superior in terms of rigidity. Ma
Compound B is added to Compound A, and a compound other than Compound B (lubricant
, nucleating agent, inorganic filler) or compound C, respectively.
Comparing Comparative Examples 2 to 6 and Examples 1 to 11 using
, the improvement effect in terms of rigidity in Comparative Examples 2 to 6 is still not sufficient.
In particular, Comparative Example 6 in which Compound A and Compound C were used in combination
It can be seen that the rigidity is lower compared to Comparative Example 1.
. Furthermore, compound C was used instead of compound C in Examples 1 to 11.
Aromatic amine or compound B which is an amine compound other than
Compounds other than compound B (ill lubricant, nucleating agent) can be used instead of compound B.
, inorganic filler) and Comparative Examples 7 to 11 and actual
Comparing Examples 1 to 1, Comparative Examples 7 to 11 are
The improvement effect in terms of rigidity is approximately the same as in Examples 2 to 5. That is, compound A and compound B contain aromatics other than compound C.
aromatic amine or compound A and compound C with compound B or more
By blending external compounds (lubricant, nucleating agent, inorganic filler)
However, it was found that almost no improvement effect on stiffness was observed.
Ru. Therefore, Compound A, Compound B and Compound B related to the present invention
Comparisons on each side that do not simultaneously satisfy the three precepts of compound C
It is clear that the effects of the present invention are not achieved. sand
Specifically, the rigid surface obtained by the present invention is made of crystalline polyolefin.
When compound A, compound B and compound C are blended into
It can be said that this is a unique effect that was first seen in Japan. Tables 4 to 15 list the crystalline polyolefins.
■Crystalline propylene homopolymer, ■Crystalline propylene
homopolymer, crystalline ethylene-propylene random copolymer
Polymer and high-density ethylene homopolymer 9 mixture,
Crystalline propylene homopolymer, crystalline ethylene-propylene
random copolymer, crystalline ethylene-propylene-butyl
Ten-13 element copolymer and high density ethylene-propylene
mixture of copolymers or crystalline ethylene-propylene
block copolymer.
However, the same effect as above was confirmed. In addition, 's6 table to 7th table and $10 table to t315 table
In each embodiment of the composition of the present invention, compound A, compound
By blending Compound B and Compound C, the rigidity can be improved.
There was no decrease in impact resistance due to the
However, it was confirmed that the impact resistance was comparable. [Effects of the Invention] The composition of the present invention has the following advantages: (1) When made into a molded product, the composition
It has outstanding rigidity. (2) Thinner molded products
It not only contributes to resource saving by being able to measure
Since the cooling rate of
It can also contribute to improving productivity. that's all

Claims (4)

[Claims] (1) A fluorophosphite compound represented by the following general formula [I] (hereinafter referred to as compound A) and the following [1] to 100 parts by weight of the crystalline polyolefin.
[12] 0.001 to 1 part by weight of one or more compounds selected from [12] (hereinafter referred to as compound B), and 0.01 to 1 part by weight of an aliphatic amine (hereinafter referred to as compound C). A crystalline polyolefin composition containing parts by weight. [1] Fats Metal salts of group polycarboxylic acids (where the metals are lithium, sodium, potassium, strontium, or barium) [4] Metal salts of aliphatic hydroxy acids having 2 to 6 carbon atoms (where the metals are lithium, sodium, potassium) , magnesium, strontium, or barium) [5] Aromatic carboxylic acid metal salt (however, the metal is lithium, sodium, strontium, barium, or aluminum) [5] Glutamate metal salt (however, the metal is lithium,
Indicates sodium, potassium, strontium or barium. ) [7] Aliphatic phosphate metal salts (however, the metal represents sodium, potassium, calcium, strontium or barium) [8] Metal salts of cyclic phosphorus compounds represented by the following general formula [II] (however, the metal indicates lithium, sodium, potassium, or barium.) [9] Metal hydroxide (however, the metal indicates magnesium or aluminum) [10] Magnesium oxide [11] Metal carbonate (however, the metal indicates magnesium or calcium) ) [12] Hydrotalcite ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, in the formula, R is an alkylidene with 1 to 4 carbon atoms. group or sulfur, Ar_1 and Ar_2 are alkylarylene groups or cycloalkylarylene groups, Ar_1 and Ar_2 are alkylarylene groups or cycloalkylarylene groups,
3 and Ar_4 are arylene group, alkylarylene group, cycloalkylarylene group, arylarylene group, or aralkylarylene group, M is lithium, sodium, potassium or barium, n is 0 or 1, m is the valence of M are shown respectively. ) (2) For 100 parts by weight of crystalline polyolefin, 0.001 to 1 part by weight of Compound A and Compound B, 0.01 to 1 part by weight of Compound C, and inorganic fillers (however, magnesium hydroxide, water A crystalline polyolefin composition containing 0.01 to 25 parts by weight of aluminum oxide, magnesium oxide, magnesium carbonate, and calcium carbonate. (3) As a crystalline polyolefin, isotactic pentad fraction (P) and melt flow rate (MFR;
10 when applying a load of 2.16 kg at 230°C
Discharge amount of molten resin per minute) is 1.00≧P≧0
．． Claim (1) or Claim (1) in which a crystalline propylene homopolymer having a
2) The crystalline polyolefin composition described. (4) As a crystalline polyolefin, the relationship between the isotactic pentad fraction (P) and melt flow rate (MFR) of the propylene homopolymer is 1.00≧P≧0.
015 log MFR + 0.955 of the first stage polymer is 70 to 95% by weight of the total polymer amount, and then ethylene or ethylene and propylene of 30 to 5 weight % of the total polymer amount is polymerized in one or more steps. Crystalline ethylene whose ethylene content is 3 to 20% by weight of the total polymer amount
The crystalline polyolefin composition according to claim (1) or claim (2), which uses a propylene block copolymer.