JPH07316362A - Crystalline propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain the composition excellent in the tensile elongation after molded, useful for injection molded products, blow molded products, films, fibers, etc., by incorporating a specific crystalline propylene homopolymer with a specific amide compound. CONSTITUTION:This composition is obtained by incorporating (A) 100 pts.wt. of a crystalline propylene homopolymer satisfying the relationship of formula I [P is isotactic pentad fraction; MFR is a 10-min-molten resin delivery (g) at 230 deg.C under a load of 2.16kg] with (B) 0.001-1 pt.wt. of a compound of formula II (R1 is a 1-24C aliphatic diamine residue, alicyclic diamine residue, or aromatic diamine residue except xylylene diamine residue; R2 and R3 each is a 3-14C cycloalkyl, cycloalkenyl, phenyl, 7-10C alkylphenyl, alkenylphenyl, 7-9C phenylalkyl, or cyclohexylalkyl).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a molded product excellent in tensile elongation which is obtained by blending a crystalline propylene homopolymer having a specific isotactic pentad fraction with a specific amount of a specific amide compound. Relates to a crystalline propylene polymer composition.

[0002]

2. Description of the Related Art Generally, a crystalline propylene polymer is relatively inexpensive and has excellent mechanical properties, and therefore, it is used for producing various molded products such as injection molded products, hollow molded products, films, sheets and fibers. There is. However, mechanical properties may not be sufficient depending on various specific uses, and there is a problem that expansion of the specific uses is limited. Especially, in terms of rigidity and rigidity such as heat resistance (hereinafter, “rigidity” means rigidity and heat resistance), it is inferior to thermoplastic polyester resins such as polystyrene, ABS resin, polyethylene terephthalate and polybutylene terephthalate. From
There is a drawback that the use of the crystalline propylene polymer is limited. Therefore, for the purpose of improving the rigidity of the crystalline propylene polymer, JP-A-58-104905, JP-A-58-104906, and JP-A-58-104907 relating to the applications of the same applicant as the present application JP-A-59-22923
In each of the publications, a crystalline propylene homopolymer having a specific isotactic pentad fraction is proposed. Further, in each of the above publications, in order to further improve the rigidity, the crystalline propylene homopolymer is added to an organic nucleating agent such as pt-butyl aluminum benzoate or 1,3,2,4-dibenzylidene sorbitol, that is, α crystal. It is described to add a nucleating agent.

On the other hand, for the purpose of obtaining a crystalline polypropylene resin composition capable of producing a large amount of β-type crystal structure, a crystalline polypropylene resin composition containing a specific bisamide as a β crystal nucleating agent is disclosed in Japanese Patent Laid-Open No. No. 107875, a transition metal compound (for example, a titanium halide such as titanium trichloride or titanium tetrachloride) is mainly used as a crystalline polypropylene resin, and a magnesium halide such as magnesium chloride is mainly used. It is described that a polypropylene resin prepared by using a catalyst system obtained by combining a catalyst supported on a carrier as a component and an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.) can also be used. Further, for the purpose of obtaining a polyolefin resin composition that significantly improves transparency and does not reduce the mechanical strength of the resin, a polyolefin resin is blended with an alicyclic carboxylic acid amide compound of a divalent or higher aliphatic amine. A polyolefin resin composition obtained by the above is proposed in Japanese Patent Application Laid-Open No. 4-261447. Further, in order to obtain a synthetic resin composition having a significantly improved transparency and exhibiting sufficient mechanical strength, an organic carboxylic acid amide of a divalent or higher aliphatic amine is added to a synthetic resin such as a crystalline polyolefin resin. Japanese Patent Application Laid-Open No. 4-370124 proposes a synthetic resin composition containing a compound, a specific organic phosphate compound or its ammonium salt, and an organic carboxylic acid metal salt having 7 or more carbon atoms.

[0004]

However, the respective publications of the above-mentioned JP-A-58-104905, JP-A-58-104906, JP-A-58-104907 and JP-A-59-22913. The crystalline propylene homopolymer having the specific isotactic pentad fraction proposed in 1) has a drawback that the tensile elongation is remarkably lowered although the rigidity is considerably improved. In JP-A-6-107875, the tensile elongation of a molded article obtained from a composition using a crystalline propylene homopolymer having a specific isotactic pentad fraction as a crystalline polypropylene resin is improved. That is, there is no description or suggestion, and the publication further comprises a combination of a catalyst obtained by supporting a transition metal compound as a crystalline polypropylene resin on a carrier containing magnesium halide as a main component and an alkylaluminum compound. Although described as a polypropylene resin prepared using a high activity catalyst system, polypropylene prepared using a high activity highly stereoregular catalyst composition in which the electron donor catalyst component is combined with the high activity catalyst system. The system resin is neither described nor suggested. Further, in JP-A-4-261447 and JP-A-4-370124, obtained from a composition using a crystalline propylene homopolymer having a specific isotactic pentad fraction as a crystalline polyolefin resin. The improvement of the tensile elongation of the molded product is
There is no description or suggestion.

The present inventors have earnestly studied to obtain a crystalline propylene polymer composition which gives a molded article having the above-mentioned problems regarding the crystalline propylene polymer composition, that is, improved tensile elongation. As a result, the inventors have found that a crystalline propylene polymer composition obtained by blending a crystalline propylene homopolymer having a specific isotactic pentad fraction with a specific amount of a specific bisamide has improved tensile elongation. Based on this finding, the present invention was completed. As is clear from the above description, an object of the present invention is to provide a crystalline propylene polymer composition having an improved tensile elongation of the molded product.

[0006]

The present invention has the following constitution. The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR: discharge amount of molten resin for 10 minutes when a load of 2.16 kg at 230 ° C. is applied) is 1.00 ≧
A crystalline propylene polymer composition prepared by adding 0.001 to 1 part by weight of the following amide compound (hereinafter referred to as compound A) to 100 parts by weight of a crystalline propylene homopolymer having P ≧ 0.015 log MFR + 0.955. object. R ₂ in _{-CONH-R 1 -NHCO-R 3} [ wherein, R ₁ is an aliphatic diamine residue having 1 to 24 carbon atoms, alicyclic diamine residue or an aromatic diamine residue (provided that
Excludes xylylenediamine residues. ), R ₂ and R ₃ are the same or different and are a cycloalkyl group or cycloalkenyl group having 3 to 14 carbon atoms, a phenyl group, or 7 to 10 carbon atoms.
Is an alkylphenyl group or alkenylphenyl group, or a phenylalkyl group having 7 to 9 carbon atoms or a cyclohexylalkyl group. ]

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

Here, the isotactic pentad fraction
(P) means Macromolecules, Volume 6, Issue 6, November
December, pp. 925-926 (1973) [Macromolecules, Vol.
6, No. 6, November-December, 925-926 (197
3)], that is, the isotactic fraction in the pentad unit in the propylene-based polymer molecular chain, which is measured using ¹³ C-NMR. In other words, the fraction means the fraction of propylene monomer units in which five propylene monomer units are continuously isotactically bonded. The assignment of the peak of the spectrum in the above-mentioned measurement using ¹³ C-NMR is determined by Macromolecules, Vol. 8, No. 5, September-October, pages 687-689 (1975).
Year) [Macromolecules, Vol. 8, No. 5, September
-October, 687-689 (1975)]. Incidentally, the measurement by ¹³ C-NMR in the examples described later was carried out by using an FT-NMR 270 MHz device, and by integrating measurement 27,000 times, the signal detection limit was improved to 0.001 in terms of isotactic pentad fraction. It was HC above
Isotactic pentad fraction (P) in PP (H)
And the melt flow rate (MFR) are required to meet the MFR requirement as a crystalline propylene homopolymer to be used, since the fraction P of the crystalline propylene homopolymer having a low MFR generally decreases. The configuration requirement is to limit the lower limit of P. Since the P is a fraction, the upper limit is 1.00, and the MFR is usually 0.05 to 10
It is 0g / 10 minutes. MFR is measured in accordance with JIS K 7210 at 230 ° C and a load of 2.16 kg.

The HCPP (H) used in the present invention contains a usual crystalline propylene-based polymer, that is, a crystalline propylene homopolymer, and a propylene component in an amount of 70% by weight or more within a range not impairing the effects of the present invention. Low crystalline or crystalline random copolymerization of propylene and one or more α-olefins such as ethylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 Polymers or crystalline block copolymers, copolymers of propylene and vinyl acetate or acrylic acid esters or saponified products of the copolymers, copolymers of propylene and unsaturated silane compounds, propylene and unsaturated carboxylic acids or The copolymer with the anhydride, the reaction product of the copolymer with the metal ion compound, or the crystalline propylene-based polymer is used as an unsaturated carbohydrate. Acid or modified propylene-based polymer modified with a derivative thereof, can be mixed and used, such as crystalline propylene polymer an unsaturated silane compound modified with silane-modified propylene-based polymer, also,
Various synthetic rubbers (eg ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, acrylonitrile-butadiene Rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer,
(Styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.)

Alternatively, a thermoplastic synthetic resin (for example, ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, amorphous ethylene-cyclic alkene copolymer ( For example, amorphous ethylene-tetracyclododecene copolymer), polybutene, polyolefin excluding crystalline propylene-based polymers such as poly-4-methylpentene-1, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene -Styrene copolymer, methacryl-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyvinyl chloride, fluororesin, petroleum resin Example, if C ₅ petroleum resin,
Hydrogenated C ₅ petroleum resin, C ₉ petroleum resin, hydrogenated C ₉ petroleum resin, C ₅ -C ₉ copolymer petroleum resin, hydrogenated C ₅ -C ₉ copolymer petroleum resin, acid-modified C ₉ petroleum Resin, etc., DCPD resin (for example, cyclopentadiene-based petroleum resin, hydrogenated cyclopentadiene-based petroleum resin, cyclopentadiene-C ₅ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymerized petroleum resin, cyclopentadiene-C ₉ copolymer) Polymerized petroleum resin, hydrogenated cyclopentadiene-C ₉ Copolymerized petroleum resin, cyclopentadiene-C ₅
-C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉
It is also possible to use a mixture of copolymerized petroleum resin and the like) having a softening point of 80 to 200 ° C.).

The compound A used in the present invention can be easily prepared by amidating a predetermined aliphatic diamine, alicyclic diamine or aromatic diamine with a predetermined monocarboxylic acid according to a conventional method. Examples of the aliphatic diamine according to the present invention include saturated or unsaturated aliphatic diamine having 1 to 24 carbon atoms, and more specifically,
Methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane,
Examples include 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane and the like. As the alicyclic diamine, diaminocyclohexane, bis (aminoalkyl) cyclohexane having 8 to 12 carbon atoms, diaminodicyclohexylmethane and diamino-dialkyldicyclohexylmethane having 15 to 21 carbon atoms, for example, 1,2-diamino Cyclohexane, 1,4-diaminocyclohexane, 4,4'-
Diaminodicyclohexylmethane, 4,4'-diamino-3,3 '
-Dimethyldicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like, as well as alicyclic diamines such as isophoronediamine and mensendiamine. Examples of aromatic diamines include phenylenediamine, naphthalenediamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl sulfide, diaminodiphenyl ketone and 2,2-bis (aminophenyl) propane.
More specifically, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino Examples thereof include diphenyl sulfone. Even if the aromatic diamine is used, xylylenediamine cannot obtain a predetermined effect. Examples of the monocarboxylic acid include phenylacetic acid, cyclohexylacetic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid. Acid, 4-t-butylcyclohexanecarboxylic acid, benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, p-ethylbenzoic acid, pn-butylbenzoic acid, pi-butylbenzoic acid, ps-butylbenzoic acid,
Examples thereof include pt-butylbenzoic acid.

Among the diamide compounds obtained from the above diamine and monocarboxylic acid, more preferable compounds are N, N'-dicyclohexanecarbonyl-p-phenylenediamine and N, N'-dibenzoyl-1,5-diaminonaphthalene. , N, N′-dibenzoyl-1,4-diaminocyclohexane, N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane and the like are exemplified. These compounds A may be used alone or in combination of two or more kinds. The compounding ratio of the compound A is HCPP.
(H) 0.001 to 1 part by weight, preferably 0.
It is from 01 to 0.5 parts by weight. If the amount is less than 0.001 part by weight, the effect of improving the tensile elongation is not sufficiently exerted, and if it exceeds 1 part by weight, the effect of improving the tensile elongation cannot be expected any further and it is not practical. It is uneconomical again.

In the composition of the present invention, various additives usually added to the crystalline propylene polymer, such as phenol-based, thioether-based, phosphorus-based antioxidants,
Light stabilizer, heavy metal deactivator (copper damage inhibitor), clarifier, nucleating agent (excluding compound A), lubricant, antistatic agent, antifogging agent, antiblocking agent, non-dripping agent, Radical generators such as organic peroxides, flame retardants, flame retardant aids, pigments, halogen scavengers, dispersants or neutralizers for metallic soaps, organic or inorganic antibacterial agents, inorganic fillers ( For example, talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, basic aluminum-lithium-hydroxy-carbonate-
Hydrate, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, calcium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate,
Such as glass fiber, potassium titanate, magnesium oxysulfate, carbon fiber, carbon black, graphite and metal fiber), coupling agent (for example, silane, titanate, boron, aluminate, zircoaluminate, etc.) The above-mentioned inorganic filler or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with the surface-treating agent can be used together within the range not impairing the object of the present invention.

The composition of the present invention comprises a compound A added to HCPP (H).
In addition, a predetermined amount of each of the above-mentioned various additives usually added to the crystalline propylene polymer is mixed with a conventional mixing device such as a Henschel mixer (trade name), a super mixer,
Mix using a ribbon blender, Banbury mixer, etc., and melt knead at a melt kneading temperature of 150 ° C to 300 ° C, preferably 180 ° C to 270 ° C with an ordinary single screw extruder, twin screw extruder, Brabender or roll. It can be obtained by pelletizing. The obtained composition is used for producing a desired molded article by various molding methods such as an injection molding method, an extrusion molding method and a blow molding method.

[0015]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. Tensile elongation: evaluated by a tensile test. That is, using the pellets obtained, a length of 175 m
A JIS No. 1 test piece of m, width 10 mm, and thickness 3.3 mm was prepared by an injection molding method, and the tensile elongation was measured using the test piece (JI
Evaluation was made according to SK 7113). A material having an excellent tensile elongation means a material having a large tensile elongation.

Production Examples 1 to 3 (Method for producing HCPP (H) used in Examples 1 to 24 and Comparative Examples 1 to 6) (1) Preparation of catalyst n-hexane 600 ml, diethyl aluminum monochloride (DEAC) 0.50 mol , 1.20 mol of diisoamyl ether were mixed at 25 ° C. for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product solution (v) (diisoamyl ether / DEAC molar ratio).
2.4) was obtained. Titanium tetrachloride 4.0 in a reactor purged with nitrogen
Add the mole and heat to 35 ° C, and add the above reaction product solution (v) to it.
After dripping the entire amount of the above in 180 minutes, keep it at the same temperature for 30 minutes, raise the temperature to 75 ℃ and react for another 1 hour, then room temperature (20 ℃)
The mixture was cooled to 4, the supernatant was removed, 4,000 ml of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain 190 g of a solid product (ii). The total amount of this solid product (ii) was suspended in 3,000 ml of n-hexane at 20 ° C.
Then, 160 g of diisoamyl ether and 350 g of titanium tetrachloride were added at room temperature for about 1 minute and reacted at 65 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, 4,000 ml of n-hexane was added, the mixture was stirred for 10 minutes, allowed to stand, and the procedure of removing the supernatant was repeated 5 times. It was dried under reduced pressure to obtain a solid product (iii). (2) Preparation of pre-activated catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 20 l with nitrogen gas, 15 l of n-hexane, 42 g of diethylaluminum monochloride, and 30 g of the solid product (iii) were stirred at room temperature. Then, add 15 Nl of hydrogen, and add propylene partial pressure of 0.588 MPa.
For 5 minutes, unreacted propylene, hydrogen and n-hexane were removed under reduced pressure to obtain pre-activated catalyst (vi) in the form of powder (82.0 g reaction of propylene per 1 g of solid product (iii)).

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

Examples 1-8, Comparative Examples 1-2 MF produced in Production Example 1 as a crystalline propylene polymer
R2.5g / 10min unstabilized powdered HCPP (H)
-[1] 100 parts by weight, as compound A, N, N'-dicyclohexanecarbonyl-p-phenylenediamine, N, N'-dibenzoyl-1,5-diaminonaphthalene or N, N'-dibenzoyl-1,4 -Add predetermined amounts of diaminocyclohexane and other additives to the Henschel mixer (trade name) at the compounding ratios shown in Table 2 below, stir and mix for 3 minutes, and then to 200 ° C with a twin-screw extruder with a diameter of 30 mm. Melted and kneaded to form pellets. Also, as Comparative Examples 1 and 2, MFR
2.5g / 10min unstabilized powdered HCPP (H)
-[1] 100 parts by weight of each of predetermined amounts of the additives shown in Table 2 described below were mixed and melt-kneaded according to Examples 1 to 8 to obtain pellets. The test piece used to evaluate the tensile elongation was obtained by pelletizing the pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Was prepared by injection molding. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 2.

Examples 9 to 16, Comparative Examples 3 to 4 MF produced in Production Example 2 as a crystalline propylene polymer
R10.6g / 10min unstabilized powdered HCPP
To 100 parts by weight of (H)-[2], N, N'-dicyclohexanecarbonyl-1,4-diaminocyclohexane as compound A,
N, N'-bis (4-t-butylbenzoyl) -1,6-diaminohexane or N, N'-bis (4-t-butylcyclohexanecarbonyl) -4,4'-diaminodiphenyl ether and other additives Put the specified amount of each of them into the Henschel mixer (trade name) in the blending ratio shown in Table 3 below, stir and mix for 3 minutes, and then melt-knead at 200 ° C. with a twin-screw extruder with a diameter of 30 mm to pelletize. did. Also, as Comparative Examples 3 to 4, 100 parts by weight of unstabilized powdered HCPP (H)-[2] having an MFR of 10.6 g / 10 min were mixed with predetermined amounts of the additives shown in Table 3 below. Melt-kneading was carried out according to Examples 9 to 16 to obtain pellets. The test piece used for the evaluation of tensile elongation is obtained pellets at a resin temperature of 250 ° C.,
It was prepared by injection molding at a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 3.

Examples 17-24, Comparative Examples 5-6 MF produced in Production Example 3 as a crystalline propylene polymer
R3 4.0g / 10min unstabilized powdered HCPP
100 parts by weight of (H)-[3], as compound A, N, N'-dibenzylcarbonyl-4,4'-diaminodiphenyl sulfone,
N, N′-dibenzylcarbonyl-4,4′-diaminodiphenyl ketone or 2,2-bis [4 ′-(N-cyclohexylmethylcarbonylamino) phenyl] propane and other additives are added in predetermined amounts, respectively, as described below. The mixture was put in a Henschel mixer (trade name) at the blending ratio shown in Table 4, stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 5 and 6, M
Unstabilized powdered HCP with FR of 34.0 g / 10 min
To 100 parts by weight of P (H)-[3] was added a predetermined amount of each of the additives shown in Table 4 described below, and the mixture was melt-kneaded in accordance with Examples 17 to 24 to obtain pellets. Test pieces used for evaluation of tensile elongation were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 4.

The compounds and additives relating to the present invention shown in Tables 2 to 4 are as follows. Compound A [1]: N, N′-dicyclohexanecarbonyl-
p-Phenylenediamine compound A [2]: N, N'-dibenzoyl-1,5-diaminonaphthalene compound A [3]: N, N'-dibenzoyl-1,4-diaminocyclohexane compound A [4]: N, N'-dicyclohexanecarbonyl-
1,4-Diaminocyclohexane compound A [5]: N, N'-bis (4-t-butylbenzoyl) -1,6-diaminohexane compound A [6]: N, N'-bis (4-t- Butylcyclohexanecarbonyl) -4,4'-diaminodiphenyl ether compound A [7]: N, N'-dibenzylcarbonyl-4,4'-
Diaminodiphenylsulfone compound A [8]: N, N'-dibenzylcarbonyl-4,4'-
Diaminodiphenyl ketone Compound A [9]: 2,2-bis [4 '-(N-cyclohexylmethylcarbonylamino) phenyl] propane Phenol-based antioxidant 1: 2,6-di-t-butyl-p-cresol phenol -Based antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Phosphorus Antioxidant 1: Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite Phosphorus Antioxidant 2: Bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite Nucleating agent: pt-butyl aluminum benzoate Ca-St: calcium stearate

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

[Table 4]

The examples and comparative examples shown in Table 2 are the cases where HCPP (H)-[1] was used as the crystalline propylene polymer. As can be seen from Table 2, Examples 1 to 8 contain the compound A according to the present invention, and comparing Examples 1 to 8 and Comparative Example 1 (without compound A), It can be seen that the tensile elongation of Comparative Example 1 is remarkably inferior, whereas the tensile elongations of Examples 1 to 8 are remarkably improved. Further, instead of the compound A, the above-mentioned JP-A-58-10 is used.
4905, JP-A-58-104906, JP-A-58-1049
Comparing Comparative Example 2 and Examples 1 to 8 containing the α-crystal nucleating agent described in JP-A No. 07 and JP-A-59-22913, the tensile elongation of Comparative Example 2 is the same as that of Comparative Example 1. As is clear from the comparison, there is almost no improvement, and it can be seen that Examples 1 to 8 have remarkably excellent tensile elongation. That is, compound A
It can be seen that the effect of improving the tensile elongation is hardly recognized even if an α crystal nucleating agent other than the above is added. Therefore, it is apparent that the comparative examples that do not satisfy the compounding of the compound A in the HCPP (H) according to the present invention do not exhibit the effects of the present invention.
That is, the tensile elongation obtained in the present invention is HCPP (H)
It can be said that this is a unique effect that can be seen only when the compound A is added to. Tables 3 to 4 show that the crystalline propylene polymers are HCPP (H)-[2] and HCPP (H), respectively.
-[3] was used, and the same effects as those described above were confirmed for these.

[0027]

EFFECTS OF THE INVENTION The composition of the present invention is a composition capable of obtaining a molded article having a remarkably excellent tensile elongation when a molded article is formed from the composition.

Claims (1)

[Claims] 1. Isotactic pentad fraction (P) and melt flow rate (MFR: load at 230 ° C. 2.16 k)
The amount of the amide compound below is 0.001 to 100 parts by weight with respect to 100 parts by weight of a crystalline propylene homopolymer having a relationship of 1.00 ≧ P ≧ 0.015 log MFR + 0.955 with respect to the amount of molten resin discharged for 10 minutes when g is added. A crystalline propylene polymer composition containing 1 part by weight. R ₂ in _{-CONH-R 1 -NHCO-R 3} [ wherein, R ₁ is an aliphatic diamine residue having 1 to 24 carbon atoms, alicyclic diamine residue or an aromatic diamine residue (provided that
Excludes xylylenediamine residues. ), R ₂ and R ₃ are the same or different and are a cycloalkyl group or cycloalkenyl group having 3 to 14 carbon atoms, a phenyl group, or 7 to 10 carbon atoms.
Is an alkylphenyl group or alkenylphenyl group, or a phenylalkyl group having 7 to 9 carbon atoms or a cyclohexylalkyl group. ]