JPH07133388A - Crystalline propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which gives a molding excellent in tensile elongation by incorporating a specified compound into a specified crystalline propylene homopolymer. CONSTITUTION:100 pts.wt. crystalline propylene homopolymer of which the relation between the isotactic pentad fraction P and the melt flow rate MFR under prescribed conditions satisfies the formula 1.00>=P>=0.015 log MFR+0.955 is mixed with 0.001-1 pt.wt. of at least one amide compound selected from those of formulas I and II (R1 is a 1-28C aliphatic, alicyclic or aromatic dicarboxylic acid residue; R2 and R3 are each 3-18C cycloalkyl, cycloalkenyl, 7-18C alkylphenyl, alkenylphenyl, cycloalkylphenyl, biphenyl, alkylcyclohexyl, alkenylcyclohexyl, cycloalkylcyclohexyl, phenylcyclohexyl, 7-10C phenylalkyl or cyclohexylalkyl; R4 is a 1-28C aliphatic, alicyclic or aromatic amino acid residue; and R5 and R6 are each R2 or phenyl).

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. In particular, regarding a rigid surface such as rigidity and heat resistant rigidity (hereinafter, rigid surface means rigidity and heat resistant rigidity), it is inferior to polyesters such as polystyrene, ABS resin, polyethylene terephthalate and polybutylene terephthalate, and therefore, crystal There is a drawback that the use of the water-soluble 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, JP-A-58-104906, and JP-A-58-104906 relating to the application of the same applicant as the present application
In each of JP-A-58-104907 and JP-A-59-22913, 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, in order to improve the impact resistance and rigidity of the crystalline polypropylene resin, an aliphatic, alicyclic or aromatic dibasic acid diamide and / or an amino acid diamide is converted into a β type crystal structure. Β that can be produced in large quantities
A crystalline polypropylene resin composition contained as a crystal nucleating agent has been proposed in JP-A-5-262936.
The publication discloses a catalyst obtained by supporting a transition metal compound (for example, titanium halides such as titanium trichloride and titanium tetrachloride) as a crystalline polypropylene resin on a carrier whose main component is magnesium halide such as magnesium chloride. It is described that a polypropylene-based resin prepared by using a catalyst system comprising a combination of the above and an aluminum aluminum compound (triethylaluminum, diethylaluminum chloride, etc.) can also be used.

[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. Further, in JP-A-5-262936, the tensile elongation of a molded product obtained from a composition using a crystalline propylene homopolymer having a specific isotactic pentad fraction as a crystalline polypropylene resin is described. There is no description or suggestion that it is improved, and further, in the publication, 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 is used. Although it is described as a polypropylene resin prepared by using a highly active catalyst system consisting of the above, it is prepared by using a highly active and highly stereoregular catalyst composition obtained by combining the highly active catalyst system with an electron donor catalyst component. There is no description or suggestion of polypropylene-based resin.

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 present inventors have identified an aliphatic, alicyclic or aromatic dibasic acid diamide and / or an amino acid diamide in a crystalline propylene homopolymer having a specific isotactic pentad fraction. It was found that the crystalline propylene polymer composition obtained by compounding in an amount to give a molded article having improved tensile elongation, and the present invention was completed based on this finding. As is clear from the above description, it is an object of the present invention to provide a crystalline propylene polymer composition capable of obtaining a molded article having an improved tensile elongation when the molded article is obtained.

[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 ≧
Based on 100 parts by weight of the crystalline propylene homopolymer having P ≧ 0.015 log MFR + 0.955, one or more amide compounds (hereinafter referred to as Compound A) selected from the following
Say. 0.001 to 1 part by weight of a crystalline propylene polymer composition. _{R 2 -NHCO-R 1 -CONH-} R 3 R 5 -CONH-R 4 in -CONH-R ₆ (wherein, R ₁ is an aliphatic saturated or unsaturated 1 to 28 carbon atoms, alicyclic or aromatic the dicarboxylic acid residues of the family, R ₂
And R ₃ are the same or different and are a cycloalkyl group or cycloalkenyl group having 3 to 18 carbon atoms, and 7 to 7 carbon atoms.
18 alkylphenyl group, alkenylphenyl group, cycloalkylphenyl group, biphenyl group, alkylcyclohexyl group, alkenylcyclohexyl group, cycloalkylcyclohexyl group or phenylcyclohexyl group or phenylalkyl group or cyclohexylalkyl group having 7 to 10 carbon atoms, R ₄ is a saturated or unsaturated aliphatic, alicyclic or aromatic amino acid residue having 1 to 28 carbon atoms, R ₅ and R ₆ are the same or different, and a cycloalkyl group having 3 to 18 carbon atoms or Cycloalkenyl group, phenyl group, alkylphenyl group having 7 to 18 carbon atoms,
An alkenylphenyl group, a cycloalkylphenyl group, a biphenyl group, an alkylcyclohexyl group, an alkenylcyclohexyl group, a cycloalkylcyclohexyl group or a phenylcyclohexyl group, or a phenylalkyl group having 7 to 10 carbon atoms or a cyclohexylalkyl group is shown. )

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 attribution of the peak of the spectrum in the measurement using the above ¹³ C-NMR is determined by Macromolecules, Volume 8, No. 5, September to October, pages 687 to 689 (1975
Year) [Macromolecules, Vol. 8, No. 5, September
-October, 687-689 (1975)]. By the way, the measurement by ¹³ C-NMR in Examples described later was carried out by using an FT-NMR 270 MHz apparatus, and by performing integrated measurement of 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 satisfy the MFR 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 amide compound shown above as the compound A used in the present invention amidates a predetermined aliphatic, alicyclic or aromatic dicarboxylic acid and a predetermined alicyclic or aromatic monoamine. Therefore, it can be easily prepared. As the aliphatic dicarboxylic acid, more specifically, malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid. , Azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid and the like. As an alicyclic dicarboxylic acid,
More specifically, 1,2-cyclohexanedicarboxylic acid, 1,
Examples thereof include 4-cyclohexanedicarboxylic acid and 1,4-cyclohexanediacetic acid. As the aromatic dicarboxylic acid, more specifically, p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-t-butylphthalic acid, isophthalic acid, 5-t-butylisophthalic acid, terephthalic acid, 1 , 8-Naphthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid , 4,4'-binaphthyldicarboxylic acid, bis (3-
Carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,
3'-sulfonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid,
3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 3,3'-thiodibenzoic acid, 4,4'-thiodibenzoic acid, 4,4 '
-(P-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyldibenzoic acid, 4,4'-terephthaloyldibenzoic acid,
Examples thereof include dithiosalicylic acid.

As the alicyclic monoamine, more specifically, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine,
4-methylcyclohexylamine, 2-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-propylcyclohexylamine, 2-isopropylcyclohexylamine, 4-propylcyclohexylamine, 4-isopropylcyclohexylamine, 2-t-butylcyclohexylamine, 4-n-butylcyclohexylamine, 4-i-butylcyclohexylamine, 4-s-butylcyclohexylamine, 4-t-butylcyclohexylamine, 4-n-amylcyclohexylamine, 4-i-amylcyclohexylamine,
4-s-amylcyclohexylamine, 4-t-amylcyclohexylamine, 4-hexylcyclohexylamine, 4-octylcyclohexylamine, 4-nonylcyclohexylamine, 4-decylcyclohexylamine, 4-undecylcyclohexylamine, 4-dodecyl Cyclohexylamine, 4-cyclohexylcyclohexylamine, 4-phenylcyclohexylamine, cycloheptylamine, cyclododecylamine, cyclohexylmethylamine, α-
Examples thereof include cyclohexylethylamine, β-cyclohexylethylamine, α-cyclohexylpropylamine, β-cyclohexylpropylamine and γ-cyclohexylpropylamine. As an aromatic monoamine,
More specifically, aniline, o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline, o-cumidine, m-cumidine, p-cumidine, ot-butylaniline, pn-butylaniline, pi-butylaniline, ps-butylaniline, p-
t-butylaniline, pn-amylaniline, pi-amylaniline, ps-amylaniline, pt-amylaniline, p-
Hexylaniline, p-heptylaniline, p-octylaniline, p-nonylaniline, p-decylaniline, p-undecylaniline, p-dodecylaniline, p-cyclohexylaniline, o-aminodiphenyl, m-aminodiphenyl, p Examples include -aminodiphenyl, p-aminostyrene, benzylamine, α-phenylethylamine, β-phenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-phenylpropylamine and the like.

The amide compound represented by the above as the compound A used in the present invention is obtained by amidating a predetermined aliphatic, alicyclic or aromatic amino acid with a predetermined monocarboxylic acid or monoamine. It can be easily prepared. As the aliphatic amino acid, more specifically, aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutyric acid,
β-aminobutyric acid, γ-aminobutyric acid, α-amino-α-methylbutyric acid, γ-amino-α-methylbutyric acid, α-amino-i-butyric acid,
β-amino-i-butyric acid, α-amino-n-valeric acid, δ-amino-n-
Valeric acid, β-aminocrotonic acid, α-amino-β-methylvaleric acid, α-amino-i-valeric acid, 2-amino-4-pentenoic acid, α-amino-n-caproic acid, 6-aminocaproic acid ,
Examples include α-amino-i-caproic acid, 7-aminoheptanoic acid, α-amino-n-caprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. It As the alicyclic amino acid, more specifically, 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2- Amino-2-norbornanecarboxylic acid and the like are exemplified. As the aromatic amino acid, more specifically, α-aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, α-
Aminocinnamic acid, 2-amino-4-phenylbutyric acid, 4-amino-3-
Phenyl butyric acid, anthranilic acid, m-aminobenzoic acid, p-
Aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 2-
Amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 3- Amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3-methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o-aminophenylacetic acid, m-aminophenyl Acetic acid, p-aminophenylacetic acid, 4- (4-aminophenyl) butyric acid, 4-aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid, p-aminocinnamic acid, p-aminohippuric acid, 2-amino-1-naphthoic acid, 3-amino-1-naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1
-Naphthoic acid, 6-amino-1-naphthoic acid, 7-amino-1-naphthoic acid, 8-amino-1-naphthoic acid, 1-amino-2-naphthoic acid, 3-amino-2-naphthoic acid, 4 -Amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-2-naphthoic acid,
Examples thereof include 7-amino-2-naphthoic acid and 8-amino-2-naphthoic acid.

As the alicyclic monocarboxylic acid, more specifically, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid,
3-methylcyclopentanecarboxylic acid, 1-phenylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid Acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid,
4-phenylcyclohexanecarboxylic acid, 1-phenylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-
Examples thereof include butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, 1-cycloheptenecarboxylic acid, 1-methylcycloheptanecarboxylic acid, 4-methylcycloheptanecarboxylic acid and cyclohexylacetic acid. As the aromatic monocarboxylic acid, more specifically, benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, p-
Ethylbenzoic acid, p-propylbenzoic acid, pn-butylbenzoic acid, pi-butylbenzoic acid, ps-butylbenzoic acid, pt-
Butylbenzoic acid, pn-amylbenzoic acid, pi-amylbenzoic acid, ps-amylbenzoic acid, pt-amylbenzoic acid, p-hexylbenzoic acid, o-phenylbenzoic acid, p-phenylbenzoic acid, p-cyclohexylbenzoic acid Examples thereof include acids, phenylacetic acid, phenylpropionic acid, phenylbutyric acid and the like. The monoamine which is a raw material of the amide compound shown above is the same as the monoamine which is a raw material of the amide compound shown above. These compounds A may be used alone or in combination of two kinds. The compounding ratio of the compound A is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, relative to 100 parts by weight of HCPP (H). 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 which are usually added to the crystalline propylene polymer, for example, phenol type, thioether type and phosphorus type 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, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide. ,
Calcium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal fiber, etc., coupling agent (for example, silane-based, titanate-based, boron-based) , An aluminate type, a zircoaluminate type, etc.), the inorganic or organic filler (eg, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with a surface treatment agent such as Can be used in combination within the range that does not impair.

The composition of the present invention is prepared by adding compound A 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.

[0017]

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 displacing a stainless steel reactor with an inclined blade with an internal volume of 20 l with nitrogen gas, n-hexane 15 l, diethylaluminum monochloride 42 g, and solid product (iii) 30 g were added to room temperature. Then, add 15Nl of hydrogen and add propylene partial pressure of 5kg / cm.
Reacted at ² G for 5 minutes, unreacted propylene, hydrogen and n-
Hexane was removed under reduced pressure to obtain the preactivated catalyst (vi) in the form of powder (82.0 g reaction of propylene per 1 g of the solid product (iii)).

(3) Polymerization of Propylene 100 liters of dried n-hexane was placed in a stainless steel polymerization vessel with a turbine type stirring blade having an internal volume of 250 liters, 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 10 kg / cm ² G. And the temperature
After continuing the polymerization for 4 hours while maintaining the pressure at 70 ° C. and the pressure at 10 kg / cm ² G, 25 l of methanol was supplied and the temperature was raised to 80 ° C. After 30 minutes, 100 g of 20% by weight sodium hydroxide aqueous solution was further added, and the mixture was stirred for 20 minutes, and after adding 50 l of pure water, residual propylene was discharged. After extracting the water layer,
Add 50 l of pure water, wash with stirring for 10 minutes, extract the water layer,
Further, extract the HCPP (H) -n-hexane slurry,
The slurry is filtered and the filtrate is dried to give white HCPP.
(H) 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 obtained in Production Examples 1 to 3
(H) is referred to as HCPP (H)-[1], HCPP
Abbreviated as (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'-dicyclohexyl terephthalamide, N, N'-dicyclohexyl-1,
4-Cyclohexanedicarboxamide or N, N'-dicyclohexyl-2,6-naphthalene dicarboxamide and other additives were added to Henschel Mixer (trade name) in the prescribed proportions shown in Table 2 below. Three
After stirring and mixing for 2 minutes, 200 ° C with a twin-screw extruder with a diameter of 30 mm
Was melt-kneaded and pelletized. Comparative Examples 1 to 1
As 100 parts by weight of powdered HCPP (H)-[1] having an MFR of 2.5 g / 10 min, which was not stabilized, was added a predetermined amount of each of the additives shown in Table 2 to be described in Examples 1 to 1. Melt-kneading was carried out according to No. 8 to obtain pellets. The test piece used for evaluation of tensile elongation was obtained by pelletizing the obtained pellets at a resin temperature of 250.
It was prepared by injection molding at a mold temperature of 50 ° C. The tensile elongation was evaluated by the above-mentioned test method using the obtained test piece. The results are shown in Table 2.

Examples 9 to 16 and Comparative Examples 3 to 4 The 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'-dicyclohexyl-4,4'-biphenyldicarboxamide as compound A, N,
N'-bis (p-methylphenyl) hexanediamide or N, N'-bis (p-ethylphenyl) hexanediamide and other additives were added in predetermined amounts in the proportions shown in Table 3 below to a Henschel mixer ( Put in product name) 3
After stirring and mixing for 2 minutes, 200 ° C with a twin-screw extruder with a diameter of 30 mm
Was melt-kneaded and pelletized. Comparative Example 3 to
No. 4 was mixed with 100 parts by weight of unstabilized powdered HCPP (H)-[2] having an MFR of 10.6 g / 10 min, and each of the additives shown in Table 3 below was added in a predetermined amount. According to No. 16, melt-kneading treatment was performed to obtain pellets. The test piece used to evaluate the tensile elongation was obtained by pelletizing the pellets at a resin temperature of 25
It was prepared by injection molding at 0 ° 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 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
To 100 parts by weight of (H)-[3], N, N'-bis (4-cyclohexylphenyl) hexanediamide as compound A, p-
(N-Cyclohexanecarbonylamino) benzoic acid cyclohexylamide or δ- (N-benzoylamino) -n
-Put each predetermined amount of anilide valerate and other additives into the Henschel mixer (trade name) in the mixing ratio shown in Table 4 below, stir and mix for 3 minutes, and then calibrate 30 mm
Was melt-kneaded at 200 ° C. with a twin-screw extruder to produce pellets. In addition, as Comparative Examples 5 and 6, 100 parts by weight of unstabilized powdered HCPP (H)-[3] having an MFR of 34.0 g / 10 min were blended with respective predetermined amounts of the additives shown in Table 4 below. The pellets were obtained by melt-kneading according to Examples 17-24. 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. These results are shown in Table 4.
It was shown to.

The compounds and additives relating to the present invention shown in Tables 2 to 4 are as follows. Compound A [1]: N, N'-dicyclohexylterephthalamide Compound A [2]: N, N'-dicyclohexyl-1,4-cyclohexanedicarboxamide Compound A [3]: N, N'-dicyclohexyl-2, 6-naphthalenedicarboxyamide compound A [4]: N, N'-dicyclohexyl-4,4'-biphenyldicarboxamide compound A [5]: N, N'-bis (p-methylphenyl) hexanediamide compound A [6]: N, N'-bis (p-ethylphenyl) hexanediamide Compound A [7]: N, N'-bis (4-cyclohexylphenyl) hexanediamide Compound A [8]: p- (N-cyclohexane Carbonylamino) benzoic acid cyclohexylamide Compound A [9]: δ- (N-benzoylamino) -n-valeric acid anilide Phenolic type antioxidant 1: 2,6-di-t-butyl-p-cresol Phenolic type 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

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[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 amount of the compound A according to the present invention do not exhibit the effects of the present invention. That is, it can be said that the tensile elongation obtained in the present invention is a unique effect that can be seen only when compound A is mixed with HCPP (H). Tables 3 to 4 use HCPP (H)-[2] and HCPP (H)-[3] as crystalline propylene polymers, respectively, and the same effects as above were confirmed for these. .

[0029]

INDUSTRIAL APPLICABILITY The composition of the present invention is a crystalline propylene polymer composition capable of obtaining a molded product having a remarkably excellent tensile elongation when the molded product is formed even though HCPP (H) is used. is there.

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[Procedure amendment]

[Submission date] January 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

In the composition of the present invention, various additives which are usually added to the crystalline propylene polymer, for example, phenol type, thioether type and phosphorus type 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.

Claims (1)

[Claims] 1. Isotactic pentad fraction (P) and melt flow rate (MFR: load at 230 ° C. 2.16 k)
The relationship with the amount of melted resin discharged for 10 minutes (when g is added) is 1.00 ≧ P ≧ 0.015 log MFR + 0.955 with respect to 100 parts by weight of a crystalline propylene homopolymer, one selected from the following Or 0.001 of two or more amide compounds
A crystalline propylene polymer composition containing 1 part by weight to 1 part by weight. _{R 2 -NHCO-R 1 -CONH-} R 3 R 5 -CONH-R 4 in -CONH-R ₆ (wherein, R ₁ is an aliphatic saturated or unsaturated 1 to 28 carbon atoms, alicyclic or aromatic the dicarboxylic acid residues of the family, R ₂
And R ₃ are the same or different and are a cycloalkyl group or cycloalkenyl group having 3 to 18 carbon atoms, and 7 to 7 carbon atoms.
18 alkylphenyl group, alkenylphenyl group, cycloalkylphenyl group, biphenyl group, alkylcyclohexyl group, alkenylcyclohexyl group, cycloalkylcyclohexyl group or phenylcyclohexyl group or phenylalkyl group or cyclohexylalkyl group having 7 to 10 carbon atoms, R ₄ is a saturated or unsaturated aliphatic, alicyclic or aromatic amino acid residue having 1 to 28 carbon atoms, R ₅ and R ₆ are the same or different, and a cycloalkyl group having 3 to 18 carbon atoms or Cycloalkenyl group, phenyl group, alkylphenyl group having 7 to 18 carbon atoms,
An alkenylphenyl group, a cycloalkylphenyl group, a biphenyl group, an alkylcyclohexyl group, an alkenylcyclohexyl group, a cycloalkylcyclohexyl group or a phenylcyclohexyl group, or a phenylalkyl group having 7 to 10 carbon atoms or a cyclohexylalkyl group is shown. )