JPH07133399A - Crystalline propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain a polymer composition excellent in tensile elongation, impact resistance, high-temperature rigidity, etc., by incorporating a specified amount of a specified amide compound into a crystalline ethylene/propylene block copolymer having a specified composition and specified properties. CONSTITUTION:A first-step polymer comprising a crystalline propylene homopolymer of which the relation between the isotactic pentad fraction P and the melt flow rate MFR satisfies the formula I is produced. 70-95wt.%, based on the total polymer, of the first-step polymer is polymerized in at least one step with 30-5wt.%, based on the total polymer, ethylene optionally mixed with propylene to produce a crystalline ethylene/propylene block copolymer having an ethylene content of 3-20wt.%. 100 pts.wt. of this copolymer is then mixed with 0.001-1 pt.wt. amide compound of formula II or III (R1 is a 1-28C dicarboxylic acid; R2, R3, R5 and R6 are each a 3-18C cycloalkyl, etc.; and R4 is a 1-28C amino acid) (e.g. N,N'-dicyclohexylterephthalamide).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a tensile elongation and a resistance to elongation obtained by blending a crystalline ethylene-propylene block copolymer having a specific isotactic pentad fraction with a specific amount of a specific amide compound. The present invention relates to a crystalline propylene polymer composition capable of obtaining a molded article excellent in impact resistance and heat resistance rigidity.

[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.

Further, depending on the specific use of the crystalline propylene polymer, it may not be said that the impact resistance is sufficient, so that it is used for a molded product which receives a mechanical shock or a molded product which is used at a low temperature. It has the drawback of being difficult. Generally, the rigidity and impact resistance of a plastic material are incompatible with each other, and it is often extremely difficult to improve and improve the former and the latter at the same time. For specific applications of the crystalline propylene polymer and further for expanding demand, it is required to further improve not only the above-mentioned impact resistance but also the rigidity. By improving these physical properties, other general-purpose resins such as high impact polystyrene (HIPS)
It is possible to use crystalline propylene polymers in fields of application where resins or ABS resins are used. Several proposals have been made for improving the impact resistance of crystalline propylene polymers. In particular, the method of block copolymerizing propylene with ethylene is well known. The obtained crystalline ethylene-propylene block copolymer has a remarkable improvement in low temperature impact resistance as compared with the crystalline propylene homopolymer, but has a drawback that the rigidity is lowered. Therefore, for the purpose of improving the rigidity of the crystalline ethylene-propylene block copolymer, it has a specific isotactic pentad fraction in JP-A-58-201816 relating to the application of the same applicant as the present application. Crystalline ethylene-propylene block copolymers have been proposed. In addition, in this publication, the crystalline ethylene-propylene block copolymer is added to the polymer for the purpose of further improving the rigidity.
It is described that an organic nucleating agent such as -t-butyl aluminum benzoate or 1,3,2,4-dibenzylidene sorbitol, that is, an α crystal nucleating agent is blended.

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.

[0005]

However, the crystalline ethylene-propylene block copolymer having a specific isotactic pentad fraction proposed in JP-A-58-201816 has a considerably improved rigidity. However, there is a drawback that the tensile elongation is significantly reduced,
In addition, impact resistance and heat resistance rigidity are not yet fully satisfactory. Further, in JP-A-5-262936, the tensile strength of a molded product obtained from a composition using a crystalline ethylene-propylene block copolymer having a specific isotactic pentad fraction as a crystalline polypropylene resin. There is no description or suggestion that the elongation, impact resistance and heat resistance are improved, and in this publication, a transition metal compound as a crystalline polypropylene resin is supported on a carrier containing magnesium halide as a main component. Although it is described as a polypropylene resin prepared by using a high activity catalyst system comprising a combination of the catalyst and an alkylaluminum compound, a high activity and high stericity obtained by combining the high activity catalyst system with an electron donor catalyst component. The polypropylene-based resin prepared using the ordered catalyst composition is neither described nor suggested.

The present inventors have sought to obtain a crystalline propylene polymer composition which gives a molded article having the above-mentioned problems relating to the crystalline propylene polymer composition, that is, tensile elongation, impact resistance and thermal rigidity. I studied hard. As a result, the crystalline ethylene-propylene block copolymer having a specific isotactic pentad fraction has an aliphatic group,
A crystalline propylene polymer composition containing a specific amount of an alicyclic or aromatic dibasic acid-based diamide and / or an amino acid-based diamide gives a molded article with improved tensile elongation, impact resistance and heat resistance. It was found that the composition was a composition, 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 product with improved tensile elongation, impact resistance and heat resistance when molded. Is.

[0007]

The present invention has the following constitution. The first-stage polymer, in which the relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of the crystalline propylene homopolymer is 1.00 ≧ P ≧ 0.015 log MFR + 0.955, is 70% of the total polymer amount. Crystals obtained by polymerizing ethylene or ethylene and propylene in one or more steps in an amount of from 30 to 5% by weight based on the total amount of the polymer, and having an ethylene content of from 3 to 20% by weight based on the total amount of the polymer. Ethylene-
A crystalline propylene polymer obtained by blending 0.001 to 1 part by weight of one or more kinds of amide compounds (hereinafter referred to as compound A) selected from the following to 100 parts by weight of propylene block copolymer. Combined 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. )

In the crystalline ethylene-propylene block copolymer used in the present invention, the relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of the crystalline propylene homopolymer is 1.00 ≧ P ≧ 0.015 log MFR +
The first stage polymer, which is 0.955, is 70 to 95% by weight of the total amount of polymer, and then 30 to 5% by weight of the total amount of ethylene or ethylene and propylene are polymerized in one or more steps to contain ethylene. It is a crystalline ethylene-propylene block copolymer (hereinafter abbreviated as HCPP (B)) in an amount of 3 to 20% by weight based on the total amount of the polymer. HCPP (B)
Is 70 to 95% of the total polymer amount (excluding the polymer soluble in the polymerization solvent) in the first stage polymerization.
Polymerize wt% propylene. Then, after the second step, ethylene or ethylene and propylene are polymerized in one or more steps. After the second step, 30 to 5% by weight of the total amount of the above-mentioned polymer, ethylene or ethylene and propylene are polymerized in one or more steps. However, the ethylene content in the finally obtained polymer (excluding the soluble polymer eluted in the polymerization solvent) must be within the range of 3 to 20% by weight based on the total amount of the polymer. Therefore, when only 70% by weight of propylene is polymerized in the first stage, the amount of ethylene that is block-copolymerized in the second stage is limited to 20% by weight or less. For the remaining 10 to 27% by weight, propylene or other α-olefins other than ethylene must be block-copolymerized. However the first
When 80% by weight of propylene is polymerized in the second stage, only 20% by weight of ethylene can be polymerized in the second stage. As described above, in the second stage, ethylene alone or ethylene and propylene or other α may be used within the limits of the stage in which ethylene can be polymerized and the ethylene content in the whole polymer. -The block copolymerization can be carried out in a single stage or in multiple stages by mixing with an olefin. Such HCPP (B) can be produced, for example, by the production method described in JP-A-58-201816, which is related to the application of the same applicant as the present application. That is, a reaction product of an organoaluminum compound (i) (eg, triethylaluminum, diethylaluminum monochloride, etc.) or an organoaluminum compound (i) and an electron donor (eg, diisoamyl ether, ethylene glycol monomethyl ether, etc.)
Solid product (i) obtained by reacting (v) with titanium tetrachloride (i
The solid product (iii) obtained by further reacting i) 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. Carboxylic acid ester
(iv) (for example, ethyl benzoate, methyl p-toluate,
p-toluylate, 2-ethylhexyl p-toluate, etc.) to prepare a catalyst having a molar ratio of the aromatic carboxylic acid ester (iv) to the solid product (iii) iv / iii = 0.1 to 10.0. In the presence of 70 to 95% by weight of total polymer of propylene is polymerized, and then 30 to 5% by weight of total polymer of ethylene or ethylene and propylene are polymerized in one step or more to give an ethylene content of 3 to 3%. It can be obtained by copolymerization so that the content of the compound becomes 20% by weight. In addition, 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 and an organoaluminum catalyst component supported on magnesium halide 70 to 95% by weight of the combined amount of propylene is polymerized, and then 30 to 5% by weight of the total amount of ethylene or ethylene and propylene are polymerized in one or more steps to obtain an ethylene content of 3 to 20% by weight. It can also be obtained by copolymerization (preferably a deashing-free process). The above-mentioned one stage means one segment of continuous or temporary supply of these monomers.

Here, the isotactic pentad fraction
(P) means Macromolecules, Volume 6, Issue 6, November
December, pp. 925-926 (1973) [Macromolecules, Vol.
6, No. 6, November-December, 925-926 (197
3)], that is, the isotactic fraction in the pentad unit in the propylene-based polymer molecular chain, which is measured using ¹³ C-NMR. In other words, the fraction means the fraction of propylene monomer units in which five propylene monomer units are continuously isotactically bonded. The attribution of the peak of the spectrum in the measurement using the above ¹³ C-NMR is determined by Macromolecules, Volume 8, No. 5, September to October, pages 687 to 689 (1975
Year) [Macromolecules, Vol. 8, No. 5, September
-October, 687-689 (1975)]. 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 (B)
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. The MFR is measured at 230 ° C. under a load of 2.16 kg according to JIS K 7210, and the ethylene content is measured by an infrared absorption spectrum method.

Further, the HCPP (B) used in the present invention contains a usual crystalline propylene 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 compounds shown above as the compound A used in the present invention amidate 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.

Specific examples of the alicyclic monoamine include 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 compounds shown above as the compound A used in the present invention are 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 (B). When the amount is less than 0.001 part by weight, the effect of improving tensile elongation, impact resistance and heat resistance is not sufficiently exerted, and when it is more than 1 part by weight, the tensile elongation, impact resistance and Not only is it impractical because the effect of improving heat resistance cannot be expected, it is also uneconomical.

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, 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 comprises the compound A added to HCPP (B).
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.

[0018]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. 1) Tensile elongation: evaluated by a tensile test. That is, a JIS No. 1 test piece with a length of 175 mm, a width of 10 mm, and a thickness of 3.3 mm was prepared by using the obtained pellets by an injection molding method, and the tensile elongation was measured using the test piece (based on JIS K 7113). did. A material having an excellent tensile elongation means a material having a large tensile elongation. 2) Heat resistance rigidity: Evaluated by a deflection temperature under load test. That is, using the obtained pellets length 130 mm, width 13 mm,
A test piece having a thickness of 6.5 mm was prepared by an injection molding method, and the heat distortion temperature was measured using the test piece (according to JIS K 7207;
4.6 kgf / cm ² load) to evaluate the heat resistance rigidity.
A material having high heat resistance and rigidity means a material having a high heat distortion temperature. 3) Impact resistance: evaluated by the Izod impact test. That is, using the obtained pellets length 63.5 mm, width 13 mm,
A 3.5 mm-thick test piece (having a notch) was prepared by an injection molding method, and the test piece was used to measure the Izod impact strength at 23 ° C. (according to JIS K 7110) to evaluate the impact resistance. A material having excellent impact resistance means a material having a high Izod impact strength.

Production Examples 1 to 3 (Examples of production of HCPP (B) used in Examples 1 to 22 and Comparative Examples 1 to 2 and 5 to 8) (1) Preparation of catalyst n-hexane 600 ml, diethyl aluminum monochloride ( DEAC) 0.50 mol and diisoamyl ether 1.20 mol were mixed at 25 ° C. for 1 minute and reacted at the same temperature for 5 minutes to produce a reaction product liquid (v) (diisoamyl ether / DEAC molar ratio).
2.4) was obtained. Titanium tetrachloride 4.0 in a reactor purged with nitrogen
Add the mole and heat to 35 ° C, and add the above reaction product solution (v) to it.
After dripping the entire amount of the above in 180 minutes, keep it at the same temperature for 30 minutes, raise the temperature to 75 ℃ and react for another 1 hour, then room temperature (20 ℃)
The mixture was cooled to 4, the supernatant was removed, 4,000 ml of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain 190 g of a solid product (ii). The total amount of this solid product (ii) was suspended in 3,000 ml of n-hexane at 20 ° C.
Then, 160 g of diisoamyl ether and 350 g of titanium tetrachloride were added at room temperature for about 1 minute and reacted at 65 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, 4,000 ml of n-hexane was added, the mixture was stirred for 10 minutes, allowed to stand, and the procedure of removing the supernatant was repeated 5 times. It was dried under reduced pressure to obtain a solid product (iii). (2) Preparation of pre-activated catalyst After 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 method Dry n-hexane 250 l was placed in a stainless steel polymerization vessel with a turbine type stirring blade having an internal volume of 400 l, which was replaced with nitrogen gas.
Then 10 g of diethylaluminum monochloride, 10 g of the preactivated catalyst (vi) and 11.0 g of methyl p-toluate.
Further, hydrogen was added so that the concentration of hydrogen in the gas phase gas was 6 mol% in Production Example 1, 8 mol% in Production Example 2 and 10 mol% in Production Example 3, respectively. Then the temperature inside the vessel
After the temperature was raised to 70 ° C., propylene was supplied into the vessel to raise the pressure in the vessel to 10 kg / cm ² G. And the temperature is 70 ℃, the pressure is
After maintaining the polymerization at 10 kg / cm ² G for 4 hours, the propylene supply was stopped, unreacted propylene was discharged, and a part of the slurry in the polymerization vessel was collected, filtered, washed and dried. A white crystalline propylene homopolymer powder was obtained.
The obtained crystalline propylene homopolymer was used for determining the melt flow rate (MFR) and the isotactic pentad fraction (P) described above. The results of these analyzes are shown in Table 1.
It was shown to. After releasing unreacted propylene, the inside of the polymerization vessel was maintained at a temperature of 60 ° C. and a pressure of 0.1 kg / cm ² G, and the supply ratio of ethylene as the second stage polymerization raw material was 33% by weight in Production Examples 1 to 3.
And the total ethylene supply is 2.4 kg in Production Example 1, 5.4 kg in Production Example 2 and 8.8 k in Production Example 3.
Ethylene and propylene were continuously fed for 2 hours so as to be g. After the polymerization for 2 hours, the supply of ethylene and propylene was stopped, and unreacted ethylene and propylene were discharged. Then, 25 l of methanol was supplied into the polymerization vessel, and the temperature was raised to 75 ° C. After 30 minutes, an additional 20% by weight
100 g of the aqueous sodium hydroxide solution was added and stirred for 20 minutes, 100 l of pure water was added, and then residual propylene was discharged. After extracting the water layer, 100 l of pure water was added, and the mixture was stirred and washed with water for 10 minutes. The water layer was extracted, and further HCPP (B) -n-
The hexane slurry was extracted, the slurry was filtered, and the filtered material was dried to obtain a white HCPP (B) powder. The obtained HCPP (B) was used to determine the above-mentioned melt flow rate (MFR) and each ethylene content. The results of these analyzes are shown in Table 1. In addition, the HCPP (B) obtained in Production Examples 1 to 3 is referred to as HCPP (B)-[1] and H, respectively.
It is abbreviated as CPP (B)-[2] and HCPP (B)-[3].

Production Example 4 (Crystalline ethylene-propylene block copolymer used in Comparative Examples 3 to 4 (hereinafter PP (B)
Is abbreviated. )) N-hexane 250 l dried in a stainless steel polymerization vessel with a turbine type stirring blade having an internal volume of 400 l, which was replaced with nitrogen gas
Next, 10 g of diethylaluminum monochloride, 30 g of a commercially available catalyst (AA type) obtained by reducing titanium tetrachloride with aluminum metal and activated by crushing, and 11.0 g of methyl p-toluate.
Was charged, and hydrogen was further added so that the concentration of the gas in the gas phase gas was maintained at 8 mol%. Then, after raising the temperature in the vessel to 70 ° C., propylene was fed into the vessel to increase the pressure in the vessel to 10 kg /
The pressure was raised to cm ² G. And the temperature is 70 ℃, the pressure is 10kg / cm ² G
After continuing the polymerization for 4 hours while maintaining at 1, the propylene supply was stopped, unreacted propylene was discharged, and a part of the slurry in the polymerization vessel was collected, filtered, washed and dried to obtain white crystalline propylene. A homopolymer powder was obtained. The obtained polymer was used to determine the melt flow rate (MFR) and the isotactic pentad fraction (P) described above. The results of these analyzes are shown in Table 1. After releasing the unreacted propylene, the temperature inside the polymerization vessel was kept at 60 ° C and the pressure was 0.1 kg / cm ² G, and the supply ratio of ethylene as the second stage polymerization raw material was changed.
Maintaining 33% by weight, the total ethylene supply is 5.
Ethylene and propylene were continuously fed for 2 hours so that the amount became 4 kg. After the polymerization for 2 hours, the supply of ethylene and propylene was stopped, and unreacted ethylene and propylene were discharged. Then, supply 25 l of methanol into the polymerization vessel,
The temperature was raised to 75 ° C. After 30 minutes, add 100 g of 20% by weight aqueous sodium hydroxide solution and stir for 20 minutes to obtain 100 parts of pure water.
After adding l, residual propylene was discharged. After extracting the aqueous layer, 100 l of pure water was further added, and the mixture was washed with stirring for 10 minutes, the aqueous layer was extracted, the PP (B) -n-hexane slurry was further extracted, the slurry was filtered, and the filtered material was dried. To obtain white PP (B) powder. The obtained PP (B) was used to determine the above-mentioned melt flow rate (MFR) and each ethylene content. The results of these analyzes are shown in Table 1.

Examples 1 to 6, Comparative Examples 1 to 4 MF produced in Production Example 2 as a crystalline propylene polymer
R9.0g / 10min unstabilized powdered HCPP (B)
-[2] (Ethylene content 8.5% by weight) 100 parts by weight, as compound A, N, N'-dicyclohexylterephthalamide, N, N'-dicyclohexyl-1,4-cyclohexanedicarboxamide or N, N'- Predetermined amounts of dicyclohexyl-2,6-naphthalene dicarboxamide and other additives were added to the Henschel mixer (trade name) at the compounding ratios shown in Table 2 below, and the mixture was stirred and mixed for 3 minutes.
A twin screw extruder having a diameter of 30 mm was melt-kneaded at 200 ° C. to form pellets. As Comparative Examples 1 to 4, MFR is 9.0 g /
10 minutes unstabilized powdered HCPP (B)-[2]
(Ethylene content 8.5% by weight) or MFR produced in Production Example 4 8.1 g / 10 min unstabilized powdered PP
Example 1 was prepared by blending 100 parts by weight of (B) (ethylene content of 8.3% by weight) with predetermined amounts of the additives shown in Table 2 below.
Melt-kneading treatment according to No. 6 to obtain pellets. The test pieces used for evaluation of tensile elongation, heat resistance and impact resistance are obtained pellets with a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Was prepared by injection molding. Using the test pieces thus obtained, the tensile elongation, heat resistance and impact resistance were evaluated by the test methods described above. The results are shown in Table 2.

Examples 7-14, Comparative Examples 5-6 MF produced in Production Example 1 as a crystalline propylene polymer
R8.5g / 10min unstabilized powdered HCPP (B)
-[1] (Ethylene content 4.2% by weight) 100 parts by weight, as compound A, N, N'-dicyclohexyl-4,4'-biphenyldicarboxamide, N, N'-bis (p-methylphenyl) hexane Predetermined amounts of diamide or N, N'-bis (p-ethylphenyl) hexanediamide and other additives were placed in a Henschel mixer (trade name) at the compounding ratios shown in Table 3 below, and stirred and mixed for 3 minutes. Then, the mixture was melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Also, as Comparative Examples 5 and 6, MFR is 8.5 g / 10
100 parts by weight of non-stabilized powdered HCPP (B)-[1] (ethylene content of 4.2% by weight) was blended with a predetermined amount of each of the additives shown in Table 3 to be described in Examples 7 to 10. Melt-kneading was carried out according to 14 to obtain pellets. Test pieces used for evaluation of tensile elongation, heat resistance and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the test pieces thus obtained, the tensile elongation, heat resistance and impact resistance were evaluated by the test methods described above. The results are shown in Table 3.

Examples 15-22, Comparative Examples 7-8 MF produced in Production Example 3 as crystalline propylene polymer
R7.7g / 10min unstabilized powdered HCPP (B)
-[3] (Ethylene content 12.1% by weight) in 100 parts by weight, as compound A, N, N'-bis (4-cyclohexylphenyl) hexanediamide, p- (N-cyclohexanecarbonylamino) benzoic acid cyclohexylamide or δ -
Predetermined amounts of (N-benzoylamino) -n-valeric acid anilide and other additives were placed in a Henschel mixer (trade name) at the compounding ratios shown in Table 4 below, and the mixture was stirred and mixed for 3 minutes, and then the bore diameter was 30 mm. Was melt-kneaded at 200 ° C. with a twin-screw extruder to produce pellets. Further, as Comparative Examples 7 to 8, unstabilized powdered HCP having MFR of 7.7 g / 10 min.
100 parts by weight of P (B)-[3] (ethylene content 12.1% by weight) was mixed with a predetermined amount of each of the additives shown in Table 4 below, and melt-kneaded according to Examples 39 to 46. To obtain pellets. Test pieces used for evaluation of tensile elongation, heat resistance and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the test pieces thus obtained, the tensile elongation, heat resistance and impact resistance were evaluated by the test methods described above. 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'-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

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

The examples shown in Table 2 are HCPP (B)-[2] as the crystalline propylene polymer, and the comparative examples are HCPP (B)-[2] or PP as the crystalline propylene polymer.
This is the case when (B) is used. As can be seen from Table 2, Examples 1 to 6 are compounds in which the compound A is blended with HCPP (B)-[2] according to the present invention. Examples 1 to 6 and Comparative Example 1
When compared with (without compounding compound A in Examples 1 to 6), Examples 1 to 6 are remarkably excellent in tensile elongation, heat resistance and impact resistance. Instead of Compound A in Examples 1 to 6, JP-A-58-201816
Comparing Comparative Example 2 and Examples 1 to 6 in which the α-crystal nucleating agent described in Japanese Patent Laid-Open No. 2003-242242 is compared, the tensile elongation of Comparative Example 2 is almost improved as compared with Comparative Example 1. However, the tensile elongations of Examples 1 to 6 are remarkably excellent, and the heat resistance of Comparative Example 2 is about the same, but the impact resistance is Comparative Example 1.
As is clear from the comparison, there is almost no improvement, and it can be seen that Examples 1 to 6 have remarkably excellent impact resistance.
That is, it can be seen that even if the α crystal nucleating agent other than the compound A is blended, the effect of improving the tensile elongation and the impact resistance is hardly recognized. Further, crystalline ethylene outside the scope of the present invention
-Impact resistance of propylene block copolymer, that is, Comparative Example 3 in which compound A is not compounded to PP (B), Comparative example 4 in which compound A is compounded, Comparative example 1 and Examples 1 to 6 by compounding compound A In comparison with the degree of improvement in heat resistance and rigidity, the HCPP (B) type as a crystalline propylene polymer composition containing compound A has a better degree of improvement in impact resistance and heat resistance than the PP (B) type. You can see that Therefore, it is apparent that the comparative examples that do not satisfy the compounding of the compound A in the HCPP (B) according to the present invention do not exhibit the effects of the present invention. That is, the tensile elongation, impact resistance and heat resistance obtained by the present invention are
It can be said that this is a unique effect that can be seen only when compound A is added to (B). Tables 3 and 4 show that HCPP (B)-[1] and HCPP are crystalline propylene polymers, respectively.
(B)-[3] was used, and the effects similar to those described above were confirmed for these.

[0031]

Industrial Applicability The composition of the present invention is a crystalline propylene polymer composition which, when formed into a molded product, gives a molded product having extremely excellent tensile elongation, impact resistance and heat resistance.

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[Procedure amendment]

[Submission date] January 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

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.

Claims (1)

[Claims] 1. An isotactic pentad fraction (P) and a melt flow rate (M) of a crystalline propylene homopolymer.
FR) has a relationship of 1.00 ≧ P ≧ 0.015 log MFR + 0.955 with 70 to 95% by weight of the total amount of polymer, followed by 30 to 5% by weight of the total amount of ethylene or ethylene. And 100% by weight of a crystalline ethylene-propylene block copolymer having an ethylene content of 3 to 20% by weight based on the total amount of polymer obtained by polymerizing propylene and propylene in one or more steps. A crystalline propylene polymer composition containing 0.001 to 1 part by weight of one or more amide compounds. _{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. )