JPH01104639A - High-rigidity propylene homopolymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having high rigidity and heat-resistant rigidity, by blending a polymer having a specific relation between isotatic pentad fraction (P) and melt index and specific values (P) of extracts with boiling n-hexane and boiling n-heptane with a specific nucleating agent. CONSTITUTION:The aimed composition obtained by polymerizing propylene using a polymerization catalyst consisting of an organoaluminum compound, electron donor and titanium tetrachloride, etc., under pressure while heating to provide crystalline propylene homopolymer having the relation between an isotatic pentad fraction (P) and melt flow rate (MFR; the amount of a molten resin discharged for 10min when a load of 2.16kg is applied at 230 deg.C) satisfying formula I and 0.450-0.700 and 0.750-0.930 isotatic pentad fractions (P) of extracts prepared by successively extracting with boiling n-hexane and boiling n-heptane and then blending 100pts.wt. resultant polymer with 0.01-1pt.wt. phosphate based compound expressed by formula II (R is H, 1-18C alkyl, phenyl, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly rigid propylene homopolymer composition. More specifically, the present invention relates to a highly rigid propylene homopolymer composition from which a molded article with significantly superior rigidity and heat-resistant rigidity can be obtained.

[Prior art] Generally, propylene polymers have excellent processability, chemical resistance,
Because it has electrical and mechanical properties, it is processed into injection molded products, blow molded products, films, sheets, fibers, etc. and used for various purposes.

However, depending on various specific uses, these properties may not be sufficient, and there is a problem in that the expansion of the specific uses is limited.

Especially when it comes to rigidity such as rigidity and heat resistance,
Because it is inferior to polyesters such as polystyrene, ABS resin, polyethylene terephthalate, and polybutylene terephthalate, it has become a serious bottleneck in expanding the use of propylene polymers. Therefore, if it is possible to improve the rigidity (rigidity and heat resistance rigidity), it will be possible to make the molded product thinner, which will not only contribute to resource conservation, but also increase the cooling rate during molding. Therefore, the molding speed per unit time can be increased, contributing to improved productivity.

For this reason, various nucleating agents have been used singly or in combination for the purpose of improving the rigidity of propylene polymers. On the other hand, JP-A-58-104905 and JP-A-58-104906 filed by the same applicant as the present application
Crystalline propylene homopolymers having a specific isotactic pentad fraction are disclosed in JP-A-58-104907 and JP-A-59-22913. Further, in each of the above-mentioned publications, an organic nucleating agent such as aluminum pt-butylbenzoate or 3,2-dibenzylidene sorbitol is added to the crystalline propylene homopolymer for the purpose of further improving the rigidity. is disclosed.

[Problems to be Solved by the Invention] However, propylene polymer compositions prepared by blending various conventionally known nucleating agents with ordinary propylene polymers still have a sufficiently satisfactory improvement effect in terms of rigidity. It's not a thing. Said JP-A-58-104905, JP-A-Sho 58
・Crystalline propylene polymers having specific isotactic pentad fractions disclosed in JP-A No. 104906, JP-A-58-104907, and JP-A-59-22913 are manufactured by Although the rigidity is considerably improved without adding a nucleating agent, it is still not completely satisfactory. In addition, ρ
-t-butylbenzoate aluminum or I-3,2
Although propylene homopolymer compositions containing organic nucleating agents such as dibenzylidene sorbitol have been shown to significantly improve stiffness, they are still not suitable for use in applications that require a high degree of stiffness. It's not completely satisfying.

The inventors of the present invention have conducted extensive research in order to solve the above-mentioned problems regarding the propylene-based polymer compositions containing the various nucleating agents described above, that is, the problems of rigidity and heat-resistant rigidity.

As a result, a composition obtained by blending a phosphate compound represented by the following formula [1] (hereinafter referred to as compound A) with a crystalline propylene homopolymer having a specific isotactic pentad fraction was obtained. discovered that the problems of the above-mentioned propylene-based polymer compositions could be solved, and based on this knowledge, completed the present invention.

(However, in the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group, or a phenoxy group.) As is clear from the above description, the purpose of the present invention is to improve rigidity. Another object of the present invention is to provide a propylene homopolymer composition from which a molded article having extremely excellent heat resistance and rigidity can be obtained.

[Means for solving problems] The present invention has the following configuration.

The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR; the amount of molten resin discharged in 10 minutes when a load of 2.16 kg is applied at 230°C) is 1.00≧P≧0. 015 Q ogM F R+ 0
．． 955, boiling 111n-hexane and boiling n-
Relative to 100 parts by weight of crystalline propylene alone, the isotactic pentad fraction (P) of the extract sequentially extracted with heptane is 0.450 to 0.700 and 0.750 to 0.930, respectively. A phosphate compound represented by the following formula [I] (hereinafter referred to as compound A).

) to 0. A highly rigid propylene homopolymer composition comprising 1 to 1 parts by weight of O.

(However, in the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group, or a phenoxy group.) The crystalline propylene homopolymer used in the present invention is an isotactic pen. The relationship between Tad fraction (P) and melt flow rate (MFR) is 1
．． 00≧P≧0.015 Q ogM F R+ 0.
955, and the isotactic pentad fraction (P) of the extract extracted sequentially with boiling Min-hexane and boiling n-heptane is 0.450, respectively.
~0.700 and 0.750-0.930.

Such a crystalline propylene homopolymer can be produced by the production method described in Japanese Patent Application Laid-open No. 104907/1985, filed by the same applicant as the present application. That is,
Organoaluminum compound (I) (e.g. triethylaluminum, diethylaluminum monochloride, etc.)
Alternatively, a solid product (n) obtained by reacting a reaction product (V) of an organoaluminum compound (I) and an electron donor (such as diisoamyl ether or ethylene glycol monomethyl ether) with titanium tetrachloride, Furthermore, a solid product (In) obtained by reacting an electron donor and an electron acceptor (for example, anhydrous aluminum chloride, titanium tetrachloride, vanadium tetrachloride, etc.) is combined with an organoaluminum compound (I) and an aromatic carboxylic acid ester ( ■)(
For example, ethyl benzoate, p-)methyl ruylate, p-
) ethyl ruylate, p-)-2-ethylhexyl ruylate, etc.), and the aromatic carboxylic acid ester (IV
) and the solid product (m) molar ratio ■/m = 0.
It can be obtained by polymerizing propylene in one or more stages in the presence of a catalyst having a molecular weight of 1 to 10.0. A stage in this case means one section of continuous or temporary feeding of these monomers. Here, isotactic pentad fraction (P) is Macromolecules, Vol. 6, No. 6, November-December, pp. 925-926 (
1973) [Macro-molecules,
Vol.6. Na6* November-D
ember.

925-926 (1973)], that is, the isotactic fraction in pentad units in a propylene polymer molecular chain measured using C-NMR. The fraction means the fraction of propylene monomer units in which five consecutive propylene monomer units are isotactic bonded.Determination of the attribution of the spectrum peak in the measurement using the above-mentioned '3C-NMR is as follows: Macromolecules, Volume 8, 5
No., September-IO month, pp. 687-689 (1975)
[Macromolecules, Vol. 8.
Na 5゜September-October,
6B? -689 (1975)]. Incidentally, for the 13C-NMR measurements in the Examples described later, a 270 MHz FT-NMR device was used.
, 000 cumulative measurements, the signal detection limit was improved to an isotactic pentad fraction of o,oot. The above isotactic pentad fraction (
The requirement for the relational expression between P) and melt flow rate (MFR) is that the fraction P of a propylene homopolymer with a low MFR generally decreases. The constituent requirement is to limit the lower limit of . Since P is a fraction, the upper limit is 1.00. Next, the boiling n-hexane extract is usually contained in the propylene homopolymer in a few percent, and the fraction thereof is, for example, o, i.

~0.70, which can vary greatly depending on the propylene polymerization method. The crystalline propylene homopolymer used in the present invention is boiled! The fraction P of the in-hexane extract must be within the range of 0.450 to 0.700; in a composition using an ungrooved homopolymer, the P of the extract must be 0.450. However, the improvement in heat resistance rigidity is insufficient. The fraction P of the extract, which is also subsequently extracted with boiling n-heptane, is equal to the boiling n-heptane mentioned above.
Regarding the residue extracted with hexane, the isotactic pentad fraction of the extract extracted with boiling Mn-heptane is 0. The crystalline propylene homopolymer used in the present invention has a P of this boiling n-heptane extract of 0. .750~0.
Must be within the range of 930, 0.
Although stiffness is improved in compositions using homopolymers with a molecular weight of less than 750, the improvement in heat-resistant stiffness is still insufficient.

Boiling n-hexane and boiling! Although the total amount of the sequential extracts with In-heptane is not limited, the total amount in the raw material crystalline propylene homopolymer is practically 1°0-10
．． Many of them are within the range of C1% by weight, and crystalline propylene homopolymers within this range give more preferable results than those outside the above range. The above-mentioned sequential extraction is performed as follows. That is, granules are prepared by mixing a small amount of antioxidant (for example, 0.1% by weight of 2,6-di-t-butyl-p-cresol) with a powdered crystalline propylene homopolymer and granulating the mixture using an extruder. The product is crushed using a crusher, and the crushed product is crushed into 20
Of the 20 meshes passed through a sieve, 3 g was extracted using a Soxhlet extractor, first with 100 d of boiling 11 en-hexane and then with 100 d of boiling an-heptane for 6 hours each. Add a negative solvent such as methanol, absolute ethanol or acetone to the liquid,
The soluble material is precipitated and the precipitate is separated, dried and weighed.

In addition, the MFR is based on JIS 721O and is 230℃.
, measured with a load of 2.16 kg.

In addition, in the crystalline propylene homopolymer used in the present invention, a crystalline propylene homopolymer or a propylene component having an isotactic pentad fraction outside the scope of the present invention is added to the crystalline propylene homopolymer. Crystalline random combination of propylene containing 70% by weight or more and one or more α-olefins such as ethylene, butene-11pentene-1,4, methyl-pentene-1, hexene-1, octene-1, etc. Polymer or crystalline block copolymer, copolymer of propylene and vinyl acetate or acrylic ester, or saponified product of the copolymer,
A copolymer of propylene and an unsaturated silane compound, a copolymer of propylene and an unsaturated carboxylic acid or its anhydride, a reaction product of the copolymer and a metal ion compound, or a crystalline propylene-based monomer It can also be used as a mixture of modified propylene polymers modified with unsaturated carboxylic acids or derivatives thereof, silane-modified propylene polymers created by modifying crystalline propylene polymers with unsaturated silane compounds, etc. Various synthetic rubbers (e.g. ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber,
Propylene-nonconjugated 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.) or thermoplastic synthetic resins (e.g., ultra-low density polyethylene, low-density polyethylene , linear low density polyethylene, medium density polyethylene, high density polyethylene,
Ultra-high molecular weight polyethylene, polybutene, polyolefins other than propylene polymers such as poly-4-methylpentene-1, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene It is also possible to use a mixture of terephthalate, polycarbonate, polyvinyl chloride, fluororesin, etc.). At this time, the mixture has the above-mentioned 1.00≧P≧
0゜015 Q ogM F R+ 0.955 is satisfied, and P of the extract extracted sequentially with boiling [1n-hexane and boiling Rh-heptane] is 0.450 to 0.7, respectively.
00 and 0.750 to 0.930.

Compound A used in the present invention includes aluminum hydroxy-di-phenyl phosphate, aluminum hydroxy-bis(p-methylphenyl) phosphate, aluminum hydroxy-bis(p-ethylphenyl) phosphate, aluminum hydroxy-bis(p-ethylphenyl) phosphate, Oxy-
Bis(p-n-propylphenyl) phosphate, aluminum hydroxy-bis(ρ-1-propylphenyl) phosphate, aluminum hydroxy-bis(p-ropylphenyl) phosphate, aluminum hydroxy-bis(p-propylphenyl) phosphate, aluminum hydroxy-bis(p-propylphenyl) phosphate, -1-butylphenyl)
phosphate, aluminum hydroxy-bis(p
-s-butylphenyl) phosphate, aluminum hydroxy-bis(p-t-butylphenyl) phosphate, aluminum hydroxy-bis(p-n-
amyl phenyl) phosphate, aluminum hydroxy-bis(p-1-amylphenyl) phosphate, aluminum hydroxy-bis(p-s-amylphenyl) phosphate, aluminum hydroxy-bis(p-t-amylphenyl) phosphate, ) phosphate aluminum hydroxy-bis(p-hexylphenyl) phosphate, aluminum hydroxy-bis(
p-n-octylphenyl) phosphate, aluminum hydroxy-bis(p-2-ethylhexylphenyl) phosphate, aluminum hydroxy-bis(ρ-t-octylphenyl) phosphate, aluminum hydroxy-bis( ρ-nonylphenyl) phosphate, aluminum hydroxy-bis(p-
dodecylphenyl) phosphate, aluminum hydroxy-bis(ρ-tridecylphenyl) phosphate, aluminum hydroxy-bis(ρ-hexadecylphenyl) phosphate, aluminum hydroxy-bis(ρ-octadecylphenyl) phosphate, Aluminum hydroxy-bis(p-methoxyphenyl) phosphate, aluminum hydroxy-
Bis(p-ethoxyphenyl) phosphate, aluminum hydroxy-bis(p-propoxyphenyl)
phosphate, aluminum hydroxy-bis(p
-butoxyphenyl) phosphate, aluminum hydroxy-bis(p-octoxyphenyl) phosphate, aluminum hydroxy-bis(p-cyclohexylphenyl) phosphate, aluminum hydroxy-bis(p-biphenylyl) phosphate and aluminum hydroxy-bis(p-phenoxyphenyl) phosphate, with aluminum hydroxy-bis(p4-butylphenyl) phosphate being particularly preferred. These phosphate compounds may of course be used alone, or two or more phosphate compounds may be used in combination. The compound plasticization into the compound is from 0.01 to 1 part by weight, preferably from 0.05 to 0.0 parts by weight, based on 100 parts by weight of the above crystalline propylene homopolymer.
．． 5 parts by weight. A blend of 0.01 part by weight without grooves does not sufficiently improve the stiffness and heat resistance stiffness;
Although it is acceptable to use more than 1 part by weight, it is not only impractical, but also uneconomical since no further improvement in the above-mentioned effects can be expected.

The composition of the present invention includes various additives that are usually added to propylene polymers, such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, Lubricants, antistatic agents, antifogging agents, antiblocking agents, anti-drop agents, pigments, heavy metal deactivators (copper damage inhibitors), radical generators such as peroxides, dispersants such as metal soaps, or medium Japanese additives, inorganic fillers (talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite, metal fiber, etc.) or coupling agents (such as silane, titanate, boron, aluminate, zirco) The above-mentioned inorganic fillers or organic fillers (for example, wood flour, valves, waste paper, synthetic fibers, natural fibers, etc.) that have been surface-treated with a surface treatment agent such as aluminate-based etc.) may be used in combination within the scope of not impairing the purpose of the present invention. can do. In particular, when an inorganic filler is used in combination, the rigidity and heat-resistant rigidity are further improved, so it is preferable to use the inorganic filler in combination.

The composition of the present invention is prepared by mixing the crystalline propylene homopolymer according to the present invention with predetermined amounts of Compound A and the various additives mentioned above that are normally added to propylene polymers using a conventional mixing device, such as a Hensel device. Mix using mixer (product name), super mixer, ribbon blender, Pan Bali mixer, etc., and mix using a regular single screw extruder, twin screw extruder,
Melt kneading temperature 170 with Brabender or roll etc.
It can be obtained by melt-mixing pelletizing at a temperature of .degree. C. to 300.degree. C., preferably 200.degree. C. to 250.degree. The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding.

[Function] In the present invention, the phosphate compound represented by compound A is disclosed in Japanese Patent Publication No. 41-16303 and Japanese Unexamined Patent Publication No. 53
It is generally known that it acts as a nucleating agent to improve rigidity and heat-resistant rigidity, similar to the phosphate compound disclosed in Japanese Patent No.-105550. However, the above-mentioned Japanese Patent Publication No. 41-16303 and Japanese Patent Application Laid-Open No. 53-1
Compound A, which is a basic aluminum salt of a phosphate compound (aluminum positive salt) disclosed in Japanese Patent No. 05550, is converted into a crystalline propylene homopolymer having a specific isotactic pentad fraction according to the present invention. It has been found that by blending these, a surprising synergistic effect that could not be predicted for the device from the blending of conventionally known nucleating agents can be obtained, and a composition with extremely excellent rigidity and heat-resistant rigidity can be obtained.

[Effects of the Invention] The composition of the present invention is significantly superior in (1) rigidity and heat-resistant rigidity compared to conventionally known propylene homopolymer compositions containing various nucleating agents.

(2) Not only can the molded product be made thinner, contributing to resource conservation, but also the cooling rate during molding is faster, which increases the molding speed per unit time, contributing to improved productivity. can. (3) It is now possible to use polypropylene resin in applications where polyesters such as polystyrene, ABS resin, polyethylene terephthalate, and polybutylene ethylene phthalate have traditionally been used, making it possible to expand the applications of polypropylene resin.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, Comparative Examples, and Production Examples, but the present invention is not limited thereto.

The evaluation method used in Examples and Comparative Examples was as follows.

l) Stiffness: length 100 mm using the obtained pellets.

A test piece with a width of 10 ws and a thickness of 4+w was created by injection molding, and the bending elastic modulus was measured using the test piece (JIS
7203)), the rigidity was evaluated. A highly rigid material is one that has a large bending modulus.

2) Heat resistance rigidity: length 130cm using the obtained pellets
A test piece with a width of 13 mm and a thickness of 6.5 m was prepared by injection molding, and the heat distortion temperature was measured using the test piece (115 according to JIS 7207, '4.6 kgf/cm' load f).
f1) The heat-resistant rigidity was evaluated. 'A material with high heat resistance and rigidity is one that has a high heat deformation temperature.

Production Examples 1 to 3 (Production method of crystalline propylene homopolymer used in Examples and Comparative Examples) (1) Preparation of catalyst 600 d of n-hexane, 0.50 mol of diethylaluminum monochloride (D E A C), 1.20 mol of isoamyl ether was mixed at 25° C. for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (■) (molar ratio of diisoamyl ether/DEAC 2.4). Put 4.0 mol of titanium tetrachloride into a reactor purged with nitrogen and heat at 35°C.
The total amount of the reaction product solution (V) was heated to 180%.
After adding dropwise for 30 minutes, the temperature was kept at the same temperature for 30 minutes, the temperature was raised to 75℃, the reaction was continued for another 1 hour, the temperature was cooled to room temperature (20℃), the supernatant was removed, 4000ml of n-hexane (i was added, and decane was added. The operation of removing the supernatant liquid in a vacuum chamber was repeated four times to obtain 190 g of solid product (II).The entire amount of this solid product (n) was suspended in 3000 d of n-hexane at 20°C. Add 160 g of diisoamyl ether and 350 g of titanium tetrachloride at room temperature for about 1 minute at 65°C.
The reaction was carried out for 1 hour. After the reaction was completed, it was cooled to room temperature and the supernatant liquid was removed by decantation.
After repeating the operation of adding mQ of n-hexane, stirring for 10 minutes, standing still and removing the supernatant liquid five times, the mixture was dried under reduced pressure to obtain a solid product (m).

(2) Preparation of preactivated catalyst After purging a stainless steel reactor with inclined blades with a volume of 20Q with nitrogen gas, 5Q of n-hexane, 42g of diethylaluminium monochloride, and 3g of solid product (II) were prepared.
After adding 0g of hydrogen at room temperature, 15NQ of hydrogen was added and reacted for 5 minutes at a propylene partial pressure of 5kg/cm2G. Unreacted propylene, hydrogen and n-hexane were removed under reduced pressure, and the preactivated catalyst (VI) was powdered. Propylene per Ig of solid product (III) obtained in granules 82. Og reaction).

(3) Polymerization of propylene Dried n-hexane 1 was placed in a stainless steel polymerization vessel with an internal volume of 250Q and equipped with a turbine type stirring blade, which was replaced with nitrogen gas.
00Q then 10g of diethylaluminum monochloride
, the preactivated catalyst (Vi)IOg and p-)methyl ruylate+1.0g were charged, and hydrogen was further added to Production Example 1.
is 100, Production Example 2 is 200, and Production Example 3 is 41.
ONQ was added respectively. Next, after raising the temperature inside the vessel to 70°C, propylene was supplied into the vessel, and the pressure inside the vessel was reduced to 1.
The pressure was increased to 0 kg/cm2G. Then set the temperature to 70℃,
1 for 4 hours while maintaining the pressure at 10kg/c112G
After continuing the mixing, 250 methanol was supplied and the temperature was raised to 80°C.
The temperature rose to . After 30 minutes, 100g of 201% sodium hydroxide aqueous solution was added and stirred for 20 minutes.
(After adding 1 liter, the remaining propylene was discharged. After extracting the aqueous layer, 50Q pure water was further added, stirred and washed with water for 10 minutes, the aqueous layer was extracted, and the crystalline propylene homopolymer-〇-hexane slurry was further added. was extracted, the slurry was filtered, and the filtrate was dried to obtain a white crystalline propylene monomer powder.The obtained polymer had the above-mentioned melt flow rate (MFR) and each isotactic pentad content. The results of these analyzes are shown in Table 1.

Production Example 4 (Production Example of Crystalline Propylene Homopolymer Used in Comparative Example) Dried n-hexane 1 was placed in a stainless steel polymerization vessel with an internal volume of 250Q and equipped with a turbine-type stirring blade and replaced with nitrogen gas.
00Q then 10g of diethylaluminum monochloride
, 40 g of a commercially available catalyst (AA type) prepared by reducing and pulverizing titanium tetrachloride with metal aluminum and 22.0 g of methyl p4 ruylate were charged, and 200 NQ of hydrogen was added.
Added. Then, after raising the temperature inside the vessel to 70°C, propylene was supplied into the vessel, and the pressure inside the vessel was increased to 10 kg/cm.
The pressure was increased to 2G. Then, the temperature is 70℃ and the pressure is 10kg.
After continuing polymerization for 4 hours while maintaining the pressure at /cm2G, 250 methanol was supplied and the temperature was raised to 80°C.

After 30 minutes, 1,008 ml of a 20% by weight aqueous sodium hydroxide solution was added, stirred for 20 minutes, and after adding 50 q of pure water, the remaining propylene was discharged. After extracting the aqueous layer, add 5012 pure water, stir and wash with water for 10 minutes, extract the aqueous layer, and further add crystalline propylene alone 1 coalesce-n
- The hexane slurry was extracted, the slurry was filtered, and the filtrate was dried to obtain a white crystalline propylene monomer powder. The obtained polymer had the aforementioned melt flow rate (MFR) and each isotactic pentad fraction (
It was used to determine P). The results of these analyzes are shown in Table 1.

Examples 1 to 3, Comparative Example i-12 Powders having each melt flow rate (MFR) and each isotactic pentad fraction (P, > produced in Production Examples 1 to 3 shown in Table 2 below) 100 parts by weight of crystalline propylene homopolymer, compound A, aluminum hydroxy-bis(pt-butylphenyl) phosphate and other additives in predetermined amounts as listed in Table 2 below. The mixture was placed in a Hensel mixer (trade name), stirred and mixed for 3 minutes, and then melted and blended at 200°C in a single-screw extruder with a diameter of 40 mm to form pellets. To 100 parts by weight of the powdered crystalline propylene homopolymer having each melt flow rate (MFR) and each isotactic pentad fraction (P) produced in Production Example 1-4 shown in Table 2, Predetermined amounts of each of the additives listed in the table were blended and melt-kneaded according to Examples 1 to 3 to obtain pellets.

The test piece used for the rigidity and heat resistance rigidity tests was prepared by injection molding the obtained pellet at a resin temperature of 250°C and a mold temperature of 50°C.

Using the obtained test piece, rigidity and heat-resistant rigidity were evaluated by the test method described above. These results are shown in Table 2.

Examples 4 to 6, Comparative Examples 13 to 24 Powder-like products having each melt flow rate (MFR) and each isotactic pentad fraction (P) manufactured in Production Examples 1 to 3 shown in Table 3 below 100 parts by weight of crystalline propylene homopolymer, aluminum hydroxy-bis(pt-butylphenyl) phosphate as compound A, fine particulate talc with an average particle size of 2 to 3 μm as an inorganic filler, and other additives. A predetermined amount was put into a Hensel mixer (trade name) at the blending ratio shown in Table 3 below, mixed with stirring for 3 minutes, and then melt-kneaded at 200°C in a 40-meter-diameter single-screw extruder to form pellets. did. In addition, Manufacturing Example 1 shown in Table 3 below as Comparative Examples 13 to 24
Each of the additives listed in Table 3 below was added to 100 parts by weight of the powdered crystalline propylene homopolymer having each melt flow rate (MFR) and each isotactic pentad fraction (P) produced in 4. Predetermined amounts were blended and melt-kneaded according to Examples 4 to 6 to obtain pellets.

The test pieces used for the rigidity and heat resistance rigidity tests were prepared by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C.

Using the obtained test piece, rigidity and heat-resistant rigidity were evaluated by the test method described above. These results are shown in Table 3.

The compounds and additives related to the present invention shown in Tables 2 and 3 are as follows.

Compound A Nialuminum hydroxy-bis(pt-
(butylphenyl) phosphate nucleating agent 1: pt-butylaluminum benzoate nucleating agent 2: l.3,2.4.dibenzylidene sorbitol nucleating agent 3: Sodium-bis(pt-butylphenyl) Phosphate [manufactured by Adeka Argus Chemical; MAR
K NA-10UFI Nucleating agent 4 Nialuminum-bis(pt-butylphenyl) phosphate Nucleating agent 5 Nialuminum-2,2'-methylene-bis(
4,6-di-t-butylphenyl)phosphate nucleating agent 6: Aluminum hydroxy-2,2'-methyl
Renbis(4,6- or t-butylphenyl)phosphate phenolic antioxidant 1: 2,6-di-t-butyl-p-cresol phenolic antioxidant 2: Tetrakis[methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phosphorus antioxidant l: Tetrakis(2,4-di-t-butylphenyl) -4,4'- Biphenylene-di-phosphonite phosphorous antioxidant 2: Bis(2,4-di-t-butylphenyl)-pentaerythritol-siphosphite Ca-5t nickel stearate lucium Inorganic filler: Talc (average Particle size 2~3μ) 1st
Table note: Total extraction amount (wt%) of Kibo 1 mL-hexane extract and boiling n-pebutane continuous extract. This is the case when a crystalline propylene homopolymer having an isotactic pentad fraction is used. As can be seen from Table 2, Examples 1 to 3 are compounds in which Compound A is blended with a crystalline propylene homopolymer having an isotactic pentad fraction within the range of the present invention. ~3 and comparative example 1~
3 (Crystalline propylene homopolymer having an isotactic pentad fraction outside the scope of the present invention has Compound A
Comparison of Examples 1 to 3 with an organic nucleating agent containing an organic nucleating agent made of a compound other than Compound A) shows that Examples 1 to 3 are superior in rigidity and heat-resistant rigidity. Furthermore, when comparing Examples 1 to 3 with Comparative Examples 4 to 6 in which no organic nucleating agent was blended to a crystalline propylene homopolymer having an isotactic pentad fraction within the range of the present invention, Comparative Examples Nos. 4 to 6 still have insufficient effects of improving rigidity and heat resistance rigidity. Furthermore, Comparative Examples 7 to 12 and Examples 1 to 3 were prepared in which an organic nucleating agent consisting of a compound other than Compound A was blended with a crystalline propylene homopolymer having an isotactic pentad fraction within the range of the present invention. Comparative example 7
Although the improvement effect of rigidity and heat-resistant rigidity is considerably recognized in ~12, it is still not sufficient, Examples 1 to 3 are significantly superior in rigidity and heat-resistant rigidity, and a remarkable synergistic effect is recognized by blending compound A. I understand that. In particular, it is clear that Comparative Example 1O, in which a positive aluminum salt of Compound A (-basic aluminum salt) according to the present invention is blended, does not exhibit the effects of the present invention, and this is explained in the above-mentioned Japanese Patent Publication No. 4116303. and JP-A-53
No.-105550 discloses anything. In other words, the stiffness and heat-resistant stiffness obtained in the present invention are unique, which can only be seen when Compound A is blended with a crystalline propylene homopolymer having an isotactic pentad fraction within the range limited in the present invention. This can be said to be the effect of

Table 3 shows the propylene polymer used in Table 2,
Furthermore, talc is used as an inorganic filler,
In this case, the same effect as described above was confirmed.

This shows that the composition of the present invention is significantly superior in terms of rigidity and heat-resistant rigidity compared to conventionally known compositions made by blending a nucleating agent with a crystalline propylene homopolymer. The remarkable effects of the composition of the present invention were confirmed.

that's all

Claims (5)

[Claims] (1) Isotactic pentad fraction (P) and melt flow rate (MFR; load at 230°C: 2.16)
1.00≧P≧0.015logMFR+0.9
55, and the isotactic pentad fractions (P) of extracts extracted sequentially with boiling n-hexane and boiling n-heptane are 0.450-0.700 and 0.700, respectively.
0.01 to 1 part by weight of a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A) is added to 100 parts by weight of a crystalline propylene homopolymer having a molecular weight of 750 to 0.930. A highly rigid propylene homopolymer composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (However, in the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group, or a phenoxy group.) (2) The highly rigid propylene homopolymer composition according to claim (1), wherein in the general formula [I], R is an alkyl group having 1 to 9 carbon atoms. (3) The highly rigid propylene homopolymer composition according to claim (1), which contains aluminum hydroxy-bis(pt-butylphenyl) phosphate as compound A. (4) Claim No. 1 containing an inorganic filler
) Highly rigid propylene homopolymer composition according to item 1. (5) Inorganic fillers such as talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide,
Claims No. 1 using one or more selected from zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite, and metal fiber. The highly rigid propylene homopolymer composition according to item (4).