JPH07316348A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To produce a crystalline polyolefin composition providing a molded article having excellent high-temperature rigidity and impact resistance and useful as hollow-molded article, film, etc., by compounding a specific crystalline polyolefin with a specific amide compound and a fatty acid metal salt or an alkanoyllactic acid metal salt. CONSTITUTION:This polyolefin composition is produced by compounding (A) 100 pts.wt. of a crystalline polyolefin containing a magnesium halide compound as a catalyst residue with (B) 0.001-1 pt.wt. of a compound of formula (R1 is a 1-24C aliphatic diamine residue, an alicyclic diamine residue or an aromatic diamine residue other than xylylenediamine; R2 and R3 each is a 3-14C cycloalkyl, cycloalkenyl, phenyl, etc.) and (C) 0.001-1 pt.wt. of a fatty acid salt of Mg, Ca or Zn or an alkanoyllactic acid salt of Mg, Ca or Zn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polyolefin composition capable of obtaining a molded article excellent in rigidity, heat resistance and impact resistance.

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties, and are therefore used in the production of various molded products such as injection molded products, hollow molded products, films, sheets and fibers. . 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, it cannot be said that the impact resistance, the heat resistance rigidity and the rigidity are sufficient, and there is a drawback that the use of the crystalline polyolefin may limit the specific application. Therefore, it is generally known that a β-crystal nucleating agent is blended with the crystalline polyolefin for the purpose of improving impact resistance, heat resistance rigidity and rigidity of the crystalline polyolefin.

On the other hand, for the purpose of obtaining a crystalline polypropylene resin composition capable of producing a large amount of β-type crystal structure, a crystalline polypropylene resin composition containing a specific bisamide as a β crystal nucleating agent is disclosed in Japanese Patent Laid-Open No. -107875 publication, in which the neutralizing agent, lubricant (aliphatic hydrocarbon, higher fatty acid and its alkali metal salt or alkaline earth metal salt, fatty acid ester, higher fatty acid amide, if necessary, It is described that a rosin derivative etc.) can be used in combination. Further, in this publication, a transition metal compound (for example, a titanium halide such as titanium trichloride or titanium tetrachloride) is supported as a crystalline polypropylene resin on a carrier whose main component is magnesium halide such as magnesium chloride. Catalyst and alkyl aluminum compound (triethyl aluminum, diethyl aluminum chloride, etc.)
It is described that a polypropylene resin prepared by using a catalyst system obtained by combining and can also be used. Further, for the purpose of obtaining a polyolefin resin composition that significantly improves transparency and does not reduce the mechanical strength of the resin, a polyolefin resin is blended with an alicyclic carboxylic acid amide compound of a divalent or higher aliphatic amine. A polyolefin-based resin composition formed of has been proposed as JP-A-4-261447, and it is described in the publication that a metal soap such as calcium stearate or calcium stearyl lactate can be used in combination if necessary. . Further, in order to obtain a synthetic resin composition having a significantly improved transparency and exhibiting sufficient mechanical strength, an organic carboxylic acid amide of a divalent or higher aliphatic amine is added to a synthetic resin such as a crystalline polyolefin resin. A synthetic resin composition comprising a compound, a specific organic phosphate compound or an ammonium salt thereof, and an organic carboxylic acid metal salt having 7 or more carbon atoms is disclosed in Japanese Patent Application Laid-Open No. Hei 4 (1999) -1998
-370124, which describes that a metal soap such as calcium stearyl lactate can be used in combination, if necessary.

On the other hand, when a halogen-containing magnesium compound is used as a catalyst carrier in the polymerization of crystalline polyolefin, a transition metal (for example, titanium) which is the main component of the catalyst is used.
When a catalyst having a polymer yield per unit of no carrier (for example, a system in which titanium tetrachloride-aluminum chloride mixture activated by reduction of titanium tetrachloride with metallic aluminum and further activated by grinding is combined with diethylaluminum monochloride) is used As a new generation catalyst that does not require catalyst removal (deashing) or amorphous polymer extraction (de-APO) processes because it is several hundred times to several thousand times higher than the above and the crystallinity of the produced polymer is high. It is in the spotlight.
Representative examples of such new type catalysts include JP-A-47-9342 and JP-A-50-126590. However, such a supported catalyst has a high polymer yield per transition metal, which is the main component of the catalyst, but has a low polymer yield per catalyst carrier corresponding to a low transition metal supported concentration, and therefore does not undergo deashing. The crystalline polyolefin is adversely affected by the residual catalyst carrier. That is, since the amount of the transition metal component supported on the catalyst carrier is 1% or less to 10% (weight) at most per solid catalyst component, the polymer yield per catalyst carrier (magnesium compound) should be about several thousand to tens of thousands. Therefore, if deashing is not performed, the residual magnesium compound (usually a magnesium halide compound) may cause deterioration of the quality of the product polymer. In particular, if a magnesium halide compound remains as a catalyst residue in the crystalline polyolefin, the magnesium halide compound (eg, magnesium chloride) is thermally decomposed to generate an acidic substance such as hydrogen halide when the crystalline polyolefin is melt-processed. However, the thermal stability, odor, hue, corrosiveness, weather resistance, etc. of the product polymer tend to deteriorate.

[0005]

However, the crystalline polyolefin in which the magnesium halide compound remains as the above catalyst residue has the β crystal nucleating agent composed of the specific bisamide proposed in the above-mentioned JP-A-6-107875. When blended, impact resistance and heat resistance are improved, but
The disadvantage is that the rigidity is hardly improved. Kohei
In JP-A 6-107875, when a composition containing a specific bisamide in a crystalline polyolefin is used in combination with fatty acid magnesium, fatty acid calcium or fatty acid zinc as a lubricant or magnesium alkanoyl lactate, calcium alkanoyl lactate or zinc alkanoyl lactate as a neutralizing agent. However, there is no description or suggestion that the rigidity of the molded article obtained from the composition is improved. In addition, the above
In JP-A 4-261447 and JP-A-4-370124, a composition in which a specific bisamide is mixed with a crystalline polyolefin resin in which a magnesium halide compound remains as a catalyst residue, fatty acid magnesium as a metal soap, fatty acid calcium, There is no description or suggestion that the combined use of fatty acid zinc, magnesium alkanoyl lactate, calcium alkanoyl lactate or zinc alkanoyl lactate improves the rigidity of the molded article obtained from the composition.

The inventor of the present invention relates to a composition in which a β-crystal nucleating agent consisting of a specific bisamide proposed in JP-A-6-107875 is blended with a crystalline polyolefin in which a magnesium halide compound remains as a catalyst residue. In order to obtain a composition that solves the above-mentioned problems, that is, a crystalline polyolefin composition with improved rigidity, the present inventors have conducted intensive studies. As a result, the present inventors have found that a crystalline polyolefin having a magnesium halide compound remaining as a catalyst residue is blended with a specific bisamide and a specific fatty acid metal salt or alkanoyl lactic acid metal salt in a specific amount. Further, they have found that the composition is a composition that gives a molded article having improved rigidity without impairing the heat resistance rigidity, and completed the present invention based on this finding. As is clear from the above description, an object of the present invention is to provide a crystalline polyolefin composition in which the molded article has improved rigidity, heat resistance and impact resistance.

[0007]

The present invention has the following constitution. (1) Based on 100 parts by weight of a crystalline polyolefin containing a magnesium halide compound as a catalyst residue, one or more kinds selected from the following amide compounds (hereinafter referred to as compound A) and Each of the compounds (hereinafter referred to as the compound B) is 0.001 to 1
A crystalline polyolefin composition blended by weight. _{R 2 -CONH-R 1 -NHCO-} R 3 [ wherein, R ₁ represents an aliphatic diamine residue having 1 to 24 carbon atoms,
An alicyclic diamine residue or an aromatic diamine residue (excluding xylylenediamine residue), R ₂ and R ₃ are the same or different and are a cycloalkyl group or a cycloalkenyl group having 3 to 14 carbon atoms; A phenyl group, an alkylphenyl group having 7 to 10 carbon atoms or an alkenylphenyl group, or a phenylalkyl group having 7 to 9 carbon atoms or a cyclohexylalkyl group is shown. ] Fatty acid metal salt (provided that the metal is magnesium, calcium or zinc) Alkanoyl lactic acid metal salt (provided that the metal is magnesium, calcium or zinc) (2) Hydrolyzed with 100 parts by weight of crystalline polyolefin Talcites (hereinafter referred to as compound C) 0.001
The crystalline polyolefin composition according to claim 1, further comprising 1 part by weight.

The crystalline polyolefin used in the present invention is
A crystalline polyolefin containing a magnesium halide compound of a catalyst residue, for example, a crystalline polyolefin obtained by polymerization in the presence of a Ziegler type complex catalyst using a halogen-containing magnesium compound as a catalyst carrier,
Crystalline polyolefins that have not yet undergone a catalyst residue removal step or that have undergone an incomplete catalyst residue removal step are preferred. The details will be described below. The Ziegler-type complex catalyst using a halogen-containing magnesium compound as a catalyst support is a Ziegler-type complex catalyst, that is, a transition metal compound of Groups 4 to 8 of the periodic table and an organometallic compound of a metal of Groups 1 to 3 of the periodic table. In the complex catalyst produced by the combination of the above, the former transition metal compound is supported on the halogen-containing magnesium compound. Here, "as catalyst carrier"
Alternatively, "supporting" means not only when the transition metal compound is merely physically mounted on the halogen-containing magnesium compound but also when both are physically, physicochemically or chemically interacting or binding to each other. This does not exclude the case where the halogen-containing magnesium compound is acting as a catalyst.

Typical examples of the transition metal used in the Ziegler type complex catalyst include titanium and vanadium. These are used in their highest valence or reduced state, halides,
It can be used in the form of a compound such as oxyhalide, alkoxide, and alkoxyhalide which is most preferable in terms of catalytic performance for individual metals. These transition metal compounds include titanium tetrachloride, titanium trichloride,
Titanium dichloride, tetrabutoxy titanium, tributoxy titanium monochloride, dibutoxy titanium dichloride,
Vanadium tetrachloride, vanadium oxymonochloride,
Vanadium trichloride and the like can be exemplified, and these can be used alone or in combination of two or more kinds. Typical of the organometallic compounds are alkylaluminum compounds, particularly trialkylaluminum, dialkylaluminum monohalides, alkylaluminum dihalides, alkylaluminum sesquihalides, dialkylaluminum monohydrides, alkylaluminum dihydrides (wherein these compounds are alkyl The group is preferably C _{1 to} C ₈ and the halogen is preferably chlorine, bromine or iodine).
Specifically, for example, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-i-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, tri-n-hexyl aluminum, tri-n. Examples thereof include octyl aluminum, tri-2-ethylhexyl aluminum, diethyl aluminum monochloride, diethyl aluminum monoiodide, ethyl aluminum dichloride, ethyl aluminum sesquichloride and diethyl aluminum monohydride.

Preferred halogen-containing magnesium compounds as the catalyst carrier are magnesium dihalide,
Oxymagnesium halogenide, oxymagnesium halogenide treated with alkylaluminum dihalogenide (for example, ethylaluminum dichloride) and part of which was converted to magnesium dihalide, magnesium dihalide treated with various electron donor compounds Examples thereof include those complexed with each other. On the other hand,
Halogen-free magnesium compounds as catalyst carriers (eg magnesium hydroxide, magnesium oxide)
In a crystalline polyolefin obtained using a halogen-containing organometallic compound,
Those containing a magnesium halide compound as a catalyst residue are also included in the crystalline polyolefin of the present invention, and the above-described effects of the present invention can be obtained. In order to carry the transition metal catalyst component on the halogen-containing magnesium compound carrier, a method of co-milling both with a milling device such as a ball mill,
A method of dispersing the latter when the former is in a liquid state (itself is in a liquid state or as a solution of a solvent such as a hydrocarbon or a halogenated hydrocarbon), or a method of dissolving both in a suitable common solvent, and other known methods. It can be implemented in any available manner. For the purpose of improving the catalyst performance, various electron donating compounds can be combined with any catalyst component at any stage of the catalyst production by any method. As a typical example, (1) as shown in JP-A-48-16986, N, N, N ′, N′-tetramethylethylenediamine is reacted with titanium tetrachloride to give a 1: 1 molecule. A catalyst for propylene polymerization by combining a compound prepared in advance and ground in an mill with anhydrous magnesium chloride (A) and a product (B) obtained by previously reacting triethylaluminum and ethyl benzoate (2) As described in JP-A-50-126590, anhydrous magnesium chloride and ethyl benzoate are co-ground in a ball mill, and then the ground product is suspended in titanium tetrachloride. Supported titanium tetrachloride on magnesium chloride, treated with hexane to wash off unsupported titanium tetrachloride to prepare a solid catalyst component, which was combined with triethylaluminum to prepare a catalyst for propylene polymerization. There are other ways to obtain a medium.

The method for polymerizing the crystalline polyolefin used in the present invention is optional and does not use suspension polymerization in a solvent, suspension polymerization in a liquefied monomer, or dilution under conditions where the monomer is present in a gaseous state. There are other methods such as gas phase polymerization. The "catalyst residue removal step" in the present invention means that, in order to positively remove the catalyst residue contained in the crystalline polyolefin obtained by the polymerization, it reacts with a catalyst like alcohols and water. Means a step of treating the crystalline polyolefin with a compound that inactivates or solubilizes, and then removing the inactivating or solubilizing catalyst by physical means such as filtration, drying, and centrifugation. Therefore,
The step of separating the produced polymer from the dispersion medium (solvent or liquefied monomer) during suspension polymerization does not correspond to the catalyst residue removal step in the present invention even if the dispersion medium-dissolved catalyst may be removed. . In addition, ether, alcohol,
Add a small amount of catalyst poison such as ketone, ester, water,
The step of treating the produced polymer suspension with a gas such as steam or nitrogen to remove the dispersion medium also does not correspond to the step of removing the catalyst residue in the present invention.

The crystalline polyolefin used in the present invention is a crystalline polyolefin containing a magnesium halide compound as a catalyst residue, such as ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1,
Crystalline homopolymers of α-olefins such as hexene-1 and octene-1, crystalline or low crystalline random copolymers or crystalline block copolymers of these two or more types of α-olefins, and the above α- Copolymer of olefin and vinyl acetate or acrylic ester, saponified product of the copolymer, copolymer of α-olefin and unsaturated silane compound, α-olefin and unsaturated carboxylic acid or anhydride thereof A copolymer, a reaction product of the copolymer and a metal ion compound, a crystalline homopolymer of the above α-olefin, a crystalline or low crystalline random copolymer or a crystalline block copolymer. Modified polyolefins modified with unsaturated carboxylic acids or their derivatives, crystalline homopolymers of the above α-olefins, crystalline or low crystalline random copolymers or binders. Examples thereof include silane-modified polyolefins obtained by modifying a crystalline block copolymer with an unsaturated silane compound. These crystalline polyolefins can be used alone or in combination of two or more crystalline polyolefins. You can also

Further, various synthetic rubbers such as the above-mentioned crystalline polyolefin (for example, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, polybutadiene, polyisoprene, polychloroprene) are used. , Chlorinated polyethylene, chlorinated polypropylene, fluoro rubber, 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 resin (for example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, Polybutylene terephthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, hydrogenated C ₅ petroleum resin, C
_9- based petroleum resin, hydrogenated C _9- based petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉ copolymerized petroleum resin, acid-modified C _9- based petroleum resin, etc., DCPD resin (eg cyclo Pentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene-C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymer petroleum resin, cyclopentadiene-C ₉ copolymer petroleum resin, hydrogenated cyclopentadiene- C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, etc., having a softening point of 80 to 200 ° C. Can also be used. Crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, crystalline ethylene-propylene random copolymer, crystalline propylene-butene-1 random copolymer,
Crystalline ethylene-propylene-butene-1 terpolymer,
Crystalline propylene-hexene-butene-1 terpolymers and mixtures of two or more thereof are particularly preferably used.

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

Among the diamide compounds obtained from the above diamine and monocarboxylic acid, more preferable compounds are N, N'-dicyclohexanecarbonyl-p-phenylenediamine and N, N'-dibenzoyl-1,5-diaminonaphthalene. , N, N′-dibenzoyl-1,4-diaminocyclohexane, N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane and the like are exemplified. These compounds A may be used alone or in combination of two or more kinds. The compounding ratio of the compound A is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the crystalline polyolefin. If the blending ratio is less than 0.001 part by weight, the effect of improving the rigidity, heat resistance and impact resistance will not be fully exerted, and if it exceeds 1 part by weight, the rigidity, heat resistance and impact resistance will not be improved. Not only is it impossible to expect an improvement effect and it is not practical, and it is also uneconomical.

As the compound B used in the present invention, magnesium hexanoate, calcium hexanoate, zinc hexanoate, magnesium sorbate, calcium sorbate, zinc sorbate, n-magnesium octanoate, n-
Calcium octanoate, n-zinc octanoate, magnesium 2-ethylhexanoate, calcium 2-ethylhexanoate, zinc 2-ethylhexanoate, magnesium nonanoate,
Calcium nonanoate, zinc nonanoate, magnesium decanoate, calcium decanoate, zinc decanoate, magnesium laurate, calcium laurate, zinc laurate, magnesium myristate, calcium myristate, zinc myristate, magnesium palmitate, calcium palmitate, calcium palmitate , Zinc palmitate, magnesium palmitoleate, calcium palmitoleate, zinc palmitoleate, magnesium stearate, calcium stearate, zinc stearate, magnesium oleate, calcium oleate, zinc oleate,
Magnesium linoleate, calcium linoleate, zinc linoleate, magnesium linolenate, calcium linolenate, zinc linolenate, magnesium behenate, calcium behenate, zinc behenate, magnesium erucate, calcium erucate, zinc erucate, lignoceric acid Magnesium, Calcium lignocerate, Zinc lignocerate, Magnesium cerotinate, Calcium serotinate, Zinc serotinate, Magnesium montanate, Calcium montanate, Zinc montanate,

Magnesium 2-hydroxytetradecanoate, calcium 2-hydroxytetradecanoate, zinc 2-hydroxytetradecanoate, magnesium iprolate,
Calcium iprolate, zinc iprolate, magnesium 2-hydroxyhexadecanoate, calcium 2-hydroxyhexadecanoate, zinc 2-hydroxyhexadecanoate, magnesium yarapinoleate, calcium yarapinoleate, zinc yarapinoleate, magnesium uniperinate, calcium uniperinate, uniperine Zinc acid, magnesium ambretoleate, calcium ambretoleate, zinc ambretoleate, magnesium aleurite, calcium aleurite, zinc aleurite, magnesium 2-hydroxyoctadecanoate, calcium 2-hydroxyoctadecanoate, Zinc 2-hydroxyoctadecanoate, magnesium 12-hydroxyoctadecanoate, calcium 12-hydroxyoctadecanoate, 12-hydroxyoctadeca Zinc, 18-hydroxy magnesium octadecanoic acid, 18-hydroxy octadecanoic acid calcium, 18-hydroxy octadecanoic acid zinc, magnesium 9,10-dihydroxy-octadecanoic acid,
Calcium 9,10-dihydroxyoctadecanoate, Zinc 9,10-dihydroxyoctadecanoate, Magnesium ricinoleate, Calcium ricinoleate, Zinc ricinoleate, Magnesium camlorenate, Calcium camlorenate, Zinc camlorenate, Magnesium licanoate, Calcium licanoate, Zinc licanoate, magnesium ferronate, calcium ferronate, zinc ferronate, magnesium cerebronate, calcium cerebronate, zinc cerebronate, magnesium dodecanoyl lactate, calcium dodecanoyl lactate, zinc dodecanoyl lactate, magnesium tetradecanoyl lactate, tetradecanoyl lactate calcium,
Examples include zinc tetradecanoyl lactate, magnesium octadecanoyl lactate, calcium octadecanoyl lactate and zinc octadecanoyl lactate, and particularly magnesium stearate, calcium stearate, zinc stearate, 12-hydroxy magnesium octadecanoate, 1
Calcium 2-hydroxyoctadecanoate and calcium octadecanoyl lactate are preferred. These compounds B may be used alone or in combination of two or more kinds. The compounding ratio of the compound B is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the crystalline polyolefin. If the compounding ratio is less than 0.001 part by weight, the effect of improving rigidity, heat resistance and impact resistance is not sufficiently exerted, and if it exceeds 1 part by weight,
Further improvement of rigidity, heat resistance and impact resistance cannot be expected, which is not practical and uneconomical.

In the crystalline polyolefin composition of the present invention, the combined use of compound C synergistically exhibits the effects of improving rigidity, heat resistance and impact resistance, and therefore it is preferably used in combination. As the compound C, M _x Al _y (OH) _{2x + 3y-2z} (A) _z · aH ₂ O (M is Mg, Ca or Zn, A is CO ₃ or HPO ₄ ,
x, y, z are positive numbers, and a is zero or a positive number). These compounds C may be used alone or in combination of two or more kinds. The compounding ratio of the compound C is crystalline polyolefin.
0.001 to 1 part by weight, preferably 0.01 to 100 parts by weight
0.5 parts by weight.

In the composition of the present invention, various additives which are usually added to crystalline polyolefins such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers and heavy metal deactivators ( Copper damage inhibitor), clarifier,
Nucleating agent (excluding compound A), lubricant (excluding compound B), antistatic agent, antifogging agent, antiblocking agent, non-dripping agent, radical generator such as peroxide, flame retardant, Flame retardant aid, pigment, halogen scavenger (excluding compound B and compound C), dispersant or neutralizing agent for metal soaps (excluding compound B), organic or inorganic antibacterial agent Agents, inorganic fillers (eg 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 oxide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, magnesium oxysulfate, carbon fiber, carbon black, graphite and metal fiber, etc., coupling agent (for example, silane-based, titanate-based, boron) System, aluminate, zircoaluminate, etc.) of the present invention, which are surface-treated with inorganic or organic fillers (eg wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.). It can be used in combination as long as the purpose is not impaired.

The composition of the present invention comprises, for example, a crystalline polyolefin and the above-mentioned compounds A and B and the above-mentioned various additives usually added to the crystalline polyolefin in predetermined amounts, respectively, in a conventional mixing device such as a Henschel mixer (commercial product). Name), a super mixer, a ribbon blender, a Banbury mixer, etc., and the melt kneading temperature of 150 ℃ ~ 300 ℃, preferably 180 ℃ with a normal single screw extruder, twin screw extruder, Brabender or roll. ~ 270
It can be obtained by melt-kneading and pelletizing at ° C. 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.

[0021]

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) Rigidity: Evaluated by a bending test. That is, a test piece having a length of 100 mm, a width of 10 mm and a thickness of 4 mm was prepared by using the obtained pellet by an injection molding method, and the flexural modulus was measured by using the test piece (according to JIS K 7203) to obtain rigidity. Was evaluated. A material having a high rigidity means a material having a large flexural modulus. 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;
The heat resistance and rigidity were evaluated by applying a load of 0.451 MPa. 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.

Examples 1-7, Comparative Examples 1-8 MFR as crystalline polyolefin (amount of molten resin discharged for 10 minutes when a load of 2.16 kg at 230 ° C. is applied) 6.
N, N'-dicyclohexanecarbonyl-p-phenylenediamine, N, N as compound A was added to 100 parts by weight of unstabilized powdery crystalline propylene homopolymer (magnesium chloride content 40 ppm) at 0 g / 10 min. '-Dibenzoyl-1,5-
Diaminonaphthalene or N, N′-dibenzoyl-1,4-diaminocyclohexane, compound B as magnesium hexanoate, calcium hexanoate, zinc 2-ethylhexanoate or octadecanoyl magnesium lactate, and other additives in predetermined amounts, respectively. The mixture was put in a Henschel mixer (trade name) at the blending ratio shown in Table 1 described below, stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 1 to 8, powdery crystalline propylene homopolymers having an MFR of 6.0 g / 10 min, which are not stabilized (a magnesium chloride content of 40
(ppm) 100 parts by weight of each of the additives described in Table 1 described below were mixed and melt-kneaded in accordance with Examples 1 to 7 to obtain pellets. The test pieces used for evaluation of rigidity, heat resistance and impact resistance were obtained by using the pellets obtained at a resin temperature of 25
It was prepared by injection molding at 0 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Table 1.

Examples 8-14, Comparative Examples 9-16 Unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight, chloride Magnesium content 54ppm) 100 parts by weight of compound A as N, N '
-Dicyclohexanecarbonyl-1,4-diaminocyclohexane, N, N'-bis (4-t-butylbenzoyl) -1,6-diaminohexane or N, N'-bis (4-t-butylcyclohexanecarbonyl)- 4,4'-diaminodiphenyl ether, magnesium stearate as compound B, calcium stearate, zinc stearate or calcium octadecanoyl lactate, and other additives in the respective prescribed amounts at the compounding ratios shown in Table 2 below, and a Henschel mixer ( Product name), stir and mix for 3 minutes, then caliber
The mixture was melt-kneaded at 200 ° C. with a 30 mm twin-screw extruder and pelletized. Further, as Comparative Examples 9 to 16, MFR is 4.0 g / 10.
To 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content: 8.5% by weight, magnesium chloride content: 54 ppm), and a predetermined amount of each additive described in Table 2 below. Blended, Examples 8-1
Melt-kneading was carried out according to No. 4 to obtain pellets. rigidity,
Test pieces used for evaluation of heat resistance rigidity 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. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Table 2.

Examples 15 to 21, Comparative Examples 17 to 24 Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight, chloride Magnesium content 95ppm) 90% by weight and MI (amount of molten resin discharged for 10 minutes when a load of 2.16kg at 190 ° C is added)
15.0g / 10min unstabilized powdered Ziegler
A total of 100 parts by weight of a Natta-based high-density ethylene homopolymer (magnesium chloride content 20 ppm) and 10% by weight was added to the compound A as N, N'-dibenzylcarbonyl-4,4'-diaminodiphenylsulfone, N, N'-dibenzylcarbonyl-4,4'-diaminodiphenyl ketone or 2,2-bis [4 '-(N-cyclohexylmethylcarbonylamino) phenyl] propane, calcium montanate as compound B, basic 12-hydroxyoctadecane Predetermined amounts of magnesium acid salt, calcium 12-hydroxyoctadecanoate or zinc octadecanoyl lactate, and other additives were added to the Henschel mixer (trade name) at the compounding ratios shown in Table 3 below, and mixed with stirring for 3 minutes. The mixture was melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 17 to 24, MFR is 7.0 g
/ 10 min unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight, magnesium chloride content 95 ppm) 90% by weight and M
The total amount of 100 parts by weight of I is 15.0 g / 10 minutes and 10% by weight of unstabilized powdered Ziegler-Natta high density ethylene homopolymer (magnesium chloride content 20 ppm) is shown in Table 3 below. Add a predetermined amount of each additive,
Melt-kneading processing was performed according to Examples 15 to 21 to obtain pellets. Test pieces used for evaluation of rigidity, 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. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Table 3.

The compounds and additives relating to the present invention shown in Tables 1 to 3 are as follows. Compound A [1]: N, N′-dicyclohexanecarbonyl-
p-Phenylenediamine compound A [2]: N, N'-dibenzoyl-1,5-diaminonaphthalene compound A [3]: N, N'-dibenzoyl-1,4-diaminocyclohexane compound A [4]: N, N'-dicyclohexanecarbonyl-
1,4-Diaminocyclohexane compound A [5]: N, N'-bis (4-t-butylbenzoyl) -1,6-diaminohexane compound A [6]: N, N'-bis (4-t- Butylcyclohexanecarbonyl) -4,4'-diaminodiphenyl ether compound A [7]: N, N'-dibenzylcarbonyl-4,4'-
Diaminodiphenylsulfone compound A [8]: N, N'-dibenzylcarbonyl-4,4'-
Diaminodiphenyl ketone Compound A [9]: 2,2-bis [4 '-(N-cyclohexylmethylcarbonylamino) phenyl] propane Compound B [1]: Magnesium hexanoate Compound B [2]: Calcium hexanoate Compound B [ 3]: zinc 2-ethylhexanoate compound B [4]: magnesium stearate compound B [5]: calcium stearate compound B [6]: zinc stearate compound B [7]: calcium montanate compound B [8]: Basic magnesium 12-hydroxyoctadecanoate Compound B [9]: calcium 12-hydroxyoctadecanoate Compound B [10]: magnesium octadecanoyl lactate Compound B [11]: calcium octadecanoyl lactate Compound B [12]: octadeca noil zinc lactate compound C: hydrotalcite (Mg _4.5 Al ₂ (O ) ₁₃ C
O ₃ · 3.5H ₂ O [manufactured by Kyowa Chemical Industry Co., Ltd. DHT-4
A])

Phenol-based antioxidant 1: 2,6-di-t-butyl-p-cresol Phenol-based antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Phosphorus Antioxidant 1: Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite Phosphorus Antioxidant 2: Bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite Metal salt compound 1: Lithium stearate Metal salt compound 2: Sodium stearate Metal salt compound 3: Strontium stearate Metal salt compound 4: Barium stearate Metal salt compound 5: Sodium stearoyl lactylate

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

The examples and comparative examples shown in Table 1 show that the crystalline polyolefin has a magnesium chloride content of 40 ppm.
This is the case of using the crystalline propylene homopolymer. As can be seen from Table 1, Examples 1 to 7 are those in which the compound A and compound B according to the present invention are blended, and Examples 1 to 7 and Comparative example 1 (no compound A and compound B are blended) From the comparison, it is understood that Examples 1 to 7 are remarkably excellent in rigidity, heat resistance rigidity and impact resistance. Comparing Comparative Example 2 in which only Compound B is blended with Examples 1 to 7, it can be seen that the rigidity, heat resistance rigidity and impact resistance of Comparative Example 2 are substantially the same as those of Comparative Example 1 and are hardly improved. Further, comparing Comparative Example 3 in which only the compound A is mixed with Examples 1 to 7, the heat resistance rigidity and the impact resistance of the both are about the same, but the rigidity of Comparative Example 3 is clear from Comparative Example 1. As you can see, there is almost no improvement. Further, compared with Comparative Examples 4 to 8 and Examples 1 to 7 in which, instead of the compound B of Examples 1 to 7, alkali metal salts or alkaline earth metal salts other than the compound B, that is, metal salt compounds 1 to 5 were respectively blended. By comparison, Comparative Examples 4 to 8
Shows the same result as in Comparative Example 3, and it can be seen that the effect of improving rigidity is hardly recognized even when the compound A is used in combination with the metal salt compounds 1 to 5, respectively. Therefore, it is apparent that the comparative examples that do not simultaneously satisfy the combination of the two components of the compound A and the compound B according to the present invention do not exhibit the effects of the present invention. That is, the rigidity, the heat resistance and the impact resistance obtained in the present invention are the unique effects that can be seen only when compound A and compound B are blended with a crystalline polyolefin containing a magnesium halide compound as a catalyst residue. I can say. Further, in the compositions of Examples 1 to 5, Examples 6 to 7 in which the compound C is used in combination are Examples 1 to 5
In comparison with Compound A and Compound B, the excellent effects of improving rigidity, heat resistance and impact resistance are not impaired,
It can be seen that a remarkable synergistic effect by the combined use of the compound C is recognized.

Tables 2 to 3 show crystalline ethylene-propylene block copolymers, crystalline ethylene-propylene random copolymers and high-density ethylene homopolymers each containing a magnesium halide compound as a catalyst residue as a crystalline polyolefin. This was a mixture of coalesced materials, and the same effects as those described above were confirmed for these.

[0032]

EFFECT OF THE INVENTION The composition of the present invention is a composition which, when formed into a molded product, gives a molded product having extremely excellent rigidity, heat resistance and impact resistance.

Claims (2)

[Claims] 1. To 100 parts by weight of a crystalline polyolefin containing a magnesium halide compound as a catalyst residue, 0.0% of each of the following amide compounds and one or more compounds selected from the following is added.
A crystalline polyolefin composition obtained by blending 0 to 1 part by weight. _{R 2 -CONH-R 1 -NHCO-} R 3 [ wherein, R ₁ represents an aliphatic diamine residue having 1 to 24 carbon atoms,
An alicyclic diamine residue or an aromatic diamine residue (excluding xylylenediamine residue), R ₂ and R ₃ are the same or different and are a cycloalkyl group or a cycloalkenyl group having 3 to 14 carbon atoms; A phenyl group, an alkylphenyl group having 7 to 10 carbon atoms or an alkenylphenyl group, or a phenylalkyl group having 7 to 9 carbon atoms or a cyclohexylalkyl group is shown. ] Fatty acid metal salt (provided that metal represents magnesium, calcium or zinc) Alkanoyl lactic acid metal salt (provided that metal represents magnesium, calcium or zinc) 2. The crystalline polyolefin composition according to claim 1, which further comprises 0.001 to 1 part by weight of hydrotalcites based on 100 parts by weight of the crystalline polyolefin.