JPH10139957A - Polypropylenic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylenic resin compsn. excellent in the balance among flowability, stiffness, impact resistance, tensile elongation, and molded appearance. SOLUTION: This compsn. comprises 100 pts.wt. compsn. consisting of 50-95wt.% polypropylene (I) having a flexural modulus of 8.000kgf/cm<2> (785MPa) or higher and a melt flow rate of 10g/10min or higher and 50-5wt.% olefinic elastomer (II). 0.1-50 pts.wt. hydrogenated block copolymer component (III) consisting of a star-type hydrogenated block copolymer (a) comprising 5-60wt.% polybutadiene block (A) having a 1,2-vinyl bond content lower than 25wt.% and 95-40wt.% conjugated diene polymer block (B) having a content of conjugated diene unit of 50wt.% or higher, the 1,2-vinyl bond content in the conjugated diene units being 65wt.% or higher, and a linear block copolymer (b) comprising 5-60wt.% polymer block A and 95-40wt.% polymer block B, and 0-50 pts.wt. inorg. filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition having a good balance of fluidity, rigidity, impact resistance and appearance of a molded product.

[0002]

2. Description of the Related Art Polypropylene has been widely used in various molded articles and sheets because of its excellent moldability, toughness, water resistance, chemical resistance, etc., low specific gravity and low cost.
However, since the impact resistance, particularly the impact strength at low temperatures, is inferior, the purpose of use may be limited. In order to solve this problem, many proposals have been made to blend rubber components such as hydrogenated styrene-butadiene-styrene block copolymer and ethylene-α-olefin copolymer rubber. However, these polypropylene-based resin compositions have improved impact resistance, but have reduced rigidity and molded appearance, which are not practically sufficient. In order to improve these, use of a high molecular weight type ethylene-α-olefin copolymer is considered. However, the use of the high molecular weight type as the rubber component is not practically preferable because the dispersibility in the resin is poor and the fluidity of the obtained composition is further reduced.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and is directed to a polypropylene, an olefin-based elastomer, a hydrogenated block copolymer having a specific structure, and if necessary, an inorganic block copolymer. An object of the present invention is to provide a polypropylene-based resin composition having a good balance of fluidity, rigidity, impact resistance, tensile elongation, and molded appearance by blending a filler.

[0004]

That is, the present invention provides: (I) a flexural modulus of 8000 kgf / cm ² (785 M
(Pa) 50 to 95% by weight of polypropylene having a melt flow rate of 10 g / 10 minutes or more at a temperature of 230 ° C. and a load of 2.16 kg, and (II) an olefin-based elastomer of 50 to 5% by weight. III) (a) Polymer blocks A and B are contained in the molecule (where A is a polybutadiene block having a 1,2-vinyl bond content of less than 25% by weight, B is a conjugated diene compound containing 50% by weight or more, And a hydrogenated block copolymer in which 80% or more of the double bond residues of the conjugated diene portion of the conjugated diene polymer block in which the vinyl bond content of the conjugated diene compound is 65% by weight or more are hydrogenated), and Star-shaped block copolymer having a block structure represented by (AB) nX (where n is an integer of 2 or more and X represents a coupling agent residue) A is, content is 5 to 60 wt% of the polymer block A, the content of the polymer block B 95 to
40% by weight (however, A + B = 100% by weight) of a star-shaped hydrogenated block copolymer and (b) polymer blocks A and B in the molecule [where A and B are the above (a) And the block structure was a linear block copolymer represented by AB. The content of the polymer block A was 5 to 60% by weight and the content of the polymer block B was 95. ~
40% by weight (however, A + B = 100% by weight)
(A) / (b) weight ratio of 100/0 to 50/50,
The total weight average molecular weight of the component (a) and the component (b) is 20.
The present invention provides a polypropylene-based resin composition containing 0.1 to 50 parts by weight of a hydrogenated block copolymer which is 10,000 to 500,000 (IV) 0 to 50 parts by weight of an inorganic filler. Hereinafter, the present invention will be described in detail.

BEST MODE FOR CARRYING OUT THE INVENTION

(I) Component (I) The polypropylene contained in the composition of the present invention comprises:
Crystalline polypropylene, a propylene homopolymer or ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 2-methyl-1-propene, 3
-Methyl-1-pentene, 4-methyl-1-pentene,
It is a copolymer containing an α-olefin such as 5-methyl-1-hexene. The copolymer may be a random copolymer, a block copolymer, a blend with a homopolymer obtained by multistage polymerization, or a normal blend. As a method for obtaining these polypropylenes, there are a method using a multi-site catalyst such as a Ziegler-Natta catalyst, a method using a single-site catalyst such as a Kaminsky catalyst, and the like. As the component, polypropylene by any polymerization catalyst is suitably used. However, the stereoregularity of the propylene unit is preferably isotactic or syndiotactic as the component (I) of the present invention. The flexural modulus of the polypropylene (I) of the present invention is 8000 kgf / cm ² (785 MPa).
Above, but preferably 10,000 to 50,000 kg
f / cm ² (981-4903 MPa), more preferably 11000-40000 kgf / cm ² (1079-
3923 MPa), more preferably 12000 to 30
000 kgf / cm ² (1177-2942 MPa), and the melt flow rate (MFR, g / 10 min) is 1
It is 0 or more, preferably 20 to 300, more preferably 30 to 200, and still more preferably 40 to 150. The flexural modulus is less than 8000 kgf / cm ² and / or
If the MFR is less than 10, the balance between fluidity and rigidity is poor, which is not preferable.

(II) Component The (II) olefin elastomer used in the present invention is a copolymer of α-olefins such as ethylene, propylene, 1-butene, 1-hexene and 1-octene,
Or copolymers thereof with non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene;
Alternatively, it is an elastomer comprising a homopolymer of a higher α-olefin such as 1-hexene and 1-octene. Among these, ethylene / propylene copolymer, ethylene / propylene
1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / 1-butene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene- Ethylene copolymers such as 2-norbornene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene .1-hexene-dicyclopentadiene copolymer, ethylene-1-octene-dicyclopentadiene copolymer, ethylene-1
Preferred are ethylene copolymers such as -hexene / 5-ethylidene-2-norbornene copolymer and ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer. These olefinic elastomers may be a mixture of two or more. The MFR of the elastomer is not particularly limited, but is preferably 0.1 to 200 g.
/ 10 minutes. The production of the olefin-based elastomer in the present invention is not limited at all, and may be performed using a single-site catalyst or a multi-site catalyst.
Any of those using a site catalyst is suitably used. The α-olefin used for the component (II) includes
Besides the above, 2-butene, 2-methyl-1-propene,
1-pentene, 2-methyl-1-butene, 4-methyl-
1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 5-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-
1-pentene, 1-decene and the like, and non-conjugated dienes include tricyclopentadiene, 5-methyl-
2,5-norbonadiene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (1-butenyl) -2-norbornene, cyclooctadiene, vinylcyclohexene , 1,5,9-cyclododecatriene,
1,4-hexadiene, 1,6-octadiene, 1,7
-Octadiene, 1,8-nonadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene and the like. These can be used alone or in combination of two or more.

(III) Component The hydrogenated block copolymer used as the component (III) of the present invention comprises (a) polymer blocks A and B in a molecule.
(Where A has a 1,2-vinyl bond content of 25
B is a polybutadiene block having a conjugated diene compound content of 50% by weight or more and a conjugated diene compound having a vinyl bond content of 65% by weight or more. -B)
a star block copolymer represented by nX (where n is an integer of 2 or more and X represents a coupling agent residue), wherein the content of the polymer block A is 5 to 60% by weight; When the content of the polymer block B is 95 to 40% by weight (however, A
+ B = 100% by weight), and (b) polymer blocks A and B are contained in the molecule of a star-type hydrogenated block copolymer in which 80% or more of the double bond residues of the conjugated diene portion are hydrogenated. [However, A and B are the same as those in the above (a)], and the content of the polymer block A, which is a linear block copolymer having a block structure represented by AB, is 5 to 5. 60% by weight,
The content of the polymer block B is 95 to 40% by weight (however, A + B = 100% by weight), and the linear hydrogenated block in which 80% or more of the double bond residue of the conjugated diene portion is hydrogenated. Consisting of a polymer and having a weight ratio of (a) / (b) of 1
It is a hydrogenated block copolymer having a total weight average molecular weight of 200,000 to 500,000, from 00/0 to 5/95, component (a) and component (b). Among them, the polymer block A is a polybutadiene block segment having a 1,2-vinyl bond content before hydrogenation of less than 25% by weight, preferably 20% by weight or less, more preferably 18% by weight or less. The polymer block A is prepared by hydrogenating ordinary low-density polyethylene (LD
It becomes a crystalline block segment having a structure similar to PE). When the 1,2-vinyl bond content of the polymer block A before hydrogenation is 25% by weight or more, the obtained hydrogenated block copolymer is soft, and when pelletized, the pellets are liable to adhere to each other, and the thermoplastic resin is used. When producing a composition with the above, operation and handling such as blending are hindered.
Further, the impact resistance of the present composition is lowered, and the mechanical properties are further deteriorated, which is not preferable.

The polymer block B before hydrogenation contains at least 50% by weight of a conjugated diene compound and has a vinyl bond content of the conjugated diene compound (where the vinyl bond is
Conjugated diene polymer block segment having a 1,2-bond and a 3,4-linkage of at least 65% by weight. The polymer block B before hydrogenation is a conjugated diene polymer or a copolymer of another monomer and a conjugated diene compound, and is a rubber-like ethylene butene copolymer or another monomer-ethylene butene copolymer obtained by hydrogenation. It becomes a block segment showing a similar structure to the union. Examples of the conjugated diene compound used for the polymer block B include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-hexadiene, 4,5-dimethyl-
One or more of 1,3-octadiene, chloroprene and the like can be mentioned, but in order to obtain a hydrogenated block copolymer which can be industrially used and has excellent physical properties, 1,3-butadiene, isoprene, 1,3-pentadiene is preferred, and 1,3-butadiene and isoprene are more preferred. Further, other monomers can be used for the polymer block B. Examples of the other monomers include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, and 1,1-diphenylstyrene. , N, N-diethyl-p-aminostyrene, vinylpyridine and the like, and styrene and α-methylstyrene are particularly preferred. The weight ratio of the conjugated diene compound and the other monomer used in the polymer block B is 100 /
0-50 / 50, preferably 100 / 0-60 / 40. Outside this range, the glass transition temperature of the polymer block rises, and the mechanical properties and the modifying effect of the obtained hydrogenated block copolymer become poor. It is not preferable because it is inferior. The vinyl bond content of the conjugated diene compound used in the polymer block B is 65% by weight or more, preferably 70% by weight or more, and if it is less than 65% by weight, after hydrogenation, the polyolefin-based resin and the polyolefin-based elastomer can be mixed. The compatibility is reduced, and the effect of improving the impact resistance of the obtained composition is reduced.

The (III) hydrogenated block copolymer used in the present invention comprises at least (a) a star-shaped block copolymer in which the block structure before hydrogenation is represented by (AB) nX;
And (b) the block structure before hydrogenation is represented by (AB), and thus comprises a chain block copolymer having a lower molecular weight than the component (a). Examples of the coupling agent in this case include 1,2-dibromoethane, methyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate, dioctyl adipate, and benzene-1 , 2,4-diisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermanium,
Tetrachlorotin, and the like. The content of the block A in the block copolymer of the component (III) is 5-6.
0% by weight, preferably 5 to 55% by weight, the content of block B is 95 to 40% by weight, preferably 95 to 45% by weight. When the content of the block A is less than 5% by weight, the obtained hydrogenated block copolymer is soft, and when formed into pellets, the adhesion of the pellets is likely to occur. Cause trouble. If it exceeds 60% by weight, the effect of improving the impact resistance of the composition will be reduced. The hydrogenated block copolymer used in the present invention has a weight ratio of the component (a) / the component (b) of 100/0 to 50/50, preferably 95/5 to 50/50.
/ 50, more preferably 95/5 to 50/50. When the proportion of the component (a) is less than 50% by weight, the obtained hydrogenated block copolymer is soft, and when formed into pellets, the adhesion of the pellets is likely to occur. This hinders handling and reduces the effect of improving the impact resistance of the resulting composition.
Further, the hydrogenated block copolymer used in the present invention,
The total weight average molecular weight of the component (a) and the component (b) is 20.
~ 500,000, preferably 250,000-500,000, more preferably 250,000-450,000. If it is less than 200,000, the effect of improving the impact resistance of the composition will be reduced, while if it exceeds 500,000, the processability will be reduced and the appearance of the molded product will be deteriorated.

The method for producing the hydrogenated block copolymer of the present invention may be any method. In general, the block copolymer before hydrogenation is obtained by subjecting living anionic polymerization to an organic alkali metal compound as an initiator in an organic solvent. , And then obtained by performing a hydrogenation reaction. As the organic solvent,
Hydrocarbon solvents such as pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, xylene, and toluene are used. As the organic alkali metal compound as a polymerization initiator, an organic lithium compound is preferable. As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, phenyl lithium, hexamethylene dilithium, butadienyl lithium, and isoprenyl dilithium. And the like, and are used in an amount of 0.02 to 0.4 part by weight per 100 parts by weight of the monomer. Also,
Adjustment of the content of the conjugated diene compound having a vinyl bond (hereinafter referred to as “vinyl bond content”) in the polymer block A and the polymer block B before hydrogenation is performed using a Lewis base such as an ether or an amine, specifically, diethyl. ether,
Tetrahydrofuran, propyl ether, butyl ether, higher ether, further ethylene glycol dibutyl ether, diethylene glycol dimethyl ether,
Ether derivatives of polyethylene glycol such as diethylene glycol dibutyl ether and triethylene glycol dimethyl ether, and amines such as tertiary amines such as tetramethylethylene diamine, pyridine, triethylamine and tributylamine are used together with the above organic solvents. Further, the polymerization reaction is usually carried out at -30 to + 150 ° C. Also, the polymerization is
The control may be performed at a constant temperature or may be performed at an elevated temperature. Although any method may be used for forming the block copolymer, generally, in the above-mentioned organic solvent, using a polymerization initiator such as the above-mentioned alkali metal compound, first hydrogenate and then polymerize butadiene so as to become a polymer block A. Then, after hydrogenation, a conjugated diene compound or a conjugated diene and another monomer are polymerized to form a polymer block B, whereby a block copolymer containing the polymer blocks A and B after hydrogenation can be obtained. it can. Thereafter, by reacting with a coupling agent, a star block copolymer can be obtained.

By hydrogenating the star block copolymer obtained as described above, the hydrogenated block copolymer (I) of the present invention in which the double bond residue of the conjugated diene portion has been hydrogenated.
II) is obtained. That is, the hydrogenated block copolymer of the present invention is obtained by dissolving the block copolymer thus obtained in an inert solvent,
It is obtained by hydrogenation in the presence of a hydrogenation catalyst under 0 kg / cm 2 G of pressurized hydrogen. At that time, the olefinically unsaturated bond in the block copolymer is 80% or more, preferably 9% or more.
It is necessary that at least 0%, more preferably at least 95%, be hydrogenated. If it is less than 80%, the heat resistance and the weather resistance are insufficient. Inert solvents used for hydrogenation include hexane, heptane, cyclohexane, benzene, toluene, hydrocarbon solvents such as ethylbenzene,
Or polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether, and tetrahydrofuran.
Examples of the hydrogenation catalyst include hydrogenation catalysts composed of dicyclopentadienyl titanium halide, nickel organic carboxylate, organic carboxylate and the like and organometallic compounds of Groups I to III of the periodic table, carbon, silica, Metal catalysts such as nickel, platinum, palladium, ruthenium, rhenium and rhodium metal catalysts supported on diatomaceous earth and the like, and cobalt, nickel, rhodium and ruthenium complexes are exemplified. Also, lithium aluminum hydride,
Hydrogenated compounds such as p-toluenesulfonyl hydrazide, Zr-Ti-Fe-V-Cr alloy, Zr-
A hydrogenation reaction using a hydrogen storage alloy such as a Ti-Nb-Fe-V-Cr alloy or LaNi5 is also mentioned as a method for producing the hydrogenated block copolymer used in the present invention. The hydrogenation rate of the conjugated diene portion is adjusted by changing the amounts of the hydrogenation catalyst and the hydrogenated compound, or the hydrogen pressure and the reaction time during the hydrogenation reaction. The catalyst residue is removed from the hydrogenated block copolymer solution, if necessary, and a phenolic or amine-based antioxidant is added to easily remove the hydrogenated block copolymer from the polymer solution. Can be isolated. Isolation of the hydrogenated block copolymer can be performed, for example, by adding acetone or alcohol to the hydrogenated block copolymer solution to precipitate the solution, adding the polymer solution to boiling water with stirring, and removing the solvent by distillation. It can be performed by such a method. The hydrogenated block copolymer of the present invention can be used as a modified hydrogenated block copolymer by introducing at least one kind of functional group into the hydrogenated block copolymer.

The composition of the present invention comprises (I) a polypropylene, (II) an olefin-based elastomer, and (III) a hydrogenated block copolymer, and has an excellent balance of fluidity, rigidity, impact resistance, and molded appearance. A composition. In the composition of the present invention, the mixing ratio of (I) polypropylene, (II) olefin-based elastomer, and (III) hydrogenated block copolymer is as follows: component (I) 50 to 95% by weight, preferably 50 to 90% by weight; (II) 50 to 5% by weight of a component,
Component (III) is 0.1 to 50 parts by weight, preferably 0.3 to 45 parts by weight, based on 100 parts by weight, preferably 50 to 10% by weight. When the amount of the component (I) is less than 50% by weight, the rigidity is reduced. When the amount exceeds 95% by weight, the effect of improving the impact resistance of the composition is insufficient, which is not preferable. In addition, the component (II) contains 5% by weight.
When the amount is less than 50%, the effect of improving the impact resistance of the composition is insufficient, and when the amount exceeds 50% by weight, the rigidity decreases, the fluidity becomes insufficient, and the object of the present invention cannot be achieved. Absent. Further, the component (III) is (I) + (I
If the amount is less than 0.1 part by weight with respect to the total 100 parts by weight of the component (I), the effect of improving the impact resistance of the composition is insufficient. If the amount exceeds 50 parts by weight, the rigidity is reduced. ,
It is not preferable because the object of the present invention cannot be achieved.

The composition of the present invention may optionally contain (I)
It is possible to add an inorganic filler as component V). By adding the component (IV), the rigidity is particularly excellent,
It is possible to obtain a composition having high rigidity and high fluidity, and excellent impact resistance and molded appearance. In the composition of the present invention, the inorganic filler constituting the component (IV) enhances the rigidity of the composition. For example, silica, talc,
Examples thereof include calcium carbonate, magnesium carbonate, glass fibers, carbon fibers, metal fibers, glass beads, mica, potassium titanate whiskers, montmorillonite, and zinc oxide whiskers. These may be used alone or as a mixture of two or more. The compounding amount of the component (IV) in the composition of the present invention is 50 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight or less. If the amount of the component (IV) exceeds 50 parts by weight, the impact resistance at a low temperature is greatly reduced, and the balance between fluidity, rigidity, impact resistance, and appearance of the molded product is poor. The production of the composition of the present invention is not particularly limited, and a known method can be used. For example, the composition of the present invention can be obtained by kneading the components with various extruders, Banbury mixers, kneaders, rolls, and the like. In the propylene-based resin composition of the present invention,
Various additives as required, for example, stabilizers such as anti-aging agents, heat stabilizers, ultraviolet absorbers, copper damage inhibitors, fillers such as carbon, aramid fiber, wood powder, cork powder, cellulose powder, rubber powder, etc. Can be used in combination. Further, the composition of the present invention may be used by blending a softener such as a plasticizer, an oil, or a low molecular weight polymer together with the above additives.

[0014]

EXAMPLES Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention. In the examples, parts and percentages are by weight unless otherwise specified. Various measurements in the examples were based on the following methods. Content of 1,2 -bonds, etc. The content of 1,2-bonds, etc. was calculated by the Hampton method using infrared analysis. Hydrogenation rate The hydrogenation rate of the conjugated diene was 10% in ethylene tetrachloride as a solvent.
Calculated from 0 MHz, 1 H-NMR spectrum. Weight average molecular weight The weight average molecular weight (hereinafter, also referred to as “molecular weight”) was determined by gel permeation chromatography (GPC) in terms of polystyrene. Fluidity 230 ° C, load 2.1 according to JIS K7210
The melt flow rate (MFR) at 6 kg was measured and used as an index of moldability. Rigidity The flexural modulus was measured according to JIS K7203 and used as an index of rigidity. Impact resistance Izod impact strength was measured according to JIS K7110 and used as an index of impact resistance. Tensile elongation Tensile elongation was measured according to JIS K7113. Molding appearance The molding appearance was visually evaluated according to the following criteria. ：: Good appearance. ×: Poor appearance phenomena such as pearl luster, flow mark, and rough surface are observed.

REFERENCE EXAMPLES Various components used in the formulations shown in Examples and Comparative Examples are as follows. Polypropylene A polypropylene (PP-1 to PP-5) having the MFR, flexural modulus and Izod impact strength shown in Table 1. Olefinic elastomer EP-1: Ethylene / propylene copolymer [EP01NS manufactured by Nippon Synthetic Rubber Co., Ltd.] EP-2: Ethylene / propylene copolymer [EP912 manufactured by Nippon Synthetic Rubber Co., Ltd.] EB-1: Ethylene / 1 -Butene copolymer [Nippon Synthetic Rubber Co., Ltd. EBM2041P] EB-2: Ethylene / 1-butene copolymer [Mitsui Petrochemical Co., Ltd. Tuffmer A4085] EH-1: Ethylene / 1-hexene copolymer Combined [EXACT2010, manufactured by Exxon Chemical] EH-2: Ethylene / 1-hexene copolymer [EXACT2009, manufactured by Exxon Chemical] EO-1: Copolymer of ethylene / 1-octene [ENGAGE EG8100, manufactured by Dow Chemical] EO-2 : Ethylene / 1-octene copolymer [ENGAGE EG manufactured by Dow Chemical 200]

[0016]

[Table 1]

The hydrogenated block copolymer in Reference Example 1 (preparation of hydrogenated block copolymer) degassing a 10 liter autoclave, dehydrated cyclohexane 5 kg, after charged with 1,3-butadiene 300 g, tetrahydrofuran 0. 25 g and 1.00 g of n-butyllithium were added to carry out constant isothermal polymerization at a polymerization temperature of 80 ° C. After the polymerization conversion reached almost 100%, the reaction solution was cooled to 15 ° C., 75 g of tetrahydrofuran and 700 g of 1,3-butadiene were added, and the temperature was elevated by polymerization. After the polymerization was completed, 0.53 g of tetrachlorosilane was added, and the reaction was carried out for about 20 minutes. After the reaction was brief, the amount of living Li was measured and found to be 3.1 mmol. 0.56 g of benzophenone was added to the system and stirred for 10 minutes. From the color change of the polymer liquid,
It was confirmed that there was no living polymer terminal lithium as a living anion. Next, a reaction product obtained by reacting 3.51 g of benzophenone dissolved in 20 ml of cyclohexane with 1.20 g of n-butyllithium in advance in a nitrogen atmosphere for 10 minutes was charged, and bis (cyclopentadienyl) titanium dichloride was added. A component in which 52 g and 1.51 g of diethyl aluminum chloride dissolved in 10 ml of toluene were previously mixed under a nitrogen atmosphere was charged into an autoclave and stirred. Hydrogen gas was supplied at a pressure of 8 kg / cm 2 G, and a hydrogenation reaction was performed at 90 ° C. for 1.5 hours. The hydrogenation rate of the obtained hydrogenated polymer was 98%, and the molecular weight was 40,000. Also, the first
The 1,3-butadiene block had a 1,2-vinyl bond content of 15% as measured at the end of the first-stage 1,3-butadiene block polymerization, and was measured at the end of the second-stage 1,3-butadiene polymerization. As a result of calculation from the 1,2-vinyl bond content and the first-stage 1,2-vinyl bond, the 1,2-butadiene block in the second stage had a 1,2-vinyl bond content of 80%. Reference Examples 2 to 17 By the same method as in Reference Example 1, varying the monomer species, the amount of the monomer, the amount of the catalyst, the polymerization time, the polymerization temperature, etc. so as to obtain each hydrogenated block copolymer in Tables 2 to 4. Produced by Tables 2 to 5 show these results.

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

Examples 1 to 5 and Comparative Example 1 The hydrogenated block copolymer (S-
1), polypropylene, and an olefin-based elastomer were mixed at a weight ratio shown in Table 6 using a 40 mmφ extruder. The mixed composition was pelletized by a pelletizer and then injection molded to prepare a test piece for evaluating physical properties. Table 6 shows the results of the physical property evaluation. These examples are:
All are compositions using a hydrogenated block copolymer within the scope of the present invention, and have excellent low-temperature impact resistance and a good balance of fluidity, rigidity, impact resistance, tensile elongation, and molded appearance. It is something. On the other hand, Comparative Example 1 is an example in which the hydrogenated block copolymer was not used. However, although the fluidity was high, the impact resistance and the rigidity were extremely poor, and the balance of physical properties was lacking as a whole. Examples 6 to 53 In the same manner as in Example 1, the composition of the hydrogenated block copolymer obtained in Reference Examples 1 to 9, the polypropylene, the olefin-based elastomer, and the talc in the weight ratios shown in Tables 6 to 14 were used. A product was prepared and each physical property was evaluated. Table 6-
It is shown in FIG. These examples are all compositions using a hydrogenated block copolymer within the scope of the present invention, and are particularly excellent in rigidity and fluidity, and these fluidity, rigidity and impact resistance, tensile elongation, It is excellent in balance with the molded appearance.

[0023]

[Table 6]

[0024]

[Table 7]

[0025]

[Table 8]

[0026]

[Table 9]

[0027]

[Table 10]

[0028]

[Table 11]

[0029]

[Table 12]

[0030]

[Table 13]

[0031]

[Table 14]

Comparative Examples 2 to 10 In the same manner as in Example 1, injection molded articles were produced using the hydrogenated block copolymers obtained in the above Reference Examples 10 to 17, and their physical properties were evaluated. The results are shown in Tables 15 and 16. A composition using a hydrogenated block copolymer that does not satisfy the requirements of the present invention lacks the balance of fluidity, rigidity, impact resistance, and molded appearance. Comparative Example 6 was an example in which the hydrogenated block copolymer was not used, and the fluidity and impact resistance were poor, and the fluidity, impact resistance and rigidity, and the balance of the molded appearance were lacking. .

[0033]

[Table 15]

[0034]

[Table 16]

[0035]

According to the present invention, polypropylene having excellent balance of fluidity, rigidity, impact resistance and molded appearance is obtained by blending polypropylene, an olefin-based elastomer and a hydrogenated block copolymer having a specific structure. A resin composition can be obtained. The composition of the present invention comprises:
Used as various molded products by injection molding, extrusion molding, vacuum molding, etc., taking advantage of its excellent characteristics, automotive interior and exterior materials, various electric and electronic parts, housings, industrial parts, stationery, medical materials, films, It can be widely used for sheet products.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI (C08K 13/04 3:36 3:34 3:26 7:04)

Claims (1)

[Claims] (I) The flexural modulus is 8000 kgf / c
m ² (785 MPa) or more, temperature 230 ° C., load 2.
(III) (a) weight in the molecule based on a total of 100 parts by weight of 50 to 95% by weight of polypropylene having a melt flow rate of 10 g / 10 min or more at 16 kg, and 50 to 5% by weight of (II) olefin elastomer. (A is a polybutadiene block having a 1,2-vinyl bond content of less than 25% by weight, B is a conjugated diene compound containing at least 50% by weight, and the vinyl bond content of the conjugated diene compound is A hydrogenated block copolymer in which at least 80% of the double bond residues in the conjugated diene portion of the conjugated diene polymer block is 65% by weight or more, and the block structure is (AB) nX (Where n is an integer of 2 or more and X represents a residue of a coupling agent), which is a star-shaped block copolymer represented by the following polymer block A: 5-60% by weight content, the content of the polymer block B is 95
40% by weight (however, A + B = 100% by weight) of a star-shaped hydrogenated block copolymer and (b) polymer blocks A and B in the molecule [where A and B are the above (a) And the block structure was a linear block copolymer represented by AB. The content of the polymer block A was 5 to 60% by weight and the content of the polymer block B was 95. ~
40% by weight (however, A + B = 100% by weight)
(A) / (b) weight ratio of 100/0 to 50/50,
The total weight average molecular weight of the component (a) and the component (b) is 20.
A polypropylene-based resin composition comprising 0.1 to 50 parts by weight of a hydrogenated block copolymer which is 10,000 to 500,000 (IV) 0 to 50 parts by weight of an inorganic filler.