JP3534479B2 - Polypropylene resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has high rigidity, high heat resistance,
The present invention relates to a polypropylene resin composition having excellent impact resistance.

[0002]

Polypropylene is excellent in rigidity, surface gloss and heat resistance, but has a drawback that it is inferior in low temperature impact resistance. As a method of improving impact resistance, a method of adding rubber by blending or multistage polymerization is widely used. However, these methods have the drawback that the original characteristics of polypropylene, such as rigidity, surface hardness, and heat resistance, are reduced. For the purpose of improving impact resistance of polypropylene resin containing rubber, talc,
Many attempts have been made to use fillers such as glass fiber, but due to increase in density, deterioration of appearance, etc., the quantity is limited, and a satisfactory material has not been obtained. The graft copolymer having improved impact resistance of polypropylene resin is a blend of styrene-grafted polypropylene and rubber containing aromatic hydrocarbon (JP-A-4-224854), styrene / methyl (meth). Blends of acrylate, styrene / acrylonitrile and other co-grafted polypropylene and polypropylene having a wide molecular weight distribution and rubber (Japanese Patent Laid-Open No. 145439/1994) can be mentioned. In these compositions, although the balance between rigidity and impact resistance is improved, heat resistance is not specified, and a polypropylene resin composition having an excellent balance of rigidity / heat resistance / impact resistance is obtained. No suitable method has been proposed.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art and provides a polypropylene resin composition having improved impact resistance without lowering rigidity and heat resistance.

[0004]

[Means for Solving the Problems] That is, as a result of intensive studies conducted by the inventors in order to solve the above-mentioned problems, as a result, the component (A): polypropylene-based resin has a glass transition point of 120 ° C.
A modified polypropylene-based resin obtained by graft-copolymerizing a vinyl monomer forming the above polymer, or a mixture of the modified polypropylene-based resin and a polypropylene-based resin, wherein the unit derived from the vinyl monomer is 0.03 to 3
50% to 95% by weight of a resin component of 0% by weight and component (B): 50% to 5% by weight of a rubber component comprising a styrene rubber or a mixture of a styrene rubber and an olefin rubber.
It was found that the polypropylene-based resin composition having the following composition has an excellent balance of rigidity / heat resistance / impact resistance. The present invention has been completed based on such findings.

The contents of the present invention will be described in detail below. The modified polypropylene resin, which is a constituent of the polypropylene resin composition according to the present invention, has a glass transition point of 120 ° C.
It is obtained by graft-copolymerizing the vinyl monomer forming the above polymer with a polypropylene resin.
Vinyl monomers forming a polymer having a glass transition point of 120 ° C. or higher include 2-methylstyrene, 2,5-dimethylstyrene, 4-dimethylaminostyrene, hydroxymethylstyrene, α-methylstyrene, N-vinylcarbazole, and 4 -Phenylstyrene, 9-vinylanthracene, 2-vinylnaphthalene, methacrylic acid and the like can be mentioned. These may be used in combination of two or more kinds at the same time. Of these, a vinyl monomer having an aromatic ring having a good miscibility with the rubber component (B) and having a high radical polymerizability is preferable.

In the modified polypropylene resin as the component (A) of the present invention, or in the mixture of the modified polypropylene resin and the polypropylene resin, the unit derived from the vinyl monomer is 0.03 to 30% by weight, Preferably 0.05 to 20% by weight, more preferably 0.1 to 20% by weight.
It is 10% by weight. When the unit derived from the vinyl monomer is less than 0.03% by weight, the impact resistance when blended with the rubber component (B) is not sufficiently improved, and when the unit derived from the vinyl monomer exceeds 30% by weight. The mechanical properties such as impact resistance of polypropylene resin are deteriorated.

In producing the modified polypropylene resin used in the present invention, various commonly known methods can be used. Solution grafting method in which polypropylene resin is dissolved in a solvent to form a solution, and a radical initiator and the vinyl monomer are mixed and reacted, melt grafting method in which the resin is modified in an extruder without using a solvent, polypropylene resin, radical initiation Agent, a low temperature grafting method of reacting the vinyl monomer below the melting point of the polypropylene-based resin, electron beam to the polypropylene-based resin, after irradiation with high energy ionizing radiation such as radiation, contact the vinyl monomer, and the polypropylene-based resin and the A method of irradiating the vinyl monomer mixture with a high-energy ionizing ray such as electron beam or radiation can be used. Further, in order to remove unreacted vinyl monomer, after the graft modification, a step of removing unreacted substances, reaction by-products and the like can be performed by washing with a solvent or warm water. As the graft modification method, a low temperature graft method and a method using a high energy ionizing ray are preferable because of a decrease in molecular weight after modification of the polypropylene resin.

As the radical initiator, an organic peroxide or an azo type initiator can be used. further,
It is preferable to use the above-mentioned initiator having a decomposition half-life at the temperature of graft modification of 300 minutes or less. Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide and o-methyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2, 5
-Dialkyl peroxide such as di (t-butylperoxy) hexane, peroxydicarbonate such as di-propylperoxydicarbonate, peroxy such as t-butylperoxypivalate, t-butylperoxylaurate Ester, methyl ethyl ketone peroxide,
Examples thereof include ketone peroxides such as cyclohexanone peroxide, peroxyketals such as 1,1-bis (t-butylperoxycyclohexane), and hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide. As the azo-based initiator, 2,2-
Examples thereof include azobisisobutyronitrile. Organic peroxides are preferable in terms of crosslinking efficiency and the like.

Examples of the polypropylene resin which is a constituent component of the component (A) of the present invention include a propylene homopolymer and a copolymer of propylene and ethylene or an α-olefin having 4 to 10 carbon atoms. Α with 4 to 10 carbon atoms
-As olefins, 1-butene, isobutylene, 1
-Pentene, 3-methyl-1-butene, 1-hexene,
3,4-dimethyl-1-butene, 1-heptene, 3-methyl-1-hexene and the like can be mentioned. The copolymer may be a random copolymer or a block copolymer, but a block copolymer is preferable, and a propylene-ethylene copolymer is more preferable.

The modified polypropylene resin as the component (A) of the present invention, or the mixture of the modified polypropylene resin and the polypropylene resin, is used in an amount of 50 to 95% by weight based on the polypropylene resin composition. The range is preferably 60 to 90% by weight. When this amount is less than 50% by weight, mechanical properties such as excellent rigidity and heat resistance of the polypropylene resin are impaired. On the other hand, if it exceeds 95% by weight, sufficient impact resistance of the polypropylene resin composition cannot be obtained. In addition, the modified polypropylene resin used here, or the MFR of a mixture of the modified polypropylene resin and the polypropylene resin (JIS K7
210 Table 1 Condition 14) is 0.01-1000 g
/ 10 minutes, preferably 0.1 to 500 g / 10 minutes.

As the styrene-based rubber which is a constituent of the rubber component which is the component (B) of the present invention, one or more monoalkenyl aromatic hydrocarbon-conjugated diene copolymers or hydrides thereof can be mentioned. Preferably, one or more monoalkenyl aromatic hydrocarbon-conjugated diene block copolymers or hydrides thereof may be mentioned.
Specific examples of the monoalkenyl aromatic hydrocarbon monomer include alkylstyrene such as styrene, α-methylstyrene and vinyltoluene. Preferably styrene is used. Specific examples of the conjugated diene monomer include butadiene and isoprene. These monomers may be used alone or in combination of two or more.

Monoalkenyl aromatic hydrocarbon-conjugated diene block copolymers are AB (diblock structure), linear ABA (triblock structure), linear ABA.
B (tetrablock structure) structure and the like. A above is a monoalkenyl aromatic hydrocarbon polymer block,
B above is a conjugated diene polymer block. Specific examples of such a styrene rubber include a styrene-butadiene block copolymer and its hydrogenated product, and a styrene-butadiene-styrene block copolymer and its hydrogenated product.

The olefinic rubber which is a constituent of the rubber component which is the component (B) of the present invention is obtained by copolymerizing ethylene and α-olefin or non-conjugated diene thereof with a Ziegler catalyst. The resulting ethylene-α-olefin-based copolymer can be mentioned. The α-olefin used as a copolymerization monomer of the ethylene-α-olefin copolymer is an α-olefin having 3 to 12 carbon atoms, and specific examples include propylene, butene-1, 4-methylpentene-1, Hexene-1, octene-1 and the like can be mentioned, and preferably propylene and butene-1 are used. These α
-The olefins may be used alone or in combination of two or more. It is also possible to copolymerize a non-conjugated diene with an α-olefin, and examples of the non-conjugated diene include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-
Ethylidene-2-norbornene, cyclooctadiene,
Vinylcyclohexene, 1,4-hexadiene, 1,6
-Octadiene, 1,8-nonadiene, 1.9-decanediene, 3,6-dimethyl-1,7-octadiene,
Examples include 4,5-dimethyl-1,7-octadiene. Specific examples of such an olefin rubber obtained by copolymerizing ethylene with an α-olefin or a non-conjugated diene include ethylene / propylene copolymer rubber and ethylene / propylene copolymer rubber.
Examples thereof include butene copolymer rubber and ethylene / propylene / non-conjugated diene copolymer rubber. The ethylene content of these olefin rubbers is preferably 30 to 80% by weight.

MFR (JIS K7210, Table 1, Condition 1) of a rubber component composed of a styrene rubber or a mixture of a styrene rubber and an olefin rubber which is the component (B) of the present invention.
4) is in the range of 0.01 to 300 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes.

M of the polypropylene resin composition of the present invention
FR (in accordance with JIS K7210 Table 1, Condition 14) is in the range of 0.1 to 500, preferably 0.3 to 300. If the MFR is out of this range and is too small or too large, molding becomes difficult, which is not preferable.

Inorganic and organic fillers and reinforcing agents are added to the polypropylene resin composition of the present invention in an amount of 5 to 100 parts by weight per 100 parts by weight of the polypropylene resin composition in any manufacturing or molding process. be able to. Specific examples of the inorganic fillers and reinforcing agents include carbonates such as calcium carbonate and magnesium carbonate, silicates such as talc, clay and mica, powders such as alumina, magnesium oxide, calcium oxide, calcium hydroxide and magnesium hydroxide. Materials, glass fibers, fibers such as metal-coated glass fibers, glass beads, spherical materials such as glass balloons, and the like. The surface of the inorganic filler and the reinforcing agent may be surface-treated with a silane compound, a titanate compound or the like. Specific examples of the organic filler and the reinforcing agent include organic fibers such as acrylic fiber, aramid fiber, nylon and polyester fiber. The amount of the filler and the reinforcing agent used is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polypropylene resin composition of the present invention. 5
If it is less than 100 parts by weight, the reinforcing effect is not sufficient, and if it exceeds 100 parts by weight, the specific gravity is increased and the appearance is deteriorated.

Further, various additives and compounding agents can be used in the polypropylene resin composition of the present invention within a range that does not impair the characteristics of the composition. Specific examples of these include antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), nucleating agents, antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), Colorants (dyes, pigments), fragrances and the like can be mentioned.

In the method for producing the polypropylene resin composition of the present invention, various commonly known resin mixing methods can be used. As a specific example, a method of mixing the components in a molten state, that is, a method of using a pressure kneader, a roll, a Banbury mixer, a static mixer, a screw type extruder and the like, which are commonly used, can be mentioned. . The polypropylene resin composition of the present invention can be easily processed into molded articles of various shapes by any conventionally known molding processing method such as injection molding method and extrusion molding method.

[0019]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto. (Evaluation method) MFR (according to JIS K7210 Table 1, condition 14) Bending elastic modulus (according to JIS K7203) Izod impact strength (according to JIS K7110 notch) HDT (JIS K7207 Table 1B method load 4.6 kg)
f / cm ² ) Method for producing polypropylene resin [Reference Example a] (Step 1) Preparation of solid catalyst 47.6 g (50) of anhydrous magnesium chloride under a nitrogen atmosphere
0 mmol), 259 ml of decane and 234 ml (1.5 mol) of 2-ethylhexyl alcohol at 130 ° C.
After heating reaction for 2 hours to form a uniform solution, 11.1 g (75 mmol) of phthalic anhydride was added to this solution,
Stirring and mixing were further performed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. After cooling the obtained homogeneous solution to room temperature, titanium tetrachloride 2.0 kept at −20 ° C.
The total amount was added dropwise to L (18 mol) over 1 hour.
After completion of the dropping, the temperature of the mixed solution was raised to 110 ° C. over 4 hours, and when reaching 110 ° C., 26.8 ml (125 mmol) of diisobutyl phthalate was added, and the mixture was stirred and reacted at 110 ° C. for 2 hours. After completion of the reaction, a solid component was collected by filtration under heating, and then 2.0 L (18 mol) of titanium tetrachloride was suspended in this reaction product, which was then heated at 110 ° C. for 2 hours.
Reacted for hours. After completion of the reaction, the solid component was collected again by hot filtration and washed with 2.0 L of decane at 110 ° C. 7 times and 2.0 L of hexane at room temperature 3 times. (Step 2) TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ )]
₂ ] Preparation of a solution of titanium tetrachloride (19 g, 100 mmol) in hexane (1.0 L): diisobutyl phthalate (27.8 g, 1)
(00 mmol) was added dropwise over about 30 minutes while maintaining 0 ° C. After completion of the dropping, the temperature was raised to 40 ° C. and the reaction was performed for 30 minutes. After the reaction was completed, the solid component was collected and hexane 500 ml
The product was washed 5 times with. (Step 3) Adjustment of Polymerization Catalyst Components 40 g of the solid catalyst obtained above was suspended in 600 ml of toluene, and TiCl ₄ [C ₆ H ₄ (COO ⁱ C
₄ H ₉ ) ₂ ] 10.3 g (22 mmol) was reacted for 1 hour. After the reaction was completed, 200 ml of titanium tetrachloride (1.8
(mol) was added and the mixture was reacted at 110 ° C. for 2 hours. After completion of the reaction, a solid component was collected by hot filtration, and then 600 ml of toluene and 200 ml of titanium tetrachloride were added to the reaction product.
After suspending (1.8 mol), the mixture was reacted at 110 ° C. for 2 hours. After completion of the reaction, the solid component was collected again by hot filtration and washed with 1.0 L of toluene at 110 ° C. seven times and with 1.0 L of hexane at room temperature three times. (Step 4) In an autoclave having an internal volume of 3 L under a prepolymerized nitrogen atmosphere,
500 ml of n-heptane, triethylaluminum 6.
0 g (0.053 mol), t-butyltrimethoxysilane 3.1 g (0.017 mol), and 100 g of the polymerization catalyst component obtained above were added, and the mixture was stirred at a temperature range of 0 to 5 ° C for 5 minutes. Next, 10 g per 1 g of polymerization catalyst component
Propylene was fed into the autoclave so that it would polymerize, and prepolymerized in the temperature range of 0 to 5 ° C for 1 hour. The obtained prepolymerization catalyst was washed 3 times with 500 ml of n-heptane and used for the following polymerization. (Step 5) Main Polymerization In a nitrogen atmosphere, polymerization was carried out as follows using an autoclave with an internal volume of 6 L equipped with a stirrer. 2.0 g of the prepolymerization catalyst component prepared by the above method, 11.4 g (100 mmol) of triethylaluminum, 5.9 g (33 mmol) of t-butyltrimethoxysilane were added, and then 18 kg of propylene and MFR of the polymer were 30 g / 1.
Hydrogen was supplied so as to reach 0 minutes, and polymerization was carried out at 70 ° C. for 30 minutes. After the polymerization, unreacted gas is removed and MFR3
A propylene homopolymer of 5 g / 10 min was obtained.

[Reference Example b] The MFR was carried out in the same manner as in Reference Example a except that the hydrogen supply amount was changed in the main polymerization step.
A propylene homopolymer of 1.5 g / 10 minutes was obtained.

[Reference Example c] (Step 1) Preparation of solid catalyst 56.8 g of anhydrous magnesium chloride was added to 10 parts of absolute ethanol.
0g, Idemitsu Kosan Vaseline oil (CP15N) 50
0 ml and Shin-Etsu Silicone Silicone Oil (KF9
6) Add 120 ml of a 500 ml mixture under a nitrogen atmosphere.
Completely dissolved at ℃. This mixture is TK manufactured by Tokushu Kika Kogyo Co., Ltd.
The mixture was stirred at 120 ° C. and 300 rpm for 3 minutes using a homomixer. Then, the mixture was transferred into 2 L of anhydrous heptane while maintaining stirring and cooling so as to maintain 0 ° C or lower. The obtained white solid was thoroughly washed in anhydrous heptane and dried under vacuum at room temperature. 30 g of the obtained white solid was suspended in 200 ml of anhydrous heptane, and 500 ml of titanium tetrachloride was added dropwise over 1 hour while stirring at 0 ° C.
Next, 4.96 g of diisobutyl phthalate was added when the temperature reached 40 ° C after heating was started, and the temperature was raised to 100 ° C in about 1 hour. After reacting at 100 ° C. for 2 hours, a solid component was collected by filtration while hot. Titanium tetrachloride (500 ml) was added to the obtained solid component, and the mixture was reacted at 120 ° C. for 1 hour under stirring, and then the solid component was collected by hot filtration again. It was washed 3 times. (Step 2) TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ )]
_[2 ] Adjustment: To a solution of 1 L of hexane containing 19 g of titanium tetrachloride, 27.8 g of diisobutyl phthalate was added, while maintaining the temperature at 0 ° C.
It was dripped in 0 minutes. After the dropping is completed, the temperature is raised to 40 ° C.
Reacted for minutes. After the reaction was completed, the solid component was collected and washed with 500 ml of hexane five times to obtain the desired product. (Step 3) Preparation of polymerization catalyst component 20 g of the solid catalyst obtained above was suspended in 300 ml of toluene, and TiCl ₄ [C ₆ H ₄ (COO ⁱ C
₄ H ₉ ) ₂ ] 5.2 g for 1 hour. After the reaction,
The solid component was collected by filtration under heat, resuspended in 300 ml of toluene and 10 ml of titanium tetrachloride, and reacted at 90 ° C. for 1 hour. After the reaction was completed, the solid component was collected again by hot filtration and washed with 500 ml of toluene at 90 ° C. five times and with 500 ml of hexane at room temperature three times. (Step 4) Prepolymerization Under a nitrogen atmosphere, in an autoclave having an internal volume of 3 L, 500 ml of n-heptane, 6.0 g of triethylaluminum,
3.9 g of dicyclopentyldimethoxysilane and 10 g of the polymerization catalyst component prepared by the above method were added, and 0 to 5 was added.
The mixture was stirred in the temperature range of ° C for 5 minutes. Next, the polymerization catalyst component 1
Propylene was fed into the autoclave so that 10 g of propylene was polymerized per g, and prepolymerized in the temperature range of 0 to 5 ° C for 1 hour. The obtained prepolymerized catalyst was washed 3 times with 500 ml of n-heptane and used for the following polymerization. (Step 5) Main Polymerization First Stage Polymerization: In a nitrogen atmosphere, an autoclave with an internal volume of 60 L equipped with a stirrer was used to prepare 2.0 g of the prepolymerized catalyst prepared by the above method, 11.4 g of triethylaluminum, and dicyclopentyldimethoxysilane. 84 g of propylene was added, and then 18 kg of propylene and hydrogen were added so that the concentration was 13,000 mol ppm based on propylene, the temperature was raised to 75 ° C., and polymerization was performed for 1 hour. Then, unreacted propylene was removed to terminate the polymerization. After the reaction was completed, the reaction product was sampled. Second-stage polymerization: After completion of the first-stage polymerization, liquid propylene is removed, and ethylene / propylene = 40/60 at a temperature of 75 ° C.
(Molar ratio) mixed gas 2.2Nm ³ / hour, hydrogen 20N
Copolymerization was carried out for 40 minutes at a feed rate of liter / hour. After the polymerization was completed, the unreacted gas was removed to terminate the polymerization. As a result, the ethylene content was 9.5% by weight and the MFR was 17 g / 1.
A propylene-ethylene block copolymer having 0 minutes was obtained.

Production Method of Modified Polypropylene Resin (Reference Example 1) MFR 35 g / 1 obtained in Reference Example a as polypropylene resin in 10 L autoclave
100 parts by weight of propylene homopolymer for 0 minutes, 10 parts by weight of N-vinylcarbazole (a glass transition point of the polymer of 190 ° C.) as a vinyl monomer, and 2.5 parts by weight of a xylene solution of 40% by weight of benzoyl peroxide as a radical initiator. Was charged and the system was thoroughly replaced with nitrogen. Rotation speed 100r
pm, the system temperature was 70 ° C., and the system temperature was 10 after stirring for 30 minutes.
It was raised to 0 ° C. and stirred for 90 minutes. Using 100 parts by weight of the obtained crude modified polypropylene resin, chloroform was used in an amount 3 times (weight ratio), and washing was performed at 50 ° C. for 1 hour. The MFR of the obtained modified polypropylene resin is 37 g / 10.
Minutes, the unit derived from N-vinylcarbazole was 1.5% by weight (determined by infrared absorption spectrum).

Reference Example 2 100 parts by weight of a propylene homopolymer having a MFR of 1.5 g / 10 min obtained in Reference Example b as a polypropylene resin, 5 parts by weight of N-vinylcarbazole as a vinyl monomer, and a radical initiator. Benzoyl peroxide / lauroyl peroxide =
After dry blending 2 parts by weight of a mixture of 50/50 by weight with a Henschel mixer, using a 30 mmφ single screw extruder,
Melt modification was performed at 180 ° C. The obtained crude modified polypropylene resin was washed in the same manner as in Reference Example 1 to obtain MFR30g.
/ 10 minutes, a unit derived from N-vinylcarbazole 1.
2% by weight of modified polypropylene resin was obtained.

Reference Example 3 As a vinyl monomer, α-
Methyl styrene (glass transition point of polymer 168 ° C.) 10
Parts by weight were carried out in the same manner as in Reference Example 1 except that methyl ethyl ketone was used as the washing solvent, and MFR 33 g / 10
Thus, a modified polypropylene resin having a unit derived from α-methylstyrene of 2.5% by weight was obtained.

Reference Example 4 As a vinyl monomer, 2,
5 dimethyl styrene (polymer glass transition point 143 ° C)
Same as Reference Example 3 except that 10 parts by weight is used,
A modified polypropylene resin having an MFR of 18 g / 10 minutes and a unit derived from 2,5 dimethylstyrene of 3.2% by weight was obtained.

Reference Example 5 The same procedure as in Reference Example 2 except that 5 parts by weight of 4-phenylstyrene (glass transition point of the polymer: 161 ° C.) was used as the vinyl monomer and methyl ethyl ketone was used as the washing solvent, and MFR of 15 g was used. / 1
At 0 minutes, a modified polypropylene resin having a unit derived from 4-phenylstyrene of 1.6% by weight was obtained.

Reference Example 6 As a polypropylene resin, a propylene-ethylene block copolymer having an MFR of 17 g / 10 min (ethylene content 9.5) obtained in Reference Example c.
Wt%) and use the same procedure as in Reference Example 4 to obtain MF
A modified polypropylene-based resin having an R of 10 g / 10 minutes and a unit derived from 2,5-dimethylstyrene of 4.2% by weight was obtained.

(Comparative Reference Example 1) N as a vinyl monomer
-Vinylcarbazole was used in the same manner as in Reference Example 1 except that 0.2 part by weight and a radical initiator of 0.1 part by weight were used.
A modified polypropylene resin having an MFR of 36 g / 10 minutes and a unit derived from N-vinylcarbazole of 0.04% by weight was obtained.

Comparative Reference Example 2 The same procedure as in Reference Example 3 was carried out except that 10 parts by weight of styrene (polymer glass transition point: 100 ° C.) was used as the vinyl monomer, and MFR of 15 g was used.
/ 10 minutes, a modified polypropylene resin having a unit derived from styrene of 4.0% by weight was obtained.

Production Method of Polypropylene Resin Composition (Example 1) As component (A), 30% by weight of the modified polypropylene resin obtained in Reference Example 1 and the propylene homopolymer obtained in Reference Example a (MFR 35 g) / 10 minutes) 45
% By weight, as a rubber component of component (B), a hydrogenated styrene-butadiene-styrene block copolymer (Asahi Kasei
Tuftec H1052, MFR 12.0g / 10
Min, unit derived from styrene 20% by weight) 25% by weight,
Commercially available stabilizer BHT 0.08 part by weight, Irganox 1010 per 100 parts by weight of component (A) + component (B)
0.05 parts by weight, 0.1 parts by weight of calcium stearate, and 0.4 parts by weight of a nucleating agent (APBB) were dry blended and then kneaded at 210 ° C. using a 20 mmφ co-rotating twin screw extruder to obtain a polypropylene resin composition. Got An injection molding machine (IS-1 manufactured by Toshiba Machine Co., Ltd.
70FII) at a temperature of 200 ° C. and a mold cooling temperature of 5
Injection molded at 0 ° C. The test piece obtained was subjected to a relative humidity of 50.
%, The sample was left in a thermostatic chamber at a temperature of 23 ° C. for 2 days to adjust the condition, and then the physical properties were evaluated. The results are shown in Table 2.

(Example 2) As the component (A), Reference Example 2
Each physical property was evaluated in the same manner as in Example 1 except that 15% by weight of the modified polypropylene resin obtained in 1 and 60% by weight of the propylene homopolymer used in Example 1 were used. The results are shown in Table 2.

(Example 3) As the component (A), Reference Example 3
Each physical property was evaluated in the same manner as in Example 1 except that 60% by weight of the modified polypropylene resin obtained in 1 and 15% by weight of the propylene homopolymer used in Example 1 were used. The results are shown in Table 2.

(Example 4) As the component (A), Reference Example 4
Each physical property was evaluated in the same manner as in Example 1 except that 30% by weight of the modified polypropylene resin obtained in 1 was used. The results are shown in Table 2.

Example 5 As the component (A), reference example 5 was used.
Each physical property was evaluated in the same manner as in Example 1 except that 15% by weight of the modified polypropylene resin obtained in 1 and 60% by weight of the propylene homopolymer used in Example 1 were used. The results are shown in Table 2.

(Example 6) As the component (A), Reference Example 6
30% by weight of the modified polypropylene resin obtained in 1., the propylene-ethylene block copolymer obtained in Reference Example c (ethylene content 9.5% by weight MFR 17 g / 10 min)
52% by weight, as component (B), hydrogenated styrene-butadiene-styrene block copolymer 1 used in Example 1
Each physical property was evaluated in the same manner as in Example 1 except that 8% by weight was used. The results are shown in Table 2.

(Example 7) As a component (A), Reference Example 1
45% by weight of the modified polypropylene resin obtained in 1., 40% by weight of propylene homopolymer used in Example 1, hydrogenated styrene-butadiene-styrene block copolymer used in Example 1 as the component (B) Each physical property was evaluated in the same manner as in Example 1 except that 15% by weight was used.
The results are shown in Table 2.

Example 8 As the component (A), Reference Example 1
75% by weight of the modified polypropylene resin obtained in 1., 15% by weight of hydrogenated styrene-butadiene-styrene block copolymer used in Example 1 as the component (B), ethylene-propylene rubber (Mitsui Petrochemical Co., Ltd. ) Toughmer P
Each physical property was evaluated in the same manner as in Example 1 except that 480 g of MFR, 1.9 g / 10 min, and a unit derived from ethylene, 70% by weight) were used. The results are shown in Table 2.

(Example 9) As the component (A), Reference Example 1
45% by weight of the modified polypropylene resin obtained in 1., 15% by weight of the propylene homopolymer used in Example 1, 15% by weight of talc as a filler (Micelleton manufactured by Hayashi Kasei Co., Ltd.)
In the same manner as in Example 8 except that was used, each physical property was evaluated. The results are shown in Table 2.

Comparative Example 1 As the component (A), Example 1 was used.
Each physical property was evaluated in the same manner as in Example 1 except that 75% by weight of the propylene homopolymer used in 1. was used. The results are shown in Table 2.

Comparative Example 2 As the component (A), Example 1 was used.
Each physical property was evaluated in the same manner as in Example 8 except that 75% by weight of the propylene homopolymer used in 1. was used. The results are shown in Table 2.

Comparative Example 3 As the component (A), Example 1
Each physical property evaluation was performed in the same manner as in Example 9 except that 60% by weight of the propylene homopolymer used in 1) was used. The results are shown in Table 2.

Comparative Example 4 As the component (A), Example 1 was used.
Each physical property was evaluated in the same manner as in Example 7 except that 85% by weight of the propylene homopolymer used in 1. was used. The results are shown in Table 2.

Comparative Example 5 The physical properties were evaluated in the same manner as in Example 2 except that 15% by weight of the modified polypropylene resin obtained in Comparative Reference Example 1 was used as the component (A). The results are shown in Table 2.

Comparative Example 6 The physical properties were evaluated in the same manner as in Example 1 except that 30% by weight of the modified polypropylene resin obtained in Comparative Reference Example 2 was used as the component (A). The results are shown in Table 2.

(Comparative Example 7) As the component (A), Reference Example 1
30% by weight of the modified polypropylene resin obtained in 1., 67% by weight of the propylene homopolymer used in Example 1, styrene-butadiene-used in Example 1 as the component (B)
Each physical property was evaluated in the same manner as in Example 1 except that 3% by weight of the hydrogenated styrene block copolymer was used. The results are shown in Table 2.

(Comparative Example 8) As the component (A), Reference Example 1
30% by weight of the modified polypropylene resin obtained in 1., 15% by weight of propylene homopolymer used in Example 1, and hydrogenated styrene-butadiene-styrene block copolymer used in Example 1 as the component (B). Each physical property was evaluated in the same manner as in Example 1 except that 55% by weight was used.
The results are shown in Table 2.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

The present invention provides a polypropylene resin composition having high rigidity, high heat resistance, and excellent impact resistance.

Claims (3)

(57) [Claims] 1. Component (A): a polypropylene resin,
2-methylstyrene, 2,5-dimethylstyrene, 4-
Dimethylaminostyrene, hydroxymethylstyrene,
α-methylstyrene, N-vinylcarbazole, 4-phenyl
Phenyl styrene, 9-vinyl anthracene and 2-vinyl
At least one selected from the group consisting of lunaphthalene
A modified polypropylene resin obtained by graft-copolymerizing the above monomer , or a mixture of the modified polypropylene resin and a polypropylene resin, in which a unit derived from the monomer is 0.03 to 30% by weight. 50-
95% by weight, and component (B): a rubber component 50 to 5 composed of styrene rubber or a mixture of styrene rubber and olefin rubber.
A polypropylene-based resin composition consisting of wt%. 2. The styrene rubber in the component (B) is one or more monoalkenyl aromatic hydrocarbon-conjugated diene copolymers or hydrides thereof, and the olefin rubber is an ethylene-propylene copolymer,
The composition according to claim 1, which is selected from the group consisting of an ethylene-butene copolymer and an ethylene-α-olefin-non-conjugated diene copolymer. 3. A filler and a reinforcing agent are included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polypropylene resin composition.
The composition according to claim 1.