JP2618169C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001]     TECHNICAL FIELD OF THE INVENTION   The present invention has excellent rigidity, heat resistance and impact resistance, especially at low temperatures.
To a polypropylene composition which is also excellent. [0002]     TECHNICAL BACKGROUND OF THE INVENTION   Molded articles made of polypropylene are excellent in rigidity, heat resistance, surface gloss, etc.
It is widely used. [0003]   On the other hand, polypropylene is usually crystalline and has high impact resistance, especially at low temperatures.
However, there is a problem that the use is limited.   To improve the impact resistance of such polypropylene, conventionally, polypropylene
Polyethylene, or polyisobutylene or polybutadiene
And a rubbery substance such as an amorphous ethylene / propylene copolymer. this
Among them, amorphous or low-crystalline ethylene / propylene random copolymer
Is often used. [0004]   However, the present inventors have developed such an amorphous or low crystalline ethylene
Polypropylene composition consisting of propylene random copolymer and polypropylene
As a result of research on amorphous and low crystalline ethylene / propylene random
Polymers have a small impact resistance improvement effect, and polypropylene is required to improve impact resistance.
Need to contain a large amount of ethylene-propylene random copolymer
is there. Therefore, the impact resistance of the polypropylene composition is improved, but the rigidity is improved.
, Heat resistance and surface hardness tend to be greatly reduced. Meanwhile polypropylene
To a small amount of the ethylene-propylene random copolymer in the composition,
When trying to maintain rigidity, heat resistance and surface hardness, impact resistance at low temperatures is not sufficient.
There was a problem that it was not improved in minutes. [0005]   Such amorphous or low crystalline ethylene / propylene random copolymer
Instead, another ethylene / α-olefin copolymer is blended with polypropylene to
Attempts have been made to obtain a polypropylene composition having excellent impact properties. And
For example, JP-B-58-25693 and JP-B-58-38459 disclose crystals.
Constituent units derived from functional polypropylene and 1-butene are 15 mol% or less A composition containing an ethylene / 1-butene copolymer is disclosed.
No. 243842 discloses the use of crystalline polypropylene and a titanium heterogeneous catalyst.
Discloses a polypropylene composition containing an ethylene / 1-butene copolymer obtained by
Have been. The polypropylene compositions disclosed in these publications have impact resistance,
Although the rigidity has been improved, further improvement in impact resistance at low temperatures is desired. [0006]   JP-B-63-42929 discloses crystalline polypropylene and 1-butene.
Is from 25 to 10% by weight and the intrinsic viscosity [η] is 1.5
propylene / propylene copolymer containing dl / g or less of ethylene / 1-butene copolymer
Although disclosed, this polypropylene composition has insufficient resistance to shock. [0007]   Further, JP-A-3-250040 discloses a structure derived from 1-butene.
An ethylene / 1-butene block copolymer having a composition unit of 10 to 90% by weight
This ethylene / 1-butene block copolymer is used as the impact resistance of
Is inferior in compatibility with polypropylene, and the effect of improving impact resistance is insufficient. [0008]   For this reason, it has excellent rigidity and heat resistance and impact resistance, especially at low temperatures.
Therefore, the appearance of an excellent polypropylene composition has been desired.   The present inventor has studied in view of the prior art as described above, and as a result, has found that polypropylene and
A polypropylene composition comprising a specific ethylene / α-olefin copolymer is a rigid
Excellent heat resistance and heat resistance, and also significantly superior impact resistance, especially at low temperatures.
The inventors have found that the present invention has been completed and completed the present invention. [0009]     [Object of the invention]   The present invention has excellent rigidity, heat resistance and impact resistance, especially at low temperatures.
Another object of the present invention is to provide an excellent polypropylene composition. [0010]     Summary of the Invention   The first polypropylene composition according to the present invention comprises:A composition for automotive interior and exterior materials hand, (A) polypropylene; 95 to 55 parts by weight; (B-1) 15 to 25 mol% of a structural unit derived from 1-butene,       A decalin intrinsic viscosity [η] of 1.5 to 3.5 dl / g,       The melting point measured as the main peak by the DSC method is 60 ° C. or less,       A glass transition temperature (Tg) of -50 ° C or less;       The degree of crystallinity measured by X-ray diffraction is less than 20%, and       ¹³The randomness parameter (B value) determined by the C-NMR method is 1.0
~ 1.4     Ethylene- 1-butene random copolymer;
It is a sign. [0011]   The second polypropylene composition according to the present invention, (A) polypropylene; 95 to 55 parts by weight; (B-2) a constitutional unit derived from 1-octene is 8 to 20 mol%,       Decalin intrinsic viscosity [η] is 1.8 to 3.5 dl / g,       The melting point measured as the main peak by the DSC method is 80 ° C. or less,       A glass transition temperature (Tg) of -50 ° C or less;       The degree of crystallinity measured by X-ray diffraction is less than 20%, and       ¹³The randomness parameter (B value) determined by the C-NMR method is 1.0
~ 1.4     Ethylene / 1-octene random copolymer; 5 to 45 parts by weight It is characterized by comprising. [0012]   The polypropylene composition as described above further comprises: (C) 30 to 60 mol% of structural units derived from ethylene,       Decalin intrinsic viscosity [η] is 2 to 12 dl / g     Propylene / ethylene copolymer; 5 to 15 parts by weight May be contained. [0013]     DETAILED DESCRIPTION OF THE INVENTION   The polypropylene composition according to the present invention will be specifically described.   The polypropylene composition according to the present invention comprises (A) polypropylene and a specific (B-
1) Ethylene / 1-butene copolymer or (A) polypropylene
It consists of a specific (B-2) ethylene / 1-octene copolymer. [0014]                           (A) Polypropylene   As the (A) polypropylene used in the present invention, a propylene homopolymer
Or 10 mol% or less of structural units derived from olefins other than propylene
And a propylene / α-olefin copolymer contained in an amount. [0015]   Such olefins include, for example, ethylene, 1-butene, 1-pentene
, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadede
Sen, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene,
Cyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1
-Butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene
, Dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene,
Trimethyl-1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,
5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-hepte
Dimethyl octene, ethyl-1-octene, methyl-1-nonene, vinylcyclo
Examples include pentene, vinylcyclohexan, and vinylnorbornane. [0016]   The copolymer of propylene and these olefins may be a random copolymer
It may be a block copolymer.   The propylene / α-olefin copolymer is 3-methyl-1-butene, 3,3-dimethyl
Cyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3,5,5-trime
Tyl-1-hexene, vinylcyclopentene, vinylcyclohexane, vinylnor
The homopolymer or copolymer of bornane is prepolymerized to the catalyst and then It may be obtained by polymerizing propylene on the combined catalyst. [0017]   In the present invention, as the polypropylene (A), a propylene homopolymer is preferable.
.   The (A) polypropylene used in the present invention conforms to ASTM-D1238.
The melt flow rate (MFR) measured under a load of 2160 g at 230 ° C.
, 0.1 to 200 g / 10 min, preferably 0.3 to 100 g / 10 min. [0018]   Polypropylene composition containing (A) polypropylene having MFR as described above
The product has excellent fluidity and is easy to mold a large molded product. Melt flow rate
The polypropylene composition containing polypropylene larger than the above has an impact strength
Inferior. [0019]   The above-mentioned polypropylene can be produced by various methods,
It can be produced using a normal stereoregular catalyst. Specifically, solid titanium
From the catalyst component, the organometallic compound catalyst component and, if necessary, the electron donor.
It can be produced using the catalyst formed. [0020]   The solid titanium catalyst component used in this method may be titanium trichloride or titanium trichloride.
A titanium chloride composition having a specific surface area of 100 m^Two/ G supported on a carrier of at least
Catalyst component or magnesium, halogen, electron donor (preferably aromatic
Carboxylic acid ester or alkyl group-containing ether) and titanium as essential components
And the specific surface area is 100m^Two/ G or more of the titanium catalyst component supported on a carrier
It is. Particularly preferred is a polypropylene produced using the latter catalyst component with a carrier.
. [0021]   As the organometallic compound catalyst component, an organoaluminum compound is preferable,
Specific examples of the organoaluminum compound include trialkylaluminum, dial
Kill aluminum halide, alkyl aluminum sesquihalide, alkyl aluminum Luminium dihalide and the like. The organic aluminum compound used
Can be appropriately selected according to the type of titanium catalyst component to be used. [0022]   Examples of the electron donor include a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom and
An organic compound having a iodine atom or the like can be used, preferably as described above.
And ether compounds having various atoms. [0023]   Such a catalyst may be further activated by a method such as co-milling. Also above
As described above, the olefin may be prepolymerized.   The method for producing polypropylene using the catalyst component with a carrier as described above is an example.
For example, JP-A-50-108385, JP-A-50-126590 and JP-A-51-108590.
20297, JP-A-51-28189, JP-A-52-151691, etc.
The details are described in the gazette, and the production method of the propylene block copolymer is,
For example, JP-A-52-98045, JP-B-57-26613, and the like.
Details are provided. The present invention also utilizes the techniques described in these.
Can be [0024]               (B-1) Ethelen / 1-butene random copolymer   The (B-1) ethylene / 1-butene random copolymer used in the present invention is 1-butene
15-25 mol%, preferably 18-20 mol%
It is contained in the amount. [0025]   Contains the structural unit derived from 1-butene used in the present invention in the amount described above.
(B-1) The glass transition temperature of the ethylene / 1-butene random copolymer is -50
C. or lower, preferably -60 C. or lower. The melting point is 60 ° C. or less, preferably
50 ° C. or less. This melting point is measured as a main peak by the DSC method.
. [0026]   The (B-1) ethylene / 1-butene random copolymer used in the present invention is 135 C., intrinsic viscosity [η] measured in decalin is 1.5 to 3.5 dl / g, preferably
Or 2.0 to 3.0 dl / g. [0027]   Crystallinity measured by X-ray diffraction is less than 20%, preferably 10% or less.
Below.   Further, (B-1) ethylene / 1-butene random copolymer used in the present invention,¹³
A parameter indicating the randomness of the copolymer monomer chain distribution determined by the C-NMR method.
The meter (B value) is 1.0 to 1.4. [0028]   The B value of such (B-1) ethylene / 1-butene random copolymer is
A finger indicating the composition distribution of constituent units derived from each monomer in the polymer chain
And the ethylene-1-butene alternating chain to all dyad chains in the copolymer.
The molar fraction is the product of the ethylene content (mol fraction) and the 1-butene content (mol fraction)
It is divided by twice. That is, the B value is obtained by the following equation. [0029] (Equation 1) [0030] (Where P_EAnd P_BIs contained in the ethylene / 1-butene copolymer, respectively.
The molar fraction of the ethylene component and the molar fraction of the 1-butene component are shown._BEIs all dya
Shows the mole fraction of d-chain 1-butene-ethylene chain. )   Such a P_E, P_BAnd P_BEThe value is specifically determined as follows:
You. [0031]   Approximately 200 mg of ethylene / 1-butene copolymer in a 10 mmφ sample tube in 1 ml
Homogeneously dissolved in hexachlorobutadiene.¹³C-NMR spectrum
Is measured under the following measurement conditions. [0032]   Measurement temperature: 120 ° C,   Measurement frequency: 25.05 MHz,   Spectral width: 1500 Hz, filter width: 1500 Hz,   Pulse repetition time: 4.2 sec, pulse width: 7 μsec,   Number of accumulation: 2000 to 5000 times. [0033]   P_E, P_BAnd P_BEValues are measured as described above¹³C-NMR spectrum
From G. J. Ray (Macromolecules,Ten, 773 (1977)); C. Randall (Ma
cromolecules,15, 353 (1982)); Polymer Science, Polymer Physics Ed.,1
1, 275 (1973)); Kimura (Polymer,twenty five, 441 (1984))
Can be [0034]   In addition, this B value is an ethylene / 1-butene random copolymer in a completely alternating copolymer.
If there is, it becomes 2, and if it is a complete block copolymer, it becomes 0.   (B-1) ethylene / 1-butene random copolymer having a B value smaller than 1.0
The impact resistance of the polypropylene composition containing the compound tends to decrease. [0035]   The (B-1) ethylene / 1-butene random copolymer as described above is
Polypropylene compositions having excellent compatibility with polypropylene and containing this copolymer
Outstanding performance, excellent impact resistance, and excellent fluidity
It is possible to form a molded product excellent in quality. [0036]   The above-mentioned (B-1) ethylene / 1-butene random copolymer is a known vanadi
It can be produced using an aluminum-based catalyst or a metallocene-based catalyst.               (B-2) Ethylene / 1-octene random copolymer   The (B-2) ethylene / 1-octene random copolymer used in the present invention is
8 to 20 mol%, preferably 10 to 15 mol% of the structural unit derived from butene
It is contained in the amount of. [0037]   The structural unit derived from 1-octene used in the present invention is contained in the amount described above.
The (B-2) ethylene / 1-octene random copolymer has a glass transition temperature of-
It is 50 ° C or less, preferably -60 ° C or less. Further, the melting point is preferably 80 ° C. or less.
Is 70 ° C. or less. This melting point was measured as the main peak by the DSC method.
You. [0038]   The (B-2) ethylene / 1-octene random copolymer used in the present invention comprises 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is preferably 1.5 to 3.5 dl / g.
Or 2.0 to 3.0 dl / g. [0039]   Crystallinity measured by X-ray diffraction is less than 20%, preferably 10% or less.
Below.   The (B-2) ethylene / 1-octene random copolymer used in the present invention is:^1
ThreeA parameter showing the randomness of the copolymer monomer chain distribution determined by the C-NMR method.
The parameter (B value) is 1.0 to 1.4. [0040]   The B value of the (B-2) ethylene / 1-octene random copolymer is as follows:
Same as the B value described for the (B-1) ethylene / 1-butene random copolymer
Then, it is obtained from the following equation. [0041] (Equation 2)[0042] (Where P_EAnd P_OAre contained in the ethylene / 1-octene copolymer, respectively.
The mole fraction of the ethylene component and the mole fraction of the 1-octene component,_OEIs all d
The molar fraction of the 1-octene-ethylene chain of the yad chain is shown. )   This B value is less than 1.0 (B-2) ethylene / 1-octene random copolymer
Polypropylene compositions containing bodies tend to have reduced impact resistance. [0043]   The (B-2) ethylene / 1-octene random copolymer as described above is
Excellent compatibility with ren, polypropylene composition containing this copolymer,
It has excellent rigidity, impact resistance, and fluidity.
A molded article excellent in appearance can be formed. [0044]   The above-mentioned (B-2) ethylene / 1-octene random copolymer is a known vana
It can be produced using a di-based catalyst or a metallocene-based catalyst.                         Polypropylene composition   The first polypropylene composition according to the present invention comprises:   95-55 parts by weight, preferably 85-65 parts by weight of the above (A) polypropylene
In parts quantity,   (B-1) an ethylene / 1-butene random copolymer, 5 to 45 parts by weight, preferably
Is contained in an amount of 15 to 35 parts by weight. [0045]   Further, the second polypropylene composition according to the present invention,   95-55 parts by weight, preferably 85-65 parts by weight of the above (A) polypropylene
In parts quantity,   (B-2) 5 to 45 parts by weight of an ethylene / 1-octene random copolymer, preferably
Or 15 to 35 parts by weight. [0046]   Such a polypropylene composition according to the present invention is rigid and excellent in heat resistance.
In addition, it has excellent impact resistance, especially at low temperatures.   Further, the polypropylene composition according to the present invention comprises (C) propylene / ethylene
5 to 15 parts by weight, preferably 5 to 10 parts by weight of a random copolymer.
You may. [0047]   The (C) propylene / ethylene random copolymer used in the present invention is an ethylene
30 to 60 mol%, preferably 35 to 45 mol%, of the structural unit derived from
It is contained in the amount. [0048]   Such a (C) propylene / ethylene random copolymer has a
The intrinsic viscosity [η] measured in phosphorus is 2 to 12 dl / g, preferably 3 to 6 dl / g.
g. [0049]   (C) a polypropylene composition containing a propylene / ethylene random copolymer
Also, it has excellent impact resistance and rigidity, and excellent fluidity.   The (A) polypropylene and (C) polypropylene in the polypropylene composition according to the present invention.
The propylene / ethylene random copolymer is defined as polypropylene and propylene / ethylene.
May be manufactured as a block copolymer with a renrandom copolymer
. [0050]   The polypropylene composition according to the present invention contains an inorganic filler as necessary.
You may. The inorganic filler is preferably contained in the composition in an amount of 5 to 20% by weight.
You. [0051]   Specific examples of such an inorganic filler include fine powder talc, kaolinite, and calcined powder.
Natural silicic acid such as synthetic clay, virophilite, sericite, wollastonite, etc.
Is silicate, precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc.
Carbonates, hydroxides such as aluminum hydroxide and magnesium hydroxide, zinc oxide
, Zinc oxide, oxides such as magnesium oxide, hydrous calcium silicate, hydrous silicate
Powders represented by synthetic silicic acid or silicate such as minium, hydrous silicic acid, silicic anhydride
Filler, flake filler such as mica, basic magnesium sulfate whisker,
Calcium titanate whisker, aluminum borate whisker, sebiolite
, PMF (Processed Mineral Fiber), Zonotorite, Potassium Titanate, Eles
Fibrous filler such as tadite, glass balun, fly ash balun, etc. Fillers and the like.   In addition to such inorganic fillers, high styrenes, lignin, recycled rubber, etc.
May be used.   Polypropylene compositions containing such fillers are particularly suitable for various automotive materials.
It is suitably used for home appliance materials and the like. [0052]   The polypropylene composition according to the present invention furthermore does not impair the object of the present invention.
In, a heat stabilizer, an aromatic carboxylic acid aluminum salt, an aromatic phosphate ester salt,
Nucleating agents such as dibenzylidene sorbitol, ultraviolet absorbers, lubricants, antistatic agents,
Flame retardants, pigments, dyes, phenol-based, sulfur-based, phosphorus-based antioxidants and dispersants
, Copper damage inhibitors, neutralizers, foaming agents, plasticizers, foam inhibitors, crosslinking agents, peroxides, etc.
Additives such as flow improvers, light stabilizers, weld strength improvers, and other heavy
Coalescence such as polyethylene (PE), propylene / ethylene run other than the above composition
It may contain a dam copolymer (EPR) or the like.   Such an additive is used in an amount of 0.00% by weight based on 100 parts by weight of the polypropylene composition.
It can be used in an amount of from 01 to 10 parts by weight. [0053]   The polypropylene composition according to the present invention comprises the above components simultaneously or sequentially.
For example, Henschel mixer, V-type blender, tumbler blender, ribbon
After charging into a blender and kneading, a single-screw extruder, multi-screw extruder, kneader,
It is obtained by melt-kneading with a blender mixer or the like. [0054]   Among these, kneading performance of multi-screw extruders, kneaders, Banbury mixers, etc.
The use of a good equipment will ensure that the components are more evenly distributed
It is preferable because a ren composition can be obtained. [0055]     【The invention's effect】   The polypropylene composition according to the present invention has excellent rigidity, heat resistance and impact resistance.
Also excellent in properties, especially impact resistance at low temperatures. [0056]   Such a polypropylene composition according to the present invention can be used for a wide range of applications.
For home appliances such as housing and washing tub, uniaxially stretched film, biaxially stretched film
Film applications such as lum and blown film, calendering, extrusion molding
Sheet applications depending on the shape, container applications such as bags and retort containers, such as birds
Automotive interior applications such as vehicle, instrument panel and column covers, fenders, bumpers,
Automotive exterior applications such as id malls, mat guards and mirror covers, and general miscellaneous goods
It can be suitably used for such purposes. [0057] 【Example】   Next, the present invention will be described specifically with reference to examples.
It is not limited. [0058]   In the following Examples, each physical property was measured as follows.   (1) Based on MFR ASTM D1238.                 Conditions: 230 ° C, 2.16 kg   (2) Flexural modulus (FM) According to ASTM D790. [0059]               Test piece 12.7 (width) x 6.4 (thickness) x 127 (length)               100mm between spans               Bending speed 2mm / min   (3) Izod impact strength (IZ)                 Compliant with ASTM D256                 Temperature 23 ℃                 Test piece 12.7 (width) x 6.4 (thickness) x 64 (length)                 Notch machined [0060]     [Examples 1 to 9]   The polypropylene composition shown in Table 2 was treated under the conditions of a resin temperature of 200 ° C and a mold temperature of 40 ° C. An ASTM test piece was molded using an injection molding machine under the following conditions, and the above-mentioned physical properties were measured. [0061]   Table 2 shows the results.   The components used in preparing the polypropylene composition are as follows.
Table 1 shows the physical properties of each component. [0062] [Table 1][0063] (A) Polypropylene   (1) PP-A: Polypropylene manufactured by Mitsui Petrochemical Co., Ltd.                 HYPOLJ800 was used. [0064]   (2) PP-B: Highly crystalline homopolypropylene produced as follows.                               Preparation of catalyst   95.2 g of anhydrous magnesium chloride, 442 ml of decane and 2-ethylhexyl
After heating 390.6 g of alcohol at 130 ° C. for 2 hours to form a homogeneous solution,
21.3 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour.
Then, phthalic anhydride was dissolved in this homogeneous solution. Uniform obtained in this way
After cooling the solution to room temperature, 75 ml of this homogeneous solution was maintained at −20 ° C.
A total amount of 200 ml of the tan was dropped over 1 hour. After charging is completed,
Was heated to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., diisophthalic acid
5.22 g of butyl (DIBP) was added, and the mixture was kept under stirring at the same temperature for 2 hours.
did. After the completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and this solid portion was collected by 275 m
After resuspending in 1 l of titanium tetrachloride, the mixture was heated again at 110 ° C. for 2 hours. [0065]   After completion of the reaction, the solid portion was collected again by hot filtration,
The washing was carried out until no free titanium compound was detected in the washing solution.   The solid titanium catalyst component [A] prepared by the above operation was mixed with decane slurry.
And saved. [0066]                                   polymerization   In a 17 liter autoclave at room temperature under propylene atmosphere,
4 kg of hydrogen and 45 liters of hydrogen were introduced, and the temperature was raised to 60 ° C.
5.0 mmol, dicyclopentyldimethoxysilane (DCPMS) 5.0
Mmol, the solid titanium catalyst component [A] was converted to Ti atom by 0.05 mmol.
The temperature was further increased to 70 ° C., and a polymerization reaction was carried out at this temperature for 40 minutes. Anti
Immediately after completion of the reaction, a small amount of ethanol is added to the system to decompose the catalyst, and the unreacted
Removal of propylene and hydrogen gave 1515 g of a white powdery solid. [0067]   The obtained polypropylene had an MFR of 15 g / 10 minutes.   (3) PP-C: Highly crystalline homopolypropylene produced using a prepolymerization catalyst.                               Prepolymerization of catalyst   In a 2-liter pressure-resistant autoclave, place 1 l of purified hexane at 20 ° C under a nitrogen atmosphere.
Toluene, 100 mmol of triethylaluminum, methyltrimethoxysilane (
TMMS) 100 mmol and the above solid titanium catalyst component [A]
After adding 10 mmol in conversion and stirring and mixing, 115 g of 3-methyl-1-butene was added.
A prepolymerization reaction was carried out under stirring for 2 hours while maintaining the temperature at 20 ° C. After the reaction, supernatant
The liquid was removed, washed twice with purified hexane, and then resuspended in purified decane.
The whole amount was transferred to a catalyst bottle to obtain a prepolymerization catalyst. [0068]                                   polymerization   Using this prepolymerization catalyst, homopolypropylene was produced in the same manner as for polypropylene-B.
The len was polymerized. [0069]   The obtained polypropylene had an MFR of 15.5 g / 10 min.   (4) PP-D: Block polypropylene produced as follows.   Replace the autoclave with an internal volume of 17 liters sufficiently with propylene,
4 kg of hydrogen and 60 liters of hydrogen were introduced, and the temperature was raised to 60 ° C.
5.0 mmol, dicyclopentyldimethoxysilane (DCPMS) 5.0
Mmol, the solid titanium catalyst component [A] was converted to Ti atom by 0.05 mmol.
Mol was added and polymerization was carried out at 80 ° C. for 1 hour. [0070]   After removing the liquid propylene, a mixed gas of ethylene and propylene was added at 60 ° C.
100 liters and 150 liters were added in 150 minutes. Unreacted mix
The gas was removed to obtain 2.1 kg of a white powdery solid. [0071]   The block polypropylene thus obtained has an MFR of 22 g / 10 min.
The structural unit derived from ethylene is 8.0% by weight, and n-decane soluble at normal temperature
Was 11.1% by weight, and the intrinsic viscosity [η] of the soluble portion was 3.0 dl / g. (B-1) Ethylene / 1-butene random copolymer     EBR-1: 1 structural unit derived from 1-butene: 19 mol%                 Intrinsic viscosity [η] = 2.5 dl / g (B-2) Ethylene / 1-octene random copolymer     EOR: structural unit derived from 1-octene: 13 mol%                 Intrinsic viscosity [η]: 2.3 dl / g (C) Propylene / ethylene random copolymer     PER-1: a structural unit derived from ethylene: 40 mol%                 Intrinsic viscosity [η] = 3.0 dl / g   Other     EBR-2: a structural unit derived from 1-butene: 11 mol%                 Intrinsic viscosity [η] = 1.8 dl / g     EPR (ethylene / propylene random copolymer): derived from ethylene                 Structural unit: 80 mol%                 Intrinsic viscosity [η] = 2.6 dl / g     Polyethylene: HIZEX 1300J manufactured by Mitsui Petrochemical Co., Ltd.     Talc: average particle size 2.5 μm               Content of particles having a particle size of 5 μm or more 3% by weight [0072]     [Comparative Examples 1 to 5]   The polypropylene compositions shown in Table 2 were molded in the same manner as in the examples, and the physical properties were measured.
Specified. Table 1 shows the physical properties of each component. [0073]   Table 2 shows the results. [0074]     Embodiments 9 to 11   The polypropylene composition shown in Table 2 was treated under the conditions of a resin temperature of 200 ° C and a mold temperature of 40 ° C
An ASTM test piece was molded using an injection molding machine under the following conditions, and the above-mentioned physical properties were measured. [0075]   Table 2 shows the results.   Table 2 shows the physical properties of each component used when preparing the polypropylene composition shown in Table 2.
It is shown in FIG. [0076] [Table 2] [0077] [Table 3][0078] [Table 4]

Claims (1)

Claims: 1. A (A) polypropylene; 95 to 55 parts by weight, and (B-1) 15 to 25 mol% of a structural unit derived from 1-butene, and a decalin intrinsic viscosity [ η] is 1.5 to 3.5 dl / g, the melting point measured as a main peak by the DSC method is 60 ° C or less, the glass transition temperature (Tg) is -50 ° C or less, and X-ray diffraction method. Is less than 20%, and the randomness parameter (B value) determined by ¹³ C-NMR method is 1.0%.
A polypropylene composition for automotive interior and exterior materials , comprising: an ethylene / 1-butene random copolymer; 2. (A) polypropylene; 95 to 55 parts by weight, (B-1) 15 to 25 mol% of a structural unit derived from 1-butene, and a decalin intrinsic viscosity [η] of 1.5. Dl3.5 dl / g, melting point measured as main peak by DSC method is 60 ° C. or less, glass transition temperature (Tg) is -50 ° C. or less, crystallization measured by X-ray diffraction method Degree is less than 20%, and the randomness parameter (B value) determined by ¹³ C-NMR method is 1.0.
An ethylene / 1-butene random copolymer having a molecular weight of 5 to 45 parts by weight; and (C) 30 to 60 mol% of a structural unit derived from ethylene, and a decalin intrinsic viscosity [η] of 2 A propylene / ethylene copolymer having a content of 5 to 15 dl / g; 3. (A) polypropylene; 95 to 55 parts by weight, (B-2) a constituent unit derived from 1-octene is 8 to 20 mol%, and a decalin intrinsic viscosity [η] is 1.5. Dl3.5 dl / g, melting point measured as main peak by DSC method is 80 ° C. or less, glass transition temperature (Tg) is -50 ° C. or less, crystallization measured by X-ray diffraction method Degree is less than 20%, and the randomness parameter (B value) determined by ¹³ C-NMR method is 1.0.
A polypropylene composition comprising: ethylene- 1-octene random copolymer; 4. (A) polypropylene; 95 to 55 parts by weight, (B-2) a constituent unit derived from 1-octene is 8 to 20 mol%, and a decalin intrinsic viscosity [η] is 1.5. Dl3.5 dl / g, melting point measured as main peak by DSC method is 80 ° C. or less, glass transition temperature (Tg) is -50 ° C. or less, crystallization measured by X-ray diffraction method Degree is less than 20%, and the randomness parameter (B value) determined by ¹³ C-NMR method is 1.0.
An ethylene / 1-octene random copolymer of 5 to 45 parts by weight; (C) 30 to 60 mol% of a structural unit derived from ethylene, and a decalin intrinsic viscosity [η] of 2 A propylene / ethylene copolymer having a content of 5 to 15 dl / g;