JP3361585B2 - Propylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene resin composition.
More specifically, excellent dynamics over a wide elastic modulus range
Characteristics and the temperature dependence of its mechanical characteristics is small
Propylene resin with no surface stickiness of the molded product
It relates to a composition. [0002] 2. Description of the Related Art A polypropylene resin is a so-called block resin.
Balun with rigidity and low-temperature impact strength
Is known to be an excellent resin, but very high
To obtain low temperature impact strength, the amount of copolymer
Had to be increased. However, this
Although the impact strength is improved, the surface properties and heat resistance are improved.
It is inevitable that it will be severely impaired, and improvement is desired.
Was. The present inventors have previously developed unprecedented excellent mechanical properties.
Disclosed a propylene-based elastomer composition having
JP-A-3-168234). However, this one
Are excellent in mechanical properties and have the above-mentioned surface properties and heat resistance.
Some improvements were also made to the title, but not necessarily
Not fully satisfactory and needs further improvement
there were. [0003] SUMMARY OF THE INVENTION The present invention
Under the circumstances, it has excellent mechanical properties over a wide elastic modulus range.
And its mechanical properties are less dependent on temperature
Provision of propylene-based resin composition without surface stickiness of products
It was done for the purpose of doing. [0004] Means for Solving the Problems The present inventors have set forth the above-mentioned advantages.
Develop a propylene resin composition with good properties
As a result of intensive studies, (a) the specific intrinsic viscosity and boiling point
The amount of insoluble n-heptane insoluble components, and
Measured rubber component relaxation time at temperatures of 30 ° C and 80 ° C
Measurement value and the amount of the boiling n-heptane insoluble component are specified.
Propylene homopolymer and / or relatively
A copolymer containing a small amount of another olefin unit;
Except for a relatively large amount of propylene with a constant intrinsic viscosity
Propylene-based random copolymer containing olefin units
And a propylene-based resin composition containing
It has been found that the object can be achieved. The present invention
It has been completed based on such knowledge. That is, the present invention relates to (a) (a) temperature 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 0.5 to 0.5.
At 10 deciliter / g, (b) boiling n-heptane insoluble
The component amount (W) is 10 to 99% by weight;
Temperature of relaxation time of rubber component measured by Loose NMR at 30 ° C
Measured at [T_2H ^R(30): μs] and at 80 ° C.
Measured value [T_2H ^R(80): μs] and the boiling n-hepta
The relationship with the amount of insoluble components (W) is T_2H ^R(80) ≦ 670−2.2 × W T_2H ^R(80) / T_2H ^R(30) ≦ 8.8 + 0.086 × W And / or 4 mol% or less of propylene homopolymer satisfying
Copolymers containing other olefin units below 10-95
% And (b) measured in decalin at a temperature of 135 ° C.
The intrinsic viscosity [η] is 0.5 to 10 deciliter / g.
Contains 10 to 80 mol% of olefin units other than propylene
From 90 to 5% by weight of the propylene random copolymer
And a propylene-based resin composition. [0006] The propylene resin composition of the present invention comprises:
(A) a propylene homopolymer and / or 4
Contains a copolymer containing less than mol% of other olefin units
I do. The propylene homopolymer or copolymer is heated at a temperature
The intrinsic viscosity [η] measured in decalin at 135 ° C is 0.5
10 to 10 deciliter / g, preferably 1.0 to 9.0 deciliter / g
It must be in the range of turtle / g. This extreme viscosity
When the degree [η] is less than 0.5 deciliter / g, the mechanical properties
Insufficient.
Workability deteriorates. Also, the amount of boiling n-heptane insoluble components
(W) is 10 to 99% by weight, preferably 20 to 99% by weight
%. The amount of this insoluble component is
If the range is out of the range, the object of the present invention cannot be sufficiently achieved.
No. The amount of the insoluble component (W) was determined using a Soxhlet extraction tester.
Extraction residue after extraction with boiling n-heptane for 6 hours
Is a boiling n-heptane-insoluble component and is represented by its weight fraction.
Value. Further, the propylene homopolymer or copolymer may be used.
The coalescence is based on the relaxation time of the rubber component measured by pulsed NMR.
Measured value at a temperature of 30 ° C [T_2H ^R(30): μs] and 8
Measured value at 0 ° C [T_2H ^R(80): μs] and the above boiling
The relationship with the amount of n-heptane insoluble component (W) is expressed by the formula T_2H ^R(80) ≦ 670−2.2 × W T_2H ^R(80) / T_2H ^R(30) ≦ 8.8 + 0.086 × W It is necessary to satisfy The above relational expression is not satisfied
In this case, the object of the present invention cannot be achieved. [0008] Relaxation of rubber component by the above-mentioned pulse NMR
Time (T_2H ^R) For the measurement method
Measurement frequency using CXP-90 NMR apparatus manufactured by Co., Ltd.
Observation nuclei at 90.1 MHz¹H is the measured pulse sequence
Was measured by the solid echo method. Set the observation pulse width to 2.
0 μs, the next pulse is given after FID (free induction decay) observation
5 seconds waiting time and the number of integrations is 300 times
Was. The FID was analyzed by the following method. (1) FID analysis method at a temperature of 30 ° C. FID measured by the above measurement method: M_exp(T)
M calculated by the formula_{ca l}Mart cart revised for (t)
Optimized by nonlinear least squares method. M_cal(t) = M₀ ^{c + G}exp ((t / T_2H ^{C + G})^Two/ 2] + M₀ ^Rexp (t / T
_2H ^R) The subscripts R, G, and C each indicate a rubbery molecular property.
An amorphous component, a glassy amorphous component and a crystalline component are shown. Ma
Also, the optimization is M₀ ^{c + G}, M₀ ^R, T_2H ^{C + G},
T_2H ^RAnd T as an initial value_2H ^R> 3T_2H ^{C + G}, 1μ
s <T_2H ^{C + G}A value of <15 μs was used. (2) FID analysis method at a temperature of 80 ° C. M_exp(T) is calculated by the following equation._cal(T)
By the nonlinear least squares method using the revised Marquardt method
Optimize. M_cal(t) = M₀ ^cexp ((t / T_2H ^C)^Two/ 2] + M₀ ^Gexp (t / T_2H
^G) + M₀ ^Rexp (t / T_2H ^R) Note that the subscripts are the same as above, and
M as a number₀ ^C, M₀ ^R, M₀ ^R, T_2H ^C, T_2H ^G, T
_2H ^RWas used. Further, the propylene-based resin composition of the present invention
Is an olefin unit other than propylene as the component (b)
10 to 80 mol%, preferably 10 to 70 mol%
Contains a propylene-based random copolymer. This prop
Len-based random copolymer is prepared in decalin at a temperature of 135 ° C.
Intrinsic viscosity [η] measured at 0.5 to 10 deciliters /
g, preferably in the range of 1.0 to 9.0 deciliter / g.
It is necessary to This intrinsic viscosity [η] is 0.5
At less than 10 g / g, the mechanical properties are insufficient and
If the amount exceeds liter / g, the moldability deteriorates. In the propylene resin composition of the present invention,
Is a propylene homopolymer or copolymer of the component (a).
10 to 95% by weight of the body, preferably 30 to 95% by weight,
(B) 90 to 5 parts of the propylene random copolymer
% By weight, preferably 70 to 5% by weight.
Is necessary. Content ratio of the components (a) and (b)
If the case deviates from the above range, the object of the present invention is not sufficiently achieved.
Not. The propylene-based resin composition of the present invention is
Various polymerization methods such as multi-phase polymerization method and multi-stage slurry method
Alternatively, it can be prepared by a blending method. For example
When prepared by a polymerization method, (A)
Consists of calcium, titanium, halogen atoms and electron donors
Solid catalyst component and (b) crystal used as needed
Solid component composed of functional polyolefin, and (B)
Aluminum compound and (C) a general formula (I) [0012] Embedded image [Wherein, R¹Is alkyl having 1 to 20 carbon atoms
Group, R^TwoIs a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or
A toro group; m is an integer of 1 to 6; n is 0 to (6-m)
Indicates an integer. Aromatization containing alkoxy group represented by
Compound and, if necessary, (D) an electron donating compound.
Propylene and other olefins in the presence of a catalyst system consisting of
What is necessary is just to polymerize with refins. The solid component (A) is a mug of the component (A).
From cesium, titanium, halogen atoms and electron donors.
Solid catalyst component and (b) component used as necessary
And a crystalline polyolefin. The
The solid catalyst component of component (a) is magnesium, titanium,
It contains a halogen atom and an electron donor as essential components.
A magnesium compound, a titanium compound and an electron donor
Can be prepared by contacting What
In this case, the halogen atom is used as a halide.
Included in gnesium compounds and / or titanium compounds
You. As the magnesium compound, for example,
Magnesium dihalides, such as gnesium chloride, acids
Magnesium fluoride, magnesium hydroxide, hydrotalsa
Site, magnesium carboxylate, diethoxymagne
Alkoxymagnesium such as calcium, allyloxymag
Nesium, alkoxymagnesium halide, alliroki
Simium halide, ethyl butyl magnesium
Which Alkyl Magnesium, Alkyl Magnesium Hara
Or an organomagnesium compound and an electron donor,
Halosilane, alkoxysilane, silanol and aluminum
Reaction products with a compound such as an aluminum compound.
However, among these, magnesium halide, alkoxymer
Gnesium, alkyl magnesium, alkyl magnesium
Um halides are preferred. Also these magnesium
Compounds may be used alone or in combination of two or more.
May be used. Further, as the magnesium compound, metal
Uses the reaction product of gnesium, halogen and alcohol
You can also be. Metal magnesium used in this case
Is not particularly limited, and metallic magnesium of any particle size, for example,
For example, use granules, ribbons, powders, etc.
Can be. In addition, the surface condition of metallic magnesium is particularly restricted.
Although there is no limit, a film such as magnesium oxide is formed on the surface
Those that have not been done are preferred. In addition, alcohol
Can be used, but may have 1 to 6 carbon atoms.
It is preferable to use lower alcohols, especially
Is a solid catalyst component that significantly enhances the performance of the catalyst.
It is preferable because it gives a minute. Alcohol purity and water content
The amount is not limited, but if alcohol with high water content is used,
Magnesium hydroxide is formed on the surface of metallic magnesium
Therefore, the water content is 1% by weight or less, especially 2000 ppm or less.
It is preferable to use the alcohol below, and
The smaller the value, the more advantageous. The halogen and / or halogen-containing compound
There is no restriction on the type, and halogen atoms are included in the molecule.
Any compound can be used. in this case,
The type of halogen atom is not particularly limited,
Sulfur, bromine or iodine, particularly iodine, is preferably used.
Among halogen-containing compounds, halogen-containing metal compounds
Particularly preferred. These conditions, shape, grain size, etc. are particularly limited.
It is not limited and may be any one, such as an alcohol-based solvent.
(Eg, ethanol).
Wear. The amount of alcohol used is 1 mole of metallic magnesium
2 to 100 mol, preferably 5 to 50 mol,
It is chosen in the box. If you have too much alcohol,
Tends to be difficult to obtain good magnesium compounds
When the amount is small, the reaction with metallic magnesium is
It may not be performed smoothly. Halogen and / or halogen-containing compounds are
Usually, 0.0001 g per mole of metallic magnesium
Ram atoms or more, preferably 0.0005 gram atoms or more,
More preferably, it is used in a proportion of 0.001 g atom or more.
Can be At less than 0.0001 g atom, the resulting mag
When nesium compound is used without grinding,
Amount, activity, tacticity, morphology of the resulting polymer
Etc. are reduced, and crushing becomes indispensable
Absent. Also, by appropriately selecting the amount of halogen used,
Control the particle size of the resulting magnesium compound.
It is possible to roll. Metallic magnesium, alcohol and halogen
And / or the reaction itself with the halogen-containing compound is
This can be done using known methods. For example, a metal mug
Nesium, alcohol and halogen are refluxed with hydrogen
Until gas generation is no longer observed, usually about 20-30
Reaction time to obtain the desired magnesium compound
is there. Specifically, for example, using iodine as a halogen
Metal magnesium and solids in alcohol
After charging iodine in the form of
Alcohol dissolution of metallic magnesium and iodine during coal
A method of heating and refluxing after adding the liquid dropwise, metallic magnesium
Iodine alcohol while heating an alcohol solution containing
A method of dropping a solution and the like can be mentioned. Either way
Are also inert gas atmospheres such as nitrogen gas and argon gas.
Under ambient atmosphere, optionally an inert organic solvent (eg, n-
(Saturated hydrocarbons such as xane)
No. For inputting metallic magnesium, alcohol and halogen
First, put the entire amount into the reaction tank from the beginning.
It is not necessary to add them, and they may be charged separately. Especially preferred
As for the form, put the whole amount of alcohol from the beginning,
This is a method in which magnesium is divided and charged several times. In this case, the hydrogen gas is temporarily
Mass production can be prevented and it is highly desirable
No. Also, the size of the reaction tank can be reduced. Further
Caused by a temporary outbreak of hydrogen gas
Alcohol and halogen can be prevented
Become. The number of divisions should be determined in consideration of the size of the reaction tank.
Normally, 5 to 10 times is preferable considering the complexity of the operation.
It is. In addition, the reaction itself can be either batch or continuous.
Needless to say, this is fine. Furthermore, as a variant,
The metal magnet in the alcohol
At first, and separate the product generated by the reaction.
After separating and removing the tank, the metallic magnesium is
It is also possible to repeat the operation of adding a small amount
is there. The magnesium compound thus obtained was subjected to the following solid catalyst.
When used for the preparation of the medium component, even if it is dried
Well, after filtration, washed with an inert solvent such as heptane
A thing may be used. In each case,
Magnesium compounds are ground or evenly distributed
Use in the next step without classifying
Can be. As the titanium compound, for example,
Tramethoxytitanium, tetraethoxytitanium, tetra-
n-propoxytitanium, tetraisopropoxytitanium,
Tetra-n-butoxytitanium, tetraisobutoxytita
, Tetracyclohexyloxytitanium, tetraphenoki
Tetraalkoxy titanium such as titanium, titanium tetrachloride
, Titanium tetrabromide, titanium tetraiodide, etc.
Titanium, methoxytitanium trichloride, ethoxy
Citanium trichloride, propoxytitanium trichloride
Chloride, n-butoxytitanium trichloride, eth
Halogenated alkoxy such as xitanium tribromide
Si titanium, dimethoxy titanium dichloride, dietoki
Citanium dichloride, dipropoxy titanium chloride
Loride, di-n-butoxytitanium dichloride, die
Dihalogenated dials such as toxic titanium dibromide
Coxy titanium, trimethoxy titanium chloride, tri
Ethoxy titanium chloride, tripropoxy titanium
Muchloride, tri-n-butoxytitanium chloride
Which monoalkoxy trialkoxy titanium etc.
Among these, titanium compounds with high halogen content
Titanium tetrachloride is preferred. In addition, these titanium compounds
You may use only one kind of thing, or combine two or more kinds
It may be used. Further, the halogen atom may be a fluorine atom.
Atom, chlorine atom, bromine atom, iodine atom
However, these halogen atoms are usually masked as halides.
Included in gnesium compounds and / or titanium compounds
Used. As the electron donor, (D)
Use those exemplified as electron-donating compounds for the components.
Can be. The preparation of the solid catalyst component (a) is performed by a known method.
(Japanese Unexamined Patent Publication No. Sho 53-43094,
No. 5102, Japanese Patent Application Laid-Open No. 55-135103,
JP-A-56-18606, JP-A-56-16620
No. 5, JP-A-57-63309, JP-A-57-63309
-190004, JP-A-57-300407
Report, JP-A-58-47003).
You. (A) Solid catalyst thus prepared
The composition of the components is usually such that the magnesium / titanium atomic ratio is 2 to 2.
100, halogen / titanium atomic ratio 5-100, electric child
The donor / titanium molar ratio is in the range of 0.1 to 10. Also,
(A) used as needed in the preparation of solid components
As the crystalline polyolefin of the component (b), for example,
Polyethylene, polypropylene, polybutene, poly 4-
Α-ole having 2 to 10 carbon atoms such as methyl-1-pentene
Crystalline polyolefins obtained from fins
You. This crystalline polyolefin is (1) the solid (a)
Catalyst component and organoaluminum compound, if necessary
Exist in combination with the electron donating compound
Below, the method of pre-polymerizing olefin (pre-polymerization
Method), (2) crystalline polyethylene or polyp with uniform particle size
A crystalline catalyst such as propylene is added to the above (a) solid catalyst.
Ingredients and optionally used organoaluminum compounds
And an electron donating compound (having a melting point of 100 ° C. or higher)
(Dispersion method), (3) the method of (1) and the method of (2)
Obtained by using a method that combines methods
be able to. In the prepolymerization method (1), the
The atomic ratio of minium / titanium is usually 0.1 to 100, preferably
Is selected in the range of 0.5 to 5, and the electron donating compound /
The molar ratio of the components is selected in the range of 0 to 50, preferably 0.1 to 2.
Devour. (A) Solid catalyst component in (A) solid component
And (b) the proportion of the crystalline polyolefin,
The weight ratio of the component (b) to the component (a) is usually 0.33.
To 200, preferably 0.10 to 50
To be elected. Next, the organic alcohol used as the component (B)
As the minium compound, a compound represented by the general formula (II) AlR^Three _PX_3-P      ... (II) [Wherein, R^ThreeIs an alkyl group having 3 to 20 carbon atoms or carbon number
6 to 20 aryl groups, X is a halogen atom, p is 1 to 3
Indicates the number of And the compound represented by
You. For example, triisopropyl aluminum, triiso
Butyl aluminum, trioctyl aluminum, etc.
Trialkyl aluminumTheIsopropyl aluminum
Mumonochloride, diisobutylaluminum monochloride
Dial, dioctyl aluminum monochloride, etc.
Kill aluminum monohalide,Lucil Aluminum
Sesquihalide and the like can be suitably used. This
These aluminum compounds may be used alone,
Two or more kinds may be used in combination. The catalyst system of the present invention comprises the component (C) and
And formula (I) [0027] Embedded image [Wherein, R¹Is alkyl having 1 to 20 carbon atoms
Group, R^TwoIs a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or
A toro group; m is an integer of 1 to 6; n is 0 to (6-m)
Indicates an integer. Aromatization containing alkoxy group represented by
Compounds are used. Specific examples of the alkoxy group-containing aromatic compound
Examples are m-methoxytoluene;
Nol; m-methoxyphenol; 2-methoxy-4-
Methylphenol; vinylanisole; p- (1-pro
Penyl) anisole; p-allylanisole; 1,3-
Bis (p-methoxyphenyl) -1-pentene; 5-a
Lyl-2-methoxyphenol; 4-hydroxy-3-
Methoxybenzyl alcohol; methoxybenzyl alcohol
Nitroanisole; nitrophenetol
Alkoxy compound, o-dimethoxybenzene; m-di
Methoxybenzene; p-dimethoxybenzene; 3,4-
Dimethoxytoluene; 2,6-dimethoxyphenol;
Dials such as 1-allyl-3,4-dimethoxybenzene
Coxy compound, 1,3,5-trimethoxybenzene; 5
-Allyl-1,2,3-trimethoxybenzene;
Ryl-1,2,4-trimethoxybenzene; 1,2,3
-Trimethoxy-5- (1-propenyl) benzene;
1,2,4-trimethoxy-5- (1-propenyl) be
1,2,3-trimethoxybenzene;
Trialkoxy compounds such as 4-trimethoxybenzene
Etc., among which dialkoxy compounds
And trialkoxy compounds are preferred. These al
The oxy group-containing aromatic compound may be used alone,
Two or more kinds may be used in combination. The catalyst may further comprise (D)
An electron donating compound is used as the component. This electron donation
The reactive compounds include oxygen, nitrogen, phosphorus, sulfur, silicon, etc.
It is a compound that contains
In this regard, it is conceivable to have regularity improving performance.
Such electron donating compounds include, for example, organic
Iodine compounds, esters, thioesters, amines,
Ketones, nitriles, phosphines, ethers,
Oethers, acid anhydrides, acid halides, acid amides,
Aldehydes, organic acids, azo compounds, etc.
Can be. For example, diphenyldimethoxysilane, diphenyl
Phenyldiethoxysilane, dibenzyldimethoxysila
, Tetramethoxysilane, tetraethoxysilane,
Traphenoxysilane, methyltrimethoxysilane,
Tyltriethoxysilane, methyltriphenoxysila
, Phenyltrimethoxysilane, phenyltriethoxy
Organic silicon such as silane and benzyltrimethoxysilane
Elemental compound, monomethyl phthalate, monoethyl phthalate
G, monopropyl phthalate, monobutyl phthalate,
Monoisobutyl phthalate, monoamyl phthalate,
Noisoamyl phthalate, monomethyl terephthalate,
Monoethyl terephthalate, monopropyl terephthalate
G, monobutyl terephthalate, monoisobutyl tereph
Tallate, dimethyl phthalate, diethyl phthalate,
Dipropyl phthalate, dibutyl phthalate, diisobu
Tilphthalate, diamylphthalate, diisoamylph
Talate, methyl ethyl phthalate, methyl isobutyl
Phthalate, methylpropyl phthalate, ethyl butyl
Phthalate, ethyl isobutyl phthalate, ethylpro
Pill phthalate, propyl isobutyl phthalate,
Cyl terephthalate, diethyl terephthalate, dipro
Pill terephthalate, diisobutyl terephthalate,
Tyl ethyl terephthalate, methyl isobutyl terephthalate
, Methyl propyl terephthalate, ethyl butyl
Terephthalate, ethyl isobutyl terephthalate, d
Propyl terephthalate, propyl isobutyl terephthalate
Phthalate, dimethyl isophthalate, diethyl isophthalate
Talate, dipropylisophthalate, diisobutylyl
Sophthalate, methyl ethyl isophthalate, methyl i
Sobutyl isophthalate, methyl propyl isophthalate
G, ethyl butyl isophthalate, ethyl isobutyl
Sophthalate, ethyl propyl isophthalate, propyl
Aromatic dicarboxylic acids such as isobutyl isophthalate
Ester, methyl formate, ethyl formate, methyl acetate, acetic acid
Ethyl, vinyl acetate, propyl acetate, octyl acetate, vinegar
Cyclohexyl acid, ethyl propionate, methyl butyrate,
Ethyl butyrate, ethyl valerate, methyl chloroacetate, dichloro
Ethyl acetate, methyl methacrylate, crotonate
, Ethyl bivalate, dimethyl maleate, cyclohexane
Ethyl xanthate, methyl benzoate, benzoic acid
Chill, propyl benzoate, butyl benzoate, o-benzoic acid
Octyl, cyclohexyl benzoate, phenyl benzoate,
Benzyl benzoate, methyl toluate, ethyl toluate
, Amyl toluate, ethyl ethyl benzoate, anise
Methyl acrylate, ethyl anisate, ethyl ethoxybenzoate,
Ethyl p-butoxybenzoate, ethyl o-chlorobenzoate
Monoesters such as ethyl and naphthoate, γ-butyro
Lactone, δ-valerolactone, coumarin, phthalide,
Esters such as ethylene carbonate, benzoic acid, p-oxy
Organic acids such as benzoic acid, succinic anhydride, benzoic anhydride
Acid, acid anhydride such as p-toluic anhydride, acetone,
Tyl ethyl ketone, methyl isobutyl ketone, acetoph
Ketones such as enones, benzophenones and benzoquinones
, Acetaldehyde, propionaldehyde, octi
Lualdehyde, tolualdehyde, benzalded, naph
Aldehydes such as tyl aldehyde, acetyl chloride
, Acetyl bromide, propionyl chloride, butyric
Ruchloride, isobutyryl chloride, 2-methylpropyl
Onyl chloride, valeryl chloride, isovaleryl chloride
Lido, hexanoyl chloride, methylhexanoyl chloride
Lido, 2-ethylhexanoyl chloride, octanoyl
Chloride, decanoyl chloride, undecanoyl chloride
, Hexadecanoyl chloride, octadecanoyl chloride
Lido, Hensyl carbonyl chloride, dicyclohexaneca
Rubonyl chloride, malonyl dichloride, succinyl di
Chloride, pentanedioyl dichloride, hexane di
Oleyl dichloride, dicyclohexanedicarbonyldic
Loride, benzoyl chloride, benzoyl bromide,
Tylbenzoyl chloride, phthaloyl chloride, isofl
Talloyl chloride, terephthaloyl chloride, benzene
Acids such as -1,2,4-tricarbonyl trichloride
Logenides, methyl ether, ethyl ether, iso
Propyl ether, n-butyl ether, isopropyl
Methyl ether, isopropyl ethyl ether, t-butyl
Tyl ethyl ether, t-butyl-n-propyl ether
, T-butyl-n-butyl ether, t-amylmethyl
Ether, t-amylethyl ether, amylate
Le, tetrahydrofuran, anisole, diphenyle
Ethers such as ethylene glycol butyl ether
, Acetic acid amide, benzoic acid amide, toluic acid amide
Acid amides, such as tributylamine, N, N'-dimethyl
Tilpiperazine, tribenzylamine, aniline, pyri
Gin, pyrroline, tetramethylethylenediamine, etc.
Amines, acetonitrile, benzonitrile, tolnit
Nitriles such as ril, 2,2'-azobis (2-methyl
Lupropane), 2,2'-azobis (2-ethylpropa
), 2,2'-azobis (2-methylpentane)
Compounds having sterically hindered substituents bonded to the azo bond of
And the like. Among these, organosilicon compounds and esters
, Ketones, ethers, thioethers, acid anhydride
And acid halides are preferred, especially diphenyldimethoate.
Organic compounds such as xysilane and phenyltriethoxysilane
Iodine compounds, di-n-butyl phthalate, diisobutyl
Aromatic dicarboxylic acid diester such as phthalate, benzoate
Carboxylic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid,
Alkyl esters of aromatic monocarboxylic acids such as toluic acid
Ter and the like are suitable. These electron donating compounds are
It may be used only for seeds, or a combination of two or more
Is also good. Regarding the amount of each component of the catalyst system, (A)
The body component was equivalent to 1 liter of reaction volume in terms of titanium atom.
The amount is usually in the range of 0.0005 to 1 mol.
Can be. Further, (B) the organoaluminum compound is
The ratio of luminium / titanium atoms is usually 1 to 3000, preferably
Preferably, the amount used is 40 to 800,
If the amount is outside the above range, the catalytic activity may be insufficient.
There is. Further, (C) an alkoxy group-containing aromatic compound
The product has a molar ratio to titanium atoms in the solid component (A).
Usually 0.01 to 500, preferably 1 to 300
If the amount is less than 0.01, the resulting polymer
May deteriorate the physical properties of
The solvent activity may be insufficient. The propylene-based resin composition of the present invention is characterized in that
Can be obtained by multistage polymerization in the presence of
Wear. The order of polymerization and the number of polymerization stages in multistage polymerization are optional
You can choose. For example, the first polymerization (first stage weight
), Homopolymerization of propylene is performed, and
Len-propylene copolymer or ethylene-propylene-poly
An ene copolymerization can be performed. Possible to use
Examples of the liene include dicyclopentadiene and tricyclopentadiene.
Clopentadiene and the like can be mentioned. Polymerization type
There are no particular restrictions on slurry polymerization, gas phase polymerization,
Bulk polymerization, solution polymerization, suspension polymerization and the like are used. Mind
When performing polymerization by phase polymerization, propylene homopolymerization stage
For floors, the polymerization pressure is usually 10-45 kg / c
m^Two, Preferably 20-30 kg / cm^Two, The polymerization temperature is
The temperature is usually in the range of 40 to 90 ° C, preferably 60 to 75 ° C.
Be chosen accordingly. In addition, ethylene-propylene copolymerization stage and
About ethylene-propylene-polyene copolymerization stage
Means that the polymerization pressure is usually 5 to 30 kg / cm^Two,Preferably
10-20 kg / cm^Two, The polymerization temperature is usually 20 to 90
° C, preferably in the range of 40 to 60 ° C. I
Even in the step of shifting, the molecular weight of the polymer is controlled by a known method.
Means, for example, by adjusting the hydrogen concentration in the polymerization vessel.
Can be performed. It also dissolves in the presence of organic peroxide.
It can also be adjusted by melt-kneading. Polymerization time
Is appropriately selected in about 5 minutes to 10 hours. In the polymerization, each component constituting the catalyst system is used.
Minutes, that is, the components (A) to (D) are mixed at a predetermined ratio.
Olefins are introduced immediately after contact.
May be started or matured for about 0.2 to 3 hours after contact
After that, an olefin may be introduced. Furthermore, this
Catalyst components are supplied suspended in an inert solvent or olefin
can do. Post-treatment after polymerization should be performed by a conventional method.
Can be. That is, in the gas phase polymerization method,
After that, the polymer powder derived from the polymerization vessel contains
Through a nitrogen stream to remove olefins
May be passed. Also, if necessary, pelletize with an extruder.
The catalyst may be completely deactivated in order to completely deactivate the catalyst.
A small amount of water, alcohol, etc.
You. In the bulk polymerization method, after polymerization,
Completely separated the monomer from the polymer derived from
That is, it can be pelletized. In addition, the professional
Pyrene-based resin compositions consist of propylene homopolymer and ethylene.
-Propylene copolymer and / or propylene-polyethylene
Copolymer with a known method (for example, dry blending or
Can be prepared by blending
it can. [0035] The present invention will be described in more detail with reference to the following examples.
However, the invention is not limited by these examples
Not something. Embodiment 1 (1) Preparation of magnesium compound A glass reactor (with an internal volume of about 6 liters) with a stirrer
Substitute sufficiently with nitrogen gas, ethanol about 2430 g,
16 g of urine and 160 g of metallic magnesium were charged and stirred.
No hydrogen gas is generated from the system under reflux conditions with stirring
Reaction under heating until a solid reaction product is obtained.
Was. The reaction solution containing the solid product is dried under reduced pressure.
Thus, a magnesium compound was obtained. (2) Preparation of solid catalyst component (A) Glass three-necked flask sufficiently purged with nitrogen gas (inside
Volume of 500 ml), the magnesium compound
(Not crushed) 16g, purified heptane 80mm
Liter, 2.4 ml of silicon tetrachloride, and phthalate
2.3 ml of diethyl acidate were added. 90 ° C inside the system
While maintaining and stirring, throw 77 ml of titanium tetrachloride.
And reacted at 110 ° C. for 2 hours.
Separated and washed with purified heptane at 80 ° C. Furthermore, four salt
Add 122 ml of titanium oxide and react at 110 ° C for 2 hours.
After washing, wash thoroughly with purified heptane
The component (A) was obtained. (3) Gas phase polymerization 5 liter stainless steel autoclave
Propylene powder 20g, triisobutylaluminum
(TIBA) 2.5 mmol, 1-allyl-3,4-di
Methoxybenzene (ADMB) 0.125 mmol, diph
0 mmol of enyldimethoxysilane (DPDMS) and
The solid catalyst component (A) is 0.05 mm in terms of titanium atom.
Add 20 ml of a heptane solution containing
After exhausting for 5 minutes, the total pressure is 28kg / cm^TwoBecome G
Gas phase polymerization for 1.7 hours while supplying propylene gas
Was done. Next, exhaust the unreacted gas in the autoclave.
A small amount of the resulting powder for analysis was sampled. Next
Then, add 0.5kg / cm of hydrogen gas.^TwoG, ethylene-pro
Pyrene mixed gas (molar ratio 1/1) at 10 kg / cm^TwoG
, And gas phase polymerization was carried out at 50 ° C. for 1.0 hour. Get
Table 1 shows the composition and physical properties of the obtained polymer. Embodiment 2 Using the same catalyst as in Example 1, TIBA,
The amount of ADMB and DPDMS was adjusted to 5.0 mmol,
0.125 mmol and 0.2 mmol, as in Example 1.
After homopolymerization of propylene in the same manner as shown in Table 1,
Gas composition and polymerization time for copolymerization
Was adjusted. The results are shown in Table 1. Embodiment 3 Using the same catalyst as in Example 1, TIBA,
The amount of ADMB and DPDMS was adjusted to 5.0 mmol,
0.125 mmol and 0.4 mmol, the same as in Example 1.
After performing propylene homopolymerization in the same manner,
Gas composition and polymerization time in copolymerization
Adjusted. The results are shown in Table 1. Embodiment 4 Using the same catalyst as in Example 1, TIBA,
The amount of ADMB and DPDMS was adjusted to 5.0 mmol,
0.125 mmol and 0.5 mmol, as in Example 1.
After performing propylene homopolymerization in the same manner,
Gas composition and polymerization time in copolymerization
Saved. The results are shown in Table 1. Embodiment 5 Performed in exactly the same manner as in Example 2 up to propylene homopolymerization,
For the copolymerization, set the gas composition so that the composition shown in Table 1 is obtained.
The formation and polymerization times were adjusted. The results are shown in Table 1. Examples 6 to 8 Propylene homopolymerization was carried out in the same manner as in Example 2.
Then, the gas in the copolymerization was adjusted to the composition shown in Table 1.
The composition and polymerization time were adjusted. The results are shown in Table 1. Comparative Example 1 (1) Preparation of solid catalyst component 500 ml glass with sufficient nitrogen replacement
20 ml purified heptane,
Mg (OC_TwoH_Five)_Two4 g and di-n-butyl phthalate 1.
Add 2 g, keep the system at 90 ° C, and stir
Cl_FourAfter dropping 4 ml, further add TiCl
_FourAdd additional 111 ml and heat up to 110 ° C
And reacted for 2 hours, then purified heptane 1 at 80 ° C.
Washed with 00 ml. Next, the resulting solid phase
TiCl_FourAdd 115 ml and heat at 110 ° C
For 2 hours. After the reaction is completed, the product is purified
Wash several times with 100 ml
did. (2) Preparation of solid component 2.5 liter glass pressure-resistant, fully purged with nitrogen
1.7 liters of purified heptane, Al in a three-necked flask
(C_TwoH_Five)_Three0.07 mol, diphenyldimethoxysilane
(DPDMS) 0.05 mmol and obtained in the above (1)
After adding 120 g of the solid catalyst component, the temperature in the system is reduced to 30 ° C.
Propylene is continuously supplied while maintaining
0.5 kg / cm^TwoG. Continue this reaction for 1 hour.
After washing, wash 5 times with 1 liter of purified heptane,
A solid component was prepared. (3) Gas phase polymerization 5 liter stainless steel autoclave
Propylene powder 20g, Al (C_TwoH_Five)_Three3 millimo
, ADMB 0.15 mmol, DPDMS 0.23 mm
Mole and 100 mg of the solid component (2) (titanium atom
Heptane solution containing 0.06 mmol)
After adding liter and evacuating the system for 5 minutes,
28kg / cm^TwoSupply propylene gas until it reaches G
The gas phase polymerization was carried out at 70 ° C. for 1.7 hours. Then
After exhausting the unreacted gas, add 0.5 kg / cm of hydrogen gas.
^TwoG, ethylene-propylene mixed gas (molar ratio 1/3)
10kg / cm^TwoG up to 50 ° C for 1.2 hours
Phase polymerization was performed. The results are shown in Table 1. Comparative Examples 2 to 4 In the first-stage polymerization (homopolymerization of propylene),
Boiling n-heptane insoluble depending on the amount of ADMB and DPDMS
Adjust the amount of component W (stereoregularity)
Comparative example except that the composition was adjusted by the composition and polymerization time
Performed in the same manner as 1. The results are shown in Table 1. [0046] [Table 1][0047] [Table 2][0048] [Table 3][0049] As described above, the propylene resin composition of the present invention is
It has high heat resistance and excellent mechanical properties in the elastic modulus range,
In addition to its small temperature dependence of its mechanical properties,
It has excellent features such as no surface tackiness. The
Propylene resin compositions include, for example,
Bar fender, mudguard, soft bumper, hand
, Shift knob, armrest, console box,
Auto parts such as seats, civil engineering and building materials, fill
It is suitably used as a material such as a rubber sheet.

────────────────────────────────────────────────── (5) References JP-A-3-234708 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/64-4/69 C08F 297 / 08 C08L 23/00-23/36

Claims (1)

(A) (a) (a) The intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. is 1.0 to 9.0 deciliter / g, and (b) Amount of boiling n-heptane insoluble component (W)
Is 10 to 99% by weight, and (c) the measured value of the relaxation time of the rubber component measured by pulse NMR at a temperature of 30 ° C. [T _2H ^R (30): μs] and the measured value at 80 ° C. [T _2H ^R (80): μs] and the amount of the boiling n-heptane-insoluble component (W) is expressed by the formula T _2H ^R (80) ≦ 670-2.2 × WT T _2H ^R (80) / T _2H ^R ( 30) a propylene homopolymer satisfying ≦ 8.8 + 0.086 × W 2 and / or a copolymer containing 4 mol% or less of other olefin units 10 to 95;
(B) a propylene-based random containing 10 to 70 mol% of olefin units other than propylene having an intrinsic viscosity [η] of 1.0 to 9.0 deciliter / g measured in decalin at a temperature of 135 ° C. 90-5% by weight of copolymer
A propylene-based resin composition comprising: