JPH11349747A - Propylene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene-based resin composition which allows easy production of moldings having excellently balanced rigidity, heat resistance, and particularly impact strength at low temperatures. SOLUTION: This propylene-based resin composition is obtained by mixing a propylene-based polymer having a propylene unit at 100-80 mol.%, a constituting unit derived from a comonomer at 0-20 mol.%, an MFR of 0.1-200 g/10 min, an average elution temperature at 75-120 deg.C, and eluted fraction dispersion of 9 or less, with an inorganic filler and, if necessary, an elastomer and/or a Tiegler-based polypropylene, wherein, eluted fraction dispersion, σ=T84.1 -T15.9 (T84.1 is temperature at the time when the accumulated amount of eluted fraction reaches 84.1 wt.%, and T15.9 is temp. when the above becomes 15.9 wt.%).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel propylene-based resin composition. More specifically, the present invention relates to a propylene-based resin composition having an excellent balance between rigidity, impact resistance (particularly low-temperature impact resistance) and heat resistance, and being useful as a material for injection molding, extrusion molding, or hollow molding. .

[0002]

2. Description of the Related Art Polypropylene has been widely used as a molding material in injection moldings, extrusion moldings, blow moldings and the like.

On the other hand, in recent years, from the viewpoint of resource and energy saving, molded articles such as injection molded articles have been required to be thinner and lighter, and the rigidity and impact resistance of polypropylene molding materials have been improved. Accordingly, various proposals have been made in order to make the molded product thinner and lighter.

[0004] For example, it is already known to reduce the wall thickness and weight by using a block copolymer produced by stepwise polymerizing propylene and ethylene or another olefin. Recently, a propylene block copolymer polymerized in the presence of a catalyst system comprising a metallocene compound and a cocatalyst has been proposed as a polypropylene having improved properties such as low-temperature impact resistance (Japanese Patent Laid-Open No. 4-337308). JP, JP-A-5-202152, JP-A-6-20
No. 6921, Japanese Unexamined Patent Publication No. Hei 8-510491, WO
95/27740, WO95 / 27741, etc.). In addition, the present bidder has also proposed an improved method using the above catalyst system using a specific carrier and a specific polymerization method (Japanese Patent Application Laid-Open No.
-172414, JP-A-6-287257, JP-A-8-27237).

However, in the polypropylene obtained by these methods, the balance between rigidity, impact resistance (particularly low-temperature impact resistance) and heat resistance is not always sufficient, and further improvement is required.

[0006]

SUMMARY OF THE INVENTION The present invention provides a propylene-based resin composition which can easily produce a molded article having an excellent balance between rigidity, impact resistance (particularly low-temperature impact resistance) and heat resistance. That is the task.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by using a propylene-based polymer having a specific range of elution temperature and elution dispersity and having no variation in crystallinity, rigidity can be improved. It has been found that a molded article having an excellent balance between the heat resistance and the impact resistance (particularly low-temperature impact resistance) and heat resistance can be obtained, and the present invention has been achieved.

That is, the present invention relates to (1) a propylene polymer satisfying the following requirements (a) to (c):
An inorganic filler, the content of the propylene-based polymer is 20 to 99% by weight, and the content of the inorganic filler is 1 to
80% by weight of a propylene-based resin composition (hereinafter, referred to as
"Composition I"). (A): Structural unit derived from propylene is 100-
80 to 20 mol% of a constituent unit derived from a comonomer selected from the group consisting of 80 mol%, ethylene and an α-olefin having 4 to 20 carbon atoms. (B): Melt flow rate is 0.1 to 200 g / 10
Be a minute. (C): the average elution temperature is in the range of 75 to 120 ° C,
The elution dispersion degree is 9 or less.

The present invention also provides (3) an elastomer in addition to (1) a propylene polymer and (2) an inorganic filler, wherein the content of the propylene polymer is 10 to 9;
8% by weight, the content of the inorganic filler is 1 to 80% by weight,
The propylene-based resin composition in which the content of the elastomer is 1 to 89% by weight (hereinafter, referred to as “composition II”)
I will provide a.

The present invention also includes (3) a polypropylene resin produced using a Ziegler-based catalyst, in addition to (1) a propylene-based polymer and (2) an inorganic filler.
The content of the propylene-based polymer is 10 to 94% by weight,
The present invention provides the propylene-based resin composition (hereinafter, referred to as "composition III") in which the content of the inorganic filler is 1 to 80% by weight and the content of the polypropylene resin is 5 to 89% by weight.

Further, the present invention comprises (3) an elastomer and (4) a polypropylene resin produced using a Ziegler catalyst in addition to (1) a propylene polymer and (2) an inorganic filler. The content of the propylene-based polymer is 10 to 93% by weight, and the content of the inorganic filler is 1 to 93% by weight.
80% by weight, the content of the elastomer is 1 to 84% by weight, and the content of the polypropylene resin is 5 to 88% by weight.
The propylene-based resin composition (hereinafter referred to as “Composition I”
V ”).

Further, the present invention provides any one of the above propylene resin compositions, wherein the polypropylene polymer satisfies the following (a) to (e). (A): Structural unit derived from propylene is 100-
94 mol%, and 0 to 6 mol% of structural units derived from a comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. (B): Melt flow rate is 0.1 to 200 g / 10
Be a minute. (C): the average elution temperature is in the range of 75 to 120 ° C,
The elution dispersion degree is 9 or less. (D): Isotactic pentad chain fraction of 9
5% or more. (E): The ratio of 1,3-asymmetric bonds is 0.06 to 3%.

According to the present invention, there is provided a molded product selected from the group consisting of an injection molded product, a hollow molded product, and an extruded molded product, characterized in that the molded product is composed of any one of the propylene resin compositions described above. A propylene-based resin molded product.

The propylene resin composition of the present invention comprises a propylene polymer and an inorganic filler and, if necessary, a polypropylene resin obtained by using an elastomer and / or a Ziegler catalyst. By using a propylene-based polymer that has a specific range of elution temperature and elution dispersion degree and has no variation in crystallinity, the balance between rigidity, impact resistance (especially low-temperature impact resistance) and heat resistance can be improved. An excellent molding material can be obtained.

[0015]

Embodiments of the present invention will be described below. The propylene-based resin composition of the present invention comprises a propylene-based polymer and components to be mixed with the propylene-based polymer.

(1) Propylene Polymer The propylene polymer of the present invention has the following requirements (a) for the constituent units, requirements (b) for the melt flow rate, and requirements for the average dissolution temperature and dissolution degree ( c) is satisfied. Preferably, in addition to these requirements (a) to (c), the requirement (d) relating to the fraction of the isotactic pentad chain and the requirement (e) relating to the ratio of the 1,3-asymmetric bond are satisfied. .

(A) Structural Units The propylene-based polymer used in the present invention has a structural unit derived from propylene (hereinafter referred to as a propylene polymer) in all the structural units.
100 to 80 mol% of a "propylene unit"), and 0 to 20 of a structural unit derived from a comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms (hereinafter, referred to as a "comonomer unit"). Molar% is present. Preferably, the propylene unit has 100
９４94 mol%, and 0-6 mol% of comonomer units. If the structural unit of the comonomer exceeds the above range, the rigidity is greatly reduced, and practicality is impaired.

As such a propylene-based polymer,
Examples thereof include a propylene homopolymer and a propylene-based copolymer. As the propylene-based copolymer, any of a propylene-based random copolymer and a propylene-based block copolymer may be used.

The comonomer used here is preferably selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms. Specific examples of the α-olefin having 4 to 20 carbon atoms include ethylene, butene-1, pentene-1, hexene-1, octene-1, and 4-methylpentene-1.

The propylene-based polymer in these propylene polymers
Pyrene units and comonomer units are ¹³C-NMR (nucleus
(Magnetic resonance method). Specifically
Is a JEOL FT-NMR 270MHz instrument.
It is a value measured more.

(B) Melt flow rate (MFR) The propylene polymer of the present invention has a melt flow rate [value measured in accordance with JIS-K7210 (230 ° C., 2.16 kg load)]. Hereinafter, abbreviated as “MFR”] is 0.1 to 200 g / 10 min, preferably 1 to 2 g / min.
00 g / 10 min, particularly preferably 4 to 200 g / 10 min. If the MFR is higher than the above range, the impact strength of the product tends to be insufficient, and if the MFR is less than the above range, poor flow may occur during molding.

(C) Average Elution Temperature (T ₅₀ ) and Elution Dispersion (σ) The propylene-based polymer of the present invention has a temperature-rise elution fraction (T
REF: average elution temperature (T ₅₀ ) of the elution curve obtained by Temperature Rising Elution Fraction is 75 to
It is in the range of 120 ° C., preferably 75 to 110 ° C., particularly preferably 75 to 100 ° C., and the dissolution degree (σ) is 9 or less, preferably 8 or less, particularly preferably 7.7 or less.

Here, the measurement of the temperature rise elution fractionation (TREF) is carried out by completely dissolving the polymer at a constant high temperature and then cooling it to form a thin polymer layer on the surface of the inert carrier. In this method, the eluted component (eluted polymer) is recovered, the concentration is continuously detected, and the amount of the eluted component and the elution temperature are determined. A graph drawn by the elution amount and the elution temperature is an elution curve, from which the composition distribution of the polymer can be measured. For details of the method and apparatus for measuring temperature rise elution fractionation (TREF), see the Journal of Applied
Polymer Science, Vol. 26, pp. 4217-4231 (1981).

The average dissolution temperature (T ₅₀ ) indicates the temperature at which the cumulative weight of the dissolution polymer becomes 50%.
If the average elution temperature (T ₅₀ ) is less than the above range, the molecular weight is too low or the melting point is too low, which causes insufficient rigidity. If it exceeds the above range, the molecular weight will be too high or the melting point will be too high, making molding difficult.

The dissolution degree (σ) is a value represented by the following formula (1), that is, the cumulative weight of the dissolution polymer is 15.9%.
(T _15.9 ) and the eluting polymer is 84.
It shows the temperature difference from the temperature (T _84.1 ) when it becomes 1%.

[0026]

Σ = T _84.1 −T _15.9 (1)

If the dissolution degree (.sigma.) Exceeds the above range, components having low stereoregularity, which inhibit crystallinity, and portions having greatly different comonomer compositions increase, and the rigidity decreases, which is not preferable.

(D) Fraction of isotactic pentad chain The propylene polymer of the present invention has the above-mentioned requirements (a) to
Although it is necessary to satisfy (c), it is preferable to satisfy the requirement (d) concerning the fraction of isotactic pentad chains described below.

That is, the propylene-based polymer of the present invention has an isotactic pentad chain (mmmm) fraction (mesopentad fraction), which is an index of stereoregularity determined according to a standard method by ¹³ C-NMR spectrum analysis. Is 95% or more, preferably 97% or more. If the stereoregularity is low, the melting point tends to decrease, and the ripening resistance tends to decrease. Depending on the production method, a small amount of the atactic polymer component may be present even if the average value (mmmm) is a high value. The atactic polymer component defined by the boiling heptane soluble matter is 5% or less, more preferably 3% or less, and still more preferably 1% or less.

The mesopentad fraction is evaluated based on the ¹³ C-NMR spectrum by a known method (Rand).
all JC Journal of Polymer Science, 1
2,7031974). In addition, the quantification of 1,3-asymmetric bond is described in A. Zam
The peaks are assigned according to bellole Macromolecules (21 (3) 617 1988), and the mole% is calculated from the sum total of the carbon atoms of —CH ₂ — and —CH—.

(E) Ratio of 1,3-asymmetric bond The propylene-based polymer of the present invention has the above-mentioned requirements (a) to
It is necessary to satisfy (c), and it is more preferable that the above requirement (d) is satisfied. More preferably, the requirement (e) relating to the ratio of 1,3-asymmetric bonds described below is satisfied.
It satisfies. That is, the propylene-based polymer of the present invention preferably has a 1,3-asymmetric bond ratio of 0.06 to 3%.

(2) Method for Producing Propylene Polymer The method for producing a propylene polymer used in the present invention is as follows.
There is no particular limitation as long as a predetermined polymer having the physical properties defined in the present invention can be obtained, and any method can be adopted. Hereinafter, a typical method for producing the propylene-based polymer of the present invention will be described.

The propylene-based polymer of the present invention can be produced by carrying out the polymerization step in the presence of a specific catalyst system.

[Catalyst] The catalyst used in the present invention is a metallocene-based α-olefin polymerization catalyst comprising the following essential components (A) and (B) and an optional component (C). . (A) A transition metal compound represented by the following general formula [1]. (B) an aluminum oxy compound, an ionic compound capable of converting the component (A) into a cation by reacting with the component (A), an ion-exchange layered compound excluding Lewis acids and silicates, and an inorganic silicate At least one compound selected from the group consisting of: (C) an organoaluminum compound.

[0035]

Embedded image

Here, in the formula [1], A and A ′ represent a conjugated five-membered ring ligand, and Q represents a bonding group that bridges the two conjugated five-membered ring ligands at arbitrary positions. , M is the periodic table 4-6
X and Y represent a hydrogen atom,
Halogen atom, hydrocarbon group, alkoxy group, amino group,
It represents a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group.
In addition, A and A 'may be mutually the same or different in the same compound.

Component (A): Specific examples of the conjugated five-membered ring ligands (A and A ′) in the transition metal compound represented by the above general formula [1] include a conjugated five-membered ring ligand, That is, a cyclopentadienyl group can be mentioned. The cyclopentadienyl group may be a group having four hydrogen atoms (a group having a hydrogen atom at a bonding site of all carbon atoms except for a carbon atom in a bridge portion: C ₅ H ₄ —). A derivative, that is, one in which some of the hydrogen atoms are substituted with a substituent, may be used.

Examples of the substituent include those having 1 to 2 carbon atoms.
0, preferably 1 to 12 hydrocarbon groups. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, when two or more of them are present, two of them are bonded at the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of the group.

As an example of the latter, two substituents are bonded at each ω-terminal to form a fused six-membered ring by sharing two adjacent carbon atoms in the cyclopentadienyl group. That is, an indenyl group, a tetrahydroindenyl group or a fluorenyl group. Two substituents bonded at each ω-terminal to share two adjacent carbon atoms in the cyclopentadienyl group to form a fused seven-membered ring, ie, azulenyl And a tetrahydroazulenyl group.

That is, specific examples of the conjugated five-membered ring ligand represented by A and A 'include a substituted or unsubstituted cyclopentadienyl group, an indenyl group, a fluorenyl group, an azulenyl group and the like.

As the substituent on the conjugated five-membered ring ligand such as cyclopentadienyl group, in addition to the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, fluorine, chlorine, bromine, etc. A halogen atom group, a C ₁ -C ₁₂ alkoxy group,
For example _{-Si (R 1) (R 2} ) a silicon-containing hydrocarbon group having 1 to 24 carbon atoms represented by _{(R 3), -P (R} 1) (R
₂ ) a phosphorus-containing hydrocarbon group having 1 to 18 carbon atoms represented by
-N _(R 1) _{(R 2)} nitrogen-containing hydrocarbon group having 1 to 18 carbon atoms represented by, or _-B (R 1) a boron-containing hydrocarbon group having 1 to 18 carbon atoms represented by _{(R 2)} Or a hydrocarbon group containing 1 to 20, preferably 1 to 12 carbon atoms containing halogen, oxygen, nitrogen, phosphorus, sulfur, boron and silicon.

When there are a plurality of these substituents, each substituent may be the same or different. Also,
The above R _{1 to} R ₃ may be the same or different and represent a hydrogen atom or a C _{1 to} C ₂₀ alkyl group, alkenyl group, aryl group and the like. They may be linked to form a cyclic substituent.

Q represents a bonding group bridging at any position between the two conjugated five-membered ligands. As a specific example of Q,
(A) alkylene groups having 1 to 20 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, and a cyclohexylene group;
(B) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group,
A silylene group such as a tetramethyldisilylene group, (c) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, and more specifically, (CH ₃ ) ₂ G
e, (C ₆ H ₅ ) ₂ Ge, (CH ₃ ) P, (C ₆ H ₅ )
P, (C ₄ H ₉ ) N, (C ₆ H ₅ ) N, (CH ₃ ) B,
(C ₄ H ₉ ) B, (C ₆ H ₅ ) B, (C ₆ H ₅ ) Al,
And a group represented by (CH ₃ O) Al. this house,
Preferred are alkylene groups, silylene groups, and germylene groups.

M is a metal atom selected from Groups 4 to 6 of the periodic table, preferably a metal atom of Group 4 of the periodic table, specifically, titanium, zirconium, hafnium and the like. Particularly, zirconium and hafnium are preferable.

X and Y each represent hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, A nitrogen-containing hydrocarbon group containing 1 to 20, preferably 1 to 10, a phosphorus-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms such as a diphenylphosphine group, or a trimethylsilyl group, bis (trimethylsilyl) methyl Group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
Is a silicon-containing hydrocarbon group. X and Y may be the same or different. Of these, halogen atoms and carbon numbers 1 to 1
A hydrocarbon group having 8 and a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms are preferred.

In the olefin polymerization catalyst according to the present invention, among the compounds represented by the general formula [1] as component (A), those having the following substituents are preferred. A, A '= cyclopentadienyl, n-butyl-
Cyclopentadienyl, indenyl, 2-methyl-indenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-methylbenzoindenyl, 2,4-dimethylazulenyl, 2-methyl-4-phenylazulenyl, 2-
Methyl-4-naphthylazulenyl, 2-ethyl-4-naphthylazulenyl, 2-ethyl-4-phenylazulenyl, 2-methyl-4- (4-chlorophenyl) azulenyl. Q = ethylene, dimethylsilylene, isopropylidene. M = Group 4 transition metal. X, Y = chlorine, methyl, phenyl, benzyl, diethylamino.

Particularly preferred are A and A '= 2,4-dimethylazulenyl, 2-methyl-4-phenylazulenyl, 2-methyl-4-naphthylazulenyl, 2-ethyl-4-naphthylazulenyl , 2-ethyl-4-phenylazulenyl, 2-isopropyl-4-naphthylazulenyl, and 2-methyl-4- (4-chlorophenyl) azulenyl.

The following are specific examples of the transition metal compound. Examples of Q = alkylene groups include (1) methylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium dichloride, (2) ethylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl) ) Zirconium dichloride, (3) ethylene bis (2
-Methyl, 4-phenyl, 4-hydroazulenyl) diloconium hydride monochloride, (4) ethylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl)
Methyl zirconium monochloride, (5) ethylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl)
Zirconium monomethoxide monochloride, (6) ethylene bis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium diethoxide, (7) ethylene bis (2-methyl, 4-phenyl, 4-hydroazure) Nil)
Zirconium dimethyl, (8) ethylene bis (2-methylindenyl) zirconium dichloride, (9) ethylene bis (2-methyl, 4,5,6,7-tetrahydroindenyl) zirconium dichloride, (10) ethylene bis (2
-Ethylindenyl) zirconium dichloride,

(11) Ethylene bis (2,4-dimethylindenyl) zirconium dichloride, (12) ethylene (2,4-dimethylindenyl)
4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (13) ethylene (2-methyl-4-tert-butylcyclopentadienyl) (3′-tert-butyl −
5'-methylcyclopentadienyl) zirconium dichloride, (14) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, ) Ethylene-1,2-bis (4-indenyl) zirconium dichloride, (16) ethylene-1,2-bis [4- (2,7
-Dimethylindenyl)] zirconium dichloride, (1
7) ethylenebis (4-phenylindenyl) zirconium dichloride, (18) ethylenebis [1,1 '-(4-hydroazulenyl)] zirconium dichloride (19) ethylenebis [1,1'-(2-ethyl, -Phenyl, 4-hydroazulenyl)] zirconium dichloride (20) ethylenebis [1,1 '-(2-methyl, 4- (4
-Chlorophenyl), 4-hydroazulenyl)] zirconium dichloride

(21) Ethylene bis (9-bicyclo [8.
3.0] Trideca-2-methylpentaenyl) zirconium dichloride (22) ethylene (1-indenyl) [1- (4-hydroazulenyl)] zirconium dichloride (23) isopropylidenebis (2-methyl, 4-phenyl, 4 -Hydroazulenyl) zirconium dichloride,
(24) isopropylidene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (25) isopropylidene (2-methyl-4-tert-butylcyclopentadiene) Enyl) (3'-tert-butyl-5-methylcyclopentadienyl) zirconium dichloride.

Examples of the compound having Q = silylene group include (1) dimethylsilylenebis (2-methylindenyl) zirconium dichloride and (2) dimethylsilylenebis (2
-Methyl, 4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, (3) dimethylsilylene bis (2-methyl-4,5-benzoindenyl) zirconium dichloride, (4) dimethylsilylenebis (2-methyl, 4-phenylindenyl) zirconium dichloride, (5) dimethylsilylene Bis (2,4-dimethylazulenyl) zirconium dichloride, (6) dimethylsilylenebis (2-methyl-4, phenyl, 4,5,6,7-
8 pentahydroazulenyl) zirconium dichloride,
(7) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (8) dimethylsilylene bis (2-ethyl, 4-phenyl, 4-hydroazulenyl) ) Zirconium dichloride, (9) dimethylsilylenebis (2-methyl-4,4-dimethyl-4,5,6,7-
Tetrahydro-4-silinedenyl) zirconium dichloride, (10) dimethylsilylenebis [4- (2-phenylindenyl)] zirconium dichloride,

(11) dimethylsilylenebis [4- (2-t
tert-butylindenyl)] zirconium dichloride, (12) dimethylsilylenebis [4- (1-phenyl-
3-methylindenyl)] zirconium dichloride, (1
3) dimethylsilylenebis [4- (2-phenyl-3-methylindenyl)] zirconium dichloride, (14) phenylmethylsilylenebis (2-methyl4-phenyl,
-Hydroazulenyl) zirconium dichloride, (15) phenylmethylsilylenebis (2-methyl-4, phenyl, 4,5,6,7-8pentahydroazulenyl) zirconium dichloride, (16) phenylmethylsilylene (2,4- Dimethylcyclopentadienyl) (3 ′,
5′-dimethylcyclopentadienyl) zirconium dichloride, (17) diphenylsilylenebis (2-methyl4
-Phenyl, 4-hydroazulenyl) zirconium dichloride, (18) tetramethyldisilylenebis (2-methyl4-phenyl, 4-hydroazulenyl) zirconium dichloride, (19) dimethylsilylenebis [1,1 '-(2
-Isopropyl, 4-phenyl, 4-hydroazulenyl)] zirconium dichloride (20) dimethylsilylenebis [1,1 '-(2-ethyl, 4-naphthyl, 4-hydroazulenyl)] zirconium dichloride

(21) Dimethylsilylene bis [1,1'-
{2-methyl-4- (4-chlorophenyl), 4-hydroazulenyl}] zirconium dichloride (22) dimethylsilylenebis (9-bicyclo [8.3.
0] trideca-2-methylpentaenyl) zirconium dichloride (23) (methyl) (phenyl) silylenebis {1,1′-
(2-methyl-4-hydroazulenyl)} zirconium dichloride and the like.

Q = As a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum,
For example, (1) dimethylgermanium bis (2-methyl 4-phenyl, 4-hydroazulenyl) zirconium dichloride,
(2) methyl aluminum bis (2-methyl 4-phenyl, 4-hydroazulenyl) zirconium dichloride,
(3) phenylaluminum bis (2-methyl4-phenylazulenyl) zirconium dichloride, (4) phenylphosphinobis (2-methyl4-phenyl, 4-hydroazulenyl) zirconium dichloride, (5) ethylboranobis (2-methyl4 -Phenylazulenyl) zirconium dichloride, (6) phenylaminobis (2-methyl 4-phenyl, 4-hydroazulenyl) zirconium dichloride and the like.

Further, those obtained by replacing chlorine in the above-mentioned compounds with bromine, iodine, hydride, methyl, phenyl and the like can also be used. Further, in the present invention, a compound in which the central metal of the zirconium compound exemplified above is replaced with titanium, hafnium, niobium, molybdenum, tungsten or the like can be used as the component (A).

Of these, preferred are zirconium compounds, hafnium compounds and titanium compounds. More preferred are zirconium compounds and hafnium compounds. These components (A) may be used in combination of two or more. Further, the component (A) may be newly added at the end of the first stage of polymerization or before the start of the second stage of polymerization.

Component (B): Component (B) of the catalyst used in the present invention is an aluminum oxy compound, an ionic compound capable of reacting with component (A) to convert component (A) into a cation. And at least one substance selected from the group consisting of an ion-exchange layered compound excluding Lewis acids and silicates, and inorganic silicates. Certain Lewis acids can be understood as ionic compounds capable of reacting with the component (A) to convert the component (A) into a cation. Therefore, compounds belonging to both the above-mentioned Lewis acids and ionic compounds are understood to belong to either one.

Specific examples of the aluminum oxy compound include compounds represented by the following general formulas [2], [3] and [4].

[0059]

Embedded image

In the above general formulas, R ₁ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, more preferably a hydrocarbon residue having 1 to 6 carbon atoms. Further, a plurality of R ₁ may be the same or different. Also, p
Represents an integer of 0 to 40, preferably 2 to 30.

The compounds represented by the general formulas [2] and [3] are compounds also called alumoxanes, and are obtained by reacting one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one type of trialkylaluminum and water, (b) two types of trialkylaluminum and Examples thereof include methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from water. Of these, methylalumoxane and methylisobutylalumoxane are preferred.

The above alumoxanes can be used in combination of two or more. The alumoxane can be prepared under various known conditions. General formula [4]
The compound represented by the formula is a 10: 1 to 1 type of trialkyl aluminum or two or more types of trialkyl aluminum and an alkyl boronic acid represented by the following general formula [5].
It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula [5], R ₃ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or a halogenated hydrocarbon group.

[0063]

Embedded image R ₃ —B— (OH) ₂ ... [5]

As the compound represented by the general formula [4],
Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid (d) 2: 2 reaction of trimethylaluminum and methylboronic acid
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1 reactant

The ionic compound capable of reacting with the component (A) to convert the component (A) into a cation includes a compound represented by the general formula [6].

[0066]

## STR00004 ## [K] ^{e +} [Z] ^e - ··· [6]

In the general formula [6], K is a cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. In addition, metal cations and organic metal cations that are easily reduced by themselves are also included.

Specific examples of the above-mentioned cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, Dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, copper ion , Palladium ion, mercury ion, ferrocenium ion and the like.

In the above general formula [6], Z is an anion component, which is a component (generally a non-coordinating component) which becomes a counter anion to the converted cation species of component (A). Examples of Z include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, an organic arsenic compound anion, an organic antimony compound anion, and the like, and specific examples include the following compounds.

(A) Tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis {3,5-bis (trifluoromethyl) phenyl} boron, tetrakis {3,5-di (t- (B) tetraphenylaluminum, tetrakis (3,
4,5-trifluorophenyl) aluminum, tetrakis {3,5-bis (trifluoromethyl) phenyl}
Aluminum, tetrakis (3,5-di (t-butyl)
Phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, etc. (c) tetraphenylgallium, tetrakis (3,4,5)
-Trifluorophenyl) gallium, tetrakis ｛3,
5-bis (trifluoromethyl) phenyl @ gallium,
Tetrakis (3,5-di (t-butyl) phenyl) gallium, tetrakis (pentafluorophenyl) gallium, etc.

(D) Tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) Tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) Tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, etc. (g ) Decaborate, undecaborate, carbado decaborate, decachloro decaborate, etc.

Examples of Lewis acids, particularly Lewis acids capable of converting component (A) into cations, include various organic boron compounds, metal halide compounds, solid acids, and the like. Is mentioned.

(A) Triphenylboron, tris (3,
Organic boron compounds such as 5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, magnesium chloride bromide, chloride Metal halide compounds such as magnesium iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide, etc. (c) Solid acids such as alumina and silica-alumina Ion-exchangeable layered compounds other than silicates are compounds that have a crystal structure in which the planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the contained ions are exchangeable. Say.

The ion-exchangeable layered compound other than the silicate is
Hexagonal close packing type, antimony type, CdCl ₂ type,
An ionic crystalline compound having a layered crystal structure such as CdI type ₂ can be exemplified. Specific examples of the ion-exchangeable layered compound having such a crystal structure include α-
Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ )
_{2, α-Zr (KPO 4} ) 2 · 3H 2 O, α-Ti (H
PO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-
Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HP
O ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄
PO ₄ ) ₂ .H ₂ O and other crystalline acidic salts of polyvalent metals.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. These may be a synthetic product or a naturally occurring mineral. Specific examples of clay and clay minerals include allophane group such as allophane, dickite, nacrite, kaolinite, kaolin group such as anoxite, metahaloisite, halloysite group such as halloysite, chrysotile,
Razardite, anti-gorite, serpentinite, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc., smectite, vermiculite, etc. vermiculite minerals, illite, sericite, mica minerals, such as chlorite, attapulgite, Sepiolite, Palygorskite, bentonite, Kibushi clay, Gairome clay, Hisingelite, pyrophyllite,
Ryokudei stone group and the like. These may form a mixed layer.

Examples of artificial synthetic products include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and the like. Among these specific examples, preferably, kaolin group such as dickite, nacrite, kaolinite, anoxite, metahalloysite, halloysite group such as halloysite, chrysotile, lizardite, serpentine group such as antigolite, montmorillonite, sauconite, beidellite , Nontronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite, illite, sericite, mica minerals such as chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and particularly preferred. Are smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite , Synthetic taeniolite. These may be used as they are without any particular treatment, or may be used after having been subjected to treatments such as ball milling and sieving. Also, even if used alone,
Two or more kinds may be used as a mixture.

The above-mentioned ion-exchange layered compound and inorganic silicate can change the solid acid strength by salt treatment and / or acid treatment. In the salt treatment, the surface area and the interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, and the like. That is, by using the ion exchange property and replacing the exchangeable ion between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

In the compounds which have not been subjected to the above pretreatment, it is preferable that the contained exchangeable metal cations are ion-exchanged with the following cations dissociated from salts and / or acids.

The salts used for the above ion exchange are 1 to
At least one element selected from the group consisting of Group 14 atoms
Is a compound containing a cation containing a proton, preferably
Is at least selected from the group consisting of atoms of groups 1 to 14
A cation containing one type of atom, a halogen atom, an inorganic acid,
At least one element selected from the group consisting of
Consisting of an anion derived from an atom or an atomic group
And more preferably a compound consisting of atoms of groups 2 to 14.
Cation containing at least one atom selected from the group consisting of
And Cl, Br, I, F, PO₄, SO₄, NO₃, C
O₃, C₂O₄, ClO₄, OOCCH₃, CH₃CO
CHCOCH₃, OCI₂, O (NO₃) ₂, O (Cl
O₄)₂, O (SO₄), OH, O₂Cl₂, OC
l₃, OOCH and OOCCH₂CH₃From the group consisting of
A compound comprising at least one selected anion
is there. Also, these salts may be used in combination of two or more.
Good.

The acid used for the above-mentioned ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and two or more of them may be used simultaneously. As a method of combining the salt treatment and the acid treatment, a method of performing an acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of simultaneously performing the salt treatment and the acid treatment,
There is a method of performing salt treatment and acid treatment at the same time after performing salt treatment. In addition, the acid treatment has an effect of removing ions on the surface and ion exchange, and has a crystal structure of Al, Fe, M
It has the effect of eluting some cations such as g and Li.

The treatment conditions with salts and acids are not particularly limited. However, usually the salt and acid concentrations are at 0.
It is preferable that the treatment is carried out under conditions of 1 to 30% by weight, a treatment temperature of room temperature to the boiling point of the solvent used, a treatment time of 5 minutes to 24 hours, and elution of at least a part of the compound to be treated. In addition, salts and acids are generally used in an aqueous solution.

In the case of performing the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. The component (B) thus obtained preferably has a pore volume of a radius of 20 ° or more measured by a mercury intrusion method of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g. Clays and clay minerals usually contain adsorbed water and interlayer water. here,
The adsorbed water is water adsorbed on the surface of the ion-exchange layered compound or the inorganic silicate or the crystal fracture surface, and the interlayer water is water existing between the crystal layers.

In the present invention, the clay or clay mineral is preferably used after removing the above-mentioned adsorbed water and interlayer water. The dehydration method is not particularly limited, and a method such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent is used. The heating temperature is in a temperature range in which adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher. However, high temperature conditions that cause structural destruction are not preferable. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, the weight loss of the component (B) after dehydration and drying was 2 ° C. at a temperature of 200 ° C. and a pressure of 1 mmHg.
It is preferable that the value when suctioned for a time is 3% by weight or less. In the present invention, when the component (B) whose weight loss is adjusted to 3% by weight or less is used, even when it comes into contact with the essential component (A) and the optional component (C) described below,
It is preferable to handle in such a state that a similar weight loss is exhibited.

Component (C): Next, the organoaluminum compound which is an optional component (C) of the catalyst used in the present invention will be described. In the present invention, an organoaluminum compound represented by the general formula [7] is suitably used.

[0085]

Embedded image AlR _a P _3-a [7]

In the general formula [7], R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, a halogen, an alkoxy group or a siloxy group, and a represents a number greater than 0 and 3 or less. Specific examples of the organoaluminum compound represented by the general formula [7] include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum; halogens such as diethylaluminum monochloride and diethylaluminum monomethoxide. Or an alkoxy-containing alkyl aluminum. Of these, trialkylaluminum is preferred. Further, as the component (C), aluminoxanes such as methylaluminoxane can be used. (When component (B) is alumoxane, alumoxane is excluded as an example of component (C).)

Preparation of Catalyst: The catalyst for olefin polymerization is prepared by bringing the essential components (A) and (B) into contact with the optional component (C). Although the contact method is not particularly limited, the following methods can be exemplified. In addition,
This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.

(1) The component (A) is brought into contact with the component (B). (2) The component (C) is added after the component (A) is brought into contact with the component (B). (3) The component (B) is added after the component (A) is brought into contact with the component (C). (4) The component (A) is added after the component (B) is brought into contact with the component (C). (5) The components (A), (B) and (C) are brought into contact simultaneously.

At the time of or after the contact of each of the above components, a solid such as a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or may be brought into contact.

The above components may be contacted in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact is carried out at a temperature between -20 ° C and the boiling point of the solvent, particularly preferably at a temperature between room temperature and the boiling point of the solvent.

The amounts of components (A) and (B) used are arbitrary. For example, in the case of solvent polymerization, the amount of component (A) used is
As the transition metal atom, usually ¹⁰ -7 ^~10 2 mmol /
L, preferably in the range of 10 ^{−4 to 1} mmol / L. In the case of an aluminum oxy compound, the molar ratio of Al / transition metal is usually 10 to 10 ⁵ , preferably 100 to 2
× 10 ^4, more preferably is in the range of 100 to 10 ^4. When an ionic compound or Lewis acid is used as the component (B), the molar ratio thereof to the transition metal is generally in the range of 0.1 to 1000, preferably 0.5 to 100, and more preferably 1 to 50. You.

When an ion-exchange layered compound other than silicate or an inorganic silicate is used as the component (B), the amount of the component (A) is usually 10 ^-4 to 1 per gram of the component (B).
0 mmol, preferably 10 ^{−3 to 5} mmol,
Component (C) is usually 0.01 to 10 ⁴ mmol, preferably from 0.1 to 100 mmol. In addition, component (A)
The atomic ratio of the transition metal in the metal to the aluminum in the component (C) is usually 1: 0.01 to 10 ⁶ , preferably 1: 0.1.
10 is ^5. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. If necessary, a new component (C)
May be used in combination. That is, component (A)
And / or when the catalyst is prepared using (B) and the component (C), the component (C) is further prepared separately from the catalyst preparation.
May be added to the reaction system. At this time, the amount of component (C) used is 1 atomic ratio of aluminum in the component (C) to the transition metal in the component (A): is selected to be 0 to 10 ^4.

Further, a fine particle carrier may be co-present as an optional component. The fine particle carrier is made of an inorganic or organic compound, and is usually 5 μm to 5 mm, preferably 10 μm.
It is a particulate carrier having a particle size of m to 2 mm.

As the above-mentioned inorganic carrier, for example, SiO
₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B
Oxides such as ₂ O ₃ and ZnO, SiO ₂ —MgO, SiO
_{2 -Al 2 O 3, SiO 2} -TiO 2, SiO 2 -Cr
Composite oxides such as ₂ O ₃ and SiO ₂ —Al ₂ O ₃ —MgO are exemplified.

Examples of the organic carrier include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, styrene, divinylbenzene and the like. And a porous polymer fine particle carrier comprising a (co) polymer of an aromatic unsaturated hydrocarbon. These specific surface areas are usually 20 to
1000 m ² / g, preferably 50~700m ² / g, pore volume is usually 0.1 cm ² / g or more, preferably 0.3 cm ² / g, more preferably 0.8 cm ² /
g or more.

The olefin polymerization catalyst used in the present invention is:
Further, as an optional component other than the fine particle carrier, for example, H
₂ O, active hydrogen-containing compounds such as methanol, ethanol, and butanol; electron-donating compounds such as ethers, esters, and amines; and alkoxy such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane. Compounds can be included.

In the catalyst for olefin polymerization, the aluminum oxy compound of the component (B), the ionic compound capable of reacting with the component (A) to convert the component (A) into a cation, Lewis acid and silicate are excluded. One or more substances selected from the group consisting of ion-exchange layered compounds and inorganic silicates can be used alone or in combination of these three components as appropriate. One or more of the lower alkylaluminum, halogen-containing alkylaluminum, alkylaluminum hydride, alkoxy-containing alkylaluminum, and aryloxy-containing alkylaluminum of component (C) are optional components, but may be aluminum oxy compounds, It is preferable to include it in the olefin polymerization catalyst in combination with the hydrophilic compound or Lewis acid.

The components (A) and (B) and the component (C)
Can be preliminarily polymerized in the presence of a monomer to be polymerized to partially polymerize the α-olefin. That is, before polymerization, ethylene,
Preliminary polymerization of olefins such as propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc., was carried out if necessary. The prepolymerized product can also be used as a catalyst. This prepolymerization is
It is preferable to carry out the reaction in an inert solvent under mild conditions, and it is preferable to carry out the reaction in such a manner that usually 0.01 to 1000 g, preferably 0.1 to 100 g of polymer is produced per 1 g of the solid catalyst.

[Polymerization] The propylene polymer of the present invention
Using the metallocene olefin polymerization catalyst described above,
It is carried out by contacting propylene alone or a mixture of propylene and a comonomer. In the case of copolymerization,
The amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio, and to change the mixing ratio of the supplied monomers over time. Is also possible. Further, any of the monomers can be dividedly added in consideration of the copolymerization reaction ratio.

As the polymerization mode, any method can be adopted as long as the catalyst component and each monomer are efficiently contacted. Specifically, a slurry method using an inert solvent, a bulk method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a method in which each monomer is substantially gaseous without substantially using a liquid solvent For example, can be employed.

The present invention is also applicable to continuous polymerization and batch polymerization. In the case of slurry polymerization, hexane, heptane, pentane, cyclohexane, benzene,
A single or mixture of a saturated aliphatic or aromatic hydrocarbon such as toluene can be used.

The polymerization conditions are that the polymerization temperature is from -78 ° C.
The temperature is 160 ° C., preferably 0 ° C. to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator in an auxiliary manner. The polymerization pressure is 0 to 90 kg / cm ² · G, preferably 0 to 60 kg / cm ² · G, particularly preferably 1 to 90 kg / cm ² · G.
50 kg / cm ² · G is appropriate.

(3) Composition I The composition I in the propylene resin composition of the present invention comprises:
An inorganic filler is blended with the propylene-based polymer described above.

Specific examples of inorganic fillers include natural silicates or silicates such as fine powder talc, kaolinite, calcined clay, virophyllite, sericite, wollastonite, precipitated calcium carbonate, heavy calcium carbonate, Carbonates such as magnesium, hydroxides such as aluminum hydroxide and magnesium hydroxide, oxides such as zinc oxide, zinc white and magnesium oxide, synthetic silica such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and silicic anhydride, or Powder filler such as silicate, flake filler such as mica, glass fiber, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processe
fibrous fillers such as d Mineral Fiber), zonotolite, potassium titanate, and elestadite; and balun-like fillers such as glass balun and fly ash balun.

In the present invention, of these, talc is preferably used, and particularly, talc fine powder having an average particle diameter of 0.1 to 40 μm is preferably used.

Incidentally, the average particle size of talc can be measured by a liquid phase sedimentation method. The inorganic filler, particularly talc, used in the present invention may be untreated or surface-treated in advance. Examples of the surface treatment include, specifically, chemical or physical treatment using a treating agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, or polyethylene glycol. Is mentioned. By using talc subjected to such a surface treatment, it is possible to obtain a resin composition having excellent weld strength, paintability, and moldability.

The above-mentioned inorganic fillers may be used alone or in combination of two or more. In the present invention, an organic filler such as high styrenes and lignin can be used together with such an inorganic filler.

The composition I of the present invention contains the above-mentioned propylene polymer in an amount of 20 to 99% by weight, preferably 50 to 95% by weight, and an inorganic filler in an amount of 1 to 80% by weight, preferably 5 to 95% by weight.
It contains 50% by weight. Such a composition I of the present invention is excellent in rigidity, impact resistance and heat resistance.

(4) Composition II The composition II in the propylene resin composition of the present invention comprises:
An inorganic filler and an elastomer are blended with the propylene-based polymer described above. Specific examples of the inorganic filler that can be used are the same as those used for the composition I.
Examples of the elastomer used include an ethylene / α-olefin random copolymer rubber and a styrene-containing thermoplastic elastomer.

[Ethylene / α-olefin random copolymer rubber] The content of α-olefin units in the ethylene / α-olefin random copolymer rubber is 15 to 70% by weight, preferably 20 to 55% by weight. If the content of the α-olefin unit is less than the above range, the impact strength is inferior.On the other hand, if the content is too large, not only the rigidity is reduced, but also it is difficult to maintain the shape of the elastomer in a pellet form, and Each of these is unsuitable because the production handling during production is significantly reduced.

As the α-olefin, those having 3 to 20 carbon atoms are preferable, and specific examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-octene. -Nonene, 1-decene, 1-
Undecene, 1-dodecene and the like can be mentioned. Among them, propylene, 1-butene, 1-pentene, 1-
Hexene, 1-heptene and 1-octene are preferred.

The ethylene / α-olefin random copolymer rubber preferably has an MFR (230 ° C., 2.16 kg load) of 0.01 to 100 g / 10 min, more preferably 0.1 to 100 g / 10 min. Are preferred. Furthermore, the density is preferably those 0.85~0.90g / cm ^3, especially 0.86~0.89g / cm ³
Are preferred.

When the MFR is less than 0.01 g / 10 minutes, sufficient dispersion cannot be obtained at the time of kneading when forming the resin composition, and the impact strength is reduced. on the other hand,
When the MFR exceeds 100 g / 10 minutes, the toughness of the copolymer rubber itself is insufficient, and the impact strength is also lowered. If the density exceeds 0.90 g / cm ³ , the impact strength will be inferior, and if it is less than 0.85 g / cm ^3, it will be difficult to pelletize itself. Further, these are preferably produced using a vanadium compound-based catalyst described later or a metallocene-based catalyst as described in WO-91 / 04257.

Here, the α-olefin content is a value measured according to a conventional method such as an infrared spectrum analysis method or a ¹³ C-NMR method. The MFR is a value measured according to JIS-K7210, and the density is a value measured according to JIS-K7112.

The ethylene / α-olefin random copolymer rubber may be polymerized by, for example, a gas-phase fluidized-bed method, a solution method, a slurry method, or a high-pressure polymerization method.
Further, a small amount of a diene component such as dicyclopentadiene and ethylidene norbornene may be copolymerized.

Examples of the polymerization catalyst include titanium compounds such as titanium halides, vanadium compounds, organoaluminum compounds such as alkylaluminum-magnesium complexes and alkylalkoxyaluminum-magnesium complexes.
So-called Ziegler-type catalysts in combination with magnesium complexes or organometallic compounds such as alkylaluminum or alkylaluminum chloride, or WO-
Metallocene catalysts such as those disclosed in JP-A-91 / 04257 and the like. The catalyst referred to as a metallocene catalyst may not contain alumoxane, but is preferably a catalyst obtained by combining a metallocene compound and alumoxane, that is, a so-called Kaminsky catalyst.

[Styrene-Containing Thermoplastic Elastomer] The styrene-containing thermoplastic elastomer used in the present invention has a polystyrene content of 5 to 60% by weight, preferably 10 to 30% by weight.
% By weight. If the polystyrene content is outside the above range, the impact resistance becomes insufficient.

The MFR (230 ° C., 2.16 k
g load) in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min. M
When the FR is out of the above range, the impact resistance is also insufficient.

A specific example of such a styrene-containing thermoplastic elastomer is styrene / ethylene / butylene / styrene block copolymer (SEBS).

The styrene / ethylene / butylene / styrene block copolymer is a thermoplastic elastomer composed of polystyrene block units and polyethylene / butylene rubber block units. In such SEBS, a polystyrene block unit, which is a hard segment, forms a physical crosslink (domain) and exists as a bridge point of a rubber block unit, and a rubber block unit existing between the polystyrene block units is a soft segment. And has rubber elasticity.

The SEBS used in the present invention desirably contains polystyrene units in an amount of 10 to 40 mol%. The content of units derived from styrene is
It is a value measured by a conventional method such as an infrared spectrum analysis method and a ¹³ C-NMR method.

This SEBS is specifically obtained by a known method described, for example, in Japanese Patent Publication No. 60-57463. As such SEBS,
More specifically, Kraton G1650, G
1652, G1657 (trade name, manufactured by Shell Chemical Co., Ltd.), Tuftec (trade name, manufactured by Asahi Kasei Corporation) and the like.

The SEBS used in the present invention is generally SBS which is a styrene / butadiene block copolymer.
(Styrene / butadiene / styrene block copolymer)
Known as hydrogenated products. In the present invention, SBS and other styrene / conjugated diene copolymers or completely or incomplete hydrides thereof may be used together with SEBS.

Specific examples of such a styrene / conjugated copolymer include SBR (styrene / butadiene random copolymer), SBS, PS-polyisobutylene block copolymer, and SIS (styrene / isobutylene / styrene). Block copolymer) and SIS hydrogenated product (SEPS)
And the like.

More specifically, Kraton (manufactured by Shell Chemical Co., Ltd.), Calibrex TR (manufactured by Shell Chemical Co., Ltd.), Sorbrene (manufactured by Philippe Petro Rifam), Eurobren SOLT (manufactured by Anich) ), Toughbren (manufactured by Asahi Kasei Corporation), Soluble-T (manufactured by Nippon Elastomer Co., Ltd.), JSRTR (manufactured by Nippon Synthetic Rubber Co., Ltd.),
Electrified STR (manufactured by Denki Kagaku Co., Ltd.), Quintac (manufactured by Zeon Corporation), Clayton G (manufactured by Shell Chemical Co., Ltd.), Tuftec (manufactured by Asahi Kasei Corporation) (all trade names) and the like.

In the present invention, the above-mentioned ethylene / α-olefin random copolymer rubber and styrene-containing thermoplastic elastomer may be used alone or in combination as appropriate, as the elastomer component.

The composition II of the present invention contains 10 to 98% by weight, preferably 49 to 94% by weight of a propylene polymer, 1 to 80% by weight, preferably 5 to 50% by weight of an inorganic filler, The elastomer is contained in an amount of 1 to 89% by weight, preferably 1 to 40% by weight. Such a composition II of the present invention is excellent in rigidity, low-temperature impact resistance and heat resistance.

Further, the composition II of the present invention may further contain, if necessary, a polyethylene resin as an optional component in addition to the above-mentioned essential components. Examples of the polyethylene resin include those polymerized by slurry, gas phase, solution, high-pressure ion, high-pressure radical polymerization, or the like using a Ziegler, chromium, metallocene catalyst, or the like.

The polyethylene resin may be an ethylene homopolymer or an ethylene / α-olefin copolymer. Of these, MFR (190 ° C., 2.16
kg load) 0.1-200 g / 10 min, density 0.9
It is preferably from 0 to 0.97 g / cm ³ . ethylene·
In the case of the α-olefin copolymer, specific examples of the α-olefin contained include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
Examples thereof include 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Further, the content of α-olefin units in the ethylene / α-olefin copolymer is from 0 to
15 mol%.

Specific examples of such polyethylene include high-density polyethylene, linear low-density polyethylene, low-density polyethylene and the like.

The content of the polyethylene resin in the composition II of the present invention is preferably 1 to 88% by weight, more preferably 1 to 88% by weight.
~ 40% by weight is preferred. In the present invention, by blending such a polyethylene resin, rigidity, impact resistance and heat resistance, as well as the adhesive strength to a coating film at the time of coating are improved, which is preferable.

(5) Composition III Composition III in the propylene-based resin composition of the present invention
Is obtained by blending the above-mentioned propylene-based polymer with an inorganic filler and a polypropylene resin produced using a Ziegler-based catalyst (hereinafter abbreviated as Ziegler-based polypropylene). Specific examples of inorganic fillers that can be used include:
The same as that used for the composition I is used.

The Ziegler-based polypropylene will be described. As a specific method for preparing a Ziegler-based catalyst, titanium tetrachloride is reduced with an organoaluminum compound,
Further, a method of combining an organic aluminum compound with a titanium trichloride composition obtained by treating with various electron donors and electron acceptors, and a supported catalyst for contacting titanium tetrachloride and various electron donors with magnesium halide Preparation methods and the like can be exemplified.

In the presence of the Ziegler catalyst thus obtained, propylene alone, block copolymerization of propylene and ethylene, or block copolymerization of propylene or propylene with a production process such as slurry polymerization, gas phase polymerization or liquid phase bulk polymerization is applied. Ziegler polypropylene of the present invention can be obtained by random copolymerizing ethylene.

Among these, when producing a propylene-ethylene block copolymer, first, propylene is homopolymerized, and then a block copolymer is formed by random copolymerization of propylene and ethylene. Is preferred.

The propylene-ethylene block copolymer is a terpolymer containing another unsaturated compound, for example, an α-olefin such as 1-butene: a vinyl ester such as vinyl acetate, as long as the effects of the present invention are not impaired. The above copolymers or mixtures thereof may be used.

The MFR of this Ziegler polypropylene
(230 ° C., 2.16 kg load) is 0.01 to 200
g / 10 minutes is preferred, especially 0.1 to 200
g / 10 minutes is preferred.

The composition III of the present invention contains 10 to 94% by weight, preferably 40 to 85% by weight of a propylene polymer, 1 to 80% by weight, preferably 5 to 50% by weight of an inorganic filler, 5-8 of the above Ziegler polypropylene
It contains 9% by weight, preferably 10 to 50% by weight. Such a composition III of the present invention is excellent in rigidity, low-temperature impact resistance and heat resistance, has good fluidity, and has improved moldability.

(6) Composition IV Composition IV in the propylene-based resin composition of the present invention comprises:
A polypropylene resin produced using an inorganic filler, an elastomer, and a Ziegler catalyst is blended with the propylene polymer described above. Specific examples of the inorganic filler that can be used are the same as those used in the composition I described above. Specific examples of the elastomer that can be used are the same as those used in the composition II described above. Further, specific examples of the polypropylene resin produced using the Ziegler-based catalyst are the same as the Ziegler-based polypropylene used in the composition III described above.

The composition IV of the present invention contains 10 to 93% by weight, preferably 39 to 84% by weight of a propylene polymer, and 1 to 80% by weight, preferably 5 to 50% by weight of an inorganic filler. The elastomer contains 1 to 84% by weight, preferably 1 to 40% by weight, and the Ziegler-based polypropylene contains 5 to 88% by weight, preferably 10 to 50% by weight.
Such a composition IV of the present invention is excellent in rigidity, low-temperature impact resistance and heat resistance, has good fluidity, and has improved moldability.

Further, the composition IV of the present invention may further contain a polyethylene resin as an optional component, if necessary, in addition to the above-mentioned essential components. Specific examples of the polyethylene resin are the same as the polyethylene resin used as an optional component in the composition II described above.

The content of the polyethylene resin in the composition IV of the present invention is preferably from 1 to 83% by weight, particularly preferably 1 to 83% by weight.
~ 40% by weight is preferred. In the present invention, by blending such a polyethylene resin, rigidity, impact resistance and heat resistance, as well as the adhesive strength to a coating film at the time of coating are improved, which is preferable.

(7) Other Components The propylene-based resin composition of the present invention (the above-described compositions I to
In IV), in addition to the above-mentioned essential components, any of the following additives and compounding materials can be compounded in a range that does not significantly impair the effects of the present invention or for further improving the performance.

Specifically, pigments for coloring, antioxidants such as phenol, sulfur and phosphorus, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, and various cores such as organic aluminum and talc. Agents, dispersants, neutralizing agents, foaming agents, copper damage inhibitors, lubricants, flame retardants, various resins other than the above-mentioned propylene-based polymers, polybutadiene, compounding materials such as various rubber components such as polyisoprene. .

Among them, for example, the compounding of various nucleating agents and various rubbers is effective for improving the balance of physical properties such as rigidity and impact strength and the improvement of dimensional stability. For example, the compounding of a hindered amine-based stabilizer is effective in improving weather resistance and durability. It is effective for improving the performance.

(8) Production of Resin Composition The production method of the propylene resin composition of the present invention is not particularly limited, and the above components are blended into a propylene polymer by a conventionally known method, followed by mixing and melt-kneading. It can be manufactured by the following.

In the present invention, the above-mentioned essential components, that is, the propylene-based polymer, the inorganic filler, and optionally the elastomer and / or the Ziegler-based polypropylene, and the optional components used as required, are added in the above-mentioned mixing ratio. The propylene-based resin composition of the present invention is compounded and kneaded and granulated using a usual kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, or a kneader. Is obtained.

In this case, it is preferable to select a kneading / granulating method capable of improving the dispersion of each component, and it is usually carried out using a twin screw extruder. During the kneading / granulation, the compound of each of the above components may be kneaded at the same time, or the components are kneaded by dividing them in order to improve the performance, that is, for example, first, a part of the propylene polymer or It is also possible to employ a method of kneading the whole and the inorganic filler, and then kneading and granulating the remaining components.

(9) Use of Propylene Resin Composition The propylene resin composition of the present invention thus obtained can be used for molding by various known methods. For example, various types of molding are performed by injection molding (including gas injection molding), injection compression molding (press injection), extrusion molding, hollow molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, and the like. Goods can be obtained. this house,
Injection molding and injection compression molding are more preferred.

The propylene-based resin composition of the present invention has a high balance of physical properties in rigidity, impact resistance and heat resistance. As a molding material for various industrial parts such as various molded articles, for example, automobile parts such as bumpers, instrument panels and garnishes, and home electric appliance parts such as TV cases, etc., they have practically sufficient performance.

[0151]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

In the examples, various physical properties were measured in the following manner. (1) MFR (unit: g / 10 min) is JIS-K721
0 (230 ° C., 2.16 kg load) (190 ° C., 2.16 kg load for polyethylene resin). (2) Stereoregularity (mesopentad fraction: mmmm,
%) Was evaluated by a known method based on the ¹³ C-NMR spectrum (Randall JC Journal of Polymer Science, 12,703 1974).

(3) The quantification of the 1,3-asymmetric bond was performed according to A. Zamb
The peaks were assigned according to elli Macromolecules (21 (3) 617 1988), and the mole% was calculated from the sum of the carbons of —CH ₂ — and —CH—. (4) The flexural modulus (unit: MPa) is JIS-K72
The measurement was performed at 23 ° C. according to the method described in No. 03. (5) Izod impact strength (unit: kJ /
m ² ) was measured at 23 ° C. in accordance with JIS-K7110. (6) The deflection temperature under load (unit: ° C) is JIS-K72
4.6 kgf / cm ² and 18.5 kg
The measurement was performed under the condition of f / cm ² .

(7) Average dissolution temperature (T ₅₀ ) and dissolution degree (σ) Average dissolution temperature (T ₅₀ : unit ° C.) and dissolution degree (σ)
Was determined from an elution curve obtained by temperature rising elution fractionation (TREF). Here, the peak measurement of the elution curve by TREF is performed by completely dissolving the polymer once at a high temperature and then cooling to form a thin polymer layer on the surface of the inert carrier, and then increasing the temperature continuously or stepwise. Then, the eluted components were collected, the concentration was continuously detected, and the elution amount and the elution temperature were measured.

The elution curve was measured under the following measurement conditions.・ Solvent: o-dichlorobenzene ・ Measured concentration: 4 mg / ml ・ Injection volume: 0.5 ml ・ Column: 4.6 mmφ × 150 mm ・ Cooling rate: 100 ° C. × 120 minutes

[0156]

[Production Example 1: Production of PP-1] (1) Preparation of catalyst component (i) Component (A) (dimethylsilylenebis {1,1'-
Synthesis of (2-methyl-4-phenyl-4-hydroazulenyl) {hafnium dichloride): The following reactions were all carried out under an inert gas atmosphere, and the reaction solvent used was previously dried.

(A) Synthesis of racemic / meso mixture 3.22 g of 2-methylazulene was dissolved in 30 ml of hexane, and 21 ml (1.0 equivalent) of a solution of phenyllithium in cyclohexane / diethyl ether was added little by little at 0 ° C. After stirring the solution at room temperature for 1.5 hours,
After cooling to ℃, 30 ml of tetrahydrofuran was added. 45 μmol of 1-methylimidazole and 1.37 ml of dimethyldichlorosilane were added to this solution, and the mixture was returned to room temperature and cooled.
Stirred for hours. Thereafter, an aqueous solution of ammonium chloride was added thereto, and after liquid separation, the organic phase was dried over magnesium sulfate,
The solvent was distilled off under reduced pressure to obtain 5.84 g of a crude product of bis {1,1 ′-(2-methyl-4-phenyl-1,4-dihydroazulenyl)} dimethylsilane.

The thus obtained bis {1,1 ′-(2
-Methyl-4-phenyl-1,4-dihydroazulenyl) ditylsilane was purified with diethyl ether 30.
Then, 14.2 ml (1.6 mol / L) of a hexane solution of n-butyllithium was added dropwise at −78 ° C., and the mixture was gradually returned to room temperature and stirred for 12 hours. After distilling off the solvent under reduced pressure, toluene / diethyl ether (40: 1) 8
0 ml was added, and 3.3 g of hafnium tetrachloride was added at −60 ° C., and the mixture was gradually returned to room temperature and stirred for 4 hours. The obtained solution is concentrated under reduced pressure, and the obtained solid is washed with toluene, extracted with dichloromethane, and dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydroazulenyl)} hafnium. 1.74 g of a racemic-meso mixture of dichloride was obtained.

(B) Purification of racemic form 1.74 g of a racemic-meso mixture obtained by repeating the above reaction was dissolved in 30 ml of dichloromethane,
It was introduced into a Pyrex glass container having a W high pressure mercury lamp. The solution was irradiated with light under normal pressure for 40 minutes while stirring to increase the ratio of the racemate, and then dichloromethane was distilled off under reduced pressure. 10 ml of toluene was added to the obtained yellow solid.
Was added and stirred, followed by filtration. The solids separated by filtration were washed with 8 ml of toluene and 4 ml of hexane, and dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-) was used.
917 mg of a racemic form of (hydroazulenyl) hafnium dichloride was obtained.

(Ii) Production of component (B): 135 ml of demineralized water and 16 g of magnesium sulfate were collected in a 500 ml round bottom flask and dissolved with stirring. 22.2 g of montmorillonite (Kunipia F, manufactured by Kunimine Industry Co., Ltd.) was added to this solution.
Was added, and the mixture was heated and treated at 80 ° C. for 1 hour. Next, 300 ml of demineralized water was added, followed by filtration to collect a solid component.

To this, 46 ml of demineralized water and sulfuric acid.
After adding 4 g and 29.2 g of magnesium sulfate, the mixture was heated and treated under reflux for 2 hours. Demineralized water 200m after treatment
1 and filtered. Further, 400 ml of demineralized water was added and the mixture was filtered, and this operation was repeated twice. Next, the resultant was dried at 100 ° C. to obtain a chemically treated montmorillonite.

1.05 g of the above-mentioned chemically treated montmorillonite was collected in a 100 ml round bottom flask,
Dry for 2 hours at ° C. To this, a toluene solution of triethylaluminum (0.5 mmol / m
l) was added and reacted at room temperature for 1 hour.
After washing twice with 30 ml of toluene, the component (B) was obtained as a toluene slurry.

(Iii) Preparation of Catalyst A toluene solution of triisobutylaluminum (0.5 mmol / ml): 0.6
ml, and dimethylsilylenebis ｛1, synthesized in (i).
1 ′-(2-methyl-4-phenyl-4-hydroazulenyl)｝ hafnium dichloridracemic toluene solution (1.5 μmol / ml): 19.1 ml, and
Contact was made at room temperature for 10 minutes.

(2) Propylene Prepolymerization Into a 2 L induction-stirring autoclave, 40 ml of toluene and the total amount of the contact product obtained in the preceding section (iii) as a prepolymerization catalyst were introduced under purified nitrogen. Propylene was introduced under stirring at a total polymerization pressure of 0.6 MPa at room temperature for 3 minutes. Next, unreacted propylene was purged and the pressure was replaced with purified nitrogen, and then the prepolymerized catalyst was taken out. This contained 2.98 g of polymer per 1 g of component (B).

(3) Polymerization of Propylene 2 L having a built-in squirt-type stirring blade replaced with purified nitrogen
Into an induction-stirring autoclave, a toluene solution of triisobutylaluminum (0.5 mmol / ml)
After adding 1 ml of hydrogen gas and charging 13.5 KPa of hydrogen gas, 700 g of liquefied propylene was charged. After that, the previous section (2)
37.5 as a solid catalyst component using the prepolymerized catalyst obtained in
After the temperature was raised, polymerization was carried out at 75 ° C. for 30 minutes. Then, propylene and hydrogen were purged to terminate the polymerization reaction. When the polymer yield was weighed, 318 g of polypropylene was obtained. The obtained polypropylene (PP-1)
Had an MFR of 30.

[0166]

[Production Example 2: Production of PP-2] [Synthesis of catalyst]
According to the method described in Example 1 of JP-A-234707, solid catalyst component- (1) was synthesized.

[Polymerization] After sufficiently replacing the inside of a stirred autoclave having an internal volume of 200 liters with propylene, 60 liters of dehydrated and deoxygenated n-heptane were introduced, and 10.5 g of triethylaluminum and the above method were used. 2.7 g of the synthesized solid catalyst component- (1) was introduced in a propylene atmosphere at 70 ° C.

Thereafter, the temperature of the autoclave was raised to 75 ° C., and propylene was fed at a feed rate of 9 kg / hour for 3 hours while maintaining the hydrogen concentration in the gas phase at 6.5% by volume. The polymerization was continued.

Thereafter, the residual gas was purged, the reaction was stopped with butanol, and the product was filtered and dried.
As a result, 30 kg of homopolypropylene (PP-2) having an MFR of 29.7 g / 10 min was obtained.

[0170]

[Production Example 3: Production of PP-3] [Synthesis of catalyst]
According to the method described in Example 1 of JP-A-234707, solid catalyst component- (1) was synthesized.

[Polymerization] After sufficiently replacing the inside of a 200-liter stirred autoclave with propylene, 60 liters of dehydrated and deoxygenated n-heptane were introduced, and 10.5 g of triethylaluminum, dicyclopentyldimethoxysilane were added. 4.2 g and 3.6 g of the solid catalyst component (1) synthesized by the above method were introduced in a propylene atmosphere at 70 ° C.

Thereafter, the temperature of the autoclave was raised to 75 ° C., and propylene was fed at a feed rate of 9 kg / hour for 3 hours while maintaining the hydrogen concentration in the gas phase at 18% by volume. Continued.

Thereafter, the residual gas was purged, the reaction was stopped with butanol, and the product was filtered and dried.
As a result, 28.5 kg of homopolypropylene (PP-3) having an MFR of 30.6 g / 10 min was obtained.

[0174]

Examples 1 and 2 and Comparative Examples 1 and 2 (1) Production of Propylene Resin Composition Propylene was prepared using propylene resins PP-1 to PP-3 including those obtained in Production Examples 1 to 3. A resin composition was produced. Table 1 shows the physical properties of PP-1 to PP-3. As the inorganic filler to be mixed with the propylene-based resins PP-1 to PP-3, talc (average particle size: 2.
7 μm). These propylene-based resins and compounding components were compounded at the compounding ratio (% by weight) shown in Table 2, and kneaded and granulated by a twin-screw extruder to obtain a pellet-shaped resin composition.

(2) Molding of test piece The obtained composition was molded at a mold temperature of 40 ° C and a cylinder temperature of 22 ° C.
The sample was introduced into an injection molding machine heated at 0 ° C., and a test piece was molded by injection molding. The flexural modulus, IZOD impact strength, and deflection temperature under load of the obtained injection molded piece were measured by the methods described above. Table 2 shows the results.

[0176]

[Table 1]

[0177]

[Table 2]

[0178]

The propylene-based resin composition of the present invention using a propylene-based polymer having a specific structure has an excellent balance of mechanical strength (particularly rigidity, low-temperature impact resistance and heat resistance), It is industrially very useful as a molding material for molding and extrusion molding.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Toshihiko Kanno 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside the Mitsubishi Chemical Research Laboratory (72) Inventor Takao Tabano 1 Tohocho, Yokkaichi-shi, Mie Mitsubishi Chemical Inside the Resin Technology Development Center of Yokkaichi Office

Claims (6)

[Claims] 1. A propylene polymer satisfying the following requirements (a) to (c) and (2) an inorganic filler, and the content of the propylene polymer is 20 to 99% by weight. %, The content of the inorganic filler is 1 to 80% by weight,
Propylene resin composition. (A): Structural unit derived from propylene is 100-
80 to 20 mol% of a constituent unit derived from a comonomer selected from the group consisting of 80 mol%, ethylene and an α-olefin having 4 to 20 carbon atoms. (B): Melt flow rate is 0.1 to 200 g / 10
Be a minute. (C): the average elution temperature is in the range of 75 to 120 ° C,
The elution dispersion degree is 9 or less. 2. An inorganic filler comprising (3) an elastomer in addition to (1) a propylene-based polymer and (2) an inorganic filler, wherein the content of the propylene-based polymer is 10 to 98% by weight. The propylene-based resin composition according to claim 1, wherein the content of the elastomer is 1 to 80% by weight and the content of the elastomer is 1 to 89% by weight. 3. In addition to (1) a propylene-based polymer and (2) an inorganic filler, it contains (3) a polypropylene resin produced using a Ziegler-based catalyst, and the content of the propylene-based polymer is The propylene-based resin composition according to claim 1, wherein the content of the inorganic filler is 1 to 80% by weight, and the content of the polypropylene resin is 5 to 89% by weight. 4. The propylene polymer containing (3) an elastomer and (4) a polypropylene resin produced using a Ziegler catalyst in addition to (1) a propylene polymer and (2) an inorganic filler. When the content of the polymer is 10 to 93
The propylene according to claim 1, wherein the content of the inorganic filler is 1 to 80% by weight, the content of the elastomer is 1 to 84% by weight, and the content of the polypropylene resin is 5 to 88% by weight. -Based resin composition. 5. The propylene-based polymer satisfies the following (a) to (e):
5. The propylene-based resin composition according to any one of 4. (A): Structural unit derived from propylene is 100-
94 mol%, and 0 to 6 mol% of structural units derived from a comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. (B): Melt flow rate is 0.1 to 200 g / 10
Be a minute. (C): the average elution temperature is in the range of 75 to 120 ° C,
The elution dispersion degree is 9 or less. (D): Isotactic pentad chain fraction of 9
5% or more. (E): The ratio of 1,3-asymmetric bonds is 0.06 to 3%. 6. A molded product selected from the group consisting of an injection molded product, a hollow molded product, and an extrusion molded product, wherein the molded product is a molded product.
5. A propylene-based resin molded product, comprising the propylene-based resin composition according to any one of 5.