JPH11349777A - Propylene-based polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent balance between weatherability and low bleeding properties by mixing a specific propylene block copolymer with a specific compound. SOLUTION: This composition is obtained by compounding (A) 100 pts.wt. of a propylene block copolymer which comprises (i) a polymer block composed of a propylene homopolymer or a random copolymer of (a) propylene and (b) <=10 mol.% of a copolymerizable monomer of ethylene and/or a 4-20C α-olefin and (ii) a polymer block composed of a random copolymer of the component (a) and 10-80 mol.% of the component (b), satisfying the equation nb <=n+1.5 (nb is the average chain length of block of the component (b); (n) is the total average chain length of the component (b)) and has 0.1-200 g/10 minutes melt flow rate with (B) 0.001-1 pt.wt. of one or more compounds selected from a hindered amine-based compound, a triazole-based compound and a benzoate- based compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel propylene-based polymer composition. More specifically, the present invention relates to a propylene-based polymer composition having an excellent balance between weather resistance and low bleedability.

[0002]

2. Description of the Related Art Propylene-based resin materials such as polypropylene are excellent in moldability and rigidity, and are also excellent in recyclability and heat resistance. Like resin, it is widely used for various uses such as automobiles, home appliances, industrial materials and the like. Such a resin material is usually processed by injection molding, extrusion molding, blow molding, or the like, and is used for these applications.

[0003] However, the conventional Ziegler-catalyzed polypropylene may be added with a weathering agent in order to impart weather resistance. In this case, however, the weathering agent bleeds into the product, which impairs the appearance. was there. On the other hand, when trying to obtain a material with less bleed, the type and amount of the weathering agent are limited. Therefore, a resin material satisfying both the weather resistance and the low bleeding property cannot be obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a propylene polymer composition having an excellent balance between weather resistance and low bleeding property.

[0005]

In view of such circumstances, the present inventors have made intensive studies to improve the bleed characteristics without impairing the weather resistance of polypropylene, and as a result, have found that polypropylene having a specific polymer structure has been identified. It has been found that a propylene-based polymer composition having excellent weather resistance and low bleeding property can be obtained by adding the above additive, and the present invention has been achieved.

That is, the present invention provides a propylene block copolymer having a melt flow rate of 0.1 to 200 g / 10 minutes, which is substantially composed of the following blocks (a) and (b). For the department,
(A) hindered amine compounds, (b) triazole compounds, (c) benzophenone compounds, and (d)
Provided is a propylene-based polymer composition comprising 0.001 to 1 part by weight of at least one compound selected from the group consisting of benzoate-based compounds.

Block (a): propylene homopolymer,
Alternatively, a polymer block comprising a random copolymer of propylene and a copolymer monomer selected from the group consisting of ethylene and a C _{4 to} C ₂₀ α-olefin, wherein the content of the copolymer monomer is 10 mol% or less.

Block (b): a random copolymer of propylene and at least one copolymer monomer selected from the group consisting of ethylene and a C _{4 to} C ₂₀ α-olefin, containing the copolymer monomer 10-8
A polymer block which is 0 mol% and has a relationship between the block average chain length and the total average chain length of the copolymerized monomer represented by the following formula (I).

[0009]

## EQU2 ## n _b ≤n + 1.5 (I)

[0010] (wherein, n _b represents a block average chain length of the copolymer monomers, n represents represents the total average chain length of the copolymer monomers.)

In the present invention, the block (a) has a weight average molecular weight (Mw) of 10,000 to 1,000,000, and a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
Is 6 or less, the fraction of isotactic pentad chain is 95% or more, and the ratio of
3%, wherein the propylene-based polymer composition is provided.

Further, the present invention provides the propylene polymer composition, wherein the propylene block copolymer has a melt flow rate of 4 to 200 g / 10 minutes.

In the present invention, with respect to a certain copolymerizable monomer, a propylene block copolymer containing a random copolymer as a polymer block, whose block average chain length and total average chain length satisfy a specific relationship, has a specific weather resistance. By blending the agent, a molding material having an excellent balance between weather resistance and low bleeding property can be obtained.

[0014]

Embodiments of the present invention will be described below. The propylene-based polymer composition of the present invention comprises a propylene block copolymer and components to be added to the copolymer.

(1) Propylene block copolymer The propylene block copolymer used in the present invention is substantially composed of the following blocks (a) and (b).

Here, the "propylene block copolymer substantially composed of the block (a) and the block (b)" of the present invention includes a block () on the unit polymer chain of the block copolymer. In addition to the case where a) and block (b) are each present in at least one block each (ie, a true “block copolymer”), both may be caused by continuing to carry out the polymerization step to produce each block. It also includes the case of a physical mixture of blocks.
Further, the propylene block copolymer of the present invention does not exclude a block polymer or a physical mixture with a third block or a third component other than both blocks.

A preferred example of the propylene block copolymer of the present invention is one in which both blocks are present on the unit polymer chain of the block copolymer, respectively. An example is obtained by generating the block (a) in the first stage and continuously generating the block (b) in the second stage.

(I) Block (a) Block (a) is a propylene homopolymer or propylene
Ren and ethylene and C ₄~ C₂₀From α-olefins
Random copolymerization with a comonomer selected from the group consisting of
It is a polymer block consisting of a body. For random copolymer
C₄~ C ₂₀As the α-olefin, 1-butyl
Ten, 1-pentene, 1-hexene, 1-heptene, 1
-Octene, 3-methyl-butene-1,4-methylpen
Ten-1 and the like. Preferred copolymerized mono
Examples of the mer include ethylene.

The ratio of the above-mentioned copolymerized monomer unit in all the structural units of the block (a) (content of the copolymerized monomer)
Is 10 mol% or less, preferably 0 to 5 mol%.
When the copolymer composition of the block (a) is out of the above range, the rigidity becomes insufficient.

The melt flow rate of the block (a) (hereinafter abbreviated as “MFR”) is preferably 5 to 40.
0 g / 10 minutes. The MFR value in the present invention is a value measured according to JIS-K7210 (230 ° C., 2.16 kg load).

The block (a) preferably has a weight average molecular weight (Mw) of 10,000 to 1,000,000, more preferably 5 to 1,000,000.
It is 10,000 to 800,000, and more preferably 100,000 to 400,000.
If the weight average molecular weight is too low, the mechanical strength decreases, while if it is too high, the melt viscosity increases during thermoplastic molding, and molding may not be free. The weight average molecular weight is measured by GPC.

More preferably, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), which is an index of the molecular weight distribution, is 6 or less. If the molecular weight distribution is too wide, the characteristic dispersion form of the present invention may not be realized.

The block (a) is a ¹³ C-NMR
An isotactic pentad chain (m
mmm) fraction (mesopentad fraction) is 95% or more,
It is preferably at least 97% and the proportion of 1,3-asymmetric bonds is preferably 0.02 to 3%. 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 as boiling heptane solubles is less than 5%, more preferably 3%.
%, 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—.

(Ii) Block (b) Block (b) is composed of propylene, ethylene and C ₄ to
It is a polymer block comprising a random copolymer of at least one copolymerizable monomer selected from the group consisting of α- olefins C _20. C in random copolymer
₄ The α- olefin -C _20, 1-butene, 1
-Pentene, 1-hexene, 1-heptene, 1-octene, 3-methyl-butene-1, 4-methylpentene-1
And the like. The copolymerized monomer is at least one selected from the group consisting of ethylene and the α-olefin. Two or more copolymer monomers may be contained as a structural unit in the random copolymer. Preferred copolymerizable monomers include ethylene.

In the block (b), the content of the copolymer monomer is 10 to 80 mol%, preferably 25 to 80 mol%.
75 mol%. That is, the copolymerized monomer is
Its constituent unit is contained in an amount of 10 to 80 mol%, preferably 25 to 75 mol%, based on all the constituent units of the block (b). When there are two or more copolymerized monomers, the content of all the copolymerized monomers is adjusted to be 10 to 80 mol% in total.

The total average chain length of the copolymerized monomer is n and the average chain length of the block (b) is n _b
Then, _nb and n must satisfy the relationship represented by the following formula (I), preferably (II).

[0028]

_Nb ≦ n + 1.5 (I) _nb ≦ n + 1.2 (II)

Here, n _b is the average block length of the copolymerized monomer, that is, in the block (b),
When the copolymer monomer forms a chain (copolymer monomer block) in which two or more are linked, the average length of the chain (block). n is the total average chain length of the copolymerized monomers, that is, the average chain length of all the chains in the block (b) including the chain composed of only one copolymerized monomer (chain length = 1).

The MFR of the block (b) is arbitrary as long as the MFR of the entire propylene block copolymer can maintain a value within a predetermined range, but is preferably 0.01 to 3 g / 10 minutes.

If the above formula regarding the average chain length of the block (b) is not satisfied, the fluidity and impact resistance become insufficient, which is not preferable. The copolymer composition of the random copolymer and the above average chain lengths are determined using ¹³ C-NMR. Hereinafter, the determination method will be described by taking, as an example, a case where the block (a), which is a typical propylene block copolymer, is a polypropylene homopolymer and the block (b) is a random copolymer of ethylene and propylene.

For the measurement of the ¹³ C-NMR spectrum, several methods can be used as long as quantitative reliability can be ensured. For example, a sample to be measured is dissolved in ortho-dichlorobenzene at 120 ° C. to prepare an ortho-dichlorobenzene solution, and measurement can be performed by the gated decoupling method with a wait time ten times longer than the relaxation time (T ₁ ). . Various average chain lengths of block (b) are described in the literature (GJRay, PE Johnson and JRKnox, Macromole
cules 10, 773 (1977), or T. Usami, Y. Gotoh, H. Umemot
o and S.Takayama, J.Appl.Polym.Sci.:Appl.Polym.Sym
p. 52, 145 (1993)) and using the notation of various methylene carbons, the integrated intensity of each NMR signal was
Can be determined as follows. In addition,
In the following formula (Equation 6), n is the total ethylene average chain length, and _nb is the block ethylene average chain length.

[0033]

[Number 4] - [total ethylene _{strength] = [I ββ + I βδ} + +
_{I γγ + I γδ + + I} δ + δ + + (I αγ + I αδ +)
/ 2] / 2 · n = 2 [ total ethylene _{strength] / (I αγ + I αδ} +) · [ Block _{ethylene] = [I βδ + + I} γγ + I
_{γδ + Iδ + δ + Iαδ +} / 2] / 2

(Iii) Propylene block copolymer The propylene block copolymer used in the present invention is substantially composed of the block (a) and the block (b). a)
And the preferred ratio of the block (b) is (a) :( b)
= 50-95: 50-5 (weight ratio), more preferably (a) :( b) = 70-95: 30-5 (weight ratio).

The propylene block copolymer has an overall MFR of 0.1 to 200 g / 10 min, preferably 4 to 200 g / 10 min. If the MFR is less than the above range, the fluidity is low and the moldability is poor, and the block (b)
Is also unfavorable because the dispersibility of is also deteriorated. On the other hand, if the MFR exceeds the above range, the impact resistance becomes insufficient.

The MFR value according to the present invention is defined by JIS
It is a value measured according to -K7210 (230 ° C, 2.16 kg load). When a propylene block copolymer is obtained by two-stage polymerization, the MFR (block MFR) of the block formed in the second stage is the same as the MFR (block copolymer MFR) of the propylene block copolymer. (Pre-stage MFR) and the polymerization ratio (weight ratio) of each stage can be determined by the following equation.

[0037]

[Mathematical formula-see original document] log (block copolymer MFR)-(preliminary polymerization ratio) x
log (first-stage MFR) = (second-stage polymerization ratio) x log (second-stage MFR)

(Iv) Method for Producing a Propylene Block Copolymer The above-mentioned method for producing a propylene block copolymer used in the present invention is not particularly limited as long as a predetermined block copolymer having the physical properties specified in the present invention can be obtained. There is no limitation, and any method can be adopted. Hereinafter, a typical method for producing the propylene block copolymer of the present invention will be described.

The propylene block copolymer of the present invention comprises:
Production by performing at least two-stage polymerization step (hereinafter, the first-stage polymerization step is sometimes referred to as a first-stage polymerization, and the second-stage polymerization step is sometimes referred to as a second-stage polymerization) in the presence of a specific catalyst system. can do.

[Catalyst] The catalyst used in the present invention is an 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.

[0041]

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 ligand (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 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 the 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. Q = alkylene group includes, for example, (1) methylenebis (2-methyl, 4-phenyl,
-Hydroazulenyl) zirconium dichloride, (2) ethylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium dichloride, (3) ethylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl) )
Diloconium hydride monochloride, (4) ethylene bis (2-methyl, 4-phenyl, 4-hydroazulenyl) methyl zirconium monochloride, (5) ethylene bis (2-methyl, 4-phenyl, 4-hydroazure) Nil) zirconium monomethoxide monochloride, (6) ethylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium diethoxide, (7) ethylenebis (2-methyl, 4-phenyl, 4- (Hydroazulenyl) 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, (2) dimethylsilylene bis (2-methyl, 4,5,6,7-tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylene bis (2-methyl-4,5-benzoindenyl) zirconium dichloride , (4) dimethylsilylene bis (2-methyl, 4-phenylindenyl) zirconium dichloride, (5) dimethylsilylenebis (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) phenyl aluminum bis (2-methyl 4-phenyl azulenyl) zirconium dichloride, 4) phenylphosphinobis (2-methyl 4-phenyl, 4-hydroazulenyl) zirconium dichloride, (5) ethylboranobis (2-methyl 4-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).

Among 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].

[0065]

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, particularly 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 kind of trialkylaluminum or two or more kinds 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.

[0069]

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

Examples of the ionic compound capable of converting the component (A) into a cation by reacting with the component (A) include a compound represented by the general formula [6].

[0072]

## 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 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) that 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 the 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 except 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 that have not been subjected to the above pretreatment, it is preferable that the exchangeable metal cation contained is ion-exchanged with a cation dissociated from the following 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 conditions for treatment 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.

[0091]

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 contact of each of the above components may be carried out 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 / g 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.

Examples of the above inorganic carrier include, for example, SiO 2
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 includes:
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 of Propylene Block Copolymer] The polymerization of the propylene block copolymer is usually carried out in two stages, preferably in the first stage, the block (a) is formed, and then in the second stage, the block (a) is produced. (B) is generated. That is, in the first stage, in the presence of component (A) and component (B), or component (A), component (B) and component (C),
A homopolymerization of propylene or a copolymerization of propylene with a copolymerization monomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms, wherein a crystalline homopolymer of propylene or propylene having a propylene content of 90 mol% or more -Produce an α-olefin copolymer.

Usually, the polymerization temperature and the polymerization time are selected so that the amount of the polymer obtained in the first step is 50 to 95% by weight of the total amount of the produced polymer. The polymerization temperature is usually -20 to 15
0 ° C, preferably selected from the range of 0 to 100 ° C. Hydrogen is preferred as the molecular weight regulator.

Next, in the second step, propylene, ethylene and C 4 -C 4 are present in the presence of the polymer formed in the first step.
Copolymerization with a copolymerization monomer selected from the group consisting of 20 α-olefins. The polymerization ratio (molar ratio) between propylene and the copolymerized monomer is usually from 5/95 to 90/1.
Polymerization is performed so that the ratio becomes 0. Usually, the polymerization temperature and the polymerization time are selected so that the amount of the polymer obtained in the second step is 5 to 50% by weight of the total amount of the produced polymer. The polymerization temperature is generally selected from the range of 1 to 100 ° C, preferably 20 to 90 ° C. Hydrogen is preferred as the molecular weight regulator.

These polymerization reactions are carried out in the presence or absence of an inert hydrocarbon such as propane, butane, hexane, heptane or toluene, or a solvent such as liquefied α-olefin. It is preferably carried out in a liquefied α-olefin or in the absence of a solvent.

After these first and second stage polymerizations,
Subsequently, after the third step, copolymerization of propylene with another α-olefin, homopolymerization of ethylene or copolymerization of ethylene with another α-olefin may be performed.

In the present invention, the “block copolymer” is
As described above, the one having the ideal form, that is, the block (block (a)) generated by the first-stage polymerization and the block (block (b)) generated by the second-stage polymerization are present on one molecular chain. Does not mean only
Includes various forms of polymers, such as physical mixtures of polymers formed in each step according to conventional practice, and chemical bonds and physical mixtures between these and the ideal block copolymers described above. It is.

(2) Ingredients The propylene polymer composition of the present invention is obtained by adding (a) a hindered amine compound, (b) a triazole compound, (c) a benzophenone compound to the propylene block copolymer described above. (D) at least one weathering agent selected from the group consisting of benzoate compounds; One of these compounds may be used alone, or two or more of them may be used in combination.

(A) Hindered amine compound Specific examples of the hindered amine compound used in the present invention include bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, dimethyl succinate and 1- (2-
(Hydroxyethyl) -4-hydroxy-2,2,6,6
Polycondensation product with tetramethylpiperidine, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, N, N-bis (3- Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6
-Chloro-1,3,5-triazine condensate, poly [$ 6
-(1,1,3,3-tetramethylbutyl) imino-
1,3,5-triazine-2,4-diyl {(2,
2,6,6-tetramethyl-4-piperidyl) imino}
Hexamethylene ｛(2,2,6,6-tetramethyl-4
-Piperidyl) imino}], poly [(6-morpholino-
s-Triazine-2,4-diyl) [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) Sebacate and the like.

Of these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,3 4-butanetetracarboxylate, N, N-bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6
-Chloro-1,3,5-triazine condensate or poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl}
｛(2,2,6,6-tetramethyl-4-piperidyl)
Imino {hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] is particularly preferred.

(B) Triazole Compounds Specific examples of the triazole compounds used in the present invention include 2- (2-hydroxy-3-t-butyl-5-methyl-phenyl) -5-chlorobenzotriazole,
2,2′-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2′-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole and the like.

(C) Benzophenone Compound Specific examples of the benzophenone compound used in the present invention include 2-hydroxy-4-n-octoxybenzophenone.

(D) Benzoate Compound Specific examples of the benzoate compound used in the present invention include 2,4-di-t-butyl-phenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like. Is mentioned.

(Iii) Other additional components (optional components) In addition to the above-mentioned nucleating agent which is an essential component, the propylene-based polymer composition of the present invention may contain other additional components to achieve the effects of the present invention. It can be blended within a range that does not significantly impair. As this optional component, sulfur-based antioxidants, neutralizing agents, lubricants, metal deactivators, coloring agents, dispersants, peroxides, fillers, fluorescent brighteners used for ordinary polyolefins,
Organic or inorganic antibacterial agents and resins other than those used in the present invention, for example, ethylene-propylene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber and the like can be mentioned.

Examples of the sulfur-based antioxidants include di-stearyl-thio-di-propionate, di-myristyl-
Thio-di-propionate, pentaerythritol-tetrakis- (3-lauryl-thio-propionate) and the like.

Examples of neutralizing agents include calcium stearate, zinc stearate, calcium behenate, zinc behenate, calcium 12-hydroxystearate,
-Zinc hydroxystearate, calcium lactate, hydrotalcite, lithium aluminum composite oxide salt compound (trade name: Mizukarac, manufactured by Mizusawa Chemical Co., Ltd.) and the like.

Examples of the lubricant include higher fatty acid amides such as oleic acid amide, stearic acid amide, behenic acid amide and ethylenebisstearoid, silicone oil, higher fatty acid esters and the like.

(3) Propylene-based polymer composition The propylene-based polymer composition of the present invention is based on 100 parts by weight of the propylene block copolymer described above, (a) the hindered amine-based compound, (b) the triazole-based compound,
(C) 0.001 to 1 part by weight, preferably 0.01 to 1 part by weight of at least one compound selected from the group consisting of benzophenone-based compounds and (d) benzoate-based compounds
It is a composition containing 0.8 parts by weight.

The method for preparing the propylene polymer composition of the present invention is not particularly limited, and the propylene polymer composition can be produced by blending the above compound with a propylene block copolymer by a conventionally known method, and mixing and melt-kneading. .

Mixing and melt kneading are usually carried out using a Henschel mixer, a super mixer, a V-blender, a tumbler mixer, a ribbon blender, a Banbury mixer,
It can be carried out by a kneader blender, a single-screw or twin-screw kneading extruder, and among them, it is preferable to perform mixing or melt kneading by a single-screw or twin-screw kneading extruder.

The propylene polymer composition of the present invention can be used as various molding materials, for example, materials for injection molding, extrusion molding, blow molding and the like. Particularly preferably, it can be used as a material for injection molding.

[0125]

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 minutes) is JIS-K712
0 (230 ° C., 2.16 kg load). (2) The total average chain length and the average block length were determined by ¹³ C-NMR spectrum according to the above-described gated decoupling method. (3) 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). (4) The content of the rubbery component was determined by immersing 2 g of the sample in 300 g of boiling xylene for 20 minutes to dissolve it, cooling to room temperature, and filtering and drying the precipitated solid phase through a glass filter. It is a value obtained by back calculation from the obtained solid phase weight.

(5) The propylene / ethylene ratio is a value measured by an infrared spectrum analysis method. (6) The weight average molecular weight Mw and the number average molecular weight Mn are G
It was measured by PC.

(7) 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—.

(8) Weather resistance was measured using a xenon weather meter (Xe-WOM) as follows. 120mm x 80mm x obtained by injection molding
A 2 mm test sheet was prepared using a black panel temperature of 63 ° C.
The sheet was exposed under the condition of rain (spray irradiation 12 minutes / 60 minutes cycle). The surface appearance of the exposed sheet was observed under a microscope at a magnification of 60 times, and the time until crack generation (unit: Hr) was measured.

(9) The bleeding property was evaluated as follows. The same test sheet as that used in the weather resistance test (one not subjected to the weather resistance test) was placed in a gear oven adjusted to 80 ° C. for 20 days, and after taking out, the external appearance was visually observed. Evaluation was based on criteria. ：: No bleed is observed. −-: Slight bleed was observed, but no problem occurred. Δ: Bleeding is easily observed. X: Bleeding was observed considerably, and it could not be used practically.

[0131]

Example 1 (I) Production of Polymer (Type; M-3) (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 a racemic-meso mixture 3.22 g of 2-methylazulene was dissolved in 30 ml of hexane, and 21 ml (1.0 equivalent) of a phenyllithium solution 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, and
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 and placed under reduced pressure for 200 minutes.
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 above 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) Propylene block copolymerization 2 L having a built-in irrigated stirring blade replaced with purified nitrogen
Into an induction-stirring autoclave, a toluene solution of triisobutylaluminum (0.5 mmol / ml)
After adding 13.1 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 in the first stage.

The polymer yield in the first stage was weighed to obtain 293 g of polypropylene. After extracting 53 g of the polymer while flowing purified nitrogen, the temperature was raised to 60 ° C. with stirring and mixing, and after the temperature was raised, propylene gas and ethylene gas were charged so that the total polymerization pressure became 1.96 MPa. Was started. The polymerization reaction was carried out at 60 ° C. for 150 minutes while supplying a mixed gas of propylene and ethylene so that the total polymerization pressure was constant at 1.96 MPa. Here, the ratio of propylene [propylene / (propylene + ethylene)] was 30 mol% on average.

Thereafter, propylene and ethylene were purged to remove the propylene block copolymer 258 in the form of white powder.
g was obtained. The MFR of the obtained block copolymer was 30.

The second in the obtained block copolymer
The polymer content (rubber amount) at the stage was 7% by weight. The MFR of the polypropylene obtained in the first stage
Is 42, stereoregularity (mmmm) is 99.3%, 1,
3-Asymmetric bond 0.5%, Mw 150,000, Mw / Mn
(Q value) was 3.1. With respect to the block copolymer obtained here, the total ethylene average chain length in the second stage was 2.82, and the average block ethylene chain length was 3.67.

(II) Production of propylene-based polymer composition 100 parts by weight of the propylene block copolymer obtained in the above (I)-(4) were added with bis (2,2,2) as a weathering agent.
0.1 parts by weight of 6,6-tetramethyl-4-piperidyl) sebacate (trade name: LS770, manufactured by Sankyo), pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate]
After adding 0.05 parts by weight, 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 parts by weight of calcium stearate, and mixing with a super mixer, the mixture was extruded by a single screw. Machine (screw diameter 30mm)
At 240 ° C. to obtain a pellet-shaped composition.

(III) Molding of Test Sheet The obtained composition was molded at a mold temperature of 40 ° C. and a cylinder temperature of 24.
It was introduced into an injection molding machine heated at 0 ° C., and a test sheet (120 mm × 80 mm × 2 mm) was formed by injection molding. The obtained sheet was evaluated for weather resistance (Xe-WOM, crack generation time) and bleeding property by the methods described above. Table 1 shows the results.

[0146]

Example 2 As a weathering agent, N, instead of LS770 was used.
N-bis (3-aminopropyl) ethylenediamine
2,4-bis [N-butyl-N- (1,2,2,6,6
-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate (trade name: CM119FL, manufactured by Ciba Specialty Chemicals).
Except that 1 part by weight was used, the composition obtained in the same manner as in Example 1 was injection-molded in the same manner as in Example 1, and weather resistance and bleeding property were evaluated using the obtained test sheet. . Table 1 shows the results.

[0147]

Example 3 Instead of LS770 as a weathering agent, 2-
Example 1 except that 0.2 parts by weight of (2-hydroxy-3-t-butyl-5-methyl-phenyl) -5-chlorobenzotriazole (manufactured by Ciba Specialty Chemicals, trade name: TNV326) was used. Using the composition obtained in the same manner as in Example 1, injection molding was performed in the same manner as in Example 1, and the weather resistance and bleeding property were evaluated using the obtained test sheet. Table 1 shows the results.

Example 4 As weathering agent, LS77 used in Example 1 was used.
0: 0.05 parts by weight and TNV32 used in Example 3
6: Injection molding was carried out in the same manner as in Example 1 using the composition obtained in the same manner as in Example 1 except that 0.05 parts by weight was blended, and the test sheet obtained was used to obtain weather resistance. And the bleeding property was evaluated. Table 1 shows the results.

Example 5 As a weathering agent, 2-LS was used instead of LS770.
Hydroxy-4-n-octoxybenzophenone (trade name: Seesorb 102, manufactured by Shiraishi Calcium Co., Ltd.)
Except for using parts by weight, the composition obtained in the same manner as in Example 1 was injection-molded in the same manner as in Example 1, and the obtained test sheet was used to evaluate the weather resistance and the bleeding property. Table 1 shows the results.

Example 6 As weathering agent, 2 was used instead of LS770.
Except that 0.2 parts by weight of 4-di-t-butyl-phenyl-3,5-di-t-butyl-4-hydroxybenzoate (Sumitomo Chemical Co., Ltd., trade name: Sumisorb 400) was used.
Example 1 was prepared using the composition obtained in the same manner as in Example 1.
Injection molding was performed in the same manner as described above, and weather resistance and bleeding property were evaluated using the obtained test sheet. Table 1 shows the results.

[0148]

COMPARATIVE EXAMPLE 1 Injection molding was carried out in the same manner as in Example 1 by using the composition obtained in the same manner as in Example 1 except that no weathering agent was added. Weather resistance and bleeding property were evaluated using the test sheet thus obtained.
Table 2 shows the results.

[0149]

Comparative Example 2 (1) Production of Polymer (Type: Z-2) [Synthesis of Catalyst] Solid catalyst component-(1) was synthesized according to the method described in Example 1 of JP-A-3-234707. did.

[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 and the above method were used. 3.2 g of the synthesized solid catalyst component- (1) was introduced in a propylene atmosphere at 70 ° C. The polymerization was performed in two stages. The pre-stage polymerization was started by heating the autoclave to 75 ° C. and then introducing propylene at a rate of 9 kg / hour while maintaining the hydrogen concentration in the gas phase at 7.2% by volume. After 231 minutes, the introduction of propylene was stopped, and the pressure in the autoclave was increased to 2.0 k while maintaining the temperature at 75 ° C.
The polymerization was continued until g / cm ² · G was reached. Thereafter, residual gas was purged until the propylene in the gas phase became 0.4 kg / cm ² · G.

Next, after the temperature of the autoclave was lowered to 65 ° C., post-stage polymerization was carried out by introducing propylene at a rate of 3.78 kg / hour and ethylene at a rate of 2.52 kg / hour for 42 minutes.

[0152] Butanol was added to the slurry thus obtained to decompose the catalyst, followed by filtration and drying.
33. Powdered propylene-ethylene block copolymer (Z-2) having an MFR of 30 g / 10 min and a rubber amount of 7% by weight.
8 kg was obtained.

(2) Molding / Evaluation of Test Sheet In Example 1, the block copolymer described in the above Z-2 was used.
Injection molding was carried out in the same manner as in Example 1 using the composition obtained in the same manner as in Example 1 except that the composition was changed to Example 1. The weather resistance and bleeding property were evaluated using the obtained test sheet. Table 2 shows the results.

[0154]

Comparative Example 3 In Example 3, the block copolymer was changed to Z
Except for changing to -2, injection molding was performed in the same manner as in Example 1 using the composition obtained in the same manner as in Example 1, and weather resistance and bleeding property were evaluated using the obtained test sheet. . Table 2 shows the results.

[0155]

Comparative Example 4 In Example 4, the block copolymer was changed to Z
Except for changing to -2, injection molding was performed in the same manner as in Example 1 using the composition obtained in the same manner as in Example 1, and weather resistance and bleeding property were evaluated using the obtained test sheet. . Table 2 shows the results.

[0156]

Comparative Example 5 In Example 5, the block copolymer was changed to Z
Except for changing to -2, injection molding was performed in the same manner as in Example 1 using the composition obtained in the same manner as in Example 1, and weather resistance and bleeding property were evaluated using the obtained test sheet. . Table 2 shows the results.

[0157]

Comparative Example 6 In Example 6, the block copolymer was changed to Z
Except for changing to -2, injection molding was performed in the same manner as in Example 1 using the composition obtained in the same manner as in Example 1, and weather resistance and bleeding property were evaluated using the obtained test sheet. . Table 2 shows the results.

[0158]

[Table 1]

[0159]

[Table 2]

In Table 1, the ingredients A-1 to A-5
Represents the following compounds. A-1: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate A-2: N, N-bis (3-aminopropyl) ethylenediamine 2,4-bis [N-butyl-N − (1, 2,
2,6,6-pentamethyl-4-piperidyl) amino]
-6-chloro-1,3,5-triazine condensate A-3: 2- (2-hydroxy-3-t-butyl-5-
Methyl-phenyl) -5-chlorobenzotriazole A-4: 2-hydroxy-4-n-octoxybenzophenone A-5: 2,4-di-t-butyl-phenyl-3,5-
Di-t-butyl-4-hydroxybenzoate

[0161]

EFFECT OF THE INVENTION The propylene polymer composition of the present invention, in which a specific additive is blended with a propylene block copolymer having a specific structure, has an excellent balance between weather resistance and low bleeding property. It is industrially useful as a molding material for extrusion molding and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takao Tagano 1st Tohocho, Yokkaichi, Mie Prefecture Mitsubishi Chemical Corporation Yokkaichi Office Resin Technology Development Center (72) Inventor Toru Suzuki Kamoshida, Aoba-ku, Yokohama-shi, Kanagawa 1000 Yokohama-cho, Mitsubishi Chemical Corporation (72) Inventor Toshihiko Sugano 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Pref.

Claims (3)

[Claims] 1. A propylene block copolymer which is substantially composed of a block (a) and a block (b) shown below, and has a melt flow rate of 0.1 to 200 g / 10 min. (A) at least one compound selected from the group consisting of hindered amine compounds, (b) triazole compounds, (c) benzophenone compounds, and (d) benzoate compounds 0.00
A propylene polymer composition comprising 1 to 1 part by weight. Block (a): A propylene homopolymer or a random copolymer of propylene and a copolymer monomer selected from the group consisting of ethylene and α-olefins of C _{4 to} C ₂₀ , wherein the content of the copolymer monomer is A polymer block of not more than 10 mol%. Block (b): propylene and ethylene and C _{4 to} C
A random copolymer with at least one copolymer monomer selected from the group consisting of ₂₀ α-olefins, wherein the content of the copolymer monomer is 10 to 80 mol%, and Is a polymer block having a relationship between the block average chain length and the total average chain length represented by the following formula (I). [Number 1] _{n b ≦ n + 1.5 ··· (} I) ( wherein, _{n b} represents a block average chain length of the copolymer monomers, n represents represents the total average chain length of the copolymer monomers.) 2. The block (a) has a weight average molecular weight (Mw) of 10,000 to 1,000,000, a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) of 6 or less, The fraction of tick pentad chains is 95% or more,
The propylene-based polymer composition according to claim 1, wherein the proportion of the 1,3-asymmetric bond is 0.02 to 3%. 3. The propylene-based polymer composition according to claim 1, wherein the propylene block copolymer has a melt flow rate of 4 to 200 g / 10 minutes.