JPH11291279A - Polypropylene injection molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide superior transparency, impact resistance and the like by forming a polypropylene injection molded body composed of polypropylene resin and a specified ethylene.α-olefin random copolymer or the like. SOLUTION: A polypropylene injection molded body is composed of polypropylene resin, an ethylene.α-olefin random copolymer and a propylene.ethylene.1-butane random copolymer. The ethylene.α-olefin random copolymer is provided with 0.9 g/cm<3> density or less, 0.1-50 g/10 minutes melt flow rate(MFR) and the molecular weight distribution based on gel permeation chromatography(GPC) is 3 or less. The propylene.ethylene.1-butane random copolymer contains 50-95 molar % propylene unit, 2-30 molar % ethylene unit and 10-40 molar % 1-butane unit. The content of 1-butane unit is set larger than the content of ethylene unit. Also MFR is set to 0.1-50 g/10 minutes, and the molecular weight distribution based on GPC is set to 3 or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection molded article comprising a polypropylene resin, and more particularly, to a polypropylene resin, a specific ethylene / α-olefin random copolymer, and a specific propylene / ethylene / 1-butene random copolymer. The present invention relates to a polypropylene injection-molded article containing the unified product.

[0002]

2. Description of the Related Art Polypropylene resins are excellent in rigidity and heat resistance, but have the disadvantage of low impact strength. For the purpose of remedying this drawback, a rubber component comprising an ethylene / propylene random copolymer or an ethylene / butene lanram copolymer has been blended with a polypropylene resin.

However, such a conventional polypropylene resin composition has a problem that the impact strength is reduced but the transparency is deteriorated.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polypropylene injection molded article having excellent transparency, impact resistance, rigidity and heat resistance.

[0005]

The present invention relates to the following molded article. (1) (A) polypropylene resin, (B) density 0.9
g / cm ³ or less, and the MFR (ASTM D-123)
8190 ° C, 2.16 kg load) 0.1 to 50 g / 1
An ethylene / α-olefin random copolymer having 0 minutes and a molecular weight distribution (Mw / Mn) of 3 or less (here, α-olefin has 3 or more carbon atoms); and (C) the following conditions: A polypropylene injection molded article containing a propylene / ethylene / 1-butene random copolymer satisfying 1) to 3). Conditions for propylene / ethylene / 1-butene random copolymer (C): 1) 50 to 95 mol% of propylene units, 2 of ethylene units
３０30 mol%, and 10-40 mol% of 1-butene unit
And the content of 1-butene units is greater than the content of ethylene units. 2) MFR (ASTM D-1238 230 ° C, 2.
16 kg load) is 0.1 to 50 g / 10 min. 3) Gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 3 or less.

(2) (A) Polypropylene resin 50 to 9
5 parts by weight, (B) 3 to 40 parts by weight of an ethylene / α-olefin random copolymer, and (C) 2 to 20 parts by weight of a propylene / ethylene / 1-butene random copolymer (where (A), (A total amount of (B) and (C) is 100 parts by weight).

(3) The polypropylene resin (A) is a propylene homopolymer, a propylene / α-olefin random copolymer having an α-olefin unit content other than propylene of 10 mol% or less, and an extraction amount of n-decane. Is 1
The polypropylene injection molded article according to the above (1) or (2), which is at least one selected from the group consisting of 0% by weight or less of a propylene / α-olefin block copolymer.

(4) The ethylene / α-olefin random copolymer (B) is a random copolymer obtained by random copolymerizing ethylene and α-olefin in the presence of a metallocene catalyst. 1) ~
The injection molded article of polypropylene according to any one of (3). (5) The (C) propylene / ethylene / 1-butene random copolymer is a random copolymer obtained by randomly copolymerizing propylene, 1-butene and ethylene in the presence of a metallocene catalyst. The above (1)
The polypropylene injection molded article according to any one of (1) to (4).

Hereinafter, the polypropylene injection molded article of the present invention will be described in detail. The polypropylene injection molded article of the present invention comprises: (A) a polypropylene resin;
An injection-molded article comprising a composition containing an α-olefin random copolymer and (C) a propylene / ethylene / 1-butene random copolymer.

First, the polypropylene resin (A) constituting the polypropylene resin composition will be described. In the present invention, a conventionally known polypropylene resin can be appropriately selected and used as the (A) polypropylene resin. Examples of such (A) polypropylene resin include propylene homopolymer, propylene / α-olefin random copolymer of propylene and other α-olefin other than propylene, and propylene / α-olefin block copolymer. Can be. Further, the (A) polypropylene resin may be modified with a polar group-containing monomer such as maleic anhydride.

The preferred (A) polypropylene resin is a propylene homopolymer, a propylene / α-olefin random copolymer containing 10 mol% or less, preferably 8 mol% or less of other α-olefin units, and n-decane A propylene / α-olefin block copolymer having an extraction amount of 10% by weight or less, particularly 8% by weight or less.

In the present invention, the "α-olefin unit" means a structural unit derived from an α-olefin and constituting a polymer. The same applies to ethylene units, propylene units, 1-butene units and the like. Also,
In the present invention, the α-olefin includes ethylene.

The other α-olefin forming the propylene / α-olefin random copolymer or propylene block copolymer is preferably an α-olefin having 2 to 20 carbon atoms other than propylene. Is ethylene, 1-butene, 1-pentene, 1-hexene,
Examples thereof include 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1-pentene.

These α-olefins can be used alone or in combination of two or more.

The polypropylene resin (A) used in the present invention can be produced by a known method using a solid titanium catalyst or a metallocene catalyst known per se.

(A) The crystallinity of the polypropylene resin by the X-ray method is preferably at least 40%, particularly preferably at least 50%, and the melting point (Tm) by the DSC method is 100-1.
Preferably it is 65 ° C. In addition, (B) ethylene
It is desirable to use (A) a polypropylene resin having a melting point higher than the melting points of the α-olefin random copolymer and (C) propylene / ethylene / 1-butene random copolymer.

Further, (A) the polypropylene resin is AS
The melt flow rate (MFR: 230 ° C., under a load of 2.16 kg) measured in accordance with TM D1238 is usually 0.1 to 300 g / 10 min, preferably 1 to 5 g.
0 g / 10 minutes. (A) The polypropylene resin is 1
Species can be used alone or in combination of two or more.

Next, (B) an ethylene / α-olefin random copolymer will be described. (B) used in the present invention
The ethylene / α-olefin random copolymer is (a)
The density is 0.9 g / cm ³ or less, preferably 0.85 to
0.88 g / cm ³ and (b) MFR (ASTM
D-1238 190 ° C, 2.16 kg load) is 0.1
５０50 g / 10 min, preferably 0.2-30 g / 10 min, and (c) gel permeation chromatography (GPC) using orthodichlorobenzene as an elution solvent and monodisperse polystyrene as a standard substance. As a measured polystyrene conversion value, the molecular weight distribution (Mw / Mn) is 3 or less.

Further, (B) the α-olefin of the ethylene / α-olefin random copolymer has 3 or more carbon atoms;
Preferably it is 3-20. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9- Methyl-1-decene, 11-methyl-1-dodecene, 12-
Ethyl-1-tetradecene and the like can be mentioned.

The (B) ethylene / α-olefin random copolymer preferably has a crystallinity measured by an X-ray diffraction method of less than 40%, more preferably 30% or less.

Further, (B) the ethylene / α-olefin random copolymer is a parameter showing the randomness of the copolymer monomer chain distribution obtained by 13 C-NMR method.
(B value) is preferably in the range of 1.0 to 1.4. The B value is an index indicating the composition distribution state of the structural units in the copolymer chain, and can be calculated by the following equation.

B = POE / (2PO.PE) (where PE and PO are the mole fraction of the ethylene component and the mole of the α-olefin component contained in the ethylene / α-olefin random copolymer, respectively) And the POE is the ratio of the number of alternating ethylene / α-olefin chains to the total number of dyad chains.) Such PE, PO and POE values are specifically:
It can be calculated as follows.

A sample was prepared by uniformly dissolving about 200 mg of the ethylene / α-olefin random copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ test tube, and the 13 C-NMR spectrum of this sample was determined as follows. Measure under conditions. [Measurement conditions] Measurement temperature: 120 ° C. Measurement frequency: 20.05 MHz Spectral width: 1500 Hz Filter width: 1500 Hz Pulse repetition time: 4.2 sec Pulse width: 7 μsec Number of times of integration: 2000 to 5000 times

The values of PE, PO and POE were determined from the 13 C-NMR spectrum measured as described above.
J. Ray (Macromolecules, 10, 773 (1977)), JC R
andall (Macro-molecules, 15, 353 (1982)), K. Kimu
ra (Polymer, 25, 4418 (1984)).

The B value obtained from the above equation is
(B) When the ethylene / α-olefin copolymer has both monomers alternately distributed, the value is 2; when the monomer is a completely block copolymer in which both monomers are completely separated and polymerized, the value is 0. Become.

When the B value is within the above range, (B) ethylene · α
-When an olefin random copolymer is used, a polypropylene resin composition having excellent heat resistance can be obtained.

The (B) ethylene / α-olefin random copolymer has an intrinsic viscosity [η] of 0.5 to 5.0 dl / g measured in decalin at 135 ° C.
The gη * value is preferably from 0.95 to 1.00. This g
The η * value is defined by the following equation. gη * = [η] / [η] blank (where [η] is the intrinsic viscosity measured above, and [η] blank is the ethylene viscosity of the intrinsic viscosity [η].
It is the intrinsic viscosity of a linear ethylene / propylene copolymer having the same weight average molecular weight (by the light scattering method) as the α-olefin random copolymer and having an ethylene content of 70 mol%. )

The ethylene / α-olefin random copolymer (B) can be obtained with a vanadium catalyst or a titanium catalyst, but ethylene and α-olefin are copolymerized in the presence of a metallocene catalyst described later. The ethylene / α-olefin random copolymer obtained by the reaction is preferred.

Next, the propylene / ethylene / 1-butene random copolymer (C) will be described. The (C) propylene / ethylene / 1-butene random copolymer used in the present invention satisfies the conditions 1) to 3) as described above. These conditions will be described sequentially.

The condition 1) specifies the composition of the (C) propylene / ethylene / 1-butene random copolymer. That is, (C) propylene / ethylene / 1
-Butene random copolymer has a propylene unit of 50 to
95 mol%, preferably 60 to 85 mol%, 2 to 30 mol% of ethylene units, preferably 3 to 20 mol%, and 10 to 40 mol% of 1-butene units, preferably 10 to 10 mol%.
-30% by mole. And the content of 1-butene units is greater than the content of ethylene units.

Since the (C) propylene / ethylene / 1-butene random copolymer has the above composition, the copolymer has elastomeric properties, (A) compatibility with the polypropylene resin and (B) ethylene / ethylene copolymer. This results in a good balance of compatibility with the α-olefin random copolymer. The (C) propylene / ethylene / 1-butene random copolymer has an α other than a propylene unit, a 1-butene unit and an ethylene unit as long as the above advantages are not impaired.
-It may contain a small amount of olefin unit, for example, 10 mol% or less.

The conditions 2) and 3) are respectively
(C) Melt flow rate (MF) which is a measure of the molecular weight of the propylene / ethylene / 1-butene random copolymer
R) and molecular weight distribution (Mw / Mn). The MFR of the (C) random copolymer (ASTM D
-1238 230 ° C, 2.16 kg load) is 0.1
５０50 g / 10 min, preferably 0.2-30 g / 10 min.

The (C) random copolymer Mw /
Mn is 3 or less. Mw / Mn is a value in terms of polystyrene measured by gel permeation chromatography (GPC) using orthodichlorobenzene as an elution solvent and monodisperse polystyrene as a standard substance.

When the (C) MFR and molecular weight distribution of the propylene / ethylene / 1-butene random copolymer are within the above ranges, (A) the compatibility with the polypropylene resin is excellent, and the obtained composition is molded. The molded product obtained is excellent in processability and excellent in transparency.

The (C) propylene / ethylene / 1-butene random copolymer used in the present invention preferably has a specific microstructure. That is, (C) propylene / ethylene / 1-butene random copolymer is (i) head-
It preferably contains a three-chain structure consisting of tail-bonded propylene units only, or (ii) a three-chain structure consisting of head-tail bonded propylene units and 1-butene units. Further, the side chain methyl group of the propylene unit of the second unit of the three-chain structure of (i) or (ii) above is
19.7 to 21.7p when measured by NMR (based on hexachlorobutadiene solution and tetramethylsilane).
Assuming that the total area of peaks appearing in pm is 100%, 21.
It is desirable that the area of the peak appearing at 2 to 21.7 ppm is 90% or more, preferably 92% or more.

Further, (C) propylene / ethylene / 1-
In the butene random copolymer, the proportion of regio-irregular units based on 2,1-insertion of propylene monomer in all propylene units measured by 13 C-NMR is 0.05% or more, preferably 0.05 to 0.1%. 4%, more preferably 0.05
It is desirable that it is about 0.3%.

Further, (C) propylene / ethylene / 1-
Butene random copolymer is a propylene monomer of 1,
3- 0.05% of irregular position unit based on insertion
The following is preferred. At the time of polymerization, the propylene monomer is 1,2-inserted (the methylene side binds to a catalyst described later), but may be rarely 2,1-inserted or 1,3-inserted. The 2,1-inserted or 1,3-inserted monomers form regio-irregular units in the polymer.

The ratio of 2,1-insertion of the propylene monomer in all the propylene units was determined by using 13 C-NMR.
It can be determined from the following formula [I] with reference to Lymer, 30 (1989) 1350.

[0039]

## EQU1 ## Ratio of regio-irregular units based on 2,1-insertion = ([0.25Iαβ [structure (i)] + 0.5Iαβ [structure (ii)]] × 100) / (Iαα + Iαβ [structure (ii )] + 0.5 [Iαγ + Iαβ [structure (i)] + Iαδ]) ... [I]

Here, the peaks are named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). Iαβ and the like indicate peak areas such as αβ peaks. When it is difficult to determine the area such as Iαβ directly from the spectrum due to overlapping peaks, a carbon peak having a corresponding area can be used instead.

The three-chain amount based on the 1,3-insertion of propylene is obtained by dividing one half of the area of the βγ peak (resonating around 27.4 ppm) by the sum of half of the total methyl group peak and half of the βγ peak. By multiplying by 100, the ratio can be calculated in%.

The (C) propylene / ethylene / 1-butene random copolymer used in the present invention is (B) ethylene / ethylene / 1
As in the case of the α-olefin random copolymer, a copolymer produced using a metallocene catalyst is preferred.

As the metallocene-based catalyst, (a) a bridge-type transition metal compound represented by the chemical formula (1) (hereinafter sometimes simply referred to as a transition metal compound) and (a) an activated (B) an organoaluminum compound, (c) an organoaluminum oxy compound, and (d) an ionized ionic compound that reacts with the (a) transition metal compound to form an ion pair. A metallocene catalyst containing at least one compound selected from the compound group of b) to (d) is preferred.

In the chemical formula (1), M is a compound of the Periodic Table IV to VIB
Group transition metals, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
Chromium, molybdenum, and tungsten are preferable, and titanium, zirconium, and hafnium are preferable, and zirconium is particularly preferable.

In the chemical formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may have 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen. A hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and a part of adjacent groups is bonded to form a ring together with a carbon atom to which those groups are bonded. It may be formed.
Incidentally, R ¹ to R ⁴ present two each in the formula indicates that it is preferable to bind a combination between the same symbols in forming these bonded to ring, for example, a R ¹ It shows that it is preferable to combine with R ¹ to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, Alkyl groups such as octyl, nonyl, dodecyl, iconosyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, Ethylphenyl, propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl,
Aryl groups such as acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like can be mentioned.

The ring formed by combining these hydrocarbon groups includes a condensed ring such as a benzene ring, a naphthalene ring, an acenaphthene ring and an indene ring, and a condensed ring such as a benzene ring, a naphthalene ring, an acenaphthene ring and an indene ring. A group in which a hydrogen atom on the group is substituted with an alkyl group such as methyl, ethyl, propyl, and butyl can be given. Further, these hydrocarbon groups may be substituted with halogen.

Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenyl Trihydrocarbon-substituted silyls such as silyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; And a silicon-substituted aryl group.

As the oxygen-containing group, a hydroxy group,
Alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound has been replaced by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, and p-toluene sulfonate. , Trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate and other sulfonate groups; methylsulfinate, phenylsulfinate, benzenesulfinate, p- Examples thereof include sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate.

Examples of the nitrogen-containing group include an amino group, an amino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenyl. An arylamino group such as amino or an alkylarylamino group can be exemplified.

Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.

In the chemical formula (1), X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen, oxygen, Or sulfur-containing groups. As these atoms or groups, specifically, R ^{1 to} R ⁴
And the same atoms and groups as those shown in the above.

In the chemical formula (1), Y is substituted by halogen.
A divalent hydrocarbon group having 1 to 20 carbon atoms which may be
Divalent silicon-containing group, divalent germanium-containing group, -O
-, -CO-, -S-, -SO-, -SO_Two-, -NR^Five
-, -P (R^Five)-, -P (O) (R ^Five)-, -BR^Five-Or
-AlR^Five-. Where R^FiveIs a hydrogen atom, as above
Halogen atoms and charcoals optionally substituted with halogen
It is a hydrocarbon group having a prime number of 1 to 20.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen include methylene,
Alkylene groups such as dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; diphenylmethylene And arylalkylene groups such as diphenyl-1,2-ethylene. Further, a halogenated hydrocarbon group obtained by halogenating the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene can be exemplified.

The divalent silicon-containing groups include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene,
Alkyl silylene such as di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene; alkylarylsilylene, arylsilylene group,
Examples thereof include an alkyldisilyl group such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl, an alkylaryldisilyl group, and an aryldisilyl group.

Examples of the divalent germanium-containing group include compounds in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium.

Specific examples of the (a) bridge type transition metal compound represented by the chemical formula (1) are described below. Bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (1- (3-methylcyclopentadienyl)) zirconium dichloride and the like.

In the present invention, among the transition metal compounds (a) represented by the above formula (1), a bridge type transition metal compound represented by the following formula (2) is preferably used.

Formula 2 is as shown below. (formula
In the formula (2), M, R ¹ , R ³ , X ¹ , X ² and Y are the same as defined in the above formula (1), and R ^{21 to} R ²⁴ and R ^{41 to} R
⁴⁴ is a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and the alkyl group or the aryl group may be substituted with a halogen or an organic silyl group).

The activating compound capable of activating the (a) transition metal compound is at least one selected from the group consisting of (b) an organoaluminum compound, (c) an organoaluminum oxy compound, and (c) an ionic compound. One compound is used.

The above-mentioned organoaluminum compound (b) is represented, for example, by the following formula (3). R ¹ nAlX _3-n (3) (in the formula (3), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3)
3. )

In the above formula (3), R ¹ has 1 to ¹ carbon atoms.
12 hydrocarbon groups, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl Group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

As the organoaluminum compound (b), a compound represented by the following formula (4) can also be used. R ¹ nAlY _3-n (4) (in the formula (4), R 1 is the same as above, and Y is —OR ²
Group, -OSiR ³³ group, -OAlR ⁴² group, -NR ⁵² group,-
A SiR ⁶³ group or a —N (R ⁷ ) AlR ⁸² group;
R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are a methyl group, an ethyl group and the like. )

Of these, the formulas R ¹³ Al, R ¹ nAl
_{^{(OR 2) 3-n,}} R 1 nAl (OAlR 42) compounds represented by _{3- n} are preferred, in particular R is an isoalkyl radical, n is 2
Are preferred. These can be used in combination.

The organoaluminum oxy compound (c) may be a conventionally known benzene-soluble aluminoxane or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807. You may.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of not more than 10%, preferably not more than 5%, particularly preferably not more than 2% in terms of Al atom. And insoluble or slightly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is determined by comparing the solubility of the organoaluminum oxy compound with 100 milligram atoms of Al to 10 mg.
After suspending in 0 ml of benzene, the mixture was mixed at 60 ° C. for 6 hours with stirring, and then subjected to hot filtration at 60 ° C. using a jacketed G-5 glass filter. It is determined by measuring the abundance (X mmol) of Al atoms present in the total filtrate after washing four times with 50 ml of benzene at 50 ° C. (X%).

The (d) ionized ionic compound is a compound which forms an ion pair by reacting with the (a) transition metal compound represented by the above formula (1). Such an ionized ionic compound (d) is described in JP-A-1-50195.
No. 0, Japanese Patent Application Laid-Open No. Hei.
JP 179005, JP-A-3-179006,
JP-A-3-207703, JP-A-3-20770
No. 4, US Pat. No. 5,321,106, Lewis acids, ionic compounds, carborane compounds and the like can be used.

The metallocene-based catalysts are described in the above (a) to (d)
A solid catalyst in which all or any of the components are supported on a granular or particulate solid (carrier) may be used.

This carrier may be an inorganic carrier or an organic carrier. As the inorganic carrier, for example, Si
Porous oxides such as O ₂ and Al ₂ O ₃ are preferably used. Examples of the organic carrier include those having 2 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
(Co) polymers formed mainly with α-olefins of No. to 14 or vinylcyclohexane, polymers or copolymers formed mainly with styrene, and the like can be used.

The injection-molded article made of the above polypropylene resin includes (A) polypropylene, (B) an ethylene / α-olefin random copolymer, and (C) propylene /
In addition to the ethylene / 1-butene random copolymer, other components such as other additives and other polymers may be contained as long as the advantages of the composition of the present invention are not impaired.

Examples of the above additives include a weather stabilizer, a heat stabilizer, an anti-fogging agent, an anti-blocking agent, a slip agent, a lubricant, an antistatic agent, a flame retardant, a pigment, a dye and a filler.

[0074]

The polypropylene resin injection molded article of the present invention contains a polypropylene resin, a specific ethylene / α-olefin random copolymer, and a specific propylene / ethylene / 1-butene random copolymer, and thus is transparent. An injection-molded article excellent in heat resistance, impact resistance, rigidity and heat resistance can be molded.

[0075]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the examples.

Production Example 1 ((B) Production of ethylene / 1-butene random copolymer) An ethylene / 1-butene random copolymer was produced using a metallocene catalyst. That is, 950 m of hexane was placed in a 2-liter autoclave sufficiently purged with nitrogen.
1, 1-butene (50 g) was added, triisobutylaluminum (1 mmol) was added thereto, and the temperature was raised to 70 ° C., and ethylene was supplied to adjust the total pressure to 7 kg / cm ² G, methylaluminoxane (0.30 mmol), rac- Dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride was added in an amount of 0.001 mmol in terms of Zr atom, and ethylene was continuously supplied. 3 while maintaining the pressure at 7 kg / cm ² G
Polymerization was performed for 0 minutes.

After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (ethylene / 1-butene random copolymer) was 28.0 g, and the polymerization activity was 56 kg · polymer / mmol Zr · hr.

The composition and physical properties of this polymer are as follows. (1) Composition Ethylene unit content: 89.0 mol% 1-butene unit content: 11.0 mol% (2) MFR (ASTM D-1238 190 ° C,
2.16 kg load): 3.6 g / 10 min (3) Molecular weight distribution by GPC (Mw / Mn): 2.0 (4) Density: 0.885 g / cm ³ (5) B value: 1.1 (6 ) Intrinsic viscosity [η]: 1.48 dl / g

Production Example 2 ((C) propylene / ethylene /
Production of 1-butene random copolymer) Propylene / ethylene / 1- using metallocene catalyst
A butene random copolymer was produced. That is, 950 ml of hexane and 75 g of 1-butene were charged into a 2 liter autoclave sufficiently purged with nitrogen, 1 mmol of triisobutylaluminum was added thereto, and the temperature was raised to 70 ° C. Pressure 7Kg /
cm ² G, 0.30 mmol of methylaluminoxane,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9
-Phenanthryl) indenyl) zirconium dichloride is added in an amount of 0.001 mmol in terms of Zr atom, and then continuously supplied so that the molar ratio of propylene to ethylene supplied (propylene / ethylene) becomes 95/5. While maintaining the total pressure at 7 kg / cm ² G.
Polymerization was performed for 0 minutes.

After the polymerization, the polymer was degassed, and the polymer was recovered in a large amount of methanol and dried at 110 ° C. under reduced pressure for 12 hours. The obtained polymer (propylene / 1-butene / ethylene copolymer) was 28.0 g, and the polymerization activity was 56 kg · polymer / mmol Zr · hr.

The composition, physical properties and the like of this polymer are as follows. 1) Composition Propylene unit content: 68.5 mol% Ethylene unit content: 10.2 mol% 1-butene unit content: 21.3 mol% 2) MFR (ASTM D-1238 230 ° C, 2.
3) Molecular weight distribution by GPC (Mw / Mn): 2.3 4) Tri-chain structure consisting of head-to-tail bonded propylene units: exists 5) Head-to-tail bonded propylene And a 1-butene unit, and a propylene unit is present in the second unit.

Example 1 Propylene content 97.3 mol%, ethylene content 2.
7 mol%, MFR (ASTMD-1238, 230 ° C,
2.16 Kg) 80% by weight of a polypropylene random copolymer (A) having 20 g / 10 min and an ethylene content of 8
MFR at 9.0 mol% and butene content of 11.0 mol%
(ASTMD-1238, 190 ° C., 2.16 Kg): 3.6 / 10 min, 15% by weight of ethylene butene copolymer (B) having a density of 0.885 and propylene butene-ethylene copolymer obtained in Production Example 2 The combined product (C) and 5% by weight were mixed by a mixer, and pellets were produced by an extruder to form an injection molded product.

Cylinder temperature: 185 ° C. Injection pressure (primary / secondary): 400/200 Kg / cm ² (specimin) 1000/800 kg / cm ² (square plate) Injection cycle (primary / secondary / cooling:・ Mold temperature: 50 ° C. Example 2 Mixing weight ratio of polypropylene random copolymer (A), ethylene butene copolymer (B) and propylene butene-ethylene copolymer (C) (A): (B): (C)
= 80:10:10, except that it was performed in the same manner as in Example 1. Comparative Example The mixing weight ratio of the polypropylene random copolymer (A) and the ethylene butene copolymer (B) was (A) :( B) = 8.
Table 1 shows the results of molding in the same manner as in Example 1 except that the ratio was set to 0:20. The evaluation method of the molded article is as follows. Tensile properties: ASTM D-638 Bending properties: ASTM D-790 Izod impact value: ASTM D-256 Haze: AS TMD-1003 Gross: AS TMD-523

[Table 1]

Embedded image [Wherein, M is a transition metal base paper of Groups IV to VIB of the periodic table, and R ¹ , R ² , R ³ , and R ⁴ are the same or different and are a hydrogen atom, a halogen atom, and a carbon atom of 1; A hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group. May be bonded to form a ring together with the carbon atom to which those groups are bonded. X ¹ and X ² are the same or different and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Y has 1 to 20 carbon atoms
A divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, —O—, —CO—, —S—, and —SO—. , -SO ₂
^{-, - NR 5 -, -} P (R 5) -, - P (= O) (R 5)
-, - BR ⁵ -, or -AlR ⁵ -, it is. here,
R5 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. ]

Embedded image (In the formula (2), M, R ¹ , R ³ , X ¹ , X ² , and Y are
As defined in the above formula (1), R ^{21 to} R ⁴⁴ are a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and the alkyl group or the aryl group is a halogen or an organic silyl group. May be substituted).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23:14) B29K 23:00

Claims (5)

[Claims] (A) a polypropylene resin; (B) a density of 0.9 g / cm ³ or less;
STM D-1238 190 ° C., 2.16 kg load) is 0.1 to 50 g / 10 min, and has a molecular weight distribution (Mw).
/ Mn) is 3 or less (here, the α-olefin has 3 or more carbon atoms), and (C) propylene that satisfies the following conditions 1) to 3). An injection molded polypropylene article containing an ethylene / 1-butene random copolymer. Conditions for propylene / ethylene / 1-butene random copolymer (C): 1) 50 to 95 mol% of propylene units, 2 of ethylene units
３０30 mol%, and 10-40 mol% of 1-butene unit
And the content of 1-butene units is greater than the content of ethylene units. 2) MFR (ASTM D-1238 230 ° C, 2.
16 kg load) is 0.1 to 50 g / 10 min. 3) Gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 3 or less. 2. (A) 50 to 95 parts by weight of a polypropylene resin, (B) 3 to 40 parts by weight of an ethylene / α-olefin random copolymer, and (C) propylene / ethylene / 1-butene random copolymer 2 The polypropylene injection-molded product according to claim 1, which contains -20 parts by weight (where the total amount of (A), (B) and (C) is 100 parts by weight). 3. The polypropylene resin (A) is a propylene homopolymer, a propylene / α-olefin random copolymer having an α-olefin unit content other than propylene of 10 mol% or less, and an extractable amount of n-decane. The polypropylene injection-molded article according to claim 1 or 2, which is at least one selected from the group consisting of 10% by weight or less of a propylene / α-olefin block copolymer. 4. The ethylene / α-olefin random copolymer (B) is a random copolymer obtained by random copolymerization of ethylene and α-olefin in the presence of a metallocene catalyst. The injection molded article of polypropylene according to any one of claims 1 to 3, 5. The method according to claim 5, wherein (C) a propylene / ethylene / 1-butene random copolymer is prepared in the presence of a metallocene catalyst.
The polypropylene injection molded article according to any one of claims 1 to 4, which is a random copolymer obtained by randomly copolymerizing propylene, 1-butene, and ethylene.