JP2000136252A - Filler-filled resin sheet and molded product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a filler-filled propylene-based resin sheet having excellent thermoformability such as vacuum moldability, air pressure forming properties, etc., having excellent rigidity and heat resistance and a molded product using the filler-filled propylene-based resin. SOLUTION: A propylene-based polymer composition in an amount of 100 pts.wt. comprising (a) 100 pts.wt. of a propylene homopolymer having 0.2-10 dl/g intrinsic viscosity [ηA] measured in tetralin at 135 deg.C or a propylene-olefin copolymer (polypropylene) containing >=50 wt.% of a propylene polymerization unit and (b) 0.01-5.0 pts.wt. of an ethylene homopolymer having 15-100 dl/g intrinsic viscosity [ηB] measured in tetralin at 135 deg.C or an ethylene-olefin random copolymer (high-molecular weight polyethylene) containing >=50 wt.% of an ethylene polymerization unit is mixed with 1-70 pts.wt. of a filler to give a resin composition. The composition is made into a filler-filled resin sheet and the sheet is thermally molded to give a molded product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is typified by a resin composition (1) in which an inorganic filler is added to a specific propylene polymer composition or a specific ethylene resin in the resin composition (1). The present invention relates to a filler-filled resin sheet having excellent rigidity and thermoformability using a resin composition (2) containing a specific amount of a third component resin, and a molded product obtained by thermoforming them.

[0002]

2. Description of the Related Art Conventionally, sheets made of a styrene resin such as polystyrene or acrylonitrile-butadiene-styrene copolymer have been used for large-sized thermoformed products such as inner boxes of refrigerators and thermoformed products such as cups with deep squeezes. Used
Due to problems in physical properties such as poor chemical resistance and environmental problems such as generation of black smoke at the time of incineration, switching to olefin resins, especially propylene resins having excellent heat resistance, has been demanded.

[0003] However, polypropylene has high crystallinity and has a high viscosity below the melting point and hardly flows.
When the temperature exceeds the melting point, the viscosity sharply decreases and remarkable fluidity is exhibited. Therefore, when a sheet using a propylene-based resin is heated and thermoforming such as vacuum forming is performed, it is difficult to maintain the viscosity of the heated sheet in a state suitable for thermoforming. In particular, a propylene-based resin sheet containing an inorganic filler to make it as rigid as a styrene-based resin had significantly poor thermoformability. In particular, in the molding of a large thermoformed product, the heat-softened sheet drastically sags, and if the sheet is heated to a temperature at which the sheet can be molded, the sheet comes into contact with the lower heater. In order to stabilize thermoformability, it is useful to increase the strength at the time of melting polypropylene, that is, the melt tension, and various methods for increasing the melt tension have been proposed.

As a method for increasing the melt tension of polypropylene, a method of reacting an organic peroxide and a crosslinking assistant with polypropylene in a molten state (JP-A-59-937).
No. 11, JP-A-61-152754, etc.), a low-decomposition temperature peroxide is reacted with a semi-crystalline polypropylene in the absence of oxygen to obtain a polypropylene having a free-end long-chain branch and containing no gel. Manufacturing method (Japanese Unexamined Patent Publication No.
No. 36) has been proposed.

As another method for improving the melt viscoelasticity such as the melt tension, a composition in which polypropylene and polyethylene or polypropylene having different intrinsic viscosities or molecular weights are blended with polypropylene, or such a composition is produced by a multistage polymerization method. A method has been proposed.

For example, a method in which ultrahigh molecular weight polypropylene is added at a ratio of 2 to 30 parts by weight with respect to 100 parts by weight of ordinary polypropylene and extruded in a temperature range from a melting point to 210 ° C. (Japanese Patent Publication No. 61-28694). Publication), an extruded sheet made of a two-component polypropylene having a limiting viscosity ratio of 2 or more and different molecular weights obtained by a multistage polymerization method (Japanese Patent Publication No. 1-1770), and 1 to 10% by weight of polyethylene having a high viscosity average molecular weight. A method of producing a polyethylene composition comprising three types of polyethylene having different viscosity average molecular weights by a melt-kneading method or a multi-stage polymerization method (Japanese Patent Publication No. 62-61057), using a highly active titanium-vanadium solid catalyst component, Ultra-high molecular weight polyethylene having an intrinsic viscosity of 20 dl / g or more is obtained by a multi-stage polymerization method. Polymerization process of polyethylene for less than an amount% polymer (KOKOKU 5-79683 JP), 1-
An ultra-high molecular weight polyethylene having an intrinsic viscosity of 15 dl / g or more was obtained by multistage polymerization using a highly active titanium catalyst component prepolymerized with butene or 4-methyl-1-pentene using a specially arranged polymerization reactor. Method for polymerizing polyethylene by polymerizing 1 to 5% by weight (JP-B-7-8890)
And so on.

Further, propylene is polymerized using a prepolymerized catalyst in which ethylene and a polyene compound are prepolymerized to a supported titanium-containing solid catalyst component and an organoaluminum compound catalyst component to produce polypropylene having a high melt tension. (Japanese Unexamined Patent Application Publication No.
No. 2) and the same catalyst component, preliminarily polymerizing ethylene alone and using an ethylene-containing prepolymerized catalyst containing polyethylene having an intrinsic viscosity of 20 dl / g or more, an ethylene / α-olefin copolymer having a high melt tension. There has been proposed a method of manufacturing a united product (Japanese Patent Laid-Open No. 4-55410).

[0008]

In the above-mentioned various compositions and their production methods, although the melt tension of the polyolefin is improved to some extent, the odor remains due to the crosslinking aid, and the molding process is carried out. There are still points to be improved such as sex.

In a multi-stage polymerization method in which a process for producing a high-molecular-weight polyolefin is incorporated into a usual propylene (co-) polymerization step in the main polymerization, an olefin (co-) is used to form a trace amount of the high-molecular-weight polyolefin.
It is difficult to control the amount of polymerization very small, and sometimes a low polymerization temperature is required to produce a polyolefin having a sufficiently large molecular weight.
Further, the productivity of the polypropylene composition also decreases.

In the method of prepolymerizing a polyene compound, it is necessary to separately prepare a polyene compound,
Further, when propylene is polymerized based on a document that discloses a method of prepolymerizing polyethylene, the dispersibility of the prepolymerized polyethylene in the finally obtained polypropylene composition is non-uniform, and the stability of the polypropylene composition is Further improvement is required in terms of aspects.

As described above, in the prior art, in addition to the problems of odor, productivity and quality stability, the improvement of the melt strength is still insufficient, and the purpose is to improve the rigidity and heat resistance of thermoformed products. In the case of a sheet containing an inorganic filler, the sagging of the heated sheet during thermoforming was large, and the thermoformability was not satisfactory. Further, the thickness of the obtained thermoformed product is not sufficiently improved, and there is a problem to be improved.

The present invention provides a filler-filled resin sheet which has good thermoformability such as vacuum formability and air pressure moldability, and provides a molded article having excellent rigidity and heat resistance, and a molded article thereof. The purpose is to:

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a propylene-based polymer composition containing a high molecular weight polyethylene having a specific intrinsic viscosity and a polypropylene having a specific intrinsic viscosity has a specific amount of an inorganic compound. By using a resin composition (1) containing a filler or a resin composition (2) obtained by further adding a specific amount of a third component resin represented by a specific ethylene resin to the composition (1). It is found that a filler-filled resin sheet having good thermoformability and a molded article having excellent rigidity can be obtained,
The present invention has been reached.

[0014]

(1) (a) The intrinsic viscosity [η _A ] measured in tetralin at 135 ° C. is 0.2 to 1
0 dl / g of propylene homopolymer or propylene containing at least 50% by weight of propylene polymerized units.
For 100 parts by weight of an olefin copolymer (collectively referred to as polypropylene), (b) intrinsic viscosity [η _B ] measured with tetralin at 135 ° C. is 15 to 100 d.
An ethylene homopolymer or an ethylene-olefin random copolymer containing 50% by weight or more of ethylene polymerized units (these are collectively referred to as high molecular weight polyethylene) in the range of 1 / g to 0.01 to 5. A filler-filled resin screen using a resin composition (1) containing 1 to 70 parts by weight of an inorganic filler with respect to 100 parts by weight of a propylene polymer composition containing 0 parts by weight. −
G.

(2) 100 parts by weight of the propylene polymer composition according to item 1 above, the inorganic filler is added in an amount of 1 to 7
Filler filling using a resin composition (2) containing 0 part by weight and 1 to 70 parts by weight of one or more third component resins selected from the following groups (P1) to (P6). Resin sheet. (P1) Density 0.910 to 0.930 g / cm
^3. Melt flow rate (MFR) [190 ° C;
18N] an ethylene homopolymer of 0.01 g / 10 min or more, (P2) density 0.920 to 0.950 g / cm ³ ,
Melt flow rate (MFR) [190 ° C; 21.18
N] ethylene-vinyl acetate copolymer of 0.01 g / 10 min or more, (P3) density 0.880 to 0.940 g / cm
^3. Melt flow rate (MFR) [190 ° C;
18N] ethylene-olefin copolymer of 0.01 g / 10 min or more, (P4) melt flow rate (MFR)
[190 ° C .; 21.18 N] ethylene-olefin copolymer rubber of 0.01 g / 10 min or more, (P5) 1-butene homopolymer or 1-butene-olefin copolymer,
(P6) Hydrogenated styrene-conjugated diene copolymer rubber.

(3) The propylene polymer composition is used in an amount of 0.0 to 1 mol of the transition metal compound catalyst component and the transition metal atom.
Group 1 of the Periodic Table (1991 version) of 1 to 1,000 moles,
Combination of an organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Groups 2, 12, and 13 and 0 to 500 moles of an electron donor (E1) per mole of a transition metal atom 2. A catalyst for producing a polyolefin, comprising: (b) the catalyst of (1) supported on the catalyst.
The propylene-based polymer composition obtained by polymerizing propylene alone or propylene and an olefin other than propylene in the presence of a preactivation catalyst containing a high-molecular-weight polyethylene as a component, or the above-mentioned item 1 or 2, The filler-filled resin sheet according to any one of claims 1 to 6.

(4) A molded article obtained by thermoforming the filler-filled resin sheet according to any one of (1) to (3).

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The polypropylene used in the present invention is a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units. A propylene-olefin random copolymer and a propylene-olefin block copolymer containing 50% by weight or more of a unit mean a high-molecular-weight polyethylene.
It means an ethylene-olefin random copolymer containing not less than 10% by weight.

The polypropylene constituting the component (a) is
Intrinsic viscosity [η _A ] measured in tetralin at 135 ° C. is 0.2 to 10 dl / g, preferably 0.5 to 8 dl / g
Which is a propylene homopolymer, a propylene-olefin random copolymer or a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units, preferably a propylene homopolymer or a propylene polymer. Unit content is 90
A propylene-olefin random copolymer having a propylene polymer unit content of 70% by weight or more, more preferably a propylene homopolymer and a propylene polymer unit content of 95% by weight. The propylene-olefin random copolymer described above and the propylene-olefin block copolymer having a propylene polymerization unit content of 80% by weight or more. These polymers and copolymers can be used alone or in combination of two or more.

When the intrinsic viscosity [η _A ] of the polypropylene is less than 0.2 dl / g, a filler-filled resin sheet using a resin composition comprising the obtained propylene-based polymer composition has mechanical properties. When it exceeds 10 dl / g, the moldability of the obtained filler-filled resin sheet deteriorates.

The olefin other than propylene copolymerized with propylene constituting the component (a) is not particularly limited, but an olefin having 2 to 12 carbon atoms is preferably used. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,
-Methyl-1-pentene, 3-methyl-1-pentene and the like. These olefins may be used alone or in combination of two or more.

The stereoregularity of the polypropylene is not particularly limited, and any polypropylene that achieves the object of the present invention may be used as long as it is a crystalline polypropylene. Specifically, the isotactic pentad fraction (m) measured by ¹³ C-NMR (nuclear magnetic resonance spectrum)
mmm) is 0.80 to 0.99, preferably 0.85 to 0.95.
Polypropylene having a crystallinity of 0.99 can also be used.

Here, the isotactic pentad fraction (mmmm) is defined as ¹³ C—produced by A. Zambelli et al. (Macromolecules 6 , 925 (1973)).
It is an isotactic fraction in pentad units in a polypropylene molecular chain measured by NMR, and a method of determining peak assignment in spectrum measurement is proposed by A. Zambelli et al. (Macromolecules 8 , 68
7 (1975)). Specifically, o-dichlorobenzene having a polymer concentration of 20% by weight /
Using a mixed solution of bromide benzene = 8/2 weight ratio, 67.
It is determined by measuring at 20 MHz and 130 ° C. As a measuring device, for example, JEOL-GX27
A 0 NMR measurement device (manufactured by JEOL Ltd.) is used.

The high molecular weight polyethylene constituting the component (b) has an intrinsic viscosity [η] measured in tetralin at 135 ° C.
_B ] is a polyethylene of 15 to 100 dl / g,
An ethylene-olefin random copolymer containing at least 50% by weight of ethylene homopolymer or ethylene-polymerized unit, preferably an ethylene-olefin random copolymer containing at least 70% by weight of ethylene-homopolymer or ethylene-polymerized unit, Particularly preferred is an ethylene homopolymer or an ethylene-olefin random copolymer containing at least 90% by weight of ethylene polymerized units. These high-molecular-weight polyethylenes may be used alone or in combination of two or more. Good.

When the intrinsic viscosity [η _B ] of the high molecular weight polyethylene (b) is less than 15 dl / g, a filler-filled resin sheet using a resin composition comprising the obtained propylene polymer composition is used. The melt tension decreases, the effect of improving the moldability becomes insufficient, and the upper limit of the intrinsic viscosity [η _B ] is not particularly limited, but the difference from the intrinsic viscosity [η _A ] of the polypropylene as the component (a) is If it is large, the dispersion of the polyethylene of the component (b) in the polypropylene of the component (a) becomes poor when the composition is formed, and as a result, the melt tension does not increase, and the effect of improving the moldability becomes insufficient. Further, from the viewpoint of manufacturing efficiency, the upper limit is preferably set to about 100 dl / g. (B) intrinsic viscosity of the component polyethylene [η
_B ] is 15 to 100 dl / g, preferably 17 to 50 d / g.
1 / g.

The olefin other than ethylene copolymerized with the ethylene constituting the component (b) polyethylene is not particularly limited, but an olefin having 3 to 12 carbon atoms is preferably used. Specifically, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-octene,
1-decene, 4-methyl-1-pentene, 3-methyl-
Examples thereof include 1-pentene, and these olefins may be not only one kind but also two or more kinds. In addition, since the intrinsic viscosity [η _B ] of the component (b), which is measured in tetralin at 135 ° C., needs to be increased to 15 dl / g, from the viewpoint of increasing the molecular weight, 50 units of ethylene polymerized units are required. It is preferred that the content be at least 10 wt%.

The density of the polyethylene as the component (b) is not particularly limited, but specifically, 0.880 to 0.8.
Those having about 980 g / cm ³ are preferable.

In the present invention, the component (a) and the component (b)
The melt tension of the propylene polymer composition containing the components is 2
It is preferable that the melt tension (MS) at 30 ° C. and the intrinsic viscosity [η _I ] measured in tetralin at 135 ° C. have a relationship represented by log (MS)> 4.24 × log [η _I ] −0.95. . The upper limit is not particularly limited, but if the melt tension is too high, the moldability of the sheet is deteriorated.
g [η _I ] +0.60> log (MS)> 4.24 × log [η _I ] −0.95,
More preferably, 4.24 × log [η _I ] +0.34> log (MS)>
4.24 × log [η _I ] −0.95, most preferably 4.24 × log
[η _I ] +0.34> log (MS)> 4.24 × log [η _I ] −0.83.

Here, the melt tension at 230 ° C. (M
In step S), using a melt tension tester type 2 (manufactured by Toyo Seiki Seisaku-sho, Ltd.), the propylene-based polymer composition was heated to 230 ° C. in the apparatus, and the molten propylene-based polymer composition was heated to a diameter of 2. A value obtained by extruding a strand from a 095 mm nozzle into the atmosphere at 23 ° C. at a speed of 20 mm / min to form a strand, and measuring the tension of the filamentous propylene polymer composition when the strand is taken off at a speed of 3.14 m / min (unit) : CN).

In the propylene polymer composition, it is preferable that the polyethylene as the component (b) is finely dispersed as fine particles in the propylene polymer composition, and the number average diameter of the polyethylene fine particles is 1 to 5000 nm. Preferably, the range of 10 to 500 nm is particularly preferred.

In the present invention, any method may be employed for producing the propylene-based polymer composition, but the propylene polymer composition may be produced in the presence of a catalyst preactivated by an olefin described below. And a method of subjecting the olefin other than propylene to (co) polymerization.

As the method, a transition metal compound catalyst component containing a titanium compound or the like, and 0.01 to 1000 mol per 1 mol of transition metal atom, periodic table (1991 edition) first
Organometallic compound of a metal selected from the group consisting of metals belonging to Group 2, Group 12, Group 12 and Group 13 (AL1)
And a polyolefin production catalyst comprising a combination of 0 to 500 mol of an electron donor (E1) per 1 mol of a transition metal atom, and a transition metal compound catalyst component 1 supported on the catalyst.
propylene alone or an olefin other than propylene and propylene in the presence of a preactivated catalyst consisting of polyethylene (B) having an intrinsic viscosity of 15 to 100 dl / g measured in tetralin of 0.01 to 5000 g per gram. This is a method characterized by performing main (co) polymerization.

More preferably, a transition metal compound catalyst component containing a titanium compound or the like, and 0.01 to 1000 mol per mol of the transition metal atom, Periodic Table (1991 edition) First
Organometallic compound of a metal selected from the group consisting of metals belonging to Group 2, Group 12, Group 12 and Group 13 (AL1)
And a polyolefin production catalyst comprising a combination of 0 to 500 mol of an electron donor (E1) per 1 mol of a transition metal atom, and a transition metal compound catalyst component 1 supported on the catalyst.
The intrinsic viscosity [η _A ] measured in tetralin of 0.01 to 100 g per g is less than 15 dl / g. Propylene alone or an olefin other than propylene with propylene other than propylene in the presence of a preactivated catalyst comprising polyethylene (B) having an intrinsic viscosity [η _B ] of 15 to 100 dl / g measured in tetralin. ) Polymerization.

As used herein, the term "pre-activation" refers to the pre-activation of a polyolefin production catalyst prior to carrying out the (co) polymerization of propylene or propylene with another olefin. This is carried out by preactivating (co) polymerizing ethylene or ethylene and another olefin in the presence of a catalyst for producing a polyolefin and supporting the catalyst on the catalyst.

The preactivated catalyst for olefin (co) polymerization of the present invention is a polyolefin production catalyst comprising a transition metal compound catalyst component conventionally used for the production of polyolefins, an organometallic compound and an optional electron donor. The catalyst is preactivated by supporting a small amount of a polyolefin for the purpose of main (co) polymerization having a specific intrinsic viscosity and a small amount of a polyolefin having a specific high intrinsic viscosity on a catalyst for use.

In the preactivated catalyst for olefin (co) polymerization of the present invention, any of the known catalyst components mainly composed of the transition metal compound catalyst component proposed for polyolefin production may be used as the transition metal compound catalyst component. Can also be used. Among them, a titanium-containing solid catalyst component is suitably used in industrial production.

As the titanium-containing solid catalyst component, a titanium-containing solid catalyst component containing a titanium trichloride composition as a main component (JP-B-56-3356, JP-B-59-2857)
No. 3, JP-B-63-66323, and the like, and a titanium-containing supported catalyst component in which titanium tetrachloride is supported on a magnesium compound and titanium, magnesium, halogen, and an electron donor are essential components (Japanese Patent Application Laid-Open No. Sho 62-63). -10481
0, Japanese Patent Application Laid-Open No. 62-104811, Japanese Patent Application Laid-Open
JP-A-2-104812, JP-A-57-63310, JP-A-57-63311, JP-A-58-83
006, JP-A-58-138712) and the like, and any of these can be used.

As the transition metal compound catalyst component other than the above, a transition metal compound having at least one π-electron conjugated ligand usually called a metallocene can also be used. The transition metal at this time is Zr, Ti, Hf, V, N
It is preferable to select from b, Ta and Cr.

Specific examples of the π-electron conjugated ligand include η-
A ligand having a cyclopentadienyl structure, an η-benzene structure, an η-cycloptatetrienyl structure, or an η-cyclooctatetraene structure may be mentioned, and particularly preferred is an η-cyclopentadienyl structure. Ligand.

The ligand having an η-cyclopentadienyl structure includes, for example, a cyclopentadienyl group, an indenyl group, a fluorenyl group and the like. These groups include hydrocarbon groups such as alkyl groups, aryl groups and aralkyl groups, silicon-substituted hydrocarbon groups such as trialkylsilyl groups, halogen atoms, alkoxy groups, aryloxy groups, chain and cyclic alkylene groups, and the like. It may be replaced.

When the transition metal compound contains two or more π-electron conjugated ligands, two of the π-electron conjugated ligands may be an alkylene group, a substituted alkylene group, a cycloalkylene group, a substituted cycloalkylene group. , A substituted alkylidene group, a phenyl group, a silylene group, a substituted dimethylsilylene group, a germyl group, or the like. The transition metal catalyst component at this time includes, in addition to having at least one π-electron ligand as described above, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and a silicon-substituted hydrocarbon group. , An alkoxy group, an aryloxy group, a substituted sulfonato group, an amidosilylene group, an amidoalkylene group, and the like. Note that a divalent group such as an amidosilylene group or an amidoalkylene group may be bonded to a π-electron conjugated ligand.

As described above, π which is usually called metallocene
The transition metal compound catalyst component having at least one electron conjugated ligand can be used by being supported on a fine particle carrier. As such a particulate carrier, even if it is an inorganic or organic compound, the particle diameter is 5 to 300 μm.
m, preferably 10 to 200 μm, of a granular or spherical fine particle solid is used. Among them, inorganic compounds used for the carrier include SiO ₂ , Al ₂ O ₃ , MgO, T
Examples include iO ₂ , ZnO, and the like, or a mixture thereof.
Among them, those containing SiO ₂ or Al ₂ O ₃ as a main component are preferable. Examples of the organic compound used for the carrier include polymers or copolymers of α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and styrene or styrene. Derivative polymers or copolymers may be mentioned.

As the organometallic compound (AL1), Periodic Table (1991 edition), Group 1, Group 2, Group 12, and Group 1
A compound having an organic group of a metal selected from the group consisting of metals belonging to Group 3, such as an organolithium compound, an organosodium compound, an organomagnesium compound, an organozinc compound, an organoaluminum compound, and the like; Can be used in combination with

In particular, the general formula is AlR ¹ _p R ² _q X
_{3- (p + q)} (wherein, R ¹ and R ² are the same or different of a hydrocarbon group such as an alkyl group, a cycloalkyl group and an aryl group and an alkoxy group, X represents a halogen atom,
p and q represent a positive number of 0 <p + q ≦ 3), and an organoaluminum compound represented by the following formula (1) can be preferably used.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-aluminum. Hexyl aluminum, trialkyl aluminum such as tri-n-octyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-i
-Butyl aluminum chloride,

Dialkylaluminum monohalides such as diethylaluminum bromide and diethylaluminum iodide; dialkylaluminum hydrides such as diethylaluminum hydride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; monoalkylaluminum dihalides such as ethylaluminum dichloride; Other alkoxyalkylaluminums such as diethoxymonoethylaluminum can be mentioned. Preferably, trialkylaluminum and dialkylaluminum monohalide are used.

These organoaluminum compounds can be used alone or in combination of two or more.

As the organometallic compound (AL1),
Aluminoxane compounds can also be used. Aluminoxane refers to the following general formula 1 or the following general formula 2
Is an organoaluminum compound represented by

[0049]

Embedded image

[0050]

Embedded image

Here, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group,
Pentyl group, alkyl group such as hexyl group, allyl group,
Alkenyl groups such as 2-methylallyl group, propenyl group, isopropenyl group, 2-methyl-1-propenyl group and butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; and aryl groups The compound which is is mentioned.
Among these, an alkyl group is particularly preferred, and each R ³ may be the same or different. p is an integer of 4 to 30, preferably 6 to 30, and particularly preferably 8 to 30.
30.

Another compound as the organometallic compound (AL1) is a boron-based organometallic compound. This boron-based organometallic compound is obtained by reacting a transition metal compound with an ionic compound containing a boron atom. As the transition metal compound used at this time, those similar to the transition metal compound catalyst component used in producing the preactivated catalyst for olefin (co) polymerization can be used. A transition metal compound catalyst component having at least one π-electron coordination ligand commonly referred to as a metallocene.

Specific examples of the ionic compound containing a boron atom include triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, and trikis (pentafluorophenyl) borate. Examples include phenyl ammonium, methyl ammonium tetrakis (pentafluorophenyl) borate, tridimethylammonium tetrakis (pentafluorophenyl) borate, and trimethylammonium tetrakis (pentafluorophenyl) borate.

The boron-based organometallic compound can also be obtained by contacting a transition metal compound with a boron atom-containing Lewis acid. The transition metal compound used at this time may be the same as the transition metal catalyst component used when producing the pre-activated catalyst for olefin (co) polymerization, but is preferably used as described above. A transition metal compound catalyst component having at least one π-electron conjugated ligand usually called a metallocene.

As the boron atom-containing Lewis acid, compounds represented by the following general formula 3 can be used.

[0056]

Embedded image BR ⁴ R ⁵ R ⁶ (wherein R ⁴ , R ⁵ and R ⁶ are each independently a phenyl group which may have a substituent such as a fluorine atom, a methyl group, a trifluorophenyl group, etc. Or a fluorine atom.)

Specific examples of the compound represented by the above general formula include tri (n-butyl) boron, triphenylboron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris (4-fluoro Methylphenyl)
Examples thereof include boron, tris (3,5-difluorophenyl) boron, tris (2,4,6-trifluorophenyl) boron, and tris (pentafluorophenyl) boron. Tris (pentafluorophenyl) boron is particularly preferred.

The electron donor (E1) is used as needed for the purpose of controlling the production rate and / or stereoregularity of the polyolefin. Electron donor (E1)
As, for example, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, ureas and thioureas, isocyanates, azo compounds, phosphines, phosphites, Organic compounds having any atom of oxygen, nitrogen, sulfur or phosphorus in the molecule such as phosphinite, hydrogen sulfide and thioethers, neoalcohols, silanols and the like, and organic silicon having a Si-OC bond in the molecule And the like.

As ethers, dimethyl ether,
Diethyl ether, di-n-propyl ether, di-n
-Butyl ether, di-i-amyl ether, di-n-
Pentyl ether, di-n-hexyl ether, di-i
-Hexyl ether, di-n-octyl ether, di-i
-Octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like.

The alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol,
Allyl alcohol, benzyl alcohol, ethylene glycol, glycerin and the like, and phenols such as phenol, cresol, xylenol, ethylphenol, naphthol and the like.

Examples of the esters include methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, butyl formate, amyl acetate, and n-butyl acetate. Octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, methyl anisate, Ethyl anisate, propyl anisate,

Monocarboxylic acid esters such as phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate and ethyl phenylacetate; diethyl succinate; Aliphatic polycarboxylic acid esters such as diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate, diethyl butylmaleate,

Monomethyl phthalate, dimethyl phthalate,
Diethyl phthalate, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-phthalate Ethylhexyl, di-n-octyl phthalate, diethyl i-phthalate, dipropyl i-phthalate,
Aromatic polycarboxylic acid esters such as dibutyl i-phthalate, di-2-ethylhexyl i-phthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, and di-i-butyl naphthalenedicarboxylate are exemplified.

The aldehydes include acetaldehyde, propionaldehyde, benzaldehyde and the like, and the carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid,
Monocarboxylic acids such as oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, and benzoic acid and acid anhydrides such as benzoic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride are used as acetone, Methyl ethyl ketone,
Examples thereof include methyl-i-butyl ketone and benzophenone.

Examples of the nitrogen-containing compound include nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, , 4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine,

[0066] 2,2,5,5, tetramethyl pyrrolidine, N, N, N ^{', N'} - tetramethylethylenediamine, aniline, amines dimethylaniline, dimethylformamide, hexamethylphosphoric triamide, N, N,
^{N ', N', N "} - pentamethyl -N ^{'-.beta.-dimethylaminomethyl} phosphoric acid triamide, amides such as octamethyl pyro ^{phosphoramide, N, N, N',} N '- urea such as tetramethylurea , Isocyanates such as phenyl isocyanate and toluyl isocyanate, and azo compounds such as azobenzene.

Examples of the phosphorus-containing compound include phosphines such as ethyl phosphine, triethyl phosphine, tri-n-octyl phosphine, triphenyl phosphine and triphenyl phosphine oxide, dimethyl phosphite,
Phosphines such as di-n-octylphosphine, triphenylphosphine and triphenylphosphine oxide, dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite and triphenyl phosphite; Phosphites are exemplified.

Examples of the sulfur-containing compound include thioethers such as diethylthioether, diphenylthioether and methylphenylthioether, ethylthioalcohol,
thioalcohols such as n-propylthioalcohol and thiophenol; and further, as an organosilicon compound, trimethylsilanol, triethylsilanol,
Silanols such as triphenylsilanol,

Trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane,
Vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, di-i-propyldimethoxysilane, di-i-butyldimethoxysilane, diphenyldiethoxysilane,
Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane,

In molecules such as vinyltriacetoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, and 2-norbornylmethyldimethoxysilane. An organic silicon compound having a Si—O—C bond may be used.

These electron donors can be used alone or as a mixture of two or more.

As the preactivation catalyst used in the production of the propylene polymer composition used in the present invention, the first and second groups of the periodic table (1991 version) are used per 1 mol of the transition metal compound catalyst component and the transition metal atom. Tribe, twelfth and first
0.01 to 1 mol of an organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 3 and 0 to 500 mol of an electron donor (E1) per 1 mol of a transition metal atom
A polyolefin production catalyst comprising a combination of
0.01 to 5,000 g per gram of the polypropylene (A) for the purpose of main (co) polymerization and the transition metal compound catalyst component having an intrinsic viscosity [η _A ] of less than 15 dl / g measured in 1 to 100 g of tetralin at 135 ° C. Has an intrinsic viscosity [η _B ] of 15 to 100 d measured in tetralin at 135 ° C.
A preactivated catalyst consisting of 1 / g of polyethylene (B) is preferred.

In the preactivated catalyst, the polyethylene (B) has an intrinsic viscosity [η _B ] of 15 to 100 dl / g, preferably 17 to 5 in tetralin at 135 ° C.
A random copolymer of ethylene and an olefin having 3 to 12 carbon atoms in which the ethylene homopolymer or ethylene polymer units in the range of 0 dl / g is 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or less. It is united.

The supported amount of polyethylene (B) per g of the transition metal compound catalyst component is 0.01 to 5,000 g, preferably 0.05 to 2,000 g, and more preferably 0.1 to 1,000 g. If the amount supported per 1 g of the transition metal compound catalyst component is less than 0.01 g, the effect of improving the melt tension of the propylene-based polymer composition obtained after the (co) polymerization is insufficient, and the effect of improving the moldability is not sufficient. Will be enough. On the other hand, when the amount exceeds 5,000 g, not only the improvement of those effects is not remarkable, but also the homogeneity of the propylene-based polymer composition may be deteriorated.

On the other hand, polypropylene (A)
Of intrinsic viscosity [η _A ] measured in tetralin of 15 dl
/ G of polypropylene having the same composition as the polypropylene of the component (a) for the purpose of main (co) polymerization, and is incorporated as a part of the polypropylene of the component (a) of the propylene-based polymer composition.

On the other hand, the amount of polypropylene (A) supported per gram of the transition metal compound catalyst component is 0.01 to 100.
g, in other words, 0.0 based on the propylene polymer composition.
A range of 01 to 1% by weight is preferred.

The preactivated catalyst is prepared in the presence of a catalyst for polyolefin production comprising a combination of a transition metal compound catalyst component, an organometallic compound (AL1) and an optional electron donor (E1). Preliminary (co) polymerization of propylene or other olefins for the purpose of polymerization to produce polypropylene (A),
Next, pre-activation (co) polymerization of ethylene or ethylene and other olefins to form polyethylene (B), and pre-activation treatment for supporting polypropylene (A) and polyethylene (B) on the transition metal compound catalyst component It is manufactured by

In this pre-activation treatment, the transition metal compound catalyst component and 0.1 mol of the transition metal in the catalyst component are added in an amount of 0.1 mol.
01 to 1,000 mol, preferably 0.05 to 500 mol, of the organometallic compound (AL1), and 0 to 500 mol, preferably 0 to 1 mol, per 1 mol of the transition metal in the catalyst component.
A combination of 00 moles of the electron donor (E1) is used as a catalyst for polyolefin production.

The polyolefin-producing catalyst is used in an amount of 0.001 to 5,000 mmol, preferably 0 to 5,000 mmol, as the transition metal atom in the catalyst component, per liter of the (co) polymerization volume of ethylene or ethylene and other olefins. In the absence of a solvent or in the presence of up to 100 liters of a solvent per gram of the transition metal compound catalyst component in the presence of propylene or propylene and other olefins for the purpose of (co) polymerization. Of the transition metal compound, and 0.01 to 500 g per 1 g of the transition metal compound catalyst component.
Of polypropylene (A), and then 0.01 g to 10,000 g of ethylene or a mixture of ethylene, ethylene and other olefins is supplied and pre-activated (co) polymerized to give 1 g of the transition metal compound catalyst component. By producing 0.01 to 5,000 g of polyethylene (B), polypropylene (A) and polyethylene (B) are coated and supported on the transition metal compound catalyst component. In the present specification, the term “polymerization volume” refers to the volume of the liquid phase portion in the polymerization vessel in the case of liquid layer polymerization.
In the case of gas phase polymerization, it means the volume of the gas phase portion in the polymerization vessel.

The amount of the transition metal compound catalyst component used is preferably in the above range in order to maintain an efficient and controlled (co) polymerization reaction rate of propylene. Also,
If the amount of the organometallic compound (AL1) is too small, the (co) polymerization reaction rate will be too slow, and if it is too large, a corresponding increase in the (co) polymerization reaction rate cannot be expected. It is not preferable because the amount of the organometallic compound (AL1) remaining in the polymer composition increases. Further, if the amount of the electron donor (E1) is too large, the (co) polymerization reaction rate is reduced. If the amount of solvent used is too large, not only will a large reaction vessel be required, but also
It is difficult to efficiently control and maintain the (co) polymerization reaction rate.

The preactivation treatment includes, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, isooctane, decane and dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; It can be carried out in a liquid phase using an aromatic hydrocarbon such as xylene or ethylbenzene, an inert solvent such as a gasoline fraction or a hydrogenated diesel oil fraction, or an olefin itself. It is also possible to do it in phase.

The pre-activation treatment is performed in the presence of hydrogen.
May be carried out, but the intrinsic viscosity [η _B] Is 15-100
Produces dl / g high molecular weight polyethylene (B)
Therefore, it is preferable not to use hydrogen.

In the preactivation treatment, the conditions for the preliminary (co) polymerization of propylene or a mixture of propylene and other olefins for the purpose of the (co) polymerization are as follows. 01
g to 100 g, and usually -40.
It is carried out at a temperature of from 100C to 100C and a pressure of from 0.1 MPa to 5 MPa for 1 minute to 24 hours.

The conditions for the pre-activation (co) polymerization of ethylene or a mixture of ethylene and other olefins are as follows.
0.01 to 5,000 g, preferably 0.05 to
2,000 g, more preferably 0.1 to 1,000 g
There is no particular limitation as long as the condition is such that the amount is formed in an amount of usually -40 ° C to 40 ° C, preferably -40 ° C to 30 ° C,
More preferably, at a relatively low temperature of about −40 ° C. to 20 ° C., 0.1 MPa to 5 MPa, preferably 0.2 MPa
The pressure is from 1 minute to 24 hours, preferably from 5 minutes to 18 hours, particularly preferably from 10 minutes to 12 hours under a pressure of from 5 to 5 MPa, particularly preferably from 0.3 to 5 MPa.

Further, after the preliminary activation treatment, propylene or a mixture of propylene and other olefins for the purpose of the main (co) polymerization is used for the purpose of suppressing a decrease in the main (co) polymerization activity due to the preactivation treatment. By addition of from 0.01 to 10 per gram of the transition metal compound catalyst component.
The reaction may be performed with a reaction amount of 0 g of the polypropylene (A).
In this case, the organometallic compound (AL1) and the electron donor (E
1), the solvent, and the amount of propylene or a mixture of propylene and other olefins can be used in the same range as the preactivated polymerization using ethylene or a mixture of ethylene and other olefins. It is preferably carried out in the presence of 0.005 to 10 mol, preferably 0.01 to 5 mol, of the electron donor per mol. The reaction is carried out at a temperature of -40 to 100 ° C and a pressure of 0.1 to 5 MPa for 1 minute to 24 hours.

The organometallic compound (A) used for the addition polymerization
L1), the electron donor (E1), and the type of the solvent,
The same ones as those used in the pre-activated polymerization using ethylene or a mixture of ethylene and other olefins can be used, and those having the same composition for the purpose of the present (co) polymerization for propylene or a mixture of propylene and other olefins can be used. be able to.

The preactivation catalyst may be used as it is or as an olefin (co) polymerization catalyst further containing an additional organometallic compound (AL2) and an electron donor (E2).
2 to 12 carbon atoms for obtaining a propylene polymer composition
Can be used for the main (co) polymerization of olefins.

The above-mentioned olefin main (co) polymerization catalyst comprises the above-mentioned preactivation catalyst and one or more transition metal atoms in the preactivation catalyst.
The sum of the organometallic compound (AL2) and the organometallic compound (AL1) in the activation catalyst per mole (AL1 + AL2)
0.05 to 3,000 mol, preferably 0.1 to 1,
The electron donor (E2) and the electron donor (E1) in the preactivated catalyst in total (E1 + E2) are 0 to 5,000 mol, preferably 0,000 mol, and 1 mol of the transition metal atom in the activated catalyst. It consists of 0-3,000 moles.

The content of the organometallic compound (AL1 + AL
If 2) is too small, the rate of the (co) polymerization reaction in the main (co) polymerization of propylene or propylene with other olefins is too slow. This is not only inefficient because no increase is observed, and the organometallic compound residue remaining in the finally obtained propylene polymer composition is undesirably increased. Further, the content of the electron donor (E
When (1 + E2) is too large, the (co) polymerization reaction rate is significantly reduced.

The types of the organometallic compound (AL2) and the electron donor (E2) that are additionally used as necessary in the olefin main (co) polymerization catalyst are as described above for the organometallic compound (AL1) and the electron donor. Those similar to the body (E1) can be used. One type may be used alone, or two or more types may be used in combination. Further, the same kind as that used in the pre-activation treatment may be different.

The catalyst for olefin main (co) polymerization may be a solvent present in the preactivated catalyst, an unreacted olefin,
A powder obtained by removing the organometallic compound (AL1) and the electron donor (E1) by filtration or decantation, or a suspension obtained by adding a solvent to the powder, and an additional organic metal The compound (AL2) and, if desired, an electron donor (E2) may be combined, and a powder obtained by removing a solvent and an unreacted olefin present by evaporation under reduced pressure or an inert gas stream or the like. A suspension obtained by adding a solvent to a body or a granular material may be combined with an organometallic compound (AL2) and an electron donor (E2), if desired.

In the method for producing a propylene polymer composition, the preactivated catalyst or the olefinic (co)
The amount of the polymerization catalyst used was 0.001 per liter of the polymerization volume, in terms of transition metal atoms in the preactivated catalyst.
~ 1,000 mmol, preferably 0.005-500
Use millimoles. By setting the amount of the transition metal compound catalyst component in the above range, it is possible to maintain an efficient and controlled (co) polymerization reaction rate of propylene or a mixture of propylene and another olefin.

For the main (co) polymerization of propylene or a mixture of propylene and another olefin in the production of the propylene-based polymer composition, an olefin (co) polymerization process known as the polymerization process can be used.
Specifically, propane, butane, pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, isooctane, decane and dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; gasoline fractions and hydrogen Slurry polymerization method to carry out (co) polymerization of olefin in an inert solvent such as petroleum diesel oil fraction, bulk polymerization method using olefin itself as a solvent,
A gas phase polymerization method in which (co) polymerization of olefins is carried out in a gas phase, a liquid phase polymerization method in which a polyolefin produced by (co) polymerization is in a liquid state, or a polymerization method combining two or more of these polymerization methods. Can be used.

When any of the above polymerization methods is used,
As polymerization conditions, the polymerization temperature is in the range of 20 to 120 ° C, preferably 30 to 100 ° C, particularly preferably 40 to 100 ° C, and the polymerization pressure is 0.1 to 5 MPa, preferably 0.3 to 5 MPa.
In the range of 5 MPa, the polymerization time is continuously, semi-continuously or batchwise, and the polymerization time is in the range of about 5 minutes to 24 hours. By adopting the above polymerization conditions,
The polypropylene as the component (a) can be produced with high efficiency and a controlled reaction rate.

In a more preferred embodiment of the method for producing a propylene polymer composition, the intrinsic viscosity [η _I ] of the propylene-olefin copolymer (a) produced in the (co) polymerization is from 0.2 to 0.2. 10 dl / g, preferably 0.7 to 5 dl / g, and the obtained propylene polymer composition contains 0.01 to 5% by weight of polyethylene (B) derived from the preactivated catalyst used. The polymerization conditions are selected so as to be within the range described above.

After completion of the (co) polymerization, a propylene copolymer composition is obtained through post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step, and a drying step, if necessary.

Examples of the inorganic filler used in the present invention include talc, calcium carbonate, potassium titanate whisker, mica, glass fiber and the like. These can be used alone or in combination of two or more.

The average particle size of the inorganic filler is 15 to 0.5.
When the average particle size is too large, the impact resistance is reduced. On the other hand, when the average particle size is too small, the inorganic filler particles are liable to agglomerate, and the appearance of the molded article is deteriorated and the impact resistance is liable to be reduced.

The mixing amount of the inorganic filler is 1 to 70 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the propylene polymer composition.
If the mixing amount of the inorganic filler is less than 1 part by weight, the rigidity of the resin sheet obtained and the molded article using the resin sheet become insufficient, and if it exceeds 70 parts by weight, the heating sheet during thermoforming. Is difficult to uniformly expand, and a local thin portion is easily generated in the obtained molded body.

In the present invention, the propylene polymer composition containing an inorganic filler in the resin composition (1) contains a third component for the purpose of further improving moldability and imparting impact resistance to the molded article. In addition, various (co) polymer resins other than the (co) polymer constituting the propylene-based polymer composition can be contained. Examples of the third component resin include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, ethylene-based resins such as ethylene-vinyl acetate copolymer, and syndiotactic. Tic polypropylene, 1-butene resin, cyclic olefin resin, petroleum resin, styrene resin, acrylic resin, fluorine resin, ethylene-olefin copolymer rubber, ethylene-olefin-nonconjugated diene copolymer rubber, hydrogenated styrene -Conjugated diene copolymer rubber, etc., and not only one kind but also two or more kinds can be used in combination.

Among the third component resins, at least one resin selected from the group consisting of (P1) to (P6) described below is preferable from the viewpoint of moldability. (P1) Density 0.910 to 0.930 g / cm ³ , melt flow rate (MFR) [190 ° C .;
N] is at least 0.01 g / 10 min, particularly preferably 0.1 g / 10 min.
~ 20 g / 10 min ethylene homopolymer, usually
It is called low density polyethylene. Examples of the method for producing the ethylene homopolymer include a method in which ethylene is polymerized by a high-pressure method using a peroxide as a catalyst.

(P2) Density of 0.920 to 0.950 g
/ Cm ³ , MFR [190 ° C .; 21.18N] is 0.0
1 g / 10 min or more, particularly preferably 0.1 to 20 g / 1
0 minute ethylene-vinyl acetate copolymer.

(P3) Density of 0.880 to 0.940 g
/ Cm ³ , MFR [190 ° C .; 21.18N] is 0.0
1 g / 10 min or more, particularly preferably 0.1 to 20 g / 1
It is a 0-minute ethylene-olefin copolymer, which is generally referred to as a linear low-density polyethylene, or a linear ultra-low-density polyethylene or an ultra-low-density polyethylene.

The ethylene-olefin copolymer comprises ethylene as a main monomer and, as a comonomer, at least one selected from the group consisting of olefins such as propylene, 1-butene, 1-hexene, 1-octene and the like as a Ziegler-Natta catalyst. And copolymerization in the presence of a metallocene catalyst or the like.

(P4) MFR [190 ° C .: 21.18]
N] is at least 0.01 g / 10 min, particularly preferably 0.1 g / 10 min.
Ethylene-olefin copolymer rubber of 10 to 10 g / 10 minutes.
The ethylene polymerization unit content is preferably from 50 to 80% by weight, particularly preferably from 65 to 80% by weight. The ethylene-olefin copolymer rubber has ethylene as a main monomer,
Propylene, 1-butene, 1-
Examples of the method include a method in which at least one selected from the group of olefins such as hexene is copolymerized in the presence of a vanadium catalyst or, in some cases, a titanium catalyst or a metallocene catalyst.

(P5) 1-butene homopolymer or 1-butene
Butene-olefin copolymer. MFR [190 ° C; 2
1.18N] is particularly preferably 0.1 to 20 g / 10 minutes.

(P6) Hydrogenated styrene-conjugated diene copolymer rubber. Butadiene and isoprene are particularly preferred as non-conjugated dienes.

The content of the third component resin is preferably from 1 to 70 parts by weight, particularly preferably from 5 to 50 parts by weight, based on 100 parts by weight of the propylene polymer. When the content is less than 1 part by weight, the effect of improving the moldability of the filler-filled resin sheet using the obtained resin composition (2) and the impact resistance of the molded article using the resin sheet are reduced. If it is insufficient, and if it exceeds 70 parts by weight, the rigidity of the obtained molded article is reduced.

Further, in addition to the above-mentioned components, the resin compositions (1) and (2) were formulated as stabilizers such as antioxidants, neutralizing agents, weathering agents, ultraviolet absorbers and other additives. A nucleating agent, an antistatic agent, a flame retardant, a coloring agent and the like can be contained within a range not to impair the object of the present invention,
The resin composition (1) also contains, as stabilizers, antioxidants, neutralizers, weathering agents, ultraviolet absorbers, and other additives such as nucleating agents, antistatic agents, flame retardants, coloring agents, and the like. It can be contained within a range that does not impair.

The resin composition (1) of the present invention is obtained by mixing the above-mentioned propylene-based copolymer composition with each component such as an inorganic filler. The resin composition (2) of the present invention can be obtained by further mixing a predetermined amount of the third component resin with the resin composition (1). For mixing these components, a conventional mixer such as a Henschel mixer (trade name) or a super mixer (trade name) with a high-speed stirrer, a ribbon blender or a tumbler may be used. When melt-kneading is required, an ordinary single-screw extruder or a twin-screw extruder is used. The kneading temperature is generally from 190 to 300C, preferably from 200 to 270C.

The filler-filled resin sheet of the present invention can be produced by a known molding method (extrusion molding, calender molding, compression molding) using the above-mentioned resin composition (1) or resin composition (2). Molding method, cast molding method, etc.). Extrusion molding is preferred among the known and commonly used molding methods because productivity is good. Specifically, the T-die method using a device (T-die sheet forming machine) having an extruder, a T-die, a cooling roll, a guide roll, a take-up roll, a trimming cutter, a masking, a fixed-size cutting cutter, a stacker and the like is more preferable. .

The extrusion temperature is 1 in terms of sheet appearance and moldability.
80-280 degreeC is preferable. When the extrusion temperature is 180 ° C. or higher, the propylene-based copolymer compositions constituting the resin compositions (1) and (2) and various resins contained for the purpose of improving moldability and impact resistance are sufficiently obtained. The surface of the filler-filled resin sheet obtained by melting is not shark-skin-like and has a good appearance. When the temperature exceeds 280 ° C., thermal degradation of the resin compositions (1) and (2) due to heat is apt to occur. As a result, the melt tension of the obtained filler-filled resin sheet is not maintained, and a good molded product cannot be obtained.

The temperature of the cooling roll is preferably 5 to 100 ° C. because a sheet having an excellent appearance can be obtained. If the cooling roll temperature is 5 ° C. or more, the cooling roll does not condense and the obtained filler-filled resin sheet does not have a spot-like pattern, and a good appearance is obtained. And a good appearance can be obtained without forming a linear pattern that occurs when unwinding a roll-shaped sheet.

The molding speed of the filler-filled resin sheet is as follows:
It is 0.1 to 100 m / min in terms of productivity. When the speed is 0.1 m / min or more, a sheet having a uniform thickness can be obtained and the defective rate is small. When the speed is 100 m / min or less, the sheet can be sufficiently cooled.

The filler-filled resin sheet of the present invention is not limited to a single layer, but also has a gloss of the surface of a molded article obtained by thermoforming and an adhesive property with other resins such as an adhesive, a printing ink, a urethane resin and the like. And a multilayer sheet with a resin other than the resin composition of the present invention for the purpose of improving. In the case of a multi-layer sheet, the thickness ratio between the resin layer using the resin composition (1) or the resin composition (2) of the present invention and the resin layer using the above-mentioned other resin is determined by the moldability during thermoforming and the obtainability. There is no particular limitation as long as the rigidity of the molded body does not significantly decrease,
The thickness of the layer using the resin composition (1) or the resin composition (2) of the present invention is preferably 50% or more of the total thickness.

The molded article of the present invention is a molded article obtained by thermoforming the above-mentioned filler-filled resin sheet. As the method of thermoforming, as vacuum forming method, pressure forming method and their application,
Free drawing molding method, plug and ridge molding method, ridge molding method, match molding method, straight molding method, drape molding method, reverse draw molding method, air slip molding method, plug assist molding method, plug assist reverse draw molding method, A snapback molding method, a method combining these, or the like can be applied.

[0117]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows.

-Propylene-based polymer composition- (1) Intrinsic viscosity [η]: The intrinsic viscosity measured in tetralin at 135 ° C, a value measured by an Ostwald viscometer (manufactured by Mitsui Toatsu Chemicals, Inc.). (Unit: dl / g).

(2) Melt tension (MS): 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 0.1 part by weight of calcium stearate based on 100 parts by weight of the propylene polymer composition. Was mixed, and the mixture was granulated at 230 ° C. using an extruder having a diameter of 40 mm to obtain pellets. The pellets are heated to 230 ° C. in the apparatus using a melt tension type 2 (manufactured by Toyo Seiki Seisaku-sho, Ltd.) and extruded from a 2.095 mm diameter nozzle into the atmosphere at 23 ° C. at a speed of 20 mm / min. And a value obtained by measuring the tension when the strand is pulled at a speed of 3.14 m / min (unit: cN).

-Formability of sheet and physical properties of molded article-Heating behavior: To evaluate the thermoformability of the sheet as a model, a sheet having a thickness of 1.5 mm was subjected to 400 mm x 400 mm.
And fix the fixed sample sheet to 3
It was placed in a heating furnace maintained at 00 ° C. and heated, and the following items were measured. (When a sheet using a propylene-based resin is heated, the following phenomenon generally occurs. First, the central portion of the sheet sags by being heated. Then, the sagging portion returns, Finally, the sagging occurs again).

The amount of droop at the time of recovery: the amount of droop when the sheet that sagged in the early stage of heating has returned most (unit: mm). The holding time: the time from the most returned state to the time of sag of 10 mm (unit: seconds). And the longer the holding time, the better the thermoforming. A sheet that does not cause a return phenomenon has very poor thermoformability.

Uneven thickness and appearance of the molded article: To evaluate the thermoformability of the sheet, a sheet having a thickness of 1.5 mm was placed at the center of a heating furnace having a ceramic heater at a temperature of 450 ° C. (350 mm between heaters) in the MD direction of the sheet. (Flow direction at the time of sheet molding) is set to be the longitudinal direction of the mold, and 7
After heating for 0 to 90 seconds, the rib 50 mm, the opening 300
mm × 600mm, depth 420mm, bottom 250mm ×
Using a 550 mm female mold (concave mold), plug-assist vacuum molding was performed, and the following evaluation was performed. Uneven thickness: The thickness of the thinnest part of the side surface of the molded body was measured. Judgment ：: The thinnest part has a thickness of 0.1 mm or more. ：: The thinnest part has a thickness of less than 0.1 mm. X: A hole is formed. Judgment ：: No wrinkles in the molded body ×: Wrinkles occurred in the molded body

Young's modulus: The bottom of the thermoformed article was cut out, and the Young's modulus was measured according to ASTM D882. The tensile direction of the molded body was the longitudinal direction of the bottom of the molded body (corresponding to the MD direction of the sheet), and the tensile speed was 5 mm / min. The higher the value of the Young's modulus, the higher the rigidity.

Example 1 (1) Preparation of transition metal compound catalyst component Decane 3 was placed in a stainless steel reactor equipped with a stirrer.
7.5 liters, 7.14 kg of anhydrous magnesium chloride,
And 35.1 liters of 2-ethyl-1-hexanol were mixed and reacted with heating at 140 ° C. for 4 hours with stirring to obtain a uniform solution. 1.67 kg of phthalic anhydride was added to the homogeneous solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the uniform solution.

After cooling the obtained homogeneous solution to room temperature (23 ° C.), the whole of the uniform solution was dropped into 200 liters of titanium tetrachloride kept at -20 ° C. over 3 hours. After the dropwise addition, the temperature was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 5.03 liters of di-i-butyl phthalate was added, and the reaction was carried out with stirring and maintaining at 110 ° C. for 2 hours.
After the completion of the reaction for 2 hours, the solid portion was collected by hot filtration, and the solid portion was resuspended with 275 liters of titanium tetrachloride. The reaction was continued at 110 ° C. for 2 hours again.

After the completion of the reaction, a solid portion was collected again by hot filtration, and sufficiently washed with n-hexane until no free titanium was detected in the washing solution. Subsequently, the solvent was separated by filtration, and the solid portion was dried under reduced pressure to obtain a titanium-containing supported catalyst component (transition metal compound catalyst component) containing 2.4% by weight of titanium.

(2) Preparation of Preactivated Catalyst After replacing a stainless steel reactor having an inner volume of 30 liters with inclined blades with nitrogen gas, 18 liters of n-hexane and 60 parts of triethylaluminum (organic metal compound (AL1)) were added.
After adding 150 mmol (75.16 mmol in terms of titanium atom) of the supported catalyst component containing titanium prepared in the preceding paragraph, 500 g of propylene was supplied, and 4 g at -2 ° C.
Preliminary polymerization was performed for 0 minutes.

Separately, after prepolymerization performed under the same conditions,
As a result of analyzing the formed polymer, the catalyst containing titanium
3.0 g of polypropylene (A) is produced per 1 g of component
Of polypropylene (A) at 135 ° C.
Intrinsic viscosity (η _AIs 2.8 dl / g
Was.

After completion of the reaction time, unreacted propylene was discharged to the outside of the reactor, and the gas phase of the reactor was replaced with nitrogen once. Then, while maintaining the temperature inside the reactor at -1 ° C, the reaction was continued. Ethylene was continuously supplied to the reactor for 5 hours so as to maintain the pressure in the vessel at 0.59 MPa, and preactivation polymerization was performed. Separately, as a result of analyzing the polymer formed after the preactivation polymerization performed under the same conditions, 63.8 g of the polymer was present per 1 g of the titanium-containing supported catalyst component, and the intrinsic polymer was measured in tetralin at 135 ° C. Viscosity [η
_T ] was 30.8 dl / g.

The amount of polyethylene (B) per gram of the titanium-containing supported catalyst component (W _B ) produced by the preactivation polymerization with ethylene is the amount of the polymer produced per gram of the titanium-containing supported catalyst component after the preactivation treatment. The difference between (W _T ) and the amount of polypropylene (A) produced per g of the titanium-containing supported catalyst component after prepolymerization (W _A ) is determined by the following equation. W _B = W _T -W _A

The intrinsic viscosity [η _B ] of the polyethylene (B) produced by the preactivation polymerization with ethylene is the intrinsic viscosity [η _A ] of the polypropylene (A) produced by the prepolymerization and the intrinsic viscosity [η _A ] produced by the preactivation treatment. It can be obtained from the intrinsic viscosity [η _T ] of the polymer obtained by the following equation. _{[Η B] = ([η} T] × W T - [η A] × W A) / (W T -
W _A ) The amount of polyethylene (B) produced by preactivated polymerization with ethylene according to the above formula is 60.8 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _B ] is 32.2 d.
1 / g.

After the completion of the reaction time, unreacted ethylene was discharged to the outside of the reactor, and the gas phase of the reactor was replaced with nitrogen once to obtain a preactivated catalyst slurry for main (co) polymerization.

(3) Production of Propylene-Based Polymer Composition (Main (Co) polymerization of Propylene) Continuous horizontal gas-phase polymerization reactor (I) equipped with a nitrogen-substituted, 110-liter internal volume stirrer (length) (Sa / diameter = 3.7)
, 25 kg of polypropylene powder was introduced, and the preactivated catalyst slurry was used as a titanium-containing supported catalyst component at 0.62 g / h, triethylaluminum (organic metal compound (AL2)) and diisopropyldimethoxysilane (electron donor (E2)). )) Was continuously supplied at a molar ratio of 90 and 15 to titanium atoms in the titanium-containing supported catalyst component.

Further, under the conditions of a polymerization temperature of 70 ° C., the ratio of the hydrogen concentration in the polymerization vessel to the propylene concentration was 0.001.
4 and then the pressure in the polymerization vessel was 1.7.
Propylene was respectively supplied into the polymerization vessel so as to maintain 7 MPa, and gas phase polymerization of propylene in the polymerization step (I) was performed. A part of the obtained polymer was extracted and analyzed. The content of polyethylene produced by preactivated polymerization in the polymer was 0.47% by weight, and the intrinsic viscosity [η] of the polymer measured in tetralin at 135 ° C. was 2.82 dl / g. The intrinsic viscosity [η _A-PP ] of the polypropylene (propylene homopolymer) in the polymerization step (I) was 2.68 dl / g.

The polymer obtained in the polymerization step (I) was
Polymerizer (II) at 0 ° C. (continuous horizontal gas phase polymerizer equipped with a stirrer having an internal volume of 110 liters, length / diameter = 3.
7), and the hydrogen concentration ratio and the ethylene concentration ratio with respect to propylene in the polymerization vessel are 0.04 and 0.
2 and the pressure in the polymerization vessel is 1.57 MPa
Was supplied so as to maintain the polymerization step (II).

During the polymerization reaction, the polymer was withdrawn at a rate of 9.5 kg / h from the polymerization vessel so as to maintain the level of the polymer in the polymerization vessel at 60% by volume.

[0137] The extracted polymer was replaced with steam at 5% by volume.
Contact treatment with nitrogen gas at 100 ° C for 30 minutes,
A polymer having an intrinsic viscosity [η _I ] of 2.82 dl / g and an ethylene polymerization unit content of 8.8% by weight was obtained.

The obtained polymer was a propylene-based polymer composition having a polyethylene content of 0.40% by weight corresponding to the component (b) and a propylene-olefin block copolymer having a content of 0.40% by weight. The copolymer has an intrinsic viscosity [η _A ] of 2.70 dl / g, an ethylene polymerization unit content of 8.4% by weight, and a polymerization ratio of the polymer obtained in the polymerization step (II) (propylene-olefin block of component (a)). The polymerization ratio in the copolymer) was 14.8% by weight, the ethylene polymerization unit content was 57% by weight, and the intrinsic viscosity [η _A-RC ] was 2.80 dl / g.

The polymer obtained in the polymerization step (II) has an ethylene polymerization unit content and a polymerization ratio of ethylene /
Prepare a copolymer in which the reaction ratio of propylene is changed,
Using this as a standard sample, a calibration curve was made by infrared absorption spectroscopy, and the ethylene / propylene reaction amount ratio in the polymerization step (II) (the content of ethylene polymerization units in the polymer obtained in the polymerization step (II)) was determined. Further, the polymerization ratio was calculated from the ethylene polymerization unit content in all the polymers.

(4) Production of Resin Composition (1) 20 parts by weight of talc (average particle size: 8 μm) as an inorganic filler was added to 100 parts by weight of a propylene polymer composition, and tetrakis [methylene-3- (3′- 5'-di-t-butyl-4'-hydroxyphenyl) propionate].
3 parts by weight, 1,1,3-tris (2-methyl-5-t-
0.1 parts by weight of butyl-4-hydroxyphenyl) butane, 0.01 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, and 0.1 parts by weight of calcium stearate are mixed. Then, a pellet-shaped resin composition (1) was obtained using a granulator having a cylinder set temperature of 230 ° C. and a barrel inner diameter of 65 mmφ.

(5) Production of Filler-Filled Resin Sheet Using the resin composition (1) obtained in the above (4), using a T-die sheet molding machine (polishing method) having an extruder barrel inner diameter of 65 mmφ, the resin temperature was measured. 230 ° C, cooling roll temperature 8
900 mm width, thickness 1. 0 ° C, take-off speed 1.0 m / min.
A 5 mm sheet was produced. Table 1 shows the moldability of the obtained filler-filled resin sheet and the Young's modulus of the molded article obtained by thermoforming.

Example 2 (1) Preparation of transition metal compound catalyst component Under the same conditions as in Example 1, a titanium-containing supported catalyst component similar to that of Example 1 was obtained.

(2) Preparation of Preactivated Catalyst In Example 1, the amount of the produced polyethylene (B) per g of the transition metal compound catalyst component (g / g) was changed to 60 by changing the conditions of the preactivated polymerization with ethylene. .8 to 7
2.2 A preactivated catalyst slurry was obtained according to Example 1, except that the intrinsic viscosity [η _B ] (dl / g) was changed from 32.2 to 31.0.

(3) Production of Propylene Polymer Composition (Propylene (Main) Polymerization) Except for changing the hydrogen concentration ratio to the propylene concentration in the polymerization vessel (I) to 0.0017 in Example 1. Carried out the polymerization step (I) under the conditions according to Example 1.
The intrinsic viscosity [η _A-PP ] of the polypropylene in the polymerization step (I) was 2.48 dl / g.

The polymerization step (II) was carried out under the same conditions as in Example 1 except that the ratio of the hydrogen concentration to the propylene concentration in the polymerization vessel (II) was changed to 0.06. A polymer having a viscosity [η _I ] of 2.62 dl / g and an ethylene polymerization unit content of 8.7% by weight was obtained. The obtained polymer is a propylene-based polymer composition having a polyethylene content of 0.47% by weight corresponding to the component (b) by preactivated polymerization. The viscosity [η _A ] is 2.49
dl / g, the content of the ethylene polymerized unit was 8.2% by weight, and the polymerization rate of the polymer obtained in the polymerization step (II) (the polymerization rate of the component (a) in the propylene-olefin block copolymer) was 14. 5% by weight, ethylene polymerization unit content is 5
The intrinsic viscosity [η _A-RC ] was 2.57 dl / g.

(4) Production of Resin Composition (1) A pellet-shaped resin composition (1) was obtained according to Example 1, except that the propylene polymer composition obtained by the above production method was used. Was.

(5) Production of Filler-filled Resin Sheet A filler-filled resin sheet was produced using the above resin composition (1) under the same conditions as in Example 1. Table 1 shows the moldability of the obtained resin sheet and the Young's modulus of the molded article obtained by thermoforming.

Comparative Example 1 (1) Preparation of Transition Metal Compound Catalyst Component The same titanium-containing supported catalyst component as in Example 1 was obtained under the same conditions as in Example 1.

(2) Preparation of preactivated catalyst In Example 1, the amount of polyethylene (B) produced per gram of the transition metal compound catalyst component (g / g) was changed to 60 by changing the conditions of the preactivated polymerization with ethylene. 0.8 to 0.
14. Increase the intrinsic viscosity [η _B ] (dl / g) from 32.2 to 2
A preactivated catalyst slurry was obtained under the same conditions as in Example 1 except that the slurry was changed to 7.9.

(3) Production of Propylene Polymer Composition (Propylene (Main) Polymerization) The polymerization step (I) was carried out under the same conditions as in Example 1. Intrinsic viscosity [η _A-PP ] of polypropylene in polymerization step (I)
Was 2.68 dl / g.

The polymerization step (II) was carried out under the same conditions as in Example 1 to obtain a polymer having an intrinsic viscosity [η _I ] of 2.70 dl / g and an ethylene polymerization unit content of 8.4% by weight. The obtained polymer is a propylene-based polymer composition having a polyethylene content of 0.00091% by weight corresponding to the component (b) obtained by preactivation polymerization, and the propylene-olefin block copolymer as the component (a) has a specific content. The viscosity [η _A ] is 2.70 dl / g, the ethylene polymerization unit content is 8.4% by weight, and the polymerization ratio (a) of the polymer obtained in the polymerization step (II) is a component of the propylene-olefin block copolymer. Is 14.8% by weight, the ethylene polymerization unit content is 57% by weight, and the intrinsic viscosity [η _A-RC ] is 2.80 dl.
/ G.

(4) Production of Resin Composition A pellet-shaped resin composition (1) was prepared in accordance with Example 1, except that the propylene polymer composition obtained above was used.
I got

(5) Production of Filler-filled Resin Sheet A filler-filled resin sheet was produced according to Example 1 except that the resin composition obtained above was used. Table 1 shows the moldability of the obtained resin sheet and the Young's modulus of the molded article obtained by thermoforming.

Comparative Example 2 Comparative Example 1 was repeated except that no inorganic filler was mixed in the production of the resin composition (1) (4) of Comparative Example 1.
A resin sheet was manufactured under the same conditions as in the above. Table 1 shows the thermoformability of the obtained resin sheet and the Young's modulus of the molded product obtained by thermoforming.

[0155]

[Table 1]

Example 3 In the preparation of the resin composition (1) in (4) of Example 1, the mixing amount of each component was changed to 100 parts by weight of the propylene-based polymer composition, and talc (average particle size) was used as an inorganic filler. 8μ diameter
m) of 30 parts by weight and low-density polyethylene [MFR (190 ° C .; 21.18 N) 2.5 g /
10 minutes, 10 parts by weight of a density of 0.918 cm ³ ] was added to tetrakis [methylene-3- (3′-5′-di-tert-butyl-
4'-hydroxyphenyl) propionate]
Parts by weight, 0.1 part by weight of 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane, and tris (2,4-di-t-butylphenyl) phosphite A filler-filled resin sheet was produced in the same manner as in Example 1 except that the resin composition (2) in which 0.01 parts by weight of calcium stearate was changed to 0.1 part by weight was used. Table 2 shows the thermoformability of the obtained sheet and the Young's modulus of the molded article obtained by thermoforming.

Example 4 In the preparation of the resin composition (1) of (4) of Example 1, the amount of each component was changed to talc (average particle size: 8 μm) based on 100 parts by weight of the propylene polymer composition. 60 parts by weight,
Low-density polyethylene [MFR (1
90 ° C .; 21.18 N) 2.5 g / 10 min, density 0.9
18 cm ³ ] and ethylene-propylene copolymer rubber [MF
R (190 ° C .; 21.18 N) 0.4 g / 10 min, propylene polymerization unit content 23% by weight], 10 parts by weight of tetrakis [methylene-3- (3′-5′-di-t-butyl- 4'-hydroxyphenyl) propionate], 0.3 parts by weight, and 1,1,3-tris (2-methyl-5-
t-butyl-4-hydroxyphenyl) butane is 0.1
In accordance with Example 1, except that the parts by weight were changed to 0.01 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, and 0.1 parts by weight of calcium stearate, the filler was changed. -A filled resin sheet was produced. Table 2 shows the thermoformability of the obtained filler-filled resin sheet and the Young's modulus of the molded article obtained by thermoforming.

Comparative Example 3 In the preparation of the resin composition (4) of Comparative Example 1, the mixing amount of each component was changed to 30 parts by weight of talc (average particle size: 8 μm) with respect to 100 parts by weight of the propylene polymer composition. Part, low density polyethylene [MFR (190
C; 21.18N) 2.5 g / 10 min, density 0.918
cm ³ ], 10 parts by weight of tetrakis [methylene-3-
(3'-5'-di-t-butyl-4'-hydroxyphenyl) propionate], 0.3 parts by weight, 1,1,3-
0.1 parts by weight of tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane, 0.01 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and calcium stearate A filler-filled resin sheet was produced under the same conditions as in Comparative Example 1 except that the ratio was changed to 0.1 parts by weight. Table 2 shows the thermoformability of the obtained sheet and the Young's modulus of the molded article obtained by thermoforming.

Comparative Example 4 In the preparation of the resin composition (4) of Comparative Example 1, the amount of each component was changed to 60 parts by weight of talc (average particle size: 8 μm) with respect to 100 parts by weight of the propylene polymer composition. Part, low density polyethylene [MFR (190
C; 21.18N) 2.5 g / 10 min, density 0.918
cm ³ ] and ethylene-propylene copolymer rubber [MFR
(190 ° C .; 21.18 N) 0.4 g / 10 min, propylene polymerization unit content 23% by weight], and 10 parts by weight of tetrakis [methylene-3- (3′-5′-di-t-butyl-4). '-Hydroxyphenyl) propionate].
3 parts by weight, 1,1,3-tris (2-methyl-5-t-
Butyl-4-hydroxyphenyl) butane was changed to 0.1 part by weight, tris (2,4-di-t-butylphenyl) phosphite was changed to 0.01 part by weight, and calcium stearate was changed to 0.1 part by weight. A filler-filled resin sheet was manufactured according to Comparative Example 1 except for the above. Table 2 shows the thermoformability of the obtained sheet and the Young's modulus of the molded article obtained by thermoforming.

[0160]

[Table 2]

Example 5 (1) Preparation of transition metal compound catalyst component Under the same conditions as in Example 1, the same titanium-containing supported catalyst component as in Example 1 was obtained.

(2) Preparation of Preactivated Catalyst Example 1 using the titanium-containing supported catalyst component obtained above.
Under the same conditions as above, a preactivated catalyst slurry was obtained.

(3) Production of Propylene Polymer Composition (Main (Co) polymerization of Propylene) Continuous horizontal gas phase polymerization reactor (length / diameter) equipped with a nitrogen-substituted, 110-liter internal volume stirrer = 3.7), 25 kg of polypropylene powder was introduced, and the preactivated catalyst slurry was added as a titanium-containing supported catalyst component at 0.65 g / h, triethylaluminum (organic metal compound (AL2)) and diisopropyldimethoxysilane (electron). A 15% by weight n-hexane solution of the donor (E2)) with respect to the titanium atom in the titanium-containing supported catalyst component.
They were continuously supplied so that the molar ratios became 90 and 15, respectively.

Further, under the condition of a polymerization temperature of 70 ° C., the ratio of the hydrogen concentration in the polymerization vessel to the propylene concentration was 0.002.
Hydrogen, and the pressure inside the polymerization vessel is 2.15.
Propylene was supplied into each polymerization vessel so as to maintain the MPa, and gas phase polymerization of propylene was continuously performed for 150 hours.

During the polymerization reaction, the polymer was withdrawn at a rate of 11 kg / h from the polymerization vessel so that the level of the polymer held in the polymerization vessel was maintained at 60% by volume.

[0166] 5% by volume of water vapor was added to the extracted polymer.
Contact treatment with nitrogen gas at 100 ° C for 30 minutes,
A polymer having an intrinsic viscosity [η _I ] of 2.75 dl / g was obtained.

The obtained polymer was a propylene copolymer composition having a polyethylene content of 0.36% by weight and produced by preactivated polymerization corresponding to the component (b).
The intrinsic viscosity [η _A ] of the polypropylene as the component (a) is 2.
It was 64 dl / g.

(4) Production of Resin Composition (2) For 100 parts by weight of the propylene-based polymer composition, 25 parts by weight of talc (average particle size: 8 μm), and low-density polyethylene [MFR ( 190 ° C; 21.18
N) 2.5 g / 10 min, density 0.918 cm ³ ] and ethylene-propylene copolymer rubber [MFR (190 ° C .;
21.18N) 0.4 g / 10 min, propylene polymerization unit content 23% by weight], and 10 parts by weight of tetrakis [methylene-3- (3'-5'-di-t-butyl-4'-hydroxyphenyl) ) Propionate], 0.3 parts by weight,
1,1,3-tris (2-methyl-5-t-butyl-4
-Hydroxyphenyl) butane at 0.1 parts by weight, tris (2,4-di-t-butylphenyl) phosphite at 0.01 parts by weight, and calcium stearate at 0.1 parts by weight, and then mixed. Cylinder set temperature 230
A pellet-shaped resin composition (2) was obtained using a granulator having a barrel inner diameter of 65 mmφ at ℃.

(5) Production of Filler-filled Resin Sheet A filler-filled resin sheet was produced in accordance with Example 1 except that the resin composition (2) obtained above was used. Table 3 shows the moldability of the obtained sheet and the Young's modulus of the molded body obtained by thermoforming.

Example 6 (1) Preparation of transition metal compound catalyst component Under the same conditions as in Example 1, the same titanium-containing supported catalyst component as in Example 1 was obtained.

(2) Preparation of Preactivated Catalyst A preactivated catalyst slurry was obtained using the titanium-containing supported catalyst component obtained above under the same conditions as in Example 2.

(3) Production of Propylene Polymer Composition (Main (Co) polymerization of Propylene) In Example 5, the supply amount of the preactivated catalyst slurry was changed to 0.64 g / h, and hydrogen in the polymerization vessel was changed. The gas phase polymerization of propylene was carried out according to Example 4 except that the ratio of the concentration to the propylene concentration was changed to 0.003, to obtain a polymer having an intrinsic viscosity [η _I ] of 2.42 dl / g. The obtained polymer is a propylene-based polymer composition having a polyethylene content of 0.42% by weight and produced by preactivated polymerization corresponding to the component (b), and has an intrinsic viscosity [η _A of polypropylene of the component (a). ] Was 2.30 dl / g.

(4) Production of Resin Composition (2) In Example 5, ethylene-propylene copolymer rubber was prepared by adding 0.7 g / 10 minutes of MFR (190 ° C .; 21.18 N)
A pellet-shaped resin composition (2) was produced in the same manner as in Example 4 except that the content of the propylene polymerization unit was changed to 27% by weight.

(5) Production of filler-filled resin sheet A filler-filled resin sheet was produced in the same manner as in Example 1 except that the resin composition (2) obtained above was used. Table 3 shows the moldability of the obtained sheet and the Young's modulus of the molded body obtained by thermoforming.

Comparative Example 5 (1) Preparation of Transition Metal Compound Catalyst Component Under the same conditions as in Example 1, a titanium-containing supported catalyst component similar to that of Example 1 was obtained.

(2) Preparation of Preactivated Catalyst Comparative Example 1 using the titanium-containing catalyst component obtained in (1)
Under the same conditions as above, a preactivated catalyst slurry was obtained.

(3) Production of Propylene Polymer Composition (Main (Co) polymerization of Propylene) Propylene was subjected to gas phase polymerization under the same conditions as in Example 5.
A polymer having an intrinsic viscosity [η _I ] of 2.64 dl / g was obtained.
The obtained polymer had a polyethylene content of 0.00083 produced by preactivation polymerization corresponding to the component (b).
% Of a propylene polymer composition, and the intrinsic viscosity [η _A ] of the polypropylene as the component (a) is 2.64 dl /
g.

(4) Production of Resin Composition In Example 5, ethylene-propylene copolymer rubber was prepared by adding 0.7 g / 10 minutes of MFR (190 ° C .; 21.18 N)
A pellet-shaped resin composition was produced in the same manner as in Example 4 except that the content of the propylene polymerization unit was changed to 27% by weight.

(5) Production of Filler-filled Resin Sheet A filler-filled resin sheet was produced according to Example 1, except that the resin composition obtained in the above (4) was used. Table 3 shows the moldability of the obtained sheet and the Young's modulus of the molded article obtained by thermoforming.

Comparative Example 6 A resin sheet was produced in the same manner as in Comparative Example 5 except that no inorganic filler was mixed in the production of the resin composition (4) of Comparative Example 5. Table 1 shows the thermoformability of the obtained resin sheet and the Young's modulus of the molded product obtained by thermoforming.

[0181]

[Table 3]

Example 7 In the preparation of the resin composition (2) of (5) of Example 5, the mixing amount of each component was changed to talc (average particle size: 8 μm) based on 100 parts by weight of the propylene polymer composition. 55 parts by weight,
Low density polyethylene [MFR (19
0 ° C .; 21.18 N) 2.5 g / 10 min, density 0.91
8 cm ³ ], 15 parts by weight, 0.4 g of ethylene-1-octene copolymer rubber [MFR (190 ° C .; 21.18 N)]
10 minutes, 1-octene polymerized unit content 28% by weight]
0 parts by weight, tetrakis [methylene-3- (3′-5′-
0.3 parts by weight of di-t-butyl-4'-hydroxyphenyl) propionate] and 0.1 parts by weight of 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane. Parts, tris (2,4-di-t-butylphenyl) phosphite was changed to 0.01 parts by weight, and calcium stearate was changed to 0.1 parts by weight. Production of a resin sheet was performed. Table 4 shows the thermoformability of the obtained sheet and the Young's modulus of the molded body obtained by thermoforming.

Comparative Example 7 In the preparation of the resin composition (4) of Comparative Example 5, the mixing amount of each component was 55 parts by weight of talc (average particle size: 8 μm) with respect to 100 parts by weight of the propylene polymer composition. Part, low density polyethylene [MFR (190 ° C .;
21.18N) 2.5 g / 10 min, density 0.918 cm
³ ] and 0.4 g / 10 of ethylene-propylene copolymer rubber [MFR (190 ° C .; 21.18 N)].
Propylene polymerized unit content of 23% by weight], 20 parts by weight of tetrakis [methylene-3- (3′-5′-di-t)
-Butyl-4'-hydroxyphenyl) propionate], 0.1 part by weight of 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane, 0.1 part by weight of tris Filler-filled resin sheet according to Example 1, except that 0.01 parts by weight of (2,4-di-t-butylphenyl) phosphite and 0.1 parts by weight of calcium stearate were used. Was manufactured. Table 4 shows the thermoformability of the obtained sheet and the Young's modulus of the molded body obtained by thermoforming.

[0184]

[Table 4]

Example 8 To 100 parts by weight of the propylene polymer composition produced in (3) of Comparative Example 5, tetrakis [methylene-3-
(3'-5'-di-t-butyl-4'-hydroxyphenyl) propionate], 0.3 parts by weight, 1,1,3-
0.1 parts by weight of tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane, 0.01 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and calcium stearate 0.1 parts by weight were mixed, and then a pellet-shaped resin composition (α) was produced using a granulator having a cylinder set temperature of 230 ° C. and a barrel inner diameter of 65 mmφ.

Using an extruder having a barrel inner diameter of 65 mmφ and a co-pressing T-die sheet molding machine having a barrel inner diameter of 40 mmφ, the same resin composition (1) as produced in (4) of Example 1 was applied to a 65 mmφ extruder. The above resin composition (α) was supplied to a 40 mmφ extruder, and the resin temperature was 230
C., a cooling roll temperature of 80.degree. C., and a take-up speed of 1.0 m / min to produce a two-layer, two-layer sheet having a width of 900 mm and a thickness of 1.5 mm. The thickness configuration of each layer is such that the layer composed of the resin composition (1) is 1.2 mm, the layer composed of the resin composition (α) is 0.1 mm.
3 mm. Table 5 shows the moldability of the obtained sheet and the Young's modulus of the molded article obtained by thermoforming. (Note that the resin composition (α) was used for the purpose of increasing the surface gloss of the molded article, etc.).

[0187]

[Table 5]

Example 9 35 parts by weight of calcium carbonate (average particle size: 2 μm) and hydrogenated styrene were added to 100 parts by weight of the same composition as the propylene polymer composition produced in Example 1, (3). -Butadiene copolymer rubber [Clayton G1 by Shell Chemical Co., Ltd.]
652], 35 parts by weight of polystyrene [Styrone 605, Asahi Kasei Corporation], tetrakis [methylene-3- (3′-5′-di-t-butyl-4 ′).
-Hydroxyphenyl) propionate], 0.1 part by weight of 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane, tris (2,4- 0.01 parts by weight of di-t-butylphenyl) phosphite and 0.1 part of calcium stearate
Mix in parts by weight and then set cylinder temperature 2
Using a granulator having a barrel inner diameter of 65 mmφ at 30 ° C., a pellet-shaped resin composition (β) was produced.

Using a co-extrusion T-die sheet molding machine having a total of three extruders, two extruders having a barrel inner diameter of 65 mmφ and two extruders having a barrel inner diameter of 40 mmφ, a 65 mmφ extruder was used. The same composition as the resin composition (2) produced in the above was used to apply the above resin composition (β) to one 40 mmφ extruder and the resin composition (α) of Example 8 to another 40 mmφ extruder. Each of them is supplied at a resin temperature of 230 ° C., a cooling roll temperature of 80 ° C., a take-up speed of 1.0 m / min, and a width of 9 m.
A three-layer, three-layer sheet having a thickness of 00 mm and a thickness of 1.5 mm was produced. The composition of each layer (thickness of each layer) is as follows: surface layer: layer (0.3 mm) composed of resin composition (β) and layer (0.2 mm) composed of resin composition (α); inner layer: ( Layer (1.0) consisting of the same composition as that produced in (4)
mm). Table 6 below shows the moldability of the obtained sheet and the Young's modulus of the molded body obtained by thermoforming.
(In addition, the resin composition (α) enhances the surface gloss of the molded article, for example, for the purpose of enhancing the adhesiveness to the urethane foam resin or the like used as a heat insulating material for the molded article. Used for the purpose of).

[0190]

[Table 6]

Example 10 A resin composition (1) or a resin composition similar to the resin composition (2) used in Examples 1, 4 and 7 was subjected to a T-die sheet molding machine having an extruder barrel inner diameter of 65 mmφ. Each of them was processed into a filler-filled resin sheet having a width of 900 mm and a thickness of 3.0 mm. The obtained sheet is heated up and down at 450 ° C. with a ceramic heater (a heater distance of 350 ° C.).
mm), set in the center of a heating furnace having
After heating for 20 seconds, rib 50mm, opening 980mm
× 510mm, depth 400mm, bottom 910mm × 44
Using a 7 mm female mold, plug assist reverse draw molding was performed.

A thermoformed article using a resin sheet obtained from the same resin composition as used in Examples 1, 4, and 7 had a uniformity without wrinkles and a portion where the thickness was significantly reduced. It was a high compact.

Comparative Example 8 Plug assist reverse draw molding was performed under the same conditions as in Example 10 except that the same resin composition as used in Comparative Examples 1, 4 and 7 was used.

The sheets processed using the same resin compositions as those used in Comparative Examples 1, 4 and 7 could not be heated until the sheets drooped significantly and softened sufficiently (the sheets were not heated). Because it will hang down and contact the lower heater). Further, in the molded article heated and molded to just before contact with the lower heater, a hole was opened in the molded article, and a good molded article could not be obtained.

Example 10 was repeated except that the same resin composition used in Comparative Examples 2 and 6 was used.
The plug assist reverse draw molding was performed under the same conditions.

The sheets processed using the same resin compositions as those used in Comparative Examples 2 and 6 could not be heated until the sheets drooped significantly and softened sufficiently (the sheets drooped downward. Contact with the heater). Further, the molded article heated and molded to just before contact with the lower heater was a defective molded article having wrinkles and a portion where the thickness was significantly reduced.

Example 11 A resin composition similar to that used in Examples 3 and 5 was prepared by using a T-die sheet molding machine having an extruder barrel inner diameter of 65 mmφ.
The sheet was processed into a sheet having a width of 900 mm and a thickness of 3.0 mm. The sheet is set in the center of a heating furnace having a ceramic heater (distance between heaters: 350 mm) at upper and lower 450 ° C., heated for 100 to 120 seconds, and then ribs 50 mm, opening 980 mm × 630 mm, depth 150 mm, bottom 9
Straight molding was performed using a female mold of 06 mm × 556 mm.

The molded articles obtained by using the resin compositions of Examples 3 and 5 had a high degree of homogeneity without wrinkles or portions where the thickness was significantly reduced.

In Example 11, Comparative Examples 2, 3, 5,
Straight molding was performed under the same conditions as in Example 10 except that the same resin composition used in Example 6 was used.

The sheets processed using the same resin composition as those used in Comparative Examples 2, 3, 5, and 6 could not be heated until the sagging of the sheet was significantly softened. The sheet sags and comes into contact with the lower heater). Further, the molded article heated and molded to just before contact with the lower heater was a defective molded article having wrinkles.

[0201]

EFFECTS OF THE INVENTION The filler-filled resin sheet of the present invention is a large molded article and a deep drawn article because the heated sheet has little sag during thermoforming and good elongation during molding. And the like can be suitably used for the production of molded articles. Also, in thermoforming of small molded articles such as cups and trays for food packaging, it is possible to increase the width of sheets, increase the number of products produced in one cycle, and improve production efficiency. Can be.

The molded article obtained by thermoforming using the filler-filled resin sheet of the present invention is excellent in rigidity, heat resistance and chemical resistance.
It can be suitably used for large products such as a roof carrier box of an automobile, a vanity table, an industrial tray, a side wall panel of a water storage tank, and a cup or tray for heating cooking by a microwave oven or the like.

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[Procedure amendment]

[Submission date] January 28, 2000 (2000.1.2
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0100

[Correction method] Change

[Correction contents]

In the present invention, the propylene polymer composition containing an inorganic filler in the resin composition (1) contains a third component for the purpose of further improving moldability and imparting impact resistance to the molded article. In addition, various (co) polymer resins other than the (co) polymer constituting the propylene-based polymer composition can be contained. As the third component resin, polypropylene
, High-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, ethylene-based resin such as ethylene-vinyl acetate copolymer, syndiotactic polypropylene,
1-butene resin, cyclic olefin resin, petroleum resin,
Styrene resin, acrylic resin, fluorine resin, ethylene-olefin copolymer rubber, for example, ethylene-propylene
Styrene copolymer rubber, ethylene-butene copolymer rubber, ethylene
-Hexene copolymer rubber, ethylene-octene copolymer rubber
Ethylene-higher olefin copolymer rubber such as rubber, ethylene-olefin-non-conjugated diene copolymer rubber, hydrogenated styrene-conjugated diene copolymer rubber, etc., and not only one kind but also two or more kinds can be used in combination. . that's all

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/12 C08L 23/12 23/14 23/14 23/16 23/16 53/00 53/00 F Terms (Reference) 4F071 AA12 AA12X AA15 AA15X AA20 AA20X AA21 AA21X AA22X AA28X AA76 AA78 AA82 AA88 AB20 AB21 AB28 AB30 AE17 AH03 AH05 AH07 AH12 BC01 4J002 AC113 BB033 BB05 BB BB BB BB 015 BB BB 015 GG01 GL00 GN00 GQ00 4J028 AA01A AB00A AB01A AC01A AC10A AC20A AC28A AC29A AC31A AC39A BA01B BB01B BC12B BC15B BC16B BC17B BC18B BC19B BC24B BC25B BC36B CA47C CB23C CB24C CB25C CB27C CB43C CB44C CB45C CB52C CB53C CB54C CB62C CB63C CB64C CB66C CB68C CB69C CB70C CB79C CB81C CB82C CB83C CB87C CB88C CB91C DA01 DA02 DA03 DA04 DA05 EB03 EB04 GA04 GA07 4J100 AA02Q AA03P AA04Q AA07Q AA16Q AA17Q AA18Q AA19Q AA21Q CA01 CA04 DA09 FA10 FA43 JA43 JA58 JA67

Claims (4)

[Claims] ( _A ) a propylene homopolymer or a propylene copolymer containing 50% by weight or more of propylene polymer units having an intrinsic viscosity [η _A ] of 0.2 to 10 dl / g measured in tetralin at 135 ° C. (B) Ethylene homopolymer having an intrinsic viscosity [η _B ] of 15 to 100 dl / g measured with tetralin at 135 ° C. with respect to 100 parts by weight of an olefin copolymer (collectively referred to as polypropylene). 50% by weight of united or ethylene polymerized units
Ethylene-olefin random copolymer containing above (collectively referred to as high molecular weight polyethylene)
Is contained with respect to 100 parts by weight of the propylene-based polymer composition containing 0.01 to 5.0 parts by weight of the inorganic filler.
(1) containing 1 to 70 parts by weight of
Filler resin sheet using 2. An inorganic filler is used in an amount of 1 to 70 parts by weight and at least one kind selected from the following groups (P1) to (P6) based on 100 parts by weight of the propylene polymer composition according to claim 1. A filler-filled resin sheet using a resin composition (2) containing a third component resin in a ratio of 1 to 70 parts by weight.
(P1) Density 0.910 to 0.930 g / cm ³ , melt flow rate (MFR) [190 ° C .; 21.18 N]
Ethylene homopolymer of 0.01 g / 10 min or more, (P
2) Density 0.920 to 0.950 g / cm ³ , melt flow rate (MFR) [190 ° C .;
01 g / 10 minutes or more ethylene-vinyl acetate copolymer,
(P3) Density 0.880 to 0.940 g / cm ³ , melt flow rate (MFR) [190 ° C .; 21.18 N]
Ethylene-olefin copolymer of 0.01 g / 10 min or more, (P4) melt flow rate (MFR) [190
° C; 21.18 N] ethylene-olefin copolymer rubber of 0.01 g / 10 min or more, (P5) 1-butene homopolymer or 1-butene-olefin copolymer, (P6)
Hydrogenated styrene-conjugated diene copolymer rubber. 3. The propylene polymer composition is used in an amount of 0.01 to 1 mol per mol of the transition metal compound catalyst component and transition metal atom.
Periodic table of 1,000 moles (1991 version), Group 1 and 2
A combination of an organometallic compound of a metal selected from the group consisting of metals belonging to Group 12, 12 and 13 (AL1) and 0 to 500 moles of an electron donor (E1) per mole of transition metal atom. Polymerization of propylene alone or propylene and olefins other than propylene in the presence of a preactivated catalyst comprising a polyolefin production catalyst and a high molecular weight polyethylene as component (b) according to claim 1 supported on the catalyst. The filler-filled resin sheet according to claim 1, which is a propylene-based polymer composition obtained by the above method. 4. A molded article obtained by thermoforming the filler-filled resin sheet according to claim 1.