JP2009149755A - PROPYLENE BLOCK COPOLYMER RESIN COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND FOAM MOLDED BODY - Google Patents

Abstract

To provide a propylene-based block copolymer resin composition having a melting property suitable for foam molding and high mechanical strength during foam molding.
To 100 parts by weight of a propylene block copolymer (B) comprising 30 to 95% by weight of a propylene polymer (B-1) and 5 to 70% by weight of an olefin random copolymer (B-2). On the other hand, a resin composition containing 0.01 to 5.0 parts by weight of an ethylene polymer (A) having an intrinsic viscosity ([η]) measured in tetralin at 135 ° C. of 15 to 100 dl / g, Propylene-based block copolymer resin composition characterized in that the ratio (Q value: Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is 10 to 20, and its production A method and a foamed molded product were provided.
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Description

  The present invention relates to a propylene-based block copolymer resin composition, a method for producing the same, and a foamed molded product using the propylene-based block copolymer resin composition, and more specifically, an ethylene polymer (A) and a propylene polymer. A propylene block copolymer resin composition having melting characteristics suitable for foam molding, comprising a propylene block copolymer (B) having a part (B-1) and an olefin random copolymer part (B-2) The present invention relates to a foam molded article using the product, its production method and its propylene-based block copolymer resin composition.

  Polypropylene resins are widely used in various molding fields because they are excellent in mechanical properties, chemical resistance, etc., and extremely useful in balance with economy. However, since the polypropylene resin is crystalline and has a low viscosity and melt tension at the time of melting, the foamability and moldability of hollow molding, extrusion molding, extrusion foam molding, injection foam molding and the like are not sufficiently satisfactory. There is no actual situation.

  As a method for producing a foam from a polypropylene resin, an extrusion foam molding in which a polypropylene resin containing a foaming agent is melted or a gas is injected into the melted polypropylene resin, and then extrusion molding is performed to form a foam sheet. There are many injection foam molding methods in which foaming is performed simultaneously with injection into an injection mold.

  Particularly in recent years, among automobile materials, weight reduction has been promoted in large-sized household goods such as exterior materials, cushion materials, refrigerators, and the like, and foam molded articles are increasingly used. Injection foam molding has been developed and widely used for the production of these large moldings. The molecular weight of the polypropylene resin homopolymer required for injection foam molding suitable for large-scale molding of automobile materials, especially instrument panels and door trims, is high in melt flow rate (hereinafter also referred to as MFR). Therefore, there is a problem that sufficient foaming performance cannot be obtained because viscosity and melt tension necessary for injection foam molding cannot be obtained.

  Similarly, in a propylene block copolymer used for injection molding, it is desired to increase the MFR of the propylene block copolymer in order to improve the productivity of the injection molding process.

In order to maintain the high quality of the propylene-based block copolymer and increase the MFR of the block copolymer, the propylene-based block copolymer component, the polymer component composed of propylene in the polymer component, propylene and other components It is desired to further increase the MFR of a component composed of a random copolymer component with a monomer, mainly a polymer component composed of propylene.
Therefore, when the propylene-based block copolymer resin is used for injection foam molding, the MFR is also increased, so that sufficient foaming performance can be obtained because the melt tension necessary for injection foam molding cannot be obtained. There was no problem.

  An injection foam molding method of a thermoplastic elastomer (for example, see Patent Document 1) is disclosed. In order to improve the foamability of a thermoplastic elastomer which is generally non-crosslinked, a gas pressure in a molding temperature range is disclosed. Since it is necessary to hold, it must be viscous. As described above, the polypropylene resin performance required for injection foam molding requires fluidity, melt tension, and foamability, but the fluidity, melt tension, and foamability are contradictory. It is.

As another method for improving melt viscoelasticity such as melt tension, a method is proposed in which a composition containing polyethylene or polypropylene having a different intrinsic viscosity or molecular weight from polypropylene is blended or produced by multistage polymerization. Yes. For example, a method has been proposed in which 2 to 30 parts by weight of ultrahigh molecular weight polypropylene is added to 100 parts by weight of ordinary polypropylene in the polymerization stage.
However, these compositions do not fully satisfy the desired melt tension. In addition, in order to produce such ultra-high molecular weight polypropylene contained in the composition, it was the fact that productivity had to be reduced by this, and sufficient inventive characteristics were not obtained. Etc. are found (for example, see Patent Documents 2 and 3).

In addition to these methods, propylene is polymerized on a supported titanium-containing solid catalyst component and an organoaluminum compound catalyst component using a prepolymerized catalyst in which polyethylene and a polyene compound are prepolymerized, thereby increasing the high melt tension. And a polyethylene-containing prepolymerization catalyst having an intrinsic viscosity of 20 dl / g or more obtained by conducting prepolymerization alone with ethylene using the same catalyst component (for example, see Patent Document 4) A method for producing an ethylene / α-olefin copolymer having a high melt tension is known (for example, see Patent Document 5).
However, in these methods, it is necessary to newly prepare a polyene compound as the third component, and as a result, the dispersibility of prepolymerized polyethylene or the like in the finally obtained polyolefin composition becomes non-uniform. There was a problem that the quality of the object tends to become unstable.

  In addition, an olefin (co) polymer composition having a high melt tension obtained by polymerizing propylene using a polyethylene-containing prepolymerization catalyst containing polyethylene having an intrinsic viscosity of 15 dl / g or more, and a method for producing the same Although it is known, there is no description about a composition suitable for injection foam molding and a production method (for example, refer to Patent Documents 6 and 7).

As described above, in terms of the injection foaming performance of the polypropylene resin, in the conventional composition, in particular, polypropylene having a high MFR, the appearance of the injection-foamed molded article is impaired. Bubbles may break and the performance as a foam may be reduced. Such a foam-molded product is disadvantageous in a field where mechanical strength is lowered and strength of automobile material or the like is required. There is no polypropylene molded body that has excellent melt characteristics and foaming performance, and the foamed molded body exhibits sufficient strength, and development of further improved technology is desired.
JP-A-8-207074 JP 2001-59949 A JP 2002-90333 A Japanese Patent No. 3176932 Japanese Patent Laid-Open No. 5-222122 JP-A-4-55410 Japanese Patent No. 3270056

  An object of the present invention is to provide a propylene-based block copolymer having an ethylene polymer (A), a propylene polymer part (B-1) and an olefin random copolymer part (B-2) in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a propylene-based block copolymer resin composition containing a polymer (B) and having high melting characteristics suitable for foam molding and high mechanical strength during foam molding.

As a result of intensive studies to solve the above problems, the present inventors have obtained a resin composition containing a propylene-based block copolymer (B) and an ethylene polymer (A),
The propylene block copolymer (B) has a low molecular weight propylene moiety (B-1) having an intrinsic viscosity ([η]) measured in o-dichlorobenzene (hereinafter abbreviated as ODCB) at 135 ° C. of less than 6 dl / g. -1) Propylene polymer comprising 5 to 50% by weight of a high molecular weight propylene part (B-1-2) having an intrinsic viscosity ([η]) of 6 to 15 dl / g measured by ODCB at 50 to 95% by weight and 135 ° C. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatograph (GPC) (Q-1) consisting of (B-1) and an olefin random copolymer (B-2) (Q Value: Mw / Mn) is a propylene-based block copolymer resin composition characterized by having a fluidity and a melt characteristic and suitable for injection foam molding by obtaining a propylene-based block copolymer resin composition having a value of 10-20. The present inventors have found a copolymer resin composition and have reached the present invention.

That is, according to the first invention of the present invention, a propylene-based block comprising 30 to 95% by weight of the following propylene polymer (B-1) and 5 to 70% by weight of an olefin random copolymer (B-2). Ethylene polymer (A) having an intrinsic viscosity ([η]) measured in tetralin at 135 ° C. of 15 to 100 dl / g with respect to 100 parts by weight of copolymer (B) 0.01 to 5.0 weights The ratio (Q value: Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 10-20. A propylene-based block copolymer resin composition is provided.
Propylene polymer (B-1): Low molecular weight propylene polymer (B-1-1) having an intrinsic viscosity ([η]) measured in o-dichlorobenzene at 135 ° C. of less than 6 dl / g, 50 to 95 wt. %, And a high molecular weight propylene polymer (B-1-2) having an intrinsic viscosity of 6 to 15 dl / g, 5 to 50% by weight.

According to the second invention of the present invention, in the first invention, the olefin random copolymer (B-2) is selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms. A propylene-based block copolymer resin obtained by polymerizing the above monomer and propylene and having an intrinsic viscosity ([η]) measured in o-dichlorobenzene at 135 ° C. of 8 to 25 dl / g A composition is provided.
Furthermore, according to the third invention of the present invention, in the first or second invention, the propylene polymer (B-1) has an MFR (230 ° C., 2.16 kg load) of 50 to 1000 g / 10 min. A propylene-based block copolymer resin composition is provided.

According to a fourth invention of the present invention, in any one of the first to third inventions, the propylene polymer (B-1) is a weight average measured by gel permeation chromatography (GPC). A propylene-based block copolymer resin composition is provided in which the ratio (Q value: Mw / Mn) of the molecular weight (Mw) to the number average molecular weight (Mn) is 5 to 18.
Furthermore, according to the fifth invention of the present invention, there is provided a propylene-based block copolymer resin composition characterized by having melt characteristics suitable for foam molding in any one of the first to fourth inventions. The

On the other hand, according to the sixth aspect of the present invention, a propylene-based block copolymer having an ethylene polymer (A), a propylene polymer part (B-1) and an olefin random copolymer part (B-2). In a method for producing a propylene-based block copolymer resin composition comprising (B),
The propylene-based block copolymer (B) is an olefin polymerization catalyst formed from (I) a solid component containing titanium, magnesium and halogen as essential components, (II) an organoaluminum compound, and (III) an electron donor. In the presence of the step (b-1-1) and the step (b-1-2) and the step (b-2). A method for producing a propylene-based block copolymer resin composition according to any one of 1 to 5 is provided.
Step (b-1-1): Propylene is polymerized in the presence of hydrogen, and a low molecular weight propylene polymer (B-1-) having an intrinsic viscosity of less than 6 dl / g measured in o-dichlorobenzene at 135 ° C. 1) The manufacturing process.
Step (b-1-2): high molecular weight propylene having an intrinsic viscosity of 6 to 15 dl / g measured in 135 ° C o-dichlorobenzene by polymerizing propylene substantially in the absence of hydrogen The process of manufacturing a polymer (B-1-2).
Step (b-2): Polymerizing one or more monomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms in the absence of hydrogen and propylene at 135 ° C. -The process of manufacturing the olefin random copolymer (B-2) whose intrinsic viscosity ([(eta))) measured in dichlorobenzene is 8-25 dl / g.

According to the seventh invention of the present invention, in the sixth invention, the steps (b-1-1), (b-1-2) and (b-2) are composed of 2 to 3 tanks. Provided is a method for producing a propylene-based block copolymer resin composition, which is a continuous polymerization step using a continuous tank.
Furthermore, according to an eighth invention of the present invention, in the sixth invention, the ethylene polymer (A) is subjected to the following step (a-2) prior to the step (b-1). A method for producing a propylene-based block copolymer resin composition is provided.
Step (a-2): In the presence of an olefin polymerization catalyst, one or more monomers selected from the group consisting of ethylene alone or ethylene and an α-olefin having 3 to 12 carbon atoms are polymerized for olefin polymerization. A preactivation step for producing 0.01 to 500 g of ethylene polymer (A) with respect to 1 g of metal atoms in the catalyst.

According to a ninth aspect of the present invention, in the eighth aspect, the following step (a-1) is performed prior to the step (a-2), and the propylene-based block copolymer resin is characterized in that: A method of manufacturing the composition is provided.
Step (a-1): Propylene is polymerized in the presence of an olefin polymerization catalyst, and (I) 0.01 to 100 g of polypropylene is added to 1 g of a solid component containing titanium, magnesium and halogen as essential components. A pre-polymerization step for producing and supporting.
According to a tenth invention of the present invention, in any one of the sixth to ninth inventions, (II) the organoaluminum compound is triethylaluminum and / or triisobutylaluminum. A method for producing a copolymer resin composition is provided.
Further, according to an eleventh aspect of the present invention, in any one of the sixth to tenth aspects, (III) the electron donor is an organosilicon compound, and the propylene-based block copolymer resin composition A method of manufacturing an article is provided.

  According to a twelfth aspect of the present invention, there is provided a foamed molded article using the propylene-based block copolymer resin composition according to any one of the first to fifth aspects of the invention.

The propylene-based block copolymer resin composition of the present invention is suitable for applications using a propylene-based block copolymer excellent in melting characteristics and foaming performance.
The propylene-based block copolymer resin composition of the present invention is used for hollow molding, extrusion foam molding, and the like, and can be suitably used particularly for injection foam molding applications represented by automobile parts and household appliance parts. . Moreover, since the propylene-based block copolymer resin composition of the present invention does not have free terminal long chain branching, it is excellent in recyclability.
Furthermore, the foam molded product using the propylene-based block copolymer resin composition of the present invention maintains the high quality of the propylene-based block copolymer, and is a large-sized automobile material such as an instrument panel or a door trim. It is suitable for a molded body.

  Below, the propylene-type block copolymer resin composition, its manufacturing method, and the foaming molding formed from this propylene-type block copolymer resin composition are demonstrated concretely and in detail.

1. Propylene Block Polymer Resin Composition (1) Polymer Resin Composition Component The propylene block polymer resin composition of the present invention (hereinafter also referred to as “propylene polymer resin composition”) is the following polymer. It consists of a resin composition component. Hereinafter, the polymer resin composition component will be described in detail.

The propylene block polymer resin composition of the present invention is a resin composition comprising a high molecular weight polyethylene (A) having a specific intrinsic viscosity and a propylene block copolymer (B).
Since the propylene-based block copolymer resin composition of the present invention is excellent in melting characteristics and foaming characteristics, it is particularly advantageous for molding that requires fluidity and foaming characteristics such as injection foam molding at the same time. .

  The measurement method of Mn, Mw, and Mz in the present invention was measured using GPC (gel permeation chromatograph) with Waters, GPC150-C type machine, and Polymer Laboratories column PlmixedB. The measurement was conducted at a measurement temperature of 135 ° C. in a solvent o-dichlorobenzene (hereinafter abbreviated as ODCB) using polystyrene as a standard substance.

Examples of information obtained by GPC include the following.
(I) Mn: Number average molecular weight: The most basic average molecular weight determined by measuring a physical property value directly related to the number of molecules of the polymer, depending on the total number of molecules.
(Ii) Mw: weight average molecular weight: an average molecular weight obtained when the measured physical property value is directly related to the weight of the polymer, which is a square average of the molecular weight and depends on a higher degree of polymerization than Mn. .
(Iii) Mz: Z average molecular weight: The highest average molecular weight, which is the cube average of the molecular weight.
(Iv) Mw / Mn: a parameter which is generally strongly influenced by the molecular weight distribution.
(V) Mz / Mw: Parameter affected by ultra high molecular weight component

  The propylene block copolymer resin composition of the present invention has a ratio of Mw (weight average molecular weight) to Mn (number average molecular weight) measured by GPC, that is, a value of Mw / Mn of 10 to 20, preferably 11 or more. 18 or less, more preferably 12 or more and 16 or less, and the ratio of Mz (Z average molecular weight) to Mw (weight average molecular weight), that is, the value of Mz / Mw is 10 or more and 20 or less, preferably 11 or more and 18 or less. More preferably, it is 12 or more and 16 or less. Since the propylene-based block copolymer resin composition of the present invention shows high values of Mw / Mn and Mz / Mw, it means that the molecular weight distribution is wide and particularly the distribution of ultrahigh molecular weight components is large. If both the values of Mw / Mn and Mz / Mw are 10 or less, sufficient melt tension cannot be obtained at the time of foaming, causing a decrease in closed cell ratio and a decrease in foaming performance, while it is 20 or more. Due to the problem of molecular weight disparity, the shape and appearance of the resulting molded product deteriorate.

Conventionally, it is a well-known fact to the business operators that by improving the molecular weight distribution of polypropylene, moldability and foaming performance have been improved by improving melt tension. On the other hand, when the molecular weight of the polypropylene composition is excessively widened by the addition of other components, a gel is generated in the molded body and the appearance is impaired.
In the propylene-based block copolymer resin composition according to the production method of the present invention, the molecular weight distribution of the block copolymer is widened by converting the olefin random copolymer portion of the block copolymer into a high molecular weight component. A propylene-based block copolymer (B) having high values of Mw / Mn and Mz / Mw, which are indicators of the above, is obtained. On the other hand, no gel is generated in the molded product and foam molding.
The ethylene polymer (A), which is a high molecular weight component, is finely dispersed in polypropylene in an average particle diameter of 1-1000 μm, more preferably 10-500 μm, as can be seen in WO 97/14725. It has been confirmed that no gel is generated in the molded body.

The molecular weight distribution curve of the propylene-based block copolymer resin composition in the present invention has a mountain-shaped distribution curve, and has high values of Mw / Mn and Mz / Mw, particularly on the polymer side. Is a monotonously decreasing curve shape.
On the other hand, in the case of having a branched structure such as electron beam irradiation, a bimodal molecular weight distribution curve is shown. Such polypropylene is very easy to deteriorate due to heat and shear, and therefore is not recyclable.
However, since the propylene-based block copolymer resin composition obtained in the present invention is linear and resistant to heat and shear, it can be recycled and used.

In the propylene-based block copolymer resin composition in the present invention, ODCB is used as a solvent, and the temperature rise separation fraction between 0 to 140 ° C is 40 to 100 ° C with respect to the elution fraction of 0 to 100 ° C. The ratio of elution is 50 to 70%, and Mw of elution at 40 to 100 ° C. is 5.0 × 10 ^{6 to} 2.0 × 10 ⁷ .

  The component soluble in ODCB at a temperature of 0 to 40 ° C. mainly comprises a low molecular weight olefin random copolymer part (B-2-1) of an olefin random copolymer part (B-2). (B-1) or by-products generated when these are produced. The component soluble in ODCB at a temperature of 40 to 100 ° C. mainly comprises a medium to high molecular weight olefin random copolymer part (B-2-2) and an ethylene polymer (A). Part of 1) is included.

  When the elution amount of 40 to 100 ° C. in the resin composition is less than the above range and the Mw is less than or equal to the above range, the melting characteristics and the foaming performance are deteriorated, while the elution amount of 40 to 100 ° C. Exceeding the range and Mw exceeding the above range are not preferable because of the occurrence of tiger stripes, silver streak, etc. during foam molding and the appearance is remarkably deteriorated.

  The MFR of the propylene-based block copolymer resin composition of the present invention is 10 to 200 g / 10 minutes, preferably 20 to 100 g / 10 minutes, and more preferably 30 to 80 g / 10 minutes. When the MFR is too low, the flow characteristics and the like are inferior. On the other hand, when the MFR is too high, physical properties such as melt tension are adversely affected and the foaming performance is deteriorated.

The constituent components of the propylene-based block copolymer resin composition relating to the present invention and the foamed molded product produced from the raw material will be described in detail.
(I) Ethylene polymer (A)
The ethylene polymer (A), which is a constituent component of the propylene-based block copolymer resin composition of the present invention, has a limiting viscosity measured in tetralin at 135 ° C. in the range of 15 to 100 dl / g.
When the intrinsic viscosity of the ethylene polymer (A) is less than 15 dl / g, a propylene polymer resin composition obtained by melt-kneading a propylene block polymer resin composition or a mixture of the polymer resin composition components is used. The effect of improving the melt tension may be insufficient.
The upper limit of the intrinsic viscosity of the ethylene polymer (A) is not particularly limited, but if the difference in intrinsic viscosity from the propylene-based block copolymer (B) is too large, the resulting resin composition will be a propylene-based block copolymer. The uniform dispersibility of the polymer (B) and the ethylene polymer (A) is lowered, and as a result, it may be difficult to obtain a polypropylene polymer resin composition having a stable high melt tension. Moreover, considering that the higher the intrinsic viscosity of the ethylene polymer (A), the lower the polymerization temperature must be set, the productivity of the ethylene polymer (A) can be improved. From this point, the upper limit of the intrinsic viscosity of the ethylene polymer (A) is preferably about 100 dl / g. The intrinsic viscosity of the ethylene polymer (A) is preferably in the range of 17 to 80 dl / g, more preferably 17 to 50 dl / g.

  Further, since the intrinsic viscosity of the ethylene polymer (A) needs to be 15 dl / g or more, it is an ethylene homopolymer or the weight of the copolymer for reasons of high molecular weight efficiency. On the basis, it is preferably an ethylene / olefin copolymer of polyethylene containing 50% by weight or more of polyethylene units and an olefin having 3 to 12 carbon atoms. More preferable is an ethylene homopolymer or an ethylene / olefin copolymer of ethylene and an olefin having 3 to 12 carbon atoms containing 70% by weight or more of ethylene units based on the weight of the copolymer. Particularly preferred is an ethylene homopolymer or an ethylene / olefin copolymer of ethylene containing 90% by weight or more of ethylene units based on the weight of the copolymer and an olefin having 3 to 12 carbon atoms.

  When the ethylene polymer (A) is an ethylene / olefin copolymer, the olefin having 3 to 12 carbon atoms to be copolymerized with ethylene is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like may be mentioned, and two or more of these olefins may be used.

  In the ethylene polymer (A), a small amount of a 4 to 12 carbon diene component may be used as a comonomer. Examples thereof include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, Examples include 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, etc. It can be. The structural unit derived from these diene components is desirably adjusted to a ratio of 2 mol% or less, preferably 1% mol or less in the ethylene polymer (A).

In the present invention, the ethylene polymer (A) is 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, more preferably 0 to 100 parts by weight of the propylene-based block copolymer (B). It is preferable to contain 0.05-2.0 weight part.
If the amount of the ethylene polymer (A) contained is less than 0.01 parts by weight relative to 100 parts by weight of the propylene-based block copolymer (B), the effect of suppressing bubbles during foam molding does not work, and foaming There is a risk that the foam tension may sometimes break and the effect of improving the melt tension of the resulting propylene-based block copolymer resin composition may be reduced. On the other hand, if it exceeds 5.0 parts by weight, the foaming performance may be reduced during foam molding. There is a risk that bubbles will not easily swell, the viscosity of the entire resin will be low, the flow characteristics may be lowered, the effect of containing the ethylene polymer (A) may be saturated, and the ethylene polymer (A) and propylene There exists a possibility that the uniform dispersibility of a block copolymer (B) may be impaired.

Such ethylene polymer (A) may be mixed only with one type of propylene block copolymer (B), or two or more types having different compositions may be mixed with propylene block copolymer (B). ).
As a production method, the ethylene polymer (A) and the propylene block copolymer (B) are physically mixed with a blender or the like, the melt kneaded method, the ethylene polymer (A) is preactivated, Subsequently, there is a method of continuously producing the propylene-based block copolymer (B), and a method of chemically mixing. From the viewpoint of imparting high melt tension of the resin composition, foaming performance, and higher closed cell ratio, the method of continuously producing the resin composition, that is, after preactivating the ethylene polymer (A) The method is desirable.

  When the ethylene polymer (A) is produced continuously with the propylene-based block copolymer (B) and physically mixed without being chemically mixed, the production method of the ethylene polymer (A) has the above physical properties. If it is satisfactory, it is not particularly limited, and examples thereof include a radical polymerization method and a catalyst polymerization method. In the case of catalytic polymerization, any of a titanium catalyst, a vanadium catalyst, a chromium catalyst, a metallocene catalyst, and a phenoxyimine catalyst can be used as the polymerization catalyst.

As the ethylene polymer (A), a commercially available product may be used. For example, a kernel manufactured by Nippon Polyethylene Co., Ltd. In addition to the EP series and EBM series manufactured by JSR Corporation, linear low density polyethylene also falls into this category.
The ethylene copolymer as the ethylene polymer (A) may be a mixture of two or more types of ethylene copolymers.

Of the propylene-based block copolymer (B) and the propylene polymer (B-1) of the ethylene polymer (A) when the ethylene polymer (A) is continuously produced with the propylene-based block copolymer (B). The analysis method can be determined by any known method.
Specifically, using the difference in crystallinity between the propylene polymer (B-1) and the ethylene polymer (A), TREF (temperature rising elution fractionation method), infrared spectroscopy (IR), As an analysis method in the propylene-based block copolymer (B), it can be analyzed by a production amount ratio, an infrared spectroscopic analysis method (IR) or the like.

(II) Propylene block copolymer (B)
The propylene block copolymer (B), which is one of the components constituting the propylene block copolymer resin composition of the present invention, comprises 30 to 95% by weight of the propylene polymer (B-1), olefin random weight. It is composed of 5 to 70% by weight of combined (B-2).
The MFR of the propylene-based block copolymer (B) is 10 to 200 g / 10 minutes, preferably 20 to 100 g / 10 minutes, and more preferably 25 to 80 g / 10 minutes. When the MFR is too low, the flow characteristics and the like are inferior. On the other hand, when the MFR is too high, physical properties such as melt tension are adversely affected and the foaming performance is deteriorated.
The MFR of the propylene-based block copolymer (B) is the MFR of the polymer component (B-1) mainly composed of propylene, the MFR of the olefin random polymer (B-2) of propylene and other monomers, the component ( It is uniquely determined by the three factors B-1) and the component (B-2). Therefore, the MFR of the block copolymer can be controlled by adjusting these three factors.

(II-1) Propylene polymer (B-1):
The content of the propylene polymer (B-1) in the present invention is preferably 30 to 95% by weight, more preferably 50 to 93% by weight, based on the weight of the propylene-based block copolymer (B). Preferably it is 70 to 90% by weight. When it is 30% by weight or less, the mechanical strength is lowered. On the other hand, when it is 95% by weight or more, the impact strength is lowered, so that the moldability is inferior.
The propylene polymer (B-1) is a low molecular weight propylene polymer (B-1-1) having an intrinsic viscosity [ηB-1-1] measured in an ODCB solvent at 135 ° C. of less than 6 dl / g, 135 ° C. It is comprised from the high molecular weight propylene polymer (B-1-2) whose intrinsic viscosity measured in the ODCB solvent of 6-15 dl / g, and low molecular weight propylene polymer (B-1-1) 50-95. It is comprised from 5 to 50 weight% of weight% and high molecular weight polypropylene polymer (B-1-2). The content of the high molecular weight propylene polymer (B-1-2) is preferably 5 to 50% by weight of the propylene polymer (B-1), more preferably 7 to 45% by weight, and still more preferably 10%. -40% by weight. If it is less than 5% by weight, the effect of suppressing the bubble growth and the mechanical strength are lowered during foam molding. On the other hand, if it exceeds 50% by weight, the moldability is deteriorated due to the inhibition of bubble growth and the deterioration of flow characteristics.

In the present invention, in order to improve the balance between the flow characteristics and the melt characteristics, the MFR of the propylene-based block copolymer (B) can be adjusted by adjusting the MFR of the component (B-1). desirable.
In the range of the intrinsic viscosity [η] (details will be described later) of the component (B-1) and the component (B-2) without departing from the gist of the present invention, the MFR of the component (B-1) is 50 g / MFR. It is preferably 10 minutes or more, more preferably MFR is 50 g / 10 minutes to 1,000 g / 10 minutes, more preferably 60 g / 10 minutes to 800 g / 10 minutes, and most preferably 100 g / 10 minutes to 500 g. / 10 minutes or less. When the MFR of the component (B-1) is 1,000 g / 10 min or more, the MFR of the polypropylene block copolymer (B) is increased and the flow characteristics are improved, but the closed cell ratio is reduced due to a decrease in melt tension. Cause a decline. On the other hand, when the MFR is 50 g / 10 min or less, the MFR of the polypropylene-based block copolymer (B) decreases and the melt tension increases, but the moldability decreases due to the deterioration of the flow characteristics.

  As a manufacturing method of the propylene polymer (B-1) of this invention, a low molecular weight propylene polymer part (B-1-1) and a high molecular weight polypropylene polymer part (B-1-2) are physically used with a blender etc. There are a mixing method, a melt-kneading method, a continuous production method by multistage polymerization, a chemical mixing method, and the like. Since the effect of imparting high melt tension and improving the mechanical strength of the resin composition is enhanced, a method of continuously producing by multistage polymerization is desirable.

When the propylene polymer (B-1) according to the present invention is produced by a continuous polymerization method, the intrinsic viscosity of the component (B-1-1 or B-1-2) produced in the second stage is directly It cannot be measured. Therefore, from the intrinsic viscosity [η1st stage] and [ηB-1] obtained from the 1st stage polymer (B-1-1 or B-1-2) component and the propylene polymer (B-1) component, The intrinsic viscosity [η2nd stage] is calculated using the following formula. The intrinsic viscosity was measured by using GPC (gel permeation chromatograph) with Waters, GPC150-C type machine, and Polymer Laboratories column PlmixedB. Measurement is performed in ODCB at a measurement temperature of 135 ° C. using polystyrene as a standard substance.
[Η2 stage] = ([ηB-1] × 100− [η1 stage] × W1 stage) ÷ W2 stage (Formula 1)
W1st stage: content of propylene polymer, second stage polymer component W2nd stage: content of propylene polymer, second stage polymer component

  The intrinsic viscosity [ηB-1-2] of the high molecular weight propylene polymer component (B-1-2) is 6 to 15 dl / g, preferably 6 to 14 dl / g, more preferably 7 to 14 dl / g. It is as follows. If it is 6 or less, the molecular weight is low, and a sufficient effect for improving the impact strength and foamability of the resulting foam cannot be obtained. On the other hand, when it is 15 or more, not only is industrial production difficult, but it is not preferable from the viewpoint of productivity. The intrinsic viscosity [ηB-1-1] of the low molecular weight propylene polymer component (B-1-1) is less than 6 dl / g.

Moreover, the propylene content of the component insoluble in ODCB at 100 ° C. and soluble in ODCB at 140 ° C. of the propylene polymer component (B-1) is 99.5% by weight or more.
ODCB is a good solvent for polyolefins and has a boiling point as high as 181 ° C., so it is used for solvent separation in a wide temperature range from low to high. The insolubility in ODCB at 100 ° C. means that the component of the block copolymer is a highly crystalline polypropylene component, and the component having poor crystallinity is removed from the propylene-based block copolymer. It has the significance of taking out only the remaining highly crystalline component. The propylene content of the component is 99.5% by weight or more, even if the component is a homopolypropylene or a copolymer of propylene and an α-olefin. It means that only a very small amount of α-olefin is contained. Therefore, the ODCB insoluble component at 100 ° C. means that it has high crystallinity and has an effect of increasing the rigidity of the propylene-based block copolymer.

  The propylene polymer (B-1) has a ratio (Q value: Mw / Mn) of 5 to the number average molecular weight (Mn) of the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). -18, preferably 5.5-17, more preferably 6-16. As described above, the Mw / Mn value is a value representing the molecular weight distribution. When the molecular weight distribution of the propylene polymer molecules is within this range, it is possible to impart an improvement in the strength and foaming performance of the foamed molded product.

The foamed molded product of the polypropylene-based block copolymer resin composition comprising the propylene polymer component (B-1) in the range of the above-mentioned intrinsic viscosity and ODCB insoluble component has high rigidity and is also in balance with impact resistance. Excellent. In order to increase the rigidity of the polypropylene-based block copolymer resin composition, the polymer component (B-1) mainly composed of propylene is preferably a propylene homopolymer, but the appearance of the foamed molded product is improved. Therefore, a copolymer with a small amount of a comonomer can be obtained without departing from the gist of the present invention.
Specifically, the component (B-1) can contain one or more monomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms in a content of 5 wt% or less. Preferably, the monomer other than propylene is ethylene and / or 1-butene, most preferably ethylene. An α-olefin having 9 or more carbon atoms is not preferable because the catalyst activity is remarkably lowered. On the other hand, when the monomer content other than propylene in the component (B-1) exceeds 5 wt%, the melt tension and foaming performance are remarkably lowered, which is not preferable.
Here, the content of other monomers can be determined by any analysis technique. Specific examples include infrared spectroscopy (IR) and nuclear magnetic resonance analysis (NMR).

(II-2) Olefin random copolymer (B-2):
In the present invention, the content of the olefin random polymer (B-2) is preferably 5 to 70% by weight, more preferably 7 to 50% by weight, based on the weight of the polypropylene block copolymer (B). More preferably, it is 10 to 30% by weight. If it is 5% by weight or less, the effect of suppressing bubble growth at the time of foam molding is reduced. On the other hand, if it is 70% by weight or more, moldability is impaired due to inhibition of bubble growth, a decrease in mechanical strength, and a deterioration in flow characteristics. descend.

The olefin random copolymer (B-2) of propylene and other monomers in the present invention is a random of one or more monomers selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms and propylene. It is a copolymer. Preferably, the monomer other than propylene is ethylene and / or 1-butene, most preferably ethylene. An α-olefin having 9 or more carbon atoms is not preferable because the catalytic activity is remarkably lowered. For example, examples of the α-olefin having 4 to 8 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene. Can be mentioned.
The content of propylene in the component (B-2) is 10% by weight or more and 70% by weight or less. When the content of propylene is outside this range, the random copolymer component is not preferable because the melt tension and foaming performance are lowered. More preferably, the content of propylene is 15% by weight or more and 65% by weight or less, and particularly preferably 20% by weight or more and 60% by weight or less. Most preferably, the content of propylene units is not less than 30% by weight and not more than 55% by weight.

  The intrinsic viscosity ([η]) of the olefin random copolymer (B-2) measured in o-dichlorobenzene at 135 ° C. is 8 or more and 25 dl / g or less. Preferably they are 9 dl / g or more and 22 dl / g or less, More preferably, they are 10 dl / g or more and 20 dl / g or less. If the intrinsic viscosity of the component (B-2) is too lower than the above range, the melt tension of the block copolymer (B) decreases, which is not preferable. If the intrinsic viscosity of the component (B-2) is higher than the above range, the dispersion becomes worse, the gel is increased, and the appearance when the block copolymer (B) is molded is undesirably deteriorated.

The intrinsic viscosity [ηB-2] of the olefin random polymer (B-2) component of the propylene-based block copolymer (B) according to the present invention cannot be directly measured. Therefore, from the intrinsic viscosity [ηB] and [ηB-1] obtained from the propylene-based block copolymer (B) and the propylene polymer (B-1) component, the intrinsic viscosity [ηB-2] Is calculated.
[ΗB-2] = ([ηB] × 100− [ηB−1] × WB−1) ÷ WB-2 (Formula 2)
WB-1: Content of propylene polymer (B-1) component WB-2: Content of olefin random polymer (B-2) component

The method for producing a propylene-based block copolymer resin composition in the present invention is a chemical mixing, that is, titanium rather than the production by physical mixing of an ethylene polymer (A) and a propylene-based block copolymer (B). The production method using the catalyst component in which the ethylene polymer (A) is supported on the solid catalyst component (I) and continuously producing the propylene-based block copolymer (B) is the propylene-based one. The block copolymer resin composition is preferred from the viewpoint of imparting high melt tension, foaming performance, and a foam having a higher closed cell ratio.
The following propylene polymer (B-1), olefin random polymer (B-2), propylene obtained by continuous polymerization using a catalyst component in which an ethylene polymer (A) is supported on a titanium-containing solid catalyst component (I) A method for analyzing the intrinsic viscosity of the system block copolymer (B) will be specifically described.

[ΗA]: The intrinsic viscosity of the ethylene polymer (A) obtained in the polymerization step (a) is measured in tetralin at 135 ° C.
[ΗB-1]: The propylene polymer (B-1) component (including ethylene polymer (A)) obtained in the polymerization step (b-1) is used as a solvent and an ODCB solvent is used, and the temperature is 0 to 140 ° C. In the temperature rising separation during the measurement, the elution components excluding the elution part of 80 to 100 ° C. were measured by GPC under the above-mentioned conditions.
[ΗB]: The propylene-based block copolymer (B) component obtained in the polymerization step (b-2) is measured by GPC under the above-described conditions.
[ΗB-2]: calculated from the following formula 3.
[ΗB-2] = ([ηB] × 100− [ηA] × WA− [ηB−1] × WB−1) ÷ WB-2 (Formula 3)
WA: Content of propylene polymer (A) component WB-1: Content of propylene polymer (B-1) component WB-2: Content of olefin random polymer (B-2) component

Similar to the ethylene polymer (A), the olefin random polymer (B-2) also has an effect of suppressing the growth of foamed bubbles during foam molding. That is, it is necessary for reducing the simultaneous bubble ratio and ensuring the impact resistance of the entire resin, the viscosity adjustment, the extensibility during container molding, and the like.
The content of the olefin random polymer (B-2) is preferably 5 to 70% by weight, more preferably 7 to 50% by weight, still more preferably based on the weight of the polypropylene block copolymer (B). 10 to 30% by weight. If it is 5% by weight or less, the effect of suppressing bubble growth at the time of foam molding is reduced. On the other hand, if it is 70% by weight or more, moldability is deteriorated due to inhibition of bubble growth and deterioration of flow characteristics.

  The weight ratio between the propylene polymer (B-1) and the olefin random polymer (B-2) can be determined by any known method. Specifically, it can be determined from the ratio of the production amounts of the first polymerization step and the second polymerization step. Moreover, using the difference in crystallinity between the propylene polymer (B-1) and the olefin random polymer (B-2), TREF (temperature rising elution fractionation method), CFC (cross fractionation method), monomer unit content It can also be analyzed by infrared spectroscopy (IR), which measures the amount.

2. Production method of propylene-based block polymer resin composition Below, production method of propylene-based block copolymer resin composition, polypropylene-based block copolymer resin composition obtained by this production method, and this polypropylene-based block copolymer The foam molded article formed from the composition will be described specifically and in detail.

The method for producing a propylene-based block copolymer resin composition of the present invention comprises an ethylene polymer (A), a propylene-based polymer having a propylene polymer part (B-1) and an olefin random copolymer part (B-2). A method for producing a propylene-based block copolymer resin composition containing a block copolymer (B), wherein the propylene-based block copolymer (B) comprises (I) titanium, magnesium and halogen as essential components. In the presence of an olefin polymerization catalyst formed from a solid component, (II) an organoaluminum compound, and (III) an electron donor, propylene is polymerized in the presence of hydrogen to produce a propylene polymer (B- 1) 1 or more selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms in the absence of hydrogen (step (b-1)) Produced by performing a step (step (b-2)) of polymerizing a monomer and propylene to produce an olefin random copolymer (B-2) having an intrinsic viscosity ([η]) of 8 to 25 dl / g. This is a method for producing a propylene-based block copolymer resin composition.
Hereinafter, each production process of the propylene-based block copolymer resin composition of the present invention is specifically exemplified.

(1) Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention comprises (I) a solid component containing titanium, magnesium and halogen as essential components, (II) an organoaluminum compound, and (III) an electron donor. It is formed from. Each component forming this olefin polymerization catalyst will be described in detail below.

(I) Solid component containing titanium, magnesium and halogen as essential components:
In the present invention, (I) a solid component containing titanium, magnesium and halogen as essential components (hereinafter also referred to as “titanium-containing solid component”) includes titanium (I-1), magnesium (I-2), and halogen. (I-3) is contained as an essential component, and an electron donor (I-4) can be used as an optional component. Here, “containing as an essential component” indicates that any component may be included in any form within the range not impairing the effects of the present invention, in addition to the listed three components. . The solid component itself containing titanium, magnesium, and halogen as essential components is known and will be described in detail below.

(I-1) Titanium:
Any titanium compound can be used as the titanium source. Typical examples include compounds disclosed in JP-A-3-234707.
With respect to the valence of titanium, a titanium compound having any valence of tetravalent, trivalent, divalent, and zero can be used, preferably tetravalent and trivalent titanium compounds, more preferably tetravalent. It is desirable to use the titanium compound.

Specific examples of the tetravalent titanium compound include titanium halide compounds typified by titanium tetrachloride, alkoxy titanium compounds typified by tetrabutoxy titanium, tetrabutoxy titanium dimer (BuO) ₃ Ti—O—Ti. Examples thereof include condensation compounds of alkoxy titanium having a Ti—O—Ti bond typified by (OBu) ₃ and organometallic titanium compounds typified by dicyclopentadienyl titanium dichloride.

Preferred tetravalent titanium compounds are those represented by the general formula: Ti (OR) _{4 -p} X _p (where R is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents a halogen, p is 0 ≦ p ≦ 4). Of these, tetravalent titanium compounds containing halogen are more preferred.

Specific examples of the tetravalent titanium compound containing halogen include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , and Ti (OC ₂ H ₅ ) ₃ Cl. , Ti (O—nC ₄ H ₉ ) ₂ Cl ₂ , Ti (O—nC ₄ H ₉ ) ₃ Cl, Ti (OC ₆ H ₅ ) Cl ₃ , Ti (O—iC ₄ H ₉ ) ₂ Cl ₂ , Ti _{(O-nC 4 H 9)} 4, Ti (O-iC 4 H 9) 4, Ti (O-nC 6 H 13) 4, Ti (O-nC 8 H 17) 4 and the like.

Further, a molecular compound obtained by reacting TiX ′ ₄ (where X ′ represents a halogen) with an electron donor described later can also be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ · CH ₃ COC ₂ H ₅ , TiCl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅ NO ₂ , TiCl ₄ · CH ₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ · C ₄ H ₄ O and the like can be mentioned.
Of these, titanium tetrachloride and tetrabutoxy titanium are particularly preferred.

Specific examples of the trivalent titanium compound include titanium halide compounds represented by titanium trichloride. As titanium trichloride, a compound produced by any known method such as a hydrogen reduction type, a metal aluminum reduction type, a metal titanium reduction type, or an organoaluminum reduction type can be used.
The above titanium compounds can be used not only alone but also in combination with a plurality of compounds.

(I-2) Magnesium:
Any magnesium compound can be used as the magnesium source. Typical examples include compounds disclosed in JP-A-3-234707.
In general, magnesium halide compounds represented by magnesium chloride, alkoxymagnesium compounds represented by diethoxymagnesium, metal magnesium, oxymagnesium compounds represented by magnesium oxide, and magnesium hydroxide Hydroxymagnesium compounds, Grignard compounds represented by butylmagnesium chloride, organometallic magnesium compounds represented by butylethylmagnesium, inorganic acid and organic acid magnesium salt compounds represented by magnesium carbonate and magnesium stearate , And mixtures thereof, and compounds whose average composition formula is a mixed formula thereof (for example, compounds such as Mg (OEt) _m Cl _2-m ; 0 <m <2), and the like can be used. Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are particularly preferred.

(I-3) Halogen:
As the halogen, fluorine, chlorine, bromine, iodine, and a mixture thereof can be used. Of these, chlorine is particularly preferred.
The halogen is generally supplied from the above titanium compounds and / or magnesium compounds, but can also be supplied from other compounds. Typical examples include silicon halide compounds typified by silicon tetrachloride, aluminum halide compounds typified by aluminum chloride, halogenated organic compounds typified by 1,2-dichloroethane and benzyl chloride, Halogenated borane compounds represented by trichloroborane, phosphorus halide compounds represented by phosphorus pentachloride, tungsten halide compounds represented by tungsten hexachloride, molybdenum halide compounds represented by molybdenum pentachloride , Etc. These compounds can be used not only alone but also in combination. Of these, silicon tetrachloride is particularly preferred.

(I-4) Electron donor:
The solid component (I) of the present invention can contain an electron donor, if necessary, in addition to the above-mentioned titanium, magnesium and halogen as long as the performance of the catalyst is not hindered. As will be described later, the compound (I-4) used as an optional component in the present invention may be the same as or different from the electron donor (III).
Representative examples of the electron donor include compounds disclosed in JP-A No. 2004-124090. In general, organic acids and inorganic acids and derivatives thereof (esters, acid anhydrides, acid halides, amides), ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amines It is desirable to use compounds.

  Examples of the organic acid compound that can be used as an electron donor include aromatic polycarboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n-butyl-malonic acid. One or two substituents such as malonic acid or 2-n-butyl-succinic acid having one or two substituents in the 2-position as shown above, or one or more in the 2-position and 3-position respectively. Aliphatic carboxylic acid compounds typified by succinic acid having the above-mentioned substituents, aliphatic carboxylic acid compounds typified by propionic acid, aromatic and aliphatic typified by benzenesulfonic acid and methanesulfonic acid Examples thereof include sulfonic acid compounds. These carboxylic acid compounds and sulfonic acid compounds may have an arbitrary number of unsaturated bonds at arbitrary positions in the molecule like maleic acid, regardless of whether they are aromatic or aliphatic.

Examples of the organic acid derivative compound that can be used as an electron donor include the above-mentioned organic acid esters, acid anhydrides, acid halides, amides, and the like.
Aliphatic and aromatic alcohols can be used as the alcohol that is a constituent of the ester. Among these alcohols, alcohols composed of aliphatic free radicals having 1 to 20 carbon atoms such as ethyl group, butyl group, isobutyl group, heptyl group, octyl group and dodecyl group are preferable. More preferably, an alcohol comprising an aliphatic radical having 2 to 12 carbon atoms is desirable. Further, an alcohol composed of an alicyclic free group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group can also be used.

Fluorine, chlorine, bromine, iodine, or the like can be used as the halogen that is a component of the acid halide. Of these, chlorine is most preferred. In the case of polyhalides of polyvalent organic acids, the plurality of halogens may be the same or different.
Aliphatic and aromatic amines can be used as the amine that is a constituent of the amide. Among these amines, ammonia, aliphatic amines typified by ethylamine and dibutylamine, amines having aromatic free radicals typified by aniline and benzylamine, and the like can be exemplified as preferable compounds. .

  Examples of inorganic acid compounds that can be used as electron donors include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid. As derivatives of these inorganic acids, it is desirable to use esters. Specific examples include tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and the like.

  Ether compounds that can be used as electron donors include aliphatic ether compounds typified by dibutyl ether, aromatic ether compounds typified by diphenyl ether, 2-isopropyl- Represented by 1,3-dimethoxypropane having one or two substituents at the 2-position, such as 2-isobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane Examples thereof include aliphatic polyvalent ether compounds and polyvalent ether compounds having aromatic free radicals represented by 9,9-bis (methoxymethyl) fluorene in the molecule. Preferred examples of the polyvalent ether compounds may be selected from the examples of compounds having at least two ether bonds in the present specification.

Examples of the ketone compound that can be used as an electron donor include aliphatic ketone compounds typified by methyl ethyl ketone, aromatic ketone compounds typified by acetophenone, 2,2,4,6,6-pentamethyl-3,5. -The polyvalent ketone compound represented by heptanedione etc. can be illustrated.
Examples of the aldehyde compound that can be used as an electron donor include aliphatic aldehyde compounds typified by propionaldehyde, aromatic aldehyde compounds typified by benzaldehyde, and the like.

  Examples of the alcohol compound that can be used as the electron donor include aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, phenol typified by phenol and cresol. Examples thereof include derivative compounds, aliphatic or aromatic polyvalent alcohol compounds represented by glycerin and 1,1′-bi-2-naphthol, and the like.

  Examples of amine compounds that can be used as electron donors include aliphatic amine compounds represented by diethylamine, nitrogen-containing alicyclic compounds represented by 2,2,6,6-tetramethyl-piperidine, and aniline. Representative aromatic amine compounds, nitrogen atom-containing aromatic compounds represented by pyridine, polyvalent amine compounds represented by 1,3-bis (dimethylamino) -2,2-dimethylpropane, etc. It can be illustrated.

  Further, as a compound that can be used as an electron donor, a compound containing a plurality of the above functional groups in the same molecule can also be used. Examples of such compounds include ester compounds having in the molecule an alkoxy group represented by acetic acid- (2-ethoxyethyl) and ethyl 3-ethoxy-2-t-butylpropionate, 2-benzoyl-benzoic acid Ketoester compounds represented by ethyl, ketoether compounds represented by (1-t-butyl-2-methoxyethyl) methylketone, N, N-dimethyl-2,2-dimethyl-3-methoxypropylamine Examples include amino ether compounds typified, halogen ether compounds typified by epoxy chloropropane, and the like.

  These electron donors can be used not only alone but also in combination with a plurality of compounds. Among these, preferred are dibutyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid ester compounds typified by diheptyl phthalate, phthalic acid halide compounds typified by phthaloyl dichloride, 2-n- Malonic acid ester compounds having one or two substituents at the 2-position such as butyl-diethyl malonate, one or two substituents at the 2-position such as 2-n-butyl-diethyl succinate, or 2 Succinic acid ester compounds having one or more substituents at each of the 3-position and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane Such aliphatic polyvalent ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position Polyhydric d having a 9,9-bis (methoxymethyl) aromatic radical of typified fluorene in the molecule - ether compounds, and the like.

The amount ratio of each component constituting the solid component (I) in the present invention may be any as long as the effects of the present invention are not impaired, but generally it is preferably within the following range.
The amount of the titanium compound used is a molar ratio (number of moles of titanium compound / number of moles of magnesium compound) with respect to the amount of magnesium compound used, and is preferably in the range of 0.0001 to 1,000. In particular, the range of 0.01 to 10 is desirable.
The amount of halogen used is the molar ratio (number of moles of the compound serving as the halogen source / magnesium) with respect to the amount of magnesium compound used, regardless of whether each of the magnesium compounds and titanium compounds contains halogen. The number of moles of the compound is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100.
When the electron donor is used, the amount used is a molar ratio (number of moles of electron donor / number of moles of magnesium compound) with respect to the amount of magnesium compound used, and is preferably in the range of 0.001 to 10. Particularly preferably, it is in the range of 0.01 to 5.

The solid component (I) in the present invention is obtained by contacting the components constituting the above in the above quantitative ratio. As the contact condition of each component, it is necessary that oxygen does not exist, but any condition can be used as long as the effect of the present invention is not impaired. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, and the like, and a method of contacting by stirring in the presence of an inert diluent.

  In preparing the solid component (I), washing with an inert solvent may be performed in the middle and / or finally. Examples of preferable solvent species include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene.

(II) Organoaluminum compound:
The obtained titanium-containing solid component (I) can be further used in combination with an organoaluminum compound (II) and an electron donor (III) as a catalyst for olefin polymerization.
As the organoaluminum compound (II), compounds disclosed in JP-A No. 2004-124090 can be used. In general, it is desirable to use a compound represented by the following general formula (1).
R ¹ aAlXb (OR ² ) c (1)
(In the general formula (1), R ¹ represents a hydrocarbon group. X represents a halogen or hydrogen. R ² represents a hydrocarbon group or a bridging group by Al. A ≧ 1, 0 ≦ b ≦ 2, 0 ≦ c ≦ 2, and a + b + c = 3.)

In general formula (1), R ¹ is a hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. Among these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In general formula (1), X is halogen or hydrogen. Examples of halogen that can be used as X include fluorine, chlorine, bromine, iodine, and the like. Of these, chlorine is particularly preferred.
In the general formula (1), R ² is a hydrocarbon group or a bridging group by Al. In addition, alumoxane compounds typified by methylalumoxane can be used as the organoaluminum compound.

Examples of compounds that can be used as the organoaluminum compound (II) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, diethylaluminum ethoxide, methylalumoxane, and the like. Can be mentioned. Of these, triethylaluminum and triisobutylaluminum are preferable.
As the organoaluminum compound (II), not only a single compound but also a plurality of compounds can be used in combination.

(III) Electron donor:
Examples of compounds that can be used as the electron donor (III) include, for example, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, Oxygen, nitrogen, in molecules such as urea and thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide and thioethers, neoalcohols, silanols, An organic compound having any atom of sulfur and phosphorus, an organic silicon compound having a Si—O—C bond in the molecule, and the like can be mentioned.

  Specific examples of ethers include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, di-i-amyl ether, and di-n-pentyl ether. 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 glyco Examples of the alcohols include methanol, ethanol, propanol, butanol, pentanole, hexanole, octanole, 2-ethylhexanol. And allyl alcohol, benzyl alcohol, ethylene glycol, glycerin and the like. Bruno - le, cresol - le, xylenol - le, Echirufeno - Le naphth - Le like.

  Specific examples of esters include methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, acetic acid-n-propyl, acetic acid-i-propyl, butyl formate, amyl acetate, acetic acid-n-butyl 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, Monocarboxylic acid esters such as ethyl aniseate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, naphthoate-2-ethylhexyl, ethyl phenylacetate , Diethyl succinate, diethyl melmalonate, Aliphatic polycarboxylic esters such as diethyl tilmalonate, dibutyl maleate, diethyl butyl maleate, 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-ethylhexyl phthalate, di-n-octyl phthalate, diethyl i-phthalate, i-phthalate Aromatic polycarboxylic acid esters such as dipropyl acid, dibutyl i-phthalate, di-2-ethylhexyl i-phthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, and di-i-butyl naphthalenedicarboxylate Can be mentioned.

  Specific examples of aldehydes include acetaldehyde, propionaldehyde, benzaldehyde, etc., and carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, benzoic acid and the like. Examples of carboxylic acids and acid anhydrides such as benzoic anhydride, phthalic anhydride, and tetrahydrophthalic acid include ketones such as acetone, methyl ethyl ketone, methyl-i-butyl ketone, and benzophenone.

  Specific examples of nitrogen-containing compounds include nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline. 2,4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine, 2,2,5,5, tetramethylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, aniline, Amines such as dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N′-β-dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide, etc. Amides, ureas such as N, N, N ′, N′-tetramethylurea, phenyl isocyanate , Tolyl diisocyanate - an isocyanate, such as bets - DOO acids, azo compounds such as azobenzene can be exemplified.

  Specific examples of phosphorus-containing compounds include phosphines such as ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide, dimethyl phosphite, di-n-octylphosphine, triphenylphosphine, Examples include phosphines such as triphenylphosphine oxide, and phosphites such as dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, and triphenyl phosphite.

  Specific examples of the sulfur-containing compound include thioethers such as diethyl thioether, diphenyl thioether, and methylphenyl thioether, ethyl thio alcohol, n-propyl thio alcohol, thiophenol, and the like. And thioalcohols.

As the organosilicon compound used in the present invention, it is desirable to use a compound represented by the following general formula.
R ² R ³ Si (OR ⁴ ) ₂ (2)
(Wherein, R ² is a chain hydrocarbon group having 2 primary carbon atoms, R ³ is R ² identical or different aliphatic hydrocarbon group or a heteroatom-containing hydrocarbon group, R ⁴ Is a hydrocarbon group.)

In the general formula (2), R ² represents a chain hydrocarbon group having a secondary carbon atom. The hydrocarbon group having a secondary carbon atom that can be used as R ² is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples include i-propyl, among others. It is desirable to use a group, i-butyl group, sec-butyl group, i-pentyl group, i-hexyl group, 2-ethylhexyl group and the like.

In general formula (2), R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. The hydrocarbon group that can be used as R ³ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ³ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ³ . It is desirable to use a cyclohexyl group or the like.
When R ³ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group R ^3, it is desirable to select from the example of the case where R ³ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

In general formula (2), R ⁴ represents a hydrocarbon group. The hydrocarbon group that can be used as R ⁴ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁴ include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And an aliphatic hydrocarbon group. Of these, a methyl group and an ethyl group are most preferable.

Preferable specific examples of the organosilicon compound used in the present invention include i-Pr ₂ Si (OMe) ₂ , i-Bu ₂ Si (OMe) ₂ , sec-Bu ₂ Si (OMe) ₂ , i-Pen ₂ Si. (OMe) ₂ , i-Pr (i-Bu) Si (OMe) ₂ , i-Pen (i-Bu) Si (OMe) ₂ , i-Pr (Me) Si (OMe) ₂ , i-Bu (Me) _{) Si (OEt) 2, sec} -BuMeSi (OMe) 2, i-Pr (Et 2 N) Si (OMe) 2, i-Bu (Et 2 N) Si (OEt) 2, and the like.

(2) Pre-polymerization and pre-activation of olefin polymerization catalyst In the method for producing a propylene-based block copolymer resin composition of the present invention, the ethylene polymer (A) is prior to the step (b-1), In the presence of an olefin polymerization catalyst, one or more monomers selected from the group consisting of ethylene alone or an α-olefin having 3 to 12 carbon atoms are polymerized to 1 g of metal atoms in the olefin polymerization catalyst. It is preferable to carry out the preactivation step (step (a-2)) for producing 0.01 to 500 g of ethylene polymer (A).
Furthermore, prior to the step (a-2), propylene is polymerized in the presence of an olefin polymerization catalyst (I) 0.01 to 1 g of a solid component containing titanium, magnesium and halogen as essential components. It is preferable to produce by carrying out a prepolymerization step (step (a-1)) for producing and supporting 100 g of polypropylene.

  The production method is preferably a continuous production method from the viewpoint of imparting high melt tension of the propylene-based block copolymer resin composition, foaming performance, and the foam has a higher closed cell ratio, that is, ethylene. A method in which the preactivation of the polymer (A) is performed prior to the production of the propylene-based block copolymer (B) is desirable.

  The polymerization conditions in the prepolymerization step are usually milder than those in the main polymerization. As the prepolymerized monomer, α-olefin can be used, and ethylene or propylene is preferable. In addition, when the polymerization is performed using a prepolymerization catalyst, an additional component can be used. At the time of or after the contact of each of the above components, a polymer such as polyethylene and polypropylene, and a solid of an inorganic oxide such as silica and titania may coexist or may be brought into contact.

As a specific step of the prepolymerization step in the production method of the present invention, a step of producing and supporting 0.01 to 100 g of polypropylene with respect to 1 g of the titanium-containing solid catalyst component (I) (step (a-1)) For example, 0.01 to 100 moles, preferably 0.1 to 50 moles, and 1 mole of titanium atoms with respect to 1 mole of titanium atoms in the titanium-containing solid catalyst component (I) Into an olefin polymerization catalyst formed by combining 0 to 50 mol, preferably 0 to 20 mol, of an organosilicon compound (III) with respect to the above, polypropylene having an intrinsic viscosity of less than 15 dl / g is added to 1 g of titanium-containing solid catalyst component (I). It is carried out by loading 0.01 to 100 g per unit.
If this prepolymerization is not performed, the powder BD (bulk density) and the powder characteristics may deteriorate.

Moreover, a preactivation process (process (a-2)) is a process of manufacturing an ethylene polymer (A) and making this carry | support to a titanium containing solid component (I). This preactivation step will be specifically exemplified.
The preactivated catalyst is obtained by supporting the ethylene polymer (A) on the titanium-containing solid component (I). As long as the conditions are such that the titanium-containing solid component (I) is produced at a rate of 0.01 to 2,000 g, preferably 0.05 to 1,000 g, more preferably 0.1 to 500 g, there is no particular limitation. However, usually at a relatively low temperature of about −40 to 40 ° C., preferably −40 to 30 ° C., more preferably about −40 to 20 ° C., 0.1 to 5 MPa, preferably 0.2 to 5 MPa, It is particularly preferably carried out under a pressure of 0.3 to 5 MPa for 1 minute to 24 hours, preferably 5 minutes to 18 hours, particularly 10 minutes to 12 hours. The preactivation may be carried out in the presence of hydrogen, but it is desirable not to use hydrogen in order to obtain an ethylene polymer (A) having an intrinsic viscosity of 15 to 100 dl / g.
The monomer supply method can be any method such as a method of maintaining the monomer in the reaction tank at a constant speed, a constant pressure state or a constant concentration, a combination thereof, or a stepwise change. .

  In the prepolymerization and preactivation, if the amount of the organoaluminum compound (II) used is too small, the polymerization reaction rate may be too slow. In addition, if the amount used is too large, the effect of improving the polymerization reaction rate will reach its peak, and the residue of organoaluminum compound (II) may increase in the finally obtained propylene block copolymer. is there. Moreover, when there is too much usage-amount of electron donor (II), there exists a possibility that a polymerization reaction rate may fall.

Prepolymerization and preactivation can be performed by, for example, butane, pentane, hexane, heptane, octane, isooctane, decane, dodecane, and other aliphatic hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane, and other alicyclic hydrocarbons, toluene, xylene. , Aromatic hydrocarbons such as ethylbenzene, other inert solvents such as gasoline fractions and hydrogenated diesel oil fractions, etc. It is also possible to carry out in the gas phase. When the amount of the solvent used is too large, not only a large reaction vessel is required, but also it is difficult to efficiently control and maintain the polymerization reaction rate. Moreover, it can wash | clean with inert solvents, such as hexane and heptane, after preliminary polymerization. After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

  The obtained preactivated catalyst is combined with an organoaluminum compound (II ′) and an electron donor (III ′) as necessary to control the production rate and / or stereoregularity of the olefin polymer. For this purpose, it can also be used for the production of propylene-based block copolymers. The newly added organoaluminum compound (II ′) and the electron donor such as the organosilicon compound (III ′) should be the same as the organoaluminum compound (II) and organosilicon compound (III) described above. These compounds can be used alone or in admixture of two or more. The newly added organoaluminum compound (II ′) and the electron donor, for example, the organosilicon compound (III ′), are independently of the organoaluminum compound (II) and organosilicon compound (III) used for the preactivation. It may be the same.

  The method for producing a propylene-based block copolymer resin composition of the present invention is a preliminarily obtained by preactivating by supporting an ethylene polymer (A) on an olefin polymerization catalyst subjected to prepolymerization with polypropylene. Propylene-based block copolymer resin composition that is more excellent in melting characteristics and suitable for foaming performance is produced by producing propylene-based block copolymer (B) that is an olefin multistage polymer in the presence of an activation catalyst. It can be obtained.

(3) Propylene-based block polymer resin composition production method (I) Polymerization method:
In the method for producing a propylene-based block polymer resin composition of the present invention, as the polymerization method, known olefins such as a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method, a liquid phase polymerization method, and a combination thereof are used. A polymerization process can be used.
Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, isooctane, decane, and dodecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, toluene, xylene, ethylbenzene, and the like Aromatic hydrocarbons, slurry polymerization methods for polymerizing olefins in inert solvents such as gasoline fractions and hydrogenated diesel oil fractions, bulk polymerization methods using olefins themselves as solvents, olefins It is possible to use a gas phase polymerization method in which the polymerization is carried out in the gas phase, a liquid phase polymerization method in which the polyolefin produced by polymerization is a liquid, or a polymerization process in which two or more of these processes are combined.

  In slurry polymerization, the polymerization temperature is 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. Below, the polymerization is carried out in a continuous, semi-continuous, or batch process under conditions where the polymerization time is from 5 minutes to 12 hours.

  In the gas phase polymerization, the polymerization temperature is 20 to 100 ° C., preferably 30 to 100 ° C., particularly preferably 40 to 90 ° C., and the polymerization pressure is 1.2 to 5 MPa, preferably 1.6 to 4.2 MPa. The pressure of is preferably. In the gas phase polymerization, the polymerization is carried out under conditions of a continuous type and a semi-continuous type and a polymerization time of 5 minutes to 12 hours.

  In bulk polymerization, the polymerization temperature is 20 to 100 ° C., preferably 30 to 100 ° C., particularly preferably 40 to 90 ° C., and the polymerization pressure is 1.5 to 5.0 MPa, preferably 1.8 to 4. A pressure of 0 MPa is preferred. In the bulk polymerization, the polymerization is carried out under conditions of continuous type and semi-continuous type and a polymerization time of 5 minutes to 12 hours.

In the production method of the present invention, a polymerization method using one polymerization apparatus continuously is preferable because it can be produced at a low cost.
Since the polymerization process of the present invention consists of three processes (b-1-1), (b-1-2), and (b-2), it is produced from a continuous polymerization process using a continuous tank consisting of 2-3 tanks. It is preferable. Specifically, it is preferable to carry out by the gas phase polymerization method throughout the production of the propylene-based block polymer resin composition, since it can be produced continuously using one polymerization apparatus.

  In the step (b-1) of producing the propylene polymer (B-1), the production of the propylene-based block polymer resin composition in the present invention is carried out by adding a molecular weight regulator such as propylene and hydrogen. A step (b-1-1) for producing the union (B-1-1) and a step for producing a high molecular weight propylene polymer by performing polymerization without substantially adding a molecular weight modifier such as hydrogen (b- 1-2), which comprises a step (b-2) of introducing a predetermined propylene and olefin gas to obtain an olefin polymer for polymerization. Each polymerization method is briefly described below.

(II) Polymerization step:
In the production method of the present invention, under the aforementioned olefin polymerization catalyst, hydrogen or the like as a molecular weight modifier is introduced in the first step (b-1-1) to produce a low molecular weight propylene polymer (B-1). -1), and in the second step (b-1-2), a high molecular weight propylene polymer (B-1-2) is produced in the substantial absence of hydrogen, and the third step (b- In the polymerization in 2), the predetermined propylene and olefin gas are introduced, and the polymerization is performed in the substantial absence of hydrogen as in the second step, whereby the resin composition of the present invention is obtained. The order of the first and second steps is not particularly limited, but in any case of gas phase polymerization, bulk polymerization, slurry polymerization, hydrogen and the like as a molecular weight regulator are not sufficiently removed, There is a possibility that the intrinsic viscosity required by the present invention is not reached in the steps (b-1-2) and (b-2).

(I) (b-1) Step:
(B-2) In the step (b-1) performed prior to the step, hydrogen or the like which is a molecular weight modifier in the step (b-1-1) is introduced, and a low molecular weight propylene polymer (B-1- 1) is manufactured, and step (b-1-2) consists of two steps of manufacturing a high molecular weight propylene polymer (B-1-2) substantially in the absence of hydrogen.

(I-1) Step (b-1-1):
The propylene-based block polymer resin composition obtained by the production method of the present invention adjusts the molecular weight of the resulting propylene-based block polymer resin composition by using hydrogen or the like during polymerization, as in the known olefin polymerization method. In the step (b-1-1), the low molecular weight propylene polymer (B-1-1) is produced in the polymerization method described above in the presence of an olefin polymerization catalyst. Molar ratio of hydrogen usage to usage: H ₂ / C ₃ (molar ratio) = 0.01-10. Preferably, the raw material is fed at a molar ratio of the amount of hydrogen used to the amount of propylene used of H ₂ / C ₃ = 0.1-10. It is more preferable to feed with H ₂ / C ₃ = 0.1-8. In a polymerization method using a polymerization solvent such as bulk polymerization and slurry polymerization, the amount of the raw material used dissolved in the polymerization solvent is not included in the amount used in the present invention.

(I-2) (b-1-2) Step:
In the step (b-1-2) performed following the step (b-1-1), propylene is polymerized substantially in the absence of hydrogen, and the intrinsic viscosity ([η]) is 6 to 15 dl / This is a step of producing a propylene polymer (B-1-2) of g.
Also in the (b-1-2) step, the molecular weight of the resulting propylene polymer can be adjusted by using hydrogen or the like during the polymerization. In the above-described polymerization method in the presence of an olefin polymerization catalyst, in the step (b-1-2), the polymerization is carried out by introducing predetermined propylene and substantially not containing hydrogen.

  As a method of adjusting the raw material and feeding, the target mixed raw material is prepared in a regulating tank in advance and fed into a reaction vessel, propylene monomer, hydrogen gas, and reaction from each pipe. A method of adjusting and feeding a target amount to a container, connecting a hydrogen gas supply pipe to a propylene monomer supply pipe, adjusting a feed amount of each raw material, and adding a target mixed raw material to a reaction container For example, a method of feeding to the above. From the viewpoint of dispersibility of raw materials in the reaction vessel and simplification of the process, a method of connecting a hydrogen gas pipe to a pipe for supplying propylene monomer is preferable. Further, there are a continuous feed method in which the raw materials are fed at a constant speed, an intermittent feed method in which the feed is periodically turned on and off, and the like. As long as the composition is not intentionally changed without departing from the present invention, the gas composition in the reaction vessel is kept constant, and the resulting propylene polymers (b-1-1) and (b-1-2) It is preferable to carry out by a continuous feed method because the composition of the above is kept constant.

(Ii) Step (b-2):
The step (b-2) performed following the step (b-1) is one or more monomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms in the substantial absence of hydrogen. And propylene are polymerized to produce an olefin random copolymer (B-2) having an intrinsic viscosity ([η]) of 8 to 25 dl / g.
Also in the (b-2) step, the molecular weight of the resulting propylene-based block polymer resin composition can be adjusted by using hydrogen or the like during the polymerization, as in the known olefin polymerization method. In the above-described polymerization method in the presence of an olefin polymerization catalyst, in the step (b-2), which is the second step, the polymerization is carried out by introducing a predetermined propylene and olefin gas and substantially not containing hydrogen. .
In the present invention, regardless of which polymerization method is employed, the hydrogen concentration in the polymerization tank in the steps (b-1-2) and (b-2) needs to be carried out under the condition of 5 ppm or less. . A hydrogen concentration of 5 ppm or more is not preferable because the intrinsic viscosity of the olefin random copolymer (B-2) is lowered and the foaming performance of the propylene block copolymer resin composition is lowered.

  In any polymerization method of slurry polymerization method using continuous polymerization, bulk polymerization method, gas phase polymerization method, liquid phase polymerization method, or combination polymerization method thereof, in the polymerization medium transferred to each step In order to remove or separate hydrogen contained in the water, it is desirable to provide a degassing tank (retention chamber) between each polymerization apparatus. In the case of utilizing batch polymerization, there is no equipment limitation because hydrogen can be removed by replacing the polymerization medium.

The degassing tank is an inert solvent such as an aliphatic hydrocarbon, an inert gas, or a polymerization of at least a part of the polymerization medium transferred from the polymerization apparatus used in the step (b-1-1) to the residence chamber. A device for performing substitution with a raw material or the like, or a device for reducing H ₂ dissolved in a polymerization medium due to temperature change, is provided in steps (b-1-2) or (b-2). The polymerization medium transferred to the polymerization apparatus to be used functions so as not to substantially contain hydrogen.

  In the present invention, when steps (b-1-1), (b-1-2) and step (b-2) are all carried out by a gas phase polymerization method, In the gas transferred from the degassing tank to the next polymerization apparatus, at least a part of the gas transferred from the polymerization apparatus to the residence chamber is replaced with an inert gas or a polymerization raw material gas. Substantially no hydrogen is contained.

In the polymerization apparatus used in steps (b-1-2) and (b-2), it is contained in the polymerization medium, propylene monomer (polymerization monomer), and α-olefin used for polymerization from within the polymerization apparatus. The following operations are performed for the purpose of eliminating trace hydrogen components.
A part of the gas phase in the polymerization apparatus is periodically or continuously extracted from the upper pipe to the condenser and condensed in the condenser. The condensed liquid is separated into components and then transferred as a polymerization medium (polymerization monomer) into each polymerization apparatus.

As a method of removing propane and trace hydrogen components accumulated in the system from the vapor phase components separated by the condenser, a method of exhausting a part of the separated gas phase components by flow control, For example, there is a method in which a part of rectification is separated or all of the rectification is separated and then transferred as a polymerization medium and a polymerization monomer into a polymerization apparatus.
By operating the degassing tank (retention chamber) and the polymerization apparatus, the hydrogen concentration in the polymerization tank in the steps (b-1-2) and (b-2) can be carried out under a condition of 5 ppm or less.

  As an example, the first, second and third polymerization apparatuses and the degassing tank can be arranged as shown in FIG. 1 in a continuous horizontal gas phase polymerization apparatus. In FIG. 1, the step (b-1-2) is performed in the reactor 20 through the degassing tank 40 from the step (b-1-1) performed in the polymerization vessel 10. According to such a method of providing a degassing tank, the receiving valve and the extracting valve are equipped, and can be completely separated from the first and second polymerization apparatuses, and can be replaced with an inert gas or a polymerization raw material. It is possible to transfer the polymer obtained in step (b-1-1) to step (b-1-2) in a low-concentration hydrogen atmosphere.

  Similarly, in FIG. 1, the polymer obtained in the step (b-1-2) after passing through the degassing tank 50 from the step (b-1-2) performed in the polymerization vessel 20 is converted into the reactor 30. Transfer is carried out in a low concentration hydrogen atmosphere.

  In the reactor 10, the step (b-1-1), in the reactor 20, the step (b-1-2) is performed, and in the reactor 30, the propylene polymer subjected to the step (b-2) is reacted. Distributed throughout the vessel. During the production of polypropylene, the operation is carried out under the temperature conditions of 1000 to 3000 kPa and about 50 to 85 ° C.

  In the reactor 10, the catalyst system and the cocatalyst system are introduced through the inlet conduits 1 and 2 arranged along the space between the front ends of the reactor 10. An inert carbon component such as liquefied propylene or hexane as a liquefied component for heat removal is introduced through the pipe 17 (pipe 27 in the reactor 20). The steam recirculation flow is introduced through the pipe 18 (pipe 28). Moreover, hydrogen for composition adjustment is connected to the pipe 4 (pipe 6) and introduced.

  The exhaust gas from the reactor is removed from the pipe 13 (pipe 23). In a gas phase polymerization reactor, generally, a certain amount of polymer fine powder is generated. Since polymer fines entrained in the reactor exhaust gas are also generated, the reactor can be used after substantially removing the polymer fines by using a trap, filter, settling machine, cyclone or scrubber, or a combination thereof. It is preferable to cool the exhaust gas with a condenser-15 (condenser-25). After leaving the condenser 15 (condenser-25), it is transferred to the gas-liquid separation tank 11 (gas-liquid separation tank 21) via a conduit.

Since the polypropylene polymers (B-1-1) and (B-1-1) obtained in the steps (b-1-1) and (b-1-2) are continuously produced, the reactor 10, Move to the downstream end of 20 reactors.
For example, in the reaction from the step (b-1-1) to the step (b-1-2) and the reaction from the reactors 10 to 20, the degassing tank 40 has a valve 41 attached to the upper part of the staying tank. Open and periodically take up the polypropylene polymer (B-1-1) and the polymerization medium (polymerization monomer). At this time, the valve 42 attached to the lower part of the staying tank is tightened. Moreover, it is preferable to hold | maintain the pressure lower than the reactor 10 at the time of reception of the polypropylene polymer (B-1-1) to the degassing tank 40. FIG. After receiving a predetermined amount of the polypropylene polymer (B-1-1) into the degassing tank 40, hydrogen, polymerization medium (polymerization monomer), etc. taken from the reactor 10 with the inert gas or polymerization raw material through the pipe 45 are replaced. To do. The replacement gas is preferably replaced with a polymerization medium (polymerization monomer), that is, a propylene gas which is a polymerization raw material gas. The use of propylene monomer is advantageous in production because the monomer partial pressure in the reactors 10 and 20 can be maintained. The discharged inert gas or polymerization raw material is returned to the condenser 15 through the pipe 46. It is preferable to perform the same operation in the steps (b-1-2) to (b-2).

The polypropylene polymer (B-1-2) is periodically discharged to the reactor 30 through the polymer supply pipe 70.
In the reactor 30, as in the reactors 10 and 20, an inert carbon component such as liquefied propylene or hexane is introduced through a pipe 37 as a liquefied component for heat removal. A recirculated stream of steam is introduced through line 38. Further, hydrogen, ethylene and α-olefin for composition adjustment are connected to the pipe 8 and introduced. In addition, an activity-suppressing additive such as oxygen, carbon dioxide, ethanol, and acetone is connected to the pipe 9 and introduced.

The reactor exhaust gas is removed from the pipe 33. Also in the reactor 30, the polymer fines entrained in the reactor exhaust gas were substantially removed by using a trap, filter, settling machine, cyclone or scrubber, or a combination thereof. It is preferable to cool the reactor exhaust gas with a condenser 35 later. The effluent leaving the condenser 35 is transferred to the gas / liquid separator 31 via a conduit. Thereafter, the trace hydrogen accumulated in the system is removed by the rectifying / separating device 60, and after passing through the compressor 36, the raw material supply pipe 8 is connected.
Since the polypropylene polymer (B-2) obtained in the step (b-2) is continuously produced, the polypropylene polymer (B-2) moves to the piping 39 side which is the outlet side of the reactor 30. After being separated from the polymerization medium, the polypropylene polymer (B) is periodically discharged through the pipe 39.

  In the step (b-1-1), when the molar ratio of the amount of hydrogen used to the amount of propylene used increases, the production amount of the boiling heptane extraction rate increases. Therefore, it is preferably carried out by a bulk polymerization method or a gas phase polymerization method that does not require a purification system. Further, in the slurry polymerization and bulk polymerization, in the step (b-2), the rubber part is dissolved in the solution part and the liquid monomer and there is a problem that the impact strength is lowered. Is preferred. Furthermore, it is preferable from the viewpoint of manufacturing cost that both the step (b-1) and the step (b-2) are performed by a gas phase polymerization method and continuously performed.

The weight ratio of (B-1) and (B-2) affects the foaming performance, rigidity, and impact strength of the resulting molded product. Therefore, in order to adjust the weight ratio between the component (B-1) and the component (B-2), the first polymerization step for producing the component (B-1) and the second for producing the component (B-2). The production ratio in the polymerization process may be controlled. It is well known to the operator that the production amount ratio of both can be controlled by changing the polymerization temperature and the residence time.
The adjustment of the production ratio is also affected by the activity of the olefin polymerization catalyst in each step, but the olefin polymerization catalyst in each step also affects the catalyst type, process, residence time, etc. used. It is an activity of 1,000 to 500,000 g-PP per 1 g of the contained solid catalyst component (I).

(III) Additive:
The polypropylene-based block copolymer resin composition obtained by the production method of the present invention includes various polymers and fillers (fillers) within the range that does not impair the object of the present invention when mixing and producing each component. Any additive may be added.
Examples of the polymer include low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene / unsaturated carboxylic acid ester copolymer, and carboxylic acid modified polyolefin.
The filler may be either an organic filler or an inorganic filler, specifically glass fiber, mineral fiber, calcium carbonate, talc, kaolin clay, mica, quartz powder, diatomaceous earth, barium sulfate, pumice powder. , Pulp powder, carbon fiber, synthetic fiber, glass hollow body and the like. Of these, glass fiber, talc, or mica is particularly preferable.
The filler content is preferably 5 to 50% by weight with respect to the entire molding material because a molded article having excellent rigidity and light weight can be obtained. When a glass fiber is blended with polypropylene as a filler to form a thermoplastic resin molding material, a modified polypropylene is used as the polypropylene because the molded article having excellent compatibility between glass and polypropylene and high rigidity can be obtained. Is preferred.
Additives include antioxidants, heat stabilizers, weather stabilizers, light stabilizers, UV absorbers, antistatic agents, anti-aging agents, fatty acid metal salts, softeners, dispersants, nucleating agents, lubricants, Examples include flame retardants, pigments, dyes, organic fillers, and inorganic fillers.

  As the antioxidant, phenolic and sulfur compounds can be blended, and the blending amount is 0.01 to 1 part by weight per 100 parts by weight of the polypropylene block copolymer resin composition. Preferably 0.05-0.3 weight part is desirable.

3. Foam Molded Article Using Polypropylene Block Polymer Resin Composition A polypropylene block polymer resin composition (hereinafter also referred to as “resin composition”) obtained by the production method of the present invention is a known extruded foam, It can be used for injection foam molding and supercritical foaming. In particular, the polypropylene block copolymer resin composition obtained in the present invention is suitable for injection foam molding because of its high MFR and excellent melting characteristics.

  As a method for producing an extrusion foamed molded article, a known method such as adding a foaming agent to the polypropylene block polymer resin composition of the present invention, melt-kneading, and then extruding the composition under a low pressure through a T die or a circular die. The extrusion foaming method can be employed. The foamed molded product can be produced by extruding directly from an extruder into a sheet or cylinder and then cutting in the extrusion direction. The amount of the foaming agent added is 0.1 to 6 parts by weight with respect to 100 parts by weight of the polypropylene block polymer resin composition of the present invention.

  As an injection molding method, a basic method for producing a foamed molded article is a process of injection-filling a foamable polymer resin composition obtained by blending a polymer resin composition with a foaming agent into an injection mold, and subsequently. It comprises at least two stages of the foam molding process. The specific method is not particularly limited.

  As the blowing agent used, volatile blowing agents include aliphatic hydrocarbons such as propane and butane, alicyclic hydrocarbons such as cyclobutane, chlorodifluoromethane, trifluoromethane, dichlorodifluoromethane, and dichlorotrifluoroethane. And halogenated hydrocarbons such as dichlorotetrafluoroethane, carbon dioxide, carbon dioxide, argon, inorganic gases such as air, water, and the like.

  The solvent-type foaming agent is a substance that functions as a foaming agent by being generally injected from the hopper or cylinder portion of the molding machine and absorbed or dissolved in the molten raw material resin, and then evaporated in an injection mold. Low boiling point aliphatic hydrocarbons such as propane, butane, neopentane, heptane, isohexane, hexane, isoheptane, heptane, low boiling point fluorine-containing hydrocarbons typified by Freon gas, and the like can be used.

  The decomposable foaming agent is pre-blended into the raw polymer resin composition and then supplied to the molding machine, and the foaming agent decomposes under the cylinder temperature conditions of the molding machine to produce gases such as carbon dioxide and nitrogen gas. It is a generated compound. It may be an inorganic foaming agent or an organic foaming agent, an organic acid such as citric acid that promotes gas generation, an organic acid metal salt such as sodium citrate, etc. May be added together as a foaming aid.

Specific examples of the decomposable foaming agent include the following compounds.
(1) Inorganic foaming agent: sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite

(2) Organic foaming agent:
(A) N-nitroso compound: N, N′-dinitrosoterephthalamide, N, N′-dinitrosopentamethylenetetramine (b) Azo compound: azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azo Diaminobenzene, barium azodicarboxylate (c) sulfonyl hydrazide compound: benzene sulfonyl hydrazide, toluene sulfonyl hydrazide, p, p'-oxybis (benzenesulfenyl hydrazide), diphenyl sulfonyl-3,3'-disulfonyl hydrazide ( d) Azide compounds: calcium azide, 4,4′-diphenyldisulfonyl azide, p-toluenesulfonyl azide

  These foaming agents may be used alone or in combination of two or more. And a foaming agent can also be previously mix | blended with a resin composition, and can also be inject | poured from the middle of a cylinder at the time of injection molding. The gaseous blowing agent may be used in a supercritical state. Further, a foaming agent, a foaming auxiliary agent or the like may be blended in advance with the polymer to make a master batch, which may be blended with the resin composition.

  The amount of the foaming agent added is selected in consideration of the amount of gas generated from the foaming agent and the desired foaming ratio in accordance with the required physical properties of the foamed molded product, but is 0.1% relative to 100 parts by weight of the resin composition. It is desirable to adjust to 1 to 6 parts by weight, preferably 0.5 to 2 parts by weight. From the foamable resin composition within this range, it is possible to obtain a foamed molded article having uniform cell diameters and uniformly dispersed cells.

  In the case of injection foam molding, particularly for the purpose of producing a foam molded product having high mechanical strength and good appearance, it is desirable to select a molding method that forms an unfoamed skin layer on the surface of the molded product. . For this purpose, a method using an injection molding machine equipped with a mold having a variable cavity volume is preferable, and foam molding is generally performed from an injection filling process and a subsequent foaming process for enlarging the cavity. In the present invention, the molding method is not particularly limited.

  Next, an example of producing a foam by an injection foam molding method will be described. Both the polypropylene block copolymer resin composition and the decomposable foaming agent are supplied to an injection molding machine, and the foaming agent is thermally decomposed and gas is generated while the resin is melt-kneaded in the cylinder part of the molding machine. . The molten resin composition in which this gas is dissolved is injected into the mold from the tip of the nozzle and molded into a foam in the mold. The molding conditions may be appropriately selected according to the type of foaming agent, the kneading conditions, the shape of the mold or the shape of the desired foam. Usually, the resin temperature is 170 to 250 ° C., the injection molding cycle time is 1 to 60 minutes, the mold temperature is 10 to 100 ° C., the mold internal pressure is 5 to 20 MPa, the injection pressure is 10 to 200 MPa, etc. Performed under the conditions of

  The injection foam molded article obtained from the present invention can be produced by the method exemplified below using the above-mentioned foam molded article material. That is, by using an injection molding machine equipped with a heating cylinder and a mold, an injection molding method including (a) an injection process, (b) a primary cooling process, (c) a foaming process, and (d) a secondary cooling process ( Cavity-expansion foaming method).

(A) Injection process:
In the injection process, the material for the foam molded body melted in the heating cylinder is injected and filled into a cavity of a mold having a volume of 10 to 95% of a predetermined volume of the polypropylene resin foam molded body.
At this time, by setting the set temperature of the front end (nozzle side) of the heating cylinder higher than the installation temperature of the rear part (hopper side), foaming in the cylinder of the foam molded body material is suppressed, and no foam is generated. The foamed molded body material in a state can be injected into the cavity. The difference in the set temperature between the tip and the rear is 20 to 100 ° C, preferably 20 to 70 ° C, more preferably 30 to 60 ° C.

Moreover, in order to suppress foaming within the cylinder of the foamed molded material, the back pressure of the heating cylinder is set to 5 MPa or more, preferably 7 MPa or more, more preferably 10 MPa or more.
In the injection process, when the cavity volume of the mold is less than 10% of the expected volume of the polypropylene resin foam molded article, the pressure gradient applied to the foam molded article material at the time of injection becomes excessive, and uniform filling becomes difficult. Sometimes. Further, in a mold in which the cavity volume exceeds 95% of the expected volume of the polypropylene resin foam molded article, foaming starts in the injection process, and a good non-foamed layer cannot be obtained on the surface of the polypropylene resin foam molded article.

(B) Primary cooling process:
Only the surface layer in contact with the mold is solidified and the inside is cooled to a molten state with respect to the foamed molded material filled in the mold in the previous step. Specifically, it is carried out by holding the mold filled with the foamed molded body material for a certain period of time without changing its volume. The holding time is empirically determined according to the mold temperature, the type of foam molded body material, the shape of the polypropylene resin foam molded body, the thickness of the non-foamed layer, etc., but is usually about 1 to 20 seconds. is there. The preferred thickness of the non-foamed layer is about 0.2 to 2 mm.

(C) Foaming process:
After completion of the primary cooling step, the mold cavity material is expanded to a predetermined volume of the foamed molded product to foam the foamed molded product material in a molten state. For expanding the cavity, a known method such as movement of a mold by a mold clamping mechanism of an injection molding machine or movement of a slide core provided in the mold can be used.

(D) Secondary cooling step:
Secondary cooling is carried out by holding the mold without changing its volume after the mold cavity is enlarged and until the shape of the polypropylene resin foam molding is stabilized.
Since the time required for the secondary cooling varies depending on the shape of the polypropylene resin foam molded article, it is determined empirically. After completion of the secondary cooling step, the mold is opened and the polypropylene resin foam molded body is taken out.

  The foam according to the present invention has a closed cell ratio of preferably 60% or more, more preferably 70% or more. A foam having such a closed cell ratio exhibits excellent heat resistance and buffering from external force, and has high compressive strength.

Further, the foam according to the present invention has an expansion ratio of preferably 1.3 to 10 times, more preferably 1.6 to 6 times, and a density of preferably 0.09 to 0.6. (G / cm ³ ), more preferably 0.15 to 0.3 (g / cm ³ ). When in this range, the foam is excellent in light weight, heat insulation, buffering of external stress, and has high compressive strength.

  Therefore, this foam has excellent surface characteristics, light weight, excellent rigidity and impact resistance, chemical resistance, and good food hygiene. In addition, the shape is in order and the appearance is beautiful. In addition, since the raw material resin composition is mainly made of polypropylene, it hardly generates harmful gas even if it is incinerated, and is excellent in recyclability.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

The measuring method of each physical property value in the present invention is shown below.
(1) MFR:
Evaluation was performed under the conditions of 230 ° C. and 0.216 N (unit: g / 10 min) based on a method defined in JIS K7210 using a melt indexer manufactured by Takara.

(2) Intrinsic viscosity [ηA]:
Using an Oswald viscometer (manufactured by Mitsui Toatsu Chemical Co., Ltd.), measurement was performed in 135 ° C. tetralin (unit: dl / g).

(3) Intrinsic viscosity [ηB], [ηB-1], [ηB-1-1], [ηB-1-2], [ηB-2]:
Intrinsic viscosities [ηB], [ηB-1-1], [ηB-1] are GPC (gel permeation chromatograph); Waters, GPC150-C type machine, Polymer Laboratories column Measured using PlmixedB. Measurement was performed in a solvent o-dichlorobenzene at a measurement temperature of 135 ° C. using polystyrene as a standard substance. From the intrinsic viscosities [ηB] and [ηB-1-1], the intrinsic viscosities [ηB-1-2] and [ηB− 2] was calculated.

(4) Molecular weight distribution, Mn, Mw, Mz:
GPC (gel permeation chromatograph): Measured using Waters, GPC150-C type machine, Polymer Laboratories column PlmixedB. Measurement was performed in a solvent o-dichlorobenzene at a measurement temperature of 135 ° C. using polystyrene as a standard substance.

(5) Determination of ethylene polymer (A) content in the propylene-based block copolymer (B) and the polypropylene polymer (B-1):
About average ethylene polymer (A) content, it measured using the infrared spectrophotometer according to the following procedure.
(I) Sample preparation:
A sample (propylene polymer (B-1)) was molded into a sheet having a thickness of 500 μm by a heat and pressure press. The pressing conditions were a temperature of 190 ° C., a preheating time of 2 minutes, a pressing pressure of 50 MPa, and a pressing time of 2 minutes.
(Ii) Measurement of absorbance with an infrared spectrophotometer:
Using the sheet obtained above, the amount of absorption was measured under the following conditions.
Equipment: Shimadzu FTIR-8300
Resolution: 4.0 cm ⁻¹
Measurement range: 4,000 to 400 cm ⁻¹
Absorbance peak area calculation range: 700 to 760 cm ⁻¹

(Iii) Calculation of ethylene polymer (A) content in propylene polymer (B-1):
A calibration curve was prepared using a sample whose ethylene content was previously quantified by NMR, and the ethylene polymer (A) content in the propylene polymer (B-1) was calculated based on the calibration curve.
(Iv) Calculation of ethylene polymer (A) content of (B) in propylene-based block copolymer:
Calculated from the production values of the polymerization step (b-1) for producing the propylene polymer and the polymerization step (b-2) for producing the olefin random copolymer (B-2) component, The value of the polymer (A) content was obtained.

(6) Determination of ethylene content in propylene-based block copolymer (B):
The average ethylene content was measured using an infrared spectrophotometer according to the following procedure.
(I) Sample preparation:
A sample (propylene polymer (B-1)) was molded into a sheet having a thickness of 200 μm by a heat and pressure press. The pressing conditions were a temperature of 190 ° C., a preheating time of 2 minutes, a pressing pressure of 30 MPa, and a pressing time of 2 minutes.
(Ii) Measurement of absorbance with an infrared spectrophotometer:
Using the sheet obtained above, the amount of absorption was measured under the following conditions.
Equipment: Shimadzu FTIR-8300
Resolution: 4.0 cm ⁻¹
Measurement range: 4,000 to 400 cm ⁻¹
Absorbance peak area calculation range: 700 to 760 cm ⁻¹

(Iii) Calculation of ethylene content of (B) in propylene-based block copolymer:
A calibration curve was prepared using a sample whose ethylene content was previously quantified by NMR, and the ethylene polymer (A) content in the propylene polymer (B-1) was calculated based on the calibration curve. Moreover, when the ethylene polymer (A) was contained in the propylene block copolymer (B), it was calculated as a value obtained by subtracting the ethylene polymer (A) content obtained in (5).

(7) Calculation of the content of the low-molecular propylene polymer (B-1-1) and the high-molecular propylene polymer (B-1-2) in the propylene polymer (B-1):
It calculated from the value of the production amount of a polymerization process (b-1-1) and (b-1-2), and obtained the value as weight%.

(8) Calculation of content of (B) olefin random copolymer (B-2) in propylene-based block copolymer:
It calculated from the production value of the polymerization step (b-1) for producing the propylene homopolymer and the polymerization step (b-2) for producing the propylene ethylene random copolymer component, and obtained the value as weight%.

(9) Calculation of ethylene content in propylene ethylene random copolymer component:
The value was obtained by calculating from the ethylene content in the propylene ethylene block copolymer and the content value of the propylene ethylene random copolymer component in the propylene ethylene block copolymer.

(10) Foaming ratio:
The specific gravity (dc0) of the unfoamed product and the specific gravity (dc1) of the foam were determined by the underwater substitution method, and [dc0 / dc1] was calculated from the values to obtain the expansion ratio. The specific gravity of the foam was measured in a state including the skin layer.

(11) Cell shape:
Microscopic observation (SEM) of the cross section of the foam was performed to examine the bubble state. The state where adjacent bubbles were independent from each other was evaluated as “independent”, and the connected state was evaluated as “communication”.

(12) Closed cell ratio:
The apparent density (D) was calculated from the weight and the volume determined by the water immersion method, and the true specific gravity (0.90) was divided by the apparent density.
That is, the closed cell ratio = 0.90 / D

(13) Appearance:
The surface of the foamed molded product was visually observed, and the quality of the appearance was evaluated according to the following criteria by the occurrence of tiger stripes and silver stripes.
○: Not seen at all on the surface.
Δ: Slightly seen on the surface.
X: Visible on a part of the surface.

(14) Elastic gradient:
A test piece of 50 x 150 mm is supported at both ends with a span of 100 mm, a load is applied to the center at a speed of 50 mm / min, and a load / deflection curve is created. As N / cm.

(15) High-speed penetration impact:
Using a rheometric high-rate impact tester, a hemispherical striker with a tip diameter of 12.6 mm was made to collide with the specimen at a speed of 4 m / sec in a 23 ° C. atmosphere and penetrated. The fracture energy J was determined.

(16) Thermal separation separation (elution separation):
The ratio of the elution fraction of 40-100 ° C. to the elution fraction of 0-100 ° C. and the Mw of the elution fraction of 40-100 ° C. in the temperature rising elution fractionation between 0-140 ° C. using ODCB as the solvent It was determined by the following method.
・ Analyzer used:
(I) Cross sorter:
Dia Instruments CFC T-100 (abbreviated as CFC) Fourier transform infrared absorption spectrum analysis (ii) Gel permeation chromatography (GPC):
A GPC column (AD806MS manufactured by Showa Denko KK) was connected in series to the subsequent stage of the CFC and used.

・ CFC measurement conditions:
(I) Solvent: orthodichlorobenzene (ODCB)
(Ii) Sample concentration: 4 mg / mL
(Iii) Injection volume: 0.4 mL
(Iv) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(V) Sorting method:
The fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, and 140 ° C., and the fraction is separated into three fractions in total. In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively It is defined as W40, W100, and W140. W40 + W100 + W140 = 100.
In the present invention, the ratio of elution at 40-100 ° C. with respect to elution at 0-100 ° C.
W100 / (W40 + W140) × 100
It can be expressed as.
Moreover, each fractionated fraction was automatically transported to GPC as it was, and the molecular weight distribution Mw was measured.

[Example 1]
(1) Preparation of titanium-containing solid component (I): catalyst for slurry In a stainless steel reactor equipped with a stirrer, 37.5 liters of decane, 7.14 kg of anhydrous magnesium chloride, and 2-ethyl-1-hexanol 35.1 liters were mixed and heated to 140 ° C. with stirring for 4 hours to obtain a uniform solution. 1.68 kg of phthalic anhydride was added to the homogeneous solution, and further stirred at 130 ° C. for 1 hour to dissolve the phthalic anhydride in the homogeneous solution. The obtained homogeneous solution was cooled to room temperature (23 ° C.), and then the entire amount of this homogeneous solution was dropped into 200 liters of titanium tetrachloride maintained at −20 ° C. over 3 hours. After dropping, the temperature was raised to 110 ° C. over 4 hours, and when 110 ° C. was reached, 5.03 liters of di-i-butyl phthalate was added, and the reaction was carried out by stirring and holding at 110 ° C. for 2 hours. .
After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 275 liters of titanium tetrachloride, and then the reaction was continued again at 110 ° C. for 2 hours. After completion of the reaction, the solid part 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 part 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. The average particle size of the solid catalyst was 20.1 μm.

(2) Preparation of preactivated catalyst:
After replacing the stainless steel reactor with inclined blades with an inner volume of 30 liters with nitrogen gas, 20 liters of n-hexane, 40 mmol of triethylaluminum, and 80 g of titanium-containing supported catalyst component prepared in the previous section (40 mmol in terms of titanium atoms) Then, 420 g of propylene was supplied at 15 ° C. for 120 minutes for prepolymerization.
After completion of the reaction time, unreacted propylene was discharged out of the reactor, and the gas phase portion of the reactor was replaced with nitrogen once. Separately, as a result of analyzing the polymer produced after the prepolymerization performed under the same conditions, 2.2 g of polypropylene (W0P) was produced per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η1] of this polypropylene was It was 2.9 dl / g.

Next, while maintaining the temperature in the reactor at −3 ° C., preactivation was performed by continuously supplying ethylene to the reactor for 6 hours so as to maintain the pressure in the reactor at 0.60 MPa. .
After completion of the reaction time, unreacted ethylene was discharged out of the reactor, and the gas phase portion of the reactor was replaced with nitrogen once to obtain a slurry of a preactivated catalyst. The amount of polymer produced after preactivation (W0T) was 75.1 g per gram of the titanium-containing solid catalyst component, and the intrinsic viscosity [η0T] of this polymer was 31.2 dl / g. there were.

The production amount (WA) of the ethylene polymer (A) contained per 1 g of the titanium-containing supported catalyst component obtained by preactivation with ethylene is the titanium-containing supported catalyst produced after the preactivation treatment. The difference between the amount of polymer produced per gram of component (W0T) and the polypropylene per gram of titanium-containing supported catalyst component after prepolymerization (W0P) is obtained by the following equation.
WA = W0T-W0P
In addition, the intrinsic viscosity [ηA] of the ethylene polymer (A) produced by the preactivation with ethylene is the intrinsic viscosity [η0P] of the polypropylene produced by the prepolymerization, and is produced after the preactivation step following the prepolymerization step. It is calculated | required by following Formula from the intrinsic viscosity [(eta) 0T] of the polymer made.
[ΗA] = ([η0T] × W0T− [η0P] × W0P) / (W0T−W0P)
According to the above formula, the amount of ethylene polymer (A) produced by preactivation with ethylene is 72.9 g per 1 g of titanium-containing supported catalyst component, and its intrinsic viscosity [ηA] is calculated to be 32.1 dl / g. It was.

(3) Polymerization step (b-1)
(3-1) Polymerization step (b-1-1):
A stainless polymerizer equipped with a stirrer with an internal volume of 500 liters was purged with nitrogen, and then 240 g of n-hexane, 780 mmol of triethylaluminum, 78 mmol of diisopropyldimethoxysilane, and 10 g of the preactivated catalyst obtained above were added ( (Excluding prepolymerized polymer). Subsequently, 880 liters of hydrogen was introduced into the polymerization vessel, and propylene was continuously supplied for 2.0 hours while maintaining the polymerization temperature at 70 ° C. and the gas phase pressure in the polymerization vessel at 1.5 MPa. Propylene polymer (B-1-1) was produced (polymerization step (b-1-1)). The ratio of hydrogen to propylene used in the polymerization step (b-1-1) at this time was H ₂ / C ₃ = 0.60 in terms of molar ratio. After completion of the polymerization, the temperature in the polymerization vessel was cooled to 30 ° C., and then hydrogen and unreacted propylene were released. Subsequently, as a result of extracting and measuring a part of polymerization slurry, [η] was 0.49 dl / g.

(3-2) Polymerization step (b-1-2):
After raising the temperature in the polymerization vessel to 60 ° C., propylene was continuously supplied for 1.0 hour while maintaining the gas phase pressure in the polymerization vessel at 2.2 MPa, and a high molecular weight propylene polymer (B-1 -2) (polymerization step (b-1-2)) was carried out. The gas phase in the reactor at this time was 1 ppm when the hydrogen concentration was measured using Micro GC-3000A manufactured by Agilent Technologies. After completion of the polymerization, the temperature in the polymerization vessel was cooled to 30 ° C., and then hydrogen and unreacted propylene were released. Subsequently, as a result of extracting and measuring a part of the polymerization slurry, [η] was 1.07 dl / g, MFR was 60 g / 10 min, and the content of the ethylene polymer (A) produced by the preactivation was 1.08. % By weight.

(4) Polymerization step (b-2):
After raising the temperature in the polymerization vessel to 60 ° C., 3.3 kg of ethylene and 9 kg of propylene were continuously supplied for 1.5 hours to produce an olefin random copolymer (B-2) (polymerization step (b- 2)) was carried out. The gas phase in the reactor at this time was 1 ppm when the hydrogen concentration was measured using Micro GC-3000A manufactured by Agilent Technologies. After completion of the polymerization, the temperature in the polymerization vessel was cooled to 30 ° C., and hydrogen and unreacted ethylene and propylene were released.
Subsequently, 50 liters of methanol was introduced into the polymerization vessel, and the catalyst deactivation reaction was carried out at 60 ° C. for 30 minutes. Further, 0.7 liter of a 20% by weight aqueous caustic soda solution was added and stirred for 20 minutes, and then 100 liters of pure water was added and stirred for 20 minutes. After extracting the aqueous layer, 300 liters of pure water was added again and stirred for 20 minutes to extract the aqueous layer.
Subsequently, the hexane slurry was extracted, filtered and dried. The powder yield after drying was 8.05 kg. Polymer after completion of polymerization step (b-2) (corresponding to “propylene block copolymer (B)” in the present invention), and olefin random copolymer obtained in polymerization step (b-2) The analysis results of (B-2) are shown in Table 1.
In addition, the amount of “propylene block copolymer (B)” referred to in the present invention is determined from the amount of polymer produced after the completion of the polymerization step (b-2) and the preactivation by the polypropylene obtained by prepolymerization. This was calculated by subtracting the amount of ethylene polymer (A) produced in (1).

  To 100 parts by weight of the resulting polymer mixture, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 0.1 part by weight of calcium stearate are mixed to obtain the mixture. Using an extrusion granulator with a screw diameter of 40 mm, the resin temperature was granulated (melt kneaded) at 300 ° C. to obtain a propylene polymer composition. The results of analysis of the resulting propylene polymer composition are shown in Table 1.

For 100 parts by weight of the resulting propylene polymer composition, 3.0 parts by weight of a foaming agent master batch (25% by weight of sodium bicarbonate, 25% by weight of citric acid, 50% by weight of low density polyethylene), 10% by weight of fine powder talc After adding parts and dry blending, injection foam molding was performed. The molding conditions for the foam molded article were as follows.
Using a heating cylinder with a screw diameter of 50 mm and an injection molding machine having a clamping control mechanism and a maximum clamping force of 300 tons, the temperature of each heating zone of the heating cylinder is changed in order from the tip to the rear. 230 ° C., 230 ° C., 230 ° C., 210 ° C., and 180 ° C., a back pressure of 9.8 MPa, a mold cooling water temperature of 40 ° C., and the distance between the movable mold and the fixed mold of the flat molded body is 2. Into a cavity having a capacity of 160 cm ³ at 0 mm, 145 g of the foamed molded material that was heated and melted was injected and filled. After the injection was completed, primary cooling was performed for 1 second, and then the movable mold was retracted by 2.0 mm to expand the cavity volume to 320 cm ³ and foam. Thereafter, secondary cooling was performed for 60 seconds to obtain a polypropylene resin foam molded article. The analysis results of the foamed molded product are shown in Table 3.

[Example 2]
(1) Preparation of titanium-containing solid component (I): Gas phase catalyst A 10 L autoclave equipped with a stirrer was sufficiently substituted with nitrogen, and 2 L of purified toluene was introduced. To this, 200 g of Mg (OEt) ₂ and 1 L of TiCl ₄ were added at room temperature. The temperature was raised to 90 ° C. and 50 ml of n-butyl phthalate was introduced. Thereafter, the temperature was raised to 110 ° C. to carry out a reaction for 3 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Furthermore, toluene was substituted with n-heptane using purified n-heptane to obtain a slurry of the titanium-containing solid component (I). A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component (I) was 2.7% by weight. The average particle size of the solid catalyst was 34 μm.

(2) Preparation of preactivated catalyst:
After replacing a stainless steel reactor with inclined blades with an inner volume of 30 liters with nitrogen gas, 20 liters of n-hexane, 40 mmol of triethylaluminum, and 40 g of titanium-containing supported catalyst component prepared in the previous section (40 mmol in terms of titanium atoms) Then, 210 g of propylene was supplied at 15 ° C. for 120 minutes for prepolymerization. After completion of the reaction time, unreacted propylene was discharged out of the reactor, and the gas phase portion of the reactor was replaced with nitrogen once. Separately, as a result of analyzing the polymer produced after the prepolymerization performed under the same conditions, 2.1 g of polypropylene (W0P) was produced per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η1] of this polypropylene was It was 2.8 dl / g.

Subsequently, while maintaining the temperature in the reactor at −3 ° C., ethylene was continuously supplied to the reactor for 6 hours so as to maintain the pressure in the reactor at 0.59 MPa, and preactivation was performed. . After completion of the reaction time, unreacted ethylene was discharged out of the reactor, and the gas phase portion of the reactor was replaced with nitrogen once to obtain a slurry of a preactivated catalyst. The amount of the polymer produced after the preactivation was 220.8 g per gram of the titanium-containing solid catalyst component, and the intrinsic viscosity [η0T] of this polymer was 30.0 dl / g.
As in Example 1, the amount of ethylene polymer (A) produced per 1 g of titanium-containing supported catalyst component produced by preactivation with ethylene and the intrinsic viscosity [ηA] thereof were calculated. 218 g and [ηA] were calculated to be 30.3 dl / g.

(3) Polymerization step (b-1)
(3-1) Polymerization step (b-1-1):
This will be described with reference to the flow sheet shown in FIG. A gas phase polymerization reactor using three polymerization tanks was used. The three polymerizers 1, the polymerizer 2 and the polymerizer 3 are a continuous horizontal gas phase polymerizer equipped with a stirrer having an inner diameter D of 340 mm, a length L of 1260 mm, a diameter of a rotating shaft of 90 mm, and an internal volume of 110 dm3. (Length / diameter = 3.7).
After replacing the insides of the polymerizers 1 and 2, 25 kg of polypropylene powder (average particle size 1500 μm) from which polymer particles of 500 μm or less were removed was introduced, and the preactivated catalyst obtained above was further added at 0.72 g / h ( However, the prepolymerized polymer component is excluded), and a 15 weight% n-hexane solution of triethylaluminum is 90 moles per mole of Ti atoms in the catalyst component (A), and diisopropyldimethoxysilane is 1 mole of Ti atoms. On the other hand, it was continuously fed into the polymerization vessel 1 so as to be 10. Further, hydrogen is used so that the molar ratio of hydrogen to propylene in the polymerization vessel 1 is 0.38, and the propylene monomer is maintained so that the pressure in the polymerization vessel 1 is 2.40 MPa and the temperature is 65 ° C. Were fed into the polymerization vessel 1 respectively. The reaction heat was removed by the vaporization heat of the raw material propylene supplied from the raw material liquefied propylene supply pipe 17. The unreacted gas discharged from the polymerization vessel 1 was extracted out of the reactor system through the unreacted gas extraction piping 13, cooled and condensed, and refluxed to the polymerization reactor 1 through the recycle gas piping 18. The propylene polymer produced in the polymerization vessel 1 is continuously extracted from the polymerization vessel 1 through the polymer extraction pipe 19 so that the retained level of the polymer is 50% by volume of the reaction volume. 2 was supplied through a polymer supply pipe 60. However, in the degassing tank 40 installed between the pipe 19 and the pipe 60 between the polymerization vessel 1 and the polymerization vessel 2, the gas phase brought in from the polymerization vessel 1 was refluxed with propylene gas.
Subsequently, as a result of extracting and measuring a part of the propylene polymer produced in the polymerization vessel 1, [η] was 0.49 dl / g. The average residence time in this step was 2.8 h.

(3-2) Polymerization step (b-1-2):
The polymer and propylene from the first polymerization step are continuously fed into the polymerization vessel 2 to produce the olefin random copolymer (B-1-2) (polymerization step (b-1-2)). did. The reaction conditions were a stirring speed of 35 rpm, a temperature of 65 ° C., and a pressure of 2.2 MPa. Hydrogen gas was not supplied. The heat of reaction was removed by the heat of vaporization of the raw material liquefied propylene supplied from the raw material liquefied propylene supply pipe 27. The unreacted gas discharged from the polymerization reactor 2 was extracted out of the reactor system through the unreacted gas extraction piping 23, cooled and condensed, and refluxed to the polymerization reactor 2 through the recycle gas piping 28. The propylene polymer produced in the polymerization vessel 2 is continuously extracted from the polymerization vessel 2 through the polymer extraction pipe 29 so that the retained level of the polymer is 50% by volume of the reaction volume, and polymerization in the third polymerization step is performed. The vessel 3 was supplied through a polymer supply pipe 70. However, in the degassing tank 50 installed between the pipe 29 and the pipe 70 between the polymerization vessel 2 and the polymerization vessel 3, the gas phase brought in from the polymerization vessel 2 was refluxed with propylene gas. At this time, the hydrogen concentration in the polymerization vessel 2 was 2 ppm.
Next, as a result of extracting and measuring a part of the propylene polymer produced in the polymerization vessel 1, [η] is 1.06 dl / g, MFR is 62 g / 10 min, ethylene polymer produced by preactivation (A) The content of was 1.19% by weight. The average residence time of this process was 2.6 hours.

(4) Polymerization step (b-2):
The polymer, propylene, and ethylene gas from the second polymerization step were continuously supplied into the polymerization vessel 3 to produce an olefin random copolymer (B-2) (polymerization step (b-2)). . The reaction conditions were a stirring speed of 25 rpm, a temperature of 65 ° C., and a pressure of 2.0 MPa. Hydrogen gas was not supplied. The reaction heat was removed by the vaporization heat of the raw material liquefied propylene supplied from the raw material liquefied propylene supply pipe 37. The unreacted gas discharged from the polymerization vessel 3 was extracted out of the reactor system through the unreacted gas extraction pipe 33, and was cooled and condensed. In the gas phase portion, a trace amount of hydrogen was separated by the rectification separator 80 and refluxed to the polymerization vessel 3 through the raw material mixed gas supply pipe 38.
The propylene polymer composition produced in the third polymerization step was continuously extracted from the polymerization vessel 3 through the polymer extraction pipe 39 so that the retained level of the polymer was 60% by volume of the reaction volume. At this time, the hydrogen concentration in the polymerization vessel 3 was 2 ppm.
The production rate of the propylene polymer composition was 11.0 kg / hr, and the average residence time in this step was 2.3 h.
The analysis results of the obtained propylene polymer composition are shown in Table 1.

  In the same manner as in Example 1, granulation (melt kneading) and foam molding were performed. As in Example 1, the analysis results of the foamed molded product are shown in Table 3.

[Example 3]
(1) Polymerization step (b-1):
The same procedure as in Example 2 was performed except that the average residence time in the polymerization vessel 2 was set to 2.4 h in the polymerization step (b-1-2).
As a result of extracting and measuring a part of the propylene polymer produced in the polymerization vessel 2, the [η] is 0.91 dl / g, the MFR is 125 g / 10 min, the content of the ethylene polymer (A) produced by the preactivation The rate was 1.23% by weight.

(2) Polymerization step (b-2):
The polymerization step (b-2) was performed in the same manner as in Example 2. At this time, the hydrogen concentration in the polymerization vessel 3 was 1 ppm, and the production rate of the propylene polymer composition was 10.3 kg / hr. The analysis results of the obtained propylene polymer composition are shown in Table 1.

  Granulation (melt kneading) and foam molding were performed in the same manner as in Example 1. As in Example 1, the analysis results of the foamed molded product are shown in Table 3.

[Example 4]
(1) Polymerization step (b-1):
The polymerization step (b-1) was performed in the same manner as in Example 3.
As a result of extracting and measuring a part of the propylene polymer produced in the polymerization vessel 2, the [η] is 0.91 dl / g, the MFR is 125 g / 10 min, the content of the ethylene polymer (A) produced by the preactivation The rate was 1.23% by weight.

(2) Polymerization step (b-2):
The polymerization step (b-2) was performed in the same manner as in Example 3 except that the average residence time in Example 3 was changed to 2.2 h. At this time, the hydrogen concentration in the polymerization vessel 3 was 1 ppm, and the production rate of the propylene polymer composition was 11.2 kg / hr. The analysis results of the obtained propylene polymer composition are shown in Table 1.

  In the same manner as in Example 1, granulation (melt kneading) and foam molding were performed. Similar to Example 1, Table 3 shows the analysis results of the foamed molded product.

[Example 5]
(1) Polymerization step (b-1):
The same procedure as in Example 3 was performed except that the pressure in the polymerization vessel 2 was changed to 2.38 MPa in the polymerization step (b-1-2) in Example 3.
As a result of extracting and measuring a part of the propylene polymer produced in the polymerization vessel 2, the [η] is 1.03 dl / g, the MFR is 69 g / 10 min, the content of the ethylene polymer (A) produced by the preactivation The rate was 1.18% by weight.

(2) Polymerization step (b-2):
The polymerization step (b-2) was performed in the same manner as in Example 3. At this time, the hydrogen concentration in the polymerization vessel 3 was 2 ppm, and the production rate of the propylene polymer composition was 11.0 kg / hr. The analysis results of the obtained propylene polymer composition are shown in Table 1.

  Granulation (melt kneading) and foam molding were performed in the same manner as in Example 1. As in Example 1, the analysis results of the foamed molded product are shown in Table 3.

[Example 6]
(1) Polymerization step (b-1):
In Example 2, the preactivation catalyst was 0.92 g / h (excluding the prepolymerized polymer) in the polymerization step (b-1-1), and the ratio of the amount of hydrogen used to propylene in the polymerization vessel 1 was The same operation as in Example 2 was conducted except that hydrogen was supplied into the polymerization vessel 1 so that the molar ratio was 0.45.
As a result of extracting and measuring a part of the propylene polymer produced in the polymerization vessel 2, the [η] is 0.96 dl / g, the MFR is 97 g / 10 min, the content of the ethylene polymer (A) produced by the preactivation The rate was 1.20% by weight.

(2) Polymerization step (b-2):
The polymerization step (b-2) was performed in the same manner as in Example 2. At this time, the hydrogen concentration in the polymerization vessel 3 was 2 ppm, and the production rate of the propylene polymer composition was 11.0 kg / hr. The analysis results of the obtained propylene polymer composition are shown in Table 1.

  Granulation (melt kneading) and foam molding were performed in the same manner as in Example 1. As in Example 1, the analysis results of the foamed molded product are shown in Table 3.

[Example 7]
(1) Polymerization step (b-1):
The polymerization step (b-1) was performed in the same manner as in Example 6.
As a result of extracting and measuring a part of the propylene polymer produced in the polymerization vessel 2, [η] is 0.95 dl / g, MFR is 100 g / 10 min, the content of the ethylene polymer (A) produced by the preactivation The rate was 1.20% by weight.

(2) Polymerization step (b-2):
In the polymerization step (b-2), polymerization was performed in Example 6 with an average residence time of 2.5 h. Other than that was carried out similarly to Example 6. At this time, the hydrogen concentration in the polymerization vessel 2 was 2 ppm, and the production rate of the propylene polymer composition was 11.9 kg / hr. The analysis results of the obtained propylene polymer composition are shown in Table 1.

  In the same manner as in Example 1, granulation (melt kneading) and foam molding were performed. As in Example 1, the analysis results of the foamed molded product are shown in Table 3.

[Comparative Example 1]
In Comparative Example 1, 600 liters of hydrogen was supplied in “Polymerization step (b-1-1)” of Example 1, and “Polymerization step (b-1-2)” performed in Example 1 was continued. There wasn't. That is, the propylene polymer (B-1) was produced without performing multistage polymerization. Other than that was carried out similarly to Example 1, and manufactured the propylene polymer.
A foamed molded article was molded according to Example 1 using the obtained propylene polymer composition. The analytical values of the propylene polymer composition and the obtained foamed molded product are shown in Tables 2 and 3.

[Comparative Example 2]
In Comparative Example 2, in the “polymerization step (b-1-1)” and “polymerization step (b-1-2)” of Example 1, the ratio of the amount of hydrogen used relative to propylene in both the polymerization vessels 1 and 2 is mol. Hydrogen and propylene are continuously supplied so that the ratio becomes 0.08. Other than that obtained the propylene polymer composition based on Example 1. FIG. At this time, the hydrogen concentration in the reactor was 12 ppm.
In addition, a foamed molded article was molded in accordance with Example 1 using the obtained propylene polymer composition. The analytical values of the propylene polymer composition and the obtained foamed molded product are shown in Tables 2 and 3.

[Comparative Example 3]
Comparative Example 3 was carried out in the same manner as in Example 1 except that in Example 1, the preparation of the titanium-containing catalyst and the prepolymerization with propylene were completed, and the subsequent preactivation treatment with ethylene was not performed.
In addition, a foamed molded article was molded in accordance with Example 1 using the obtained propylene polymer composition. The analytical values of the propylene polymer composition and the obtained foamed molded product are shown in Tables 2 and 3.

[Comparative Example 4]
In Comparative Example 4, 600 liters of hydrogen was supplied in “Polymerization step (b-1-1)” of Example 2, and “Polymerization step (b-1-2)” performed in Example 1 was continued. There wasn't. That is, the propylene polymer (B-1) was produced without performing multistage polymerization. Other than that was carried out similarly to Example 1, and manufactured the propylene polymer.
Using the resulting propylene polymer composition, a foamed molded article was molded according to Example 1. The analytical values of the propylene polymer composition and the obtained foamed molded product are shown in Tables 2 and 3.

[Comparative Example 5]
Comparative Example 5 is based on Example 2 except that in the “polymerization step (b-2)” of Example 2, in addition to continuously supplying propylene and ethylene gas, hydrogen is also continuously supplied. A propylene polymer composition was obtained. At this time, the hydrogen concentration in the polymerization vessel 3 was 25 ppm.
In addition, a foamed molded article was molded in accordance with Example 1 using the obtained propylene polymer composition. The analytical values of the propylene polymer composition and the obtained foamed molded product are shown in Tables 2 and 3.

[Comparative Example 6]
Comparative Example 6 was carried out in the same manner as Example 7 except that the average residence time was changed to 2.8 h in the “polymerization step (b-2)” of Example 7. The production rate of the propylene polymer composition obtained at this time was 11.6 kg / hr.
In addition, a foamed molded article was molded in accordance with Example 1 using the obtained propylene polymer composition. The analytical values of the propylene polymer composition and the obtained foamed molded product are shown in Tables 2 and 3.

[Comparative Example 7]
Comparative Example 7 was performed in the same manner as in Example 2, except that in Example 2, the preparation of the titanium-containing catalyst and the prepolymerization with propylene were completed, and the subsequent preactivation treatment with ethylene was not performed.
In addition, a foamed molded article was molded in accordance with Example 1 using the obtained propylene polymer composition. The analytical values of the propylene polymer composition and the obtained foamed molded product are shown in Tables 2 and 3.

  From the results of Tables 1 to 3, when Examples 1 to 7 and Comparative Example 1 or 4 are compared, “Propylene polymer (B-1): in o-dichlorobenzene at 135 ° C.” which is a specific matter of the present invention. Low molecular weight propylene polymer (B-1-1) having a measured intrinsic viscosity ([η]) of less than 6 dl / g, 70 to 99.5% by weight, and high molecular weight propylene having an intrinsic viscosity of 6 to 15 dl / g In the comparative example which is a composition of the propylene polymer (B-1) which does not satisfy the requirement of "the propylene polymer comprising 0.5 to 30% by weight of the polymer (B-1-2)", the obtained foam molding Although the closed cell ratio and cell shape of the body are good, the foaming ratio is low and the strength of the molded body is not sufficient as compared with the polypropylene block copolymer compositions of the examples. In the examples, all of the closed cell ratio, cell shape and the like of the foam molded article are good, and the composition has melting characteristics suitable for foam molding, and a good foam molded article is obtained.

  Moreover, when Examples 1-7 and Comparative Example 2 or 5 are contrasted from the result of Tables 1-3, "weight average molecular weight measured with the gel permeation chromatograph (GPC)" which is a specific matter of the present invention. (Mw) is a composition that does not satisfy the requirement of “a propylene-based block copolymer resin composition,” wherein the ratio (Q value: Mw / Mn) to the number average molecular weight (Mn) is 10-20. In a certain comparative example, compared to the low Q value, the expansion ratio and appearance of the obtained foamed molded article is poor, the polypropylene-based block copolymer composition according to the example, the expansion ratio of the foamed molded article, The composition has good rigidity and appearance, and has melt characteristics suitable for foam molding, and a good foam molded article is obtained.

  On the other hand, from the results of Tables 1 to 3, when Examples 1 to 7 and Comparative Example 6 are compared, “weight average molecular weight (measured by gel permeation chromatograph (GPC)” which is a specific matter of the present invention ( Mw) is a composition that does not satisfy the requirement of “a propylene-based block copolymer resin composition characterized in that the ratio (Q value: Mw / Mn) to the number average molecular weight (Mn)” is 10-20. In the comparative example, the Q value was high, and the obtained foamed molded product had poor bubble breaking and cell shape, whereas the polypropylene block copolymer composition according to the example was a closed cell of the foamed molded product. The ratio and cell shape are all good, and the composition has melting characteristics suitable for foam molding, and a good foam molded article is obtained.

  Furthermore, from the results of Tables 1 to 3, when Examples 1 to 7 and Comparative Example 3 or 7 are compared, the specific matter of the present invention is “100 parts by weight of the propylene-based block copolymer (B), In “resin composition containing 0.01 to 5.0 parts by weight of ethylene polymer (A) having an intrinsic viscosity ([η]) of 15 to 100 dl / g measured in tetralin at 135 ° C.”, the ethylene polymer (A In the comparative example in which the polypropylene-based block copolymer (B) that does not contain) was produced, the polypropylene foam according to the example was poorer than the foaming ratio, closed cell ratio, and cell shape of the obtained foamed molded article. The block copolymer composition is a composition having good closed cell ratio, cell shape, etc. of the foam molded article, and having melting characteristics suitable for foam molding, and a good foam molded article is obtained. Yes.

  The propylene-based block copolymer composition of the present invention can be used for any application, and in particular, can be suitably used for fields where a high MFR propylene-based block copolymer is desired. Particularly preferred examples include foam molding fields such as extrusion foam molding and injection foam molding. The obtained foam can be used for automobile parts, for example, automobile interior parts such as door trims, instrument panels, side protection molds, bumper, soft fascia, mudguards and other automobile exterior parts, or fresh foods and processed foods. It can be used as a packaging material for food, particularly as a container for cup ramen and ice cream, a tray for fish, meat and the like.

It is a flow sheet of a continuous horizontal gas phase polymerization apparatus according to the production method of the present invention.

Explanation of symbols

1, 2, Catalyst component supply piping 3, 5, 7 Raw material propylene supply piping 4, 6, 8 Raw material supply piping (hydrogen etc.)
9 Pipe for adding activity inhibitor 10 Polymerizer (first polymerization step)
11, 21, 31 Gas-liquid separation tank 12, 22, 32 Reactor upstream end 13, 23, 33 Unreacted gas extraction pipe 14, 24, 34 Reactor downstream end 15, 25, 35 Condenser
16, 26, 36 Compressor 17, 27, 37 Raw material liquefied propylene supply piping 18, 28, 38 Raw material mixed gas supply piping 20 Polymerizer (second polymerization step)
30 Polymerizer (third polymerization process)
40, 50 Degassing tank 19, 29, 39 Polymer extraction piping 60, 70 Polymer supply piping 80 Rectification separation device 41, 43 Accepting valve 42, 44 Extraction valve 45, 46, 47, 48 Piping

Claims (12)

With respect to 100 parts by weight of a propylene-based block copolymer (B) comprising 30 to 95% by weight of the following propylene polymer (B-1) and 5 to 70% by weight of an olefin random copolymer (B-2), A resin composition comprising 0.01 to 5.0 parts by weight of an ethylene polymer (A) having an intrinsic viscosity ([η]) measured in tetralin at 135 ° C. of 15 to 100 dl / g,
Propylene-based block, characterized in that the ratio (Q value: Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 10-20 Copolymer resin composition.
Propylene polymer (B-1): Low molecular weight propylene polymer (B-1-1) having an intrinsic viscosity ([η]) measured in o-dichlorobenzene at 135 ° C. of less than 6 dl / g, 50 to 95 wt. %, And a high molecular weight propylene polymer (B-1-2) having an intrinsic viscosity of 6 to 15 dl / g, 5 to 50% by weight.   The olefin random copolymer (B-2) is obtained by polymerizing one or more monomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms with propylene, and 135 ° C. o-dichlorobenzene. The propylene-based block copolymer resin composition according to claim 1, wherein the intrinsic viscosity ([η]) measured in is 8 to 25 dl / g.   3. The propylene-based block copolymer resin composition according to claim 1, wherein the propylene polymer (B-1) has an MFR (230 ° C., 2.16 kg load) of 50 to 1000 g / 10 minutes. object.   The propylene polymer (B-1) has a ratio (Q value: Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 5 to 5. 18. The propylene block copolymer resin composition according to claim 1, wherein the propylene block copolymer resin composition is 18.   The propylene-based block copolymer resin composition according to any one of claims 1 to 4, which has a melting characteristic suitable for foam molding. A propylene-based block copolymer resin comprising an ethylene polymer (A) and a propylene-based block copolymer (B) having a propylene polymer part (B-1) and an olefin random copolymer part (B-2) In a method of producing a composition,
The propylene-based block copolymer (B) is an olefin polymerization catalyst formed from (I) a solid component containing titanium, magnesium and halogen as essential components, (II) an organoaluminum compound, and (III) an electron donor. And (b-2) and (b-2) comprising the following steps (b-1-1) and (b-1-2): Item 6. The method for producing a propylene-based block copolymer resin composition according to any one of Items 1 to 5.
Step (b-1-1): Propylene is polymerized in the presence of hydrogen, and a low molecular weight propylene polymer (B-1-) having an intrinsic viscosity of less than 6 dl / g measured in o-dichlorobenzene at 135 ° C. 1) The manufacturing process.
Step (b-1-2): high molecular weight propylene having an intrinsic viscosity of 6 to 15 dl / g measured in 135 ° C o-dichlorobenzene by polymerizing propylene substantially in the absence of hydrogen The process of manufacturing a polymer (B-1-2).
Step (b-2): Polymerizing one or more monomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms in the absence of hydrogen and propylene at 135 ° C. -The process of manufacturing the olefin random copolymer (B-2) whose intrinsic viscosity ([(eta))) measured in dichlorobenzene is 8-25 dl / g.   The said process (b-1-1), (b-1-2) and (b-2) is a continuous polymerization process by the continuous tank which consists of 2-3 tanks, It is characterized by the above-mentioned. A method for producing a propylene-based block copolymer resin composition. The propylene block copolymer according to claim 6, wherein the ethylene polymer (A) is produced by performing the following step (a-2) prior to the step (b-1). A method for producing a coalesced resin composition.
Step (a-2): In the presence of an olefin polymerization catalyst, one or more monomers selected from the group consisting of ethylene alone or ethylene and an α-olefin having 3 to 12 carbon atoms are polymerized for olefin polymerization. A preactivation step for producing 0.01 to 500 g of ethylene polymer (A) with respect to 1 g of metal atoms in the catalyst. Prior to the step (a-2), the following step (a-1) is carried out. The method for producing a propylene-based block copolymer resin composition according to claim 8.
Step (a-1): Propylene is polymerized in the presence of an olefin polymerization catalyst, and (I) 0.01 to 100 g of polypropylene is added to 1 g of a solid component containing titanium, magnesium and halogen as essential components. A pre-polymerization step for producing and supporting.   (II) The method for producing a propylene-based block copolymer resin composition according to any one of claims 6 to 9, wherein the organoaluminum compound is triethylaluminum and / or triisobutylaluminum.   (III) The method for producing a propylene-based block copolymer resin composition according to any one of claims 6 to 10, wherein the electron donor is an organosilicon compound.   A foam-molded article using the propylene-based block copolymer resin composition according to any one of claims 1 to 5.

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