JP6045412B2 - Propylene polymer and propylene resin composition containing the propylene polymer - Google Patents

Description

  The present invention relates to a propylene-based polymer used as a moldability modifier suitable for producing an injection-foamed molded body, and a propylene-based resin composition containing the propylene-based polymer.

  Propylene polymers have a low specific gravity and are excellent in moldability and recyclability, so they are used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, and automobile parts. It's being used. As for automotive parts, the proportion of propylene-based resin composition containing propylene-based polymer tends to increase with the increase in the safety, comfort and comfort of automobiles, and the increase in IT equipment. Is growing. In particular, a foam-molded article made of a propylene-based resin composition is suitably used for automobile parts because it is lightweight and excellent in molding appearance. For example, in the case of automobile interior parts and the like, it is necessary that the foamed molded product also has mechanical strength. Patent Document 1 discloses a propylene / ethylene block copolymer, an ethylene-α-olefin copolymer rubber, and an inorganic material. A foam molded article made of a propylene-based resin composition comprising a filler is disclosed.

  Here, in recent years, against the background of energy saving, the number of applicable hybrid vehicles and electric vehicles has increased. However, the travel distance of these vehicles is limited due to the battery capacity. Therefore, it has been proposed to reduce the power consumption of air conditioners by applying heat-insulating materials to automobile interior parts, etc., from the viewpoint that the cruising distance can be increased if the power consumption of hybrid vehicles and electric vehicles is reduced. (See Non-Patent Document 1). Conventionally, it has been considered to use a foam-molded body made of a propylene-based resin composition as the heat insulating material. However, it is necessary to impart further heat insulating properties to improve the navigation distance of the electric vehicle. In order to improve the heat insulating property of the foamed molded product, it is conceivable to increase the expansion ratio or to reduce the size of the expanded cell. To that end, techniques for increasing the melt tension of the propylene-based resin composition are being studied.

  As a technique for increasing the melt tension of a propylene resin composition, for example, Patent Document 2 discloses a propylene resin composition containing an ultrahigh molecular weight propylene polymer having an intrinsic viscosity [η] of 8 to 13 dl / g. However, when the ultrahigh molecular weight propylene-based polymer is added to the propylene-based resin-modified material as a modifier, there is a problem that it is difficult to achieve both high melt tension and injection molding fluidity. Patent Document 3 discloses a propylene polymer containing an ultrahigh molecular weight propylene polymer having an intrinsic viscosity [η] of 13 to 20 dl / g. The ultrahigh molecular weight propylene polymer is a modifier. However, when added to a propylene-based resin reformed material, the propylene-based resin composition can be increased in melt tension, but the injection molding fluidity is lowered, so that it is not suitable for injection foam molding of large parts. was there.

  Accordingly, there has been a demand for technical development of a molding modifier capable of achieving a high melt tension without significantly reducing the injection molding fluidity of the propylene-based resin composition.

International Publication 2009/041361 Pamphlet Japanese Patent No. 4083820 Japanese Patent No. 4889483

Polyfile2011.1, P13

  An object of the present invention is to provide a propylene-based polymer having a high melt tension, and a propylene-based resin composition including the propylene-based polymer and excellent in injection molding fluidity and high melt tension characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have found that a high-melting propylene polymer containing a specific amount of a propylene polymer having a molecular weight of 1 million or more and a propylene polymer having a molecular weight of 10,000 or less. The present invention was completed by finding that it exhibits tension.

That is, the present invention relates to the following [1] to [4].
[1] The following propylene polymer components (I) to (III) are included (the total amount of (I) to (III) is 100 parts by weight), and the following (i) and (ii) Propylene polymer that meets the requirements.
(I) In the molecular weight distribution curve measured by gel permeation chromatography (GPC), the content of propylene polymer component having a molecular weight of 1 million or more with respect to the total amount is 10 to 30 parts by weight. (II) Gel permeation chromatography In the molecular weight distribution curve measured by (GPC), the content of propylene polymer component having an average molecular weight of 10,000 or less relative to the total amount is 10 to 20 parts by weight (III) Molecular weight measured by gel permeation chromatography (GPC) In the distribution curve, the content of the propylene polymer component with an average molecular weight of more than 10,000 and less than 1 million is 50 to 80 parts by weight based on the total amount (i) Measured at 230 ° C. under a 2.16 kg load in accordance with ASTM D1238E. Melt flow rate (MFR) of 0.5 to 6 g / 10 Min
(Ii) Isotactic pendant fraction (mmmm) is 95% or more

[2] Two or more continuous steps including a step of producing a relatively high molecular weight propylene polymer component (H) and a step of producing a relatively low molecular weight propylene polymer component (L) The propylene polymer according to [1], wherein the high molecular weight propylene polymer component (H) satisfies the following requirements (iii) and (iv):
(Iii) The content of the high molecular weight propylene polymer component (H) in the total amount of the propylene polymer is 10 to 40% by weight.
(Iv) Intrinsic viscosity [η] measured in 135 ° C. tetralin is 7 to 10 dl / g

  [3] A propylene-based resin composition comprising 1 to 30 parts by weight of the propylene-based polymer according to [1] or [2] and 100 parts by weight of a propylene-based resin-modified material.

  [4] The polypropylene-based material to be modified is 40 to 99 parts by weight of a propylene-based block copolymer (Bb), 1 to 40 parts by weight of a filler (C), and 0 to 35 parts by weight of an elastomer (D). (However, the total of (B-b), (C), and (D) is 100 parts by weight.) The propylene-based resin composition according to the above [3].

  Since the propylene polymer according to the present invention exhibits high melt tension and high fluidity, the propylene resin composition containing the propylene polymer is excellent in injection molding fluidity and high melt tension characteristics. From this, the said propylene-type resin composition can be used conveniently as a raw material of an injection foaming molded article.

FIG. 1 is a schematic diagram when the injection mold is in a clamped state. FIG. 2 is a schematic diagram when the injection mold is in a core back state.

Hereinafter, the propylene-based polymer of the present invention and the propylene-based resin composition containing the propylene-based polymer will be specifically described.
[Propylene polymer]
The propylene polymer of the present invention includes the following propylene polymer components (I) to (III) (the total amount of (I) to (III) is 100 parts by weight), and the following (i ) And (ii).
(I) In the molecular weight distribution curve measured by gel permeation chromatography (GPC), the content of propylene polymer component having a molecular weight of 1 million or more with respect to the total amount is 10 to 30 parts by weight. (II) Gel permeation chromatography In the molecular weight distribution curve measured by (GPC), the content of propylene polymer component having a molecular weight of 10,000 or less relative to the total amount is 10 to 20 parts by weight (III) Molecular weight distribution measured by gel permeation chromatography (GPC) In the curve, the content of the propylene polymer component having a molecular weight of more than 10,000 and less than 1,000,000 with respect to the total amount is 50-80 parts by weight (i) Melt measured at 230 ° C. under a 2.16 kg load in accordance with ASTM D1238E The flow rate (MFR) is 0.5-6 g / 10 min (ii And (i), (ii) the propylene-based polymer component (I) to (III) constituting the propylene-based polymer and the propylene-based polymer satisfy the isotactic pendart fraction (mmmm) of 95% or more. ) Requirements in detail.

<Ingredient (I)>
In the molecular weight distribution curve measured by gel permeation chromatography (GPC), the content of the propylene polymer component having a molecular weight of 1 million or more is usually 10 to 30% by weight, preferably 12%, based on the total amount of the propylene polymer. -25% by weight, more preferably 15-20% by weight.

  If the content of the component having a molecular weight of 1 million or more exceeds the above upper limit value, in the propylene-based resin composition containing the propylene-based polymer, the injection molding fluidity is lowered, so that it may not be suitable for a large injection foam molded part. . If the content of the component having a molecular weight of 1,000,000 or more is less than the above lower limit, the melt tension of the propylene-based polymer is lowered, which is not preferable.

<Ingredient (II)>
In the molecular weight distribution curve measured by gel permeation chromatography (GPC), the content of the propylene polymer component having a molecular weight of 10,000 or less is usually 10 to 20% by weight, preferably 10%, based on the total amount of the propylene polymer. -18% by weight, more preferably 10-15% by weight.

  When the content of a component having a molecular weight of 10,000 or less exceeds the above upper limit, the dispersibility of the component (I) in the high molecular weight component deteriorates, and a propylene-based resin composition containing a propylene-based modified material is molded. When doing so, appearance defects such as bumps may occur. Since the melt tension of a propylene polymer falls, it is not preferable. Moreover, since the melt tension of a propylene polymer falls that content of the component of molecular weight 10,000 or less is less than the said lower limit, it is unpreferable.

<Component (III)>
In the molecular weight distribution curve measured by gel permeation chromatography (GPC), the content of the propylene polymer component having a molecular weight of more than 10,000 and less than 1,000,000 is usually 50 to 80 parts by weight with respect to the total amount of the propylene polymer. The amount is preferably 57 to 78 parts by weight, more preferably 65 to 75 parts by weight.

  If the content of the component having a molecular weight larger than 10,000 and smaller than 1,000,000 exceeds the above upper limit, the melt tension of the propylene-based polymer is lowered, which is not preferable. Further, when the content of the component having a molecular weight larger than 10,000 and smaller than 1,000,000 falls below the lower limit, the dispersibility of the polymer corresponding to the component (I) and the polymer corresponding to the component (II) decreases. This is not preferable because the melt tension of the propylene-based polymer is lowered.

<Requirement (i)>
The melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238E of the propylene-based polymer is usually 0.5 to 6 g / 10 minutes, preferably 0.5 to 5 g / 10 minutes, more preferably 0.5 to 4 g / 10 minutes.

If the MFR exceeds the above upper limit, the melt tension of the propylene polymer is lowered, which is not preferable. In addition, when the MFR is less than the lower limit, in the propylene resin composition containing the propylene polymer, the injection molding fluidity is lowered, so that it may not be suitable for a large injection foam molded part.
The MFR of the propylene polymer can be adjusted by the kind of the polymerization catalyst at the time of polymer production, the reaction conditions, and the amount of hydrogen added to the polymerization system.

<Requirement (ii)>
The isotactic pendant fraction (mmmm) of the propylene-based polymer is usually 95% or more, preferably 96% or more, and more preferably 97% or more.

  When the isotactic pendant fraction (mmmm) of the propylene polymer is less than the lower limit, the propylene resin composition containing the propylene polymer may have reduced rigidity.

The isotactic pentad fraction (mmmm) indicates the proportion of isotactic chains in the pentad unit in the propylene polymer molecular chain measured using ¹³ C-NMR. Specifically, it is determined as the ratio of the ¹³ C-NMR spectral absorption intensity of the methyl group of the propylene monomer unit at the center of the chain meso-bonded to 5 consecutive propylene monomer units to the total absorption intensity in the methyl carbon region. .

The isotactic pendant fraction of the propylene-based polymer can be adjusted by the kind of the polymerization catalyst at the time of polymer production.
Further, the propylene polymer of the present invention is a process for producing a relatively high molecular weight propylene polymer component (H) (hereinafter sometimes simply referred to as “propylene polymer component (H)”). And two or more continuous processes comprising the step of producing a relatively low molecular weight propylene polymer component (L) (hereinafter sometimes simply referred to as “propylene polymer component (L)”). It is preferable that the high molecular weight propylene polymer component (H) is obtained by the above-described steps and satisfies the following requirements (iii) and (iv).
(Iii) The content of the high molecular weight propylene polymer component (H) in the total amount of the propylene polymer is 10 to 40% by weight.
(Iv) Intrinsic viscosity [η] measured in 135 ° C. tetralin is 7 to 10 dl / g
Hereinafter, the requirements (iii) and (iv) that the propylene polymer preferably satisfies will be described in detail.

<Requirement (iii)>
The content of the propylene polymer component (H) in the total amount of the propylene polymer is usually 10 to 40% by weight, preferably 14 to 36% by weight, and more preferably 18 to 32% by weight.

  When the content of the propylene polymer component (H) in the total amount of the propylene polymer exceeds the above upper limit value, in the propylene resin composition containing the propylene polymer, the injection molding fluidity is lowered. May not be suitable for foam molded parts. In addition, when the content of the propylene polymer component (H) in the total amount of the propylene polymer is less than the lower limit, the melt tension of the propylene polymer is lowered, which is not preferable.

When the propylene polymer is produced by two-stage polymerization, the polymer obtained in the process of producing a polymer having a high molecular weight in the two-stage polymerization process corresponds to the propylene polymer component (H). To do. Further, when the propylene polymer is produced by multistage polymerization of three or more stages, the polymer obtained in the process of obtaining the polymer having the highest molecular weight among the respective polymerization processes is a propylene polymer component ( H).
On the other hand, other than the propylene polymer component (H) among the propylene polymers produced in the production process corresponds to the propylene polymer component (L).

<Requirement (iv)>
The intrinsic viscosity [η] measured in tetralin at 135 ° C. of the propylene polymer component (H) is usually 7 dl / g to 10 dl / g, preferably 7.5 dl / g to 10 dl / g, more preferably 8 dl / g. g to 10 dl / g.

  When the intrinsic viscosity [η] measured in tetralin at 135 ° C. exceeds the above upper limit value, in the propylene resin composition containing the propylene polymer, the injection molding fluidity is lowered. It may not be suitable. Moreover, since intrinsic viscosity [(eta)] measured in 135 degreeC decalin is less than the said lower limit, since the melt tension of a propylene-type polymer falls, it is unpreferable.

[Propylene-based polymer production method]
The propylene-based polymer of the present invention is obtained by (co) polymerizing propylene and, if necessary, olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of an olefin polymerization catalyst described later. . The polymerization reaction is carried out by two or more continuous processes, and a process for producing a relatively high molecular weight propylene polymer component (H) and a relatively low molecular weight propylene polymer (L) are produced. Including the step of:

  The propylene-based polymer of the present invention may be a propylene homopolymer or a copolymer of propylene and another polymerizable monomer. In this case, other polymerizable monomers include ethylene and α-olefins having 4 to 10 carbon atoms. Specific examples of α-olefins having 4 to 10 carbon atoms include 1-butene and 1-hexene. 1-octene is a preferred example. Further, as other polymerizable monomers, non-conjugated dienes can also be used. For example, 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, Cyclic non-conjugated dienes such as 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, norbornadiene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Examples of the chain non-conjugated dienes such as 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene, 7-methyl-1,6-octadiene, etc. be able to. The other copolymerizable monomer can be contained in an amount of 1 to 50 mol%, preferably 2 to 30 mol%, more preferably 5 to 20 mol% with respect to the total amount of polypropylene (A).

  In the method for producing a propylene-based polymer, the method for adjusting the molecular weight and the intrinsic viscosity [η] of the polymer obtained in two or more successive steps is not particularly limited, but a method using hydrogen as a molecular weight adjusting agent is preferable.

  The order of production of the propylene-based polymer is as follows. In the first stage, after the relatively high molecular weight propylene-based polymer component (H) is polymerized substantially in the absence of hydrogen, the second and subsequent stages are polymerized. It is preferable to produce a relatively low molecular weight propylene polymer component (L).

  The manufacturing order can also be changed. For example, after a relatively low molecular weight propylene polymer component (L) is polymerized in the first stage, a relatively high molecular weight propylene polymer component (H) may be polymerized in the second stage and thereafter. However, in this case, it is necessary to remove the molecular weight regulator such as hydrogen contained in the reaction product of the first stage as much as possible before the polymerization of the second and subsequent stages is started. It becomes complicated and the intrinsic viscosity [η] after the second stage is difficult to increase.

  A preferred method for producing the propylene-based polymer of the present invention is that in the presence of an olefin polymerization catalyst described later, in the first stage polymerization step, propylene and optionally ethylene and An olefin selected from α-olefins having 4 to 10 carbon atoms is (co) polymerized to have an intrinsic viscosity [η] of 7 dl / g to 10 dl / g, preferably 7.5 dl / g to 10 dl / g, more preferably 8 dl / g to 10 dl / g of propylene polymer component (H) is 15% to 35% by weight, preferably 17% to 35% by weight, more preferably 20% by weight, based on the total amount of the propylene polymer. -30% by weight, and then, in the second and subsequent polymerization steps, from propylene and optionally ethylene and a C4-10 alpha-olefin (Co) polymerization of the olefin to be produced, and propylene polymer component (with intrinsic viscosity [η] of 6 dl / g or less, preferably 0.1 dl / g to 6 dl / g, more preferably 5 to 0.1 dl / g) L) is a multi-stage polymerization of two or more stages.

  The intrinsic viscosity [η] of the propylene polymer component (L) cannot be measured directly from the propylene polymer obtained in the multistage polymerization. Therefore, the intrinsic viscosity [η] of the propylene polymer component (L) is a value estimated based on the following formula (1).

[Η] (1) × w (1) + [η] (2) × w (2)... [Η] (n) × w (n) = [η] (t) (1)
(In formula (1), [η] (1) is the intrinsic viscosity of the polymer produced in the first stage, [η] (2) is the intrinsic viscosity of the polymer produced in the second stage, [η] (n ) Is the intrinsic viscosity of the polymer produced in the nth stage, [η] (t) is the intrinsic viscosity of all polymers after completion of the nth stage, w (1) is the mass fraction of the first stage, w (2 ) Indicates the mass fraction of the second stage.)

  The melt flow rate (MFR) of the propylene polymer is determined by the intrinsic viscosity [η] and the content of the propylene polymer component (H) and the propylene polymer component (L) produced in each stage. Therefore, by selecting these combinations, the MFR of the finally obtained propylene polymer can be adjusted within the range of the requirement (1).

<Olefin polymerization catalyst>
Examples of the olefin polymerization catalyst used in the method for producing the propylene polymer include known catalysts such as a titanium catalyst, a vanadium catalyst, and a metallocene catalyst. Among these, a titanium catalyst is more preferably used. .

Specifically, as the titanium-based catalyst, a solid titanium catalyst component (I), an organometallic compound (II) containing a metal atom selected from Group 1, Group 2 and Group 13 of the periodic table, and necessary Accordingly, an olefin polymerization catalyst containing an electron donor (III) may be mentioned.
Hereinafter, a preferred olefin polymerization catalyst for production of the propylene-based polymer in the present invention will be described in detail.

[Solid titanium catalyst component (I)]
The solid titanium catalyst component (I) contains a titanium compound, a magnesium compound and an electron donor compound.

  Examples of the electron donor compound include a cyclic ester compound described in International Publication No. 2006/077945, International Publication No. 2006/077946, International Publication No. 2010/032793, International Publication No. 2008/010459, International Publication No. 2000 / Examples include succinic acid ester compounds described in pamphlet No. 063261, polyol ester compounds described in pamphlet of international publication 2003/032793, dibasic acid ester compounds described in pamphlet of international publication 2005/105858, and the like.

  Of these, the electron donor compound is particularly preferably a combination of the cyclic ester compound (a) specified by the following formula (1) and the cyclic ester compound (b) specified by the following formula (2). .

<Cyclic ester compound (a)>
The cyclic ester compound (a) has a plurality of carboxylic acid ester groups and is represented by the following formula (1).

式（１）において、ｎは、５〜１０の整数、好ましくは５〜７の整数であり、特に好ましくは６である。またＣ^aおよびＣ^bは、炭素原子を表わす。
Ｒ²およびＲ³はそれぞれ独立にＣＯＯＲ¹またはＲであり、Ｒ²およびＲ³のうちの少なくとも１つはＣＯＯＲ¹である。

In the formula (1), n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6. C ^a and C ^b represent carbon atoms.
R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ .

The carbon-carbon bonds in the cyclic skeleton are preferably all single bonds, but in the cyclic skeleton, other than the C ^a -C ^a bond and the C ^a -C ^b bond when R ³ is R, Any single bond may be replaced with a double bond. That is, the C—C ^b bond in the cyclic skeleton, the C ^a —C ^b bond when R ³ is COOR ¹ , and the C—C bond (when n is 6 to 10) are replaced with double bonds. It may be done.

A plurality of R ¹ are each independently a monovalent hydrocarbon having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, and particularly preferably 4 to 6 carbon atoms. It is a group. As this hydrocarbon group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, Examples include alkyl groups such as tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, etc. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are more preferable for molecular weight distribution. It is particularly preferable because a wide propylene polymer can be produced.

  A plurality of R's are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group; A group, but at least one R is not a hydrogen atom.

  Among these, R other than a hydrogen atom is preferably a hydrocarbon group having 1 to 20 carbon atoms, and examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. Group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, alicyclic hydrocarbon group such as octyl group, alicyclic hydrocarbon group such as cyclopentyl group, cyclohexyl group , Aromatic hydrocarbon groups such as phenyl groups, and vinyl groups. Among them, an aliphatic hydrocarbon group is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a sec-butyl group are preferable.

R may be bonded to each other to form a ring, and the ring skeleton formed by bonding R to each other may contain a double bond, and the ring skeleton In the case where two or more C ^a bonded with COOR ¹ are contained, the number of carbon atoms constituting the skeleton of the ring is 5 to 10.

Examples of such a ring skeleton include a norbornane skeleton and a tetracyclododecene skeleton.
A plurality of R may be a carbonyl structure-containing group such as a carboxylic acid ester group, an acyl group, or a ketone group, and these substituents include one or more hydrocarbon groups having 1 to 20 carbon atoms. It is preferable that

Specific examples of such cyclic ester compound (a) are described in International Publication No. 2009/069483 pamphlet.
The cyclic ester compound (a) having a diester structure as described above has isomers such as cis and trans derived from a plurality of COOR ¹ groups in the formula (1), and any structure is suitable for the present invention. Although it has an effect that matches the purpose, it is preferable that the trans content is higher. The higher the trans isomer content, the higher the catalyst activity and the stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution.

  Specific examples of the cyclic ester compound (a) include compounds represented by the following formulas (1-1) to (1-6).

〔上記式（１−１）〜（１−６）中の、Ｒ¹およびＲは式（１）での定義と同様である。上記式（１−１）〜（１−３）において、環状骨格中の単結合（ただしＣ^a−Ｃ^a結合およびＣ^a−Ｃ^b結合を除く。）は、二重結合に置き換えられていてもよい。上記式（１−４）〜（１−６）において、環状骨格中の単結合（ただしＣ^a−Ｃ^a結合を除く。）は、二重結合に置き換えられていてもよい。また、上記式（１−３）および（１−６）においてｎは７〜１０の整数である。〕

[R ¹ and R in the formulas (1-1) to (1-6) are the same as defined in the formula (1). In the above formulas (1-1) to (1-3), the single bond in the cyclic skeleton (except for the C ^a -C ^a bond and the C ^a -C ^b bond) is replaced with a double bond. Also good. In the above formulas (1-4) to (1-6), the single bond in the cyclic skeleton (excluding the C ^a -C ^a bond) may be replaced with a double bond. Moreover, in said formula (1-3) and (1-6), n is an integer of 7-10. ]

  The cyclic ester compound (a) is particularly preferably a compound represented by the following formula (1a) (for example, the compounds (1-1) to (1-3)).

〔式（１ａ）中の、ｎ、Ｒ¹およびＲは式（１）での定義と同様であり、環状骨格中の単結合（ただしＣ^a−Ｃ^a結合およびＣ^a−Ｃ^b結合を除く。）は、二重結合に置き換えられていてもよい。すなわち、環状骨格中のＣ−Ｃ結合（ｎが６〜１０の場合）、Ｃ^a−Ｃ結合およびＣ^b−Ｃ結合は、二重結合に置き換えられていてもよい。〕

[N, R ¹ and R in the formula (1a) are the same as defined in the formula (1), except for ^a single bond in the cyclic skeleton (except for a C ^a -C ^a bond and a C ^a -C ^b bond). .) May be replaced by a double bond. That is, the C—C bond (when n is 6 to 10), the C ^a —C bond, and the C ^b —C bond in the cyclic skeleton may be replaced with a double bond. ]

Specific examples of the compound represented by the above formula (1a) are described in International Publication No. 2009/069483 pamphlet.
Among these compounds, the compound (1-2) exemplified in the representative examples is more preferable, and among them, diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, 3,6-dimethylcyclohexane-1,2-dicarboxylic Di-n-hexyl acid, di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, 3-methyl-6-ethylcyclohexane- Di-n-hexyl 1,2-dicarboxylate, di-n-octyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylic acid di-n-hexyl, 3-methyl Di-n-octyl 6-n-propylcyclohexane-1,2-dicarboxylate, diisobutyl 3,6-diethylcyclohexane-1,2-dicarboxylate, di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate More preferred is di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate.

These compounds can be produced using the Diels Alder reaction.
The cyclic ester compound (a) having a diester structure as described above has isomers such as cis and trans, and any structure has an effect meeting the object of the present invention. A higher rate is particularly preferable because not only the effect of broadening the molecular weight distribution but also the catalytic activity and the stereoregularity of the resulting polymer tend to be higher.

  The ratio of the trans form of the cis form and the trans form is preferably 51% or more. A more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%. On the other hand, the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%.

<Cyclic ester compound (b)>
The cyclic ester compound (b) has a plurality of carboxylic acid ester groups and is represented by the following formula (2).

式（２）において、ｎは、５〜１０の整数、好ましくは５〜７の整数であり、特に好ましくは６である。またＣ^aおよびＣ^bは、炭素原子を表わす。

In the formula (2), n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6. C ^a and C ^b represent carbon atoms.

The carbon-carbon bonds in the cyclic skeleton are preferably all single bonds, but other than the C ^a -C ^a bond and the C ^a -C ^b bond in the case where R ⁵ is a hydrogen atom in the cyclic skeleton. Any single bond may be replaced with a double bond. That is, in the cyclic skeleton, the C—C ^b bond, the C ^a —C ^b bond when R ⁵ is COOR ¹ , and the C—C bond (when n is 6 to 10) are replaced with double bonds. It may be done.

R ⁴ and R ⁵ are each independently COOR ¹ or a hydrogen atom, at least one of R ⁴ and R ⁵ is COOR ¹ , and R ¹ is independently a monovalent group having 1 to 20 carbon atoms. It is a hydrocarbon group.

A plurality of R ¹ are each independently a monovalent hydrocarbon having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, and particularly preferably 4 to 6 carbon atoms. It is a group. As this hydrocarbon group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, Examples include alkyl groups such as tetradecyl group, hexadecyl group, octadecyl group, and eicosyl group. Among them, n-butyl group, isobutyl group, hexyl group, and octyl group are preferable, and n-butyl group and isobutyl group have molecular weight distribution. This is particularly preferable because a wide propylene-based block copolymer can be produced.

Specific examples of such cyclic ester compound (b) are described in International Publication No. 2009/069483 Pamphlet.
The compound having a diester structure as described above has isomers such as cis and trans, and any structure has an effect that meets the object of the present invention.

  The ratio of the trans form of the cis form and the trans form is preferably 51% or more. A more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%. On the other hand, the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%. The reason for this is unknown, but it is presumed that the variation of the stereoisomer described later is in a region suitable for wide molecular weight distribution.

In particular, the trans purity of cyclohexane-1,2-dicarboxylic acid diester in which n = 6 in the above formula (2) is in the above range.
If the trans purity is less than 51%, the effect of wide molecular weight distribution, catalytic activity, stereospecificity, etc. may be insufficient. On the other hand, if the trans purity exceeds 79%, the effect of wide molecular weight distribution may be insufficient. That is, if the trans purity is within the above range, it is advantageous to achieve both a high level of both the effect of broadening the molecular weight distribution of the polymer obtained and the activity of the catalyst and the high stereoregularity of the polymer obtained. There are many.

  The cyclic ester compound (b) is particularly preferably a compound having a cycloalkane-1,2-dicarboxylic acid diester structure or a cycloalkene-1,2-dicarboxylic acid diester structure represented by the following formula (2a).

〔式（２ａ）中の、ｎ、Ｒ¹は前記同様（すなわち、式（２）での定義と同様）であり、環状骨格中の単結合（ただしＣ^a−Ｃ^a結合およびＣ^a−Ｃ^b結合を除く。すなわち、Ｃ−Ｃ^a結合、Ｃ−Ｃ^b結合およびＣ−Ｃ結合（ｎが６〜１０の場合））は、二重結合に置き換えられていてもよい。〕

[In formula (2a), n and R ¹ are the same as described above (that is, as defined in formula (2)), and a single bond in the cyclic skeleton (however, a C ^a -C ^a bond and a C ^a -C ^{The b} bond is excluded, that is, the C—C ^a bond, the C—C ^b bond and the C—C bond (when n is 6 to 10) may be replaced with a double bond. ]

Specific examples of the compound represented by the above formula (2a) are described in International Publication No. 2009/069483 pamphlet.
Among these compounds, cyclohexane-1,2-dicarboxylate diisobutyl, cyclohexane-1,2-dicarboxylate dihexyl, cyclohexane-1,2-dicarboxylate diheptyl, cyclohexane-1,2-dicarboxylate dioctyl, cyclohexane More preferred is di-2-ethylhexyl -1,2-dicarboxylate.

The reason is not only the catalyst performance, but also that these compounds can be produced relatively inexpensively using the Diels Alder reaction.
The cyclic ester compounds (a) and (b) may be used alone or in combination of two or more.

  The combination molar ratio of the cyclic ester compound (a) and the cyclic ester compound (b) [cyclic ester compound (a) / (cyclic ester compound (a) + cyclic ester compound (b)) × 100 (mol%)] is 10 It is preferably at least mol%. More preferably, it is 30 mol% or more, Especially preferably, it is 40 mol% or more, Most preferably, it is 50 mol% or more. A preferable upper limit is 99 mol%, preferably 90 mol%, more preferably 85 mol%, and particularly preferably 80 mol%.

  The solid titanium catalyst component (I) of the present invention is a combination of the cyclic ester compound (a) and the cyclic ester compound (b) having a wide variety of steric structures, that is, the solid titanium catalyst component. Even if the content of the cyclic ester compound (a) of (I) is low, an olefin polymer having an extremely wide molecular weight distribution can be provided. The cause of this effect is unknown, but the present inventors presume as follows.

  It is self-evident that the cyclic ester compound (a) has a large number of steric structural variations that can be formed compared to the cyclic ester compound (b) due to the presence of the substituent R. For this reason, the influence of the cyclic ester compound (a) is dominant on the molecular weight distribution, and it is considered that an olefin polymer having an extremely wide molecular weight distribution can be provided even if the combination molar ratio is low.

  On the other hand, since the cyclic ester compound (a) and the cyclic ester compound (b) are relatively similar in structure, the basic performance such as catalytic activity and stereoregularity hardly affects the effects of each other (structure). In the case of using a compound having a different number, there are many examples in which the catalytic activity, stereoregularity, etc. change drastically and the effect of one compound is dominant).

  Therefore, the solid titanium catalyst component (I) used in the present invention gives an olefin polymer having a very wide molecular weight distribution and high stereoregularity with high activity even if the content of the cyclic ester compound (a) is low. be able to.

The propylene-based (block copolymer) polymer of the present invention is a polymer having a wide molecular weight distribution. The reason for this is currently unknown, but the following causes are presumed.
It is known that the cyclic hydrocarbon structure forms various three-dimensional structures such as a chair type and a boat type. Furthermore, if the cyclic structure has a substituent, the possible three-dimensional structure variations are further increased. Further, of the carbon atoms forming the cyclic skeleton of the cyclic ester compounds, the bond between the ester group (COOR ¹ group) carbon atom is bonded with an ester group (COOR ¹ group) other carbon atoms bound If it is a single bond, the variation of the three-dimensional structure which can be taken spreads. The ability to take such a variety of three-dimensional structures leads to the formation of a variety of active species on the solid titanium catalyst component (I). As a result, when an olefin is polymerized using the solid titanium catalyst component (I), an olefin polymer having various molecular weights can be produced at one time, that is, a propylene polymer having a wide molecular weight distribution is produced. Can do.

  In the present invention, the cyclic ester compounds (a) and (b) may be formed in the process of preparing the solid titanium catalyst component (I). For example, when preparing the solid titanium catalyst component (I), a step in which the carboxylic anhydride or carboxylic acid dihalide corresponding to the cyclic ester compounds (a) and (b) substantially contacts with the corresponding alcohol. By providing, the cyclic ester compounds (a) and (b) can be contained in the solid titanium catalyst component.

  For the preparation of the solid titanium catalyst component (I) used in the present invention, a magnesium compound and a titanium compound are used in addition to the cyclic ester compounds (a) and (b). Moreover, unless the objective of this invention is impaired, you may use the catalyst component (c) and catalyst component (d) which are mentioned later in combination.

<Magnesium compound>
Specific examples of magnesium compounds used in the preparation of the solid titanium catalyst component (I) used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxyhalogenations such as methoxymagnesium chloride and ethoxymagnesium chloride. Magnesium; aryloxymagnesium halides such as phenoxymagnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, 2-ethylhexoxymagnesium; aryloxymagnesium such as phenoxymagnesium; Known magnesium compounds such as acid salts can be mentioned.

  These magnesium compounds may be used alone or in combination of two or more. These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.

  Among these, a magnesium compound containing a halogen is preferable, and a magnesium halide, particularly magnesium chloride is preferably used. In addition, alkoxymagnesium such as ethoxymagnesium is also preferably used. The magnesium compound may be derived from other substances, for example, obtained by contacting an organic magnesium compound such as a Grignard reagent with a halogenated titanium, a halogenated silicon, a halogenated alcohol, or the like. Good. For example, when alkoxymagnesium and tetraalkoxytitanium are combined, it is preferable to react with silicon tetrachloride or the like as a halogenating agent to obtain magnesium halide.

<Titanium compound>
Examples of titanium compounds include general formulas;
Ti (OR ") _g X _4-g
(Wherein R ″ is a hydrocarbon group, X is a halogen atom, and g is 0 ≦ g ≦ 4). More specifically, a tetravalent titanium compound can be given. Titanium halides such as TiCl ₄ and TiBr ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H) _{5) Br 3, Ti (O} -isoC 4 H 9) trihalide, alkoxy titanium such as Br _3; Ti (dihalogenated alkoxy titanium such as _{OCH 3) 2 Cl 2, Ti} (OC 2 H 5) 2 Cl 2; Monohalogenated alkoxytitanium such as Ti (OCH ₃ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC _{2) H 5) 4, Ti (OC} 4 H 9) 4, Ti (O-2- Echiruhe Such as tetra-alkoxy titanium such as Sil) ₄ can be mentioned.

Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more.
Examples of the magnesium compound and the titanium compound as described above may include compounds described in detail in Patent Document 1, Patent Document 2, and the like.

  For the preparation of the solid titanium catalyst component (I) used in the present invention, a known method is used without limitation except that the cyclic ester compounds (a) and (b) are included in the catalyst component. can do. Specific preferred methods include, for example, the following methods (P-1) to (P-4).

  (P-1) A solid adduct comprising a magnesium compound and a catalyst component (c), a cyclic ester compound (a) and (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. Method to contact in turbid state.

  (P-2) A method in which a solid adduct comprising a magnesium compound and a catalyst component (c), cyclic ester compounds (a) and (b), and a titanium compound in a liquid state are contacted in a plurality of times.

  (P-3) A solid adduct comprising a magnesium compound and a catalyst component (c), a cyclic ester compound (a) and (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. The method of making it contact in a cloudy state, and making it contact in several steps.

  (P-4) A method of contacting a magnesium compound in a liquid state comprising a magnesium compound and a catalyst component (c), a titanium compound in a liquid state, and the cyclic ester compounds (a) and (b).

  A preferable reaction temperature in the preparation of the solid titanium catalyst component (I) is preferably in the range of −30 ° C. to 150 ° C., more preferably −25 ° C. to 140 ° C., and further preferably −25 to 130 ° C.

  The production of the solid titanium catalyst component can also be carried out in the presence of a known medium, if necessary. Examples of this medium include aromatic hydrocarbons such as slightly polar toluene and known aliphatic hydrocarbons such as heptane, hexane, octane, decane, and cyclohexane, and alicyclic hydrocarbon compounds. Aliphatic hydrocarbons are preferred examples.

  When the olefin polymerization reaction is carried out using the solid titanium catalyst component (I) produced in the above range, the effect of obtaining a polymer having a wide molecular weight distribution, the activity of the catalyst and the high stereoregulation of the obtained polymer Sex at a higher level.

<Catalyst component (c)>
As the catalyst component (c) used for forming the solid adduct or the liquid magnesium compound, a known compound capable of solubilizing the magnesium compound in a temperature range of about room temperature to about 300 ° C. is preferable. Aldehydes, amines, carboxylic acids and mixtures thereof are preferred. Examples of these compounds include compounds described in detail in Patent Document 1 and Patent Document 2.

  More specifically, the alcohol having the ability to solubilize the magnesium compound includes methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, and n-octanol. Aliphatic alcohols such as 2-ethylhexanol, decanol and dodecanol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; alkoxy such as n-butyl cellosolve Examples thereof include aliphatic alcohols having a group.

Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid and 2-ethylhexanoic acid.
Examples of the aldehyde include aldehydes having 7 or more carbon atoms such as capric aldehyde and 2-ethylhexyl aldehyde.

Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine.
As said catalyst component (c), said alcohol is preferable, and especially ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol, etc. are preferable.

  The amount of the magnesium compound and catalyst component (c) used in preparing the solid adduct or liquid magnesium compound varies depending on the type, contact conditions, and the like. It is used in an amount of 0.1 to 20 mol / liter, preferably 0.5 to 5 mol / liter per unit volume of c). Further, if necessary, a medium inert to the solid adduct can be used in combination. As said medium, well-known hydrocarbon compounds, such as heptane, hexane, octane, decane, are mentioned as a preferable example.

  The composition ratio of magnesium to the catalyst component (c) in the solid adduct or liquid magnesium compound obtained varies depending on the type of compound used, but cannot be specified unconditionally, but with respect to 1 mol of magnesium in the magnesium compound. The catalyst component (c) is preferably in the range of 2.0 mol or more, more preferably 2.2 mol or more, further preferably 2.3 mol or more, particularly preferably 2.4 mol or more and 5 mol or less. .

<Catalyst component (d)>
The solid titanium catalyst component (I) used in the present invention further comprises an aromatic carboxylic acid ester and / or a compound having two or more ether bonds via a plurality of carbon atoms (hereinafter referred to as “catalyst component (d)”. May also be included.). When the solid titanium catalyst component (I) of the present invention contains the catalyst component (d), the catalyst activity may be improved, the stereoregularity may be increased, or the molecular weight distribution may be further broadened.

  As the catalyst component (d), known aromatic carboxylic acid esters and polyether compounds that are preferably used in conventional olefin polymerization catalysts, such as those described in Patent Document 1 and Japanese Patent Application Laid-Open No. 2001-354714 are described. The compound can be used without limitation.

Specific examples of the aromatic carboxylic acid ester include aromatic carboxylic acid monoesters such as benzoic acid esters (such as ethyl benzoate) and toluic acid esters, and aromatic polyvalent carboxylic acid esters such as phthalic acid esters. Can be mentioned. Among these, aromatic polycarboxylic acid esters are preferable, and phthalic acid esters are more preferable. As the phthalic acid esters, phthalic acid alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferable, and diisobutyl phthalate is particularly preferable.
More specifically, examples of the polyether compound include compounds represented by the following formula (3).

なお、上記式（３）において、ｍは１〜１０の整数、より好ましくは３〜１０の整数であり、特に好ましくは３〜５である。Ｒ¹¹、Ｒ¹²、Ｒ³¹〜Ｒ³⁶は、それぞれ独立に、水素原子、あるいは炭素、水素、酸素、フッ素、塩素、臭素、ヨウ素、窒素、硫黄、リン、ホウ素およびケイ素から選択される少なくとも１種の元素を有する置換基である。

In the above formula (3), m is an integer of 1 to 10, more preferably an integer of 3 to 10, and particularly preferably 3 to 5. R ¹¹ , R ¹² , R ^{31 to} R ³⁶ are each independently at least one selected from a hydrogen atom or carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon. A substituent having a seed element.

R ¹¹ and R ¹² are preferably a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 2 to 6 carbon atoms, and R ^{31 to} R ³⁶ are preferably a hydrogen atom or 1 to 1 carbon atom. 6 hydrocarbon groups.

Specific examples of R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2 -Alkyl groups, such as an ethylhexyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, are mentioned, Preferably, they are an ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group.

Specific examples of R ^{31 to} R ³⁶ include a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group), preferably a hydrogen atom, It is a methyl group.

Arbitrary R ¹¹ , R ¹² , R ^{31 to} R ³⁶ , preferably R ¹¹ and R ¹² may jointly form a ring other than a benzene ring, and an atom other than carbon is contained in the main chain. May be.
Specific compounds having two or more ether bonds as described above include 2-isopropyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cumyl-1,3. 1-substituted dialkoxypropanes such as dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-di Toxipropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2,2-di-s-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl 2-substituted dialkoxypropanes such as 2-isopentyl-1,3-dimethoxypropane and 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-dicyclohexyl-1,4-dimethoxybutane, 2, 3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1, Dialkoxyalkanes such as dimethoxypentane and 2,4-diisoamyl-1,5-dimethoxypentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1, Trialkoxyalkanes such as 3-diethoxypropane and 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxy-4-cyclohexene, 2-isopropyl-2-isoamyl 1,3-dimethoxy-4-cyclohexene, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxy-4-cyclohexene, 2-isopropyl-2-methoxymethyl-1,3-dimethoxy-4-cyclohexene, 2-isobutyl- 2-methoxymethyl-1,3-dimethoxy-4- Cyclohexene, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexene, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexene, 2-isobutyl-2-ethoxymethyl-1,3 Examples thereof include dialkoxycycloalkanes such as -dimethoxy-4-cyclohexene.

  Of these, 1,3-diethers are preferable, and in particular, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl. -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane are more preferable.

These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The cyclic ester compounds (a) and (b), the catalyst component (c), and the catalyst component (d) may be considered to belong to a component called an electron donor among those skilled in the art. The above-mentioned electron donor component has the effect of increasing the stereoregularity of the resulting polymer while maintaining the high activity of the catalyst, the effect of controlling the composition distribution of the resulting copolymer, the particle shape of the catalyst particles, It is known to show an aggregating agent effect for controlling the particle size.

The above-mentioned cyclic ester compounds (a) and (b) are considered to have an effect of further controlling the molecular weight distribution by themselves being electron donors.
In the solid titanium catalyst component (I) of the present invention, the halogen / titanium (atomic ratio) (that is, the number of moles of halogen atoms / number of moles of titanium atoms) is 2 to 100, preferably 4 to 90.

  Cyclic ester compound (a) / titanium (molar ratio) (that is, number of moles of cyclic ester compound (a) / number of moles of titanium atom) and cyclic ester compound (b) / titanium (molar ratio) (that is, cyclic ester compound) The number of moles of (b) / number of moles of titanium atoms is 0.01 to 100, preferably 0.2 to 10.

In the catalyst component (c), the catalyst component (c) / titanium atom (molar ratio) is 0 to 100, preferably 0 to 10.
Here, as a preferable ratio of the cyclic ester compound (a) and the cyclic ester compound (b), the value of 100 × cyclic ester compound (a) / (cyclic ester compound (a) + cyclic ester compound (b)) ( The lower limit of (mol%) is preferably 5 mol%, more preferably 25 mol%, still more preferably 40 mol%, and particularly preferably 50 mol%. The upper limit is preferably 99 mol%, more preferably 90 mol%, still more preferably 85 mol%, particularly preferably 80 mol%.

Magnesium / titanium (atomic ratio) (that is, the number of moles of magnesium atoms / the number of moles of titanium atoms) is 2 to 100, preferably 4 to 50.
Further, the components other than the cyclic ester compounds (a) and (b) described above, for example, the content of the catalyst component (c) and the catalyst component (d) are determined depending on the cyclic ester compounds (a) and (b). Is preferably 20% by weight or less, more preferably 10% by weight or less, with respect to the total of 100% by weight.

  Except for using the cyclic ester compounds (a) and (b) as more detailed preparation conditions for the solid titanium catalyst component (I), for example, EP585869A1 (European Patent Application Publication No. 0585869) and the aforementioned Patent Document 2 Etc. can be preferably used.

<Organic metal compound catalyst component (II)>
Examples of the organometallic compound catalyst component (II) include organometallic compounds containing a metal atom selected from Group 1, Group 2 and Group 13 of the periodic table. Specifically, a compound containing a Group 13 metal, for example, an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like can be used. Among these, an organoaluminum compound is preferable.
Specific examples of the organometallic compound catalyst component (II) include organometallic compound catalyst components described in known documents such as EP585869A1.

<Electron Donor (III)>
Moreover, the catalyst for olefin polymerization of the present invention may contain an electron donor (III) as necessary together with the organometallic compound catalyst component (II). The electron donor (III) is preferably an organosilicon compound. As this organosilicon compound, for example, a compound represented by the following general formula (4) can be exemplified.
R _n Si (OR ′) _4-n (4)
(In the formula, R and R ′ are hydrocarbon groups, and n is an integer of 1 to 3.)

  In the formula (4), R and R ′ are hydrocarbon groups having 1 to 6 carbon atoms, preferably an unsaturated or saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 6 carbon atoms. Can be mentioned. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, t-butylmethyl group, and n-pentyl group. , Iso-pentyl group, t-amyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, vinyl group, phenyl group, etc., among which methyl group, ethyl group, cyclopentyl group, cyclohexyl group, vinyl group, phenyl group Etc. are preferred.

  Specific examples of the organosilicon compound represented by the general formula (4) include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methyl Cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxy Orchids, dicyclopentyl methylmethoxysilane, dicyclopentyl ethyl silane, etc. cyclopentyl dimethylethoxysilane is used.

  Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferred.

In addition, a silane compound represented by the following formula (5) described in International Publication No. 2004/016662 pamphlet is also a preferable example of the organosilicon compound.
Si (OR ^a ) ₃ (NR ^b R ^c ) (5)
In the formula (5), ^Ra is a hydrocarbon group having 1 to 6 carbon atoms, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a carbon number. 2-6 saturated aliphatic hydrocarbon groups are mentioned. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.

In the formula (5), R ^b is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom. . Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, and a cyclopentyl group. , N-hexyl group, cyclohexyl group, octyl group and the like, among which ethyl group is particularly preferable.

Wherein (5), R ^c is a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms, preferably, like an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, an octyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.

  Specific examples of the compound represented by the above formula (5) include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, diethylaminotrin-propoxysilane, di-n-propylamino. Examples include triethoxysilane, methyl-n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethyl-iso-propylaminotriethoxysilane, and methylethylaminotriethoxysilane. It is done.

Another example of the organosilicon compound is a compound represented by the following formula (6).
RNSi (OR ^a ) ₃ (6)
In the formula (6), RN represents a cyclic amino group. Examples of the cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, 2,3,4-tetrahydroisoquinolino group, octamethyleneimino group and the like can be mentioned. Examples of ^Ra include the same as defined in Formula (5).

  Specific examples of the compound represented by the above formula (6) include (perhydroquinolino) triethoxysilane, (perhydroisoquinolino) triethoxysilane, and (1,2,3,4-tetrahydroquinolino) tri. Examples include ethoxysilane, (1,2,3,4-tetrahydroisoquinolino) triethoxysilane, octamethyleneiminotriethoxysilane, and the like.

These organosilicon compounds can be used in combination of two or more.
Other useful compounds as the electron donor (III) include the aromatic carboxylic acid ester defined as the catalyst component (d) and / or two or more ether bonds via a plurality of carbon atoms. A compound (polyether compound) is also a preferred example.

  The olefin polymerization catalyst of the present invention may contain other components useful for olefin polymerization as necessary in addition to the above components. Examples of other components include a carrier such as silica, an antistatic agent, a particle flocculant, and a storage stabilizer. As a particle aggregating agent, for example, sorbitan distearate is used as a preferred compound when particles are produced using magnesium chloride and ethanol.

<Production conditions for propylene polymer>
As described above, the propylene-based polymer of the present invention is obtained by (co) polymerizing propylene and, if necessary, an olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms. The polymerization reaction is carried out by two or more continuous processes, and a process for producing a relatively high molecular weight propylene polymer component (H) and a relatively low molecular weight propylene polymer (L) are produced. It can manufacture by superposing | polymerizing in the aspect including the process to do.

  In this case, as the olefin polymerization catalyst to be used, the aforementioned olefin polymerization catalyst may be used as it is, or a prepolymerization catalyst (prepolymerization catalyst) obtained by prepolymerization (prepolymerization) may be used. .

  The prepolymerization is performed by prepolymerizing the olefin in an amount of usually 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g per 1 g of the olefin polymerization catalyst.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used.
The concentration of the solid titanium catalyst component (I) in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, and particularly preferably about 0.1 to 50 mmol in terms of titanium atom per liter of the liquid medium. A range of 1 to 20 mmol is desirable.

  The amount of the organometallic compound (II) in the prepolymerization may be an amount that usually produces 0.1 to 1000 g, preferably 0.3 to 500 g of polymer per 1 g of the solid titanium catalyst component (I). The amount is usually about 0.1 to 300 mol, preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol, per mol of titanium atom in the solid titanium catalyst component (I). .

  In the prepolymerization, the electron donor component or the like can be used as necessary. In this case, these components are usually from 0.1 to 50 per mole of titanium atom in the solid titanium catalyst component (I). It is used in an amount of mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol.

The prepolymerization can be performed under mild conditions by adding an olefin and the above catalyst components to an inert hydrocarbon medium.
In this case, specific examples of the inert hydrocarbon medium used include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, methylcyclopentane, cyclohexane, cyclohexane And alicyclic hydrocarbons such as heptane, methylcycloheptane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or a mixture thereof. .

  Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Thus, when using an inert hydrocarbon medium, it is preferable to perform prepolymerization by a batch type.

  On the other hand, prepolymerization can be carried out using olefin itself as a solvent, or it can be prepolymerized in a substantially solvent-free state. In this case, it is preferable to perform preliminary polymerization continuously.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, but is preferably propylene.
The temperature during the prepolymerization is usually -20 to + 100 ° C, preferably -20 to + 80 ° C, more preferably 0 to + 40 ° C.

Next, the main polymerization carried out after passing through the preliminary polymerization or without going through the preliminary polymerization will be described.
As described above, the main polymerization is performed by two or more successive steps of propylene and, if necessary, an olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms.

The prepolymerization and the main polymerization can be performed by any of a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization, and a suspension polymerization, or a gas phase polymerization method.
In addition, about two or more continuous processes, although superposition | polymerization of each stage can also be performed continuously, it can also carry out by batch type or semi-continuous type, It is preferable to carry out continuously. The polymerization after the second stage is preferably carried out continuously following the polymerization at the previous stage. When the polymerization is carried out batchwise, it is possible to carry out multistage polymerization using a single polymerization vessel.

  When the main polymerization takes the form of slurry polymerization, the reaction solvent may be an inert hydrocarbon used during the above-described prepolymerization, or an olefin that is liquid at the reaction temperature and pressure.

  In the main polymerization, the solid titanium catalyst component (I) is usually about 0.0001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol in terms of titanium atom per liter of polymerization volume. Used in quantity.

  The organometallic compound (II) is used in an amount of usually about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst component in the polymerization system.

In the main polymerization, the polymerization temperature of the olefin is usually about 0 to 200 ° C, preferably about 30 to 100 ° C, more preferably 50 to 90 ° C. The polymerization pressure (gauge pressure) is usually set to normal pressure to 100 kgf / cm ² (9.8 MPa), preferably about ^{2 to} 50 kgf / cm ² (0.20 to 4.9 MPa).

[Propylene-based resin composition]
The propylene-based resin composition of the present invention includes 1 to 30 parts by weight of the propylene-based polymer with respect to 100 parts by weight of the propylene-based resin modified material.

The content of the propylene polymer in the propylene resin composition is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight, with respect to 100 parts by weight of the propylene resin modified material.
The propylene-based resin-modified material includes a propylene-based polymer (B), an inorganic filler (C), and, if necessary, an elastomer (D). Hereinafter, each component will be described in detail.

[Propylene polymer (B)]
The propylene-based polymer (B), which is an essential constituent component of the propylene-based resin-modified material, is a homopolymer of propylene (Bh), a copolymer of propylene, ethylene, and other α-olefins ( Br), selected from block copolymers (Bb) of propylene with ethylene and other α-olefins. Specific examples of the α-olefin include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 2-ethyl-1-butene. 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl -1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1- Hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1- Ndesen, 1-dodecene, and the like can be given. Among these, α-olefins of 1-butene, 1-pentene, 1-hexene and 1-octene can be preferably used.

  The propylene polymer (B) has a melting point (Tm) of usually 145 to 170 ° C, preferably 155 to 167 ° C. The melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the polypropylene polymer (B) is usually 0.3 to 200 g / 10 minutes, preferably 2 to 150 g / 10 minutes, more preferably. Is 10 to 100 g / 10 min.

In the present invention, the propylene polymer (B) is preferably a block copolymer (Bb) of propylene, ethylene and other α-olefins.
The propylene block copolymer (Bb) has a propylene homopolymer portion having an MFR of 5 to 400 g / 10 min, preferably 20 to 350 g / 10 min, and more preferably 50 to 300 g / 10 min. When the MFR of the propylene homopolymer part is lower than the lower limit, the fluidity of the propylene-based resin composition is lowered, and the injection molding fluidity in the mold is lowered at the time of injection foam molding. Moreover, when MFR of a propylene homopolymer part is higher than the said upper limit, since the mechanical strength of the injection foaming molding obtained from the propylene-type resin composition may fall, it is unpreferable.

[Inorganic filler (C)]
As the inorganic filler (C) that is an essential constituent of the propylene-based resin-modified material, talc, magnesium sulfate fiber, glass fiber, carbon fiber, mica, calcium carbonate, magnesium hydroxide, ammonium phosphate salt, It is broadly classified into inorganic fillers such as silicates, carbonates and carbon black, and organic fillers such as wood powder, cellulose, polyester fiber, nylon fiber, kenaf fiber, bamboo fiber, jude fiber, rice flour, starch and corn starch.
As the inorganic filler, talc, magnesium sulfate fiber, glass fiber, and carbon fiber are preferably used. Details will be described below.

(talc)
Talc is pulverized hydrous magnesium silicate. The crystal structure of hydrous magnesium silicate is a pyrophyllite type three-layer structure, and talc is a stack of these structures. The talc is more preferably a flat plate obtained by finely pulverizing hydrous magnesium silicate crystals to a unit layer level.

The average particle diameter of the talc is preferably 3 μm or less. Here, the average particle size of talc is equivalent to 50% obtained from an integral distribution curve of a sieving method measured by suspending talc in a dispersion medium that is water or alcohol using a centrifugal sedimentation type particle size distribution measuring device. It means particle diameter D _50. Talc may be used as it is, or various silane couplings may be used to improve interfacial adhesion with the propylene-based (block copolymer) polymer of the present invention and dispersibility in the propylene-based resin composition. The surface may be treated with an agent, a titanium coupling agent, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty acid salt, or another surfactant.

(Magnesium sulfate fiber)
When magnesium sulfate fiber is used, the average fiber length is preferably 5 to 50 μm, more preferably 10 to 30 μm. Moreover, as an average fiber diameter of a magnesium sulfate fiber, Preferably it is 0.3-2 micrometers, More preferably, it is 0.5-1 micrometer. Products include Ube Industries, Ltd. “Moss Heidi”.

(Glass fiber)
As glass fibers, glass such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali-resistant glass is melt-spun into filamentous fibers. Can be mentioned. The glass fiber is contained in the propylene resin composition in the form of a short fiber of 1 mm or less and a long fiber of 1 mm or more.

(Carbon fiber)
The carbon fiber has a fiber diameter of more than 2 μm and 15 μm or less, preferably 3 μm to 12 μm, more preferably 4 μm to 10 μm. When the fiber diameter is 2 μm or less, the rigidity of the fiber is remarkably reduced, and when it exceeds 15 μm, the aspect ratio of the fiber (the ratio of length (L) to thickness (D): L / D) is reduced. Therefore, sufficient reinforcement efficiency such as rigidity and heat resistance cannot be obtained, which is not preferable. Here, the fiber diameter can be determined by cutting the fiber perpendicular to the fiber direction, observing the cross section under a microscope, measuring the diameter, and calculating the number average of the diameters of 100 or more fibers.

The carbon fiber has a fiber length of usually 1 to 20 mm, preferably 2 to 15 mm, more preferably 3 to 10 mm. When the fiber length is less than 1 mm, the aspect ratio is low and sufficient reinforcement efficiency cannot be obtained. When the fiber length exceeds 20 mm, the workability and appearance are remarkably deteriorated.
Here, the fiber length can be obtained by measuring using a caliper or the like and calculating the number average of the fiber lengths of 100 or more fibers.

  As the carbon fiber used in the present invention, a conventionally known carbon fiber can be used without particular limitation as long as the above-described shape is satisfied. Examples of the carbon fiber include polyacrylonitrile (PAN) -based carbon fiber using polyacrylonitrile as a raw material, and pitch-based carbon fiber using pitch as a raw material. These carbon fibers can be used as so-called chopped carbon fibers obtained by cutting a fiber yarn into a desired length, and may be converged using various sizing agents as necessary. . Since the sizing agent used for the convergence treatment needs to be melted in melt kneading with the polypropylene resin, it is preferable that the sizing agent is melted at 200 ° C. or lower.

  Specific examples of such chopped carbon fibers include PAN-based carbon fibers, trade name “Torayca Chop” manufactured by Toray Industries, Inc., product name “Pyrofil (chop)” manufactured by Mitsubishi Rayon Co., Ltd., Toho Tenax ( The product name “Besfite (chop)”, etc., can be mentioned, and for pitch-based carbon fiber, the product name “Dialead” manufactured by Mitsubishi Chemical Industries, Ltd., manufactured by Osaka Gas Chemical Co., Ltd. Product names such as “Donna Carbo (chop)” and Kureha Chemical Co., Ltd. product name “Kureka Chop” can be listed.

(Wood flour)
As the wood powder, it is possible to use a material obtained by breaking wood with a cutter mill or the like and then pulverizing it with a ball mill or impeller mill to make it into a fine powder. The average particle size is usually 1 to 200 μm, preferably 10 to 150 μm. Those having an average particle size of less than 1 μm are difficult to handle, and especially when the amount of the wood-based filler is large, if the dispersion in the resin is poor, the mechanical strength of the wood-resin foamed molded article to be produced Decrease occurs. On the other hand, if it is larger than 200 μm, the homogeneity, flatness and mechanical strength of the molded product are lowered.

(cellulose)
Cellulose fibers and crystalline cellulose are preferably used as the cellulose.
The cellulose fiber is preferably a fiber having a high purity, for example, a fiber having an α-cellulose content of 80% by weight or more. As organic fibers such as cellulose fibers, fibers having an average fiber diameter of 0.1 to 1000 μm and an average fiber length of 0.01 to 5 mm can be used.

  Crystalline cellulose is a product obtained by partially depolymerizing α-cellulose obtained as a pulp from a fibrous plant and purifying it with a mineral acid, and examples of the product include “Seolus” manufactured by Asahi Kasei Corporation.

[Elastomer (D)]
The propylene-based resin modified material may contain an elastomer (D) as necessary.

  Examples of the elastomer (D) include an ethylene / α-olefin random copolymer (Da), an ethylene / α-olefin / non-conjugated polyene random copolymer (Db), and a hydrogenated block copolymer (D -C), other elastic polymers, and mixtures thereof.

  The ethylene / α-olefin random copolymer (Da) is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene and the like. These α-olefins can be used alone or in combination. Of these, propylene, 1-butene, 1-hexene and 1-octene are particularly preferably used.

  The ethylene / α-olefin random copolymer (Da) has a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of 95/5 to 70/30, preferably 90/10 to 75/25. It is. The ethylene / α-olefin random copolymer (Da) has an MFR of 0.1 g / 10 min or more, preferably 0.5 to 5 g / 10 min at 230 ° C. and a load of 2.16 kg.

  The ethylene / α-olefin / non-conjugated polyene random copolymer (Db) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. As said C3-C20 alpha-olefin, the same thing as the above is mentioned. Examples of the non-conjugated polyethylene include 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, and 5-isopropylidene-2- Acyclic dienes such as norbornene and norbornadiene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1 , 5-heptadiene, 6-methyl-1,7-octadiene, 7-methyl-1,6-octadiene and other chain non-conjugated dienes; and trienes such as 2,3-diisopropylidene-5-norbornene It is done. Among these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used.

  The ethylene / α-olefin / non-conjugated polyene random copolymer (Db) has a molar ratio of ethylene, α-olefin and non-conjugated polyene (ethylene / α-olefin / non-conjugated polyene) of 90/5/5. -30/45/25, preferably 80/10/10 to 40/40/20.

  The ethylene / α-olefin / non-conjugated polyene random copolymer (Db) has an MFR of 0.05 g / 10 min or more, preferably 0.1 to 10 g / 10 min at 230 ° C. and a load of 2.16 kg. Specific examples of the ethylene / α-olefin / non-conjugated polyene random copolymer (Db) include an ethylene / propylene / diene terpolymer (EPDM).

  The hydrogenated block copolymer (Dc) is a hydrogenated product of a block copolymer whose block form is represented by the following formula (x) or (y), and the hydrogenation rate is 90 mol% or more The hydrogenated block copolymer is preferably 95 mol% or more.

X (YX) n (x)
(XY) n (y)
Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymerization block represented by X in the formula (x) or (y) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, lower alkyl-substituted styrene, vinylnaphthalene. And styrene or its derivatives. These can be used individually by 1 type, and can also be used in combination of 2 or more type.

  Examples of the conjugated diene constituting the polymer block represented by Y in the formula (x) or (y) include butadiene, isoprene, chloroprene and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more type. n is an integer of 1 to 5, preferably 1 or 2.

  Specific examples of the hydrogenated block copolymer (Dc) include styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / ethylene / propylene / styrene block copolymer (SEPS), and styrene. -Styrene-type block copolymers, such as ethylene propylene block copolymer (SEP), etc. are mentioned.

  The block copolymer before hydrogenation can be produced, for example, by a method in which block copolymerization is performed in an inert solvent in the presence of a lithium catalyst or a Ziegler catalyst. A detailed production method is described in, for example, Japanese Patent Publication No. 40-23798. The hydrogenation treatment can be performed in an inert solvent in the presence of a known hydrogenation catalyst. Detailed methods are described in, for example, JP-B Nos. 42-8704, 43-6636, and 46-20814.

  When butadiene is used as the conjugated diene monomer, the ratio of the 1,2-bond amount in the polybutadiene block is 20 to 80% by weight, preferably 30 to 60% by weight.

  A commercial item can also be used as a hydrogenated block copolymer (Dc). Specific examples include Kraton G1657 (trademark, manufactured by Shell Chemical Co., Ltd.), Septon 2004 (trademark, manufactured by Kuraray Co., Ltd.), Tuftec H1052 (trademark, manufactured by Asahi Kasei Corporation), and the like. An elastomer (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

[Content of each component of propylene-based reformed material]
As described above, the propylene-based material to be modified includes a propylene-based polymer (B), an inorganic filler (C), and, if necessary, an elastomer (D). The content of each component is as follows.

  The content of the propylene polymer (B) is 40 to 99 parts by weight, preferably 45 to 97 parts by weight, and more preferably 50 to 95 parts by weight per 100 parts by weight of the propylene based material to be modified.

The content of the inorganic filler (C) is 1 to 40 parts by weight, preferably 3 to 35 parts by weight, and more preferably 5 to 30 parts by weight per 100 parts by weight of the propylene-based material to be modified.
The content of the elastomer (D) is from 0 to 35 parts by weight, preferably from 0 to 30 parts by weight, more preferably from 0 to 25 parts by weight, per 100 parts by weight of the propylene-based modified material, from the viewpoint of impact strength and rigidity. is there. In addition, although it is prescribed | regulated as a preferable range also about the case where content of an elastomer (D) is 0, this is the above-mentioned propylene-type polymer (B) and is a propylene-type block copolymer (Bb). In some cases, it is assumed that the propylene-ethylene copolymer rubber component exhibits effects from the viewpoint of impact strength and rigidity equivalent to the addition of the elastomer (D).

  Note that the propylene-based material to be modified may contain other components described later as necessary. Appropriate amounts of other components are appropriately added in accordance with the effects of the added components.

[Other ingredients]
The propylene-based resin composition of the present invention may contain components other than the above as long as the effects of the present invention are not impaired. Other components that can be contained in the propylene-based resin composition are described below.

(Crystal nucleating agent)
A crystal nucleating agent may be added to the propylene-based resin composition of the present invention as required for improving rigidity, heat resistance, and moldability.

  Examples of the crystal nucleating agent used in the present invention include sorbitol compounds such as dibenzylidene sorbitol, organophosphate compounds, rosinate compounds, aliphatic dicarboxylic acids and metal salts thereof.

  Of these, organophosphate compounds are preferred. The organic phosphate ester compound is a compound represented by the following general formula [N-1] and / or [N-2].

前記の式［Ｎ−１］、［Ｎ−２］中、Ｒ¹は、炭素数１〜１０の２価の炭化水素基であり、Ｒ²およびＲ³は、水素または炭素数１〜１０の炭化水素基であって、Ｒ²とＲ³とは同じであっても異なっていてもよく、Ｍは、１〜３価の金属原子であり、ｎは１〜３の整数であり、ｍは１または２である。

In the above formulas [N-1] and [N-2], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are hydrogen or 1 to 10 carbon atoms. It is a hydrocarbon group, R ² and R ³ may be the same or different, M is a 1-3 valent metal atom, n is an integer of 1-3, m is 1 or 2.

  Specific examples of the organic phosphate ester compound represented by the general formula [N-1] include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2. , 2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2 , 2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium -2,2'-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-tert-butyl phosphate) Nyl) phosphate, sodium-2,2′-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-butylidene-bis (4,6-di-t-butylphenyl) Phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-t -Butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4 , 6-di-t-butylphenyl) phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate] Sodium-2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate Fate, sodium-2,2′-ethylidene-bis (4-m-butyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4,6-di-methylphenyl) phosphate Fate, sodium-2,2′-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, Calcium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-ethylidene -Bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [ 2,2′-methylene-bis (4,6-di-t-butylfel) phosphate], aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] And a mixture of two or more of these.

A hydroxyaluminum phosphate compound represented by the general formula [N-2] is also an organophosphate compound, and in particular, R ² and R ³ are both tert-butyl groups. ] The compound represented by this is preferable.

式［Ｎ−３］において、Ｒ¹は、炭素数１〜１０の２価の炭化水素基であり、ｍは１または２である。特に好ましい有機リン酸エステル系化合物は、一般式［Ｎ−４］で表わされる化合物である。

In the formula [N-3], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m is 1 or 2. A particularly preferred organophosphate compound is a compound represented by the general formula [N-4].

式［Ｎ−４］において、Ｒ¹は、メチレン基またはエチリデン基である。

In the formula [N-4], R ¹ represents a methylene group or an ethylidene group.

  Specifically, hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] or hydroxyaluminum-bis [2,2-ethylidene-bis (4,6- Di-t-butyl) phosphate]. Specific examples of the sorbitol compound include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4- p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4 -P-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4 -Di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylyl) ) Sorbitol, 1,3,2,4-di (p-i-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4- Di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3 , 2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3- p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbi 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol or 1,3,2,4-di (P-chlorobenzylidene) sorbitol and the like can be exemplified. In particular, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol or 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol preferable.

Specific examples of C4-C12 aliphatic dicarboxylic acids and metal salts thereof that can be used in the present invention include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and their Li, Na, Mg, Ca, Ba, Al salt, etc. can be mentioned. In addition, the aromatic carboxylic acid and its metal salt that can be used as a crystal nucleating agent in the present invention are benzoic acid, allyl-substituted acetic acid, aromatic dicarboxylic acid and group 1 to 3 metal salts of these periodic tables. Specifically, benzoic acid, p-isopropylbenzoic acid, o-tertiary butyl benzoic acid, p-tertiary butyl benzoic acid, monophenylacetic acid, diphenylacetic acid, phenyldimethylacetic acid, phthalic acid, and their Li , Na, Mg, Ca, Ba, Al salt and the like.
Further, as the crystal nucleating agent, a nucleating agent represented by the following formula [N-5] may be used.

式［Ｎ−５］において、ｎは、０〜２の整数であり、Ｒ¹〜Ｒ⁵は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ⁶は、炭素数が１〜２０のアルキル基である。

In the formula [N-5], n is an integer of 0 to 2, and R ^{1 to} R ⁵ are the same or different and each is a hydrogen atom or an alkyl group, alkenyl group, or alkoxy group having 1 to 20 carbon atoms. , A carbonyl group, a halogen group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms.

In the formula [N-5], n is preferably an integer of 0 to 2, R ¹ , R ² , R ⁴ and R ⁵ are each a hydrogen atom, and R ³ and R ⁶ are the same or different. And an alkyl group having 1 to 20 carbon atoms.

More preferably, in the formula [N-5], n is an integer of 0 to 2, R ¹ , R ² , R ⁴ and R ⁵ are each a hydrogen atom, and R ³ is —CH ₃ , _{-CH 2 CH 3, -CH 2 CH} 2 CH 3, -CH 2 CH 2 CH 2 CH 3, -CH 2 CH = CH 2, -CH (CH 3) CH = CH 2, -CH 2 CH-X 1 _{^{-CH 2 -X 2, -CH 2 CH}} -X 3 -CH 2 CH 3, a _{^{-CH 2 CH-X 4 -CH 2}} OH or _{-CH 2 OH-CH (OH)} -CH 2 OH ( where X ^{1 to} X ⁴ are each independently a halogen group.), R ⁶ is an alkyl group having 1 to 20 carbon atoms.

  Examples of the method for producing the crystal nucleating agent represented by the formula [N-5] include methods described in International Publication No. 2005/111134 pamphlet and the like. Commercially available products can also be easily obtained, for example, Mirad NX8000 (manufactured by Milliken & Company).

(Foaming agent)
The propylene-based resin composition of the present invention can be applied to a foamed molded product, and here, the foamed molded product is produced using a foaming agent.

  For example, the foaming agent used in the method for producing an injection foamed molded article is not particularly limited, and may be a chemical foaming agent or a physical foaming agent. Or a gaseous physical foaming agent and a combination thereof.

  Solvent-type foaming agents are generally injected from the cylinder part of the injection molding machine and absorbed or dissolved in the molten raw material resin, and then evaporated in the injection mold to function as a blowing agent propane, butane, neopentane, Low boiling point aliphatic hydrocarbons such as heptane, isohexane, hexane, isoheptane and heptane, low boiling point fluorine-containing hydrocarbons typified by Freon gas, and the like can be used.

  The decomposable foaming agent is pre-blended with the raw material resin composition and then supplied to the injection molding machine. The foaming agent decomposes under the cylinder temperature conditions of the injection molding machine to generate gases such as carbon dioxide and nitrogen gas. A compound. It may be an inorganic foaming agent or an organic foaming agent, and an organic acid such as citric acid that promotes the generation of gas or an organic acid metal salt such as sodium citrate is used as a foaming aid. You may add together as an agent.

Specific examples of the decomposable foaming agent include the following compounds.
(1) Inorganic foaming agent: sodium bicarbonate, sodium bicarbonate, sodium carbonate, sodium bicarbonate, 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, azodiaminobenzene, barium azodicarboxylate (C) sulfonyl hydrazide compound: benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p′-oxybis (benzenesulfenyl hydrazide), diphenylsulfone-3,3′-disulfonyl hydrazide; (d) azide compound: calci Ummazide, 4,4′-diphenyldisulfonyl azide, p-toluenesulfonyl azide.

The gaseous foaming agent is not particularly limited as long as it is a normal physical foaming agent, and examples thereof include inert gases such as carbon dioxide, nitrogen, argon, helium, neon, and astatine.
Among these, carbon dioxide, nitrogen, and argon are the most excellent because they do not need to be vaporized, are inexpensive, and have very little environmental pollution and fire hazard. Moreover, you may use a gaseous foaming agent in a supercritical state.

  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.

  Among these foaming agents, carbonates or bicarbonates such as sodium bicarbonate and sodium bicarbonate are preferable, and it is desirable to use an organic carboxylic acid in combination as a foaming aid.

  The blending ratio of carbonate or bicarbonate to organic carboxylic acid (foaming aid) is preferably in the range of 30 to 65 parts by weight of carbonate or bicarbonate and 35 to 70 parts by weight of organic carboxylic acid. Here, the total amount of both is 100 parts by weight. In addition, in using a foaming agent and a foaming auxiliary agent, the masterbatch containing them may be made beforehand, and the formulation which mix | blends it with the remaining propylene-type resin composition for foam molding may be taken.

The addition amount of the foaming agent is selected in consideration of the amount of gas generated from the foaming agent and the desired foaming ratio depending on the required properties of the foamed molded article to be produced. The amount is usually 0.1 to 10 parts by weight, preferably 0.4 to 5.0 parts by weight, more preferably 0.7 to 3.0 parts by weight with respect to parts.
When the addition amount of the foaming agent is within such a range, it is possible to obtain a foamed molded article in which the cell diameter is uniform and the cells are uniformly dispersed.

(Stabilizer)
Stabilizers used in the present invention include heat stabilizers, weather stabilizers, light stabilizers, chloride absorbers, fillers, crystal nucleating agents, softeners, antistatic agents, slip agents, antiblocking agents, antifogging agents, Known stabilizers such as lubricants, dyes, pigments, natural oils, synthetic oils and waxes can be used without limitation. For example, known phenol stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, higher fatty acid metal salts such as calcium stearate, inorganic oxides and the like.

  The propylene-based polymer used in the present invention is characterized by containing a relatively large amount of high molecular weight components as described above. It is known that high molecular weight components tend to be relatively easily cut by energy such as heat, light, and shear. When molecular cutting occurs, the molecular weight distribution becomes narrow, which may cause problems such as a reduction in high-speed molding performance and difficulty in manufacturing a large molded product. Therefore, it is preferable to select an additive having a higher effect than the conventional additive and increase the amount of the additive.

[Molded body]
The propylene-based resin composition of the present invention can be applied to various molded products. Molded products made of propylene resin compositions include foam molded products, injection foam molded products, extruded molded products, blow molded products, vacuum / pressure molded products, calendar molded products, stretched films, inflation films, injection molded products, etc. Can be used for In particular, it can be suitably used for injection foam molded products, foam molded products, and stretched films. Hereinafter, the injection foam molded article will be described in detail.

(Injection foam molding)
Injection foam molding is performed by injection-filling a plasticized resin composition from an injection molding machine into a mold cavity, and then increasing the volume of the cavity to foam the plasticized resin composition to produce a foam molded article. .

A mold used for injection foam molding is composed of a fixed mold and a movable mold, and these are preferably in a mold-clamped state when the plasticized resin composition is injected and filled.
The volume of the cavity can be increased by retracting the movable mold (core back) to widen the cavity, and it is preferable to increase the volume after an injection filling, particularly after an appropriate time.

Hereinafter, a cavity structure including a fixed mold and a movable mold will be described with reference to FIGS. 1 and 2.
The initial position (FIG. 1) of the movable mold 2 is the position when the fixed mold 1 and the movable mold 2 are in the closest clamping state, and the melting of the foamable resin composition used for one molding is performed. A cavity that is almost the same volume as the volume that is filled in the unfoamed body and that is close to the product shape is formed.

In the present invention, the length in the expanding direction at the start of injection of the cavity 3 formed between the fixed mold 1 and the movable mold 2, that is, the cavity clearance (T ₀ ) of the mold at the start of injection is preferably 1. A range of 0 to 2.0 mm, more preferably 1.0 to 1.8 mm, and still more preferably 1.0 to 1.5 mm is desirable.

If the cavity clearance (T ₀ ) is less than 1.0 mm, the injection filling cavity is narrow, and the plasticized resin composition may not be sufficiently supplied and filled into the cavity due to an increase in viscosity or solidification of the plasticized resin composition.

  In addition, if injection filling is performed at a high pressure for sufficient filling, the resin is rapidly cooled by the mold, and even if the core is backed up, foaming does not occur sufficiently, resulting in poor foaming, and the generation of burrs due to high injection filling pressure is suppressed. Therefore, the equipment cost becomes high.

  The injection time of the plasticized resin composition into the mold cavity is not particularly limited, but preferably 0.7 to 5.0 s, more preferably about 0.7 to 4.0 s. After the completion of injection, a delay time of preferably 0 to 3 s, more preferably 0.5 to 3 s is provided, and then the movable mold constituting the cavity is preferably 1 to 50 mm / s, more preferably 1 to 20 mm / s. It is desirable to expand the cavity volume by retreating (core back) with (FIG. 2).

  By providing this delay time, the thickness of the skin layer can be controlled, and when the delay time is lengthened, the skin layer can be thickened, and as a result, mechanical properties such as rigidity can be enhanced.

Here, the enlargement ratio of the cavity volume is usually 1.1 to 4.0 times, preferably 1.5 to 3.0 times, and more preferably 2.0 to 2.5 times.
Further, T ₀ and the ratio (T ₁ / T ₀₎ of the cross-sectional expanding direction length of the cavity 3 after the movable mold 2 backward (T ₁₎ is 1.1 to 5.0, preferably 1.5 to 4.0.

When T ₁ / T ₀ is less than 1.1, it is the same as an unfoamed molded article, and a desired rigidity cannot be obtained.
The core moving speed during core back varies depending on the thickness of the molded body, the type of resin, the type of foaming agent, the mold temperature, and the resin temperature. For example, carbon dioxide is used as a physical foaming agent, and ordinary polypropylene is used. In this case, about 0.5 to 30 mm / s is preferable.

  If the core moving speed is too slow, the resin will solidify in the middle of the core back, and sufficient foaming ratio will not be obtained, and if it is too fast, cell generation and growth will not follow the core movement, and the cell will break and the appearance will be good Can not be obtained.

  The temperature of the resin to be injected and the mold temperature vary depending on the thickness of the molded body, the type of resin, the type and amount of foaming agent, etc., but the temperatures usually used for molding propylene resins are sufficient, and the product thickness is In order to obtain a thin product or a product with a high expansion ratio, it is preferable to set it higher than the normal mold temperature. Specifically, for example, the temperature of the resin to be injected is 170 to 250 ° C., preferably 180 to 220 ° C. The mold temperature of the fixed mold and the movable mold is 10 to 100 ° C., preferably 30 to 80 ° C. The pressure inside the mold is 5 to 50 MPa, preferably 10 to 30 MPa. The injection pressure is usually 10 to 250 MPa, preferably 12 to 200 MPa.

  As in the present invention, after filling the cavity with the resin composition at one time and then foaming, the resin in the portion in contact with the mold is solidified faster than the internal resin, and the solid skin is not foamed on the surface of the molded product An injection foam molded article having a layer and a foam layer in the center is obtained.

  Since the injection-foamed molded body has an unfoamed solid skin layer on the surface of the molded product, it is possible to obtain and maintain a hard product shape and to obtain a highly rigid molded body. Moreover, even if some distribution occurs in the cell shape, cell density, and expansion ratio of the foam layer inside the molded body, a molded body having a good appearance can be obtained due to the smoothness and rigidity of the skin layer. The thickness of the solid skin layer is not particularly limited, but is preferably 0.1 to 0.5 mm, more preferably 0.3 to 0.5 mm. The thickness of the central foam layer is preferably 2 to 4 mm, more preferably 1.8 to 3.5 mm. The timing of the core back for forming the skin layer having the above thickness is the type of resin, the foaming agent. However, when normal polypropylene is used, it is preferably about 0 to 3 s, more preferably about 0.5 to 3 s after completion of injection filling. If the time from the completion of injection filling to the core back is too short, a skin layer with sufficient thickness will not be formed, and if it is too long, the resin will solidify and sufficient foaming ratio will not be obtained even if the core is back. .

  The expansion ratio can be appropriately controlled by the resin temperature, injection speed, waiting time from the end of injection filling to the start of core back, core back amount, core back speed, cooling time after the end of core back, etc. 3.0 times is preferable.

In addition, the core back can be performed in several stages, whereby a molded body in which the cell structure and the end shape are controlled is obtained.
Further, the expansion ratio limited to the foam layer is preferably 2 to 6 times, and more preferably 3 to 5 times.

In the present invention, a hot runner, a shut-off nozzle (5), a valve gate (4), etc. that are used in normal injection molding can also be used.
Valve gates and hot runners not only suppress the generation of waste resin such as runners, but also prevent the occurrence of defects in foamed molded products in the next cycle by leakage of the propylene resin composition for foam molding from the mold into the cavity. effective.

  After completion of foaming, it can be cooled as it is and the foamed molded product can be taken out, or the molding cycle can be shortened by controlling the contact state between the molded product and the mold by slightly clamping, thereby promoting cooling. It is also possible to obtain a molded article having a good dent and cell shape.

In the propylene resin composition of the present invention, for example, an injection foam molded article having a thickness of about 1.2 to 5.0 mm can be suitably obtained.
When this injection-foamed molded article has closed cells, the average cell diameter is about 0.01 to 1.0 mm. However, depending on the shape and use of the molded article, even if the cell diameter is several mm, the cell There may be a part of the communication. Furthermore, the injection-foamed molded product of the present invention obtained by the above-described production method has a cross section of the molded product cut in parallel with the movable mold retreat direction, and in the region of the foamed layer center portion of 10 to 50%, “perpendicular to the solid skin layer”. 70% or more of the cells having a ratio of cell diameter / cell diameter along the solid skin layer of 0.7 to 1.4, and in the remaining foam layer cells, the cell diameter perpendicular to the solid skin layer / The ratio of the “cell diameter along the solid skin layer” is 0.1 to 0.9. In this way, if there are many cells along the skin layer, heat conduction due to radiation and convection in the foam layer can be suppressed, so the molded body should have a low thermal conductivity between the front and back sides of the molded body. Can do. In addition, when the expansion ratio is increased, the cells meet together and communicate with each other, and the inside of the molded body becomes hollow. However, since the resin pillar is formed in the cavity, the molded body is highly lightweight. And has a strong rigidity.

  Such foamed molded products can be suitably used for various applications such as automotive interior and exterior parts, cardboard substitutes, electrical appliances, building materials, etc., and particularly suitable for automotive interior parts and automotive exterior parts. Can be used.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the following examples, the physical properties of the propylene polymer and the propylene resin composition were measured by the following methods.

(1) Melt flow rate (MFR: [g / 10 min]):
Based on ASTM D1238E, it was measured with a 2.16 kg load. The measurement temperature was 230 ° C.

(2) Intrinsic viscosity ([η]: [dl / g]):
It measured at 135 degreeC using the tetralin solvent.

(3) Molecular weight distribution:
Liquid chromatograph: Waters ALC / GPC 150-C plus type (Suggested refractometer detector integrated type)
Column: Tosoh Corporation GMH6-HTx2 and GMH6-HTLx2 were connected in series.
Mobile phase medium: o-dichlorobenzene Flow rate: 1.0 ml / min Measurement temperature: 140 ° C.
Calibration curve creation method: Standard polystyrene sample used Sample concentration: 0.10% (w / w)
Sample solution volume: 500 μl
Mw / Mn value and Mz / Mw value were calculated by analyzing the obtained chromatogram by a known method. The measurement time per sample was 60 minutes.

(4) Isotactic pendant fraction (mmmm: [%])
It is one of the indexes of the stereoregularity of the polymer, and the pentad fraction (mmmm,%) for which the microtacticity was examined was assigned to ¹³ C-- which was assigned in the propylene polymer based on Macromolecules 8,687 (1975). It calculated from the peak intensity ratio of the NMR spectrum. ^{The 13} C-NMR spectrum was measured using an EX-400 device manufactured by JEOL, based on TMS, using a temperature of 130 ° C. and an o-dichlorobenzene solvent.

(5) Room temperature n-decane soluble (insoluble) component amount ([wt%])
About 3 g of a propylene-based block copolymer (measured to a unit of 10 ^-4 g. In addition, this weight was expressed as b (g) in the following formula), 500 ml of decane, and decane. A small amount of a heat-resistant stabilizer was charged, and the mixture was heated to 150 ° C. in 2 hours while stirring with a stirrer in a nitrogen atmosphere to dissolve the propylene-based block copolymer, and kept at 150 ° C. for 2 hours. It was gradually cooled to 23 ° C. over 8 hours. The liquid containing the obtained propylene-based block copolymer precipitate was filtered under reduced pressure using a 25G-4 standard glass filter manufactured by Iwata Glass Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the decane-soluble component, and this weight was measured to the unit of 10 ⁻⁴ g (this weight is expressed as a (g) in the following equation). did). After this operation, the amount of decane soluble component was determined by the following formula.
Room temperature n-decane soluble component (Dsol) content = 100 × (500 × a) / (100 × b)
Room temperature n-decane insoluble component (Dinsol) content = 100-100 × (500 × a) / (100 × b)

(6) Content of skeleton derived from ethylene (C2 amount)
In order to measure the skeleton concentration derived from ethylene in Dsol, 20-30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, and then carbon nuclear magnetic resonance analysis ( ¹³ C-NMR). Propylene and ethylene were quantitatively determined from the dyad chain distribution. In the case of a propylene-ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, and EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ were used, and the following formula was used.
Propylene (mol%) = (PP + 1 / 2EP) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)
Ethylene (mol%) = (1 / 2EP + EE) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)

(7) Melt tension Melt tension was measured using a melt tension measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd.), orifice (L = 8.00 mm, D = 2.095 mm), set temperature 230 ° C., piston descending speed 15 mm. This is a value obtained by measuring the winding load of the pulley with load cell detection under the conditions of / m and winding speed of 15 m / min.

(8) Swell Swell was measured according to the following using a capillograph (manufactured by Toyo Seiki Co., Ltd.).
<Test conditions>
Capillary length: 40mm
Capillary diameter: 1mm
Measurement temperature: 230 ° C
Shear rate: 1216 sec ^-1

(9) Thermal conductivity Thermal conductivity was measured under conditions of room temperature (23 ± 2 ° C.) and 50 ± 5% RH in accordance with ISO / CD22007-2.
Measuring device: Hot disk method thermophysical property measuring device TPA-501 (manufactured by Kyoto Electronics Industry)

(10) Evaluation of injection foam molding In the following Examples and Comparative Examples, injection foam molding was performed under the following conditions.
Injection molding machine: MD350S-III type (clamping force 350t), manufactured by Ube Machinery Co., Ltd.
Mold: Cavity size: Length 400mm, width 200mm, thickness 2mm
Gate: Single point direct gate in the cavity Injection temperature: 210 ° C
Mold surface temperature: 45 ° C
Injection time: 1.0 s (Time from the start of injection to the end of injection of molten resin)
Foam molding conditions Mold clearance after foaming process: 5.0mm
Core back speed: 20 mm / s
Foam start delay time after resin filling: 1 s
Injection mold cavity clearance (L0): 2mm
・ Characteristics of foam molding

(10-1) Foaming ratio achievement degree It was evaluated according to the following criteria whether or not the foaming start delay time after resin filling was 2.5 times.
A: When the thickness t0 = 2 mm before foaming, the thickness t = 5 mm or more of the molded article after foaming, and when the foaming ratio 2.5 times is achieved C: When the thickness t0 = 2 mm before foaming When the thickness of the molded product after foaming is less than 5mm and the expansion ratio of 2.5 is not achieved

(10-2) Cell shape The cross section of the molded product was evaluated according to the following criteria.
A: Closed cell without bubble breakage B: Slightly open cell due to bubble breakage C: Open cell due to bubble breakage and crack in foamed layer The average cell diameter was measured by observing the cross section of the molded product with a stereoscopic microscope image.

(10-3) Thermal conductivity The thermal conductivity was measured for an injection foam molded product (1.5 times foaming) molded with the mold clearance after the foaming step under the above foam molding conditions as 1.0 mm.

[Example 1]
(1) Production of solid catalyst After a high-speed stirring device (made by Tokushu Kika Kogyo Co., Ltd. (TK homomixer M type)) with an internal volume of 2 liters was sufficiently substituted with nitrogen, 700 ml of purified decane, 10 g of commercially available magnesium chloride, 24. 2 g and 3 g of the trade name Leodol SP-S20 (sorbite distearate manufactured by Kao Corporation) were added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. did. Next, 1 liter of purified decane that had been cooled to −10 ° C. in advance was put into this suspension using a Teflon (registered trademark) tube having an inner diameter of 5 mm while stirring at a high speed so as not to cause precipitation. Transferred to a 2 liter glass flask (with a stirrer). The solid produced by the transfer was filtered and washed thoroughly with purified n-heptane to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with respect to 1 mol of magnesium chloride.

  This solid adduct was suspended in decane, and 23 mmol of the above solid adduct in terms of magnesium atom was introduced into 100 ml of titanium tetrachloride maintained at −20 ° C. with stirring and mixed. A liquid was obtained. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (cis isomer, trans isomer mixture) was converted into a solid adduct. Was added in an amount of 0.085 mol per 1 mol of magnesium atom, and the temperature was raised to 110 ° C. in 40 minutes. When the temperature reached 110 ° C., cyclohexane 1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was further added in an amount of 0.0625 mol with respect to 1 mol of magnesium atom in the solid adduct, and the temperature was adjusted. These were reacted by holding at 110 ° C. with stirring for 90 minutes.

  After completion of the reaction for 90 minutes, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated to 110 ° C. and stirred for 45 minutes. These were allowed to react by holding. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and washed sufficiently with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.

The solid titanium catalyst component (α-1) prepared by the above operation was stored as a decane suspension, and a part of this was dried for the purpose of examining the catalyst composition.
The composition of the solid titanium catalyst component (α-1) thus obtained was 3.2 mass% titanium, 17 mass% magnesium, 57 mass% chlorine, diisobutyl 3,6-dimethylcyclohexane 1,2-dicarboxylate. They were 10.6% by mass, 8.9% by mass of diisobutyl cyclohexane 1,2-dicarboxylate, and 0.6% by mass of an ethyl alcohol residue.

(2) Production of prepolymerization catalyst 180 g of the solid catalyst component prepared in (1) above, 89.3 mL of triethylaluminum, and 180 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 10 to 18 ° C. Was inserted and reacted with stirring for 60 minutes. This prepolymerization catalyst contained 6 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization Propylene was continuously supplied at 82.4 kg / hour to a vessel polymerization apparatus with a stirrer having an internal volume of 1000 L, and the slurry level was maintained at 300 L. The catalyst slurry was continuously supplied as a solid catalyst component at 1.12 g / hour, triethylaluminum 5.4 mL / hour, and dicyclopentyldimethoxysilane 13.2 mL / hour. did. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 51 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 15.1 mol%. Polymerization was performed at a polymerization temperature of 57 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was continuously supplied at 12 kg / hour, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase became 14.9 mol%. Polymerization was performed at a polymerization temperature of 56 ° C. and a pressure of 2.8 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. 100 parts by weight of the resulting propylene polymer, 0.2 parts by weight of heat stabilizer IRGANOX 1010 (trade name, Ciba Geigy Corp.), 0.3 parts by weight of heat stabilizer IRGAFOS 168 (trademark of Ciba Geigy Corp.), 0.1 part of calcium stearate After mixing a weight part with a tumbler, it melt-kneaded with the single screw extruder, and prepared the pellet-form propylene polymer (A-1). Table 1 shows the product properties of the propylene polymer (A-1).

<Melting and kneading conditions>
Single screw extruder: TLC35-20 (manufactured by Tsukada Tree Machine)
Kneading temperature: 230 ° C
Screw rotation speed: 70rpm

[Example 2]
The polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization 92.3 kg / hour of propylene was continuously supplied to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L to maintain the slurry level at 300 L. The catalyst slurry was continuously supplied as a solid catalyst component at 1.98 g / hour, triethylaluminum 5.85 mL / hour, and dicyclopentyldimethoxysilane 14.1 mL / hour. . Polymerization was performed at a polymerization temperature of 74 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 70 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 10.1 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 15 kg / hour of propylene was continuously supplied, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase became 10.0 mol%. Polymerization was performed at a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene polymer (A-2). Table 1 shows the physical properties of the propylene polymer (A-2).

[Example 3]
The polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization Propylene was continuously supplied at 53 kg / hour to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and the slurry level was maintained at 300 L. The catalyst slurry was continuously supplied as a solid catalyst component at 2.16 g / hour, triethylaluminum 6.0 mL / hour, dicyclopentyldimethoxysilane 12.9 mL / hour, and hydrogen supply was not performed to make it substantially hydrogen-free. . Polymerization was performed at a polymerization temperature of 74 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization apparatus, 87 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 9.7 mol%. Polymerization was performed at a polymerization temperature of 62 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was continuously supplied to the polymerization vessel at a rate of 20 kg / hour, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 9.8 mol%. Polymerization was performed at a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene polymer (A-3). Table 1 shows the physical properties of the propylene-based polymer (A-3).

[Example 4]
The polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization Propylene was continuously supplied to a vessel polymerization vessel with an internal volume of 1000 L with a stirrer at 119 kg / hour to maintain the slurry level at 300 L. The catalyst slurry was continuously supplied as a solid catalyst component at 1.21 g / hour, triethylaluminum 5.8 mL / hour, and dicyclopentyldimethoxysilane 14.3 mL / hour, and hydrogen supply was not performed to make it substantially hydrogen-free. . Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 13 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 14.3 mol%. Polymerization was performed at a polymerization temperature of 57 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was continuously supplied to the polymerization vessel at 12 kg / hour, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 14.3 mol%. Polymerization was performed at a polymerization temperature of 56 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene polymer was blended with additives and melt kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene polymer (A-4). Table 1 shows the physical properties of the propylene polymer (A-4).

[Comparative Example 1]
(1) Production of solid catalyst component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a homogeneous solution, and then phthalic anhydride 21 was added to this solution. .3 g was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added and stirred at the same temperature for 2 hours. Retained.

  After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

Here, the detection of this free titanium compound was confirmed by the following method. 10 ml of the supernatant of the above solid catalyst component was collected with a syringe into a 100 ml branched Schlenk previously purged with nitrogen and charged. Next, the solvent hexane was dried in a nitrogen stream, and further vacuum-dried for 30 minutes. To this, 40 ml of ion-exchanged water and 10 ml of (1 + 1) sulfuric acid were charged and stirred for 30 minutes. This aqueous solution was transferred to a 100 ml volumetric flask through a filter paper, followed by conc. As a masking agent for iron (II) ions. Add 1 ml of H ₃ PO ₄ and 5 ml of 3% H 2 O 2 as a coloring reagent for titanium, and shake and mix this volumetric flask up to 100 ml with ion-exchanged water. After 20 minutes, the absorbance at 420 nm is observed using UV. Free titanium was removed by washing until no longer observed.

  The solid titanium catalyst component (A) prepared as described above was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was 2.2% by weight of titanium, 61% by weight of chlorine, 19.1% by weight of magnesium and 12.5% by weight of DIBP.

(2) Production of prepolymerization catalyst 180 g of the solid catalyst component prepared in the above (1), 29.1 mL of triethylaluminum, and 180 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 200 L, and the internal temperature was maintained at 10 to 18 ° C. Was inserted and reacted with stirring for 60 minutes. This prepolymerization catalyst contained 6 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization Propylene was continuously supplied at 100 kg / hour to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and the slurry level was maintained at 300 L. 1.47 g / hour, triethylaluminum 6.0 mL / hour, and dicyclopentyldimethoxysilane 13.8 mL / hour are continuously fed as the solid catalyst component as the above catalyst slurry, and the hydrogen is not supplied and is substantially in a hydrogen-free state. did. Polymerization was performed at a polymerization temperature of 74 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was continuously supplied to the polymerization vessel at a rate of 58 kg / hour, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 5.3 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 19 kg / hour of propylene was continuously supplied, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 5.5 mol%. Polymerization was performed at a polymerization temperature of 65 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene-based polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene-based polymer (A′-1). Table 2 shows the physical properties of the propylene-based polymer (A′-1).

[Comparative Example 2]
The polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization Propylene was continuously supplied at 105 kg / hour to a vessel polymerization vessel with an internal volume of 1000 L with a stirrer, and the slurry level was maintained at 300 L. The catalyst slurry was continuously supplied as a solid catalyst component at 1.50 g / hour, triethylaluminum 6.0 mL / hour, and dicyclopentyldimethoxysilane 13.8 mL / hour, and hydrogen supply was not performed to make it substantially hydrogen-free. . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization reactor, 55 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 6.1 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 2.8 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 17 kg / hour of propylene was continuously supplied, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase became 6.4 mol%. Polymerization was performed at a polymerization temperature of 61 ° C. and a pressure of 2.7 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene-based polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene-based polymer (A′-2). Table 2 shows the physical properties of the propylene-based polymer (A′-2).

[Comparative Example 3]
The polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization Propylene was continuously supplied at 114 kg / hour to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and the slurry level was maintained at 300 L. The catalyst slurry was continuously supplied as a solid catalyst component at 1.50 g / hour, triethylaluminum 6.0 mL / hour, and dicyclopentyldimethoxysilane 13.8 mL / hour, and hydrogen supply was not performed to make it substantially hydrogen-free. . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 47 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 9.3 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.8 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization reactor, 16 kg / hour of propylene was continuously supplied, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 9.2 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.7 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene polymer (A'-3). Table 2 shows the physical properties of the propylene-based polymer (A′-3).

[Comparative Example 4]
The polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization Propylene was continuously supplied at 166 kg / hour to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and the slurry level was maintained at 300 L. 1.67 g / hour of catalyst slurry as a solid catalyst component, 4.8 mL / hour of triethylaluminum, and 11.8 mL / hour of dicyclopentyldimethoxysilane are continuously supplied, and the hydrogen concentration in the gas phase becomes 60 molppm. Was fed as Polymerization was performed at a polymerization temperature of 74 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, 5 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 14.3 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was continuously supplied to the polymerization vessel at 3 kg / hour, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 14.3 mol%. Polymerization was performed at a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene-based polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene-based polymer (A′-4). Table 2 shows the physical properties of the propylene-based polymer (A′-4).

[Comparative Example 5]
The polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization Propylene was continuously supplied at 123 kg / hour to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and the slurry level was maintained at 250 L. The catalyst slurry was continuously supplied as a solid catalyst component at 1.20 g / hour, triethylaluminum 5.8 mL / hour, and dicyclopentyldimethoxysilane 14.2 mL / hour, and hydrogen was not supplied to make it substantially hydrogen-free. . Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization reactor, 11 kg / hour of propylene was continuously supplied, the slurry level was maintained at 300 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 14.0 mol%. Polymerization was performed at a polymerization temperature of 57 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was continuously supplied to the polymerization vessel at 9 kg / hour, the slurry level was maintained at 260 L, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 14.1 mol%. Polymerization was performed at a polymerization temperature of 56 ° C. and a pressure of 2.8 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene polymer (A'-5). Table 2 shows the physical properties of the propylene-based polymer (A′-5).

[Comparative Example 6]
The polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization method was changed as follows.
(3) Main polymerization Into a vessel polymerization vessel with an internal volume of 100 L, 110 kg / hour of propylene, 1.40 g / hour of catalyst slurry as a solid catalyst component, 5.8 ml / hour of triethylaluminum, dicyclopentyldimethoxysilane 6 mL / hour was continuously supplied, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.8 mol%. Polymerization was carried out at a polymerization temperature of 73 ° C. and a pressure of 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. Propylene was supplied to the polymerization vessel at 30 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 1.1 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 46 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 1.1 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was deactivated and then sent to a washing tank to wash the propylene polymer powder with liquid propylene. Thereafter, gas-solid separation was performed to obtain a propylene polymer. The resulting propylene polymer was vacuum dried at 80 ° C. The obtained propylene polymer was blended with additives and melt-kneaded in the same manner as in Example 1 to prepare a pellet-shaped propylene polymer (A'-6). Table 2 shows the physical properties of the propylene-based polymer (A′-6).

[Production Example 1]
(1) Production of Solid Catalyst After heating and reacting 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol at 130 ° C. for 2 hours, a uniform solution was obtained. 3 g was added and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added and stirred at the same temperature for 2 hours. Retained.

  After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

Here, the detection of this free titanium compound was confirmed by the following method. 10 ml of the supernatant of the above solid catalyst component was collected with a syringe into a 100 ml branched Schlenk previously purged with nitrogen and charged. Next, the solvent hexane was dried in a nitrogen stream, and further vacuum-dried for 30 minutes. To this, 40 ml of ion-exchanged water and 10 ml of (1 + 1) sulfuric acid were charged and stirred for 30 minutes. This aqueous solution was transferred to a 100 ml volumetric flask through a filter paper, followed by conc. As a masking agent for iron (II) ions. Add 1 ml of H ₃ PO ₄ and 5 ml of 3% H 2 O 2 as a color developing reagent for titanium, and shake and shake this volumetric flask made up to 100 ml with ion-exchanged water. Free titanium was removed by washing until no longer observed.

  The solid titanium catalyst component (A) prepared as described above was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was 2.2% by weight of titanium, 61% by weight of chlorine, 19.1% by weight of magnesium and 12.5% by weight of DIBP.

(2) Production of prepolymerization catalyst 120 g of the solid catalyst component prepared in (1) above, 150.5 mL of triethylaluminum, 42.8 mL of diethylaminotriethoxysilane, and 12 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 20 L. While maintaining the temperature at 15 to 20 ° C., 1200 g of propylene was inserted and reacted while stirring for 100 minutes. After completion of the polymerization, the solid component was settled, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 1.0 g / L.

(3) Main polymerization A jacketed circulation type tubular polymerizer having an internal capacity of 58 L, propylene 40 kg / hour, hydrogen 256 NL / hour, the above catalyst slurry as a solid catalyst component, 0.41 g / hour, triethylaluminum 2.8 ml / hour Then, 1.9 ml / hour of diethylaminotriethoxysilane was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.45 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 7.6 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.30 MPa / G.

  The obtained slurry was transferred to a transfer pipe having an internal volume of 2.4 L, gasified and gas-solid separated, and then the polypropylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L. / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.21 (molar ratio) and hydrogen / ethylene = 0.12 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.0 MPa / G. The resulting propylene block copolymer was vacuum dried at 80 ° C. Table 3 shows the physical properties of the propylene-based polymer (Bb-1).

[Production Example 2]
66 parts by weight of a propylene-based polymer (B-b-1), ethylene-butene copolymer rubber (Tuffmer A4050 (trade name, Mitsui Chemicals)), ethylene-butene copolymer rubber (Tuffmer A-35070S ( Mitsui Chemicals Co., Ltd.)) 10 parts by weight, talc (JM-209 (trademark), Asada Flour Mills Co., Ltd.) 12 parts by weight, heat stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.) 0.1 part by weight, heat resistance Stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat-resistant stabilizer IRGANOX 1076 (Ciba Geigy Co., Ltd.) 0.1 parts by weight, calcium stearate 0.1 parts by weight are mixed in a tumbler and then twin screw extrusion A pellet-shaped propylene resin composition (K-1) was prepared by melt-kneading with a machine.

<Melting and kneading conditions>
Coaxial twin-screw kneader: Product number TEX-30α, manufactured by Nippon Steel Works, Ltd. Kneading temperature: 180 ° C
Screw rotation speed: 600rpm
Feeder rotation speed: 60 kg / h

[Example 5]
100 parts by weight of the propylene-based resin composition (K-1), 11 parts by weight of the propylene-based polymer (A-1) produced in Example 1, and 0.1 parts by weight of the heat-resistant stabilizer IRGANOX 1010 (trademark of Ciba Geigy Corp.) , 0.1 parts by weight of heat stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGANOX 1076 (Trademark of Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate were mixed in a tumbler. The propylene resin composition was prepared by melt-kneading with a shaft extruder. Table 4 shows the physical properties of the resulting propylene resin composition.

<Melting and kneading conditions>
Coaxial twin-screw kneader: Product number TEX-30α, manufactured by Nippon Steel Works, Ltd. Kneading temperature: 180 ° C
Screw rotation speed: 600rpm
Feeder rotation speed: 60 kg / h

[Example 6]
In Example 5, in place of 11 parts by weight of the propylene polymer (A-1), the same propylene system was used except that 11 parts by weight of the propylene polymer (A-3) produced in Example 3 was used. A resin composition was prepared. Table 4 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 7]
In Example 5, instead of 11 parts by weight of the propylene polymer (A-1), propylene was similarly used except that 11 parts by weight of the propylene polymer (A′-1) produced in Comparative Example 1 was used. A system resin composition was prepared. Table 4 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 8]
In Example 5, in place of 11 parts by weight of the propylene polymer (A-1), propylene was similarly used except that 11 parts by weight of the propylene polymer (A′-6) produced in Comparative Example 1 was used. A system resin composition was prepared. Table 4 shows the physical properties of the resulting propylene-based resin composition.

  The propylene polymer according to the present invention provides a propylene polymer excellent in high melt tension, and a propylene resin composition including the propylene polymer and excellent in injection molding fluidity and high melt tension characteristics. Since it can be used, it can be used suitably for injection foam molded products.

DESCRIPTION OF SYMBOLS 1 Fixed type 2 Movable type 3 Cavity 4 Valve gate 5 Injection molding machine nozzle 6 Melt of foamable resin composition T ₀ Cavity clearance T ₁ Expanding length of cross section of cavity 3 after core back

Claims (4)

The following propylene polymer components (I) to (III) are included (the total amount of (I) to (III) is 100 parts by weight), and the following requirements (i) and (ii) are satisfied. Propylene polymer.
(I) In the molecular weight distribution curve measured by gel permeation chromatography (GPC), the content of propylene polymer component having a molecular weight of 1 million or more with respect to the total amount is 10 to 30 parts by weight. (II) Gel permeation chromatography in the molecular weight distribution curve measured by (GPC), the content of based on the total amount molecular weight of 10,000 or less of the propylene-based polymer component was measured by the 10 to 20 parts by weight (III) gel permeation chromatography (GPC) in the molecular weight distribution curve, the content of molecular weight of 10,000 greater than 1,000,000 is smaller than the propylene-based polymer component with respect to the total amount conforms to 50-80 parts by weight (i) ASTM D1238E, 230 ℃ , 2.16kg load The melt flow rate (MFR) measured at 0.5 to 6 g / 10 minutes,
(Ii) Isotactic pendant fraction (mmmm) is 95% or more Having two or more consecutive steps, including a step of producing a relatively high molecular weight propylene polymer component (H) and a step of producing a relatively low molecular weight propylene polymer component (L). The method for producing a propylene polymer according to claim 1, wherein the high molecular weight propylene polymer component (H) satisfies the following requirements (iii) and (iv).
(Iii) The content of the high molecular weight propylene polymer component (H) in the total amount of the propylene polymer is 10 to 40% by weight.
(Iv) Intrinsic viscosity [η] measured in 135 ° C. tetralin is 7 to 10 dl / g   A propylene-based resin composition comprising 1 to 30 parts by weight of the propylene-based polymer according to claim 1 and 100 parts by weight of a propylene-based resin-modified material.   The propylene-based resin-modified material is a propylene-based block copolymer (Bb) 40 to 99 parts by weight, a filler (C) 1 to 40 parts by weight, and an elastomer (D) 0 to 35 parts by weight (however, The sum of (B-b), (C), and (D) is 100 parts by weight.) The propylene-based resin composition according to claim 3.

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