JP2011132294A - Propylene-based resin composition and molding obtained from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a propylene-based resin composition having excellent molded appearance, balance between rigidity and impact resistance, and flowability in injection molding, and to provide an injection molding obtained from the resin composition and automobile parts comprising the injection molding. <P>SOLUTION: The propylene-based resin composition contains 40-99 pts.wt. of a propylene-based block copolymer (A), which is obtained by the steps of producing a propylene polymer component and producing a propylene-ethylene copolymer rubber component and which is produced by using a specific catalyst, 0-35 pts.wt. of an elastomer (B), and 1-40 pts.wt. of a filler (E), wherein the total of (A), (B), and (E) is 100 pts.wt. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a propylene-based block copolymer, a propylene-based resin composition containing the copolymer, and a molded product obtained therefrom. Specifically, the present invention relates to a propylene-based resin composition having an excellent balance between rigidity and impact resistance, further having good moldability, and extremely excellent appearance characteristics at the time of molding, and a molded product obtained therefrom.

  Propylene-based resins are used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automobile parts, and various additives depending on the required performance. It is blended. Especially in automotive parts applications, a composition in which an α-olefin copolymer rubber and an inorganic filler such as talc are blended with a propylene resin has an excellent balance between rigidity and impact resistance of the molded product. Have been used in large quantities.

  Automotive interior / exterior parts are often molded by injection molding from the viewpoint of productivity. However, when injection molding is performed using propylene-based resin compositions known so far, multiple periodic striped patterns called flow marks and tiger marks are generated in the direction intersecting the flow direction of the surface of the injection molded product. It is known to stand out. If the flow mark generated on the surface of the molded product is conspicuous, the appearance of the molded product will be damaged. Therefore, painting is performed as necessary to remove the flow mark. As a result, the manufacturing process of automobile parts is complicated. I have to be.

  Several flow mark generation mechanisms have been proposed, and one of them is considered to be related to the destabilization phenomenon of the flow front (melt front) in the mold during injection molding. (Non-Patent Document 1). With this concept, the melt front shape periodically becomes unstable during injection molding, and the mold transfer state of the molten resin periodically fluctuates and solidifies. ).

  Based on this concept, the melt elasticity of the propylene-based resin composition is increased, and in particular, assuming transfer to the mold, by increasing the melt elasticity in the low shear rate region, Attempts have been made to stabilize the flow front and improve the flow mark. For example, JP-A-9-87482 (Patent Document 1) discloses a propylene resin composition comprising a propylene block copolymer containing an ultrahigh molecular weight propylene-ethylene copolymer. In the above invention, an injection-molded product with few flow marks can be obtained, but an appearance defect called a weld line that occurs at the joining point of the molten resin flow may occur. The weld line is a phenomenon in which the traces of the molten resin flow merged to solidify and appear to be streak-like appearance defects. In the above invention, a large amount of ultrahigh molecular weight propylene-ethylene copolymer is contained in the propylene-based block copolymer. Is dispersed as an island structure of sea-island structure, it is presumed that the weld line has become conspicuous as a result of the difficulty of disappearing (relaxing) the merged traces of the molten resin flow. If the weld line is conspicuous, a pre-treatment step for removing the weld line is required at the time of painting, so that there are some restrictions in applying the above technique to automobile parts.

On the other hand, attempts to improve the flow mark by increasing the molecular weight distribution of the propylene polymer component and improving the flow mark are also being studied. In Japanese Patent Laid-Open No. 2000-204111 (Patent Document 2), a propylene polymer component is broadened by an olefin polymerization catalyst using a solid titanium catalyst component, an aluminum-alkyl compound and a nitrogen-containing aliphatic silicon compound as promoters. A propylene block having a molecular weight distribution is disclosed. Although the melt elasticity of the polypropylene resin composition is increased and the flow mark is improved to some extent by the above technology, the flow mark is improved to some extent, but the propylene polymer portion has not been sufficiently widened, so further improvement of the flow mark is necessary. there were. Furthermore, in the above technique, improvement in rigidity and impact resistance balance has been demanded.

  In addition, International Publication No. 98/47959 pamphlet has a wide molecular weight distribution propylene polymer part by polymerizing a low molecular weight propylene polymer after polymerizing an ultra high molecular weight propylene polymer in a multistage polymerization method. A polypropylene resin composition comprising a block copolymer is disclosed. In automotive interior / exterior parts, the propylene-based resin composition is required to have high fluidity during injection molding. However, in the above technology, when attempting to increase the fluidity of the propylene polymer portion, an ultrahigh molecular weight propylene polymer is produced. In some cases, it becomes difficult to uniformly disperse or dissolve in the low-molecular propylene polymer, resulting in problems such as a reduction in impact resistance and occurrence of irregularities on the surface of the molded product.

  As mentioned above, although the improvement example of the flow mark was mentioned, the further improvement of the propylene-type resin composition is calculated | required in consideration of the elimination of the appearance defect, the improvement of the mechanical property balance, the improvement of the injection molding fluidity, and the like.

JP-A-9-87482 JP 2000-204111 A International Publication No. 98/47959 Pamphlet

Journal of Japanese Society of Rheology Vol. 35, no. 5,293-299

  The present invention provides a propylene-based resin composition having an excellent balance of molding appearance and rigidity-impact resistance and excellent injection molding fluidity, an injection-molded body obtained from the propylene-based resin composition, and the injection molding It is an object of the present invention to provide automobile parts made of a body.

  As a result of intensive studies to solve the above problems, the present inventors have a propylene polymer component having a broad molecular weight distribution controlled to a specific range and a broad molecular weight distribution and narrow copolymer composition distribution controlled to a specific range. A propylene resin composition containing a propylene block copolymer having a propylene-ethylene copolymer rubber component has been developed. In the propylene-based block copolymer, by controlling the molecular weight distribution to a specific range, it is possible to increase the melt elasticity by the high molecular weight propylene polymer component, particularly the melt elasticity in the low shear rate region, It has been found that the flow mark can be remarkably improved at the time of injection molding of a propylene-based resin composition, together with the effect of high melt elasticity by the broad molecular weight distribution propylene-ethylene copolymer rubber component. Surprisingly, it has been found that the propylene-based block copolymer has a weld line that is hardly noticeable in the propylene-based resin composition according to the present invention by controlling the molecular weight distribution within a specific range.

  Further, the present inventors have found that the propylene block copolymer can achieve high rigidity. Here, although the mechanism for increasing the rigidity has not been fully clarified, since the propylene polymer component has high stereoregularity and a wide molecular weight distribution, the high molecular weight propylene polymer serves as a crystal nucleus, and the low molecular weight component forms a plate. It is presumed that crystals are formed or that the orientation of the high molecular weight propylene polymer is easily frozen during injection molding.

  Further, the propylene-ethylene copolymer rubber component of the propylene-based block copolymer has a wide molecular weight distribution, but it has been focused on controlling the composition distribution of the propylene-ethylene copolymer rubber component narrowly, and the rigidity / impact resistance The sex balance could be remarkably improved. Here, the polyethylene resin component by-produced during the production of the propylene-ethylene polymer rubber component can be reduced, and in addition to suppressing the decrease in the rigidity / impact resistance balance due to the polyethylene resin, the low molecular weight propylene-ethylene copolymer is reduced. It is presumed that the impact resistance was significantly improved because the impact of the polymer rubber component on the impact resistance was small.

  As described above, the propylene-based block copolymer is composed of a propylene polymer component having a wide molecular weight distribution in a specific range and a wide molecular weight distribution and a narrow copolymer composition distribution. Propylene-based resin composition mainly composed of propylene-based block copolymer has a high level of all requirements for good molding appearance, good rigidity / impact balance, and high fluidity during injection molding. Thus, the present invention has been completed.

That is, the propylene-based resin composition of the present invention is obtained by a production method including a step of producing a propylene polymer component and a step of producing a propylene-ethylene copolymer rubber component, and the following requirements [1] to [8] ] 40-99 parts by weight of the propylene-based block copolymer (A), 0-35 parts by weight of the elastomer (B), and 1-40 parts by weight of the filler (E) (however, (A), (B), And the sum of (E) is 100 parts by weight).
[1] According to ASTM D1238E, the melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 20 to 150 g / 10 min.
[2] Consists of 5 to 50% by weight of a part soluble in room temperature n-decane (Dsol) and 50 to 95% by weight of a part insoluble in room temperature n-decane (Dinsol) (however, the sum of Dsol and Dinsol) The amount is 100% by weight),
[3] A molecular weight distribution (Mw / Mn) which is a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of Dsol is 7.0 or more, 20 or less,
[4] The ethylene content of Dsol is 25 to 45 mol%,
[5] [η] of Dsol is 1.8 to 4.0 dl / g,
[6] The molecular weight distribution (Mw / Mn) of Dinsol is 7.0 or more and 20 or less, and the ratio of the Z average molecular weight (Mz) and the weight average molecular weight (Mw) is Mz / Mw of 6.0 or more, 20 Less than,
[7] The pentad fraction (mmmm) of Dinsol is 95% or more,
[8] In Dsol, the value of CSD defined by the following formula (i) is 1.0 to 2.0.

(In formula (i), [EE] is the mole fraction of ethylene chains in Dsol, [PP] is the mole fraction of propylene chains in Dsol, and [PE] is the mole fraction of propylene-ethylene chains. )
It is preferable that the propylene-based block copolymer (A) further satisfies the following requirement [9].
[9] In the GPC-IR measurement of Dsol, the ethylene content (C2 (H5)) (mol%) and 50% from the high molecular weight side of the eluted component at the high molecular weight side 5% in the GPC curve area fraction.
The difference (Δ (C2)) (the following formula (ii)) in the ethylene content (C2 (H50)) (mol%) of the elution component is 1.5 or less.

  Moreover, it is preferable that the said propylene-type block copolymer (A) performs the process which manufactures a propylene polymer component in a front | former stage, and performs the process of manufacturing a propylene-ethylene copolymer rubber component in a back | latter stage.

  Furthermore, the step of producing the propylene polymer component is preferably performed in two or more polymerization tanks, and the intrinsic viscosity [η] of the propylene polymer produced in each tank is preferably 4 dl / g or less. Moreover, it is preferable that the process which manufactures the said propylene-ethylene copolymer rubber component is performed by the polymerization tank of 1 tank of propylene and ethylene.

The propylene-based block copolymer (A) includes titanium, magnesium, and halogen, a cyclic ester compound (a) specified by the following formula (1), and a cyclic ester compound specified by the following formula (2) ( b) 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 electron donation as required And (III) in the presence of an olefin polymerization catalyst.

  In Formula (1), n is an integer of 5-10.

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 . A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ³ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.

R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.

A plurality of Rs 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. Group, which may be bonded to each other to form a ring, but at least 1
One R is not a hydrogen atom.

A double bond may be included in the ring skeleton formed by bonding R to each other, and when the ring skeleton includes two or more C ^a to which COOR ¹ is bonded, The number of carbon atoms constituting the skeleton is 5-10.

  In Formula (2), n is an integer of 5-10.

R ⁴ and R ⁵ are each independently COOR ¹ or a hydrogen atom, and at least one of R ⁴ and R ⁵ is COOR ¹ . R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ⁵ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.

  Here, in the formula (1) and / or (2), it is preferable that all the bonds between carbon atoms in the cyclic skeleton are single bonds. In the above formula (1) and / or (2), it is also preferable that n = 6.

  Furthermore, it is preferable that the said cyclic ester compound (a) is following formula (1a), and the said cyclic ester compound (b) is following formula (2a).

  In Formula (1a), n is an integer of 5-10.

Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds.

R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.

  A plurality of Rs are each independently an atom selected from a hydrogen atom or 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 which may be bonded to each other to form a ring, but at least one R is not a hydrogen atom.

A double bond may be included in the ring skeleton formed by bonding R to each other, and when the ring skeleton includes two or more C ^a to which COOR ¹ is bonded, The number of carbon atoms constituting the skeleton is 5-10.

  In Formula (2a), n is an integer of 5-10.

R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds.

  Here, in the formulas (1a) and (2a), it is preferable that all the bonds between carbon atoms in the cyclic skeleton are single bonds. In the above formulas (1a) and (2a), it is also preferable that n = 6.

  The present invention is characterized by a molded body comprising the propylene-based block copolymer (A). Moreover, it is preferable that the said molded object is a motor vehicle part obtained by injection molding.

  The propylene-based resin composition according to the present invention has good mechanical properties such as rigidity and impact resistance, but has few molding appearance defects such as flow marks and weld lines, and good fluidity in the mold during injection molding. Therefore, it can be suitably used for thin large injection molded products such as automobile interior and exterior parts.

It is the figure which showed the calculation method of PDI-P. It is the schematic of the injection molded product for flow mark evaluation. It is the schematic of the injection molded product for weld evaluation.

  Hereinafter, the propylene block copolymer (A), the elastomer (B), and the filler (E) constituting the propylene resin composition of the present invention will be specifically described.

[Propylene-based block copolymer (A)]
The propylene-based block copolymer (A) is obtained by a step of producing a propylene polymer component and a step of producing a propylene-ethylene copolymer rubber component, and simultaneously satisfies the following requirements [1] to [8]. And preferably satisfies the requirement [9]. The propylene polymer is crystalline, and is a copolymer of propylene and a small amount of another α-olefin, or a propylene homopolymer.
[1] According to ASTM D1238E, the melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 20 to 150 g / 10 min.
[2] It is composed of 5 to 50% by weight of a part soluble in room temperature n-decane (Dsol) and 50 to 95% by weight of a part insoluble in room temperature n-decane (Dinsol) (however, the total amount of Dsol and Dinsol) Is 100% by weight),
[3] The molecular weight distribution (Mw / Mn) of Dsol is 7.0 or more and 30 or less,
[4] The ethylene content of Dsol is 25 to 45 mol%,
[5] The intrinsic viscosity [η] of Dsol is 1.8 to 4.0 dl / g,
[6] Dinsol molecular weight distribution (Mw / Mn) is 7.0 or more and 30 or less, and Mz / Mw is 6.0 or more and 20 or less,
[7] The pentad fraction (mmmm) of Dinsol is 95% or more,
[8] In Dsol, the value of CSD defined by the following formula (i) is 1.0 to 2.0.

(In formula (i), [EE] is the mole fraction of ethylene chains in Dsol, [PP] is the mole fraction of propylene chains in Dsol, and [PE] is the mole fraction of propylene-ethylene chains. )
[9] In the GPC-IR measurement of Dsol, the ethylene content (C2 (H5)) (mol%) of the eluted component at 5% of the high molecular weight side and the eluted component at 50% from the high molecular weight side in the area fraction of the GPC curve The difference (Δ (C2)) in the ethylene content (C2 (H50)) (mol%) of the following formula (ii) is 1.5 or less.

  Hereinafter, each requirement that the propylene-based block copolymer (A) satisfies will be described in detail.

Requirement [1]
The melt flow rate (MFR) of the propylene-based block copolymer (A) measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238E is 20 to 150 g / 10 minutes, preferably 25 to 120 g. / 10 minutes, more preferably 30 to 100 g / 10 minutes.

  When MFR exceeds the above upper limit, the impact resistance of the propylene-based resin composition is lowered, and may not be suitable for structural parts such as automobile parts. Moreover, when MFR is less than the said lower limit, the fluidity | liquidity of a propylene-type resin composition falls and it may not be suitable for the injection moldability of large parts, such as a motor vehicle part.

Requirement [2]
Of the propylene-based block copolymer (A), a part soluble in room temperature n-decane (Dsol) and a part insoluble in room temperature n-decane (Dinsol) are 5 to 50% by weight of Dsol and 50 in Dinsol. ~ 95 wt% (however, the total amount of Dsol and Dinsol is 100 wt%), preferably 7-40 wt% Dsol, 60-93 wt% Dinsol, more preferably 10-35 wt% Dsol %, Dinsol is 65 to 90% by weight.

  Here, Dsol is mainly composed of a propylene-ethylene copolymer rubber component, and Dinsol is mainly composed of a propylene polymer component and a polyethylene resin as a by-product.

  When Dsol is less than the above lower limit value and Dinsol is greater than the above upper limit value, the impact resistance of the propylene-based resin composition is deteriorated, so that application to various structural parts becomes difficult. If Dsol is greater than the above upper limit value and Dinsol is less than the lower limit value, the rigidity of the propylene resin composition is lowered, so that it is difficult to apply to various structural parts.

Requirement [3]
The propylene block copolymer (A) has a molecular weight distribution (Mw / Mn), which is a ratio of the weight average molecular weight (Mw) of Dsol and the number average molecular weight (Mn), of 7.0 or more, preferably 20 or less, preferably , Mw / Mn is 7.0 or more and 15 or less, more preferably 7.0 or more and 10 or less.

When Mw / Mn is in the above range, an injection molded product with few flow marks can be obtained from the propylene-based resin composition. This is because, as a result of Mw / Mn being within the above range, high shearing elasticity of the propylene resin composition by the high molecular weight propylene-ethylene copolymer rubber component, particularly low shear corresponding to transfer of the molten resin to the mold It is presumed that the flow mark can be greatly improved as a result of achieving high melt elasticity in the velocity region and stabilizing the flow front in the injection mold. Further, when Mw / Mn is in the above range, it is presumed that the impact resistance of the propylene-based resin composition can be maintained because there is little influence of the impact resistance reduction by the low molecular weight propylene-ethylene copolymer rubber component. Yes.

  When Mw / Mn is larger than the above upper limit, low molecular weight propylene-ethylene copolymer rubber increases in the propylene block copolymer, and the impact resistance of the propylene resin composition may be lowered. Further, if Mw / Mn is smaller than the above lower limit value, the melt elasticity of the propylene-based block copolymer is lowered, so that when a propylene-based resin composition is injection-molded, a flow mark may be easily generated. .

  In the present invention, the molecular weight distribution (Mw / Mn) is a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by GPC. Ed., Published in 1978) P117.

Requirement [4]
The propylene block copolymer (A) has an ethylene content of Dsol of 25 to 45 mol%, preferably 27 to 42 mol%, more preferably 30 to 40 mol%.

  When the ethylene content of Dsol is less than the above lower limit value, the propylene-ethylene copolymer rubber component in the propylene-based block copolymer tends to be compatible with the propylene polymer component, and the resulting propylene-based polymer The impact resistance of the resin composition may be reduced, making it difficult to apply to various structural parts. The reason for the above phenomenon is not clear, but as a result of the dispersed particle size of the propylene-ethylene copolymer rubber existing as a dispersed phase in the propylene-based block copolymer becoming too fine, the propylene-ethylene copolymer rubber is stressed. Since it does not act as a concentrated point, it is presumed that the impact resistance has decreased. When the ethylene content of Dsol is higher than the above upper limit, the affinity between the propylene-ethylene copolymer rubber component and the propylene polymer component in the propylene block copolymer decreases, and the resulting propylene resin composition The impact resistance and elongation of the object may be reduced.

Requirement [5]
The propylene block copolymer (A) has an intrinsic viscosity [η] of Dsol of 1.8 to 4.0 dl / g, preferably 2.0 to 3.5 dl / g, more preferably 2.2 to 3 0.0 dl / g.

  When the intrinsic viscosity [η] of Dsol is less than the above lower limit, the impact resistance of the propylene-based block copolymer is lowered, and the impact resistance of the obtained propylene-based resin composition may be lowered. When the [sol] of Dsol exceeds the above upper limit value, it is necessary to increase the MFR of the propylene polymer component in order to improve the fluidity at the time of injection molding of the propylene-based resin composition. At this time, the impact resistance of the propylene-based block copolymer may decrease. At the same time, fish eyes may be easily generated in the propylene-based block copolymer, and at this time, appearance defects such as bumps may be conspicuous on the surface of the molded product obtained from the propylene-based resin composition.

Requirement [6]
The propylene block copolymer (A) has a Dinsol molecular weight distribution (Mw / Mn) of 7.0 or more and 20 or less, and a ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw). / Mw is 6.0 or more and 20 or less, preferably Mw / Mw is 8.0 or more and 20 or less, and Mz / Mw is 7.0 or more and 20 or less, more preferably Mw / Mn is 9.0 or more, 15 or less, and Mz / Mw is 8.0 or more and 20 or less.

  When Mw / Mn and Mz / Mw are in the above ranges, an injection molded product with very few flow marks can be obtained from the propylene-based resin composition. This is because, as a result of Mw / Mn and Mz / Mw being in the above ranges, the high molecular weight propylene polymer component makes the propylene resin composition highly melt elastic, particularly high melt elastic in the low shear rate region. As a result, the flow mark in the injection mold is stabilized, and as a result, the flow mark is presumably improved.

  When Mw / Mn and Mz / Mw are smaller than the lower limit, the melt elasticity of the propylene-based polymer component in the propylene-based block copolymer is lowered, and an injection molded product obtained from the propylene-based resin composition is obtained. Since the flow mark becomes conspicuous and the fluidity at the time of injection molding decreases, it may not be suitable for large injection molded products such as automobile parts. Moreover, since the rigidity of this propylene-type resin composition will fall when Mw / Mn is smaller than the said lower limit, it may be unpreferable. Furthermore, when Mw / Mn is larger than the above upper limit, the low molecular weight propylene polymer component increases in the propylene block copolymer, and the impact resistance of the propylene resin composition may be lowered.

  Here, in the present invention, the molecular weight distribution (Mw / Mn) is the ratio of the weight average molecular weight (Mw) measured by GPC to the number average molecular weight (Mn), and Mz / Mw is the Z average molecular weight measured by GPC. The ratio between (Mz) and the weight average molecular weight (Mw). These definitions were made according to the foundation of polymer chemistry (edited by the Society of Polymer Science, published in 1978) P117.

  In addition, the melt elasticity index of the propylene polymer can be qualitatively evaluated by melt viscoelasticity measurement. As an example, it can be qualitatively evaluated by a polydispersity index (PDI-P) represented by the following formula (iii).

  When PDI-P is large, the storage elastic modulus (melt elasticity) tends to be large even in a low angular frequency region (low shear rate). Here, if the melt elasticity in the low shear rate region is large, the shape of the melt front at the time of injection molding tends to be stable, so it is presumed that the flow mark becomes good.

Requirement [7]
The propylene block copolymer (A) has a Dinsol pendant fraction (mmmm) of 95% or more, preferably 96% or more, and more preferably 97% or more.

  If the Dinsol mmmm is lower than the above%, the rigidity of the propylene-based resin composition is lowered, which is not preferable.

Requirement [8]
In the Dsol of the propylene-based block copolymer (A), the CSD value defined by the following formula (i) is 1.0 to 2.0, preferably 1.0 to 1.8, more preferably 1. .0
~ 1.6.

(In formula (i), [EE] is the mole fraction of ethylene chains in Dsol, [PP] is the mole fraction of propylene chains in Dsol, and [PE] is the mole fraction of propylene-ethylene chains. )
In the formula (i), CSD can be used as an index representing the propylene / ethylene copolymerizability of the propylene-ethylene copolymer.

  Dsol is mainly composed of a propylene-ethylene copolymer. In Dsol, when the value of CSD defined by the following formula (i) is larger than the upper limit, ethylene chains and propylene chains increase in Dsol, Propylene-ethylene chains tend to decrease. In this case, since the crystalline ethylene chain and propylene chain increase, the propylene block copolymer tends to become brittle, and the impact resistance of the propylene block copolymer decreases. Therefore, the impact resistance of the obtained propylene-based resin composition may be deteriorated.

Requirement [9]
In the GPC-IR measurement of Dsol of the propylene-based block copolymer (A), the elution component ethylene content (C2 (H5)) (mol%) at 5% on the high molecular weight side in the area fraction of the GPC curve The difference (Δ (C2)) (formula (ii) below) in the ethylene content (C2 (H50)) (mol%) of the eluted component at 50% from the high molecular weight side is preferably 1.5 mol% or less, more preferably 1.0 mol% or less.

  When Δ (C2) is larger than 1.5 mol%, the ethylene amount in each molecular weight in Dsol varies, and the ethylene composition distribution in Dsol may be broadened. At this time, from the viewpoint of highly controlling the physical property balance such as rigidity / impact resistance of the propylene-based resin composition, it may not be preferable if the ethylene composition distribution in Dsol becomes wide.

  The propylene-based block copolymer (A), characterized in that the above requirements [1] to [8] are satisfied at the same time, and more preferably, the requirement [9] is satisfied, is produced using the following olefin polymerization catalyst. It is preferable.

[Olefin polymerization catalyst]
The propylene-based block copolymer (A) includes 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; The polymer is preferably obtained by polymerization in the presence of an olefin polymerization catalyst containing an electron donor (III) as necessary. Hereinafter, each component relating to the olefin polymerization catalyst will be described in detail.

[Solid titanium catalyst component (I)]
The solid titanium catalyst component (I) includes titanium, magnesium, and halogen and a cyclic ester compound (a) specified by the following formula (1) and a cyclic ester compound (b) specified by the following formula (2). Including.

<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).

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 s} are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably 4 to 6 carbon atoms. It is a hydrogen 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, Tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like are mentioned. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are propylene type having wide molecular weight distribution. The block copolymer is particularly preferable because it 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. Or 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. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso group. Aliphatic hydrocarbon groups such as -propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, vinyl group, phenyl group, octyl group , An alicyclic hydrocarbon group, and an aromatic hydrocarbon group. 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 Rs may be a carbonyl structure-containing group such as a carboxylic acid ester group, an acyl group, and a ketone group, and these substituents include one or more hydrocarbon groups having 1 to 20 carbon atoms. It is preferable to include.

Such a cyclic ester compound (a) is described in International Publication No. 2006/077945 pamphlet. In particular,
Diethyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3-methylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methylcyclohexane-1,2-dicarboxylate,
Dihexyl 3-methylcyclohexane-1,2-dicarboxylate,
3-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3-methylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,3-dicarboxylate diethyl,
4-methylcyclohexane-1,3-dicarboxylate diisobutyl,
4-methylcyclohexane-1,2-dicarboxylate diethyl,
Di-n-propyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisobutyl,
4-methylcyclohexane-1,2-dicarboxylic acid dihexyl,
4-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 4-methylcyclohexane-1,2-dicarboxylate,
Didecyl 4-methylcyclohexane-1,2-dicarboxylate 4-methylcyclohexane-1,2-dicarboxylate,
Diethyl 5-methylcyclohexane-1,3-dicarboxylate,
Diisobutyl 5-methylcyclohexane-1,3-dicarboxylate,

Diethyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
3,4-dimethylcyclohexane-1,2-dicarboxylic acid dihexyl,
Diheptyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Dioctyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Didecyl 3,4-dimethylcyclohexane-1,2-dicarboxylate 3,2-dimethylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
3,6-dimethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
3,6-dimethylcyclohexane-1,2-dicarboxylic acid dihexyl;
Diheptyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Dioctyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Didecyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
3,6-diphenylcyclohexane-1,2-dicarboxylic acid dihexyl;
Dioctyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Didecyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

Diethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl-6-ethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-ethylcyclohexane-1,2-dicarboxylic acid dihexyl;
3-methyl-6-ethylcyclohexane-1,2-dicarboxylic acid diheptyl,
Dioctyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Dimethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl-6-ethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-ethylcyclohexane-1,2-dicarboxylic acid dihexyl;
3-methyl-6-ethylcyclohexane-1,2-dicarboxylic acid diheptyl,
Dioctyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Dimethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylic acid di-n-propyl, 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylic acid diisopropyl, 3-methyl-6-n-propyl Cyclohexane-1,2-dicarboxylate di-n-butyl,
Diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-n-propylcyclohexane-1,2-dicarboxylate dihexyl;
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diethyl 3-hexylcyclohexane-1,2-dicarboxylate,
3-hexylcyclohexane-1,2-dicarboxylate diisobutyl,
Diethyl 3,6-dihexylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-pentylcyclohexane-1,2-dicarboxylate diisobutyl,

Diethyl 3-methylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3-methylcyclopentane-1,2-dicarboxylate,
3-methylcyclopentane-1,2-dicarboxylic acid diheptyl;
Didecyl 3-methylcyclopentane-1,2-dicarboxylate,
4-methylcyclopentane-1,3-dicarboxylate diethyl,
4-methylcyclopentane-1,3-dicarboxylate diisobutyl,
4-methylcyclopentane-1,2-dicarboxylate diethyl,
4-methylcyclopentane-1,2-dicarboxylate diisobutyl,
4-methylcyclopentane-1,2-dicarboxylic acid diheptyl,
Didecyl 4-methylcyclopentane-1,2-dicarboxylate,
Diethyl 5-methylcyclopentane-1,3-dicarboxylate,
Diisobutyl 5-methylcyclopentane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
3,4-dimethylcyclopentane-1,2-dicarboxylic acid diheptyl,
Didecyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
Diethyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diheptyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Didecyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diethyl 3-hexylcyclopentane-1,2-dicarboxylate,
Diethyl 3,5-dihexylcyclopentane-1,2-dicarboxylate,
3-hexyl-5-pentylcyclopentane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
3-methyl-5-n-propylcyclopentane-1,2-dicarboxylic acid di-n-propyl, 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylic acid diisopropyl, 3-methyl-5-n -Di-n-butyl propylcyclopentane-1,2-dicarboxylate,
3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate diisobutyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate dihexyl;
Dimethyl of 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Didecyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

Diethyl 3-methylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methylcycloheptane-1,2-dicarboxylate,
3-methylcycloheptane-1,2-dicarboxylic acid diheptyl,
Didecyl 3-methylcycloheptane-1,2-dicarboxylate,
4-methylcycloheptane-1,3-dicarboxylate diethyl,
4-methylcycloheptane-1,3-dicarboxylate diisobutyl,
4-methylcycloheptane-1,2-dicarboxylate diethyl,
4-methylcycloheptane-1,2-dicarboxylate diisobutyl,
4-methylcycloheptane-1,2-dicarboxylic acid diheptyl,
Didecyl 4-methylcycloheptane-1,2-dicarboxylate,
Diethyl 5-methylcycloheptane-1,3-dicarboxylate,
Diisobutyl 5-methylcycloheptane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diheptyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Didecyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diethyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diheptyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Didecyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diethyl 3-hexylcycloheptane-1,2-dicarboxylate,
Diethyl 3,7-dihexylcycloheptane-1,2-dicarboxylate,
3-hexyl-7-pentylcycloheptane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
3-methyl-7-n-propylcycloheptane-1,2-dicarboxylic acid di-n-propyl, 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylic acid diisopropyl, 3-methyl-7-n -Di-n-butyl propylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
3-methyl-7-n-propylcycloheptane-1,2-dicarboxylic acid dihexyl;
Dioctyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Didecyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

Diethyl 3-methylcyclooctane-1,2-dicarboxylate,
Diethyl 3-methylcyclodecane-1,2-dicarboxylate,
Diisobutyl 3-vinylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-dicyclohexylcyclohexane-1,2-dicarboxylate,
Norbornane-2,3-dicarboxylate diisobutyl,
Tetracyclododecane-2,3-dicarboxylate diisobutyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Di-n-propyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diisobutyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,6-dimethyl-4-cyclohexene-1,2-dicarboxylic acid dihexyl;
Diheptyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Dioctyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Di-2-ethylhexyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate, didecyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diethyl 3,6-dihexyl-4-cyclohexene-1,2-dicarboxylate,
3-hexyl-6-pentyl-4-cyclohexene-1,2-dicarboxylate diisobutyl,
Etc.

In addition, the following compounds:
3,6-dimethylcyclohexane-1,2-diacetate,
3,6-dimethylcyclohexane-1,2-dibutanate,
3-methyl-6-propylcyclohexane-1,2-diol acetate,
3-methyl-6-propylcyclohexane-1,2-dibutanate,
3,6-dimethylcyclohexane-1,2-dibenzoate,
3,6-dimethylcyclohexane-1,2-ditoluate,
3-methyl-6-propylcyclohexane-1,2-dibenzoate,
3-methyl-6-propylcyclohexane-1,2-ditoluate,
Etc. can also be mentioned as a preferable example.

In the compound having the diester structure as described above, there are isomers such as cis and trans derived from a plurality of COOR ¹ groups in the formula (1), and any structure is effective to meet the object of the present invention. However, it is preferable that the trans isomer content is higher. The higher the content of the trans isomer, the higher the activity and the stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution.

  As the cyclic ester compound (a), compounds represented by the following formulas (1-1) to (1-6) are preferable.

[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. ]
As the cyclic ester compound (a), a compound represented by the following formula (1a) is particularly preferable.

[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. ]
Specifically, as the compound represented by the above formula (1a),
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-ethylcyclohexane-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-dicarboxylate di-n-hexyl, 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate di-n-octyl, 3,6-diethylcyclohexane -1,2-dicarboxylate diisobutyl,
Di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate, di-n-octyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate, 3,5- Diisobutyl diethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3,5-diethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3,5-diethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate, diisobutyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Etc.

Among the above compounds,
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-ethylcyclohexane-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-dicarboxylate di-n-hexyl, 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate di-n-octyl, 3,6-diethylcyclohexane -1,2-dicarboxylate diisobutyl,
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. Higher rates are particularly preferred because they tend to have higher activity and stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution. 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).

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, a C—C ^b bond in the cyclic skeleton,
The C ^a -C ^b bond and the C—C bond (when n is 6 to 10) when R ⁵ is COOR ¹ may be replaced with a double bond.

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

A plurality of R ^{1 s} are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably 4 to 6 carbon atoms. It is a hydrogen 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, Tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like are mentioned. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are propylene type having wide molecular weight distribution. The block copolymer is particularly preferable because it can be produced.

As such a cyclic ester compound (b),
Cyclohexane-1,2-dicarboxylate diethyl,
Di-n-propyl cyclohexane-1,2-dicarboxylate,
Diisopropylcyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-n-butyl,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexylcyclohexane-1,2-dicarboxylate didecyl,
Cyclohexane-1,3-dicarboxylate diethyl,
Cyclohexane-1,3-dicarboxylate diisobutyl,
Diethyl cyclopentane-1,2-dicarboxylate,
Diisopropyl cyclopentane-1,2-dicarboxylate,
Diisobutyl cyclopentane-1,2-dicarboxylate,
Cycloheptane-1,2-dicarboxylate diheptyl,
Didecyl cyclopentane-1,2-dicarboxylate,
Diethyl cyclopentane-1,3-dicarboxylate,
Cyclopentane-1,3-dicarboxylate diisobutyl,
Diethyl cycloheptane-1,2-dicarboxylate,
Diisopropyl cycloheptane-1,2-dicarboxylate,
Diisobutyl cycloheptane-1,2-dicarboxylate,
Diheptyl cycloheptane-1,2-dicarboxylate,
Didecyl cycloheptane-1,2-dicarboxylate,
Diethyl cycloheptane-1,3-dicarboxylate,
Diisobutyl cycloheptane-1,3-dicarboxylate,
Diethyl cyclooctane-1,2-dicarboxylate,
Diethyl cyclodecane-1,2-dicarboxylate,
4-cyclohexene-1,2-dicarboxylate diethyl,
Di-n-propyl 4-cyclohexene-1,2-dicarboxylate,
Diisopropyl 4-cyclohexene-1,2-dicarboxylate,
Di-n-butyl 4-cyclohexene-1,2-dicarboxylate,
Diisobutyl 4-cyclohexene-1,2-dicarboxylate,
4-cyclohexene-1,2-dicarboxylic acid dihexyl;
4-cyclohexene-1,2-dicarboxylate diheptyl,
Dioctyl 4-cyclohexene-1,2-dicarboxylate,
Didecyl 4-cyclohexene-1,2-dicarboxylate,
4-cyclohexene-1,3-dicarboxylate diethyl,
Diisobutyl 4-cyclohexene-1,3-dicarboxylate,
Diethyl 3-cyclopentene-1,2-dicarboxylate,
Diisopropyl 3-cyclopentene-1,2-dicarboxylate,
Diisobutyl 3-cyclopentene-1,2-dicarboxylate,
Diheptyl 3-cyclopentene-1,2-dicarboxylate,
Didecyl 3-cyclopentene-1,2-dicarboxylate,
Diethyl 3-cyclopentene-1,3-dicarboxylate,
Diisobutyl 3-cyclopentene-1,3-dicarboxylate,
4-cycloheptene-1,2-dicarboxylate diethyl,
4-cycloheptene-1,2-dicarboxylate diisopropyl,
4-cycloheptene-1,2-dicarboxylate diisobutyl,
4-cycloheptene-1,2-dicarboxylic acid diheptyl,
Didecyl 4-cycloheptene-1,2-dicarboxylate,
4-cycloheptene-1,3-dicarboxylate diethyl,
Diisobutyl 4-cycloheptene-1,3-dicarboxylate,
Diethyl 5-cyclooctene-1,2-dicarboxylate,
Examples include diethyl 6-cyclodecene-1,2-dicarboxylate.

In addition, the following compounds:
Cyclohexane-1,2-diacetate,
Cyclohexane-1,2-dibutanate,
Cyclohexane-1,2-dibenzoate,
Cyclohexane-1,2-ditoluate,
Etc. can also be mentioned as preferable examples.

  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, activity, stereospecificity and the like 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).

[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. ]
Specifically, as the compound represented by the above formula (2a),
Cyclohexane-1,2-dicarboxylate di-n-butyl,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl,
Diisobutyl cyclopentane-1,2-dicarboxylate,
Diheptyl cyclopentane-1,2-dicarboxylate,
Diisobutyl cycloheptane-1,2-dicarboxylate,
And cycloheptane-1,2-dicarboxylic acid diheptyl.

Among the above compounds,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl,
Is more preferable. 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, particularly preferably 40 mol% or more, and particularly preferably 50 mol%. A preferred upper limit is 99 mol%, preferably 90 mol%. More preferably, it is 85 mol%, Most preferably, it is 80 mol%.

  The solid titanium catalyst component (I) of the present invention has a low content of the cyclic ester compound (a) of the solid titanium catalyst component (I) under conditions of a wide range of combined molar ratios of the cyclic ester compound (a). However, an olefin polymer having a very 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 activity and stereoregularity hardly affects the effect of each other compound (the structure is When different compounds are used, there are many examples in which the activity, stereoregularity, etc. change drastically, and the effect of one compound becomes 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 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 solid 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 olefin polymerization is performed using the solid titanium catalyst component (I), olefin polymers having various molecular weights can be produced at the same time, that is, a propylene block copolymer 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 it combining the catalyst component (c) and catalyst component (d) which are mentioned later.

<Magnesium compound>
Specifically, as the magnesium compound used for the preparation of the solid titanium catalyst component (I) used in the present invention,
Magnesium halides such as magnesium chloride and magnesium bromide;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy magnesium chloride;
Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, 2-ethylhexoxy magnesium;
Aryloxymagnesium such as phenoxymagnesium;
Known magnesium compounds such as magnesium carboxylates such as magnesium stearate 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 as a halogenating agent to form magnesium halide.

<Titanium compound>
Examples of titanium compounds include general formulas;
Ti (OR) _g X _4-g
(R is a hydrocarbon group, X is a halogen atom, and g is 0 ≦ g ≦ 4.)
The tetravalent titanium compound shown by these can be mentioned. More specifically,
Titanium tetrahalides such as TiCl ₄ and TiBr ₄ ;
_{Ti (OCH 3) Cl 3,} Ti (OC 2 H 5) Cl 3, Ti (O-n-C 4 H 9) Cl 3, Ti (OC 2 H 5) Br 3, Ti (O-isoC 4 H 9 ) Trihalogenated alkoxytitanium such as Br ₃ ;
Dihalogenated alkoxytitanium such as Ti (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;
Examples thereof include tetraalkoxytitanium such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , and Ti (O-2-ethylhexyl) ₄ .

  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 preparation of the solid titanium catalyst component (I) of the present invention, the cyclic ester compounds (a) and (
A known method can be used without limitation, except that b) is included in the catalyst component. 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, as an alcohol having the above-mentioned solubilizing ability of magnesium compound,
Aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol;
Cycloaliphatic alcohols such as cyclohexanol and methylcyclohexanol;
Aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol;
Examples thereof include aliphatic alcohols having an alkoxy group such as n-butyl cellosolve.

  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. .

<Aromatic carboxylic acid ester and / or compound having two or more ether bonds via a plurality of carbon atoms>
The solid titanium catalyst component (I) of the present invention further includes an aromatic carboxylic acid ester and / or a compound having two or more ether bonds via a plurality of carbon atoms (hereinafter also referred to as “catalyst component (d)”). .) May 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 these 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).

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 a carbon atom. It is a hydrocarbon group of number 1-6.

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 -An ethylhexyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, Preferably they are an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group.

Specific examples of R ^{31 to} R ³⁶ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group, with a hydrogen atom and a methyl group being preferred.

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.

As specific compounds having two or more ether bonds as described above,
2-isopropyl-1,3-dimethoxypropane,
2-s-butyl-1,3-dimethoxypropane,
Monosubstituted dialkoxypropanes such as 2-cumyl-1,3-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-diethoxypropane,
2,2-diisobutyl-1,3-dibutoxypropane,
2,2-di-s-butyl-1,3-dimethoxypropane,
2,2-dineopentyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2-substituted dialkoxypropanes such as 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-1,5-dimethoxypentane,
Dialkoxyalkanes such as 2,4-diisoamyl-1,5-dimethoxypentane,
2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,
Trialkoxyalkanes such as 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,
Examples thereof include dialkoxycycloalkanes such as 2-isobutyl-2-ethoxymethyl-1,3-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 preferred.

  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 atom / number of moles of titanium atom) is 2 to 100, preferably 4 to 90. Desirable,
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 0.01-100, preferably 0.2-10,
The catalyst component (c) should have a catalyst component (c) / titanium atom (molar ratio) of 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). Preferably it is 20 weight% or less with respect to 100 weight%, More preferably, it is 10 weight% or less.

  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, such as 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 0 <n <4.)
Specific examples of the organosilicon compound represented by the general formula (4) as described above 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 preferably used.

  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), R ^a is a hydrocarbon group having 1 to 6 carbon atoms, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, particularly preferably. Examples thereof include saturated aliphatic hydrocarbon groups having 2 to 6 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, 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. Can be mentioned. 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.

In the formula (5), R ^c 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. 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.

As a specific example of the compound represented by the above formula (5),
Dimethylaminotriethoxysilane,
Diethylaminotriethoxysilane,
Dimethylaminotrimethoxysilane,
Diethylaminotrimethoxysilane,
Diethylaminotri-n-propoxysilane,
Di-n-propylaminotriethoxysilane,
Methyl-n-propylaminotriethoxysilane,
t-butylaminotriethoxysilane,
Ethyl-n-propylaminotriethoxysilane,
Ethyl-iso-propylaminotriethoxysilane,
Mention may be made of methylethylaminotriethoxysilane.

  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). Specifically as a compound represented by the said Formula (6),
(Perhydroquinolino) triethoxysilane,
(Perhydroisoquinolino) triethoxysilane,
(1,2,3,4-tetrahydroquinolino) triethoxysilane,
(1,2,3,4-tetrahydroisoquinolino) triethoxysilane,
Examples include octamethyleneiminotriethoxysilane.

  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.

[Producing method of propylene-based block copolymer (A)]
The production method of the propylene-based block copolymer (A) according to the present invention is not limited as long as the requirements [1] to [8] and preferably the requirement [9] are satisfied.

  In the method for producing a propylene-based block copolymer of the present invention, the main polymerization is carried out in the presence of a prepolymerization catalyst obtained by prepolymerization of an olefin in the presence of the above-mentioned olefin polymerization catalyst. It is also possible. This prepolymerization is performed by prepolymerizing 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, particularly preferably 0, in terms of titanium atom per liter of the liquid medium. Desirably, the range is from 1 to 20 mmol.

  The amount of the organometallic compound catalyst component (II) in the prepolymerization is such an amount that usually 0.1 to 1000 g, preferably 0.3 to 500 g of polymer is formed 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). It is desirable.

  In the prepolymerization, the electron donor (III) or the like can be used as necessary. In this case, these components are usually 0.1 per mol of titanium atom in the solid titanium catalyst component (I). It is used in an amount of ˜50 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, specifically as the inert hydrocarbon medium used,
Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene;
Cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cycloheptane, methylcycloheptane, cyclooctane;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Halogenated hydrocarbons such as ethylene chloride and chlorobenzene;
Alternatively, a mixture thereof can be used.

  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, the prepolymerization can be carried out using the olefin itself as a solvent, or the prepolymerization can be carried out 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 (polymerization) performed after passing through the pre-polymerization or without going through the pre-polymerization will be described.

  In the present invention, the main polymerization is divided into a process for producing a propylene polymer component and a process for producing a propylene-ethylene copolymer rubber component.

  In the present invention, 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. A preferred process for producing the propylene polymer component is liquid phase polymerization such as bulk polymerization or suspension polymerization, or gas phase polymerization. Further, a preferred process for producing the propylene-ethylene copolymer rubber component is a liquid phase polymerization or gas phase polymerization method such as bulk polymerization or suspension polymerization, and more preferably a gas phase polymerization method.

  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 in the method for producing a propylene block copolymer of the present invention, the solid titanium catalyst component (I) is usually about 0.0001 to 0.5 in terms of titanium atoms per liter of polymerization volume. Used in an amount of millimolar, preferably about 0.005 to 0.1 millimolar. The organometallic compound catalyst component (II) is usually used in an amount of 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. Used. When the electron donor (III) is used, it is 0.001 to 50 mol, preferably 0.01 to 30 mol, particularly preferably, relative to 1 mol of the organometallic compound catalyst component (II). Is used in an amount of 0.05 to 20 mol.

  If the main polymerization is carried out in the presence of hydrogen, the molecular weight of the resulting polymer can be adjusted (lowered), and a polymer having a high melt flow rate can be obtained. Since the amount of hydrogen necessary for adjusting the molecular weight varies depending on the type of production process used, the pressure, and the temperature, the range cannot be determined unconditionally. Therefore, in the process of producing the propylene polymer component, it is desirable to determine the amount of hydrogen in consideration of pressure and temperature so that the target MFR is obtained in the range of 0.01 to 1000 g / 10 minutes. Also, in the process of producing a propylene-ethylene copolymer rubber component, the amount of hydrogen can be determined in consideration of pressure and temperature so that the intrinsic viscosity [η] of Dsol is obtained in the range of 1 to 10 dl / g. desirable.

In the main polymerization in the present invention, the polymerization temperature of the olefin is usually about 20 to 200 ° C, preferably about 30 to 100 ° C, more preferably 50 to 90 ° C. The pressure (gauge pressure) is usually normal pressure to 100 kgf / cm ² (9.8 MPa), preferably about ^{2 to} 50 kgf /
It is set to cm ² (0.20 to 4.9 MPa). In the method for producing a propylene block copolymer of the present invention, the polymerization can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

  Further, the α-olefin / (α-olefin + propylene) gas ratio is controlled in order to obtain the propylene block copolymer in the present invention. The α-olefin is preferably an alkene having 2 to 20 carbon atoms other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1 -Linear olefins such as tetradecene, 1-hexadecene and 1-eicosene, and branched olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene and 3-methyl-1-butene. Among them, ethylene, 1-butene, and 4-methyl-1-pentene are preferable, and ethylene is more preferable. The α-olefin / (α-olefin + propylene) gas ratio is 5 to 80 mol%, preferably 10 to 70 mol%, more preferably 15 to 60 mol%.

  The production method of the propylene-based block copolymer (A) according to the present invention will be described in more detail.

  According to the knowledge of the present inventors, the portion (Dinsol) insoluble in room temperature n-decane constituting the propylene-based block copolymer (A) of the present invention is mainly composed of a propylene polymer component.

  On the other hand, the portion soluble in room temperature n-decane (Dsol) is mainly composed of a propylene-ethylene copolymer rubber component.

  Therefore, the propylene-based block copolymer (A) of the present invention can be produced by the following production method.

Production method;
Propylene-based block copolymer (A) satisfying requirements [1] to [8] and preferably requirement [9] by continuously performing the following two polymerization steps (polymerization step 1 and polymerization step 2): ) (Hereinafter, this method is referred to as “straight weight method”).

[Polymerization step 1] A step of producing a propylene polymer component by polymerizing propylene and, if necessary, another α-olefin in the presence of a solid titanium catalyst component (a propylene polymer production step).

  [Polymerization step 2] A step of copolymerizing propylene and ethylene in the presence of a solid titanium catalyst component to produce a propylene-ethylene copolymer rubber component (copolymer rubber production step).

  In producing the propylene-ethylene copolymer rubber, the ethylene / (ethylene + propylene) gas ratio is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 15 to Polymerization is carried out while controlling at 60 mol%.

  The propylene-based block copolymer (A) according to the present invention is preferably produced by the production method described above, and it is more preferred that the polymerization step 1 is performed in the previous stage and the polymerization step 2 is performed in the subsequent stage. Each polymerization step (polymerization step 1, polymerization step 2) can also be performed using two or more polymerization vessels.

  Here, when the step of producing the propylene polymer component (polymerization step 1 of the above production method) is performed in two or more tanks, the intrinsic viscosity [η] of the propylene polymer produced in each tank is 4 dl. / G or less is preferable.

  Moreover, it is preferable to superpose | polymerize in 1 step in the process (polymerization process 2 of the said manufacturing method) which manufactures the said propylene-ethylene copolymer rubber component.

[Elastomer (B)]
The propylene-based resin composition according to the present invention may contain an elastomer (B). Examples of the elastomer (B) include an ethylene / α-olefin random copolymer (Ba), an ethylene / α-olefin / non-conjugated polyene random copolymer (BB), and a hydrogenated block copolymer (B). -C), other elastic polymers, and mixtures thereof.

  The ethylene / α-olefin random copolymer (Ba) 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 (Ba) 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 desirable that The ethylene / α-olefin random copolymer (Ba) has an MFR at 230 ° C. and a load of 2.16 kg of 0.1 g / 10 min or more, preferably 0.5 to 5 g / 10 min.

The ethylene / α-olefin / non-conjugated polyene random copolymer (Bb) 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 (Bb) 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 (Bb) 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. desirable. Specific examples of the ethylene / α-olefin / non-conjugated polyene random copolymer (Bb) include an ethylene / propylene / diene terpolymer (EPDM).

  The hydrogenated block copolymer (Bc) is a hydrogenated block copolymer having a block form 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 (Bc) 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 (Bc). 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.

[Filler (E)]
The filler (E) which is a constituent of the propylene-based resin composition according to the present invention is talc, magnesium sulfate fiber, glass fiber, carbon fiber, mica, calcium carbonate, magnesium hydroxide, ammonium phosphate, silicates, It is roughly classified into inorganic fillers such as 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, glass fiber, and carbon fiber are preferably used. This will be described in detail 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 without treatment, or various silane coupling agents, titanium couplings may be used to improve interfacial adhesion with propylene-based block copolymers and dispersibility in propylene-based resin compositions. The surface may be treated with an agent, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty acid salt, or other 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 composition in the form of a short fiber of 1 mm or less and a long fiber of 1 mm or more.

When long fiber glass is used, a known blending method can be used. In particular, as described in JP-A-2006-117839 and JP-A-2004-2837, a fiber-reinforced propylene system containing surface-treated glass fibers treated with a sizing agent containing a modified polyolefin resin for glass fiber treatment It is desirable to process the resin into a pellet having a length of 2 to 200 mm to prepare a polypropylene resin composition together with a modified propylene resin modified with an ethylenically unsaturated bond-containing monomer such as maleic anhydride.

(Carbon fiber)
The carbon fiber used in the polypropylene resin composition of the present invention 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. This is not preferable because sufficient reinforcement efficiency such as rigidity and heat resistance cannot be obtained. 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 carbon fiber used by the polypropylene resin composition of this invention, if the above-mentioned shape is satisfy | filled, a conventionally well-known carbon fiber can be used without a restriction | limiting in particular. Examples of the carbon fiber include 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 the fiber yarn into a desired length, and may be subjected to convergence treatment 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.

  These carbon fiber components are combined with other components constituting the polypropylene resin composition of the present invention using a melt-kneading apparatus such as an extruder. During the melt-kneading, the carbon fiber components are combined. It is preferable to select a composite method that prevents excessive breakage. As a method for realizing this, for example, in melt kneading by an extruder, components other than the carbon fiber component are sufficiently melt kneaded, and then the carbon fiber component is removed from the complete melting position of the resin component by a side feed method or the like. Also, a method of feeding the convergent fibers while feeding from a downstream position and minimizing fiber breakage can be exemplified.

  The propylene-based resin composition according to the present invention containing carbon fiber is a modified propylene modified with a monomer containing an ethylenically unsaturated bond such as maleic anhydride on a carbon fiber surface-treated with a sizing agent having a reactive functional group. You may use in the form of the carbon long fiber reinforced propylene resin pellet formed by impregnating a polypropylene resin composition with resin. In the carbon long fiber reinforced propylene-based resin pellet, it is desirable that the carbon long fibers are arranged in parallel in the length direction of the pellet, and the length of the carbon long fibers is 4 to 50 mm.

  In addition, the propylene-based resin composition according to the present invention containing carbon fiber was modified with a monomer containing an ethylenically unsaturated bond such as maleic anhydride on carbon fiber surface-treated with a sizing agent having a reactive functional group. You may use with the shape of the carbon fiber reinforced sheet formed by impregnating a polypropylene resin composition with a modified propylene resin.

(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.

[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 included in the propylene-based resin composition of the present invention are described below.

(Propylene polymer)
The propylene resin composition of the present invention may contain a propylene polymer (A ′) other than the propylene block copolymer (A) as long as the effects of the present invention are not impaired. Such a propylene-based polymer (A ′) is a homopolymer of propylene, a copolymer of propylene, ethylene and other α-olefins, or a block copolymer of propylene, 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 (A ′) has a melting point (Tm) of 145 to 170 ° C., preferably 155 to 167 ° C. Further, the melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the polypropylene-based polymer (A ′) is usually 0.00.
It is 3 to 200 g / 10 minutes, preferably 2 to 150 g / 10 minutes, and more preferably 10 to 100 g / 10 minutes.

(Crystal nucleating agent)
In the propylene-based resin composition of the present invention, a crystal nucleating agent may be added as necessary to improve 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, C4-C12 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].

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 C atoms. 10 hydrocarbon groups, R ² and R ³ may be the same or different, M is a 1 to 3 valent metal atom, n is 1 to 1
It is an integer of 3, and 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-butylphenyl) phosphate 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, sodium-2 , 2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, 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-butyl) Phenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-methylene-bis (4,6 -Di-t-butylfell) phosphate], aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and mixtures of two or more thereof be able to.

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.

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].

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.

  Moreover, you may use the nucleating agent shown by following formula [N-5] as a crystal nucleating agent.

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, -CH 2 CH-X 4 -CH 2 OH or _{-CH 2 OH-CH (OH)} -CH ₂ OH (wherein X ^{1 to} X ⁴ are each independently a halogen group), and 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) can be mentioned.

(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 block copolymer (A) 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.

[Propylene-based resin composition]
The propylene-based resin composition of the present invention includes a propylene-based block copolymer (A), an elastomer (B) and a filler (E) that simultaneously satisfy the above requirements [1] to [8], and other than those described above as necessary. Of ingredients.

The contents of the propylene-based block copolymer (A), the elastomer (B) and the filler (E) in the propylene-based resin composition according to the present invention are as follows.

  The content of the propylene-based block copolymer (A) is 40 to 99 parts by weight, preferably 45 to 97 parts by weight, more preferably 50 to 95 parts by weight with respect to 100 parts by weight of the propylene-based resin composition.

  The content of the elastomer (B) is 0 to 35 parts by weight, preferably 0 to 30 parts by weight, and more preferably 0 to 25 parts by weight with respect to 100 parts by weight of the propylene-based resin composition from the viewpoint of impact strength and rigidity. Part. In addition, although it is prescribed | regulated as a preferable range also about the case where content of an elastomer (B) is 0, this is a propylene-ethylene copolymer rubber component in an above-described propylene-type block copolymer (A), and an elastomer. (B) It assumes the case where the effect from a viewpoint of impact strength and rigidity equivalent to addition is shown.

  Content of a filler (E) is 1-40 weight part with respect to 100 weight part of propylene-type resin compositions, Preferably it is 3-35 weight part, More preferably, it is 5-30 weight part.

  In addition, the above-mentioned other components added as necessary may be appropriately added in an appropriate amount in accordance with the manifestation of the effect of the added component.

  The propylene-based resin composition of the present invention has a weight average molecular weight (Mw) and a number average of components eluted in a temperature range of 100 ° C. to 135 ° C. by cross fraction chromatography (CFC) using o-dichlorobenzene. The ratio of molecular weight (Mn) (molecular weight distribution: Mw / Mn) is preferably 6.0 or more and 16 or less, and more preferably 7.0 or more and 16 or less. When Mw / Mn and Mz / Mw are in the above ranges, an injection molded product with very few flow marks can be obtained from the propylene-based resin composition. This is because, as a result of Mw / Mn and Mz / Mw being in the above ranges, the high molecular weight propylene polymer component is used to increase the melt elasticity of the propylene-based resin composition, particularly to transfer the molten resin to the mold. It is presumed that the flow mark can be greatly improved as a result of achieving high melt elasticity in the shear rate region and stabilizing the flow front in the injection mold.

  When Mw / Mn is smaller than 6.0, the melt elasticity of the propylene polymer component in the propylene block copolymer is lowered, and the flow mark is conspicuous in the injection molded product obtained from the propylene resin composition. In addition, the fluidity at the time of injection molding is reduced, so that it may not be suitable for large injection molded products such as automobile parts. Further, if Mw / Mn is less than 7.0, the rigidity of the propylene-based resin composition is lowered, which may not be preferable. Furthermore, when Mw / Mn is larger than 16, the low molecular weight propylene polymer component increases in the propylene block copolymer, and the impact resistance of the propylene resin composition may be lowered.

[Molded body]
The propylene-based resin composition according to the present invention can be applied to various molded products. Molded articles made of a propylene-based resin composition include injection molded articles, foam molded articles, injection foam molded articles, extrusion molded articles, blow molded articles, vacuum / compressed molded articles, calendar molded articles, stretched films, inflation films, and the like. In particular, it can be suitably used for injection molded articles. Hereinafter, the injection molded body will be described in detail.

[Injection molded body]
The injection-molded article has a good balance between rigidity and low-temperature impact resistance, and further has a good appearance of the molded article, such as no defects such as flow marks and bumps. Therefore, the use of the injection-molded body is not limited, but in particular, automotive exterior parts such as bumpers, side moldings, fenders, undercovers, automotive interior parts such as instrument panels, door trims, pillars, and engine room peripheral parts. In addition, it can be suitably used for automobile parts, home appliance parts, food containers, beverage containers, medical containers, containers and the like. Conventionally known conditions can be adopted without limitation for the molding conditions of the injection-molded article of the present invention.

  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 block copolymer 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 decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (ηsp / C) (C → 0)
(3) 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)
(4) 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.

(5) Pentad 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 was 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.
(6) Content of skeleton derived from ethylene In order to measure the skeleton concentration derived from ethylene in Dsol, 20 to 30 mg of a sample was 0.6 ml of a 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution. Then, carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed. 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)
In this example, the unit of ethylene amount of Dsol was expressed in terms of% by weight.
In Dsol, CSD was calculated according to the following formula (i).

(In formula (i), [EE] is the mole fraction of ethylene chains in Dsol, [PP] is the mole fraction of propylene chains in Dsol, and [PE] is the mole fraction of propylene-ethylene chains. )
(7) GPC-IR measurement Using the Idemitsu Kosan Co., Ltd. GPC-FTIR apparatus, ethylene content was computed as follows.

Millipore / Waters model 150C was used as the high-temperature high-speed GPC apparatus, and the developing solvent used was trichlorobenzene (TCB) purified and added with a stabilizer and the like. The separation column used was a Showa Denko non-aqueous GPC column (Shodex UT-806L (2)), and the eluate after the column separation was a liquid for FTIR controlled at the same temperature by a transfer tube whose temperature was controlled at 145 ° C. from the GPC device. Led to the flow cell. Then, the infrared spectrum was measured with a Nicolet Inc. Magna560FTIR, using SEC-FTIR analysis software (Nicolet Co.), analyzes the CH ₂ stretching vibration of C-CH ₃ stretching vibration and 2920 cm ^-1 of 2955Cm ^-1 Thus, the ethylene content was calculated. The content of components having a molecular weight of 1.5 million or more was calculated by the GPC measurement.

(GPC measurement conditions)
GPC column: Shodex UT-806L (two)
Solvent: TCB (Temperature: 145 ° C., flow rate 1.0 ml / min)
Molecular weight conversion: General calibration method (PP conversion)
(FT-IR measurement conditions)
Detector: MGNA-IR560 (Nikolay)
Injection concentration: 0.3 w / v%
Injection volume: 750 μl
(8) CFC (cross fractional chromatographic measurement)
Analysis of components soluble in o-dichlorobenzene at each temperature was performed by cross-fractionation chromatographic measurement (CFC). CFC was measured under the following conditions using the following apparatus equipped with a temperature rising elution fractionation (TREF) part for performing composition fractionation and a GPC part for performing molecular weight fractionation, and the amount at each temperature was calculated.

Measuring device: CFC T-150A type, manufactured by Mitsubishi Yuka Co., Ltd.
Column: Shodex AT-806MS (x 3)
Solution: o-dichlorobenzene Flow rate: 1.0 ml / min
Sample concentration: 0.3 wt% / vol% (with 0.1% BHT)
Injection volume: 0.5ml
Solubility: Complete dissolution Detector: Infrared absorption detection method, 3.42 μ (2924 cm ⁻¹ ), NaCl plate Elution temperature: 0 to 135 ° C., 28 fractions 0, 10, 20, 30, 40, 45, 50, 55 , 60, 65, 70, 75, 80, 85, 90, 94, 97, 100, 103, 106, 109, 112, 115, 118, 121, 124, 127, 135 (° C.)
For details of the measurement, the sample was heated at 145 ° C. for 2 hours to dissolve, held at 135 ° C., then cooled to 0 ° C. at 10 ° C./hr, and further held at 0 ° C. for 60 minutes to coat the sample. It was. The temperature rising elution column capacity is 0.83 ml, and the pipe capacity is 0.07 ml. The detector was an infrared spectrometer MIRAN 1A CVF type (CaF ₂ cell) manufactured by FOXBORO, and infrared light of 3.42 μm (2924 cm ⁻¹ ) was detected by setting the absorbance mode with a response time of 10 seconds. The elution temperature was divided into 28 fractions from 0 ° C to 135 ° C. All temperature indications are integers. For example, the elution fraction at 94 ° C. indicates a component eluted at 91 to 94 ° C. The molecular weight of components that were not coated even at 0 ° C. and the fraction eluted at each temperature were measured, and the molecular weight in terms of polypropylene was determined using a general-purpose calibration curve. The SEC temperature is 135 ° C., the internal standard injection amount is 0.5 ml, the injection position is 3.0 ml, and the data sampling time is 0.50 seconds. Data processing was performed with the analysis program “CFC data processing (version 1.50)” attached to the apparatus.

(9) Flexural modulus The flexural modulus (FM: [MPa]) was measured under the following conditions in accordance with JIS K7171.

<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Bending span: 64 mm
(10) Charpy impact test The Charpy impact test ([kJ / m ² ]) was measured in accordance with JIS K7111, under the following conditions.

<Test conditions>
Temperature: 23 ° C, -30 ° C
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
The notch is machined. (11) Heat deformation temperature The heat deformation temperature (HDT: [° C.]) was measured according to JIS K7191 under the following conditions.
<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Load: 0.45 MPa
(12) Swell Swell was measured according to the following using a capillograph (manufactured by Toyo Seiki Co., Ltd.).

<Test conditions>
Capillary length: 20mm
Capillary diameter: 1mm
Measurement temperature: 230 ° C
Shear rate: 1216 sec ^-1
(13) Polydispersity index (PDI-P)
PDI-P was measured for melt viscoelasticity according to the following conditions, and was calculated according to the formula (iii) from the relationship between the angular frequency ω (rad / s) and the storage elastic modulus G ′ (FIG. 1).

PDI-P = ω2 / ω1 (iii)
ω1; G ′ (storage modulus) = 2 × 10 ² angular frequency (rad / s)
ω2; G ′ (storage modulus) = 2 × 10 ⁴ angular frequency (rad / s)
<Test conditions>
Test apparatus: DAR-100 (manufactured by Jusco International)
Measuring jig: Parallel plate (φ = 1 inch, gap = 1 mm)
Test temperature: 175 ° C
Angular frequency: 17 points at ω = 1 × 10 ⁻² to 1 × 10 ² (rad / s) (FIG. 1)
Sample preparation:
When PDI-P was measured for the propylene polymer component in the propylene-based block copolymer, a small sample was extracted after completion of the propylene polymer production process. Here, with respect to 100 parts by weight of the propylene polymer component, 0.1 parts by weight of heat-resistant stabilizer IRGANOX 1010 (trademark of Ciba Geigy), 0.1 parts by weight of heat-resistant stabilizer IRGAFOS168 (trademark of Ciba-Geigy), heat-resistant and stable A dry blend of 0.1 parts by weight of the agent IRGANOX 1076 (trademark of Ciba-Geigy Co., Ltd.) and 0.1 parts by weight of calcium stearate, pelletized with a small single screw extruder, press-molded, and a sample for measuring melt viscoelasticity Prepared.

<Melting and kneading conditions>
Single-shaft kneader: Product No. Labo Plast Mill 10M100, manufactured by Toyo Seiki Co., Ltd.
Screw rotation speed: 60rpm
Nitrogen flow in hopper <Press molding conditions>
Press molding temperature: 200 ° C (heating temperature 200 ° C, preheating time: 2 minutes)
Press molding time: 1 minute After press molding, cool for 1 minute with a mold of about 23 ° C (14) Appearance of injection molded product (flow mark)
As the flow mark of the injection molded product, an injection mold having a gate of 350 mm in length, 100 mm in width and 3 mm in thickness and having a gate at the center (50 mm) was used (FIG. 2). Here, the area where the flow mark was generated from the gate was visually evaluated. In this test, in order to make it easy to determine the flow mark, 2 parts by weight of a black colored master batch was dry blended with 100 parts by weight of the propylene-based resin composition, and injection molding was performed.

<Test piece injection molding conditions>
Injection molding machine: Part number SE220HDZ, manufactured by Sumitomo Heavy Industries, Ltd. Cylinder temperature: 210 ° C
Mold temperature: 40 ℃
Injection time (primary filling time): 3 seconds Holding pressure time: 10 seconds Shape of molded product: as shown in FIG.

Flow mark evaluation: Full score of 10 points (flow mark not generated), 0 point (flow mark generated on the entire surface)
(15) Injection molded product appearance (weld)
An injection mold having a gate at a central portion (50 mm) having a length of 350 mm, a width of 100 mm, and a thickness of 3 mm and having a width of 100 mm was used (FIG. 3). A weir that prevents the flow of resin having a diameter of 45 mm and a thickness of 3 mm centered on the point was provided at a position 25 mm immediately below the flow direction from the gate. The weld length was determined by measuring the length until the weld that cannot be discriminated by visual inspection of the weld generated after the weir when the mold was used for injection molding. In order to make it easy to determine welds, 2 parts by weight of a black colored master batch was dry blended with 100 parts by weight of the propylene-based resin composition, and injection molding was performed.
<Test piece injection molding conditions>
Injection molding machine: Part number SE220HDZ, manufactured by Sumitomo Heavy Industries, Ltd. Cylinder temperature: 210 ° C
Mold temperature: 40 ℃
Injection time (primary filling time): 3 seconds Holding pressure time: 10 seconds Molded product shape: as shown in FIG.
[Production Example 1]
A high-speed agitator (made by Tokushu Kika Kogyo Co., Ltd. (TK homomixer M type)) with an internal volume of 2 liters was sufficiently purged with nitrogen, and then 700 ml of purified decane, 10 g of commercially available magnesium chloride, 24.2 g of ethanol and the trade name Leodor SP- 3 g of S20 (sorbite distearate manufactured by Kao Corporation) was added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. 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. 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 sufficiently washed 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.

(Solid titanium catalyst component (α-1) prepolymerization)
Next, dehydrated hexane was added to a three-necked flask equipped with a stirrer with an internal volume of 200 milliliters purged with nitrogen, 0.75 mmol of triethylaluminum, and a suspension of the above solid titanium catalyst component (α-1). Was added in an amount of 0.25 mmol in terms of titanium atom, and the total amount was 50 ml. Under stirring, a predetermined amount of propylene was absorbed for 60 minutes while maintaining 20 ° C. Thereafter, residual propylene was replaced with nitrogen, and washing was sufficiently performed using hexane to obtain a prepolymerized catalyst component (3 g-PP / g-solid titanium catalyst component).

(Main polymerization)
After adding 500 g of propylene and 7.5 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of diethylaminotriethoxysilane, and a solid titanium catalyst component (α The prepolymerization catalyst component of -1) was added in an amount of 0.0035 mmol in terms of titanium atom at 60 ° C, and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 20 minutes (propylene bulk polymerization), propylene was purged while the temperature was lowered. Thereafter, the nitrogen substitution was repeated several times. And after adding hydrogen 0.08NL, it was set as the gas ratio of ethylene / (ethylene + propylene) = 43 mol%, and the vapor phase polymerization was performed by the total pressure of 0.4 MPa. Polymerization was performed until the rubber amount (Dsol) reached about 12%. After completion of the reaction, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A-1). The physical properties of the polymer obtained were: MFR = 98 g / 10 min, room temperature n-decane soluble part (Dsol) 11.9 wt%, Dsol ethylene content 39 mol%, Dsol [η] 2 .4 dl / g.

[Production Example 2]
Polymerization was conducted in the same manner as in Production Example 1 except that hydrogen during gas phase polymerization was changed to 0.02 NL. The obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A-2). The physical properties of the obtained polymer were: MFR = 80 g / 10 min, room temperature n-decane soluble part (Dsol) was 11.8 wt%, Dsol ethylene content was 40 mol%, Dsol [η] was 3 0.6 dl / g.
[Production Example 3]
Polymerization was conducted in the same manner as in Production Example 1 except that ethylene / (ethylene + propylene) at the time of gas phase polymerization was changed to 32 mol%. The obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A-3). The physical properties of the obtained polymer were as follows: MFR = 97 g / 10 min, room temperature n-decane soluble part (Dsol) 11.7 wt%, Dsol ethylene content 30 mol%, Dsol [η] 2 0.5 dl / g.
[Production Example 4]
Polymerization was conducted in the same manner as in Production Example 1 except that ethylene / (ethylene + propylene) at the time of gas phase polymerization was changed to 25 mol%. The obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-1). The physical properties of the polymer obtained were as follows: MFR = 97 g / 10 min, room temperature n-decane soluble part (Dsol) 12.1 wt%, Dsol ethylene content 23 mol%, Dsol [η] 2 0.6 dl / g.
[Production Example 5]
Polymerization was conducted in the same manner as in Production Example 1 except that ethylene / (ethylene + propylene) in the gas phase polymerization was changed to 62 mol%. The resulting polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-2). The physical properties of the polymer obtained were: MFR = 96 g / 10 min, room temperature n-decane soluble part (Dsol) 12.0 wt%, Dsol ethylene content 59 mol%, Dsol [η] 2 0.5 dl / g.
[Production Example 6]
Polymerization was conducted in the same manner as in Production Example 1 except that hydrogen at the time of propylene bulk polymerization was 9.0 NL, hydrogen at the time of gas phase polymerization was 0.02 NL, and the pressure was 0.7 MPa. The obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-3).
The physical properties of the polymer obtained were as follows: MFR = 85 g / 10 min, room temperature n-decane soluble part (Dsol) was 11.8 wt%, Dsol ethylene content was 40 mol%, Dsol [η] Was 5.0 dl / g.
[Production Example 7]
A high-speed agitator (made by Tokushu Kika Kogyo Co., Ltd. (TK homomixer M type)) with an internal volume of 2 liters was sufficiently purged with nitrogen, and then 700 ml of purified decane, 10 g of commercially available magnesium chloride, 24.2 g of ethanol and the trade name Leodor SP- 3 g of S20 (sorbite distearate manufactured by Kao Corporation) was added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. 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 phthalate was added in an amount of 0.15 mol with respect to 1 mol of magnesium atom of the solid adduct, The temperature was raised to 120 ° C. in 50 minutes. These were reacted by holding the temperature at 120 ° 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. 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 sufficiently washed with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.

  The solid titanium catalyst component (α-2) 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-2) thus obtained was 2.5% titanium, 19% magnesium, 58% chlorine, 6.5% diisobutyl phthalate and 0% ethyl alcohol residue. It was 2% by mass.

(Solid titanium catalyst component (α-2) prepolymerization)
Next, dehydrated hexane was added to a three-necked flask equipped with a stirrer with an internal volume of 200 ml substituted with nitrogen, 0.75 mmol of triethylaluminum, and a suspension of the above solid titanium catalyst component (α-2). Was added in an amount of 0.25 mmol in terms of titanium atom, and the total amount was 50 ml. Under stirring, a predetermined amount of propylene was absorbed for 60 minutes while maintaining 20 ° C. Thereafter, residual propylene was replaced with nitrogen, and washing was sufficiently performed using hexane to obtain a prepolymerized catalyst component (3 g-PP / g-solid titanium catalyst component).

(Main polymerization)
After adding 500 g of propylene and hydrogen 5.0 NL at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of diethylaminotriethoxysilane, and solid titanium catalyst component (α -2) 0.0035 mmol in terms of titanium atom was added at 60 ° C., and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 20 minutes, propylene was purged while the temperature was lowered. Thereafter, the nitrogen substitution was repeated several times. And after adding hydrogen 0.04NL, it was set as the gas ratio of ethylene / (ethylene + propylene) = 43 mol%, and the vapor phase polymerization was performed by the total pressure of 0.4 Mpa. Polymerization was performed until the rubber amount (Dsol) reached about 12%. After completion of the reaction, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-4). The physical properties of the obtained polymer were MFR = 9.
5 g / 10 min, room temperature n-decane soluble part (Dsol) was 11.8 wt%, Dsol ethylene content was 40 mol%, and Dsol [η] was 2.5 dl / g.
[Production Example 8]
Polymerization was conducted in the same manner as in Production Example 7 except that hydrogen at the time of propylene bulk polymerization was 6.5 NL, hydrogen at the time of gas phase polymerization was 0.01 NL, and the pressure was 1.0 MPa. The obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-5).
The physical properties of the polymer obtained were: MFR = 82 g / 10 min, room temperature n-decane soluble part (Dsol) 11.9 wt%, Dsol ethylene content 40 mol%, Dsol [η] Was 7.0 dl / g.
[Production Example 9]
After adding 500 g of propylene and 0.2 NL of hydrogen to a polymerization vessel having an internal volume of 2 liters at room temperature, 0.5 mmol of triethylaluminum, 0.1 mmol of diethylaminotriethoxysilane, and a solid titanium catalyst component (α -2) 0.0035 mmol in terms of titanium atom was added at 60 ° C., and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 2 minutes, 4.9 NL of hydrogen was further added and polymerization was performed for 18 minutes. After 18 minutes, propylene was purged while the temperature was lowered. Thereafter, the nitrogen substitution was repeated several times. And after adding hydrogen 0.04NL, it was set as the gas ratio of ethylene / (ethylene + propylene) = 43 mol%, and the vapor phase polymerization was performed by the total pressure of 0.4 Mpa. Polymerization was performed until the rubber amount (Dsol) reached about 12%. After completion of the reaction, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-6). The physical properties of the obtained polymer were as follows: MFR = 97 g / 10 min, room temperature n-decane soluble part (Dsol) was 12.0 wt%, Dsol ethylene content was 40 mol%, and Dsol [η] was 2 0.5 dl / g.

After polymerizing at 70 ° C. for 2 minutes, the reaction was stopped with a small amount of methanol, and polymer particles obtained by removing propylene were dried under reduced pressure at room temperature overnight. [Η] of the obtained polymer was 7.1 dl / g. The content of this polymer in the homo part of the propylene-based block copolymer (A′-6) was 4.5% by weight.
[Production Example 10]
After adding 500 g of propylene and 7.8 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of diethylaminotriethoxysilane, and a solid titanium catalyst component (α The prepolymerization catalyst component of -1) was added in an amount of 0.0035 mmol in terms of titanium atom at 60 ° C, and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 20 minutes, propylene was purged while the temperature was lowered. Thereafter, the nitrogen substitution was repeated several times. And after adding hydrogen 0.08NL, it was set as the gas ratio of ethylene / (ethylene + propylene) = 43 mol%, and the vapor phase polymerization was performed by the total pressure of 0.4 MPa. Polymerization was performed until the rubber amount (Dsol) reached about 30%. After completion of the reaction, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A-4). The physical properties of the polymer obtained were: MFR = 39 g / 10 min, room temperature n-decane soluble part (Dsol) 30.2 wt%, Dsol ethylene content 41 mol%, Dsol [η] 2 .4 dl / g.
[Production Example 11]
After adding 500 g of propylene and hydrogen 5.2 NL at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of diethylaminotriethoxysilane, and a solid titanium catalyst component (α -2) 0.0035 mmol in terms of titanium atom was added at 60 ° C., and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 20 minutes, propylene was purged while the temperature was lowered. Thereafter, the nitrogen substitution was repeated several times. And after adding hydrogen 0.04NL, it was set as the gas ratio of ethylene / (ethylene + propylene) = 43 mol%, and the vapor phase polymerization was performed by the total pressure of 0.4 Mpa. Polymerization was performed until the rubber amount (Dsol) reached about 30%. After completion of the reaction, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-7). The physical properties of the obtained polymer are MFR = 3.
9 g / 10 min, room temperature n-decane soluble part (Dsol) was 30.1% by weight, Dsol ethylene content was 42 mol%, and Dsol [η] was 2.4 dl / g.
[Production Example 12]
A high-speed agitator (made by Tokushu Kika Kogyo Co., Ltd. (TK homomixer M type)) with an internal volume of 2 liters was sufficiently purged with nitrogen, and then 700 ml of purified decane, 10 g of commercially available magnesium chloride, 24.2 g of ethanol and the trade name Leodor SP- 3 g of S20 (sorbite distearate manufactured by Kao Corporation) was added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. 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., cyclohexane 1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was added to 1 mol of magnesium atom in the solid adduct. Was added in an amount of 0.15 mol, and the temperature was raised to 110 ° C. in 30 minutes. When the temperature reached 110 ° C., these were further reacted by maintaining the temperature 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-3) prepared by the above operation was stored as a decane suspension, and a part thereof was dried for the purpose of examining the catalyst composition.

  The composition of the solid titanium catalyst component (α-3) thus obtained was 2.7% by mass of titanium, 18% by mass of magnesium, 58% by mass of chlorine, and 12.9% by mass of diisobutyl cyclohexane 1,2-dicarboxylate. The ethyl alcohol residue was 0.4% by mass.

(Solid titanium catalyst component (α-3) prepolymerization)
Next, dehydrated hexane was added to a three-necked flask equipped with a stirrer with an internal volume of 200 ml substituted with nitrogen, 0.75 mmol of triethylaluminum, and a suspension of the above solid titanium catalyst component (α-3). Was added in an amount of 0.25 mmol in terms of titanium atom, and the total amount was 50 ml. Under stirring, a predetermined amount of propylene was absorbed for 60 minutes while maintaining 20 ° C. Thereafter, residual propylene was replaced with nitrogen, and washing was sufficiently performed using hexane to obtain a prepolymerized catalyst component (3 g-PP / g-solid titanium catalyst component).

(Main polymerization)
After adding 500 g of propylene and 7.8 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of diethylaminotriethoxysilane, and a solid titanium catalyst component (α -3) 0.0035 mmol of the prepolymerization catalyst component in terms of titanium atom was added at 60 ° C, and the temperature in the polymerization vessel was quickly raised to 70 ° C. After polymerization at 70 ° C. for 20 minutes, propylene was purged while the temperature was lowered. Thereafter, the nitrogen substitution was repeated several times. And after adding hydrogen 0.04NL, it was set as the gas ratio of ethylene / (ethylene + propylene) = 43 mol%, and the vapor phase polymerization was performed by the total pressure of 0.4 Mpa. Polymerization was performed until the rubber amount (Dsol) reached about 30%. After completion of the reaction, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-8). The physical properties of the obtained polymer are MFR = 3.
8 g / 10 min, room temperature n-decane soluble part (Dsol) was 30.3% by weight, Dsol had an ethylene content of 41 mol%, and Dsol [η] was 2.5 dl / g.

[Example 1]
60 parts by weight of the propylene-based block copolymer (A-1) produced in Production Example 1, 20 parts by weight of ethylene-butene copolymer rubber (Tuffmer A1050 (trademark of Mitsui Chemicals), talc (white filler 5000PJ ( Trademark), Matsumura Sangyo Co., Ltd.) 20 parts by weight, heat stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.) 0.1 part by weight, heat stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) 0.1 part by weight, heat stable IRGANOX 1076 (trade name of Ciba Geigy Co., Ltd.) 0.1 parts by weight and calcium stearate 0.1 parts by weight are mixed with a tumbler, and then melt-kneaded with a twin screw extruder to prepare a pellet-shaped polypropylene resin composition and injection Create a test piece (small test piece, flow mark appearance evaluation test piece, weld appearance evaluation test piece) with a molding machine. . Shows the mechanical properties and appearance of the molded article in Table 4.

<Melting and kneading conditions>
Same-direction biaxial kneader: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm
Nitrogen flow in hopper <JIS small test piece / injection molding conditions>
Injection molding machine: Part number EC40, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 190 ° C
Mold temperature: 40 ℃
Injection time-pressure holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds [Example 2]
In Example 1, it is the same except having used 60 weight part of propylene type block copolymers (A-2) manufactured by manufacture example 2 instead of 60 weight parts of propylene type block copolymers (A-1). Went to. Table 4 shows the mechanical properties and appearance of the molded product.

[Example 3]
In Example 1, the same procedure except that 60 parts by weight of the propylene-based block copolymer (A-3) produced in Production Example 3 was used instead of 60 parts by weight of the propylene-based block copolymer (A-1). Went to. Table 4 shows the mechanical properties and appearance of the molded product.

[Comparative Example 1]
In Example 1, 60 parts by weight of the propylene-based block copolymer (A′-1) produced in Production Example 4 was used instead of 60 parts by weight of the propylene-based block copolymer (A-1). The same was done. Table 5 shows the mechanical properties and appearance of the molded product.

[Comparative Example 2]
In Example 1, instead of 60 parts by weight of the propylene-based block copolymer (A-1), 60 parts by weight of the propylene-based block copolymer (A′-2) produced in Production Example 5 was used. The same was done. Table 5 shows the mechanical properties and appearance of the molded product.

[Comparative Example 3]
In Example 1, 60 parts by weight of the propylene-based block copolymer (A′-3) produced in Production Example 6 was used instead of 60 parts by weight of the propylene-based block copolymer (A-1). The same was done. Table 5 shows the mechanical properties and appearance of the molded product.

[Comparative Example 4]
In Example 1, instead of 60 parts by weight of the propylene-based block copolymer (A-1), 60 parts by weight of the propylene-based block copolymer (A′-4) produced in Production Example 7 was used. The same was done. Table 5 shows the mechanical properties and appearance of the molded product.

[Comparative Example 5]
In Example 1, 60 parts by weight of the propylene-based block copolymer (A′-5) produced in Production Example 8 was used instead of 60 parts by weight of the propylene-based block copolymer (A-1). The same was done. Table 5 shows the mechanical properties and appearance of the molded product.

[Comparative Example 6]
In Example 1, 60 parts by weight of the propylene-based block copolymer (A′-6) produced in Production Example 9 was used instead of 60 parts by weight of the propylene-based block copolymer (A-1). The same was done. Table 5 shows the mechanical properties and appearance of the molded product.

[Example 4]
80 parts by weight of the propylene-based block copolymer (A-4) produced in Production Example 10, 20 parts by weight of talc (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), heat resistance stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.) ) Trademark) 0.1 part by weight, heat stabilizer IRGAFOS168 (Ciba Geigy Corp.) 0.1 part by weight, heat stabilizer IRGANOX 1076 (Ciba Geigy Corp.) 0.1 part by weight, calcium stearate 0.1 part by weight After mixing with a tumbler, a pellet-shaped polypropylene resin composition was prepared by melting and kneading with a twin screw extruder as in Example 1, and a test piece (small test piece) with an injection molding machine as in Example 1. , Flow mark appearance evaluation test piece, weld appearance evaluation test piece). Table 6 shows the mechanical properties and appearance of the molded product.

[Comparative Example 7]
In Example 4, instead of 80 parts by weight of the propylene-based block copolymer (A-4), 80 parts by weight of the propylene-based block copolymer (A′-7) produced in Production Example 11 was used. The same was done. Table 6 shows the mechanical properties and appearance of the molded product.

[Comparative Example 8]
In Example 4, instead of 80 parts by weight of the propylene-based block copolymer (A-4), 80 parts by weight of the propylene-based block copolymer (A′-8) produced in Production Example 12 was used. The same was done. Table 6 shows the mechanical properties and appearance of the molded product.

  The propylene-based resin composition according to the present invention has good mechanical properties such as rigidity and impact resistance, but has few molding appearance defects such as flow marks and weld lines, and good fluidity in the mold during injection molding. Therefore, it is possible to reduce the thickness and weight of various molded products, particularly large injection molded parts such as automobile interior and exterior parts.

Claims (14)

A propylene-based block copolymer (A) obtained by a production method including a step of producing a propylene polymer component and a step of producing a propylene-ethylene copolymer rubber component and simultaneously satisfying the following requirements [1] to [8] (A 40-99 parts by weight,
Propylene-based resin containing 0 to 35 parts by weight of elastomer (B) and 1 to 40 parts by weight of filler (E) (however, the sum of (A), (B), and (E) is 100 parts by weight) Composition.
[1] According to ASTM D1238E, the melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 20 to 150 g / 10 min.
[2] Consists of 5 to 50% by weight of a part soluble in room temperature n-decane (Dsol) and 50 to 95% by weight of a part insoluble in room temperature n-decane (Dinsol) (however, the sum of Dsol and Dinsol) The amount is 100% by weight),
[3] The molecular weight distribution (Mw / Mn) of Dsol is 7.0 or more and 20 or less,
[4] The ethylene content of Dsol is 25 to 45 mol%,
[5] The intrinsic viscosity [η] of Dsol is 1.8 to 4.0 dl / g,
[6] Dinsol molecular weight distribution (Mw / Mn) is 7.0 or more and 20 or less, and Mz / Mw is 6.0 or more and 20 or less,
[7] The pentad fraction (mmmm) of Dinsol is 95% or more, and [8] In Dsol, the value of CSD defined by the following formula (i) is 1.0 to 2.0.
(In formula (i), [EE] is the mole fraction of ethylene chains in Dsol, [PP] is the mole fraction of propylene chains in Dsol, and [PE] is the mole fraction of propylene-ethylene chains. ) The propylene-based resin composition according to claim 1, wherein the propylene-based block copolymer (A) further satisfies the following requirement [9].
[9] In the GPC-IR measurement of Dsol, the ethylene content (C2 (H5)) (mol%) of the eluted component at 5% of the high molecular weight side and the eluted component at 50% from the high molecular weight side in the area fraction of the GPC curve The difference (Δ (C2)) (the following formula (ii)) in the ethylene content (C2 (H50)) (mol%) is 1.5 or less.
  3. The propylene-based resin composition according to claim 1, wherein the step of producing the propylene polymer component is performed in the previous stage, and the step of producing the propylene-ethylene copolymer rubber component is performed in the subsequent stage.   The step of producing the propylene polymer component is performed in two or more polymerization tanks, and the intrinsic viscosity [η] of the propylene polymer produced in each tank is 4 dl / g or less. The propylene-based resin composition according to any one of 1 to 3.   5. The propylene-based resin composition according to claim 1, wherein the step of producing the propylene-ethylene copolymer rubber is performed in one polymerization tank. The propylene-based block copolymer (A) is composed of titanium, magnesium, and halogen and a cyclic ester compound (a) specified by the following formula (1) and a cyclic ester compound (b) specified by the following formula (2) A solid titanium catalyst component (I) containing
An organometallic compound (II) containing a metal atom selected from Group 1, Group 2 and Group 13 of the Periodic Table;
6. The polymer according to claim 1, which is obtained by polymerizing an olefin containing propylene in the presence of an olefin polymerization catalyst containing an electron donor (III) as necessary. The propylene-based resin composition according to Item.
In Formula (1), n is an integer of 5-10.
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 . A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ³ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A plurality of Rs 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 which may be bonded to each other to form a ring, but at least one R is not a hydrogen atom.
A double bond may be included in the ring skeleton formed by bonding R to each other, and when the ring skeleton includes two or more C ^a to which COOR ¹ is bonded, The number of carbon atoms constituting the skeleton is 5-10.
In Formula (2), n is an integer of 5-10.
R ⁴ and R ⁵ are each independently COOR ¹ or a hydrogen atom, and at least one of R ⁴ and R ⁵ is COOR ¹ . R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ⁵ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.   The propylene-based resin composition according to claim 6, wherein in the formula (1) and / or (2), all the bonds between carbon atoms in the cyclic skeleton are single bonds.   In the said Formula (1) and / or (2), it is n = 6, The propylene-type resin composition of Claim 6 characterized by the above-mentioned. The said cyclic ester compound (a) is following formula (1a), and the said cyclic ester compound (b) is following formula (2a), The propylene-type resin composition of Claim 6 characterized by the above-mentioned.
In Formula (1a), n is an integer of 5-10.
Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A plurality of Rs are each independently an atom selected from a hydrogen atom or 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 which may be bonded to each other to form a ring, but at least one R is not a hydrogen atom.
A double bond may be contained in the ring skeleton formed by bonding R to each other, and when the ring skeleton contains two or more C ^a bonded with COOR ¹ , The number of carbon atoms constituting the skeleton is 5 to 10.
In Formula (2a), n is an integer of 5-10.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds.   The propylene-based resin composition according to claim 9, wherein in the formulas (1a) and (2a), all of the bonds between carbon atoms in the cyclic skeleton are single bonds.   The propylene-based resin composition according to claim 9, wherein n = 6 in the formulas (1a) and (2a).   Ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) of components eluted in a temperature range of 100 ° C. to 135 ° C. by cross-fractionation chromatography (CFC) using o-dichlorobenzene ) Is 6.0 or more and 16 or less, The propylene-type resin composition of any one of Claims 1-11 characterized by the above-mentioned.   The molded object which comprises the propylene-type resin composition of any one of Claims 1-12.   The molded article according to claim 13, wherein the molded article is an automobile part obtained by injection molding.