JP5580630B2 - Foam molded body produced from propylene resin composition - Google Patents

Description

  The present invention relates to a molded article obtained from a propylene-based resin composition suitable for foam molding, particularly injection foam molding. Specifically, the present invention relates to a molded article obtained from a propylene-based resin composition having good molding processability, excellent fluidity and foamability, and extremely excellent appearance characteristics during molding.

  Propylene-based resins are used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, and automotive parts. In recent years, especially automobile parts have improved fuel economy and global warming. There is a strong demand for weight reduction in order to reduce gas, and the use of foamed molded products is increasing especially in interior parts. However, parts for automobile interior and exterior are required to be further reduced in weight and to maintain or improve mechanical properties. For this reason, the appearance of an injection foam molded article having a higher expansion ratio and excellent mechanical properties is demanded.

  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. Such a flow mark results in a significant deterioration in appearance by overlapping with a swirl mark, particularly in foam molding.

  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 propylene-based resin composition is increased and the flow mark is improved to some extent by the above technique, further improvement of the flow mark is necessary because the wide molecular weight distribution of the propylene polymer part is insufficient. there were. Furthermore, in the above technique, improvement in rigidity and impact resistance balance has been demanded.

  Further, it is generally said that a high molecular weight component is effective for improving the foamability of a resin. For example, in the pamphlet of International Publication No. 98/47959, a propylene-based polymer having a wide molecular weight distribution propylene polymer portion by polymerizing a low molecular weight propylene polymer after polymerizing an ultrahigh molecular weight propylene polymer in a multistage polymerization method. A polypropylene resin composition comprising a block copolymer is disclosed. For automotive interior and exterior parts that are mainly aimed at weight reduction, such as injection foam molding, the propylene resin composition is required to have high fluidity during injection molding. It is difficult to secure the properties, and when trying to increase the fluidity of the propylene polymer part, it becomes difficult for the ultrahigh molecular weight propylene polymer to be uniformly dispersed or compatible with the low molecular weight propylene polymer, resulting in reduced impact resistance, In some cases, the surface of the molded product has a defect such as scumming.

  As mentioned above, the improvement example of the flow mark was mentioned, but further improvement of the propylene-based resin composition is required in consideration of elimination of appearance defects, balance of mechanical properties, improvement of injection molding fluidity, improvement of foamability, etc. Yes.

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 foam molded article obtained from a propylene-based resin composition having excellent molding appearance and rigidity, and excellent fluidity during molding, particularly injection molding, and an automobile part comprising the injection foam molded article. The task is to do.

  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 foam molded article produced from 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, together with the effect of high melt elasticity by the broad molecular weight distribution propylene-ethylene copolymer rubber component, the foamability of the propylene-based resin composition and the flow mark can be significantly improved during injection molding. 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 inferred that crystals are formed or the orientation of the high molecular weight propylene polymer is easily frozen during molding, particularly during injection molding.

  In this way, the propylene polymer component in the propylene-based block copolymer has a wide molecular weight distribution in a specific range, and is composed of a propylene-ethylene copolymer rubber having a wide molecular weight distribution and a narrow copolymer composition distribution. The propylene resin composition mainly composed of a propylene block copolymer that meets the requirements for good molding appearance, good rigidity, high fluidity during injection molding, and improvement of foamability at a high level. As a result, the present invention has been completed.

  That is, the foamed molded product 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 satisfies the following requirements [1] to [8]. Simultaneously satisfying propylene block copolymer (A) 40 parts by weight or more and 95 parts by weight or less, elastomer (B) 5 parts by weight or more and 30 parts by weight or less, and filler (E) 0 parts by weight or more and 30 parts by weight or less ( However, the total of (A), (B), and (E) is 100 parts by weight).

[1] Based on ASTM D1238E, a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 20 g / 10 min or more, 150 g / 10 min or less,
[2] A part soluble in room temperature n-decane (Dsol) 5% by weight to 50% by weight and a part insoluble in room temperature n-decane (Dinsol) 50% by weight to 95% by weight ( However, the total amount of Dsol and Dinsol 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 mol% or more and 60 mol% or less,
[5] [sol] of Dsol is 1.5 dl / g or more and 5.0 dl / g or less,
[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, and in [8] Dsol, the value of CSD defined by the following formula (i) is 1.0 or more and 2.0 or less.

(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%) 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 ethylene content (C2 (H50)) (mol%) 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.

  Further, the step of producing the propylene polymer component is performed in two or more series 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. 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.

  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.

  In the present invention, a foam molded article obtained by foam molding by adding 0.1 parts by weight or more and 10 parts by weight or less of a foaming agent to 100 parts by weight of the propylene-based block copolymer (A) is preferable. . Moreover, it is preferable that the said molded object is obtained by injection molding. The molded body is preferably used as an automobile part.

  The foamed molded product according to the present invention has good mechanical properties such as rigidity, but has few molding appearance defects such as flow marks, weld lines, and swirl marks generated by foam molding, and the flow during the production of the molded product. For example, since the fluidity in a mold at the time of injection molding is good, it can be suitably used for thin large injection molded products such as automobile interior and exterior parts.

(A) is a cross-sectional photograph of the foam obtained in Example 1, and (b) is a cross-sectional photograph of the foam obtained in Comparative Example 1. It is the figure which showed the calculation method of PDI-P. It is the figure which showed the schematic of the injection foaming molded product for evaluation, and the board thickness evaluation position.

  Hereinafter, the propylene-based block copolymer (A), the elastomer (B), and the filler (E) contained in the propylene-based resin composition used in the foamed molded product 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] Based on ASTM D1238E, a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 20 g / 10 min or more, 150 g / 10 min or less,
[2] A part soluble in room temperature n-decane (Dsol) 5% by weight to 50% by weight and a part insoluble in room temperature n-decane (Dinsol) 50% by weight to 95% by weight ( 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 20 or less,
[4] The ethylene content of Dsol is 25 mol% or more and 60 mol% or less,
[5] The intrinsic viscosity [η] of Dsol is 1.5 dl / g or more and 5.0 dl / g or less,
[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,
[8] In Dsol, the value of CSD defined by the following formula (i) is 1.0 or more and 2.0 or less.

(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 g / 10 minutes or more, preferably 30 g / 10 minutes. As mentioned above, More preferably, it is 40 g / 10min or more. The MFR is 150 g / 10 min or less, preferably 145 g / 10 min or less, more preferably 140 g / 10 min or less.

  If the MFR exceeds the above upper limit, the impact resistance of the foamed molded product is lowered and may not be suitable for structural parts such as automobile parts. Further, if the MFR is less than the lower limit, the fluidity of the propylene-based resin composition used for the foamed molded product is lowered, and may not be suitable for molding large parts such as automobile parts, particularly injection molding.

Requirement [2]
Part of the propylene-based block copolymer (A) soluble in room temperature n-decane (Dsol) and insoluble in room temperature n-decane (Dinsol) (however, the total amount of Dsol and Dinsol is 100% by weight) As for D), Dsol is 5% by weight or more, preferably 7% by weight or more, and more preferably 10% by weight or more. The Dsol is 50% by weight or less, preferably 40% by weight or less, and more preferably 35% by weight or less. Dinsol is 50% by weight or more, preferably 60% by weight or more, and more preferably 65% by weight or more. The Dinsol is 95% by weight or less, preferably 93% by weight or less, and more preferably 90% by weight or less.

  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.

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, the foamed molded product has few flow marks. 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 high melt elasticity in the speed region, for example, stabilization of the flow front in the injection mold. In addition, when Mw / Mn is in the above range, it is presumed that the impact resistance of the foamed molded product can be maintained because the impact resistance of the low molecular weight propylene-ethylene copolymer rubber component is less affected.

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

  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 ethylene content of Dsol of the propylene-based block copolymer (A) is 25 mol% or more, preferably 27 mol% or more, more preferably 30 mol% or more. The ethylene content is 60 mol% or less, preferably 55 mol% or less, more preferably 50 mol% or less.

  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 obtained foam molding The impact resistance of the body 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. If 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-based block copolymer is reduced, and Impact resistance and elongation may be reduced.

Requirement [5]
The intrinsic viscosity [η] of Dsol of the propylene-based block copolymer (A) is 1.5 dl / g or more, preferably 1.8 dl / g or more, more preferably 2.0 dl / g or more. . The intrinsic viscosity [η] is 5.0 dl / g or less, preferably 4.8 dl / g or less, more preferably 4.5 dl / g or less.

  If the intrinsic viscosity [η] of Dsol is less than the lower limit, the impact resistance of the foamed molded product may be lowered. When the [η] of Dsol exceeds the above upper limit, it is necessary to increase the MFR of the propylene polymer component in order to increase the fluidity during the production of the foamed molded product, for example, during injection molding. At this time, the impact resistance of the foamed molded product may decrease. At the same time, fish eyes may easily be generated in the foamed molded product, and at this time, appearance defects such as blisters may be conspicuous on the surface of the foamed molded product.

Requirement [6]
The molecular weight distribution (Mw / Mn) of Dinsol of the propylene-based block copolymer (A) is 7.0 or more, preferably 8.0 or more, more preferably 9.0 or more, and the Mw / Mn is 20 or less. In addition to Mw / Mn, Mz / Mw, which is the ratio of Dinsol Z-average molecular weight (Mz) to weight-average molecular weight (Mw), is 6.0 or more, preferably 7.0 or more. More preferably, it is 8.0 or more, and the Mz / Mw is 20 or less.

  When Mw / Mn and Mz / Mw are in the above ranges, a foamed molded article having very few flow marks can be obtained. 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. For example, it is presumed that the flow mark has been greatly improved as a result of stabilization of the flow front in the injection mold.

  When Mw / Mn and Mz / Mw are smaller than the lower limit, the melt elasticity of the propylene polymer component in the propylene block copolymer is lowered, and the foamed molded product obtained from the propylene resin composition Since the flow mark becomes conspicuous and the fluidity at the time of molding, particularly at the time of injection molding, decreases, it may not be suitable for large injection molded products such as automobile parts. On the other hand, if Mw / Mn is smaller than the lower limit, the rigidity of the foamed molded product is lowered, which may not be preferable. Furthermore, when Mw / Mn is larger than the above upper limit, the low molecular weight propylene polymer component increases in the propylene-based block copolymer, and the impact resistance of the foamed molded product 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).

ω1; G ′ (storage modulus) (Pa) = 2 × 10 ² angular frequency (rad / s)
ω2; G ′ (storage modulus) (Pa) = 2 × 10 ⁴ angular frequency (rad / s)
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, for example, the shape of the melt front (melt front) at the time of injection molding tends to be stable.

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 foamed molded product is lowered, which is not preferable.
Requirement [8]
In the Dsol of the propylene-based block copolymer (A), the value of CSD defined by the following formula (i) is 1.0 or more and 2.0 or less, preferably 1.0 or more and 1.9. Or less, more preferably 1.0 or more and 1.8 or less.

(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 foamed molded product 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 foamed molded article, it may not be preferable if the ethylene composition distribution in Dsol is 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 2-ethylhexyl 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 2-ethylhexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

Diethyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
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,
Di-n-propyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-5-n-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,
Di-n-propyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-7-n-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,
Di-n-hexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
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,
Diisobutyl 3,5-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,
Di-n-hexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
More preferred is di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate. These compounds can be produced using the Diels Alder reaction.

  The cyclic ester compound (a) having a diester structure as described above has isomers such as cis and trans, and any structure has an effect meeting the object of the present invention. 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, in the cyclic skeleton, the C—C ^b bond, the C ^a —C ^b bond when R ⁵ is COOR ¹ , and the C—C bond (when n is 6 to 10) are replaced with double bonds. It may be done.

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

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 can be 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 three-dimensional structure which can be taken spreads. The ability to take such a variety of three-dimensional structures leads to the formation of a variety of active species on the solid titanium catalyst component (I). As a result, when 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.

  In preparing the solid titanium catalyst component (I) of the present invention, a known method can be used without limitation, except that the cyclic ester compounds (a) and (b) are included in the catalyst component. it can. 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 the phthalic acid esters, phthalic acid alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferable, and diisobutyl phthalate is particularly preferable.

  More specifically, examples of the polyether compound include compounds represented by the following formula (3).

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, for example, an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like can be used. Among these, an organoaluminum compound is preferable.
Specific examples of the organometallic compound catalyst component (II) include organometallic compound catalyst components described in known documents such as EP585869A1.

<Electron Donor (III)>
Moreover, the catalyst for olefin polymerization of the present invention may contain an electron donor (III) as necessary together with the organometallic compound catalyst component (II). The electron donor (III) is preferably an organosilicon compound. As this organosilicon compound, for example, a compound represented by the following general formula (4) can be exemplified.
R _n Si (OR ′) _4-n (4)
(In the formula, R and R ′ are hydrocarbon groups, and n is an integer of 0 <n <4.)

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

  Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are 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 production method of the propylene block copolymer, the solid titanium catalyst component (I) is usually about 0.0001 to 0.5 mmol in terms of titanium atom per liter of polymerization volume, Preferably it is used in an amount of about 0.005 to 0.1 mmol. 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 the propylene-ethylene copolymer rubber component, the pressure and temperature are taken into consideration so that the intrinsic viscosity [η] of Dsol is obtained in the range of 1.5 dl / g to 5.0 dl / g. It is desirable to determine the amount of hydrogen.

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 set to normal pressure to 100 kgf / cm ² (9.8 MPa), preferably about ^{2 to} 50 kgf / cm ² (0.20 to 4.9 MPa). 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) used in 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. Moreover, each superposition | polymerization process (The superposition | polymerization process 1 and the superposition | polymerization process 2) can also be performed using the superposition | polymerization tank of 2 or more tanks in series.

  Here, when the step of producing a propylene polymer component (polymerization step 1 of the above production method) is performed in two or more polymerization tanks in series, the intrinsic viscosity [η] of the propylene polymer produced in each tank Is preferably 4 dl / g or less. The intrinsic viscosity [η] corresponding to the molecular weight of the propylene polymer grown in each tank is calculated by the following equation.

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 190 ° C. and a load of 2.16 kg of 0.1 g / 10 min or more as a lower limit, preferably 0.5 g / min or more, and an upper limit. Is preferably 50 g / 10 min or less.

  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. Details will be described below.

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

The average particle diameter of the talc is preferably 3 μm or less. Here, the average particle size of talc is equivalent to 50% obtained from an integral distribution curve of a sieving method measured by suspending talc in a dispersion medium that is water or alcohol using a centrifugal sedimentation type particle size distribution measuring device. It means particle diameter D _50. Talc may be used 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 propylene-based 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 propylene 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 the carbon fiber used in the propylene-based resin composition of the present invention, a conventionally known carbon fiber can be used without particular limitation as long as the above-described shape is satisfied. Examples of the carbon fiber include 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 the melt kneading with the polypropylene resin, it is preferable that the sizing agent is melted at 200 ° C. or less.

  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 propylene-based 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, after components other than the carbon fiber component are sufficiently melt kneaded, 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 propylene 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 reinforcement sheet | seat formed by impregnating a propylene-type 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. The melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the propylene polymer (A ′) is usually 0.3 to 200 g / 10 minutes, preferably 2 to 150 g / 10 minutes, Preferably, it is 10 to 100 g and / 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 1-3 valent metal atom, n is an integer of 1-3, m Is 1 or 2.

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

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

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, a _{^{-CH 2 CH-X 4 -CH 2}} OH or _{-CH 2 OH-CH (OH)} -CH 2 OH ( where X ^{1 to} X ⁴ are each independently a halogen group.), R ⁶ is an alkyl group having 1 to 20 carbon atoms.

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

(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 the propylene-based block copolymer (A) and the elastomer (B) that simultaneously satisfy the above requirements [1] to [8], and, if necessary, the filler (E) and the above-described components. Other components are included, and their contents are as follows.

  The content of the propylene-based block copolymer (A) is 40 parts by weight or more, preferably 45 parts by weight or more, more preferably 100 parts by weight in total of (A), (B), and (E). Is 50 parts by weight or more. Further, the content of the propylene-based block copolymer (A) is 95 parts by weight or less, preferably 90 parts by weight or less, with respect to 100 parts by weight as a total of (A), (B), and (E). More preferably, it is 88 parts by weight or less.

  From the viewpoint of impact strength and rigidity, the content of the elastomer (B) is 5 parts by weight or more, preferably 10 parts by weight with respect to a total of 100 parts by weight of (A), (B), and (E). More preferably, it is 12 parts by weight or more, and the blending amount of the elastomer (B) is 30 parts by weight or less with respect to 100 parts by weight in total of (A), (B), and (E). , Preferably 25 parts by weight or less, more preferably 20 parts by weight or less.

  The content of the filler (E) is 0 part by weight or more, preferably 1 part by weight or more, more preferably 2 parts per 100 parts by weight in total of (A), (B), and (E). It is more than part by weight. Further, the content of the filler (E) is 30 parts by weight or less, preferably 25 parts by weight, more preferably 20 parts with respect to 100 parts by weight in total of (A), (B), and (E). Less than parts by weight.

  Even when the content of the filler (E) is 0, it is defined as a preferable range. This is because, depending on the product used, the necessary rigidity may be ensured without adding a filler.

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 foamed molded article of the present invention can be produced by adding a foaming agent to the propylene-based resin composition and performing foam molding. The propylene-based resin composition can be suitably used particularly for injection foam molding. The type and amount of the foaming agent are selected in consideration of the amount of gas generated from the foaming agent and the desired foaming ratio, depending on the composition of the resin composition and the required physical properties of the foamed molded product.

Production Method of Foam Molded Article The foam molded article of the present invention is produced by melt-kneading the above-described propylene-based resin composition and a foaming agent described later and performing foam molding, for example, injection foam molding.

The foaming agent is not particularly limited as long as the foamed molded article of the present invention can be produced. Typically, the foaming agent is classified into a physical foaming agent and a chemical foaming agent.
Examples of the physical foaming agent include a solvent-type foaming agent and a gaseous foaming agent.

  The solvent-type foaming agent is generally a substance that functions as a foaming agent by being injected from a cylinder portion of an injection molding machine, absorbed or dissolved in a molten raw material resin, and then evaporated in an injection mold. Examples of the solvent-type blowing agent include low-boiling point aliphatic hydrocarbons such as propane, butane, neopentane, heptane, isohexane, hexane, isoheptane, heptane, and low-boiling point fluorine-containing hydrocarbons typified by CFCs. It is done.

  Examples of the gaseous foaming agent include inert gases such as carbon dioxide, nitrogen, argon, helium, neon, and astatine. Among these physical foaming agents, a gaseous foaming agent composed of an inert gas such as carbon dioxide, nitrogen, and argon is preferable because it does not need to be vaporized, is inexpensive, and has extremely low risk of environmental pollution and fire. The gaseous foaming agent may be used in a supercritical state.

Examples of the chemical foaming agent include a decomposable foaming agent.
The decomposable foaming agent is generally pre-blended with the raw material resin composition and then supplied to a molding machine such as an injection molding machine. In the case of injection foam molding, the foaming agent is used under the cylinder temperature conditions of the injection molding machine. Is a compound that decomposes to generate gases such as carbon dioxide and nitrogen. The decomposable foaming agent includes an inorganic decomposable foaming agent and an organic decomposable foaming agent.

Examples of the inorganic decomposable foaming agent include sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite.
Examples of the organic decomposable foaming agent include N-nitroso compounds such as N, N′-dinitrosoterephthalamide and N, N′-dinitrosopentamethylenetetramine; azodicarbonamide, azobisisobutyronitrile, azocyclohexyl Azo compounds such as nitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfenylhydrazide), diphenylsulfone-3,3'-disulfonylhydrazide, etc. Sulfonyl hydrazide compounds; azide compounds such as 4,4′-diphenyldisulfonyl azide, p-toluenesulfonyl azide and the like.

  These foaming agents may be used alone or in combination of two or more. Further, the foaming agent can be molded after previously blended with the propylene-based resin composition, or can be added separately during molding, for example, in the case of injection molding, from the middle of the cylinder. Among these foaming agents, carbonates or bicarbonates such as sodium bicarbonate are preferable.

  Moreover, when using the said decomposable foaming agent, you may use together foaming adjuvants, such as organic acid, such as organic acids, such as a citric acid which accelerates | stimulates generation | occurrence | production of gas, and sodium citrate. For example, when using a carbonate or bicarbonate such as sodium bicarbonate as a foaming agent, it is desirable to use an organic carboxylic acid as a foaming aid. The compounding ratio of the carbonate or bicarbonate and the organic carboxylic acid is 30 to 90 parts by weight of the carbonate or bicarbonate and 30 to 90 parts by weight of the total amount of carbonate or bicarbonate and the organic carboxylic acid. A range of 10 to 70 parts by weight of acid is preferred. In addition, in using a foaming agent and a foaming adjuvant, you may take the prescription which makes the masterbatch containing them previously and mix | blends it with the said propylene-type resin composition used for foam molding.

  The amount of the foaming agent added is selected in consideration of the amount of gas generated from the foaming agent and the desired expansion ratio depending on the required properties of the foamed molded product to be produced. It is 0.1-10 weight part normally with respect to 100 weight part, Preferably it is 0.3-5.0 weight part, More preferably, it is the range of 0.7-4.0 weight part. When the addition amount of the foaming agent is within such a range, it is possible to obtain a foamed molded article in which the cell diameter is uniform and the cells are uniformly dispersed.

  The foamed molded article of the present invention is prepared by adding a foaming agent to the above-described propylene-based resin composition, and plasticizing and kneading with a molding machine, for example, an injection molding machine, to produce a plasticized resin composition. Preferably, injection foam molding is performed. The foaming agent may be added to the propylene-based resin composition before being supplied to the injection molding machine or by supplying the foaming agent into an injection molding machine in which the propylene-based resin composition is melt-kneaded. May be.

  Injection foam molding can be roughly divided into two types depending on whether the volume of the cavity is changed during molding. As a method of not changing the cavity volume, the plasticizing resin composition is injected and filled into the mold cavity from the injection molding machine, and then the resin shrinks while keeping the cavity volume constant without moving the mold. With a low-magnification foaming method in which the foaming agent dissolved in the resin is gasified and the inside of the molded body is foamed due to the pressure drop accompanying the molding, it is possible to obtain a molded product with prevention of sink marks and reduced weight by 1 to 20%. it can. In addition, as a method of changing the cavity volume, a molten resin containing a foaming agent is injected and filled, and the cavity volume is increased by moving a movable core or a slide core in the mold in the middle or after completion of injection and filling of the resin. This is a method of producing foamed molded products by foaming the resin composition by finally expanding the volume of the cavity beyond the amount of filled resin, and greatly improving the effect of preventing sink marks, light weight effect, and improving rigidity. This is a foaming method for obtaining a molded body. In this construction method, the foaming ratio can be improved to about 1.1 to 20 times, and the lightening effect in isorigidity can be effectively utilized.

  The foam molded article obtained by the injection foam molding of the present invention can be manufactured by foam molding that does not change the cavity volume, but by a cavity volume expansion method (also called a core back method) in which the cavity volume is expanded by moving the mold. It is preferably manufactured. This construction method will be described below.

A mold used for injection foam molding is composed of a fixed mold and a movable mold, and these are preferably in a mold-clamped state when the plasticized resin composition is injected and filled. When in the mold-clamped state, the position at the time of injection filling of the movable mold, that is, the initial position is the state where the fixed mold and the movable mold are closest to each other, and the foamable resin composition used for one molding There is a movable mold at a position where the volume of the melt is almost equal to the volume filled in an unfoamed state, and a cavity close to the product shape is formed. In the present invention, the length in the expansion direction at the start of injection formed between the fixed mold and the movable mold, that is, the cavity clearance (T ₀ ) of the mold at the start of injection is preferably 0.8-3. The range is 0 mm, more preferably 0.9 to 2.0 mm, and still more preferably 1.0 to 1.5 mm. If the cavity clearance (T ₀ ) is less than 0.8 mm, the injection filling cavity is narrow, and the plasticized resin composition may not be sufficiently supplied and filled into the cavity due to an increase in viscosity or solidification of the plasticized resin composition. For example, even if injection filling is performed at a high pressure to sufficiently fill such a thin cavity, the mold will open as a result of the resin pressure in the cavity increasing significantly and exceeding the mold clamping force of the molding machine. In some cases, burrs may be generated, and thin molding itself may not be performed. Further, when performing such thin-wall molding, the resin temperature is significantly cooled, so that even if the cavity volume is increased, foaming does not occur sufficiently, resulting in poor foaming. Even in the case of thin molding of less than 0.8 mm, shot shots can be solved by having a thick portion to flow the molten resin in a part of the molded product. It may become impossible to obtain the light weight effect of molding itself.

  Further, the rigidity of the foam molded product can be improved by improving the elastic modulus of the material itself, but the rigidity can also be increased by increasing the thickness of the foam molded article. Therefore, if you want to increase the rigidity of a flat part or only part of it, increase the initial thickness of the molded product to increase the thickness after foaming and improve the rigidity, or form ribs and bosses on the back of the molded product By doing so, it is possible to improve the rigidity, or to reduce foaming by reducing the plate thickness, thereby adjusting the partial rigidity and impact of the molded product.

  In addition, in foam molding, which is performed by moving the mold as described this time, the rigidity is improved by the effect of increasing the plate thickness by foaming in the direction perpendicular to the direction of movement of the mold, but almost foaming is achieved in the direction of movement of the mold. There is almost no change in thickness and no change in thickness, and improvement in rigidity cannot be expected. Therefore, it is necessary to widen the initial cavity clearance and secure rigidity with the initial resin filling thickness.

Therefore, when you want to improve partial rigidity and impact, or when you want to obtain the light weight reduction effect required for molded products with a three-dimensional shape, injection of 0.8 mm to 3.0 mm that can be foamed optimally It is desirable to have a cavity clearance (T ₀ ) region at the start in the mold cavity of 50% or more, more preferably 60% or more, and even more preferably 70% or more.

  The injection time of the plasticized resin composition into the mold cavity is not particularly limited, but preferably 0.7 to 5.0 s, more preferably about 0.7 to 4.0 s. It is desirable to provide a delay time of preferably 0 to 5 s, more preferably 0.5 to 3 s after completion of the injection, and then enlarge the cavity volume. By providing this delay time, the thickness of the skin layer can be controlled, and when the delay time is lengthened, the skin layer can be thickened, and as a result, mechanical properties such as rigidity can be enhanced. Here, the enlargement ratio of the cavity volume is usually 1.1 to 5.0 times, preferably 1.3 to 4.0 times, and more preferably 1.5 to 3.5 times.

Further, T ₀ ratio (T ₁ / T ₀₎ of the expanded length of the cavity section after the movable mold and retraction (T ₁₎ is 1.1 or more, preferably 1.5 or more, more preferably 2 0.0 or more. When T ₁ / T ₀ is less than 1.1, it is the same as an unfoamed molded article, and a desired rigidity cannot be obtained.

  The mold partition wall moving speed when expanding the cavity volume varies depending on the thickness of the molded body, the type of resin, the type of foaming agent, the mold temperature, and the resin temperature.For example, in the case of injection foam molding using ordinary polypropylene, 0.5-100 mm / s, More preferably, 1-50 mm / s, More preferably, 1-30 mm / s is preferable. If the core moving speed is too slow, the resin solidifies in the middle of the cavity volume expansion, and sufficient foaming ratio cannot be obtained.If the core moving speed is too fast, the cell generation / growth does not follow the core movement, and the cell breaks and the appearance is deteriorated. There is a possibility that a good molded article cannot be obtained.

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

  As in the present invention, after filling the cavity with the resin composition at one time and then foaming, the resin in the part in contact with the mold is solidified faster than the resin inside and the unfoamed skin layer on the surface of the molded product Can be formed. Thereby, a hard product shape can be obtained and maintained, and a highly rigid molded product can be obtained. Moreover, even if some distribution occurs in the cell shape, cell density, and expansion ratio inside the molded body, a molded body having a good appearance can be obtained due to the smoothness and rigidity of the skin layer. The thickness of the skin layer is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, and further preferably 0.3 mm or more. The timing of expanding the cavity volume to form the skin layer with the above thickness depends on the type of resin, the type of foaming agent, the mold temperature, and the resin temperature, but when normal polypropylene is used, after completion of injection filling Is preferably about 0 to 5 s, more preferably about 0.5 to 3 s. If the time from completion of injection filling to the expansion of the cavity volume is too short, a skin layer with sufficient thickness will not be formed, and if it is too long, the resin will solidify and a sufficient expansion ratio will be obtained even if the cavity volume is expanded. I can't.

  The expansion ratio should be appropriately controlled by the resin temperature, injection speed, waiting time from the end of injection filling to the start of cavity volume expansion, the amount of partition movement when the cavity volume is expanded, the partition wall movement speed, the cooling time after the end of cavity volume expansion, etc. 1.1 to 5.0 times, preferably 1.3 to 4.0 times, and more preferably 1.5 to 3.5 times. The cavity volume can be expanded in several stages, whereby a molded body with a controlled cell structure and end shape can be obtained.

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

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

  Since the resin composition used for the foam of the present invention can increase the expansion ratio as compared with a general propylene-based resin composition, the rigidity improving effect and the degree of freedom of the shape of the molded product are easily increased.

  Moreover, according to this invention, the injection foaming molded object whose thickness is about 1.0-15.0 mm can be obtained suitably, for example. The average cell diameter of this injection-foamed molded product is about 0.01 to 1.0 mm, but depending on the shape and application of the molded product, even if the cell diameter is several mm, part of the cells communicated. May be partially present. In particular, when the expansion ratio is increased, the cells meet together and communicate with each other, and the inside of the molded body becomes hollow. However, since the resin pillars are formed in the cavity, the molded body is highly lightweight. And has a strong rigidity. Such foamed molded products can be suitably used for various applications such as automotive interior and exterior parts, cardboard substitutes, electrical appliances, building materials, etc., and particularly suitable for automotive interior parts and automotive exterior parts. Can be used.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the following examples, the physical properties of the propylene 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- 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) Evaluation of Injection Foam Molded Product Characteristics of Foam Molded Product (a) Degree of Achievement of Foaming Ratio The foaming ratio of the injection foam molded product is determined by the molded product thickness t ₁ after foaming and the amount of filled resin t ₀ before expanding the cavity volume. The value divided by x, t ₁ / t ₀ was expressed as the expansion ratio.
At this time, whether or not a foaming ratio of 2.5 times was achieved was evaluated according to the following criteria.
◯: When the plate thickness t ₀ before foaming is 1.2 mm, when the plate thickness t of the molded product after foaming is 3.0 or more and a foaming ratio of 2.5 times is achieved ×: plate thickness before foaming When t ₀ = 1.2 mm, the thickness of the molded article after foaming is less than t = 3.0, and the expansion ratio of 2.5 times is not achieved.

(B) Cell shape The cross section of the molded product was evaluated according to the following criteria.
○: When the cell wall of the foam cell inside the surface skin layer of the molded body is not broken and the upper and lower skin layers are not separated (FIG. 1A).
X: When the cell wall of the foam cell on the inside of the surface skin layer of the molded body is broken and the upper and lower skin layers are separated (FIG. 1 (b)).

  If the cell walls inside the foamed molded product are kept in shape without breaking, there is almost no change in the thickness of the molded product even when subjected to bending load by holding the upper and lower skin layers, resulting in reduced rigidity due to deformation It can be said that it is a good molded product with almost no. On the other hand, when the cell wall breaks and the upper and lower skin layers are separated, when the load is applied to the surface of the molded body, it deforms in the direction that the plate thickness becomes thinner, so the rigidity decreases significantly, and the function as a molded body Cannot be fully demonstrated.

(C) Planarity The flatness of the molded body is obtained by cutting the molded body diagonally and dividing it into four equal parts between the gate portion and the end portion (see the thickness measurement position in FIG. 3). A thickness comparison was performed and evaluated.
○: The thickness error of the entire molded body is less than ± 0.2 mm. Δ: The thickness error of the entire molded body is ± 0.2 mm or more and less than 0.3 mm. X: The thickness error of the entire molded body is ± 0.3 mm or more.

(D) Moldability stability Thin moldability of 1.2 mm by injection molding, load on the molding machine due to injection pressure, and thickness of the foam molded body at the intermediate portion between the gate and the end (see plate thickness measurement position in FIG. 3) The moldability was compared by the repetitive stability of
○: No short shot occurs in the molded product, the injection pressure at the time of molding is less than the maximum injection pressure (250 MPa) of the injection molding machine, and the repetition error of the molded product thickness is ± 0.2 mm or less Δ: Short shot in the molded product Does not occur and the injection pressure during molding is less than the maximum injection pressure (250 MPa) of the injection molding machine, or the repeated error of the molded product thickness exceeds ± 0.2 mm and is 0.3 mm or less ×: A short shot occurs in the molded product Or, the injection pressure at the time of molding exceeds the maximum injection pressure (250 MPa) of the injection molding machine, or the repetition error of the molded product thickness exceeds ± 0.3 mm.

(E) Flow Mark / Swirl Mark For the flow mark and swirl mark of the injection molded product, the surface of the molded product was visually evaluated. In this test, in order to easily determine the flow mark and swirl mark, 3 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.
○: Conspicuous swirl mark and flow mark are not seen on the molded product surface ×: Swirl mark and flow mark can be clearly confirmed on the molded product surface

(F) Rigidity (bending elastic gradient)
Rigidity was evaluated by comparing the bending elastic gradients of the molded products with reference to a molded body having a bending elastic modulus of 1000 MPa and a plate thickness of 2.3 mm.
○: High rigidity (high bending elastic gradient)
×: Evaluation is not possible due to low rigidity (low bending elastic gradient) or deformation of molded body or defective foaming. The bending elastic gradient used for evaluation of rigidity is obtained by cutting the obtained molded product into a size of 50 mm × 150 mm and having a support interval of 100 mm. In a “load-deflection curve” obtained when a bending test is performed at a bending speed of 50 mm / min at the center position, the initial load (the load when deflected by 1.0 mm) is the deflection amount (1 0.0 mm), that is, the initial inclination of the load-deflection curve was used as a bending elastic gradient (N / cm) for comparison.

(G) Impact property Impact property was evaluated using a high-speed impact tester (HTM-1 manufactured by Shimadzu Corporation), and cut out from an arbitrary area at 100 mm x 100 mm from a flat foamed molded product. 1/2 inch, cradle diameter 3 inch, hitting speed The fracture energy was measured and evaluated at 0 m / sec.
○: Breaking energy is 1.0 J or more ×: Breaking energy is less than 1.0 J

<Injection foam molding conditions>
In the following examples and comparative examples, injection foam molding was performed under the following conditions.
・ Injection molding machine: Ube Industries, Ltd., MD350S-III type (clamping force 350t)
・ Die Cavity Size: Vertical 400mm, Horizontal 200mm, Cavity Clearance 1.2mm between Fixed Mold and Movable Mold when Clamping
Gate: Single point direct gate in the cavity Injection temperature: 210 ° C
Mold surface temperature: 45 ° C
Injection time: 1.0 s (Time from the start of injection to the end of injection of molten resin)
-Foam molding conditions Cavity clearance (T) between fixed mold and movable mold after foaming process: 3.0 mm
Bulkhead moving speed when the cavity volume is expanded: 20 mm / s
Foam start delay time after resin filling: 0 to 1 s
Cavity clearance (T ₀ ) between fixed mold and movable mold at the start of injection: 1.2 mm
Shape of molded product: as shown in FIG.

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

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

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

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

(2) Production of prepolymerization catalyst 52.0 g of the solid catalyst component prepared in (1) above, 13.3 mL of triethylaluminum, and 7.4 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 20 L, and an internal temperature of 15 to 20 While maintaining the temperature, 520 g of propylene was inserted and reacted while stirring for 100 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 0.7 g / L.

(3) Main polymerization In a jacketed circulation type tubular polymerizer with an internal capacity of 58 L, propylene is 30 kg / hour, hydrogen is 370 NL / hour, the catalyst slurry produced in (2) is 0.37 g / hour as a solid catalyst component, triethylaluminum 1.6 ml / hour and cyclohexylmethyldimethoxysilane 1.4 ml / hour were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 66 ° C., and the pressure was 3.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 18.8 mol%. Polymerization was carried out at a polymerization temperature of 60 ° C. and a pressure of 3.4 MPa / G.

  The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, gasified and subjected to gas-solid separation, and then propylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L, / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.30 (molar ratio) and hydrogen / ethylene = 0.027 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.78 MPa / G.

The resulting propylene block copolymer was vacuum dried at 80 ° C.
The physical properties of the obtained polymer were: MFR = 85 g / 10 min, room temperature n-decane soluble part (Dsol) 13.2 wt%, Dsol ethylene content 45 mol%, Dsol [η] 4 .4 dl / g.

[Production Example 2]
Production Example 2 is a production example except that the gas composition in the gas phase polymerization apparatus was changed to ethylene / (ethylene + propylene) = 0.30 (molar ratio) and hydrogen / ethylene = 0.090 (molar ratio). 1 was carried out.

  The physical properties of the polymer obtained were as follows: MFR = 100 g / 10 min, room temperature n-decane soluble part (Dsol) 13.0 wt%, Dsol ethylene content 45 mol%, Dsol [η] 3 0.0 dl / g.

[Production Example 3]
30 kg / hour of propylene, 261 NL / hour of hydrogen, 0.27 g / hour of the catalyst slurry obtained in (2) of Production Example 1 as a solid catalyst component, triethylaluminum 1.1 ml / hour and 1.3 ml / hour of dicyclopentyldimethoxysilane were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 66 ° C., and the pressure was 3.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization vessel, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 12.6 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 3.2 MPa / G.

  The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, gasified and subjected to gas-solid separation, and then propylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L, / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization reactor is ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene = 0.034 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.80 MPa / G.

The resulting propylene block copolymer was vacuum dried at 80 ° C.
The physical properties of the obtained polymer were as follows: MFR = 43 g / 10 min, room temperature n-decane soluble part (Dsol) 12.4 wt%, Dsol ethylene content 30 mol%, Dsol [η] 4 0.1 dl / g.

[Production Example 4]
30 kg / hour of propylene, 293 NL / hour of hydrogen, 0.27 g / hour of the catalyst slurry obtained in (2) of Production Example 1 as a solid catalyst component, triethylaluminum 1.1 ml / hour and 1.3 ml / hour of dicyclopentyldimethoxysilane were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 66 ° C., and the pressure was 3.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 14.4 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 3.3 MPa / G.

  The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, gasified and subjected to gas-solid separation, and then propylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L, / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene = 0.085 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.82 MPa / G.

The resulting propylene block copolymer was vacuum dried at 80 ° C.
The physical properties of the polymer obtained were: MFR = 59 g / 10 min, room temperature n-decane soluble part (Dsol) was 14.4% by weight, Dsol had an ethylene content of 30 mol%, and Dsol [η] was 3 0.1 dl / g.

[Production Example 5]
30 kg / hour of propylene, 210 NL / hour of hydrogen, 0.37 g / hour of the catalyst slurry obtained in (2) of Production Example 1 as a solid catalyst component, triethylaluminum 1.6 ml / hour and cyclohexylmethyldimethoxysilane 1.4 ml / hour were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 66 ° C., and the pressure was 3.6 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 11.9 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 3.3 MPa / G, and the resulting propylene homopolymer was vacuum dried at 80 ° C.
The physical property of the obtained polymer was MFR = 110 g / 10 min.

[Production Example 6]
(1) Production of solid catalyst After a high-speed stirring device (made by Tokushu Kika Kogyo Co., Ltd. (TK homomixer M type)) with an internal volume of 2 liters was sufficiently substituted with nitrogen, 700 ml of purified decane, 10 g of commercially available magnesium chloride, 24. 2 g and 3 g of the trade name Leodol SP-S20 (sorbite distearate manufactured by Kao Corporation) were added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. did. Next, 1 liter of purified decane that had been cooled to −10 ° C. in advance was put into this suspension using a Teflon (registered trademark) tube having an inner diameter of 5 mm while stirring at a high speed so as not to cause precipitation. Transferred to a 2 liter glass flask (with a stirrer). The solid produced by the transfer was filtered and washed thoroughly with purified n-heptane to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with respect to 1 mol of magnesium chloride.

  This solid adduct was suspended in decane, and 23 mmol of the above solid adduct in terms of magnesium atom was introduced into 100 ml of titanium tetrachloride maintained at −20 ° C. with stirring and mixed. A liquid was obtained. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., diisobutyl 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, and then heated to 130 ° 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-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.

(2) Production of prepolymerization catalyst 68.0 g of solid titanium catalyst component (α-2) prepared in (1) above, 14.5 mL of triethylaluminum, and 9.7 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 20 L. Then, maintaining the internal temperature at 15 to 20 ° C., 680 g of propylene was inserted, and the reaction was carried out with stirring for 100 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 0.7 g / L.

(3) Main polymerization In a jacketed circulation tubular polymerizer with an internal capacity of 58 L, propylene is 43 kg / hour, hydrogen is 280 NL / hour, and the catalyst slurry produced in (2) is 0.42 g / hour, using triethylaluminum as a solid catalyst component. 1.8 ml / hour and 0.65 ml / hour of cyclohexylmethyldimethoxysilane were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 69 ° C., and the pressure was 3.4 MPa / G.
The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 8.6 mol%. Polymerization was carried out at a polymerization temperature of 67 ° C. and a pressure of 3.2 MPa / G.

  The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, gasified and subjected to gas-solid separation, and then propylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L, / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.43 (molar ratio) and hydrogen / ethylene = 0.018 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.63 MPa / G.

The resulting propylene block copolymer was vacuum dried at 80 ° C.
The physical properties of the obtained polymer were as follows: MFR = 120 g / 10 min, room temperature n-decane soluble part (Dsol) was 12.0 wt%, Dsol ethylene content was 45 mol%, and Dsol [η] was 3 0.1 dl / g.

[Production Example 7]
(1) Production of prepolymerization catalyst 68.0 g of solid titanium catalyst component (α-2) prepared in Production Example 6 (1), 14.5 mL of triethylaluminum, 9.7 L of heptane, autoclave with stirrer having an internal volume of 20 L 680 g of propylene was inserted while maintaining the internal temperature at 15 to 20 ° C., and the reaction was carried out with stirring for 100 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 0.7 g / L.

(2) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 43 kg / hour, hydrogen is 62 NL / hour, the catalyst slurry produced in (2) is 0.45 g / hour as a solid catalyst component, triethylaluminum 1.9 ml / hour and cyclohexylmethyldimethoxysilane 1.2 ml / hour were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70.5 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 1.1 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, gasified and subjected to gas-solid separation, and then propylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L, / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization reactor is ethylene / (ethylene + propylene) = 0.51 (molar ratio) and hydrogen / ethylene = 0.033 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.65 MPa / G.

  The resulting propylene block copolymer (a′-1) was vacuum dried at 80 ° C. Thermal stabilizer IRGANOX 1010 (registered trademark, Ciba Geigy Co., Ltd.) 0.1 part by weight and thermal stabilizer IRGAFOS 168 (registered trademark, Ciba Geigy Co., Ltd.) with respect to 100 parts by weight of the propylene-based block copolymer (a′-1) 0.1 parts by weight, calcium stearate 0.1 parts by weight, Kayahexa AD (trademark, manufactured by Kayaku Akzo Co., Ltd.) 0.55 parts by weight are mixed with a Henschel mixer and then melt-kneaded with a twin screw extruder. A pellet-shaped propylene-based block copolymer (A′-2) was prepared. The physical properties of this propylene-based block copolymer were MFR = 60 g / 10 min, room temperature n-decane soluble part (Dsol) was 12.2 wt%, Dsol ethylene content was 51 mol%, and Dsol [η] was It was 1.4 dl / g.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 230 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm

[Production Example 8]
A jacketed circulation tubular polymerizer with an internal capacity of 58 L, 43 kg / hour of propylene, 130 NL / hour of hydrogen, 0.42 g / hour of the catalyst slurry obtained in (2) of Production Example 6 as a solid catalyst component, triethylaluminum 1.8 ml / hour and cyclohexylmethyldimethoxysilane 1.1 ml / hour were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70.5 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 3.0 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, gasified and subjected to gas-solid separation, and then propylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L, / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.36 (molar ratio) and hydrogen / ethylene = 0.051 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.70 MPa / G.

The resulting propylene block copolymer was vacuum dried at 80 ° C.
The physical properties of the obtained polymer were as follows: MFR = 30 g / 10 min, room temperature n-decane soluble part (Dsol) 13.5 wt%, Dsol ethylene content 41 mol%, Dsol [η] 3 .2 dl / g.

[Example 1]
Component (A-2) 83 parts by weight of the propylene-based block copolymer produced in Production Example 2, component (B) produced with a single site catalyst, density = 0.87 g / cm ³ , MFR ₁₉₀ = 35 g / 10 min Low molecular weight ethylene / 1-butene copolymer (EBR) (A-35070S manufactured by Mitsui Chemicals): 17 parts by weight were mixed and granulated to obtain a resin composition for foam molding.

  This resin composition was mixed with sodium bicarbonate-based inorganic foaming agent masterbatch (Polyslen EE25C manufactured by Eiwa Kasei Kogyo Co., Ltd.) in an amount of 6 parts by weight based on 100 parts by weight of the resin composition. After dry blending (so as to be 1.8 parts by weight with respect to 100 parts by weight of the composition), injection molding was performed under the above-mentioned conditions to obtain a foam molded article. The appearance and physical properties of this foamed molded product were evaluated, and the results are shown in Table 3. The plate thickness of the obtained molded product was 3.1 mm, and the cell also maintained its shape.

[Example 2]
Example 1 is the same as Example 1 except that the amount of component (A-2) used is 73 parts by weight and component (C) fine powder talc (average particle size: 4.1 μm): 10 parts by weight. Similarly, a foam molding resin composition was produced to obtain a foam molding. The results are shown in Table 3.

[Example 3]
In Example 1, the component (A-2) was replaced with 68 parts by weight of the propylene block polymer produced in Production Example 1, 21 parts by weight of component (B), and 11 parts by weight of component (C). Except for the above, a resin composition for foam molding was produced in the same manner as in Example 2 to obtain a foam molded article. The results are shown in Table 3.

[Example 4]
In Example 1, instead of component (A-2), the amount of component (A-3) used was 61 parts by weight,
Component (E) The implementation was carried out except that the homopropylene produced in Production Example 5 was 12 parts by weight, the amount of component (B) used was 17 parts by weight, and the amount of component (C) used was 10 parts by weight. A resin composition for foam molding was produced in the same manner as in Example 1 to obtain a foam molded article. The results are shown in Table 3.

[Example 5]
In Example 4, the component (A-3) was used in place of the component (A-4) in an amount of 52 parts by weight and the component (E) in an amount of 21 parts by weight. In the same manner as described above, a foam molding resin composition was produced to obtain a foam molding. The results are shown in Table 3.

[Comparative Example 1]
A resin composition for foam molding was produced in the same manner as in Example 1 except that the material used was 100 parts by weight of the component (A-1), and a foam molded article was obtained and evaluated. The results are shown in Table 3. At this time, the plate thickness was 2.9 mm, the foamed cell wall was broken, and a crack was generated at the center of the molded body.

[Comparative Example 2]
A resin composition for foam molding was produced in the same manner as in Example 1 except that the material used was 100 parts by weight of component (A-2), and a foam molded article was obtained and evaluated. The results are shown in Table 3.

[Comparative Example 3]
A resin composition for foam molding was produced in the same manner as in Example 1 except that the material used was 83 parts by weight of component (A′-1) and the amount of component (B) used was 17 parts by weight. A foamed molded product was obtained and evaluated. The results are shown in Table 3.

[Comparative Example 4]
In Comparative Example 3, the resin composition for foam molding was the same as Comparative Example 2 except that the amount of component (A′-1) used was 73 parts by weight and the amount of component (C) used was 10 parts by weight. A product was manufactured, and a foam-molded article was obtained and evaluated. The results are shown in Table 3.

[Comparative Example 5]
Except that the material used was a propylene-based block copolymer (A′-2), a resin composition for foam molding was produced in the same manner as in Comparative Example 1, and a foam molded body was obtained and evaluated. . The results are shown in Table 3.

[Comparative Example 6]
Except that the material used was a propylene-based block copolymer (A′-3), a resin composition for foam molding was produced in the same manner as in Comparative Example 1, and a foam molded body was obtained and evaluated. . The results are shown in Table 3.

  The foamed molded product according to the present invention has good mechanical properties such as rigidity, has few molding appearance defects such as flow marks and weld lines, and has good fluidity, particularly fluidity in the mold during injection molding. In addition, since it is excellent in foaming properties, particularly injection foaming properties, it is suitable as an injection foam molding product that achieves thinning, weight reduction, and heat insulation of various molded products, particularly large-sized injection molded parts such as automobile interior and exterior parts. .

Claims (15)

A solid titanium catalyst component (I) comprising 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 metal source selected from Groups 1, 2 and 13 of the periodic table
In the presence of an olefin polymerization catalyst containing an organic metal compound (II) containing a polymer, it is obtained by a production method comprising a step of producing a propylene polymer component and a step of producing a propylene-ethylene copolymer rubber component, 40 parts by weight or more and 95 parts by weight or less of a propylene-based block copolymer (A) that simultaneously satisfies the following requirements [1] to [8]
Elastomer (B) 5 parts by weight or more and 30 parts by weight or less and filler (E) 0 parts by weight or more and 30 parts by weight or less (provided that the total of (A), (B), and (E) is 100 parts by weight. A foam molded article obtained by foam molding by adding a foaming agent to a propylene-based resin composition.
[1] Based on ASTM D1238E, a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 20 g / 10 min or more, 150 g / 10 min or less,
[2] A part soluble in room temperature n-decane (Dsol) 5% by weight to 50% by weight and a part insoluble in room temperature n-decane (Dinsol) 50% by weight to 95% by weight ( 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 20 or less,
[4] The ethylene content of Dsol is 25 mol% or more and 60 mol% or less,
[5] The intrinsic viscosity [η] of Dsol is 1.5 dl / g or more and 5.0 dl / g or less,
[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 or more and 2.0 or less.
(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 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 foamed molded product according to claim 1, wherein the propylene-based block copolymer (A) contained in the propylene-based resin composition 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.
  2. The method for producing a propylene-based block polymer (A), wherein the step of producing a propylene polymer component is carried out in the preceding stage, and the step of producing a propylene-ethylene copolymer rubber component is carried out in the latter stage. Or the foaming molding of 2.   The step of producing the propylene polymer component of the propylene-based block polymer (A) is performed in two or more polymerization tanks configured in series, and the intrinsic viscosity [η] of the propylene polymer produced in each tank Is 5.0 dl / g or less, The foaming molding of any one of Claims 1-3 characterized by the above-mentioned.   The foaming according to any one of claims 1 to 4, wherein the step of producing the propylene-ethylene copolymer rubber of the propylene-based block polymer (A) is performed in a single polymerization tank. Molded body. The foam molded article according to any one of claims 1 to 5, wherein the olefin polymerization catalyst further contains an electron donor (III) . In the said Formula (1) and / or (2), all the bonds between carbon atoms in the said cyclic | annular frame | skeleton are single bonds, The foaming molding of Claim 1 characterized by the above-mentioned. In the said Formula (1) and / or (2), it is n = 6, The foaming molding of Claim 1 characterized by the above-mentioned. The foamed molded article according to claim 1 , wherein the cyclic ester compound (a) is represented by the following formula (1a), and the cyclic ester compound (b) is represented by the 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 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.   In the said Formula (1a) and (2a), all the bonds between carbon atoms in the said cyclic | annular frame | skeleton are single bonds, The foaming molding of Claim 9 characterized by the above-mentioned.   In the said Formula (1a) and (2a), it is n = 6, The foaming molding of Claim 9 characterized by the above-mentioned.   The foaming molding which added 0.1 to 10 weight part foaming agent with respect to 100 weight part of propylene-type resin compositions of any one of Claims 1-11, and carried out foam molding. The foamed molded product according to any one of 11.   The foaming agent according to any one of claims 1 to 12 is a chemical foaming agent and / or a physical foaming agent, and the foamed molded article is produced by injection foaming. 2. A foamed molded article according to item 1. 14. The injection foam molding according to claim 13, wherein the cavity clearance (T ₀ ) between the movable mold and the fixed mold at the start of injection has a region where the area is 0.8 mm or more and 3.0 mm or less by 50% or more. The foamed molded article according to claim 13, having a foaming ratio of 1.1 to 5.0 times, obtained by injecting and filling the propylene-based resin composition and a foaming agent into a cavity and expanding the cavity volume.   The foam molded article according to any one of claims 1 to 14, wherein the foam molded article is an automotive interior / exterior part.