阅读说明：本技术 多相丙烯聚合材料 (Heterophasic propylene polymeric material ) 是由 小野寺徹 大桥龙二 神崎进 于 2019-03-12 设计创作，主要内容包括：一种多相丙烯聚合材料,其包含丙烯共聚物(I)、乙烯-α-烯烃共聚物(II-1)和乙烯-α-烯烃共聚物(II-2)。丙烯共聚物(I)：其中衍生自除丙烯以外的烯烃的单体单元的含量大于等于0.05重量％且小于10重量％,并且特性粘度[η]<Sub>I</Sub>小于1.50dL/g。乙烯-α-烯烃共聚物(II-2)：其中衍生自乙烯的单体单元的含量为10重量％以上且30重量％以下,并且乙烯-α-烯烃共聚物(II-2)的特性粘度高于乙烯-α-烯烃共聚物(II-1)的特性粘度。(A heterophasic propylene polymeric material comprising a propylene copolymer (I), an ethylene-alpha-olefin copolymer (II-1) and an ethylene-alpha-olefin copolymer (II-2). Propylene copolymer (I): wherein the content of monomer units derived from an olefin other than propylene is 0.05% by weight or more and less than 10% by weight, and the intrinsic viscosity [ eta ] is] I Less than 1.50 dL/g. Ethylene- α -olefin copolymer (II-2): wherein the content of the monomer unit derived from ethylene is 10% by weight or more and 30% by weight or less, and the ethylene-alpha-olefin copolymer (II-2) has a higher intrinsic viscosity than the ethylene-alpha-olefin copolymer (II-1) The intrinsic viscosity of (2).)

1. A heterophasic propylene polymeric material comprising the following propylene copolymer (I), the following ethylene-alpha-olefin copolymer (II-1) and the following ethylene-alpha-olefin copolymer (II-2), wherein,

intrinsic viscosity [ eta ] of propylene copolymer (I)]_ILess than 1.50dL/g,

propylene copolymer (I): which is a copolymer comprising a monomer unit derived from propylene and a monomer unit derived from at least one olefin selected from the group consisting of ethylene and an alpha-olefin having 4 or more and 12 or less carbon atoms, wherein,

a content of a monomer unit derived from at least one olefin selected from the group consisting of ethylene and an α -olefin having 4 to 12 carbon atoms is 0.05 wt% or more and less than 10 wt% (wherein the total weight of the propylene copolymer (I) is set as 100 wt%);

ethylene- α -olefin copolymer (II-1): which is a copolymer comprising a monomer unit derived from ethylene and a monomer unit derived from at least one olefin selected from the group consisting of propylene and an alpha-olefin having 4 or more and 12 or less carbon atoms, wherein,

a content of a monomer unit derived from ethylene is 10% by weight or more and 30% by weight or less (wherein the total weight of the ethylene- α -olefin copolymer (II-1) is set to 100% by weight);

ethylene- α -olefin copolymer (II-2): which is a copolymer comprising a monomer unit derived from ethylene and a monomer unit derived from at least one olefin selected from the group consisting of propylene and an alpha-olefin having 4 or more and 12 or less carbon atoms, wherein,

the content of monomer units derived from ethylene is 10% by weight or more and 30% by weight or less (wherein the total weight of the ethylene- α -olefin copolymer (II-2) is set to 100% by weight), and

the intrinsic viscosity of the ethylene- α -olefin copolymer (II-2) is higher than that of the ethylene- α -olefin copolymer (II-1).

2. The heterophasic propylene polymeric material according to claim 1, wherein the intrinsic viscosity [ η ] of the xylene soluble fraction of the heterophasic propylene polymeric material]_CXSRelative to the intrinsic viscosity [ eta ] of the xylene-insoluble fraction of the heterophasic propylene polymer material]_CXISRatio of ([ eta ]) of]_CXS/[η]_CXIS) Is 1.0 or more.

3. Heterophasic propylene polymeric material according to claim 1 or 2, wherein the content of ethylene-a-olefin copolymer (II-1) is given as a₁The content of the ethylene-alpha-olefin copolymer (II-2) is represented by a% by weight₂(wherein the total weight of the heterophasic propylene polymeric material is taken as 100 wt%);

the content of a monomer unit derived from ethylene in the ethylene-alpha-olefin copolymer (II-1) is set as b₁(wherein, the total weight of the ethylene- α -olefin copolymer (II-1) is set to 100% by weight); and is

The content of a monomer unit derived from ethylene in the ethylene-alpha-olefin copolymer (II-2) is set as b₂(wherein the total weight of the ethylene-alpha-olefin copolymer (II-2) is 100 wt%),

satisfies the following formula (3):

X＝(a₁b₁+a₂b₂)/(a₁+a₂) (1)

Y＝a₁+a₂(2)

Y≤4.37X-32.4 (3)。

4. a propylene resin composition comprising a thermoplastic elastomer (III) and the heterophasic propylene polymer material according to any of claims 1 to 3.

5. The propylene resin composition according to claim 4, wherein the propylene resin composition further comprises a filler (D).

6. A propylene resin composition comprising a filler material (D) and the heterophasic propylene polymer material according to any of claims 1 to 3.

7. A shaped body comprising the heterophasic propylene polymeric material of any of claims 1 to 3.

8. A molded article comprising the propylene resin composition according to any one of claims 4 to 6.

9. A method for producing a heterophasic propylene polymer material according to any of claims 1 to 3, wherein the method comprises the following step (1-1), the following step (1-2-1) and the following step (1-2-2),

step (1-1): a step of copolymerizing propylene with at least one olefin selected from the group consisting of ethylene and α -olefins having 4 to 12 carbon atoms in the presence of a propylene polymerization catalyst by a multi-stage polymerization method to obtain a propylene copolymer (I);

step (1-2-1): a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of the propylene copolymer (I) to obtain a mixture of the propylene copolymer (I) and the ethylene- α -olefin copolymer (II-1);

step (1-2-2): and a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and an alpha-olefin having 4 to 12 carbon atoms in the presence of the mixture to obtain a heterophasic propylene polymer material comprising a propylene copolymer (I), an ethylene-alpha-olefin copolymer (II-1) and an ethylene-alpha-olefin copolymer (II-2).

Technical Field

The present invention relates to heterophasic propylene polymeric materials.

Background

The heterophasic propylene polymer materials are widely used in the fields of automobile parts, household electrical appliances, food and medical containers, building materials, civil engineering materials, etc. by virtue of their characteristics. For example, patent document 1 discloses a heterophasic propylene polymer material containing a propylene homopolymer portion and a propylene-ethylene random copolymer portion.

Disclosure of Invention

Problems to be solved by the invention

In recent years, resin molded bodies of various designs have been used in the above-mentioned fields, and materials capable of exhibiting various designs have been demanded. For example, there is a demand for a heterophasic propylene polymer material which, when a black shaped body having an embossed design surface is produced, gives a blacker looking shaped body.

The invention aims to provide a multiphase propylene polymer material which can obtain a blacker molded body when a black molded body with an embossed design surface is prepared.

Means for solving the problems

The present invention provides the following polymeric materials.

[1] A heterophasic propylene polymeric material comprising the following propylene copolymer (I), the following ethylene-alpha-olefin copolymer (II-1) and the following ethylene-alpha-olefin copolymer (II-2), wherein,

intrinsic viscosity [ eta ] of propylene copolymer (I)]_ILess than 1.50dL/g,

propylene copolymer (I): which is a copolymer comprising a monomer unit derived from propylene and a monomer unit derived from at least one olefin selected from the group consisting of ethylene and an alpha-olefin having 4 or more and 12 or less carbon atoms, wherein,

a content of a monomer unit derived from at least one olefin selected from the group consisting of ethylene and an α -olefin having 4 to 12 carbon atoms is 0.05 wt% or more and less than 10 wt% (wherein the total weight of the propylene copolymer (I) is set as 100 wt%);

ethylene- α -olefin copolymer (II-1): which is a copolymer comprising a monomer unit derived from ethylene and a monomer unit derived from at least one olefin selected from the group consisting of propylene and an alpha-olefin having 4 or more and 12 or less carbon atoms, wherein,

a content of a monomer unit derived from ethylene is 10% by weight or more and 30% by weight or less (wherein the total weight of the ethylene- α -olefin copolymer (II-1) is set to 100% by weight);

ethylene- α -olefin copolymer (II-2): which is a copolymer comprising a monomer unit derived from ethylene and a monomer unit derived from at least one olefin selected from the group consisting of propylene and an alpha-olefin having 4 or more and 12 or less carbon atoms, wherein,

the content of monomer units derived from ethylene is 10% by weight or more and 30% by weight or less (wherein the total weight of the ethylene- α -olefin copolymer (II-2) is set to 100% by weight), and

the intrinsic viscosity of the ethylene- α -olefin copolymer (II-2) is higher than that of the ethylene- α -olefin copolymer (II-1).

[2]Such as [1]]The heterophasic propylene polymer material, wherein the intrinsic viscosity [ η ] of the xylene soluble fraction of the heterophasic propylene polymer material]_CXSRelative to the intrinsic viscosity [ eta ] of the xylene-insoluble fraction of the heterophasic propylene polymer material]_CXISRatio of ([ eta ]) of]_CXS/[η]_CXIS) Is 1.0 or more.

[3]Such as [1]]Or [ 2]]The heterophasic propylene polymer material, wherein the ethylene-alpha-olefin copolymer (II-1) is contained in an amount of a₁The content of the ethylene-alpha-olefin copolymer (II-2) is represented by a% by weight₂(wherein the total weight of the heterophasic propylene polymeric material is taken as 100 wt%);

the content of a monomer unit derived from ethylene in the ethylene-alpha-olefin copolymer (II-1) is set as b₁(wherein, the total weight of the ethylene- α -olefin copolymer (II-1) is set to 100% by weight); and is

Mixing ethylene-alpha-olefin copolymer (I)The content of the monomer units derived from ethylene in I-2) is set as b₂(wherein the total weight of the ethylene-alpha-olefin copolymer (II-2) is 100 wt%),

satisfies the following formula (3):

X＝(a₁b₁+a₂b₂)/(a₁+a₂) (1)

Y＝a₁+a₂(2)

Y≤4.37X-32.4 (3)。

[4] a propylene resin composition comprising a thermoplastic elastomer (III) and the heterophasic propylene polymer material of any one of [1] to [3 ].

[5] The propylene resin composition according to [4], wherein the propylene resin composition further comprises a filler (D).

[6] A propylene resin composition comprising a filler (D) and the heterophasic propylene polymer material of any one of [1] to [3 ].

[7] A molded article comprising the heterophasic propylene polymeric material according to any one of [1] to [3 ].

[8] A molded article comprising the propylene resin composition according to any one of [4] to [6 ].

Effects of the invention

According to the present invention, a heterophasic propylene polymer material can be provided which, when produced into a black molded article having an embossed design surface, can give a molded article that looks darker.

Detailed Description

< constitution of the heterophasic propylene polymer Material >

The heterophasic propylene polymeric material of the present invention is a propylene polymeric material comprising a propylene copolymer (I), an ethylene-alpha-olefin copolymer (II-1) and an ethylene-alpha-olefin copolymer (II-2).

The propylene copolymer (I) is a copolymer comprising a monomer unit derived from propylene and a monomer unit derived from at least one olefin selected from the group consisting of ethylene and an alpha-olefin having 4 or more and 12 or less carbon atoms, wherein the content of the monomer unit derived from at least one olefin selected from the group consisting of ethylene and an alpha-olefin having 4 or more and 12 or less carbon atoms is 0.05% by weight or more and less than 10% by weight relative to 100% by weight of the total weight of the propylene copolymer (I). The content of the monomer unit derived from at least one olefin is preferably 4% by weight or more and 7% by weight or less.

Intrinsic viscosity [ eta ] of propylene copolymer (I)]_ILess than 1.50 dL/g. From the viewpoint of flowability, the intrinsic viscosity [ eta ] of the propylene copolymer (I)]_IPreferably 1.0dL/g or less, more preferably 0.95dL/g or less. [ eta ]]_IPreferably 0.7dL/g or more, more preferably 0.8 dL/g or more.

Intrinsic viscosity [ eta ] of propylene copolymer (I)]_IFor example, the hydrogen concentration in the production of the propylene copolymer (I) can be adjusted. By increasing the hydrogen concentration in the production of the propylene copolymer (I), it is possible to reduce [ eta ]]_I。

In this specification, the intrinsic viscosity is an intrinsic viscosity measured in tetralin at a temperature of 135 ℃ and is determined by the calculation method described in reference "polymer solution, polymer experiment 11" (published by co-pending published 1982) item 491, that is, an extrapolation method in which reduced viscosity is plotted against concentration and the concentration is extrapolated to zero. As for reduced viscosity, reduced viscosities at 3 points of concentrations of 0.1g/dL, 0.2g/dL and 0.5g/dL were measured by an Ubbelohde viscometer under the conditions of a tetralin solvent at a temperature of 135 ℃.

Examples of the propylene copolymer (I) include:

(1) a propylene-ethylene copolymer having a content of a monomer unit derived from propylene of more than 90% by weight and 99.95% by weight or less and a content of a monomer unit derived from ethylene of 0.05% by weight or more and less than 10% by weight (wherein the total weight of the propylene-ethylene copolymer is set as 100% by weight);

(2) a propylene-ethylene- α -olefin copolymer having a content of a monomer unit derived from propylene of more than 90% by weight and 99.95% by weight or less, a content of a monomer unit derived from ethylene of more than or equal to 0.05% by weight and less than 10% by weight, and a content of a monomer unit derived from an α -olefin having 4 or more and 12 or less carbon atoms of more than 0% by weight and less than 10% by weight (wherein the total weight of the propylene-ethylene- α -olefin copolymer is set to 100% by weight); and

(3) a propylene- α -olefin copolymer having a content of a monomer unit derived from propylene of greater than 90% by weight and 99.95% by weight or less and a content of a monomer unit derived from an α -olefin having 4 or more and 12 or less carbon atoms of greater than or equal to 0.05% by weight and less than 10% by weight (wherein the total weight of the propylene- α -olefin copolymer is set to 100% by weight).

The ethylene- α -olefin copolymer (II-1) is a copolymer comprising a monomer unit derived from ethylene and a monomer unit derived from at least one olefin selected from the group consisting of propylene and an α -olefin having 4 or more and 12 or less carbon atoms, wherein the content of the monomer unit derived from ethylene is 10% by weight or more and 30% by weight or less with respect to 100% by weight of the total weight of the ethylene- α -olefin copolymer (II-1). The content of the monomer unit derived from ethylene is preferably 15% by weight or more and 25% by weight or less, more preferably 18% by weight or more and 25% by weight or less.

The ethylene- α -olefin copolymer (II-2) is a copolymer comprising a monomer unit derived from ethylene and a monomer unit derived from at least one olefin selected from the group consisting of propylene and an α -olefin having 4 or more and 12 or less carbon atoms, wherein the content of the monomer unit derived from ethylene is 10% by weight or more and 30% by weight or less relative to 100% by weight of the total weight of the ethylene- α -olefin copolymer (II-2), and the intrinsic viscosity of the ethylene- α -olefin copolymer (II-2) is higher than that of the ethylene- α -olefin copolymer (II-1). The content of the monomer unit derived from ethylene is preferably 15% by weight or more and 25% by weight or less, more preferably 18% by weight or more and 25% by weight or less.

The propylene copolymer (I), the ethylene- α -olefin copolymer (II-1), and the ethylene- α -olefin copolymer (II-2) have a monomer unit derived from at least one olefin selected from the group consisting of α -olefins having 4 to 12 carbon atoms derived from α -olefins having 4 to 12 carbon atoms, and specific examples thereof include: 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2, 4-trimethyl-1-pentene and the like, preferably 1-butene, 1-hexene or 1-octene, more preferably 1-butene.

In one example, the propylene copolymer (I) may be a random copolymer. In one example, the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) may be random copolymers.

Examples of the propylene copolymer (I) include: propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-1-decene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, propylene-ethylene-1-octene copolymers, propylene-ethylene-1-decene copolymers and the like, with propylene-ethylene copolymers, propylene-1-butene copolymers or propylene-ethylene-1-butene copolymers being preferred.

Examples of the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) include: ethylene-propylene copolymers, ethylene-propylene-1-butene copolymers, ethylene-propylene-1-hexene copolymers, ethylene-propylene-1-octene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers and the like, preferably ethylene-propylene copolymers, ethylene-1-butene copolymers or ethylene-1-octene copolymers, more preferably ethylene-propylene copolymers.

In the present specification, a specific example of the heterophasic propylene polymer material is described as "(propylene copolymer (I)) - (ethylene- α -olefin copolymer) heterophasic polymer material". For example, the description of "(ethylene-propylene) - (ethylene-propylene) heterophasic polymeric material" refers to a heterophasic propylene polymeric material in which the propylene copolymer (I) is an ethylene-propylene copolymer and the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) are ethylene-propylene copolymers.

In the case where the propylene copolymer (I) in the heterophasic propylene polymeric material is an ethylene-propylene copolymer, examples of such polymeric materials include: (ethylene-propylene) - (ethylene-propylene) heterophasic polymeric material, (ethylene-propylene) - (ethylene-propylene-1-butene) heterophasic polymeric material, (ethylene-propylene) - (ethylene-propylene-1-octene) heterophasic polymeric material, (ethylene-propylene) - (ethylene-1-butene) heterophasic polymeric material, (ethylene-propylene) - (ethylene-1-octene) heterophasic polymeric material, etc.

As the heterophasic propylene polymer material, a (ethylene-propylene) - (ethylene-propylene) heterophasic polymer material, an (ethylene-propylene) - (ethylene-propylene-1-butene) heterophasic polymer material, an (ethylene-propylene) - (ethylene-1-butene) heterophasic polymer material, or an (ethylene-propylene) - (ethylene-1-octene) heterophasic polymer material is preferred.

In the present description, the "xylene insoluble fraction" of the heterophasic propylene polymeric material refers to the fraction insoluble in p-xylene contained in the heterophasic propylene polymeric material, and refers to the solid matter obtained by the following process.

2g of a heterophasic propylene polymer material was completely dissolved in 2000mL of boiling p-xylene to obtain a solution, which was subsequently cooled to 25 ℃ and left to stand, as a solid material precipitated in the 25 ℃ solution.

In the present description, the "xylene soluble fraction" of the heterophasic propylene polymeric material refers to the fraction of the heterophasic propylene polymeric material other than the xylene insoluble fraction.

For the heterophasic propylene polymeric material of the present invention, the intrinsic viscosity [ eta ] of the xylene soluble fraction of the heterophasic propylene polymeric material]_CXSRelative to the intrinsic viscosity [ eta ] of the xylene-insoluble fraction of the heterophasic propylene polymer material]_CXISRatio of ([ eta ]) of]_CXS/[η]_CXIS) Preferably 1.0 or more. [ eta ]]_CXS/[η]_CXISMore preferably 1.1 or more, still more preferably 1.2 or more, and still more preferably 1.3 or more.

[η]_CXS/[η]_CXISFor example, the hydrogen concentration in the production of the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) can be adjusted. When each copolymer is produced, the intrinsic viscosity of the copolymer can be reduced when the hydrogen concentration is increased, and the intrinsic viscosity of the copolymer can be increased when the hydrogen concentration is decreasedIntrinsic viscosity of the copolymer. As a result of]_CXS/[η]_CXISThe intrinsic viscosity of the propylene copolymer (I) is adjusted to 1.0 or more, and a method of making the intrinsic viscosity of the propylene copolymer (I) smaller than the intrinsic viscosity of at least one of the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) is mentioned, and preferably a method of making the intrinsic viscosity of the propylene copolymer (I) smaller than the intrinsic viscosity of the ethylene- α -olefin copolymer (II-1) and the intrinsic viscosity of the ethylene- α -olefin copolymer (II-2). The hydrogen concentration at the time of producing each copolymer was adjusted in such a manner.

The heterophasic propylene polymer material of the present invention is given the content of the ethylene-alpha-olefin copolymer (II-1) as a₁The content of the ethylene-alpha-olefin copolymer (II-2) is represented by a% by weight₂(wherein the total weight of the heterophasic propylene polymeric material is taken as 100 wt%);

the content of a monomer unit derived from ethylene in the ethylene-alpha-olefin copolymer (II-1) is set as b₁(wherein, the total weight of the ethylene- α -olefin copolymer (II-1) is set to 100% by weight); and is

The content of a monomer unit derived from ethylene in the ethylene-alpha-olefin copolymer (II-2) is set as b₂(wherein the total weight of the ethylene-alpha-olefin copolymer (II-2) is 100 wt%),

it preferably satisfies the following formula (3).

X＝(a₁b₁+a₂b₂)/(a₁+a₂) (1)

Y＝a₁+a₂(2)

Y≤4.37X-32.4 (3)

The formula (3) can be adjusted by adjusting, for example, the polymerization temperature, the polymerization pressure and the residence time in producing the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2). When the polymerization temperature is increased, the content of the copolymer produced in the reactor can be increased. When the polymerization pressure is increased, the content of the monomer unit derived from ethylene in the copolymer produced in the reactor can be increased. When the residence time is prolonged, the content of the copolymer produced in the reactor can be increased.

X is preferably 17 or more and 23 or less. Y is preferably 30 or more and 50 or less, more preferably 40 or more and 50 or less, and further preferably 42 or more and 50 or less.

The total content of the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) contained in the heterophasic propylene polymer material is preferably 20 wt% or more and 70 wt% or less, more preferably 30 wt% or more and 60 wt% or less, and still more preferably 30 wt% or more and 50 wt% or less (the total weight of the heterophasic propylene polymer material is taken as 100 wt%). The content of the ethylene- α -olefin copolymer (II-2) contained in the heterophasic propylene polymer material is preferably 5 wt% or more and 15 wt% or less (wherein the total weight of the heterophasic propylene polymer material is taken as 100 wt%).

The intrinsic viscosity of the ethylene- α -olefin copolymer (II-1) measured in tetralin at 135 ℃ is preferably 0.1dL/g or more and 5dL/g or less, more preferably 1.0dL/g or more and 5.0dL/g or less, and still more preferably 1.5dL/g or more and 4.0dL/g or less.

The intrinsic viscosity of the ethylene- α -olefin copolymer (II-2) measured in tetralin at 135 ℃ is preferably 5.0 to 10dL/g, more preferably 5.0 to 9.0dL/g, and still more preferably 5.0 to 8.0 dL/g. The intrinsic viscosity of the ethylene- α -olefin copolymer (II-2) is higher than that of the ethylene- α -olefin copolymer (II-1), and the difference between the intrinsic viscosity of the ethylene- α -olefin copolymer (II-2) and the intrinsic viscosity of the ethylene- α -olefin copolymer (II-1) is preferably 4dL/g to 8 dL/g.

Intrinsic viscosity [ eta ] of xylene soluble fraction of heterophasic propylene polymer materials]_CXSPreferably 0.1dL/g or more and 10dL/g or less, more preferably 1.0dL/g or more and 5.0dL/g or less, and still more preferably 1.5dL/g or more and 4.0dL/g or less.

The molecular weight distribution (Mw/Mn) of the xylene-soluble fraction of the heterophasic propylene polymer material is preferably 4.0 or more, more preferably 5.0 or more, even more preferably 6.0 or more, even more preferably 7.0 or more. The molecular weight distribution (Mw/Mn) of the xylene soluble fraction of the heterophasic propylene polymer material is preferably 50 or less.

The content of the monomer units derived from ethylene in the heterophasic propylene polymeric material is preferably 8 wt% or more and 30 wt% or less, more preferably 9 wt% or more and 25 wt% or less, even more preferably 10 wt% or more and 20 wt% or less (wherein the total weight of the heterophasic propylene polymeric material is taken as 100 wt%).

The melt flow rate of the heterophasic propylene polymeric material and compositions thereof is preferably 1g/10 min or more and 100g/10 min or less, more preferably 2g/10 min or more and 80g/10 min or less, even more preferably 3g/10 min or more and 60g/10 min or less. The melt flow rate was measured at 230 ℃ under a load of 2.16kg according to the method specified in JIS K6758.

In one example, the Izod impact strength of the heterophasic propylene polymer material and compositions thereof of the present invention, determined by the methods described in the examples to be described later, is preferably 3.0kJ/m²Above, more preferably 3.5kJ/m²Above, more preferably 4.0kJ/m²The above. The larger the value, the more excellent the low-temperature impact properties.

< method for producing heterophasic propylene polymer material >

The heterophasic propylene polymer material can be obtained by producing the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) in the same reactor by stepwise polymerization, or the heterophasic propylene polymer material can be obtained by producing the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) in steps in consecutive multi-stage reactors, or the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) produced in separate reactors can be blended. As the blending method, blending in a solution state, blending in a molten state, and the like can be cited.

The propylene copolymer (I), the ethylene-alpha-olefin copolymer (II-1) and the ethylene-alpha-olefin copolymer (II-2) are preferably produced stepwise in a continuous multistage reactor (multistage polymerization). The number of multistage reactors is not particularly limited, and for example, may be 6 stages in the polymerization of the propylene copolymer (I), and may be 2 stages in the polymerization of the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2). The propylene copolymer (I) may be polymerized first, or the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) may be polymerized first. The heterophasic propylene polymer material obtained by multistage polymerization has properties of higher physical properties such as low temperature impact properties because the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) are more uniformly dispersed than those obtained by blending the components produced in the respective reactors.

The following methods can be mentioned as methods for producing the heterophasic propylene polymer material of the present invention.

< manufacturing method 1 >

A method for producing a heterophasic propylene polymer material, comprising the following step (1-1) and the following step (1-2).

Step (1-1): a step of copolymerizing propylene with at least one olefin selected from the group consisting of ethylene and α -olefins having 4 to 12 carbon atoms in the presence of a propylene polymerization catalyst by a multi-stage polymerization method to obtain a propylene copolymer (I);

step (1-2): a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of the propylene copolymer (I) by a multistage polymerization method to obtain a heterophasic propylene polymer material containing the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1), and the ethylene- α -olefin copolymer (II-2).

< manufacturing method 2 >

A method for producing a heterophasic propylene polymer material, comprising the following step (2-1) and the following step (2-2).

Step (2-1): a step of copolymerizing ethylene and at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of a propylene polymerization catalyst by a multi-stage polymerization method to obtain an ethylene- α -olefin copolymer (II-1) and an ethylene- α -olefin copolymer (II-2).

Step (2-2): and (b) a step of copolymerizing propylene with at least one olefin selected from the group consisting of ethylene and an α -olefin having 4 to 12 carbon atoms in the presence of the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) by a multi-stage polymerization method to obtain a heterophasic propylene polymer material containing the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1), and the ethylene- α -olefin copolymer (II-2).

< production method 1-1 >

A method for producing a heterophasic propylene polymer material, which comprises the following step (1-1), the following step (1-2-1) and the following step (1-2-2).

Step (1-1): a step of copolymerizing propylene with at least one olefin selected from the group consisting of ethylene and α -olefins having 4 to 12 carbon atoms in the presence of a propylene polymerization catalyst by a multi-stage polymerization method to obtain a propylene copolymer (I);

step (1-2-1): a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of the propylene copolymer (I) to obtain a mixture of the propylene copolymer (I) and the ethylene- α -olefin copolymer (II-1);

step (1-2-2): and a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and an alpha-olefin having 4 to 12 carbon atoms in the presence of the mixture to obtain a heterophasic propylene polymer material comprising a propylene copolymer (I), an ethylene-alpha-olefin copolymer (II-1) and an ethylene-alpha-olefin copolymer (II-2).

< production method 1-2 >

A method for producing a heterophasic propylene polymer material, which comprises the following step (1-1), the following step (1-2-3) and the following step (1-2-4).

Step (1-1): a step of copolymerizing propylene with at least one olefin selected from the group consisting of ethylene and α -olefins having 4 to 12 carbon atoms in the presence of a propylene polymerization catalyst by a multi-stage polymerization method to obtain a propylene copolymer (I);

step (1-2-3): a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of the propylene copolymer (I) to obtain a mixture of the propylene copolymer (I) and the ethylene- α -olefin copolymer (II-2).

Step (1-2-4): and a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and an alpha-olefin having 4 to 12 carbon atoms in the presence of the mixture to obtain a heterophasic propylene polymer material comprising a propylene copolymer (I), an ethylene-alpha-olefin copolymer (II-1) and an ethylene-alpha-olefin copolymer (II-2).

More specifically, the production method 2 is the following production method 2-1 or production method 2-2.

< production method 2-1 >

A method for producing a heterophasic propylene polymer material, which comprises the following step (2-1-1), the following step (2-1-2) and the following step (2-2).

Step (2-1-1): and (II) a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of a propylene polymerization catalyst to obtain an ethylene- α -olefin copolymer (II-1).

Step (2-1-2): a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of the ethylene- α -olefin copolymer (II-1) to obtain a mixture of the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2).

Step (2-2): and (b) a step of copolymerizing propylene with at least one olefin selected from the group consisting of ethylene and an α -olefin having 4 to 12 carbon atoms in the presence of the mixture by a multistage polymerization method to obtain a heterophasic propylene polymer material comprising the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1), and the ethylene- α -olefin copolymer (II-2).

< manufacturing method 2-2 >

A method for producing a heterophasic propylene polymer material, which comprises the following step (2-1-3), the following step (2-1-4) and the following step (2-2).

Step (2-1-3): and (II) a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of a propylene polymerization catalyst to obtain an ethylene- α -olefin copolymer (II-2).

Step (2-1-4): a step of copolymerizing ethylene with at least one olefin selected from the group consisting of propylene and α -olefins having 4 to 12 carbon atoms in the presence of the ethylene- α -olefin copolymer (II-2) to obtain a mixture of the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2).

Step (2-2): and (b) a step of copolymerizing propylene with at least one olefin selected from the group consisting of ethylene and an α -olefin having 4 to 12 carbon atoms in the presence of the mixture by a multistage polymerization method to obtain a heterophasic propylene polymer material comprising the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1), and the ethylene- α -olefin copolymer (II-2).

The step (1-2-1), the step (1-2-2), the step (1-2-3), the step (1-2-4), the step (2-1-1), the step (2-1-2), the step (2-1-3) and the step (2-1-4) may be a multi-step polymerization or a one-step polymerization, independently of each other.

The multi-step polymerization method is a polymerization method in which monomers are polymerized in the presence of a polymerization catalyst in a plurality of reaction zones connected in series and includes the following steps a to c.

Step a: and a step of supplying a polymerization catalyst and a monomer to the first reaction zone at the most upstream side to polymerize the monomer, thereby obtaining a polymer.

And a step b: and a step of transferring the polymer obtained in the first reaction zone to a second reaction zone connected to the first reaction zone.

And c: and a step of supplying a monomer to the second reaction zone and polymerizing the monomer in the presence of the polymer obtained in the first reaction zone to obtain a polymer.

When the number of reaction regions connected in series is 3 or more, the steps corresponding to the step b and the step c are performed in the third reaction region and the reaction regions subsequent to the third reaction region.

As the multistage polymerization, there may be mentioned:

in a system in which a plurality of reactors each having one reaction region in one reactor are connected in series;

in the case of a reactor having a plurality of reaction zones in one reactor; and

the reaction is carried out in a system in which a reactor having one reaction region in one reactor and a reactor having a plurality of reaction regions in one reactor are connected.

As a reactor having a plurality of reaction zones in one reactor, a multi-stage spouted bed type reactor can be cited.

The number of reaction zones in the multi-step polymerization process is not particularly limited. In the step (1-1) or the step (2-2), the number of reaction zones in the multi-step polymerization method is preferably 6 to 10. In the step (1-2) or the step (2-1), the number of reaction zones in the multi-step polymerization method is preferably 2 to 5.

The method for producing a heterophasic propylene polymer material of the present invention may comprise the steps of: a catalyst component whose surface is covered with a polymer of an olefin is produced by polymerizing a small amount of the olefin (at least one of the olefins used in the original polymerization (generally referred to as main polymerization)) in the presence of a solid catalyst component and an organoaluminum compound (a chain transfer agent such as hydrogen may be used or an external electron donor may be used in order to adjust the molecular weight of the olefin polymer to be produced) (the polymerization is generally referred to as prepolymerization, and therefore the catalyst component is generally referred to as a prepolymerization catalyst component).

In the method for producing a heterophasic propylene polymer material of the present invention, the propylene polymerization catalyst described below is preferably used.

In one embodiment, a propylene polymerization catalyst obtained by, for example, contacting a solid catalyst component with an organoaluminum compound by a known method can be used. In another embodiment, a propylene polymerization catalyst obtained by contacting a solid catalyst component, an organoaluminum compound, and an external electron donor may be used.

As the solid catalyst component, the following solid catalyst components are preferably used.

A solid catalyst component for olefin polymerization, which contains at least one internal electron donor selected from the group consisting of a monoester compound, an aliphatic dicarboxylic acid ester compound, a diol diester compound, a β -alkoxy ester compound, and a diether compound, a titanium atom, a magnesium atom, and a halogen atom, and satisfies the following requirements (I) to (IV).

(I) According to standard ISO 15901-1: 2005 and a total pore volume, determined by mercury intrusion methods, of from 0.95mL/g to 1.80mL/g and according to Standard ISO 15901-1: 2005 and specific surface area measured by mercury intrusion method 60m²/g～170m²/g。

(II) in a reaction mixture according to standard ISO 13320: 2009 in a volume-based particle size distribution measured by a laser diffraction/scattering method, the cumulative percentage of components having a particle size of 10 μm or less is 6.5% or less.

(III) a reaction between a compound of formula (III) in a reaction mixture according to standard ISO 15472: 2001 and the peak component obtained by waveform separation of the peak attributed to the 1s orbital of the oxygen atom obtained by X-ray photoelectron spectroscopy, wherein the ratio (G/F) of the area (G) of the peak component having the peak top in the range of binding energy of 529eV or more and 532eV or less to the area (F) of the peak component having the peak top in the range of binding energy of 532eV or more and 534eV or less is 0.33 or less.

(IV) the titanium content is 1.50 to 3.40% by weight.

Such a solid catalyst component can be produced, for example, by the following method for producing a solid catalyst component: the production method comprises a step (I) of contacting a titanium halide compound solution containing a titanium halide compound and a solvent with a magnesium compound to obtain a slurry containing a solid product, wherein in the step (I), the ratio (A/C) of A represented by the following formula (1) to C represented by the following formula (2) is 3 or less.

A＝a/b (1)

a: volume (mL) of titanium halide compound contained in titanium halide compound solution

b: volume (mL) of solvent contained in titanium halide compound solution

C＝a/c (2)

a: volume (mL) of titanium halide compound contained in titanium halide compound solution

c: volume of solvent (mL) contained in slurry containing solid product

As the monoester compound used as the internal electron donor, an aromatic carboxylic acid ester compound and an aliphatic carboxylic acid ester compound are preferable. As the aromatic carboxylic acid ester compound, there may be mentioned: methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, octyl benzoate, methyl benzoate, ethyl methyl benzoate, propyl methyl benzoate, butyl methyl benzoate, pentyl methyl benzoate, hexyl methyl benzoate, octyl methyl benzoate and the like. As the aliphatic carboxylic acid ester compound, there may be mentioned: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, hexyl propionate, octyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, octyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, pentyl valerate, octyl valerate, methyl hexanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, pentyl hexanoate, hexyl hexanoate, octyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, butyl heptanoate, pentyl heptanoate, hexyl heptanoate, octyl heptanoate, methyl octanoate, ethyl octanoate, propyl octanoate, butyl octanoate, pentyl octanoate, hexyl octanoate, octyl octanoate, methyl nonanoate, ethyl nonanoate, propyl nonanoate, Butyl pelargonate, pentyl pelargonate, hexyl pelargonate, octyl pelargonate, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, pentyl caprate, hexyl caprate, octyl caprate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, hexyl laurate, octyl laurate, methyl myristate, ethyl myristate, propyl myristate, butyl myristate, pentyl myristate, hexyl myristate, octyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, pentyl palmitate, hexyl palmitate, octyl palmitate, methyl heptadecanoate, ethyl heptadecanoate, propyl heptadecanoate, butyl heptadecanoate, pentyl heptadecanoate, hexyl heptadecanoate, octyl heptadecanoate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, hexyl palmitate, octyl heptadecanoate, methyl heptadecanoate, octyl heptadecanoate, ethyl stearate, propyl stearate, butyl stearate, Amyl stearate, hexyl stearate, and octyl stearate.

Examples of the aliphatic dicarboxylic acid ester compound include: dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, dipentyl oxalate, dihexyl oxalate, dioctyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, dipentyl malonate, dihexyl malonate, dioctyl malonate, dimethyl succinate, diethyl succinate, dipropyl succinate, dipentyl succinate, dihexyl succinate, dioctyl succinate, dimethyl succinate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate, dipentyl glutarate, dihexyl glutarate, dioctyl glutarate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, dihexyl adipate, dioctyl adipate, dimethyl fumarate, diethyl fumarate, dioctyl phthalate, and the like, Dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, dioctyl fumarate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dioctyl maleate, dimethyl cyclohexane-1, 2-dicarboxylate, diethyl cyclohexane-1, 2-dicarboxylate, dipropyl cyclohexane-1, 2-dicarboxylate, dibutyl cyclohexane-1, 2-dicarboxylate, dipentyl cyclohexane-1, 2-dicarboxylate, dihexyl cyclohexane-1, 2-dicarboxylate, dioctyl cyclohexane-1, 2-dicarboxylate, dimethyl 1, 2-dicarboxylate, diethyl 1, 2-cyclohexene-1, 2-dicarboxylate, 1, 2-cyclohexene-1, 2-dicarboxylic acid dipropyl ester, 1, 2-cyclohexene-1, 2-diformyl dibutyl ester, 1, 2-cyclohexene-1, 2-diformyl dipentyl ester, 1, 2-cyclohexene-1, 2-diformyl dihexyl ester, 1, 2-cyclohexene-1, 2-diformyl dioctyl ester, 3-methylcyclohexane-1, 2-diformyl dimethyl ester, 3-methylcyclohexane-1, 2-diformyl diethyl ester, 3-methylcyclohexane-1, 2-diformyl dipropyl ester, 3-methylcyclohexane-1, 2-diformyl dibutyl ester, 3-methylcyclohexane-1, 2-diformyl dipentyl ester, 3-methylcyclohexane-1, dihexyl-2-dicarboxylate, dioctyl-3-methylcyclohexane-1, 2-dicarboxylate, dimethyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, diethyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dipropyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dibutyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dipentyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dihexyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dioctyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, and the like.

As the diol diester compound, there may be mentioned: 1, 2-propanediol dibenzoate, 1, 2-propanediol diacetate, 1, 2-butanediol dibenzoate, 1, 2-butanediol diacetate, 1, 2-cyclohexanediol dibenzoate, 1, 2-cyclohexanediol diacetate, 1, 3-propanediol dibenzoate, 1, 3-propanediol diacetate, 2, 4-pentanediol dibenzoate, 2, 4-pentanediol diacetate, 1, 2-cyclopentanediol dibenzoate, 1, 2-cyclopentanediol diacetate, 4-tert-butyl-6-methylcatechol dibenzoate, 4-tert-butyl-6-methylcatechol diacetate, 4-tert-butyl-6-methylresorcinol dibenzoate, and 4-tert-butyl-6-methylresorcinol diacetate, and the like.

As the β -alkoxy ester compound, there can be mentioned: methyl 2-methoxymethyl-3, 3-dimethylbutyrate, ethyl 2-methoxymethyl-3, 3-dimethylbutyrate, propyl 2-methoxymethyl-3, 3-dimethylbutyrate, butyl 2-methoxymethyl-3, 3-dimethylbutyrate, pentyl 2-methoxymethyl-3, 3-dimethylbutyrate, hexyl 2-methoxymethyl-3, 3-dimethylbutyrate, octyl 2-methoxymethyl-3, 3-dimethylbutyrate, methyl 3-methoxy-2-phenylpropionate, ethyl 3-methoxy-2-phenylpropionate, propyl 3-methoxy-2-phenylpropionate, butyl 3-methoxy-2-phenylpropionate, ethyl 2-methoxymethyl-3, 3-methoxymethyl-2-phenylpropionate, ethyl 3-methoxymethyl-2-phenylpropionate, butyl 3-methoxy-2-phenylpropionate, pentyl 3-methoxy-2-phenylpropionate, hexyl 3-methoxy-2-phenylpropionate, octyl 3-methoxy-2-phenylpropionate, methyl 2-ethoxymethyl-3, 3-dimethylbutyrate, ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate, propyl 2-ethoxymethyl-3, 3-dimethylbutyrate, butyl 2-ethoxymethyl-3, 3-dimethylbutyrate, pentyl 2-ethoxymethyl-3, 3-dimethylbutyrate, hexyl 2-ethoxymethyl-3, 3-dimethylbutyrate, octyl 2-ethoxymethyl-3, 3-dimethylbutyrate, methyl 3-ethoxy-2-phenylpropionate, Ethyl 3-ethoxy-2-phenylpropionate, propyl 3-ethoxy-2-phenylpropionate, butyl 3-ethoxy-2-phenylpropionate, pentyl 3-ethoxy-2-phenylpropionate, hexyl 3-ethoxy-2-phenylpropionate, octyl 3-ethoxy-2-phenylpropionate, methyl 2-propoxymethyl-3, 3-dimethylbutyrate, ethyl 2-propoxymethyl-3, 3-dimethylbutyrate, propyl 2-propoxymethyl-3, 3-dimethylbutyrate, butyl 2-propoxymethyl-3, 3-dimethylbutyrate, pentyl 2-propoxymethyl-3, 3-dimethylbutyrate, 2-propoxymethyl-3, hexyl 3-dimethylbutyrate, octyl 2-propoxymethyl-3, 3-dimethylbutyrate, methyl 3-propoxy-2-phenylpropionate, ethyl 3-propoxy-2-phenylpropionate, propyl 3-propoxy-2-phenylpropionate, butyl 3-propoxy-2-phenylpropionate, pentyl 3-propoxy-2-phenylpropionate, hexyl 3-propoxy-2-phenylpropionate, octyl 3-propoxy-2-phenylpropionate, methyl 2-methoxybenzoate, ethyl 2-methoxybenzoate, propyl 2-methoxybenzoate, butyl 2-methoxybenzoate, pentyl 2-methoxybenzoate, hexyl 3-propoxy-2-phenylpropionate, ethyl 3-propoxy-2-phenylpropionate, propyl 3-propoxy-2-phenylpropionate, octyl 2-methoxybenzoate, butyl 2, 2-methoxy octyl benzoate, 2-ethoxy methyl benzoate, 2-ethoxy ethyl benzoate, 2-ethoxy propyl benzoate, 2-ethoxy butyl benzoate, 2-ethoxy pentyl benzoate, 2-ethoxy hexyl benzoate, 2-ethoxy octyl benzoate and the like.

As the diether compound, there can be mentioned: 1, 2-dimethoxypropane, 1, 2-diethoxypropane, 1, 2-dipropoxypropane, 1, 2-dibutoxypropane, 1, 2-di-tert-butoxypropane, 1, 2-diphenoxypropane, 1, 2-dibenzyloxypropane, 1, 2-dimethoxybutane, 1, 2-diethoxybutane, 1, 2-dipropoxybutane, 1, 2-dibutoxybutane, 1, 2-di-tert-butoxybutane, 1, 2-diphenoxybutane, 1, 2-dibenzyloxybutane, 1, 2-dimethoxycyclohexane, 1, 2-diethoxycyclohexane, 1, 2-dipropoxycyclohexane, 1, 2-dibutoxycyclohexane, 1, 2-di-tert-butoxycyclohexane, 1, 2-diphenoxycyclohexane, 1, 2-dibenzyloxycyclohexane, 1, 3-dimethoxypropane, 1, 3-diethoxypropane, 1, 3-dipropoxypropane, 1, 3-dibutoxypropane, 1, 3-di-tert-butoxypropane, 1, 3-diphenoxypropane, 1, 3-dibenzyloxypropane, 2, 4-dimethoxypentane, 2, 4-diethoxypentane, 2, 4-dipropoxypentane, 2, 4-dibutoxypentane, 2, 4-di-tert-butoxypentane, 2, 4-diphenoxypentane, 2, 4-dibenzyloxypentane, 1, 2-dimethoxycyclopentane, 1, 2-diethoxycyclopentane, 1, 2-dipropoxycyclopentane, 1, 2-dibutoxycyclopentane, 1, 3-dimethoxypropane, 1, 3-diethoxypropane, 2-diethoxypentane, 1, 2-di-tert-butoxycyclopentane, 1, 2-diphenoxycyclopentane, 1, 2-dibenzyloxycyclopentane, 9-bis (methoxymethyl) fluorene, 9-bis (ethoxymethyl) fluorene, 9-bis (propoxymethyl) fluorene, 9-bis (butoxymethyl) fluorene, 9-bis (tert-butoxymethyl) fluorene, 9-bis (phenoxymethyl) fluorene, 9-bis (benzyloxymethyl) fluorene, 1, 2-dimethoxybenzene, 1, 2-diethoxybenzene, 1, 2-dipropoxybenzene, 1, 2-dibutoxybenzene, 1, 2-di-tert-butoxybenzene, 1, 2-diphenoxybenzene, and 1, 2-dibenzyloxybenzene, etc.

Further, the internal electron donor described in Japanese patent application laid-open No. 2011-246699 can also be used.

As the internal electron donor, a dicarboxylic acid ester compound, a diol diester compound, and a β -alkoxy ester compound are preferable. The internal electron donors can be used independently or in combination of two or more.

Examples of the organoaluminum compound include those described in Japanese patent application laid-open No. 10-212319. Among them, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane is preferable, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldialumoxane is more preferable.

Examples of the external electron donor include compounds described in Japanese patent No. 2950168, Japanese patent application laid-open No. 2006-96936, Japanese patent application laid-open No. 2009-173870, and Japanese patent application laid-open No. 2010-168545. Among them, oxygen-containing compounds or nitrogen-containing compounds are preferable. Examples of the oxygen-containing compound include silicon alkoxides, ethers, esters, and ketones. Among them, silicon alkoxides or ethers are preferable, and examples thereof include: cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, isobutyltriethoxysilane, vinyltriethoxysilane, sec-butyltriethoxysilane, cyclohexyltriethoxysilane, cyclopentyltriethoxysilane.

As the solvent, inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene are preferable.

The method for producing a heterophasic propylene polymer material may comprise a step of polymerizing a small amount of olefin in the presence of a solid catalyst component and an organoaluminum compound to produce a catalyst component having a surface covered with a polymer of the olefin (this polymerization is usually referred to as prepolymerization, and therefore this catalyst component is usually referred to as a prepolymerization catalyst component). The olefin used for the prepolymerization is at least one of the olefins constituting the heterophasic propylene polymer material. In the preliminary polymerization step, a chain transfer agent such as hydrogen may be used or an external electron donor may be used in order to adjust the molecular weight of the olefin polymer to be produced.

In one embodiment, the organoaluminum compound is preferably 0.1 to 700 moles, and preferably 0.2 to 200 moles per 1 mole of the transition metal atom contained in the solid catalyst component in the preliminary polymerization. The external electron donor is preferably 0.01 to 400 moles per 1 mole of the transition metal atom contained in the solid catalyst component. The solid catalyst component contained in 1L of the solvent is preferably 1g to 500 g. The amount of the olefin to be prepolymerized is usually 0.1g to 200g per 1g of the solid catalyst component.

In one embodiment, the propylene copolymer (I) may be produced by multi-stage polymerization, followed by producing the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2) by multi-stage polymerization. More specifically, the propylene copolymer (I) can be produced by multi-stage polymerization using a vessel type reactor and a gas phase reactor, followed by producing the ethylene- α -olefin copolymer (II-1) using a gas phase reactor, followed by producing the ethylene- α -olefin copolymer (II-2) using a gas phase reactor.

In the first step in the production of the propylene copolymer (I), for example, a vessel type reactor can be used. The polymerization temperature may be, for example, 0 ℃ to 120 ℃. The polymerization pressure may be, for example, from atmospheric pressure to 10 MPaG.

In the second step in the production of the propylene copolymer (I), for example, a gas phase reactor may be used. The polymerization temperature is, for example, preferably 40 to 80 ℃ and more preferably 40 to 75 ℃. The polymerization pressure is, for example, preferably from atmospheric pressure to 10MPaG, more preferably from atmospheric pressure to 2.0 MPaG.

In the production of the ethylene- α -olefin copolymer (II-1), for example, a gas phase reactor can be used. The polymerization temperature is preferably 0 to 120 ℃ for example. The polymerization pressure is, for example, preferably from atmospheric pressure to 10MPaG, more preferably from atmospheric pressure to 2.0 MPaG.

In the production of the ethylene- α -olefin copolymer (II-2), for example, a gas phase reactor can be used. The polymerization temperature is preferably 0 to 120 ℃ for example. The polymerization pressure is, for example, preferably from atmospheric pressure to 10MPaG, more preferably from atmospheric pressure to 2.0 MPaG.

< propylene resin composition >

The heterophasic propylene polymer material may be combined with other ingredients to make a propylene resin composition.

As one embodiment of the propylene resin composition of the present invention, a propylene resin composition containing the above-mentioned heterophasic propylene polymer material and the thermoplastic elastomer (III) is preferred from the viewpoint of impact strength of a molded article or from the viewpoint of blacker appearance when a black molded article having an embossed design surface is produced.

The content of the thermoplastic elastomer (III) in the propylene resin composition is preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the content of the heterophasic propylene polymer material.

Examples of the thermoplastic elastomer (III) include olefinic thermoplastic elastomers and styrenic thermoplastic elastomers.

As olefinic thermoplastic elastomersThe body may be, for example: propylene-1-butene copolymer having a density of less than 0.880g/cm³An ethylene-propylene copolymer of (1). The content of the monomer unit derived from 1-butene in the propylene-1-butene copolymer is preferably 4% by weight or more and 10% by weight or less. The density is less than 0.880g/cm³The content of the monomer unit derived from ethylene in the ethylene-propylene copolymer of (3) is preferably 4% by weight or more and 10% by weight or less.

In the present specification, the styrenic thermoplastic elastomer means a block copolymer and a hydrogenated product thereof as follows: the block copolymer has a polymer block comprising monomer units derived from an aromatic vinyl compound and a polymer block comprising monomer units derived from a conjugated diene compound. Examples of the styrenic thermoplastic elastomer include: styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, and the like.

The thermoplastic elastomer (III) is preferably chosen from the group consisting of propylene-1-butene copolymers and having a density of less than 0.880g/cm³At least one polymer of the group consisting of ethylene-propylene copolymers of (a).

The propylene resin composition containing the above-mentioned heterophasic propylene polymer material and the thermoplastic elastomer (III) preferably further comprises a filler (D) as described later.

As one embodiment of the propylene resin composition of the present invention, there can be mentioned a propylene resin composition comprising the above-mentioned heterophasic propylene polymer material and a filler (D). Examples of the filler (D) include inorganic fibers and organic fibers. The filler (D) is preferably an inorganic fiber.

Examples of the inorganic fibers include glass fibers and carbon fibers; examples of the organic fiber include polyester fiber and aramid fiber.

The average length of the filler (D) in the propylene resin composition of the present invention is preferably from 400 to 800. mu.m, more preferably from 450 to 700. mu.m.

In the present specification, the average length of the filler (D) in the propylene resin composition means a weight-average fiber length measured by the method described in Japanese patent application laid-open No. 2002-5924.

The average length of the filler (D) in the propylene resin composition can be controlled by appropriately adjusting the kneading strength in producing the propylene resin composition by melt-kneading. For example, when a twin-screw kneader is used, the kneading strength is stronger than when a single-screw kneader is used, and the average length of the filler (D) can be made shorter than before kneading. Further, by increasing the groove depth of the screw in the kneader, the kneading strength can be weakened, and the average length of the filler (D) can be made longer.

In the propylene resin composition of the present invention, the content of the filler (D) is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight to 20 parts by weight, and even more preferably 1 part by weight to 15 parts by weight, with respect to 100 parts by weight of the polymer component in the propylene resin composition, from the viewpoint of strength, heat resistance, dimensional stability, and weight reduction of a molded article including the propylene resin composition.

One embodiment of the propylene resin composition of the present invention includes a propylene resin composition comprising the above-mentioned heterophasic propylene polymer material and an olefin-based polymer other than the propylene copolymer (I), the ethylene- α -olefin copolymer (II-1) and the ethylene- α -olefin copolymer (II-2). Examples of the olefin-based polymer include ethylene-based polymers. In the present specification, an ethylene-based polymer refers to a polymer having a content of monomer units derived from ethylene of more than 50% by weight. Examples of the ethylene polymer include: ethylene homopolymers, copolymers of ethylene and propylene, copolymers of ethylene and alpha-olefins having 4 to 20 carbon atoms, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, and the like. As the ethylene homopolymer, low density polyethylene, medium density polyethylene and high density polyethylene can be cited. Examples of the copolymer of ethylene and an α -olefin having 4 to 20 carbon atoms include: ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and the like.

The olefin-based polymer may be one kind or two or more kinds. The amount of the olefinic polymer to be blended is preferably from 0.1 to 40% by weight, more preferably from 1 to 30% by weight, relative to the entirety of the heterophasic propylene polymeric material.

Additives such as a heat-resistant stabilizer, an ultraviolet stabilizer, an antioxidant, a crystal nucleating agent, a lubricant, a colorant, an anti-blocking agent, an antistatic agent, an antifogging agent, a flame retardant, a petroleum resin, a foaming agent, a foaming aid, an organic filler, an inorganic filler and the like may be added to the heterophasic propylene polymer material of the present invention as required. The additive is preferably added in an amount of 0.01 wt% or more, and preferably 30 wt% or less, relative to the entire heterophasic propylene polymer material. One additive may be used alone, or two or more additives may be used in combination at an arbitrary ratio.

As the colorant, there may be mentioned: inorganic pigments, organic pigments. Examples of the inorganic pigment include: carbon black, iron oxide, titanium oxide, zinc oxide, red iron oxide, cadmium red, cadmium yellow, ultramarine, cobalt blue, titanium yellow, lead white, red lead, lead yellow, Prussian blue and the like. Examples of the organic pigment include: quinacridone, polyazo yellow, anthraquinone yellow, polyazo red, azo lake yellow, perylene, phthalocyanine green, phthalocyanine blue, isoindolinone yellow, and the like. The amount of the colorant added is preferably 0.05% by weight or more, and preferably 5% by weight or less, relative to the entire heterophasic propylene polymer material.

The method for producing the propylene resin composition of the present invention includes, for example, a case where a colorant is added, and the following methods:

(1) a method in which a prescribed amount of a heterophasic propylene polymer material, and if necessary, a thermoplastic elastomer, a filler, a colorant and other ingredients are dry-blended and then melt-kneaded; (2) a method of directly charging and kneading a heterophasic propylene polymer material and, if necessary, a thermoplastic elastomer, a filler, a colorant and other components into a kneading apparatus of a molding machine in the production process of a molded article; and the like.

In addition, in the production of the propylene resin composition of the present invention, a master batch containing a thermoplastic resin containing a colorant whose concentration is adjusted can be used.

The heterophasic propylene polymer material of the present invention can be suitably used in molding methods such as extrusion molding, injection molding, compression molding, foam molding, blow molding, vacuum molding, powder molding, calendering, inflation, and press molding.

Examples of uses of the heterophasic propylene polymer material of the present invention include: automobile parts such as automobile interior parts and exterior parts, food and medical containers, parts of furniture or electric products, civil engineering and construction materials, and the like. Examples of the automobile interior parts include: instrument panels, interior trim, door panels, body molding, inter-seat storage bins, pillar covers, and the like. Examples of the automobile exterior parts include: bumpers, fenders, wheel covers, and the like. Examples of the food and medical containers include: preservative films, food containers, infusion bags, infusion bottles and the like. Examples of the parts of furniture or electric appliances include: wallpaper, floor material, decorative sheet, drainage hose of washing machine, etc. Examples of civil engineering and construction materials include: waterproof sheet, water retaining sheet, hose, pipeline, gasket, etc. The water guard sheet is a sheet laid in a final disposal site or the like so as not to allow water, rainwater, or the like contained in waste to seep out.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. Needless to say, the present invention is not limited to the following examples, and various modes can be provided for details. The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and embodiments obtained by appropriately combining the respective disclosed technical means are also included in the technical scope of the present invention. In addition, all documents described in the present specification are incorporated by reference.