JP6143876B2 - PP compound with excellent mechanical properties, improved or non-occurring tiger stripes - Google Patents

Description

  The present invention relates to a polypropylene composition (PP), the use of said polypropylene composition to produce molded articles and articles comprising said polypropylene composition (PP) and to reduce the tiger stripe on the surface of the article. To the use of said polypropylene composition (PP).

  Currently, polypropylene is generally preferred as a polymer for automotive parts such as bumpers, door panels, dashboards or door cladding. In particular, heterophasic propylene copolymers are suitable because they combine rigidity and good impact behavior. Heterogeneous propylene copolymers are well known in the art and include a matrix that is either a polypropylene homopolymer or a random polypropylene copolymer, in which an elastic copolymer is dispersed. That is, the polypropylene matrix contains inclusions that are not (partially) dispersed that are not part of the matrix, and the inclusions contain elastomers. The term inclusions indicates that the matrix and inclusions form different phases in the heterophasic propylene copolymer and that the inclusions are visible, for example, with a high resolution microscope, such as an electron microscope or an atomic force microscope.

  While commercially available polypropylene achieves a very good balance between stiffness and impact resistance, the overall profile requirements of such systems are constantly becoming more stringent. For example, polypropylene is typically injection molded into desired articles such as automotive and household items. However, such articles are relatively large, such as automobile bumpers, door panels, dashboards, or door exterior materials, which can cause optical irregularities due to the need for long polypropylene resin flow paths. There are many.

  Such surface defects, also known as tiger stripes, flow marks or flow lines, are continuous during injection molding as a band-like strong and weak part perpendicular to the direction of the melt flow. Appear alternately, deteriorating the beauty of the surface.

  In this regard, many attempts have been made to avoid these surface defects while maintaining a good balance of other physical properties, eg DE 19754061. However, it has been found that either the occurrence of tiger stripes cannot be sufficiently prevented or the mechanical properties of the polymer composition are not satisfactory.

  Thus, there is still a need in the art to further reduce the occurrence of tiger stripes. In addition, it is necessary not only to reduce the occurrence of tiger stripes, but also to keep mechanical properties such as impact / rigid behavior at a very high level.

  Accordingly, it is an object of the present invention to provide a polypropylene composition that exhibits no or very little tiger stripes on the surface of the manufactured article. In addition, it is an object of the present invention to provide a polypropylene composition that does not exhibit tiger stripes but also retains mechanical properties such as excellent balanced stiffness / impact behavior.

  The foregoing and other objectives are solved by the subject matter of the present invention.

A particular finding of the present invention is to provide a polypropylene composition (PP) comprising a combination of two heterophasic propylene copolymers that differ in melt flow rate MFR _{2 and} are present in specific amounts.

According to a first aspect of the invention,
a) a first heterophasic propylene copolymer (HPP1) having a melt flow rate MFR ₂ (230 ° C., 2.16 kg) from 20.0 g / 10 min to 80.0 g / 10 min, and b) 0.05 g / 10 min to 2 Second heterophasic propylene copolymer (HPP2) having a melt flow rate MFR ₂ (230 ° C., 2.16 kg) up to 0.0 g / 10 min
A polypropylene composition (PP) comprising
i) The amount of the first heterophasic propylene copolymer (HPP1) is from 66.6 wt% to 95.2 wt% based on the total weight of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) Within the range of
ii) The amount of the second heterophasic propylene copolymer (HPP2) is from 4.8 wt% to 33.4 wt% based on the total weight of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) Is within the range of
The polypropylene composition (PP) is provided.

  Surprisingly, it has been found that the polypropylene composition (PP) of the present invention shows no or very little tiger stripes on the surface of the manufactured article. Furthermore, the parts of the polypropylene composition (PP) of the present invention do not show tiger stripes, but also have important mechanical properties such as stiffness and impact behavior, which are at the same high level as prior art products.

  For the purposes of the present invention, it should be understood that the following terms have the following meanings:

  The expression “heterophasic” indicates that the elastic copolymer is (finely) dispersed in the matrix. In other words, the elastic propylene copolymer forms inclusions in the matrix. Thus, the matrix contains (finely) dispersed inclusions that are not part of the matrix, said inclusions containing an elastic propylene copolymer. The term “inclusions” in the present invention preferably means that the matrix and inclusions form different phases in the heterophasic propylene copolymer, said inclusions being, for example, a high resolution microscope such as an electron microscope or an atomic force microscope. It shows that it can be seen.

  The final composition probably has a complex structure. For example, the matrix of the heterophasic propylene copolymer forms a continuous or discontinuous phase that is the matrix of the composition, in which the elastic copolymer and any additives are dispersed together or individually in the matrix. There is a possibility of forming an object.

  According to another aspect of the present invention there is provided an article comprising said polypropylene composition (PP), preferably consisting of said polypropylene composition (PP). The article is preferably a molded article, preferably an injection molded article. A still further aspect of the invention relates to the use of said polypropylene composition (PP) for producing a molded article, preferably an injection molded article. A still further aspect of the invention relates to the use of said polypropylene composition (PP) in the manufacture of an article for reducing tiger stripes on the surface of the article.

  In the following, when reference is made to preferred embodiments or technical details of the polypropylene composition (PP) of the present invention, these preferred embodiments or technical details refer to articles and moldings of the present invention comprising the polypropylene composition (PP). It is understood that the present invention also relates to the use of the polypropylene composition (PP) of the present invention to produce articles and the use of the polypropylene composition (PP) of the present invention in articles to reduce tiger stripes on the surface of the article. Should.

According to one embodiment of the present invention, the first heterophasic propylene copolymer (HPP1) has a) a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 20.0 g / 10 min to 75.0 g / 10 min. And / or b) a low temperature xylene soluble fraction (XCS) fraction (25 ° C.) of 15.0 wt% to 25.0 wt% relative to the total weight of the first heterophasic propylene copolymer (HPP1), and / or c) an ethylene content of less than 15.0 wt% relative to the total weight of the first heterophasic propylene copolymer (HPP1), and / or d) an intrinsic viscosity (IV) of 2.0 dl / g to 3.0 dl / g 33.0 wt% to 40.0 w based on the total weight of the amorphous (AM) phase and / or e) the amorphous (AM) phase of the first heterophasic propylene copolymer (HPP1) Having an amorphous (AM) phase having a% of ethylene content.

According to another embodiment of the present invention, the second heterophasic propylene copolymer (HPP2) is a) a melt flow rate MFR ₂ (230 ° C., 2.16 kg) from 0.1 g / 10 min to 2.0 g / 10 min. And / or b) a low temperature xylene soluble fraction (XCS) fraction (25 ° C.) from 9.0 wt% to 20.0 wt% with respect to the total weight of the second heterophasic propylene copolymer (HPP2), and / or c ) Ethylene content from 3.0 wt% to 8.0 wt% with respect to the total weight of the second heterophasic propylene copolymer (HPP2), and / or d) intrinsic viscosity from 3.0 dl / g to 4.0 dl / g 30.0 wt% to 37 wt% with respect to the total weight of the amorphous (AM) phase with (IV) and / or the amorphous (AM) phase of the e) second heterophasic propylene copolymer (HPP2). Having an amorphous (AM) phase having an ethylene content of 0 wt%.

According to yet another embodiment of the present invention, the first heterophasic propylene copolymer (HPP1) comprises a polypropylene homopolymer matrix (PM1) and an elastic propylene copolymer (AM1) dispersed in the matrix (PM1). And / or the second heterophasic propylene copolymer (HPP2) comprises a polypropylene homopolymer matrix (PM2) and an elastic propylene copolymer (AM2) dispersed in said matrix (PM2). The polypropylene homopolymer matrix (PM1) of the first heterophasic propylene copolymer (HPP1) is a) a melt flow rate MFR ₂ (230 ° C., 2.16 kg) from 30.0 g / 10 min to 250.0 g / 10 min, and / or Or b) Low temperature xylene soluble fraction (XCS) fraction (25 ° C.) from 0.8 wt% to 3.0 wt% based on the total weight of the polypropylene homopolymer matrix (PM1) of the first heterophasic propylene copolymer (HPP1) It is preferable to have. The polypropylene heteropolymer matrix (PM2) of the second heterophasic propylene copolymer (HPP2) is a) a melt flow rate MFR ₂ (230 ° C., 2.16 kg) from 0.1 g / 10 min to 3.0 g / 10 min, and / or Or b) having a low temperature xylene soluble fraction (XCS) fraction (25 ° C.) of less than 2.0 wt% relative to the total weight of the polypropylene homopolymer matrix (PM2) of the second heterophasic propylene copolymer (HPP2). preferable.

  According to one embodiment of the present invention, the polypropylene composition (PP) comprises 40.0 wt% to 60.0 wt% of the first heterophasic propylene copolymer (HPP1) relative to the total weight of the polypropylene composition (PP). ), 3.0 wt% to 20.0 wt% of the second heterophasic propylene copolymer (HPP2) based on the total weight of the polypropylene composition (PP), 5.0 wt% based on the total weight of the polypropylene composition (PP) ˜20.0 wt% elastic ethylene copolymer (EE), said elastic ethylene copolymer (EE) having an ethylene unit content of at least 50.0 wt% relative to the total weight of the elastic ethylene copolymer (EE), polypropylene composition 5.0 wt% to 10.0 wt% high density polyethylene (HDPE) and polypropylene based on the total weight of (PP) 15.0wt% ~25.0wt% of an inorganic filler relative to the total weight of the alkylene composition (PP) including (F). Compositions containing EE, HDPE and F can exhibit excellent mechanical properties such as excellent balance of stiffness / impact behavior without exhibiting tiger stripes.

According to another embodiment of the invention, the elastic ethylene copolymer (EE) comprises a) comonomer units selected from ethylene units and C _{4 to} C ₁₂ α-olefins and / or b) elastic ethylene copolymers ( EE) having an ethylene unit content from 50.0 wt% to 75.0 wt% with respect to the total weight of and / or c) a melt flow rate MFR ₁ (from 0.25 g / 10 min to 30.0 g / 10 min) 190 ° C., 2.16 kg).

According to yet another embodiment of the invention, the high density polyethylene (HDPE) is melt flow rate MFR ₁ (190 ° C., 2.16 kg) from 0.2 g / 10 min to 15.0 g / 10 min, and / or It has a density of at least 930 kg / m ³ .

According to one embodiment of the present invention, the inorganic filler (F) is selected from the group consisting of talc, mica, calcium carbonate, diatomaceous earth, wollastonite and kaolin and / or from 0.65 μm to 20 μm. having an average particle size _{d 50 of.}

According to another embodiment of the invention, the polypropylene composition (PP) has a) a flexural modulus of at least 1500 MPa, and / or b) a notched Izod impact strength (23 ° C.) higher than 30 kJ / m ^2. Have.

  According to yet another embodiment of the present invention, the first heterophasic propylene copolymer (HPP1) and / or the second heterophasic propylene copolymer (HPP2) is α-nucleated, preferably the first heterophasic propylene copolymer. (HPP1) and a second heterophasic propylene copolymer (HPP2) are α-nucleated.

  In the following, the present invention is described in more detail.

The polypropylene composition (PP) of the present invention comprises a first heterophasic propylene copolymer (HPP1) and a second heterophasic propylene copolymer (HPP2). Furthermore, the first heterophasic propylene copolymer (HPP1) has a melt flow rate MFR ₂ (230 ° C., 2.16 kg) from 20.0 g / 10 min to 80.0 g / 10 min measured according to ISO 1133, The heterophasic propylene copolymer (HPP2) has a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 0.05 g / 10 min to 2.0 g / 10 min measured according to ISO 1133. In addition, the amount of the first heterophasic propylene copolymer (HPP1) is from 66.6 wt% to 95.2 wt%, based on the total weight of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2). % And the amount of the second heterophasic propylene copolymer (HPP2) is in the range of 4.8 wt% to 33.4 wt%.

  In one embodiment of the present invention, the polypropylene composition (PP) is preferably highly rigid, ie at least 1,500 MPa, preferably 1,500 MPa to 2,700 MPa, more preferably 1,600 MPa to 2, Characterized by a flexural modulus up to 600 MPa. For example, the polypropylene composition (PP) of the present invention is characterized by a flexural modulus from 1,700 MPa to 2,500 MPa, for example from 1,720 MPa to 2,500 MPa.

  In one embodiment of the invention, the polypropylene composition (PP) has a tensile strength higher than 15 MPa, more preferably higher than 17 MPa, most preferably higher than 17 MPa and up to 30 MPa.

In addition or alternatively, the impact strength should also be higher. Thus, the polypropylene composition (PP) is preferably characterized by a notched Izod impact strength (+ 23 ° C.) higher than 30 kJ / m ² , more preferably 40 kJ / m ² or higher. For example, the polypropylene composition (PP) is preferably a feature 40 kJ / from ^{m 2} to 60 kJ / ^{m 2} or 45 kJ / notched in the range from ^{m 2} to 55 kJ / ^{m 2} Izod impact strength a (+ 23 ° C.) To do.

The polypropylene composition (PP) preferably has a flexural modulus of at least 1500 MPa and / or a notched Izod impact strength (+ 23 ° C.) higher than 30 kJ / m ² . In one embodiment of the invention, the polypropylene composition (PP) has a flexural modulus of at least 1500 MPa and a notched Izod impact strength (+ 23 ° C.) greater than 30 kJ / m ² .

  The polypropylene composition (PP) is in particular defined by a first heterophasic propylene copolymer (HPP1) and a second heterophasic propylene copolymer (HPP2).

  Accordingly, all components are defined in more detail below.

  The first heterophasic propylene copolymer (HPP1) is preferably a heterogeneous phase in which the polypropylene homopolymer matrix (PM1) as defined herein constitutes the matrix and the elastic propylene copolymer (AM1) is dispersed therein. It is a system.

Therefore, the first heterophasic propylene copolymer (HPP1) constituting the polypropylene composition (PP) contains a comonomer in addition to propylene. Preferably, the first heterophasic propylene copolymer (HPP1) constituting the polypropylene composition (PP) contains ethylene and / or C _{4 to} C ₁₂ α-olefin in addition to propylene. Accordingly, the term first heterophasic propylene copolymer (HPP1) of the present invention is
It is understood as a polypropylene comprising units derived from (a) propylene and (b) ethylene and / or C _{4 to} C ₁₂ α-olefins, preferably consisting of said units.

Therefore, the first heterophasic propylene copolymer (HPP1) of the present invention, that is, the first heterophasic propylene copolymer (HPP1) constituting the polypropylene composition (PP) is a monomer copolymerizable with propylene, such as ethylene and / or Or a comonomer such as C _{4 to} C ₁₂ α-olefin, in particular ethylene and / or C _{4 to} C ₈ α-olefin, for example 1-butene and / or 1-hexene. Preferably, the first heterophasic propylene copolymer (HPP1) of the present invention comprises monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene, in particular consisting of said monomers. More specifically, the first heterophasic propylene copolymer (HPP1) of the present invention contains units derived from ethylene and / or 1-butene in addition to propylene. In a preferred embodiment, the first heterophasic propylene copolymer (HPP1) of the present invention comprises only units derived from propylene and ethylene. Even more preferably, only the elastic propylene copolymer (AM1) contains an ethylene comonomer.

Thus, the elastic propylene copolymer (AM1) dispersed in the polypropylene homopolymer matrix (PM1) preferably includes propylene monomer units and comonomer units selected from ethylene and / or C _{4 to} C ₁₂ α-olefins. . For example, an elastic propylene copolymer (AM1) dispersed in a polypropylene homopolymer matrix (PM1) includes propylene monomer units and ethylene comonomer units.

  Accordingly, the elastic propylene copolymer (AM1) is preferably ethylene propylene rubber (EPR), and the matrix in which the elastic propylene copolymer (AM1) is dispersed is a polypropylene homopolymer matrix (PM1).

  The first heterophasic propylene copolymer (HPP1) constituting the polypropylene composition (PP) is preferably less than 15.0 wt%, preferably 12.0 wt%, based on the total weight of the first heterophasic propylene copolymer (HPP1) It is preferred to have a comonomer content of less than, more preferably from 3.0 wt% to 10.0 wt%, most preferably from 5.0 wt% to 10.0 wt%, preferably ethylene content.

  The low temperature xylene soluble fraction (XCS) fraction (23 ° C.) of the first heterophasic propylene copolymer (HPP1) comprising the polypropylene composition (PP) is preferably based on the total weight of the first heterophasic propylene copolymer (HPP1). On the other hand, it is 15.0 wt% to 25.0 wt%, preferably 18.0 wt% to 22.0 wt%, and most preferably 18.0 wt% to 20 wt%.

In addition, or alternatively, the first heterophasic propylene copolymer (HPP1) constituting the polypropylene composition (PP) is 20.0 g / 10 min to 80.0 g / 10 min, preferably 20.0 g / 10 min to 75.0 g. / 10 min, more preferably from 20.0 g / 10 min to 60.0 g / 10 min, most preferably from 30.0 g / 10 min to 50.0 g / 10 min melt flow rate MFR ₂ (230 ° C., 2.16 kg). Have. For example, the first heterophasic propylene copolymer (HPP1) constituting the polypropylene composition (PP) has a melt flow of 30.0 g / 10 min to 40.0 g / 10 min or 35.0 g / 10 min to 40.0 g / 10 min. It has a rate MFR ₂ (230 ° C., 2.16 kg).

  The polypropylene homopolymer matrix (PM1) constituting the first heterophasic propylene copolymer (HPP1) is a propylene homopolymer. In other words, the comonomer content of the polypropylene homopolymer matrix (PM1) is 0.5 wt% or less, more preferably 0.3 wt% or less, and most preferably 0.1 wt% or less. The weight percent is based on the total weight of the polypropylene homopolymer matrix (PM1).

  In other words, the expression polypropylene homopolymer or polypropylene homopolymer matrix (PM1) used throughout the present invention relates to polypropylene consisting essentially of propylene units, ie consisting of 99.5 wt% or more of propylene units. In a preferred embodiment, only propylene units are detectable in the polypropylene homopolymer.

  Furthermore, it is preferable that the low-temperature xylene soluble fraction (XCS) fraction of the polypropylene homopolymer matrix (PM1) constituting the first heterophasic propylene copolymer (HPP1) is small. Therefore, the low temperature xylene soluble fraction (XCS) fraction (25 ° C.) of the polypropylene homopolymer matrix (PM1) is preferably based on the total weight of the polypropylene homopolymer matrix (PM1) of the first heterophasic propylene copolymer (HPP1). 0.8 wt% to 3.0 wt%, more preferably 1.0 wt% to 3.0 wt%, and most preferably 1.3 wt% to 2.5 wt%. For example, the low temperature xylene soluble fraction (XCS) fraction (25 ° C.) of the polypropylene homopolymer matrix (PM1) is 1. to the total weight of the polypropylene homopolymer matrix (PM1) of the first heterophasic propylene copolymer (HPP1). 4 wt% to 2.3 wt%.

In addition or alternatively, the polypropylene homopolymer matrix (PM1) constituting the first heterophasic propylene copolymer (HPP1) has a higher melt flow rate. Accordingly, the polypropylene homopolymer matrix (PM1) is 30.0 g / 10 min to 250.0 g / 10 min, preferably 40.0 to 160.0 g / 10 min, more preferably 80.0 g / 10 min to 120.0 g / min. Up to 10 min, even more preferably from 90.0 g / 10 min to 110.0 g / 10 min, most preferably from 95.0 g / 10 min to 105.0 g / 10 min melt flow rate MFR ₂ (230 ° C., 2.16 kg). It is preferable to have.

  A further essential component of the first heterophasic propylene copolymer (HPP1) that constitutes the polypropylene composition (PP) is an elastic propylene copolymer (AM1) dispersed in a polypropylene homopolymer matrix (PM1).

With respect to the comonomer used in the elastic propylene copolymer (AM1), reference is made to the information given for the first heterophasic propylene copolymer (HPP1). Thus, the elastic propylene copolymer (AM1) is a monomer copolymerizable with propylene, such as ethylene and / or C _{4 to} C ₁₂ α-olefins, in particular ethylene and / or C _{4 to} C ₈ α-olefins, such as 1 Comonomer such as butene and / or 1-hexene. Preferably, the elastic propylene copolymer (AM1) comprises a monomer copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene, in particular consisting of said monomer. More specifically, the elastic propylene copolymer (AM1) contains units derived from ethylene and / or 1-butene in addition to propylene. Thus, in a particularly preferred embodiment, the elastic propylene copolymer (AM1) contains only units derived from propylene and ethylene.

Thus, the elastic propylene copolymer (AM1) dispersed in the polypropylene homopolymer matrix (PM1) may contain propylene monomer units and comonomer units selected from ethylene and / or C _{4 to} C ₁₂ α-olefins. preferable. For example, an elastic propylene copolymer (AM1) dispersed in a polypropylene homopolymer matrix (PM1) includes propylene monomer units and ethylene comonomer units.

  Since most of the elastic propylene copolymer (AM1) is soluble in xylene at ambient temperature (XCS content; ie low temperature xylene soluble content), the XCS content of the first heterophasic polypropylene composition (HPP1) is (AM1), ie related to the amount of amorphous phase, but not necessarily exactly the same. For example, the elastic propylene copolymer (AM1) may also contain portions of very high ethylene concentration that are crystalline and therefore will be insoluble in low temperature xylene.

  According to one embodiment of the present invention, the first heterophasic propylene copolymer (HPP1) constituting the polypropylene composition (PP) is from 2.0 dl / g to 3.0 dl / g, preferably 2.0 dl. Having an amorphous (AM) phase with an intrinsic viscosity (IV) of from / g to 2.7 dl / g.

  The comonomer content, preferably the ethylene content, in the elastic propylene copolymer (AM1) is relatively low. Thus, in one embodiment, the comonomer content, more preferably the ethylene content, of the amorphous fraction of the first heterophasic propylene copolymer (HPP1) is greater than the amorphous (AMP) of the first heterophasic propylene copolymer (HPP1). ) 33.0 wt% to 40.0 wt%, preferably 33.0 wt% to 38.0 wt%, most preferably 34.0 wt% to 38.0 wt%, based on the total weight of the phase.

Alternatively, the first heterophasic propylene copolymer (HPP1) is a propylene homopolymer or random propylene copolymer or block having a melt flow rate MFR ₂ (230 ° C., 2.16 kg) from 20.0 g / 10 min to 80.0 g / 10 min. Propylene copolymer.

  Like the first heterophasic propylene copolymer (HPP1), the second heterophasic propylene copolymer (HPP2) also comprises a polypropylene homopolymer matrix (PM2) as defined herein, in which It is a heterogeneous system in which an elastic propylene copolymer (AM2) is dispersed.

Therefore, the second heterophasic propylene copolymer (HPP2) constituting the polypropylene composition (PP) contains a comonomer in addition to propylene. Preferably, the second heterophasic propylene copolymer (HPP2) constituting the polypropylene composition (PP) contains, in addition to propylene, ethylene and / or C _{4 to} C ₁₂ α-olefin. Accordingly, the term second heterophasic propylene copolymer (HPP2) of the present invention is
It is understood as a polypropylene comprising units derived from (a) propylene and (b) ethylene and / or C _{4 to} C ₁₂ α-olefins, preferably consisting of said units.

Therefore, the second heterophasic propylene copolymer (HPP2) of the present invention, that is, the second heterophasic propylene copolymer (HPP2) constituting the polypropylene composition (PP), is a monomer copolymerizable with propylene, such as ethylene and / or Or a comonomer such as C _{4 to} C ₁₂ α-olefin, in particular ethylene and / or C _{4 to} C ₈ α-olefin, for example 1-butene and / or 1-hexene. Preferably, the second heterophasic propylene copolymer (HPP2) of the present invention comprises monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene, in particular consisting of said monomers. More specifically, the second heterophasic propylene copolymer (HPP2) of the present invention contains units derived from ethylene and / or 1-butene in addition to propylene. In a preferred embodiment, the second heterophasic propylene copolymer (HPP2) of the present invention comprises only units derived from ethylene and propylene. Even more preferably, only the elastic propylene copolymer (AM2) contains an ethylene comonomer.

Thus, the elastic propylene copolymer (AM2) dispersed in the polypropylene homopolymer matrix (PM2) preferably includes propylene monomer units and comonomer units selected from ethylene and / or C _{4 to} C ₁₂ α-olefins. . For example, an elastic propylene copolymer (AM2) dispersed in a polypropylene homopolymer matrix (PM2) includes propylene monomer units and ethylene comonomer units.

  Accordingly, the elastic propylene copolymer (AM2) is preferably an ethylene propylene elastomer, and the matrix in which the elastic propylene copolymer (AM2) is dispersed is a polypropylene homopolymer matrix (PM2).

  The second heterophasic propylene copolymer (HPP2) constituting the polypropylene composition (PP) is preferably from 3.0 wt% to 8.0 wt%, preferably based on the total weight of the second heterophasic propylene copolymer (HPP2) Has a comonomer content from 3.0 wt% to 7.0 wt%, more preferably from 4.0 wt% to 6.0 wt%, most preferably from 4.1 wt% to 5.1 wt%, preferably ethylene content Is preferred.

  In one embodiment of the invention, the second heterophasic propylene copolymer (HPP2) is 9.0 wt% to 20.0 wt%, preferably 10 wt%, based on the total weight of the second heterophasic propylene copolymer (HPP2). It has a low temperature xylene soluble (XCS) fraction (25 ° C.) from 0.0 wt% to 15.0 wt%, most preferably from 12.0 wt% to 14.0 wt%.

In addition or alternatively, the second heterophasic propylene copolymer (HPP2) constituting the polypropylene composition (PP) is 0.05 g / 10 min to 2.0 g / 10 min, preferably 0.1 g / 10 min to 2.0 g. / 10 min, more preferably 0.2 g / 10 min to 1.0 g / 10 min, most preferably 0.2 g / 10 min to 0.5 g / 10 min melt flow rate MFR ₂ (230 ° C., 2.16 kg). Have. For example, the second heterophasic propylene copolymer (HPP2) constituting the polypropylene composition (PP) has a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 0.2 g / 10 min to 0.3 g / 10 min. .

Thus, the melt flow rate MFR ₂ of the first heterophasic propylene copolymer (HPP1) is different from the melt flow rate MFR ₂ (230 ° C., 2.16 kg) of the second heterophasic propylene copolymer (HPP2). One of the basic requirements. In one embodiment of the present invention, the first heterophasic propylene copolymer (HPP1) of the polypropylene composition (PP) has a melt flow rate MFR ₂ (230 ° C., 2 ° C.) of 20.0 g / 10 min to 80.0 g / 10 min. The second heterophasic propylene copolymer (HPP2) of the polypropylene composition (PP) has a melt flow rate MFR ₂ (230 ° C., 2.16 kg) from 0.05 g / 10 min to 2.0 g / 10 min. Have For example, a first heterophasic propylene copolymer (HPP1) of a polypropylene composition (PP) has a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 20.0 g / 10 min to 75.0 g / 10 min, The second heterophasic propylene copolymer (HPP2) of the polypropylene composition (PP) has a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 0.2 g / 10 min to 0.5 g / 10 min.

  The polypropylene homopolymer matrix (PM2) that constitutes the second heterophasic propylene copolymer (HPP2) is a propylene homopolymer. In other words, the comonomer content of the polypropylene homopolymer matrix (PM2) is 0.5 wt% or less, more preferably 0.3 wt% or less, and most preferably 0.1 wt% or less. The weight percent is based on the total weight of the polypropylene homopolymer matrix (PM2).

  In other words, the expression polypropylene homopolymer or polypropylene homopolymer matrix (PM2) used throughout the present invention relates to polypropylene consisting essentially of propylene units, i.e. consisting of 99.5 wt% or more of propylene units. In a preferred embodiment, only propylene units are detectable in the polypropylene homopolymer.

  Furthermore, it is preferable that the low-temperature xylene soluble fraction (XCS) fraction of the polypropylene homopolymer matrix (PM2) constituting the second heterophasic propylene copolymer (HPP2) is small. Thus, the low temperature xylene soluble fraction (XCS) fraction (25 ° C.) of the polypropylene homopolymer matrix (PM2) is 2. based on the total weight of the polypropylene homopolymer matrix (PM2) of the second heterophasic propylene copolymer (HPP2). It is less than 0 wt%, preferably from 0.1 wt% to 2.0 wt%, more preferably from 0.5 wt% to 2.0 wt%. For example, the low temperature xylene soluble fraction (XCS) fraction (25 ° C.) of the polypropylene homopolymer matrix (PM2) is 1. to the total weight of the polypropylene homopolymer matrix (PM2) of the second heterophasic propylene copolymer (HPP2). From 0 wt% to 2.0 wt%.

In addition or alternatively, the polypropylene homopolymer matrix (PM2) comprising the second heterophasic propylene copolymer (HPP2) also has a lower melt flow rate. Therefore, the polypropylene homopolymer matrix (PM2) is from 0.1 g / 10 min to 3.0 g / 10 min, preferably from 0.1 g / 10 min to 2.0 g / 10 min, more preferably from 0.1 g / 10 min to 1. g. It is preferred to have a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of up to 0 g / 10 min, most preferably from 0.1 g / 10 min to 0.5 g / 10 min.

  A further essential component of the second heterophasic propylene copolymer (HPP2) that constitutes the polypropylene composition (PP) is an elastic propylene copolymer (AM2) dispersed in a polypropylene homopolymer matrix (PM2).

With respect to the comonomer used in the elastic propylene copolymer (AM2), reference is made to the information given for the second heterophasic propylene copolymer (HPP2). Thus, the elastic propylene copolymer (AM2) is a monomer copolymerizable with propylene, such as ethylene and / or C _{4 to} C ₁₂ α-olefins, in particular ethylene and / or C _{4 to} C ₈ α-olefins such as 1 Comonomer such as butene and / or 1-hexene. Preferably, the elastic propylene copolymer (AM2) comprises a monomer copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene, in particular consisting of said monomer. More specifically, the elastic propylene copolymer (AM2) contains units derived from ethylene and / or 1-butene in addition to propylene. Thus, in a particularly preferred embodiment, the elastic propylene copolymer (AM2) contains only units derived from propylene and ethylene.

  According to one embodiment of the present invention, the second heterophasic propylene copolymer (HPP2) constituting the polypropylene composition (PP) is from 3.0 dl / g to 4.0 dl / g, preferably 3.5 dl. Amorphous (AM) phase having an intrinsic viscosity (IV) of from / g to 4.0 dl / g.

  In one embodiment of the present invention, the comonomer content, more preferably the ethylene content, of the amorphous (AM) phase of the second heterophasic propylene copolymer (HPP2) is the amorphous content of the second heterophasic propylene copolymer (HPP2). 30.0 wt% to 37.0 wt%, preferably 30.0 wt% to 35.0 wt%, based on the total weight of the quality (AM) phase.

  As indicated above, it is a requirement of the present invention that the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) comprising the polypropylene composition (PP) are provided in specific amounts. One.

  The polypropylene composition (PP) of the present invention is in the range of 66.6 wt% to 95.2 wt% based on the total weight of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2). Preferably, the amount of the first heterophasic propylene copolymer (HPP1) is included and the amount of the second heterophasic propylene copolymer (HPP2) is in the range of 4.8 wt% to 33.4 wt%.

  For example, the polypropylene composition (PP) has a first amount of 70.0 wt% to 95.0 wt% of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) in an amount of 10.0 wt%. Of a heterophasic propylene copolymer (HPP1) and a second heterophasic propylene copolymer (HPP2) in an amount of 5.0 wt% to 30.0 wt%. Alternatively, the polypropylene composition (PP) may comprise the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) in a first amount in the amount of 80.0 wt% to 95.0 wt%. Of a heterophasic propylene copolymer (HPP1) and a second heterophasic propylene copolymer (HPP2) in an amount of 5.0 wt% to 20.0 wt%. In one embodiment of the present invention, the polypropylene composition (PP) is 85.0 wt% to 95.95% based on the total weight of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2). A first heterophasic propylene copolymer (HPP1) in an amount of up to 0 wt%, for example 90.0 wt% to 95.0 wt%, and from 5.0 wt% to 15.0 wt%, for example 5.0 wt% to 10.0 wt% Up to a second heterophasic propylene copolymer (HPP2).

  In addition or alternatively, the weight ratio [(HPP1) / (HPP2)] of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) is in the range of 20/1 to 2/1 More preferably, it is in the range of 15/1 to 3/1, most preferably in the range of 12/1 to 3/1.

  The polypropylene composition (PP) of the present invention preferably further contains usual additives such as acid scavengers, antioxidants, nucleating agents, light stabilizers, slip agents, and / or pigments. Preferably, the amount of additive excluding the inorganic filler should not exceed 7.0 wt%, more preferably not exceed 5.0 wt%, based on the total weight of the polypropylene composition (PP). .

  In one embodiment of the present invention, the polypropylene composition (PP) is a first heterophasic propylene copolymer (HPP1) in an amount of 40.0 wt% to 60.0 wt% based on the weight of the polypropylene composition (PP). And a second heterophasic propylene copolymer (HPP2) in an amount of 3.0 wt% to 20.0 wt%. For example, the polypropylene composition (PP) has a first heterophasic propylene copolymer (HPP1) in an amount of 45.0 wt% to 55.0 wt% and 3.0 wt% to 15. A second heterophasic propylene copolymer (HPP2) is included in an amount of 0 wt%.

  Preferably, the polypropylene composition (PP) of the present invention comprises an elastic ethylene copolymer (EE) next to the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) to improve impact properties. ) May further be included. The elastic ethylene copolymer (EE) is composed of the elastic propylene copolymer (AM1) of the first heterophasic propylene copolymer (HPP1) and the elastic propylene copolymer (AM2) of the second heterophasic propylene copolymer (HPP2) that constitutes the polypropylene composition (PP). Note that (chemically) is different from

Elastic ethylene copolymers (EE) are ethylene units and comonomer units selected from C _{4 to} C ₁₂ α-olefins, in particular ethylene units and comonomer units selected from C _{4 to} C ₈ α-olefins, such as 1-butene and And / or 1-hexene and / or 1-octene. Preferably, the elastic ethylene copolymer (EE) comprises ethylene units and comonomer units selected from 1-butene, 1-hexene and 1-octene, in particular consisting of said units. More specifically, the elastic ethylene copolymer (EE) contains units derived from 1-butene and / or 1-octene in addition to ethylene. Thus, in a particularly preferred embodiment, the elastic ethylene copolymer (EE) comprises only units derived from ethylene and 1-octene.

  The ethylene content in the elastic ethylene copolymer (EE) is relatively high. Therefore, in a preferred embodiment, the ethylene content of the elastic ethylene copolymer (EE) constituting the polypropylene composition (PP) is at least 50.0 wt%, preferably 50.0 wt%, based on the total weight of the elastic ethylene copolymer (EE). % To 75.0 wt%. For example, the ethylene content of the elastic ethylene copolymer (EE) constituting the polypropylene composition (PP) is from 60.0 wt% to 70.0 wt%, for example 65.0 wt%, based on the total weight of the elastic ethylene copolymer (EE). To 70.0 wt%.

In addition or alternatively, the elastic ethylene copolymer (EE) constituting the polypropylene composition (PP) is from 0.25 g / 10 min to 30.0 g / 10 min, preferably from 0.25 g / 10 min to 20.0 g / 10 min. More preferably, it has a melt flow rate MFR ₁ (190 ° C., 2.16 kg) of from 0.25 g / 10 min to 15.0 g / 10 min, most preferably from 0.25 g / 10 min to 10.0 g / 10 min.

Accordingly, the elastic ethylene copolymer (EE) constituting the polypropylene composition (PP) preferably has an ethylene content of at least 50.0 wt%, and from 0.25 g / 10 min to 30 based on the total weight of the elastic ethylene copolymer (EE). It is preferably an elastic ethylene-1-octene copolymer having a melt flow rate MFR ₁ (190 ° C., 2.16 kg) up to 0.0 g / 10 min. For example, the elastic ethylene copolymer (EE) constituting the polypropylene composition (PP) has an ethylene content of 65.0 wt% to 70.0 wt% with respect to the total weight of the elastic ethylene copolymer (EE), and 0.25 g / It is an elastic ethylene-1-octene copolymer having a melt flow rate MFR ₁ (190 ° C., 2.16 kg) from 10 min to 10.0 g / 10 min.

  In one embodiment of the present invention, the polypropylene composition (PP) comprises an elastic ethylene copolymer (EE) in an amount of 5.0 wt% to 20.0 wt% based on the total weight of the polypropylene composition (PP). . For example, the polypropylene composition (PP) may be an elastic ethylene copolymer (5.0 wt% to 15.0 wt% or 5.0 wt% to 10.0 wt% of an elastic ethylene copolymer (PP) based on the total weight of the polypropylene composition (PP). EE).

  The polypropylene composition (PP) of the present invention is also a first heterophasic propylene copolymer to improve the anti-scratch property of the surface of articles molded from the polypropylene composition (PP) of the present invention. Next to (HPP1), second heterophasic propylene copolymer (HPP2) and optional elastic ethylene copolymer (EE), high density polyethylene (HDPE) may also be included. High density polyethylene (HDPE) is composed of an elastic propylene copolymer (AM1) of a first heterophasic propylene copolymer (HPP1) and an elastic propylene copolymer (AM2) of a second heterophasic propylene copolymer (HPP2) constituting a polypropylene composition (PP). And (chemically) different from any elastic ethylene copolymer (EE).

  High density polyethylene (HDPE) used according to the present invention is well known in the art and is commercially available.

High density polyethylene (HDPE) is preferably from 0.2 g / 10 min to 15.0 g / 10 min, preferably from 0.5 g / 10 min to 10.0 g / 10 min, more preferably from 1.0 g / 10 min to 10. It has a melt flow rate MFR ₁ (190 ° C., 2.16 kg) of up to 0 g / 10 min, most preferably from 5.0 g / 10 min to 10.0 g / 10 min.

High density polyethylene (HDPE) usually has a density of at least 930 kg / m ³ , preferably 930 to 970 kg / m ³ , more preferably 930 to 950 kg / m ³ .

  In one embodiment of the present invention, the polypropylene composition (PP) comprises high density polyethylene (HDPE) in an amount of 5.0 wt% to 10.0 wt% based on the total weight of the polypropylene composition (PP). . For example, the polypropylene composition (PP) includes high density polyethylene (HDPE) in an amount of 5 wt% to 8 wt% based on the total weight of the polypropylene composition (PP).

  In order to reach the desired level of stiffness, the polypropylene composition (PP) of the present invention preferably comprises a selected amount of inorganic filler (F). Therefore, the polypropylene composition (PP) of the present invention preferably contains the inorganic filler (F) in an amount of 15.0 wt% to 25.0 wt% based on the total weight of the polypropylene composition (PP). In one embodiment of the present invention, the polypropylene composition (PP) of the present invention is preferably an inorganic loading in an amount of 15.0 wt% to 20.0 wt%, based on the total weight of the polypropylene composition (PP). Contains agents.

  According to one embodiment of the present invention, the inorganic filler (F) is selected from the group consisting of talc, mica, calcium carbonate, diatomaceous earth, wollastonite and kaolin. For example, the inorganic filler (F) is talc.

In one embodiment of the present invention, the inorganic filler (F) has an average particle diameter d ₅₀ from 0.65 μm to 20 μm.

For example, the polypropylene composition (PP) contains talc as the inorganic filler (F). According to one embodiment of the present invention, the inorganic filler used in the polypropylene composition (PP) is talc having an average particle diameter d ₅₀ from 0.65 μm to 20 μm.

Therefore, the polypropylene composition (PP) of the present invention is preferably
a) 40.0 wt% to 60.0 wt% of the first heterophasic propylene copolymer (HPP1), based on the total weight of the polypropylene composition (PP),
b) 3.0 wt% to 20.0 wt% of a second heterophasic propylene copolymer (HPP2) based on the total weight of the polypropylene composition (PP);
c) 5.0 wt% to 20.0 wt% elastic ethylene copolymer (EE) based on the total weight of the polypropylene composition (PP), and at least 50.0 wt% based on the total weight of the elastic ethylene copolymer (EE) Said elastic ethylene copolymer (EE) having an ethylene unit content of
d) 5.0 wt% to 10.0 wt% high density polyethylene (HDPE) based on the total weight of the polypropylene composition (PP), and e) 15.0 wt% based on the total weight of the polypropylene composition (PP). ~ 25.0wt% inorganic filler (F)
including.

For example, the polypropylene composition (PP) of the present invention is preferably
a) 45.0 wt% to 55.0 wt% of the first heterophasic propylene copolymer (HPP1), based on the total weight of the polypropylene composition (PP),
b) 3.0 wt% to 15.0 wt% of a second heterophasic propylene copolymer (HPP2) based on the total weight of the polypropylene composition (PP);
c) 5.0 wt% to 15.0 wt% elastic ethylene copolymer (EE) based on the total weight of the polypropylene composition (PP), and at least 50.0 wt% based on the total weight of the elastic ethylene copolymer (EE) Said elastic ethylene copolymer (EE) having an ethylene unit content of
d) 5.0 wt% to 8.0 wt% high density polyethylene (HDPE) based on the total weight of the polypropylene composition (PP), and e) 15.0 wt% based on the total weight of the polypropylene composition (PP). ~ 20.0wt% inorganic filler (F)
including.

  Preferably, the polypropylene composition (PP) of the present invention comprises an acid scavenger, an antioxidant, a nucleating agent, a light stabilizer, an ultraviolet stabilizer, a slip agent, an anti-scratch agent (eg, an organosilicon compound), a dispersant and It may further comprise at least one conventional additive selected from the group consisting of colorants. For example, the polypropylene composition (PP) further includes additives such as an antioxidant, an ultraviolet stabilizer, an anti-scratch agent (for example, an organosilicon compound), a dispersant, and a colorant. Preferably the amount of these additives, excluding the inorganic filler (F), does not exceed 14.0 wt% in the polypropylene composition (PP) of the present invention relative to the total weight of the polypropylene composition (PP). For example, it is 11.0 wt% or less. In one embodiment of the invention, the polypropylene composition (PP) is in an amount from 3.0 wt% to 11.0 wt%, preferably from 3.0 wt%, relative to the total weight of the polypropylene composition (PP). In an amount up to 8.0 wt%, antioxidants, UV stabilizers, anti-scratch agents (eg, organosilicon compounds), dispersants and colorants are included as additives.

  A preferred scratch inhibitor is an organosilicon compound. For example, the polypropylene composition (PP) is not more than 3.0 wt%, preferably from 1.0 wt% to 2.0 wt%, more preferably about 1.0 wt%, based on the total weight of the polypropylene composition (PP). % Of an anti-scratch agent such as an organosilicon compound.

The polypropylene composition (PP) of the present invention preferably contains an α-nucleating agent. Even more preferably, the present invention does not include a β-nucleating agent. According to the invention, the nucleating agent is understood as a nucleating agent different from the inorganic filler (F). Thus, the nucleating agent is preferably
(I) salts of mono- and polycarboxylic acids such as sodium benzoate or tert-butylaluminum benzoate and (ii) dibenzylidene sorbitol (eg 1,3: 2,4 dibenzylidene sorbitol) and C ₁ -C _8- alkyl substituted dibenzylidene sorbitol derivatives such as methyl dibenzylidene sorbitol, ethyl dibenzylidene sorbitol or dimethyl dibenzylidene sorbitol (such as 1,3: 2,4 di (methylbenzylidene) sorbitol), or substituted nonitol derivatives such as 1,2 , 3, -trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol and the like, and (iii) diester salts of phosphoric acid, such as sodium 2,2'-methylenebis (4, 6, − Di-tert-butylphenyl) phosphate or aluminum-hydroxy-bis [2,2′-methylene-bis (4,6-di-tert-butylphenyl) phosphate], and (iv) vinylcycloalkane and vinylalkane polymers (As discussed above), and (v) selected from the group consisting of mixtures thereof.

  Such additives are generally commercially available and are described, for example, in Hans Zweifel's “Plastic Additives Handbook” (5th edition, 2001).

  Most preferably, the α-nucleating agent comprises a first heterophasic propylene copolymer (HPP1) and / or a second heterophasic propylene copolymer (HPP2) (and thus a polypropylene composition (PP)). Accordingly, the α-nucleating agent content of the heterophasic propylene copolymer (HPP1) and / or heterophasic propylene copolymer (HPP2) (and thus the polypropylene composition (PP)) is preferably up to 5.0 wt%. In a preferred embodiment, the heterophasic propylene copolymer (HPP1) and / or heterophasic propylene copolymer (HPP2) (and thus the polypropylene composition (PP)) is 3000 ppm or less, more preferably 1 ppm to 2000 ppm, in particular dibenzylidene sorbitol (eg 1, 3: 2,4 dibenzylidene sorbitol), dibenzylidene sorbitol derivatives, preferably dimethyl dibenzylidene sorbitol (eg 1,3: 2,4 di (methylbenzylidene) sorbitol), or substituted nonitol derivatives such as 1,2,3, -Trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol, etc., selected from the group consisting of vinylcycloalkane polymers, vinylalkane polymers, and mixtures thereof The containing α- nucleating agent.

  In a preferred embodiment, the heterophasic propylene copolymer (HPP1) and / or the heterophasic propylene copolymer (HPP2) (and thus the polypropylene composition (PP)) comprises a polymer of vinylcycloalkane, such as vinylcyclohexane (VCH) and / or vinylalkane polymer. Contains as α-nucleating agent. Preferably in this embodiment, the heterophasic propylene copolymer (HPP1) and heterophasic propylene copolymer (HPP2) contain a polymer of vinylcycloalkane, such as vinylcyclohexane (VCH) and / or a vinylalkane polymer, preferably vinylcyclohexane (VCH). To do. Preferably, the vinylcycloalkane is a vinylcyclohexane (VCH) polymer introduced into the heterophasic propylene copolymer (HPP1) and / or heterophasic propylene copolymer (HPP2) (and thus in the polypropylene composition (PP)) by BNT technology. . More preferably in this preferred embodiment, the amount of vinylcycloalkane, for example vinylcyclohexane (VCH) polymer and / or vinylalkane polymer, more preferably vinylcyclohexane (VCH) polymer, in the heterophasic propylene copolymer (HPP1) is 500 ppm. Below, more preferably from 1 ppm to 200 ppm, most preferably from 5 ppm to 100 ppm, a polymer of vinylcycloalkane in the heterophasic propylene copolymer (HPP2), for example vinylcyclohexane (VCH) and / or vinylalkane polymer, more preferably vinyl. The amount of cyclohexane (VCH) polymer is 500 ppm or less, more preferably 1 ppm to 200 ppm, and most preferably 5 ppm to 100 ppm. Accordingly, the polypropylene composition (PP) preferably contains 500 ppm or less, more preferably 1 ppm to 200 ppm, and most preferably 5 ppm to 100 ppm.

With regard to BNT technology, reference is made to international applications WO 99/24478, WO 99/24479 and in particular WO 00/68315. According to this technique, a catalyst system, preferably a Ziegler-Natta procatalyst, is modified, in particular, by polymerizing vinyl compounds in the presence of a catalyst system comprising a special Ziegler-Natta procatalyst, external donor and cocatalyst. And the vinyl compound has the formula:
_{^{CH 2 = CH-CHR 3 R}} 4
Wherein R ³ and R ⁴ together form a 5- or 6-membered saturated, unsaturated or aromatic ring, or independently an alkyl group containing 1 to 4 carbon atoms. And the modified catalyst is a heterophasic polypropylene composition of the present invention, ie heterophasic propylene copolymer (HPP1) and / or heterophasic propylene copolymer (HPP2), most preferably heterophasic propylene copolymer (HPP1) and heterophasic propylene. Used for production of copolymer (HPP2). The polymerized vinyl compound acts as an α-nucleating agent. The weight ratio of vinyl compound to solid catalyst component in the catalyst modification step is preferably up to 5 (5: 1), preferably up to 3 (3: 1), most preferably from 0.5 (1: 2) to 2 ( 2: 1). The most preferred vinyl compound is vinylcyclohexane (VCH).

  According to another aspect of the invention, the polypropylene composition (PP) comprises a first heterophasic propylene copolymer (HPP1), a second heterophasic propylene copolymer (HPP2), an optional elastic ethylene copolymer (EE), an optional Blending in the extruder with high density polyethylene (HDPE), optional inorganic filler (F) and further optional additives, and first heterophasic propylene copolymer (HPP1), second heterophase in the extruder Produced by extruding the resulting blend of propylene copolymer (HPP2) and optional elastic ethylene copolymer (EE), high density polyethylene (HDPE), inorganic filler (F) and further additives. The term “blending” means according to the invention at least two different existing materials: a first heterophasic propylene copolymer (HPP1), a second heterophasic propylene copolymer (HPP2) as well as any elastic ethylene copolymer. Refers to the act of providing a blend from (EE), high density polyethylene (HDPE), inorganic filler (F) and further additives.

  In order to blend the individual components of the composition of the present invention, ie the first heterophasic propylene copolymer (HPP1) into the second heterophasic propylene copolymer (HPP2) as well as any elastic ethylene copolymer (EE), high density polyethylene (HDPE). ), Inorganic fillers (F) and further additives, conventional compound or blending equipment such as Banbury mixers, two roll rubber roll machines, Buss kneaders or twin screw extruders can be used. The polymeric material recovered from the extruder is usually in the form of pellets. These pellets are then preferably further processed, for example by injection molding, into articles and products of the composition of the present invention.

  The residence time in the blender or the screw speed of the extruder must be selected so that a sufficiently high degree of homogenization is achieved.

  All ingredients used to produce the polypropylene composition (PP) of the present invention are known and commercially available. Their manufacture is therefore also well known. For example, the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) of the present invention are preferably produced independently of one another in a sequential polymerization process known in the art, ie in a multi-stage process. And corresponding matrices (polypropylene homopolymer matrix (PM1) and polypropylene homopolymer matrix (PM2)) are produced independently of one another in at least one slurry reactor, followed by an elastic copolymer (elastic propylene copolymer (AM1) and The elastic propylene copolymer (AM2)) is produced independently of one another in at least one, ie one or two gas phase reactors.

  More specifically, the first heterophasic propylene copolymer (HPP1) is produced by producing a polypropylene homopolymer matrix (PM1) in at least one reactor system having at least one reactor, the polypropylene homopolymer matrix (PM1). ) Is transferred to a subsequent reactor system having at least one reactor to produce an elastic propylene copolymer (AM1) in the presence of a polypropylene homopolymer matrix (PM1).

  Additionally or alternatively, the second heterophasic propylene copolymer (HPP2) can produce a polypropylene homopolymer matrix (PM2) in at least one reactor system having at least one reactor, the polypropylene homopolymer matrix (PM2 ) Is transferred to a subsequent reactor system having at least one reactor to produce an elastic propylene copolymer (AM2) in the presence of a polypropylene homopolymer matrix (PM2).

  Thus, each of the polymerization systems can have one or more conventional stirred slurry reactors and / or one or more gas phase reactors. Preferably, the reactor used is selected from the group of loop reactors and gas phase reactors, in particular the process uses at least one loop reactor and at least one gas phase reactor. Several reactors of each type may be used in series, for example one loop reactor and two or three gas phase reactors, or two loop reactors and one or two gas phase reactors. It is also possible.

  Preferably, the process for producing the first heterophasic propylene copolymer (HPP1) and / or the second heterophasic propylene copolymer (HPP2) comprises a Ziegler-Natta procatalyst, an external donor and a cocatalyst and is described in detail below. Including prepolymerization with selected catalyst systems.

  In a preferred embodiment, the prepolymerization is carried out as a bulk slurry polymerization in liquid propylene, i.e. the liquid phase contains mainly propylene in which small amounts of other reactants and optionally inert components are dissolved.

  The prepolymerization reaction is usually carried out at a temperature from 0 ° C to 50 ° C, preferably from 10 ° C to 45 ° C, more preferably from 15 ° C to 40 ° C.

  The pressure in the prepolymerization reactor is not critical but must be high enough to maintain the reaction mixture in the liquid phase. Thus, the pressure may be from 20 bar to 100 bar, for example from 30 bar to 70 bar.

  All catalyst components are preferably introduced into the prepolymerization step. However, if the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, only a part of the cocatalyst is introduced during the prepolymerization stage and the remaining part is introduced during the subsequent polymerization stage. Is possible. In such a case, it is also necessary to introduce a cocatalyst sufficient to obtain a sufficient polymerization reaction during the prepolymerization stage.

  It is also possible to add other components to the prepolymerization stage. Thus, as is known in the art, hydrogen may be added to the prepolymerization stage to adjust the molecular weight of the prepolymer. Furthermore, an antistatic additive may be used to prevent the particles from sticking to each other or from the inner wall of the reactor.

  Strict control of prepolymerization conditions and reaction parameters is within the skill of one of ordinary skill in the art.

  A slurry reactor refers to any reactor, such as a continuous or simple batch stirred tank reactor or loop reactor, that operates in bulk or slurry state and in which the polymer is in particulate form. “Bulk” means polymerization in a reaction medium comprising at least 60.0 wt% monomer. According to a preferred embodiment, the slurry reactor comprises a bulk loop reactor.

  “Gas phase reactor” means any mechanically mixed or fluidized bed reactor. Preferably, the gas phase reactor comprises a mechanically stirred fluidized bed reactor with a gas velocity of at least 0.2 m / sec.

  A particularly preferred embodiment for producing the first heterophasic propylene copolymer (HPP1) and / or the second heterophasic propylene copolymer (HPP2) of the present invention comprises one loop reactor and one or two gas phase reactors. Or conducting the polymerization in a process having either a combination of two loop reactors and one or two gas phase reactors.

  A preferred multi-stage process is a slurry-gas phase process such as that developed by Borealis and known as Borstar® technology. In this respect, reference is made to EP 0 879 379 A1, WO 92/12182, WO 2004/000899, WO 2004/11105, WO 99/24478, WO 99/24479 and WO 00/68315. These are hereby incorporated by reference.

  A further suitable slurry-gas phase process is the Basell Spheripol® process.

  Preferably, the first heterophasic propylene copolymer (HPP1) and / or the second heterophasic propylene copolymer (HPP2) of the present invention is described in detail below, preferably in the Spheripol® or Borstar®-PP process. By using a special Ziegler-Natta procatalyst in combination with a special external donor described in 1.

Thus, one preferred multi-stage process may include the following steps:
-In the first slurry reactor and optionally in the second slurry reactor, both slurry reactors use the same polymerization conditions, and the special Ziegler-Natta procatalyst (i), external donor (iii) and Producing a polypropylene matrix in the presence of a selected catalyst system comprising cocatalyst (ii), for example as described in detail below,
Transferring the slurry reactor product into at least one first gas phase reactor, for example one gas phase reactor or first and second gas phase reactors connected in series;
-Producing an elastic copolymer in the at least first gas phase reactor in the presence of a polypropylene matrix and in the presence of a catalyst system;
-Recovering the polymer product for further processing.

  For the preferred slurry-gas phase process described above, the following general information about the process conditions can be presented.

  The temperature is preferably between 40 ° C. and 110 ° C., preferably between 50 ° C. and 100 ° C., in particular between 60 ° C. and 90 ° C., and the pressure is in the range from 20 bar to 80 bar, preferably 30 bar to 60 bar. Optionally, hydrogen is added to control the molecular weight in a manner known per se.

  The reaction product of slurry polymerization, preferably performed in a loop reactor, is then transferred to a subsequent gas phase reactor. Here, the temperature is preferably in the range from 50 ° C. to 130 ° C., more preferably from 60 ° C. to 100 ° C., the pressure in the range from 5 bar to 50 bar, preferably from 8 bar to 35 bar, again optional Optionally, hydrogen is added to control the molecular weight in a manner known per se.

  The average residence time can be varied in the reactor zone identified above. In one embodiment, the average residence time in a slurry reactor, such as a loop reactor, is in the range of 0.5 hours to 5 hours, such as 0.5 hours to 2 hours, while the gas phase reaction The average residence time in the vessel is generally from 1 hour to 8 hours.

  If desired, the polymerization may be carried out in a known manner under supercritical conditions in a slurry, preferably a loop reactor, and / or as a condensed mode in a gas phase reactor.

  According to the present invention, the heterophasic polypropylene is preferably a multistage polymerization process as described above in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procatalyst containing a transesterification product of a lower alcohol and a phthalate ester. Is obtained.

（式中、Ｒ^１’及びＲ^２’は独立に、少なくともＣ_５アルキルである。）
と、前記Ｃ_１〜Ｃ_２アルコールと前記式（Ｉ）のフタル酸ジアルキルのエステル交換が起こる条件下で反応させて内部供与体を形成すること、
ｃ）段階ｂ）の生成物を洗浄すること、又は
ｄ）任意に、工程ｃ）の生成物をさらにＴｉＣｌ_４と反応させること
により製造される。 The procatalyst used according to the invention is
a) reacting a spray crystallized or emulsion solidified adduct of MgCl ₂ and a C ₁ -C ₂ alcohol with TiCl ₄ ,
b) the product of step a) is dialkyl phthalate of formula (I)

(Wherein R ¹ ′ and R ² ′ are independently at least C ₅ alkyl.)
When, said C ₁ -C ₂ alcohol with the formula is reacted under conditions where a transesterification of dialkyl phthalate occurs in (I) to form the internal donor,
c) It is prepared by washing the product of step b), or d) optionally by reacting the product of step c) further with TiCl ₄ .

  The procatalyst is prepared, for example, as defined in the patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0491565. The contents of these documents are included herein by reference.

First, an adduct of MgCl ₂ of formula MgCl ₂ * nROH and a C ₁ -C ₂ alcohol (wherein R is methyl or ethyl and n is 1 to 6) is formed. Preferably ethanol is used as the alcohol.

  The adduct is first melted and then spray crystallized or emulsion coagulated, which is used as the catalyst support.

（式中、Ｒ^１及びＲ^２はメチル又はエチル、好ましくはエチルである。）
を形成する工程であって、式（ＩＩ）のフタル酸ジアルキル（ｄｉａｌｋｙｌｐｈｔｈａｌａｔ）が内部供与体である、上記工程、及び
前記エステル交換生成物をプロ触媒組成物（成分（ｉ））として回収する工程。 In the next step, the adduct of formula MgCl ₂ * nROH (wherein R is methyl or ethyl, preferably ethyl and n is 1 to 6), which is spray crystallized or emulsion coagulated, is TiCl _4. To form a titanized carrier, followed by the following steps.
In the titanium-treated carrier,
(I) dialkylphthalates of formula (I), wherein R ¹ ′ and R ² ′ are independently at least C ₅ alkyl, such as at least C ₈ alkyl,
Or preferably (ii) R ¹ ′ and R ² ′ are the same and are at least C ₅ alkyl, such as at least C ₈ alkyl, dialkyl phthalates of formula (I),
Or more preferably (iii) Formula (I) selected from the group consisting of propylhexyl phthalate (PrHP), dioctyl phthalate (DOP), di-iso-decyl phthalate (DIDP), and ditridecyl phthalate (DTDP) And more preferably dioctyl phthalate (DOP) such as di-iso-octyl phthalate or diethyl hexyl phthalate, in particular diethyl hexyl phthalate. Forming a first product,
The first product is subjected to suitable transesterification conditions, i.e. a temperature above 100 ° C, preferably between 100 ° C and 150 ° C, more preferably between 130 ° C and 150 ° C, so that the methanol Or ethanol is transesterified with the ester group of the dialkyl phthalate of formula (I), preferably at least 80 mol%, more preferably 90 mol%, most preferably 95 mol% of the dialkyl phthalate of formula (II).

(Wherein R ¹ and R ² are methyl or ethyl, preferably ethyl)
Wherein the dialkyl phthalate of formula (II) is an internal donor and the transesterification product is recovered as a procatalyst composition (component (i)) .

The adduct of formula MgCl ₂ * nROH, wherein R is methyl or ethyl and n is 1 to 6, is melted in a preferred embodiment, and then the melt is preferably cooled with a solvent. Alternatively, it is injected by gas into a cooled gas, so that the adduct is crystallized into a morphologically favorable form, for example as described in WO 87/07620.

  As described in WO 92/19658 and WO 92/19653, this crystallized adduct is preferably used as a catalyst support and reacted with a procatalyst useful in the present invention.

  Since the catalyst residue is removed by extraction, an adduct of a titanium-treated support and an internal donor in which the group derived from the ester alcohol has changed is obtained.

  If enough titanium remains on the support, this acts as an active element for the procatalyst.

  Otherwise, the titanium treatment is repeated after the above treatment to ensure sufficient titanium concentration and thus activity.

  Preferably, the procatalyst used according to the present invention contains 2.5 wt% or less, preferably 2.2% wt% or less, more preferably 2.0 wt% or less of titanium. The donor content is preferably between 4 wt% and 12 wt%, more preferably between 6 wt% and 10 wt%.

  More preferably, the procatalyst used according to the invention uses ethanol as the alcohol and dioctyl phthalate (DOP) as the dialkyl phthalate of formula (I) to give diethyl phthalate (DEP) as the internal donor compound. It is manufactured by this.

  Even more preferably, the catalyst used according to the invention is the catalyst described in the Examples section, in particular using dioctyl phthalate as the dialkyl phthalate of formula (I) according to WO 92/19658.

In a further embodiment, the Ziegler-Natta procatalyst can be modified by polymerizing a vinyl compound in the presence of a catalyst system comprising a special Ziegler-Natta procatalyst, an external donor and a cocatalyst, wherein the vinyl compound is formula:
_{^{CH 2 = CH-CHR 3 R}} 4
Wherein R ³ and R ⁴ together form a 5- or 6-membered saturated, unsaturated or aromatic ring, or independently an alkyl group containing from 1 to 4 carbon atoms And a modified catalyst is used in the production of the heterophasic polypropylene composition of the present invention. The polymerized vinyl compound can act as an α-nucleating agent. This modification is used in particular for the production of heterophasic polypropylene (H-PP1).

  For the modification of the catalyst, reference is made to international applications WO 99/24478, WO 99/24479 and in particular WO 00/68315, which are hereby incorporated by reference with respect to the reaction conditions for the modification of the catalyst and with respect to the polymerization reaction.

  In order to produce the heterophasic polypropylene of the present invention, the catalyst system used preferably comprises an organometallic cocatalyst as component (ii) in addition to the special Ziegler-Natta procatalyst.

  Accordingly, it is preferred to select the cocatalyst from the group consisting of trialkylaluminum such as triethylaluminum (TEA), dialkylaluminum chloride and alkylaluminum sesquichloride.

The component (iii) of the catalyst system used is an external donor represented by the formula (IIIa) or (IIIb). Formula (IIIa) is
Si (OCH ₃ ) ₂ R ₂ ⁵ (IIIa)
Wherein R ⁵ is a branched alkyl group having 3 to 12 carbon atoms, preferably a branched alkyl group having 3 to 6 carbon atoms, or 4 to 12 carbons. Represents a cycloalkyl having an atom, preferably a cycloalkyl having 5 to 8 carbon atoms.

R ⁵ is particularly preferably selected from the group consisting of isopropyl, isobutyl, isopentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

Formula (IIIb) is
Si (OCH ₂ CH ₃ ) ₃ (NR ^x R ^y ) (IIIb)
Wherein R ^x and R ^y can be the same or different and represent a hydrocarbon group having from 1 to 12 carbon atoms.

R ^x and R ^y are linear aliphatic hydrocarbon groups having 1 to 12 carbon atoms, branched aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and 1 to 12 Independently selected from the group consisting of cycloaliphatic hydrocarbon groups having the following carbon atoms: ^Rx and ^Ry consist of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl It is particularly preferred that they are selected independently from the group.

More preferably, R ^x and R ^y are both the same, even more preferably R ^x and R ^y are both ethyl groups.

  More preferably, the external donor of formula (IIIb) is diethylaminotriethoxysilane.

Most preferably, the external donor is of the formula (IIIa), such as dicyclopentyldimethoxysilane [Si (OCH ₃ ) ₂ (cyclo-pentyl) ₂ ] or diisopropyldimethoxysilane [Si (OCH ₃ ) ₂ (CH (CH _{3 2} ) ₂ ].

  The polypropylene composition of the present invention is suitable for a wide range of applications. In particular, the polypropylene composition of the present invention preferably retains mechanical properties such as excellent balanced rigidity / impact behavior without exhibiting tiger stripes.

  In view of the very good results obtained with the polypropylene composition (PP) of the present invention, the polypropylene composition (PP) is particularly suitable for the production of molded articles. Thus, another aspect of the present invention relates to an article comprising a polypropylene composition (PP) as defined above.

  For example, the article comprises a polypropylene composition (PP) in an amount of at least 60.0 wt%, more preferably at least 80.0 wt%, and most preferably at least 95.0 wt%, based on the total weight of the article. In one embodiment of the present invention, the article consists of the polypropylene composition (PP) of the present invention.

  The article is preferably a molded article, preferably an injection molded article. A preferred example of such an injection molded article is a large part for use in the automotive or household products industry. For example, the invention relates to automotive articles, in particular automotive interiors and exteriors, such as bumpers, body panels, spoilers, dashboards and / or door panels.

  Thus, the present invention particularly comprises at least 60.0 wt%, more preferably at least 80.0 wt%, even more preferably at least 95.0 wt% of the polypropylene composition (PP) of the present invention, for example said polypropylene composition ( PP), automotive interiors, in particular automotive interiors and exteriors, for example bumpers, body panels, spoilers, dashboards, door panels, etc., in particular bumpers and / or door panels.

  Accordingly, a further aspect of the present invention relates to the use of a polypropylene composition (PP) as defined above for producing a molded article. The polypropylene composition (PP) defined above is preferably used for the production of injection molded articles.

  A still further aspect of the present invention is a polypropylene composition as defined above for reducing tiger stripes on the surface of an article comprising an inventive polypropylene composition (PP), preferably consisting of said polypropylene composition (PP). (PP) is used.

  The invention will now be described in further detail by the following examples.

  The definitions and determination methods of the following terms apply not only to the examples described below but also to the general description of the invention described above, unless otherwise specified.

A. Definitions / Measurement Methods The definitions and determination methods of the following terms apply not only to the examples below but also to the general description of the invention described above, unless otherwise specified.

  Density is measured according to ISO1183-1-Method A (2004). The sample is manufactured by compression molding according to ISO 1872-2: 2007.

  The average particle size d50 (laser diffraction) is calculated from the particle size distribution [mass percent] determined by laser diffraction (Mastersizer) according to ISO 13320-1.

MFR ₂ (230 ° C.) is measured according to ISO 1133 (230 ° C., 2.16 kg load).

MFR ₁ (190 ° C.) is measured according to ISO 1133 (190 ° C., 2.16 kg load).

  Low temperature xylene solubles (XCS, wt%): The content of low temperature xylene solubles (XCS) is determined at 23 ° C. according to ISO 6427.

The amorphous content (AM) is measured by separating the low temperature xylene soluble fraction (XCS) and precipitating the amorphous part with acetone. The precipitate was filtered and dried in a 90 ° C. vacuum oven.
AM% = (100 × m ₁ × v ₀ ) / (m ₀ × v ₁ )
(Where “AM%” is the amorphous fraction,
“M ₀ ” is the initial polymer amount (g),
“M ₁ ” is the weight (g) of the precipitate,
“V ₀ ” is the initial volume (ml),
“V ₁ ” is the volume (ml) of the analyzed sample. )

  Intrinsic viscosity is measured according to DIN ISO 1628/1 (October 1999) (in decalin, 135 ° C.).

  Tensile strength; Tensile strain at break (or elongation at break) is an injection molded specimen as described in EN ISO 1873-2 (dogbone type, 4 mm thickness) Is measured according to ISO 527-2 (crosshead speed = 50 mm / min; 23 ° C.).

  The flexural modulus is determined by a three-point bend according to ISO 178 in an 80 × 10 × 4 mm injection molded test piece manufactured according to ISO 294-1: 1996.

  The notched Izod impact strength is determined at 23 ° C. according to ISO 180 / 1A by using test pieces (80 × 10 × 4 mm) injection-molded as described in EN ISO 1873-2.

The comonomer content, in particular ethylene content, is measured using Fourier transform infrared spectroscopy (FTIR) calibrated with ¹³ C-NMR. When measuring the ethylene content in polypropylene, a thin film of a sample (thickness of about 250 μm) is produced by a hot press method. Absorption peak areas at 720 cm ⁻¹ and 733 cm ⁻¹ were measured for the propylene-ethylene-copolymer using a Perkin Elmer FTIR 1600 spectrometer. The propylene-1-butene-copolymer was evaluated at 767 cm ⁻¹ . The method was calibrated with ethylene content data measured by ¹³ C-NMR. See also "IR-Spectroscopie fuer anneander"; WILEY-VCH, 1997 and "Valididiung in der Anallyik", WILEY-VCH, 1997.

  Tiger stripes: Tiger stripes are more likely to occur as 356 (L) x 70 (W) x produced by injection molding the extruded compound using an injection molding machine at an injection speed of 30 mm / s. A black sheet having a size of 2 (T) mm is visually evaluated. The tiger stripe on the surface of the black sheet is determined with the naked eye under the light source of a 40 W fluorescent lamp. “Eliminated” refers to a sheet that does not have any tiger stripes across the entire sheet surface under test conditions. “Distinguished” means that tiger stripes appear on the surface of the test sheet under the test conditions. “Inconspicuous” means that a slight tiger stripe occurs on the surface of the test sheet under test conditions, but is not noticeable.

B. Examples Polymers (HPP1a), (HPP1b), (HPP1c), (HPP1d) and (HPP2) were produced in a Borstar pilot plant having a prepolymerization reactor, one slurry loop reactor and two gas phase reactors. . After producing the matrix in the loop reactor and the first gas phase reactor, the elastic phase is produced in the second gas phase reactor.

The catalyst used in the polymerization process was prepared as follows. First, 0.1 mol of MgCl ₂ × 3 EtOH was suspended in 250 ml of decane in the reactor at atmospheric pressure under inert conditions. The solution was cooled to a temperature of −15 ° C. and 300 ml of cold TiCl ₄ was added while maintaining the temperature at the level. The slurry temperature was then slowly raised to 20 ° C. At this temperature, 0.02 mol of dioctyl phthalate (DOP) was added to the slurry. After the addition of the phthalate ester, the temperature was raised to 135 ° C. in 90 minutes and the slurry was allowed to stand for 60 minutes. An additional 300 ml of TiCl ₄ was then added and the temperature was kept at 135 ° C. for 120 minutes. After this, the catalyst was filtered from the liquid and washed 6 times with 300 ml heptane at 80 ° C. The solid catalyst component was then filtered and dried. Catalysts and their manufacturing concepts are generally described, for example, in patent publications EP49151566, EP5912224 and EP586390. Triethyl-aluminum (TEAL) was used as a cocatalyst and dicyclopentyldimethoxysilane (D donor) as a donor. The ratio of aluminum to donor is shown in Table 1.

  Prior to polymerization, the catalyst was prepolymerized with an amount of vinylcyclohexane that achieves a concentration of 200 ppm of poly (vinylcyclohexane) (PVCH) in the final polymer. The respective processes are described in EP1028984 and EP1183307.

  The compositions of Examples 1 to 10 are made using a Coperion STS-35 twin screw extruder based on the recipe summarized in Table 2.

^* The balance up to 100 wt% is usual additives such as antioxidants and UV stabilizers.

EE: A commercially available product “POE8150” from Dow Chemical Company (Shanghai, China). This is an elastic copolymer of ethylene and octene having an ethylene content of 61 wt%, an MFR ₁ (190 ° C., 2.16 kg) of 0.5 g / 10 min, and a density of 0.868 g / cm ³ .
HDPE: Panjin Petrochem. With a density of 0.95 g / cm ³ and MFR ₁ (190 ° C., 2.16 kg) of 7.5 g / 10 min. Co. A commercially available polyethylene product “HD5070EA” available from (Panjin, Liaing, China).
_{F: d 50} is 0.65 .mu.m, which is IMI Fabi China-made commercial talc "HTP Ultra 5".
P: Shanhai Yuchencancing Plastic Material Ltd. It is a commercially available pigment “CMB899-Black 9557” manufactured by (Shanghai, China).
AC: MFR ₂ (230 ° C., 2.16 kg) is a commercially available polypropylene powder “HC001A-B1” manufactured by Borealis AG, having a weight of 2.5 g / 10 min.

  For the manufacture of examples comprising the polypropylene composition of the present invention, a Coperion STS-35 twin screw extruder (available from Coperion (Nanjing) Corporation, China) is used with a diameter of 35 mm. The twin screw extruder is operated at an average rotational speed of 400 rpm with a zone temperature profile of 190 ° C to 235 ° C. The L / D of the extruder is 44. Table 3 lists the temperature in each zone, the throughput of the extruder to produce the compositions of the examples of the present invention, and the screw speed.

TZ zone temperature TD die temperature MT melting temperature T throughput SS screw speed V degree of vacuum

  The temperature, throughput and screw speed of each zone of the extruder are active parameters and are set on the control panel of the extruder. Melting temperature (temperature of the melt in the die) and extruder torque are passive parameters shown on the extruder control panel. The vacuum pump is located in zone 9 and generates a vacuum of -0.01 MPa inside the extruder.

  AC is used as a carrier and dispersant for further additives (scratch inhibitors, antioxidants and UV stabilizers). AC and further additives are premixed and then the resulting mixture is fed into the extruder from feeder 1 located in zone 1 of the extruder together with HPP1a / HPP1b / HPP1c / HPP1d, HPP2, EE, HDPE and P Supply. F is fed into the extruder from a side feeder located in zone 3 of the extruder. The contents of the extruder are heated, mixed through the zones 1-11 of the extruder, and granulated through the die head of the extruder.

  To produce standard molded specimens used to measure mechanical properties such as tensile, bending, and impact properties (eg notched Izod, 23 ° C.), and molded sheets for measuring “tiger stripes” The injection molding machine Victory 120 available from Engel Machinery (Shanghai) Ltd. is used. The injection molding machine has a single screw plasticizing part and an injection part. The single screw plasticizer has three heating zones. The injection unit has a nozzle and a mold. In the production of standard test samples for measuring mechanical properties, the mold is optionally provided with a small “V” notch on one side edge as shown in the test method described above. A standard mold having a dogbone or rectangular internal hollow cavity.

  The pellets of each composition of IE1 to IE10 obtained from the extruder as described above are fed into an injection molding machine. “Dogbone” or rectangular shape with “V” notch to measure the mechanical properties by heating the pellets in 3 heating zones, melting, mixing and then pouring into the mold from the nozzle The test sample is formed.

  The above-described injection molding machine is also used to produce a molded sample sheet for measuring “tiger stripe”, but the mold has dimensions of 356 (L) mm × 70 (W) mm × 2 (T) mm. Replace with molds suitable for manufacturing rectangular sheets. The dimensions and shape of the internal hollow cavity of the mold correspond to the mirror image of the sheet for testing the “tiger stripe”.

  The pellets of the composition of each example obtained in the extruder as described above are fed into an injection molding machine. The pellets are heated in three heating zones, melted, mixed and then injected through a nozzle into the hollow cavity of the mold to obtain a sheet for testing “tiger stripes”.

  Table 4 lists the processing parameters related to injection molding of molded specimens for measuring the mechanical properties of each example.

  Table 5 lists the processing parameters for sheet injection molding for measuring the “tiger stripe” of each example.

  The mechanical properties of the molded specimens and the “tiger stripe” of the molded sheet were measured according to the method described above and are shown in Table 6. The mechanical and optical properties (tiger stripe) profiles of Comparative Example 1 (CE1) and Comparative Example 2 (CE2), prior art formulations, are also summarized in Table 6 (6a-6b). The mechanical and optical properties of the prior art products (CE1 and CE2) are also tested according to the same method used in Examples 1-10.

E No occurrence C Conspicuous UC Inconspicuous

CE1 is a commercial product containing 67 wt% heterophasic propylene copolymer, 8 wt% HDPE, and 20 wt% talc, and balanced additive, the heterophasic propylene copolymer being 18 g / 10 min MFR _2. (230 ° C., 2.16 kg), 20% ethylene content, 30 wt% XCS, 29 wt% AM, the AM of the heterophasic propylene copolymer has an ethylene content of 69 wt%.
CE2 is a Pret Compositions Co. A commercial product of Ltd. (Shanghai, China) “C3322T-2”, polypropylene with MFR ₂ (230 ° C., 2.16 kg) higher than 60 g / 10 min, C2-C8 elastomeric copolymer, HDPE, talc, and balanced Contains added additives.

It can be seen from Tables 6a and 6b that no tiger stripes were produced in the examples of the present invention compared to Comparative Examples CE1 and CE2.
Furthermore, the examples of the present invention including EE, HDPE and F have a good balance of mechanical properties such as notched impact strength, stiffness and tensile strength, which is a comparative example containing similar components. Retained or better than CE1 and CE2.

Claims (18)

a) A first heterophasic propylene copolymer (HPP1) having a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 20.0 g / 10 min to 80.0 g / 10 min, measured according to ISO 1133, is converted into a polypropylene composition (PP 40.0 wt % to 60.0 wt % with respect to the total weight of
b) A second heterophasic propylene copolymer (HPP2) having a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 0.05 g / 10 min to 0.5 g / 10 min , measured according to ISO 1133, is converted into a polypropylene composition ( PP) for the total weight of 3) . 0 wt% to 20.0 wt%,
c) The elastic ethylene copolymer (EE) having an ethylene unit content of at least 50.0 wt% with respect to the total weight of the elastic ethylene copolymer (EE) is 5.0 wt% with respect to the total weight of the polypropylene composition (PP). ~ 20.0wt%,
d) high density polyethylene (HDPE), 5.0wt% ~10.0wt% against the total weight of the polypropylene composition (PP), and
e) 15.0 wt % to 25.0 wt % of the inorganic filler (F) with respect to the total weight of the polypropylene composition (PP) ,
A polypropylene composition (PP) comprising
i) The amount of the first heterophasic propylene copolymer (HPP1) is 66.6 wt% to 95.2 wt% based on the total weight of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2). Is within the range
ii) The amount of the second heterophasic propylene copolymer (HPP2) is from 4.8 wt% to 33.4 wt% based on the total weight of the first heterophasic propylene copolymer (HPP1) and the second heterophasic propylene copolymer (HPP2) range der of is,
The second heterophasic propylene copolymer (HPP2) is
a ') ISO16152 (measured according to 25 ° C.), 20.0 wt% of the low-temperature xylene-soluble fraction from 9.0 wt% relative to the total weight of the second heterophasic propylene copolyarylene Rimmer (HPP2) (XCS) fraction,
b ′) an ethylene content of 3.0 wt% to 8.0 wt% relative to the total weight of the second heterophasic propylene copolymer (HPP2) ;
c ′) an amorphous (AM 3 ) phase having an intrinsic viscosity (IV) of 3.0 dl / g to 4.0 dl / g , and
d ′) Amorphous (AM) phase having an ethylene content of 30.0 wt % to 37.0 wt % with respect to the total weight of the amorphous (AM) fraction of the second heterophasic propylene copolymer (HPP2)
Having
The polypropylene composition (PP). The first heterophasic propylene copolymer (HPP1) is
a) a melt flow rate MFR ₂ (230 ° C., 2.16 kg) of 20.0 g / 10 min to 75.0 g / 10 min measured according to ISO 1133, and / or b) a first measured according to ISO 16152 (25 ° C.) 15.0 wt% to 25.0 wt% low temperature xylene soluble fraction (XCS) fraction with respect to the total weight of the heterophasic propylene copolymer (HPP1), and / or c) the total weight of the first heterophasic propylene copolymer (HPP1) And / or d) an amorphous (AM) phase having an intrinsic viscosity (IV) of 2.0 dl / g to 3.0 dl / g, and / or e) 33.0 wt% to 40.0 wt% ethylene content based on the total weight of the amorphous (AM) phase of one heterophasic propylene copolymer (HPP1). Having an amorphous (AM) phase having a polypropylene composition according to claim 1 (PP).   The first heterophasic propylene copolymer (HPP1) has a polypropylene homopolymer matrix (PM1) and an elastic propylene copolymer (AM1) dispersed in said matrix (PM1) and / or a second heterophasic propylene copolymer ( The polypropylene composition (PP) according to claim 1 or 2, wherein the HPP2) has a polypropylene homopolymer matrix (PM2) and an elastic propylene copolymer (AM2) dispersed in the matrix (PM2). A polypropylene homopolymer matrix (PM1) of a first heterophasic propylene copolymer (HPP1)
a) a melt flow rate MFR ₂ (230 ° C., 2.16 kg) measured from 30.0 g / 10 min to 250.0 g / 10 min measured according to ISO 1133, and / or b) measured according to ISO 16152 (25 ° C.), first The polypropylene of claim 3 having a low temperature xylene solubles (XCS) fraction of 0.8 wt% to 3.0 wt% based on the total weight of the polypropylene homopolymer matrix (PM1) of the heterophasic propylene copolymer (HPP1). Composition (PP). A polypropylene homopolymer matrix (PM2) of a second heterophasic propylene copolymer (HPP2)
a) 0.1 g / 10 min to 3.0 g / 10 min melt flow rate MFR ₂ (230 ° C., 2.16 kg) measured according to ISO 1133, and / or b) measured according to ISO 16152 (25 ° C.), second The polypropylene composition according to claim 1 or 3 , having a low temperature xylene soluble fraction (XCS) fraction of less than 2.0 wt% relative to the total weight of the polypropylene homopolymer matrix (PM2) of the heterophasic propylene copolymer (HPP2). (PP). Elastic ethylene copolymer (EE)
a) comprising ethylene units and comonomer units selected from C _{4 to} C ₁₂ α-olefins and / or b) 50.0 wt% to 75.0 wt% ethylene relative to the total weight of the elastic ethylene copolymer (EE) Having a unit content and / or c) having a melt flow rate MFR ₁ (190 ° C., 2.16 kg) of 0.25 g / 10 min to 30.0 g / 10 min measured according to ISO 1133,
The polypropylene composition (PP) according to claim 1 . High density polyethylene (HDPE)
a) melt from 0.2 g / 10min as measured according to ISO1133 of 15.0 g / 10min Flow rate _{MFR 1 (190 ℃, 2.16kg)} , and / or b) having a density of at least 930 kg / ^{m 3,} claim The polypropylene composition (PP) according to 1 or 6 . Inorganic filler (F)
a) selected from the group consisting of talc, mica, calcium carbonate, diatomaceous earth, wollastonite and kaolin, and / or b) having an average particle size d ₅₀ of 0.65 μm to 20 μm,
The polypropylene composition (PP) according to any one of claims 1 to 7 . flexural modulus of at least 1500MPa measured according a) ISO178, and / or b) ISO180 (1A; having + 23 ° C.) is the 30 kJ / with ^m greater than ² notched Izod impact strength measured according to, claims 1 to 8 The polypropylene composition (PP) according to any one of the above. The polypropylene composition (PP) according to any one of claims 1 to 9 , wherein the first heterophasic propylene copolymer (HPP1) and / or the second heterophasic propylene copolymer (HPP2) is α-nucleated. First heterophasic propylene copolymer (HPP1) and second heterophasic propylene copolymer ( The polypropylene composition (PP) according to claim 10, wherein HPP2) is α-nucleated. . An article comprising the polypropylene composition (PP) , comprising the polypropylene composition (PP) according to any one of claims 1 to 11 . It consists of the polypropylene composition (PP) of any one of Claims 1-11. Item 13. The article according to Item 12. The article of claim 12 , which is a molded article . The article of claim 14 which is an injection molded article. Use of the polypropylene composition (PP) according to any one of claims 1 to 11 for producing a shaped article . Use according to claim 16, for the manufacture of injection molded articles. Use of a polypropylene composition (PP) in the manufacture of an article according to claim 12 or 13 for reducing tiger stripes on the surface of the article.