JP5052490B2 - Crystalline polypropylene resin composition and automotive interior / exterior parts - Google Patents

Description

  The present invention relates to a crystalline polypropylene resin composition that is less prone to surface tension in injection molding and an interior / exterior component for automobiles.

Polypropylene-based composite resin compositions are often used as injection-molded parts such as automobile parts and home appliance parts. In order to reduce the manufacturing cost of products, attempts have been made to shorten the time required for one molding (molding cycle) and increase the number of products molded per unit time. However, when the molding is simply performed to shorten the molding cycle, a defective phenomenon of poor surface tension occurs, and a good product cannot be obtained.
Accordingly, there is a demand for the development of materials that do not easily cause these defective phenomena even if the molding cycle is shortened.

As a material excellent in moldability, Patent Document 1 discloses a rigidity comprising polypropylene having a specific melt flow rate (MFR), an elastomer of an ethylene-α-olefin structure having a specific dynamic cutting property and talc— Excellent flowability, high rigidity, and low temperature comprising a polypropylene resin composition having an excellent balance between low temperature impact strength and moldability, and a propylene-ethylene block copolymer and an ethylene-α-olefin copolymer rubber of a specific MFR A propylene-based resin composition having impact strength is disclosed. Patent Document 2 discloses a propylene-ethylene block copolymer excellent in rigidity, impact resistance, and melt fluidity in which the molecular weight distribution of the crystalline polypropylene portion is in a specific range and the MFR is in a specific range. It is disclosed. Patent Document 3 discloses a specific MFR propylene-ethylene block copolymer, a specific melt index (MI) styrene- (ethylene / 1-butene) -styrene block copolymer, and styrene- (ethylene / propylene). A polypropylene composition for automobile parts, which is excellent in moldability, appearance, rigidity and impact resistance, comprising a styrene copolymer and an ethylene-α-olefin elastomer having a specific MI and talc is disclosed. Further, Patent Document 4 discloses two types of propylene-ethylene in which the intrinsic viscosity of the homopolypropylene part is in a specific range, and the ratio of the intrinsic viscosity of the ethylene-propylene copolymer part to the viscosity of the homopolypropylene part is in a specific range. A propylene-based resin composition having a high rigidity, a high impact property and a high fluidity comprising a block copolymer or a propylene-ethylene block copolymer, an elastomer having a specific intrinsic viscosity, and talc is disclosed.
However, when the molding cycle is shortened using the materials disclosed above, the filling time can be shortened. However, when the pressure holding time is shortened, voids and waviness are generated. For this reason, the materials disclosed above have a problem that there is a limit to shortening the molding cycle.
Japanese Patent Laid-Open No. 10-45969 JP-A-10-36466 Japanese Patent Laid-Open No. 2001-2841 JP 2000-344978 A

  An object of the present invention is to provide a polypropylene-based composite resin composition that hardly causes a defective phenomenon of surface tension even when the molding cycle in injection molding is shortened in view of the current state of the prior art.

  As a result of intensive investigations on the above-mentioned problems, the present inventors blended other general propylene polymers having specific physical properties with crystalline polypropylene having specific physical properties, and further used them as necessary. By combining the thermoplastic elastomer and the inorganic filler to be produced, it has been found that poor surface tension is hardly caused in injection molding, and the present invention has been completed based on this finding.

That is, according to the first invention of the present invention, the following component (A) is 1 to 80% by weight, component (B) is 5 to 95% by weight, component (C) is 0 to 30% by weight and component ( A crystalline polypropylene resin composition comprising 0 to 30% by weight of D) is provided.
Component (A): Propylene ethylene block copolymer (Ai) which is a crystalline polypropylene satisfying the following requirements (Ai) to (A-ii) Melt flow rate (MFR) (230 ° C., 2.16 kg) Load) is 10 to 200 g / 10 min.
(A-ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 5 or less.
Component (B): Propylene polymer satisfying the following requirements (Bi) to (B-vi) (Bi) Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.01 to 100 g / 10 min.
(B-ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
(B-iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(B-iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(Bv) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(B-vi) The degree of strain hardening (λmax) in the measurement of elongational viscosity is 6.0 or more.
Component (C): Thermoplastic elastomer Component (D): Inorganic filler

According to the second invention of the present invention, there is provided a crystalline polypropylene resin composition according to the first invention, wherein the component (B) further satisfies the following requirement (B-vii): Is done.
(B-vii) (ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]

According to the third aspect of the present invention, in the first or second aspect, the component (B) further satisfies the following requirement (B-viii): Is provided.
(B-viii) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where the peak height is 50% is L ₅₀ and H ₅₀ (L ₅₀ Is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 , Less than 2.0.

According to a fourth aspect of the present invention, there is provided an interior / exterior part for automobiles formed by injection molding the crystalline polypropylene resin composition according to any one of the first to third aspects.

As described above, the present invention relates to a crystalline polypropylene resin composition and the like, and preferred embodiments include the following.
(1) In any one of the above inventions, the propylene-based polymer of the component (B) is further a total skeleton-forming carbon of branched carbon (Cbr) observed at 31.6 to 31.7 ppm by ¹³ C-NMR. A crystalline polypropylene resin composition, wherein the number of branches per 1000 is 0.01 or more and 0.4 or less.
(2) In any one of the above inventions, the propylene-based polymer of component (B) further has a branched chain length of skeleton carbon number 500 (molecular weight conversion: 11,000) or more. -Based polypropylene resin composition.
(3) In any one of the above inventions, the propylene-based polymer of component (B) further has a stereoregularity of branched chain of 0.95 or more in mm. .

According to the crystalline polypropylene resin composition of the present invention, the molded product obtained from the composition can be suppressed from occurrence of poor surface tension and excellent in surface appearance.
Further, the crystalline polypropylene resin composition of the present invention has excellent impact resistance, rigidity and tensile strength, and is excellent in surface appearance, and therefore can be used as an interior / exterior part for automobiles. It is particularly effective for bumpers, side moldings, front and rear fenders, back door panels, instrument panels, trims, pillars, and the like.

  The crystalline polypropylene resin composition of the present invention may be abbreviated as crystalline polypropylene (A) (hereinafter simply referred to as “component (A)”) that satisfies the following requirements (Ai) to (A-ii). ) 1 to 80% by weight, and a propylene polymer (B) satisfying the following requirements (Bi) to (B-vii) (hereinafter sometimes simply referred to as “component (B)”). 5 to 95% by weight, and, if necessary, 0 to 30% by weight of the thermoplastic elastomer of the component (C) and 0 to 30% by weight of the inorganic filler of the component (D).

(Ai) The melt flow rate (MFR) (230 ° C., 2.16 kg load) is 10 to 200 g / 10 minutes.
(A-ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 5 or less.

(Bi) Melt flow rate (MFR) (230 degreeC, 2.16kg load) is 0.01-100 g / 10min.
(B-ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
(B-iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(B-iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(Bv) The isotactic triad fraction (mm fraction) measured by ¹³ C-NMR is 95% or more.
(B-vi) The degree of strain hardening (λmax) in the measurement of elongational viscosity is 6.0 or more.

  Hereinafter, each component of the crystalline polypropylene resin composition of the present invention, its production, production of the resin composition, molded article and the like will be described in detail.

[I] Constituent Component of Crystalline Polypropylene Resin Composition [I-1] Component (A): Crystalline Polypropylene Crystalline polypropylene used as component (A) in the present invention is the above-mentioned requirements (Ai) to ( A-ii) has only to have the characteristics and properties, and examples thereof include propylene homopolymers and propylene / α-olefin random copolymer having an α-olefin polymerization unit of 3% by weight or less. And a propylene block copolymer containing a propylene homopolymer or a crystalline polypropylene portion made of the propylene / α-olefin random copolymer and a propylene / α-olefin random copolymer portion. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-pentene-1. A highly crystalline polypropylene resin, which is a general-purpose product that is economically available, is advantageously applied to the present invention.

Component (A) has a melt flow rate (MFR, JIS K7210, 230 ° C., 2.16 kg load) of 10 to 200 g / 10 minutes, preferably 20 to 150 g / 10 minutes, more preferably 50 to 120 g / 10 minutes. is there. If the MFR exceeds the above range, the impact strength of the product will be insufficient, and the fluidity will become too large, making injection molding difficult, which is not preferable. On the other hand, if the MFR is below the above range, flow failure occurs during injection molding, which is not preferable.
The fluidity of the component (A) is appropriately selected using MFR as an index. The intrinsic viscosity [η] _P of the component (A) is usually 0.3 to 2.0 dl / g, preferably 0.5. Since it is -1.3 dl / g, it can also be managed together with MFR. The intrinsic viscosity is measured in 135 ° C. tetralin.

  The component (A) is also characterized in that the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn: Q value) is 5 or less. The Q value is preferably 1 to 4.5, and more preferably 3.5 to 4. Here, it is evaluated that the larger the Q value, the wider the molecular weight distribution. Voids are less likely to occur due to the narrow molecular weight distribution and the higher mold pressure. Since automobile parts are required to have a high cycle and a high appearance, if the molecular weight distribution of component (A) is too wide, the commercial value may be impaired. Therefore, in order to satisfy such a demand, the component (A) preferably has a molecular weight distribution within the above range. By adding the component (B) described later, it is possible to achieve both high cycle and high appearance. It becomes.

Component (A) has an isotactic triad fraction (mm) of preferably 95% or more, more preferably 96% or more, and still more preferably 97% or more. If the value of the isotactic triad fraction is too low, the rigidity of the finally obtained resin composition may be insufficient. In addition, an isotactic triad fraction represents the isotactic triad fraction in the triad unit in the polypropylene molecular chain measured using < ¹³ > C-NMR (nuclear magnetic resonance method).
The isotactic triad fraction is measured according to the method described later.

  Furthermore, the component (A) used in the present invention has a strain hardening degree (λmax) in the measurement of elongational viscosity of preferably less than 1.5, more preferably less than 1.1, and still more preferably 1. It is less than 05. By doing so, the molding temperature region is greatly improved by improving the surface appearance.

[I-2] Component (B): Propylene-based polymer The propylene-based polymer [hereinafter also referred to as propylene-based polymer (B)] used as the component (B) in the present invention is the above-mentioned requirement (Bi ) To (B-vi), or in addition to these, the following characteristics (B-vii) and / or requirements (B-viii) have characteristics and properties.
(B-vii): ME (memory effect) satisfies the following relational expression.
(ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]
(B-viii): In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position that is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is a lower molecular weight side than Tp, H ₅₀ is a higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is from 0.9 Large and less than 2.0.
Hereinafter, each item will be described sequentially.

I. Propylene polymer (B) structure, long chain branch structure definition and identification method Propylene polymer (B) has a balance between physical properties and melt processability with controlled melt fluidity (melt stretchability) and melt tension. Is a long-chain branched propylene-based polymer.
The propylene-based polymer is considered to have a markedly improved melt property due to the introduction of the long chain branching.
In general, ¹³ C-NMR is used for directly detecting and quantifying the branched structure and the number of branches. Further, ¹³ C-NMR, GPC-vis, and GPC-malls are used for detection and quantification of the number of branches and branch distribution. However, the above method has a limit of quantification. At present, rheological methods are considered to have the highest sensitivity as a method for evaluating branching. For example, measurement of flow activation energy in linear viscoelasticity measurement and strain hardening degree in elongational viscosity measurement are generally used at this stage as a method for detecting a small amount of branching.
Regarding the branched structure, the mechanism and mechanism capable of forming the branched structure are considered as follows.

That is, from the active species derived from the catalyst component [A-1] used in the method for producing a propylene-based polymer, which will be described later, one end of the polymer mainly has a propenyl structure (by a special chain transfer reaction generally called β-methyl elimination). Vinyl structure) and so-called macromers are formed.
The terminal propenyl structure (vinyl structure) terminated by the β-methyl elimination reaction is shown below (reference document: Macromol. Rapid Commun. 2000, 21, 1103-1107).

This macromer, which will be described later, is capable of generating a higher molecular weight and is incorporated into the active species derived from the catalyst component [A-2] having better copolymerization properties, and it is assumed that the macromer copolymerization is in progress. .
Therefore, the propylene polymer (B) has a specific branched structure as shown in the following structural formula (2).
In Structural Formula (2), Ca, Cb, and Cc represent methylene carbon adjacent to the branched carbon, Cbr represents the methine carbon at the root of the branched chain, and P ¹ , P ² , and P ³ represent propylene-based heavy ions. Combined residues are indicated.
P ¹ , P ² , and P ³ may contain a branched carbon (Cbr) different from Cbr described in the structural formula (2) in itself.

Such a branched structure is identified by ¹³ C-NMR analysis. The assignment of each peak is described in Macromolecules, Vol. 35, no. 10. The description of 2002, pages 3839-3842 can be referred to. That is, a total of three methylene carbons (Ca, Cb, Cc) were observed, each at 43.9-44.1 ppm, 44.5-44.7 ppm, and 44.7-44.9 ppm. Methine carbon (Cbr) is observed at ˜31.7 ppm. Hereinafter, the methine carbon observed at 31.5 to 31.7 ppm may be abbreviated as branched carbon (Cbr).
It is characterized in that three methylene carbons adjacent to the branched methine carbon Cbr are observed in three non-equivalent diastereotopics.

The branched chain assigned by ¹³ C-NMR referred to in the present invention represents a propylene polymer residue having 5 or more carbon atoms branched from the main chain of the propylene polymer (B). It can be distinguished from a branch having 4 or less carbon atoms by the difference in the peak position of the branched carbon (see Macromol. Chem. Phys. 2003, Vol. 204, p. 1738).

In general, considering the definition of the number of branches and the length of the polymer, the higher the number of branches, the better the melt properties. On the other hand, it is considered that if the number of branches is unevenly distributed between the molecules, a gel is generated and the effect of improving the melt properties is reduced.
The number of branches is defined as the number of branches (density) per 1000 total skeleton-forming carbons of the branched carbon (Cbr) observed at 31.5 to 31.7 ppm using the assignment by ¹³ C-NMR. . However, the total skeleton-forming carbon means all carbon atoms other than methyl carbon.

As a result of ¹³ C-NMR measurement, it can be seen that a small amount of branched components are present in the propylene polymer (B) exhibiting improved melt properties.
On the other hand, when the amount of branching is too large, there is a concern that gel is generated and the appearance of the molded product is impaired. Furthermore, there is a problem of causing deterioration of melt fluidity.
Therefore, the number of branches is 0.01 or more as a lower limit, 0.4 or less, and preferably 0.2 or less as an upper limit.
Even in the case of using the current ¹³ C-NMR of high magnetic field NMR, it is difficult to determine with a small amount of about 0.1 unless measurement is performed for a very long time. When the amount of branching was small, instead of this, branching was evaluated by a more sensitive rheological method. As a result, the obtained strain hardening degree (λmax) is defined to be 6.0 or more.

Moreover, in order to show high strain hardening like the propylene polymer (B), it is considered that a branching length of 7000 or more, which is an entanglement molecular weight of polypropylene, is necessary (reference: Macromolecules. 1998, 31, 1335, Macromolecules). 2002, 35, 10062).
This corresponds to about 400 or more in terms of the number of skeleton carbon atoms. As used herein, skeletal carbon means all carbon atoms other than methyl carbon. It is considered that the melt physical properties are further improved as the branch length becomes longer.
Therefore, the branched chain length of the propylene-based polymer (B) is not less than 500 skeletal carbon (polypropylene molecular weight conversion: 11,000), preferably not less than 1000 skeleton carbon atoms (polypropylene molecular weight conversion: 21,000). More preferably, it has 2000 or more skeleton carbon atoms (polypropylene molecular weight conversion: 42,000).

The polypropylene molecular weight converted value here is strictly different from the molecular weight value measured by GPC, but approximates the number average molecular weight (Mn) measured by GPC.
Therefore, the branch length of the propylene-based polymer (B) is 11,000 or more, preferably 21,000 or more, more preferably 42,000 or more in terms of number average molecular weight (Mn) measured by GPC, Replaced.

Further, when considering the polymerization mechanism, the macromer generated from the active species derived from the catalyst component [A-1] is incorporated into the main chain to form a branched structure, so that the average molecular weight of the macromer is that of the incorporated branched chain. Characterized as average molecular weight.
For example, in the propylene-based polymer (B), when the molecular weight of the macromer generated from the active species derived from [A-1] is 50,000 in the number average molecular weight, the average molecular weight of the incorporated branched chain is 50,000, Converted to skeleton carbon, it is interpreted as 2400.
The number average molecular weight of the macromer generated from the active species derived from the above [A-1] is based on the molecular weight when the polymerization is carried out by the peak top of the portion derived from [A-1] in GPC or [A-1] alone. Can be estimated.

On the other hand, the branched distribution of the polymer can be measured by GPC-vis or GPC-malls, but from the polymerization mechanism, the macromer derived from [A-1] is a component having a higher molecular weight and higher copolymerization [ It is considered that a long-chain branch is introduced into the molecular weight component derived from [A-2] because it is considered that a branch is generated by incorporation into the active species derived from A-2].
Since the molecular weight component derived from the catalyst component [A-2] has a higher molecular weight than the molecular weight component derived from [A-1], the branched distribution has a high molecular weight side ([A-2] derived side). In addition, it is considered that the distribution form is introduced with branching.
In addition, the molecular weight component derived from [A-1] also has a branched structure formed by incorporating the macromer by [A-1] itself.
An example of the molecular weight distribution derived from [A-1] and [A-2] is shown in FIG.

The relation between the number of branches and the branch distribution will be explained. In order to improve the melt properties, it is generally considered that a large number of branches is necessary. As a conventional branched propylene polymer, for example, No. -154121 discloses a propylene homopolymer having a branch number of 0.1 / 1000 skeleton carbon or more.
However, the strain hardening degree (λmax) in the measurement of the extensional viscosity of the disclosed propylene homopolymer is less than 6.0, and the strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (B) is less than 6.0. Even compared with 6.0 or more, the improvement effect is not sufficient. This is because the desired branching component is not sufficiently introduced because it is produced from a single complex, meaning that the effect of improving the melt properties is small even if the number of branches is simply large on average.
The propylene-based polymer (B) does not necessarily have a larger number of branches (average value) than a conventional branched polymer, but by introducing multiple branches into the high molecular weight side by combining a plurality of complexes. The melt properties are remarkably improved.

Further, the stereoregularity of the side chain will be described. The stereoregularity of the main chain and the side chain is determined by the stereoregular ability of [A-1] and [A-2] used, respectively. If the stereoregularity of the side chain is low, even if the crystallinity of the main chain is high, the overall crystallinity is deteriorated. Therefore, in order to obtain a higher-rigidity polymer, it is preferable that the side chain and the main chain have high stereoregularity. As the value, both the main chain and the side chain are 95% or more in mm fraction. Especially preferably, it is 96% or more, More preferably, it is 97% or more.
The stereoregularity of the side chain is considered to be equal to the stereoregularity of the polymer by [A-1] alone.
The details of the stereoregularity of the main chain and side chain will be described later.

II. Physical Properties of Propylene Polymer (B) The propylene polymer (B) is excellent in the balance between physical properties and melt processability with controlled melt fluidity (melt spreadability) and melt tension. The physical properties of the propylene polymer (B) will be described.
1. Melt flow rate (MFR)
As shown in the requirement (i), the propylene polymer (B) has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 Kg of 0.01 g / 10 min or more and 100 g / 10 min or less. Need to be.
MFR is an indicator of fluidity, and this value decreases as the molecular weight of the polymer increases, while this value increases as the molecular weight decreases. When this value is small, the fluidity is deteriorated. Accordingly, the MFR needs to be 0.01 g / 10 min or more, preferably 0.1 g / 10 min or more, and more preferably 0.3 g / 10 min or more.
On the other hand, when this value is large, the fluidity is improved, but the molecular weight is too small, which causes a deterioration in mechanical properties such that the impact strength is reduced when formed into a molded body. Therefore, the MFR needs to be 100 g / 10 min or less, preferably 80 g / 10 min or less, more preferably 60 g / 10 min or less.

The melt flow rate (MFR) is a test condition in accordance with JIS K6921-2 “Plastics—Polypropylene (PP) molding and extrusion materials—Part 2: How to make test pieces and properties”. : A value measured at 230 ° C. and a load of 2.16 kgf.
The melt flow rate (MFR) of the propylene polymer (B) can be easily changed by changing the temperature and pressure conditions of propylene polymerization, or by adding a chain transfer agent such as hydrogen during polymerization as the most general technique. Adjustments can be made.

2. Average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC
As shown in the requirement (ii), the propylene-based polymer (B) is a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), Mw / Mn (Q Value) in the range of 3.5 or more and 10.5 or less.
The Q value is an index representing the spread of the molecular weight distribution, and the larger the value, the wider the molecular weight distribution. If the Q value is too small, the distribution is narrow, and the balance between melt fluidity and workability becomes poor. Accordingly, the Q value needs to be 3.5 or more, and is preferably a value larger than 4.0. More preferably, the value is greater than 4.5. On the other hand, if the Q value is too large, the amount of unnecessary (low) molecular weight components increases, which may deteriorate the melt fluidity. Therefore, the Q value needs to be 10.5 or less, preferably less than 8.0, and more preferably less than 7.5.
The average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC of the propylene polymer (B) can be changed by changing the temperature and pressure conditions of propylene polymerization, or the most common technique is hydrogen or the like The chain transfer agent can be easily adjusted by adding the chain transfer agent during propylene polymerization. Furthermore, when using 2 or more types of the metallocene complex to be used, it can control by changing the quantity ratio.

3. Biasing of molecular weight distribution obtained from GPC molecular weight distribution curve toward high molecular weight side As shown in the above requirement (viii), the propylene polymer (B) has a peak position in the molecular weight distribution curve obtained by GPC. The common logarithm of the corresponding molecular weight is Tp, and the common logarithm of the molecular weight at the position where the peak height is 50% is L ₅₀ and H ₅₀ (L ₅₀ is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp) , Α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, it is desirable that α / β is greater than 0.9 and less than 2.0. Here, α / β is an index representing the deviation of the molecular weight distribution toward the high molecular weight side.
The spread of the molecular weight distribution is indicated by a molecular weight distribution curve obtained by GPC. That is, a graph is created in which the common logarithm of molecular weight (MW) is plotted on the horizontal axis and the relative differential mass of the molecule corresponding to the MW is plotted on the vertical axis.
The molecular weight (MW) referred to here is the molecular weight of individual molecules constituting the propylene polymer, and is different from the weight average molecular weight (Mw) of the propylene polymer. FIG. 1 is a diagram showing an example of a molecular weight distribution curve. Α and β are obtained from the created graph. In the present invention, as described above, it is desirable that α / β is greater than 0.9 and less than 2.0.

Usually, when uniform polymerization is carried out with a catalyst having a single active site, the molecular weight distribution has the most probable distribution shape. The most probable distribution α / β is calculated as 0.9.
Therefore, the molecular weight distribution of the propylene-based polymer (B) means that the molecular weight distribution of the propylene-based polymer (B) is further widened to the higher molecular weight side than the molecular weight distribution of the polymer that is uniformly polymerized at a single active site.
If α / β is 0.9 or less, the amount of the high molecular weight component is relatively insufficient, so the swell ratio becomes small and the moldability deteriorates.
Therefore, it is desirable that the propylene polymer (B) has an α / β value greater than 0.9, preferably 1.0 or more, and more preferably 1.1 or more.

On the other hand, when α / β is 2.0 or more, the amount of the high molecular weight component is too large, which causes deterioration of melt fluidity.
Accordingly, the propylene-based polymer (B) desirably has an α / β of less than 2.0, preferably less than 1.8, more preferably less than 1.7, and still more preferably less than 1.6. It is.
In the molecular weight distribution curve, two or more peaks may appear. In that case, the maximum peak can be replaced with the peak of the present invention. Also, if the H ₅₀ appears two or more may be replaced with the molecular weight of the lowest molecular weight side. Similarly, when two or more L ₅₀ appear, the molecular weight on the lowest molecular weight side can be replaced.
For the bias of the molecular weight distribution obtained from the molecular weight distribution curve by GPC of the propylene polymer (B) to the high molecular weight side, select one that can produce a high molecular weight polymer as one of the two types of metallocene complexes used In addition, adjustment can be easily performed by controlling the amount of hydrogen added during polymerization. It can also be adjusted by changing the amount ratio of the two metallocene complexes used.

4). Ratio of components having a molecular weight (M) of 2 million or more in the molecular weight distribution curve by GPC As shown in the above requirement (iii), the propylene-based polymer (B) has a total molecular weight in the molecular weight distribution curve obtained by GPC. On the other hand, the ratio of components having a molecular weight (M) of 2 million or more (W (2 million or more)) is 0.4% by weight or more and less than 10% by weight.
The ratio of 2 million or more (W (2 million or more)) is an index indicating the ratio of a very high molecular weight component contained in the polymer.
The very high molecular weight component ratio W (2 million or more) is an integral molecular weight distribution curve obtained by GPC (the total amount is normalized to 1), and the molecular weight (M) is 2 million (Log (M) = 6). .3) The integral value up to the following is defined as a value obtained by subtracting from 1. An example of the integrated molecular weight distribution curve is also shown in FIG.

As described above, when the amount of the high molecular weight component is insufficient, the swell ratio becomes small and the moldability deteriorates. Therefore, a component having a high molecular weight is necessary, and the moldability is efficiently improved by containing a small amount of a component having a very high molecular weight. This very high molecular weight component is considered to contain a branched component as described above.
Therefore, the propylene polymer (B) desirably has W (2 million or more) of 0.4% by weight or more, preferably 1.0% by weight or more, and more preferably 2.0%. % By weight or more.
However, when the ratio of this component is too high, the fluidity is deteriorated. In addition, since it is a component having a very high molecular weight, a gel is generated, resulting in a problem that the appearance of the molded product is impaired. Moreover, when the ratio of this component is too high, deterioration of melt fluidity will be caused.
Therefore, the propylene polymer (B) desirably has W (2 million or more) less than 10% by weight, preferably less than 6.0% by weight, and more preferably less than 5% by weight.
The proportion of the component having a molecular weight (M) of 2 million or more in the molecular weight distribution curve by GPC of the propylene polymer (B) is selected after selecting a metallocene complex that can produce a high molecular weight polymer. Adjustment can be easily made by controlling the amount ratio of the metallocene complex to the metallocene complex, the amount of hydrogen added during propylene polymerization, and the polymerization temperature.
So far, adjustment methods related to the molecular weight of the propylene-based polymer such as the ratio of components having MFR, Q value, α / β and molecular weight (M) of 2 million or more have been described. For example, control of the amount of hydrogen can be given as a common control method. When the amount of hydrogen is increased, the MFR of the propylene polymer increases, and the ratio of components having a Q value, α / β, and molecular weight (M) of 2 million or more tends to decrease. On the other hand, it is possible to increase the MFR by increasing the polymerization temperature or decreasing the monomer partial pressure. In this case, the ratio of components having a molecular weight (M) of 2 million or more decreases, but the Q value and α / Β is not significantly affected. In addition, the ratio of components having a molecular weight (M) of 2 million or more with respect to MFR can be controlled by changing the amount and type of the metallocene complex that produces the high molecular weight side. In this way, the regulation can be controlled by changing the catalyst used and the polymerization conditions.

  The weight average molecular weight (Mw), Q value, α / β, and W (over 2 million) values defined above are all obtained by gel permeation chromatography (GPC). Details of the measuring method and measuring equipment are as follows.

Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The sample is prepared by preparing a 1 mg / ml solution using ODCB (containing 0.5 mg / ml BHT) and dissolving it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are as shown in FIG.
Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is generated by injecting 0.2 ml of a solution dissolved in ODCB (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml. The calibration curve uses a cubic equation obtained by approximation by the least square method.
Viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

5. Elevated temperature elution fractionation with orthodichlorobenzene (ODCB) (TREF)
As shown in the requirement (iv), for example, the propylene homopolymer elutes at a temperature of 40 ° C. or less in the elution curve obtained by the temperature rising elution fractionation (TREF) measurement. The component is 3.0% by weight or less.
A component that elutes at a temperature of 40 ° C. or lower is a low crystalline component. If the amount of this component is large, the crystallinity of the entire product is lowered, and the mechanical strength such as the rigidity of the product is lowered.
Therefore, this amount needs to be 3.0% by weight or less, preferably 2.0% by weight or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. .
The temperature rising elution fractionation (TREF) of the propylene polymer (B) with orthodichlorobenzene (ODCB) can generally be kept low by using a metallocene complex. In addition to maintaining, it is necessary that the catalyst production method and the reaction conditions during polymerization are not extremely high, and that the amount ratio of the organoaluminum to the metallocene complex is not excessively increased.

The details of the measurement method of the eluted component by temperature rising elution fractionation (TREF) are as follows.
A sample is dissolved in orthodichlorobenzene at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, and then cooled to 40 ° C. at a rate of 4 ° C./min, and held for 10 minutes. Thereafter, orthodichlorobenzene as a solvent is allowed to flow through the column at a flow rate of 1 ml / min, and components dissolved in orthodichlorobenzene at 40 ° C. are eluted in the TREF column for 10 minutes, and then the heating rate is 100 ° C./hour. The column is linearly heated to 140 ° C. to obtain an elution curve.

Column size: 4.3mmφ × 150mm
Column packing material: 100 μm surface inert treatment glass beads Solvent: Orthodichlorobenzene Sample concentration: 5 mg / ml
Sample injection volume: 0.1 ml
Solvent flow rate: 1 ml / min Detector: Fixed wavelength infrared detector, manufactured by FOXBORO, MIRAN, 1A
Measurement wavelength: 3.42 μm

6). Isotactic triad fraction (mm) measured by ¹³ C-NMR
As shown in the requirement (v), the propylene-based polymer (B) has a stereoregularity in which the mm fraction of the three propylene unit chains obtained by ¹³ C-NMR is 95% or more.
The mm fraction is the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same among arbitrary three propylene unit chains composed of head-to-tail bonds in the polymer chain. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control.
If the mm fraction is smaller than this value, the mechanical properties such as the elastic modulus of the product are lowered. Therefore, the mm fraction is preferably 96% or more, and more preferably 97% or more.
Further, the stereoregularity of the main chain and the side chain is determined by the stereoregular ability of the catalyst components [A-1] and [A-2] used in the production method of the propylene polymer (B) described later. If the stereoregularity of the side chain is low, even if the crystallinity of the main chain is high, the overall crystallinity is degraded. Therefore, in order to obtain a higher rigidity polymer, it is preferable that the side chain and the main chain have high stereoregularity. As the value, the main chain and the side chain are 95% or more in mm fraction. Especially preferably, it is 96% or more, More preferably, it is 97% or more.
The isotactic triad fraction (mm) measured by ¹³ C-NMR of the propylene polymer (B) can be easily adjusted by the selection of the metallocene complex to be used and the polymerization temperature.

The detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg was completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift was set to 74.2 ppm in the middle of the three peaks of deuterated 1,1,2,2-tetrachloroethane. The chemical shift of other carbon peaks is based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768

The mm fraction is measured using a ¹³ C-NMR spectrum measured under the above conditions.
Spectral assignments were made with reference to Macromolecules, (1975) 8６８, 687 and Polymer, 30: 1350 (1989).

A more specific method for determining the mm fraction will be described below.
Peaks derived from the methyl group of the three-chain central propylene bonded head-to-tail around the propylene unit occur in three regions depending on the configuration.
mm: about 24.3 to about 21.1 ppm
mr: about 21.2 to about 20.5 ppm
rr: about 20.5 to about 19.8 ppm
The chemical shift range of each region slightly shifts depending on the molecular weight and copolymer composition, but the above three regions can be easily identified.
Here, mm, mr, and rr are each represented by the following structure.

The mm fraction is calculated from the following mathematical formula (I).
mm fraction = mm area peak area / (mm area peak area + mr area peak area + rr area peak area) × 100 [%] (I)

  Further, the propylene polymer (B) may have the following partial structure containing an ethylene unit.

  The methyl group (PPE-methyl group) of the central propylene unit of the partial structure PPE resonates in the mr region around 20.9 ppm, and the methyl group (EPE-methyl group) of the central propylene unit of the partial structure EPE is 20.2 ppm. Since resonance occurs in the vicinity of the rr region, in the case of having such a partial structure, it is necessary to reduce the peak areas based on the PPE-methyl group and the EPE-methyl group from the peak areas of both the mr and rr regions. The peak area based on the PPE-methyl group can be evaluated by the peak area of the corresponding methine group (resonance at around 31.0 ppm), and the peak area based on the EPE-methyl group is resonant at the corresponding methine group (around 33.3 ppm). ) Peak area.

  Moreover, as a partial structure containing a position irregular unit, it may have the following structure (5-a), structure (5-b), structure (5-c), and structure (5-d).

Among them, the carbon A, A ′, A ″ peaks appear in the mr region, and the carbon B, B ′ peaks appear in the rr region. Further, the carbon C, C ′ peaks appear in 16.8 to 17.8 ppm. .
Therefore, when calculating the mm fraction in the formula (I), the carbon appearing in the mr and rr regions from the peak area of the mr region and the peak area of the rr region, respectively, from the peak not based on the head-to-tail three-linkage. It is necessary to reduce the peak area based on A, A ′, A ″, B, B ′.

The peak areas based on carbon A are carbon D (resonance around 42.4 ppm), carbon E and G (resonance around 36.0 ppm) and carbon F (38 in the position irregular substructure [structure (5-a)]). It can be evaluated from 1/4 of the sum of the peak areas of resonance at around .7 ppm.
The peak areas based on carbon A ′ are carbon H and I (resonance around 34.7 ppm and around 35.0 ppm) and carbon J It can be evaluated by 2/5 of the sum of peak areas (resonance around 34.1 ppm) and the sum of peak areas of carbon K (resonance around 33.7 ppm).
The peak area based on carbon A ″ can be evaluated by the sum of peak areas of carbon L (resonance in the vicinity of 27.7 ppm) of the position irregular partial structure [structure (5-d)].
The peak area based on carbon B can be evaluated by carbon J. The peak area based on carbon B ′ can be evaluated by carbon K.
Note that the positions of the carbon C peak and the carbon C ′ peak need not be considered because they are not related to the focused mm, mr, and rr regions.
As described above, since the peak areas of mm, mr, and rr can be evaluated, it is possible to obtain the mm fraction of the triple chain portion composed of the head-to-tail bond with the propylene unit as the center according to the above formula (I).

7). Strain hardening degree (λmax) in measurement of elongational viscosity
The propylene-based polymer (B) needs to have a strain hardening degree (λmax) of 6.0 or more in the measurement of elongational viscosity as shown in the requirement (vi).
The strain hardening degree (λmax) is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension. As a result, for example, the ME effect during injection molding can be increased.
Therefore, the strain hardening degree is required to be 6.0 or more, preferably 7.0 or more, more preferably 8.0 or more, and further preferably 9.0 or more.
The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain.
Therefore, the greater the amount of branching and the longer the branching length, the greater the degree of strain hardening.
At the present time, it is considered to be the most sensitive method for evaluating branching. Since the branched structure cannot be directly evaluated by ¹³ C-NMR, the strain hardening degree is used as an index of branching instead of the method. It was.

In general, in order to show a high degree of strain hardening, a branching length of 7,000 or more, which is an entanglement molecular weight of polypropylene, is required. When converted into skeleton carbon number, it corresponds to about 400 or more. As used herein, skeletal carbon means all carbon atoms other than methyl carbon. It is considered that the melt physical properties are further improved as the branch length becomes longer. In particular, when a longer branched chain is introduced, strain hardening is considered to be detected even in a slower strain rate region in the measurement of elongational viscosity.
Therefore, the branched chain length of the propylene-based polymer (B) is not less than 500 skeletal carbon (converted to polypropylene molecular weight: 11,000) as described above, preferably 1000 skeletal carbon (converted to polypropylene molecular weight: 2. 10,000) or more, and more preferably 2000 or more skeleton carbon atoms (polypropylene molecular weight conversion: 42,000).
As described above, the polypropylene molecular weight conversion value here is strictly different from the molecular weight value measured by GPC, but approximates the number average molecular weight (Mn) measured by GPC.
Therefore, the branch length of the propylene-based polymer (B) is 11,000 or more, preferably 21,000 or more, more preferably 42,000 or more in terms of number average molecular weight (Mn) measured by GPC, Can be replaced.
The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene polymer (B) is controlled by selecting the two types of metallocene complexes constituting the catalyst used for propylene polymerization, the amount ratio thereof, and the prepolymerization conditions. It can be increased to 6 or more. That is, one of the two types of metallocene complexes is selected so as to easily generate a macromer, and the other is selected so that the macromer can be easily incorporated into the polymer and can generate a high molecular weight polymer. Furthermore, by performing prepolymerization, long chain branches are uniformly distributed among the polymer particles.

  Here, as to the method for measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial extensional viscosity can be measured. For example, details of the measuring method and measuring instrument can be found in the publicly known document Polymer 42 ( 2001) 8663, but preferable measuring methods and measuring instruments include the following.

Measuring method 1:
Apparatus: Ales manufactured by Rheometrics
Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and a thickness of 0.7 mm is formed by press molding.

Measurement method 2:
Apparatus: Toyo Seiki Co., Ltd., Melten Rheometer
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: Extruded strands are prepared at a speed of 10 to 50 mm / min using an orifice with an inner diameter of 3 mm at 180 ° C. using a Capillograph manufactured by Toyo Seiki Co., Ltd.

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η _E (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before the strain hardening is approximated by a straight line, the maximum value (ηmax) of the elongational viscosity η _E until the strain amount becomes 4.0 is obtained, and the approximate straight line up to that time Let the upper viscosity be ηlin.
FIG. 4 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The strain rate can be measured in the range of 0.001 / sec to 10.0 / sec, and the strain hardening degree varies depending on the difference in strain rate. The strain rate dependence of the strain hardening degree is considered to change depending on the form and length of the introduced branch.

8). Memory effect (ME)
As for propylene polymer (B), as shown to said requirement (vii), it is desirable for a memory effect (ME) to satisfy | fill the following relational expression (I-1).
(ME) ≧ −0.26 × log (MFR) +1.9 (I-1)
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]

In the propylene-based polymer (B), preferably, a correlation between a memory effect (ME) that is an index indicating the abundance ratio of a high molecular weight component in a polymer and an MFR that is an index indicating an average molecular weight of the polymer is a specific relationship ( It is characterized by being in the above formula (I-1)).
ME is an index representing the non-Newtonian property of a polymer, and a large ME indicates that a component having a long relaxation time exists in the polymer. That is, when ME is large with the same MFR, it means that the long-term relaxation component is distributed in the polymer.
Further, it is empirically known that ME has a first-order correlation with Log (MFR), and generally, the larger the molecular weight (that is, the smaller the MFR value), the larger the ME value. .

The propylene polymer (B) is characterized in that the ME in the MFR match is larger than that of conventionally known polymers due to the presence of a branching component in the polymer chain. When the amount of the long-term relaxation component is large, the swell becomes large, and it is known that the molding characteristics are excellent, such as the generation of flow marks during injection molding, and the propylene-based polymer (B) according to the present invention is Excellent molding characteristics.
More preferably, the following relational expression (I-2) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.20 (I-2)
More preferably, the following relational expression (I-3) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.40 (I-3)

  The memory effect (ME) was measured using a melt indexer manufactured by Takara, and extruded at 190 ° C. with an orifice diameter of 1.0 mm and length of 8.0 mm under a load. The extrusion speed was 0.1 g. At the time of / min, the polymer extruded from the orifice is quenched in ethanol, and the value of the strand diameter at that time is divided by the orifice diameter.

9. Melt tension and maximum winding speed Since the propylene polymer (B) has a controlled branch structure (branch amount, branch length, branch distribution), the melt physical properties are remarkably improved. That is, it has excellent melt spreadability while having high melt tension. As an index of melt tension and melt spreadability, it can be expressed by a balance between melt tension (MT) and maximum winding speed (MaxDraw) measured by the following measuring method.

A method for measuring the melt tension (MT) and the maximum winding speed (MaxDraw) will be described.
Using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd., the tension detected by the pulley when the resin is extruded in a string shape under the following conditions and wound on a roller is defined as a melt tension (MT).
Capillary: 2.1mm in diameter
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10 mm / min Winding speed: 4.0 m / min Temperature: 230 ° C.

When the winding speed is gradually increased from 4.0 m / min (acceleration: 5.4 cm / s ² ), the winding speed immediately before the string-like material is cut is the maximum winding speed (MaxDraw). To do.
Here, a larger MT value means higher melt tension, and a larger MaxDraw means better fluidity and spreadability.
The propylene-based polymer (B) has improved melt tension by broadening the molecular weight distribution and introducing branching. Therefore, MT is 5 g or more, preferably 10 g or more, more preferably 15 g or more. .

In addition, as described above, when the high molecular weight component is increased or the number of branches is increased, the MT value can be increased, but conversely, the polymer has too many high molecular weight components or the branches are unevenly distributed. Then, the viscosity becomes too high during winding, causing breakage of the string-like material, and MaxDraw does not increase. That is, the melt ductility is deteriorated.
The propylene-based polymer (B) can have a large MaxDraw while maintaining a high MT by controlling the branching component, and the balance between melt tension and melt spreadability is improved.
Therefore, the propylene polymer (B) has a MaxDraw of 10 m / min or more, preferably 20 m / min or more, and more preferably 30 m / min or more.

As described above, the propylene-based polymer (B) is a long-chain branched type in which the melt fluidity is controlled and the balance between physical properties and processability is excellent. In contrast to the conventional propylene-based polymer, for example, the above-mentioned Japanese Patent Application Laid-Open No. 2007-154121 discloses a propylene homopolymer having a branch number of 0.1 / 1000 skeleton carbon or more, but the measurement of elongational viscosity. The strain hardening degree (λmax) is less than 6, and the effect of improving the melt properties is not sufficient even when the strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene polymer (B) is 6.0 or more. Absent. In addition, in the commercial product of polypropylene that is crosslinked by electron beam irradiation and has a high degree of long-chain branching (base melt high melt tension polypropylene, “PF814”), the branched carbon of the structural formula (2) described above is not detected. The isotactic triad fraction (mm) by ¹³ C-NMR is low (92.5%), and it is considered that molecular cutting and isomerization occur simultaneously with crosslinking upon irradiation with an electron beam. Solvent soluble components are increasing. In addition, as another general method for controlling the molding processing characteristics, control is performed by expanding the molecular weight distribution. However, when the molecular weight distribution is expanded, the low molecular weight component is increased, resulting in molding. Demerits such as deterioration of the surface characteristics of the body, deterioration of mechanical properties and heat sealability occur.
However, the propylene-based polymer (B) is controlled by expanding the molecular weight distribution by broadening the molecular weight distribution and introducing branching, but the high molecular weight component increases without increasing the low molecular weight component. Therefore, the above disadvantages do not occur.
Thus, since the propylene-based polymer (B) is a long-chain branched type, it has excellent balance between physical properties and processability, controlling melt fluidity not found in conventional propylene-based polymers. It has become.

III. Production method of propylene polymer (B) The method of producing the propylene polymer (B) is excellent in the balance between physical properties and workability by controlling the melt fluidity and melt tension, which are the characteristics of the present invention. There is no particular limitation as long as it is a method capable of obtaining a long-chain branched propylene polymer. For example, examples of a method for introducing a controlled branched component include a method using a plurality of complexes as described below. Can do.
That is, a method for producing the above long-chain branched propylene polymer, characterized in that propylene polymerization is performed in the presence of a catalyst containing at least the components shown in the following (A) to (C). Examples include a method for producing a propylene-based polymer.
Catalyst component (A): From component [A-1] which is a compound represented by the following general formula (a1) and from component [A-2] which is a compound represented by the general formula (a2) At least one, two or more selected Group 4 transition metal compounds of the periodic table Component [A-1]: Compound represented by general formula (a1) Component [A-2]: Represented by general formula (a2) Compound Catalyst Component (B): Ion Exchange Layered Silicate Catalyst Component (C): Organoaluminum Compound

Hereinafter, the catalyst components (A), (B), and (C) will be described in detail.
(1) Catalyst component (A)
(I) Component [A-1]: Compound represented by general formula (a1)

[In General Formula (a1), each of R ¹¹ and R ¹² independently represents a heterocyclic group containing nitrogen, oxygen, or sulfur having 4 to 16 carbon atoms. In addition, each of R ¹³ and R ¹⁴ is independently halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a C 6-16 aryl that may contain a plurality of hetero elements selected from these Represents a heterocyclic group containing a group, nitrogen or oxygen having 6 to 16 carbon atoms, and sulfur. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen, or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted group. 2-furfuryl group, more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples thereof include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.

Carbon atoms 6 to 16 of the R ¹³ and R ^14, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or, as the aryl group which may contain a plurality of hetero elements selected from these, In the range of 6 to 16 carbon atoms, on the aryl cyclic skeleton, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogens having 1 to 6 carbon atoms You may have a containing hydrocarbon group as a substituent.
At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-t-butylphenyl group, a 2,3-dimethylphenyl group, a 3,5-dit-butylphenyl group, or a 4-phenyl-phenyl group. , A chlorophenyl group, a naphthyl group, or a phenanthryl group, and more preferably a phenyl group, a 4-t-butylphenyl group, and a 4-chlorophenyl group. Moreover, the case where two R < ₂ > is mutually the same is preferable.

In the general formula (a1), X ¹¹ and Y ¹¹ are auxiliary ligands and react with the cocatalyst of the component (B) to generate an active metallocene having an olefin polymerization ability. Therefore, as long as this purpose is achieved, X ¹ and Y ¹ are not limited to the type of ligand, and each independently represents hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown. .

In the general formula (a1), Q ¹¹ is a silylene that may have a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings. Represents either a group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (a1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-Phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4- Enyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-methyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4-isopropyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5 -Methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-Methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4 -(4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1 , 1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] Hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, and the like. .

  Of these, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethyl gel are more preferable. Mylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-naphthyl-indenyl}] hafnium, dichloro [1,1′-dimethyl Silylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.

  Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4-naphthyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t -Butylphenyl) -indenyl}] hafnium.

(Ii) Component [A-2]: Compound represented by general formula (a2)

[In General Formula (a2), each of R ²¹ and R ²² is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, It is a C6-C16 aryl group which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon number It represents a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. M ²¹ is zirconium or hafnium. ]

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ²³ and R ²⁴ each independently contain a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, halogen, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5 -Dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like.

Further, the X ²¹ and Y ²¹ are auxiliary ligands to generate an active metallocene having olefin polymerizability reacts with the cocatalyst component (B). Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently hydrogen, halogen group, hydrocarbon group having 1 to 20 carbon atoms, carbon An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown.

Q ²¹ is a binding group that crosslinks two conjugated five-membered ring ligands, and a silylene having a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. Or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked. Specific examples include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene and the like.

Further, M ²¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the metallocene compound represented by the general formula (a2) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Moreover, although the compound whose center metal is hafnium was described, it is obvious that the same zirconium compound can be used, and various ligands, crosslinking groups, or auxiliary ligands can be arbitrarily used.
Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl)- 4-Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl) -4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium , Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl -4- (1-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1, 1'-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazule Nil}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl-] 4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1 1'-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (3-Methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 '-(9-silafluorene- 9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (2-fluoro- 4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) ) -4-hydroazurenyl}] hafnium, and the like.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

(2) Catalyst component (B)
Next, the catalyst component (B) is an ion-exchange layered silicate.
(I) Types of ion-exchange layered silicates The ion-exchange layered silicate used as a raw material (hereinafter simply abbreviated as silicate) is a structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other by a binding force. This refers to a silicate compound having a crystal structure and containing exchangeable ions. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can. Depending on the type, amount, particle diameter, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in component (B).
In addition, a raw material refers to the silicate of the previous stage which performs the chemical process mentioned later. The silicate is not limited to a natural product, and may be an artificial synthetic product. You may include them.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectite groups, vermiculite groups such as vermiculite, mica, illite, sericite, sea chlorite and other mica groups, attapulgite, sepiolite, palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.

  The silicate used as a raw material is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

(Ii) Chemical treatment of ion-exchangeable layered silicate The ion-exchangeable layered silicate of the catalyst component (B) can be used as it is without any particular treatment, but it is preferable to perform chemical treatment. Here, the chemical treatment of the ion-exchange layered silicate can be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Treatment, alkali treatment, salt treatment, organic matter treatment and the like.

<Acid treatment>:
In addition to removing impurities on the surface, the acid treatment can elute part or all of cations such as Al, Fe, Mg, etc. having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
Two or more salts (described in the next section) and acid may be used for the treatment. The treatment conditions with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.
In the present invention, a combination of the following acids and salts may be used as the treating agent. A combination of these acids and salts may also be used.

<Salt treatment>:
40% or more, preferably 60% or more of the exchangeable Group 1 metal cation contained in the ion-exchange layered silicate before being treated with salts, cations dissociated from the following salts and ions It is preferable to exchange.
The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of 2 to 14 atoms, and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

Specific examples of such _{salts, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4 , LiClO ₄ , Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg ( PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.
Further, Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr _{3 and the} like.

Also, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Mn (OOCCH ₃ ) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , Fe (OOCCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ FeCl ₃ , FeC ₆ H ₅ O _{7 and the} like.

In addition, Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.

Furthermore, Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

<Alkali treatment>:
In addition to acid and salt treatment, the following alkali treatment or organic matter treatment may be performed as necessary. Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.

<Organic treatment>:
Examples of the organic treatment agent used for organic treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. It is not limited to these.

  Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the catalyst component (B).
The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the catalyst component (B) after the removal is 3% by weight or less when the water content when dehydrating for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight, It is preferably 1% by weight or less.

  As described above, as the catalyst component (B), an ion-exchange layered silicate having a water content of 3% by weight or less obtained by performing salt treatment and / or acid treatment is particularly preferable.

  The ion-exchange layered silicate is preferable because it can be treated with a catalyst component (C) described later before use as a catalyst or as a catalyst. Although there is no restriction | limiting in the usage-amount of the catalyst component (C) with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

  The catalyst component (B) is preferably spherical particles having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.

Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

(3) Catalyst component (C)
The catalyst component (C) is an organoaluminum compound. As an organoaluminum compound, a general formula:
(AlR ¹¹ _q Z _3-q ) _p
(In the formula, R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, Z represents a halogen, hydrogen, an alkoxy group, an amine residue, q represents an integer of 1 to 3, and p represents an integer of 1 to 2. )
Are suitable. R ¹¹ is preferably an alkyl group, and Z is chlorine when it is halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 carbon atom when it is an amine residue. ~ 8 are preferred.
The compound represented by this general formula may be used individually by 1 type, and multiple types may be mixed or used together.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride having p = 1 and q = 3 are preferable. More preferably, R ¹¹ is a trialkylaluminum having 1 to 8 carbon atoms.

(4) Catalyst Formation / Preliminary Polymerization The catalyst according to the present invention is formed by bringing the above-mentioned components into contact with each other in the (preliminary) polymerization tank simultaneously or continuously, or once or multiple times. Can do.
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When the catalyst component (C) is used, before the catalyst component (A) and the catalyst component (B) are contacted, the catalyst component (A), or the catalyst component (B), or the catalyst component (A) and the catalyst Contacting catalyst component (C) with both components (B), or contacting catalyst component (C) with catalyst component (A) and catalyst component (B), or catalyst component Although it is possible to contact the catalyst component (C) after bringing the catalyst component (B) into contact with (A), it is preferable that the catalyst component be brought into contact with the catalyst component (A) before contacting the catalyst component (B). It is a method of contacting any of the component (C).
Moreover, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of the catalyst components (A), (B) and (C) used in the present invention is arbitrary. For example, the amount of the catalyst component (A) used relative to the catalyst component (B) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the catalyst component (B). The amount of the catalyst component (C) with respect to the catalyst component (A) is preferably a transition metal molar ratio of preferably 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1000.

Although the ratio of component [A-1] and component [A-2] used by this invention is arbitrary in the range with which the characteristic of a propylene polymer (B) is satisfy | filled, each component [A-1] and [A The molar ratio of the transition metal of [A-1] to the total amount of [-2] is preferably 0.30 or more and 0.99 or less.
From component [A-1], a low molecular weight terminal vinyl macromer is produced, and from component [A-2], a high molecular weight product obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [A-1], the average molecular weight, molecular weight distribution, bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branch (amount, length, Distribution) can be controlled, whereby the melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled. In order to produce the propylene polymer (B) for applications that require higher melt properties and higher catalyst activity, it is particularly preferably 0.40 or more, and further preferably 0.5 or more. The upper limit is particularly preferably 0.90 or less, and more preferably 0.8 or less.
Further, it is possible to adjust the balance between the average molecular weight and the catalyst activity with respect to the amount of hydrogen used.

  The catalyst according to the present invention is subjected to a prepolymerization treatment consisting of a small amount of polymerization by bringing an olefin into contact therewith. By performing the prepolymerization treatment, gel formation can be prevented when the main polymerization is performed. The reason is considered to be that long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed, and the melt properties can be improved thereby.

  The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Styrene and the like can be exemplified. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 with respect to the component (B). Moreover, a component (C) can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.

  In addition, a method of coexisting a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or titania, at the time of contacting or after contacting each of the above components is also possible.

(5) Use of Catalyst / Propylene Polymerization As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst including the catalyst components (A), (B) and (C) and the monomer efficiently contact each other. .
Specifically, a slurry method using an inert solvent, a so-called bulk method using a propylene as a solvent without using an inert solvent as a solvent, a solution polymerization method, or a monomer without using a liquid solvent substantially. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.

In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.
The polymerization temperature is 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

The polymerization pressure is 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, when using vapor phase polymerization, 1.2 MPa or more is preferable, and 1.5 MPa or more is more preferable. The upper limit is preferably 3.0 MPa or less, more preferably 2.5 MPa or less.

Further, hydrogen can be used as a molecular weight regulator and for the purpose of improving the activity.
Hydrogen is used in a feed ratio of 0 to 1 mol% with respect to propylene, preferably 0.0001 mol% or more, and more preferably 0.001 mol% or more.
By changing the amount of hydrogen used, in addition to the average molecular weight of the polymer produced, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, distribution) The melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled.

The propylene-based polymer (B) used in the present invention may be a propylene homopolymer, or in addition to a propylene monomer, an α-olefin having about 2 to 20 carbon atoms (excluding those used as monomers) is a comonomer. It may be a propylene α-olefin copolymer obtained by carrying out the copolymerization used as. The (total) comonomer content in the propylene polymer (B) is preferably in the range of 0 mol% or more and 20 mol% or less. Specifically, the α-olefin used as a comonomer is ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., and these may be used alone. A plurality of types may be used in combination.
In order to obtain a good balance between the melt properties and the catalytic activity of the propylene polymer (B), the comonomer such as ethylene is preferably 5 mol% or less. In order to obtain a polymer having particularly high rigidity, the comonomer contained in the polymer should be 1 mol% or less, and more preferably a propylene homopolymer.

(6) Consideration of polymerization mechanism It is considered that the formation of a macromer is generated by a special chain transfer reaction generally called β-methyl elimination. In the present invention, the component [A-1] having a specific structure is In a relatively low temperature range (40 ° C. to 80 ° C.), the selectivity of the β-methyl elimination reaction during the growth termination reaction is high, and the ratio of the β-methyl elimination reaction to the polymer growth reaction is that of the conventional structure. The inventors have found that it is larger than the complex.
Conventionally, in order to preferentially cause the β-methyl elimination reaction, it could only be produced under special conditions (low pressure, high temperature polymerization, no hydrogen addition) in slurry polymerization with a low propylene concentration, By using the component [A-1] having a specific structure, industrially effective bulk polymerization or gas phase polymerization, and practical pressure conditions (1.0 to 3.0 MPa) and temperature conditions (40 ° C. It was found that the production is possible under ˜80 ° C.).

Furthermore, surprisingly, by adding hydrogen, the chain transfer reaction by hydrogen is superior to the β-methyl elimination reaction in the conventional method, whereas the cause is unknown, but It has been found that the method for producing the union (B) has a small change in the balance between macromer formation and growth reaction even when hydrogen is added, and the macromer selectivity is hardly changed even in the presence of hydrogen. Moreover, hydrogen has an activity improving effect.
This is because, in the past, it has been necessary to perform a multi-stage polymerization in which a macromer copolymerization is performed after a macromer generation step which is a special condition (low pressure, high temperature, no hydrogen addition), whereas the component [A-2 ], It was found that the macromer production step and the macromer copolymerization step can be performed under the same conditions, that is, simultaneous polymerization and single-stage polymerization can be performed.

On the other hand, since the component [A-2] has a specific structure, it has a high ability to copolymerize a macromer even though it does not have the ability to form a terminal vinyl structure, and further compared to the component [A-1]. And has the ability to produce higher molecular weight polymers. Further, when hydrogen is added, the activity is improved, and the molecular weight is lowered due to chain transfer by hydrogen.
Conventionally, macromer formation and macromer copolymerization are produced by a single complex, that is, in order to produce a polymer with the same complex of component [A-1] and component [A-2], If either the capacity or the macromer copolymerization capacity is insufficient, the amount of branching component introduced is insufficient on the high molecular weight side, or if hydrogen is used to adjust the molecular weight, the production amount of the macromer itself decreases. There was a problem of doing.

However, in the present invention, the component [A-1] having a specific structure having macromer generation ability and the component [A-2] having a specific structure having high molecular weight and macromer copolymerization ability are combined in a specific method. By using it as a catalyst, it is an industrially effective method such as bulk polymerization or gas phase polymerization, especially in single-stage polymerization under practical pressure-temperature conditions, and using hydrogen as a molecular weight regulator. It has been found that it is possible to produce a long-chain branched propylene-based polymer having the following physical properties:
Further, conventionally, it has been necessary to increase the branch generation efficiency by reducing the crystallinity by using a component having low stereoregularity, but in the method of the present invention, a component having sufficiently high stereoregularity, It can be introduced into the side chain by a simple method.

[I-3] Component (C)
In the crystalline polypropylene resin composition of the present invention, a thermoplastic elastomer can be used as the component (C) for the purpose of improving impact resistance and dimensional stability.

Examples of the component (C) used in the present invention include an ethylene / propylene copolymer elastomer (ethylene propylene rubber; EPR), an ethylene / butene copolymer elastomer (EBR), and an ethylene / hexene copolymer elastomer (EHR). , Ethylene / α-olefin copolymer elastomers such as ethylene / octene copolymer elastomer (EOR); ethylene / propylene / ethylidenenorbornene copolymer, ethylene / propylene / butadiene copolymer, ethylene / propylene / isoprene copolymer Ethylene / α-olefin / diene terpolymer elastomers such as styrene / butadiene / styrene triblock (SBS), hydrogenated styrene / butadiene / styrene triblock (SEBS), styrene isop Examples thereof include styrene-based elastomers such as a hydrogenated styrene / isoprene / styrene triblock (SEPS), a styrene / isoprene / styrene triblock (SIS), and the like.
These elastomers can be used in combination of two or more.

[I-4] Component (D)
In the crystalline polypropylene resin composition of the present invention, an inorganic filler can be used as the component (D) for the purpose of improving rigidity and dimensional stability.

Examples of the component (D) used in the present invention include silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice, pumice balun and other oxides, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate and other hydroxides. , Carbonates such as calcium carbonate, magnesium carbonate, dolomite, dosonite, sulfates or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, talc, clay, mica, glass fiber, glass balloon, glass beads, silicic acid Carbons such as calcium, wollastonite, montmorillonite, bentonite, carbon black, graphite, carbon fiber, carbon hollow sphere, molybdenum sulfide, boron fiber, zinc borate, barium metaborate, calcium borate, Boric acid Thorium, magnesium oxysulfate, basic magnesium sulfate fibers, may be mentioned potassium titanate fibers, aluminum borate fibers, calcium silicate fibers, calcium fibers carbonate, various metal fibers and the like.
These inorganic fillers can be used in a mixture of two or more.

[I-5] Other components (E)
The crystalline polypropylene resin composition of the present invention contains the above-described components (A) to (B), and optionally components (A) to (D) as essential components. Other additional components can be blended within a range that does not significantly impair the effects of the present invention. Examples of such additional components include crystallization nucleating agents, lubricants such as fatty acid amides, fatty acid glycerin esters and amine- or amide-based antistatic agents, peroxides and other molecular weight regulators, foaming agents, organic or inorganic substances. Pigments, dispersants, light stabilizers, UV absorbers, antioxidants, neutralizers, antacids, metal deactivators, surfactants, antibacterial agents, flame retardants, organic fillers, etc. Can do.

  Examples of the crystallization nucleating agent include inorganic substances such as talc, aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, and rosin metal salts. Among them, preferred is an AL salt of p-t-butyl-benzoate, sodium benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 1,2,3,4- Dibenzylidenesorbitol, 1,2,3,4-bis (paramethylbenzylidene) sorbitol, 1,2,3,4-bis (paraethylbenzylidene) sorbitol, 1,2,3,4-bis (parachlorbenzylidene) Examples thereof include metal salts of sorbitol and rosin (lithium, sodium, potassium, magnesium salts).

  As the antibacterial agent, either an organic type or an inorganic type may be used. Examples of organic materials include chlorine, phenol, imidazole, thiazole, and quaternary ammonium compounds. Examples of inorganic systems include zeolite, apatite system, silica alumina system, ceramic system, zirconium phosphate system, phosphate glass system, silica gel system, hydroxyapatite as examples of holding and containing metals such as silver and zinc. System, calcium silicate system and the like.

[II] Crystalline polypropylene resin composition Ratio of each component The mixing ratio of each component in the crystalline polypropylene resin composition of the present invention is 1 to 80% by weight of component (A), 5 to 95% by weight of component (B), and 0 to 0 of component (C). 30 wt%, component (D) 0-30 wt%, preferably component (A) 5-70 wt%, component (B) 5-60 wt%, component (C) 5-25 wt% %, Component (D) is 5 to 20% by weight, more preferably component (A) is 5 to 50% by weight, component (B) is 5 to 50% by weight, and component (C) is 10 to 25% by weight. Component (D) is 10 to 20% by weight. Here, the total amount of the components (A) to (D) is 100% by weight.

  If the amount of the component (A) is too large, the wave will be easily generated or the tiger mark will be deteriorated. If the amount is too small, voids will be generated or the weld appearance will be deteriorated. If the component (B) is too much, the weld appearance is adversely affected. If it is too little, sufficient surface tension performance cannot be exhibited. When there are too many components (C), product rigidity will fall. When there are too many components (D), the weight of a product will increase and impact performance will fall.

2. Production The production method of the crystalline polypropylene resin composition of the present invention is not particularly limited, and may be a conventionally known method such as mixing and melt-kneading each compounding component. For example, each compounding component is predetermined. Examples thereof include a method of blending at a blending ratio and kneading and granulating using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, and a kneader.

3. Properties The MFR of the crystalline polypropylene resin composition of the present invention is preferably 10 g / 10 min or more, more preferably 15 g / 10 min or more. Furthermore, if it is 20 g / 10min or more, it is more preferable. If the MFR is 10 g / 10 min or less, short shots are likely to occur during molding.

[III] Polypropylene-based resin molded product The crystalline polypropylene resin composition of the present invention can be used to form various molded products by known molding methods such as injection molding, extrusion molding, hollow molding, foam molding, and the like. it can. In particular, in injection molding, the occurrence of poor surface tension can be suppressed, and a molded product having an excellent surface appearance can be obtained.
The obtained molded product can be suitably used for interior and exterior parts for automobiles. Examples of exterior parts for automobiles include bumpers, side moldings, front and rear fenders, back door panels, spoilers, door mirror housings, door knobs, front grills, and lamp housings. In addition, examples of interior parts for automobiles include instrument panels, pillars, door trims, glove boxes, door knobs, and the like.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, the physical property measurement, analysis, evaluation, and the like in the following examples are according to the following methods. In addition, the following materials were used as materials such as resin.

1. Physical property measurement (1) Melt flow rate (MFR):
In accordance with JIS K6921-2, “Plastics—Polypropylene (PP) molding and extrusion materials—Part 2: How to make test pieces and properties” Test flow: 230 ° C., load 2 .16 kgf) was measured. The unit is g / 10 minutes.
(2) Molecular weight and molecular weight distribution (Mw, Mn, Q value, α / β, W (2 million or more)):
It was measured by the method described in the present specification by gel permeation chromatography (GPC).
(3) mm fraction:
The measurement was carried out by the method described in the present specification using GSX-400 and FT-NMR manufactured by JEOL. The unit is%.
(4) Measurement of ethylene content:
^A calibration curve was prepared using ¹³ C-NMR and measured using IR.
(5) Elongation viscosity:
It was measured by the method described in the present specification.
(6) Composition analysis:
A calibration curve was prepared by chemical analysis according to JIS method and measured by fluorescent X-ray.

2. Evaluation test method by injection molding (1) Surface tension:
Using a crystalline polypropylene resin composition in the form of pellets, an injection molding machine (Toshiba Machine, IS170FII) is used. , 6 s, and 9 s, a sheet test piece (3 × 120 × 120 mmt) having a pin gate of 1 mm at the center of the side surface thickness was prepared, and the appearance was observed. The evaluation criteria are as follows.
(A) Void:
○: No void was observed on the test piece surface.
X: Void was recognized on the test piece surface.
(B) Wave out:
A: No waviness was observed on the surface of the test piece.
○: Some undulations were observed on the test piece surface.
X: Waves were observed on the entire surface of the test piece.

3. Materials used (I) Crystalline polypropylene resin (A)
Propylene ethylene block copolymers (A-1) to (A-2) having physical properties shown in Table 1 below were used.

(II) Propylene polymer (B)
The propylene resins (B-1) to (B-5) produced in the following polymerization examples 1 to 5 were used.

(1) Production of propylene polymer (B) [Catalyst Synthesis Example 1]:
(1-1) Chemical treatment of ion-exchange layered silicate:
In a separable flask, 96% sulfuric acid (1044 g) was added to 3456 g of distilled water, and then 600 g of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2400 g of distilled water and then filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

(1-2) Catalyst preparation and prepolymerization:
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (65 ml) was added to form a slurry. 6 ml) and stirred for 1 hour, washed with heptane to a residual liquid ratio of 1/100, and heptane was added so that the total volume became 100 ml.
In another flask (volume 200 ml), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) indenyl}] Hafnium (105 μmol) was dissolved in toluene (30 ml) (solution 1), and in another flask (volume 200 ml), rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4 -Chlorophenyl) -4-hydroazurenyl}] hafnium (45 μmol) was dissolved in toluene (12 ml) (solution 2).

Triisobutylaluminum (0.6 mmol: 0.83 ml of a heptane solution with a concentration of 143 mg / ml) was added to a 1 L flask containing the above chemically treated smectite, then the above solution 1 was added, and after 5 minutes, the above solution 2 was added. And stirred at room temperature for 1 hour.
Thereafter, 356 ml of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 2 hours. Thereafter, the propylene feed was stopped, the temperature was raised to 50 ° C., and residual polymerization was performed until the pressure in the autoclave reached 0.05 MPa. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.3 ml of a heptane solution having a concentration of 143 mg / ml) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 2 hours to obtain 27.5 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.75 (preliminary polymerization catalyst 1).

[Catalyst synthesis example 2]:
In (1-2) catalyst preparation and prepolymerization in Catalyst Synthesis Example 1, rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] Hafnium (135 μmol) was dissolved in toluene (38 mL) to form solution 1, and rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium ( 15 μmol) was dissolved in toluene (4 mL) and used as Solution 2, and the same experiment as in Catalyst Synthesis Example 1 was performed.
As a result, 28.4 g of a dry prepolymerized catalyst was obtained. The prepolymerization ratio was 1.84 (preliminary polymerization catalyst 2).

[Polymerization Example 1]:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 ml of a heptane solution of triisobutylaluminum (143 mg / ml), 120 Nml of hydrogen was introduced. Next, after introducing 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 120 mg of the above prepolymerized catalyst 1 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 3 hours, 5 ml of ethanol was injected to stop the polymerization to obtain 456 g of a polymer.
Table 2 shows the analysis results of the polymer (B-1) thus obtained.

[Polymerization Example 2]:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (143 mg / mL), 300 NmL of hydrogen was introduced. Next, after introducing 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 100 mg of the prepolymerized catalyst 1 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 1 hour, 5 ml of ethanol was injected to stop the polymerization. As a result, 405 g of a polymer was obtained.
Table 2 shows the evaluation results of the obtained polymer (B-2).

[Polymerization Example 3]:
In a 1 L autoclave thoroughly purged with nitrogen, 500 ml of heptane, 2.5 ml of MMAO, 2.5 ml of MMAO and 1 ml of a toluene solution of dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride (1 mg / ml) were added. What was activated by contact was introduced and kept at 50 ° C. Propylene was slowly introduced, and finally polymerization was carried out for 1 hour while maintaining the pressure in the polymerization tank at 0.5 MPa. After completion of the polymerization, the polymer was collected by filtration and dried under reduced pressure to obtain 35 g of polymer.
The evaluation results of the obtained polymer (B-3) are shown in Table 2.

[Polymerization Example 4]:
[Synthesis of Solid Catalyst Component (Z)]
A 10 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified n-heptane was introduced. Further, 250 g of MgCl ₂ and 1.8 L of Ti (On-Bu) ₄ were added, and a reaction was performed at 95 ° C. for 2 hours. The reaction product was cooled to 40 ° C. and 500 ml of methyl hydrogen polysiloxane (20 centistokes) was added. After 5 hours of reaction at 40 ° C., the precipitated solid product was thoroughly washed with purified n-heptane.
Subsequently, purified n-heptane was introduced to adjust the concentration of the solid product to 200 g / L. Here, 300 ml of SiCl ₄ was added and a reaction was carried out at 90 ° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so that the concentration of the reaction product was 100 g / L. A liquid prepared by mixing 30 ml of phthalic acid dichloride with 270 ml of purified n-heptane was prepared in advance, and the mixed liquid was added to an autoclave and reacted at 90 ° C. for 1 hr. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so that the concentration of the reaction product was 200 g / L. To this, 1 L of TiCl ₄ was added and a reaction was carried out at 95 ° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a slurry of the solid component (ZA1). A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component (ZA1) was 2.5% by weight.
Next, a 20 L autoclave equipped with a stirring device was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component (ZA1) was introduced as a solid component (ZA1). Purified n-heptane was introduced to adjust the liquid level to 4L. Here, components 25ml trimethylvinylsilane as (ZA2), the component (ZA3) as t-Bu (Me) Si ( OMe) 2 to 20 ml, _Et 3 the n- heptane dilution of _Et 3 Al as the component (ZA4) Al As a result, 40 g was added, and the reaction was performed at 40 ° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane, and a portion of the resulting slurry was sampled and dried. As a result of analysis, the solid component contained 1.8 wt% Ti and 4.5 wt% t-Bu (Me) Si (OMe) ₂ .
Prepolymerization was performed by the following procedure using the solid component obtained above. Purified n-heptane was introduced into the slurry, and the solid component concentration was adjusted to 20 g / L. After cooled slurry to 10 ° C., 10 g was added n- heptane dilution of _Et 3 Al as _Et 3 Al, were fed over 4hr of propylene 240 g. After the supply of propylene was completed, the reaction was continued for another 30 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum dried to obtain a solid catalyst component (Z). This solid catalyst component (Z) contained 2.1 g of polypropylene per 1 g of the solid component. As a result of analysis, the portion of the solid catalyst component (A) excluding polypropylene contained 1.6% by weight of Ti and 4.3% by weight of t-Bu (Me) Si (OMe) ₂ .

[Polypropylene polymerization]
A stainless steel autoclave having an internal volume of 3.0 liters having a stirring and temperature control device was heated and dried under a nitrogen flow, cooled to room temperature and substituted with propylene, and then 400 mg of triethylaluminum and 4000 ml of hydrogen were introduced, Next, 750 grams of liquid propylene was introduced and the internal temperature was adjusted to 70 ° C., and then 10 milligrams of the above solid catalyst component was injected to polymerize propylene. After 1 hour, 10 ml of ethanol was injected to terminate the polymerization. When the polymer was dried and weighed, 320 g of polymer was obtained.
The evaluation results of the obtained polymer (B-4) are shown in Table 2.

[Polymerization Example 5]:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. 2.86 mL of a heptane solution of triisobutylaluminum (143 mg / mL) was added, and 450 Nml of hydrogen was introduced. Next, after introducing 750 g of liquid propylene, the temperature was raised to 70 ° C.
Thereafter, 100 mg of the prepolymerized catalyst 2 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon, and polymerization was started. After maintaining at 70 ° C. for 1 hour, 5 ml of ethanol was injected to stop the polymerization. As a result, 315 g of a polymer was obtained.
Table 2 shows the evaluation results of the obtained polymer (B-5).

(III) Component (C): Thermoplastic Elastomer “Tuffmer A1050S” manufactured by Mitsui Chemicals, Inc. was used as the thermoplastic elastomer (rubber) of component (C).

(IV) Component (D): Inorganic filler As the inorganic filler of the component (D), "MPA25" manufactured by Fuji Talc Industrial Co., Ltd. was used.

[Examples 1-6, Comparative Examples 1-8]
Examples 1 to 6 are as shown in Table 3 and Comparative Examples 1 to 8 are as shown in Table 4. After blending each composition component and mixing with a mixer, the mixture was melt-kneaded with a twin screw extruder, and an extrusion temperature of 200 ° C. The strand was extruded, cooled, cut and granulated to obtain a pellet-shaped resin composition. Tables 3 and 4 show the evaluation results of the resin composition.

  From the evaluation results of Tables 3 and 4, it can be seen that the molded product of each comparative example has a poor surface tension, whereas the molded product of each example has a good surface tension.

That is, according to the resin composition of each example, which is based on the crystalline polypropylene of the component (A), the component (B), and the components (C) and (D) are contained in a predetermined blending ratio. A compact with good tenacity can be obtained. On the other hand, as can be seen in Comparative Examples 1, 2, 7, and 8, when λmax of component (B) is low, the surface tension is poor when the pressure holding time is short (3 s, 6 s). As seen in Comparative Examples 4 to 6, even when the Q value of the component (A) is larger than 5, the surface tension is particularly poor when the pressure holding time is short (3 s, 6 s).
From the results of the examples and comparative examples described above, the rationality and significance of the configuration and requirements of the present invention are demonstrated, and the superiority of the present invention over the prior art is also apparent.

  When the propylene-based resin composition of the present invention is molded, particularly injection-molded, it becomes possible to provide a molded article having excellent surface tension, and its industrial applicability is very large.

It is a figure which shows an example of the molecular weight distribution curve in GPC. It is a figure which shows the base line and area of the chromatogram in GPC. It is a figure which shows an example of the molecular weight distribution derived from [A-1] in GPC, and [A-2] origin. It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer.

Claims (4)

It contains 1 to 80% by weight of the following component (A), 5 to 95% by weight of component (B), 0 to 30% by weight of component (C) and 0 to 30% by weight of component (D). A crystalline polypropylene resin composition.
Component (A): Propylene ethylene block copolymer (Ai) which is a crystalline polypropylene satisfying the following requirements (Ai) to (A-ii) Melt flow rate (MFR) (230 ° C., 2.16 kg) Load) is 10 to 200 g / 10 min.
(A-ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 5 or less.
Component (B): Propylene polymer satisfying the following requirements (Bi) to (B-vi) (Bi) Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.01 to 100 g / 10 min.
(B-ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
(B-iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(B-iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(Bv) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(B-vi) The degree of strain hardening (λmax) in the measurement of elongational viscosity is 6.0 or more.
Component (C): Thermoplastic elastomer Component (D): Inorganic filler The crystalline polypropylene resin composition according to claim 1, wherein the component (B) further satisfies the following requirement (B-vii).
(B-vii) (ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ] The crystalline polypropylene resin composition according to claim 1 or 2, wherein the component (B) further satisfies the following requirement (B-viii).
(B-viii) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where the peak height is 50% is L ₅₀ and H ₅₀ (L ₅₀ Is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 , Less than 2.0. An interior / exterior part for automobiles obtained by injection-molding the crystalline polypropylene resin composition according to any one of claims 1 to 3 .

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