JP4920379B2 - Propylene resin film or sheet, or laminate comprising the film or sheet, propylene polymer composition, and pellets comprising the composition - Google Patents

Description

  The present invention relates to a propylene-based resin film or sheet, or a laminate comprising the film or sheet, a propylene-based polymer composition, and a pellet made of the composition.

  Conventionally, an adhesive film has been produced by applying an adhesive acrylic or urethane adhesive to a substrate such as polyethylene, polypropylene or PET. Although such a film is excellent in adhesiveness, it requires a pretreatment of the base material and a coating process, which is costly, and further uses an organic solvent, which is not preferable for environmental conservation.

  Therefore, in recent years, for example, polyolefins grafted with polar groups such as maleic anhydride are used as adhesive or tacky films. In this case, since extrusion molding can be performed together with the substrate and the like, the cost is excellent, but the balance between transparency and heat resistance is not sufficient, and the film is not satisfactory.

  An object of the present invention is to solve the above-described points, and is composed of a film or sheet excellent in adhesiveness or tackiness, and excellent in transparency, heat resistance, and flexibility, and the film or sheet. The object is to provide a laminate.

  In addition, even if a film or a sheet is laminated, scratch resistance is maintained.

  Therefore, as a result of intensive research, the present inventors have used a specific propylene-based resin to form a film or sheet having transparency, heat resistance and flexibility, and the film or sheet, and have scratch resistance. It has been found that a laminate that retains the properties can be obtained.

That is, the propylene-based resin film or sheet of the present invention, or a laminate comprising the film or sheet,
The propylene-derived structural unit is contained in an amount of 50 mol% or more (the total of the propylene-derived structural unit and the optional component derived from an α-olefin having 2 to 20 carbon atoms is 100 mol%), and the following requirements ( z) consisting of a graft-modified propylene resin satisfying
The following requirements (1) to (3) are satisfied:
(Z) The graft-modified propylene resin is obtained by graft-modifying a propylene resin with a polar monomer, and the graft amount of the polar monomer is 0.02% by weight or more and 10% by weight with respect to 100% by weight of the graft-modified propylene resin. Is
(1) The needle entry temperature (TMA temperature) is 120 ° C. or higher.
(2) Flexible Young's modulus (YM) is 1 to 500 MPa.
(3) The internal haze of the film or sheet is 0.1% to 50% or less.

As the film or sheet, the propylene-based resin is
(AA) 10 to 95 parts by weight of a graft-modified propylene polymer obtained by graft-modifying a propylene-based polymer (A) satisfying the following requirement (a) with a polar monomer, and
(BB) Propylene / α-olefin copolymer (B) satisfying the following requirement (b) and / or
Alternatively, the graft-modified propylene / α-olefin copolymer (B1) obtained by graft-modifying the propylene / α-olefin copolymer (B) with a polar monomer is 90 to 5 parts by weight in total (however, (AA) and (BB) ) And 100 parts by weight)
A film or sheet which is a propylene-based polymer composition (X) comprising;
(A): Melting point (Tm) measured by a differential scanning calorimeter (DSC) is 140 ° C. or more, and 90 mol% of structural units derived from propylene (however, from propylene in the polymer (A)) In an amount exceeding the sum of the derived structural units and the structural units derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) which may be included as necessary. is there,
(B): 30 to 90 mol% of structural units derived from propylene (provided that the structural units derived from propylene in the copolymer (B) and α-olefins having 2 to 20 carbon atoms (excluding propylene) At least 1 selected from α-olefins (excluding propylene) having 2 to 20 carbon atoms.
10 to 70 mol% of structural units derived from various olefins (however, the total of structural units derived from propylene and structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) is 100 mol) %) And MFR measured at 230 ° C. under a 2.16 kg load in accordance with JIS K-6721 is in the range of 0.01 to 100 g / 10 min, and the following requirements (b -1) satisfying any one or more of (b-2);
(B-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B-2): Intrinsic viscosity [η] (dL / g) measured in decalin at 135 ° C. and the MFR (
g / 10min, 230 ° C, 2.16kg load)
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
Meet.

As the propylene polymer (A), a syndiotactic propylene polymer (A1) satisfying the following requirement (c) or an isotactic propylene polymer (A2) satisfying the following requirement (d): It is possible to use.
(C): Syndiotactic pentad fraction (rrrr) measured by ¹³ C-NMR method
The fraction) is 85% or more, and the melting point (Tm) measured by DSC is 145 ° C. or more.
(D): The isotactic pentad fraction (mmmm fraction) measured by ¹³ C-NMR method is 85% or more.

  The propylene polymer (A) contains a structural unit derived from propylene in an amount exceeding 90 mol% (provided that the total amount of the structural units in the polymer (A) is 100 mol%). Or it may be a sheet.

As a laminated body, it has a layer which consists of the said film or sheet, You may have at least one part the structure which the layer which consists of these films or sheets, and the base material adjoined.
The propylene polymer composition (X) is:
(AA) 10 to 95 parts by weight of a graft-modified propylene polymer obtained by graft-modifying with a polar monomer with respect to the propylene-based polymer (A) satisfying the following requirement (e), and
(BB) Propylene / α-olefin copolymer (B) satisfying the following requirement (f) and / or
Alternatively, a total of 90 to 90 graft-modified propylene / α-olefin copolymers (B1) obtained by graft-modifying with a polar monomer to the propylene / α-olefin copolymer (B)
5 parts by weight (however, the sum of (AA) and (BB) is 100 parts by weight)
including;
(E): Melting point (Tm) measured by DSC is 140 ° C. or higher, and 90 mol% of structural units derived from propylene (provided that structural units derived from propylene in the polymer (A)) The total amount with the structural unit derived from a C2-C20 α-olefin (excluding propylene) which may be included as required is 100 mol%).
(F): 30 to 90 mol% of structural units derived from propylene (provided that the structural units derived from propylene in the copolymer (B) and α-olefins having 2 to 20 carbon atoms (excluding propylene) At least 1 selected from α-olefins (excluding propylene) having 2 to 20 carbon atoms.
10 to 70 mol% of structural units derived from various olefins (however, the total of structural units derived from propylene and structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) is 100 mol) %) And MFR measured at 230 ° C. under a 2.16 kg load in accordance with JIS K-6721 is in the range of 0.01 to 100 g / 10 min, and the following requirements (b -1) satisfying any one or more of (b-2);
(B-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B-2): Intrinsic viscosity [η] (dL / g) measured in decalin at 135 ° C. and the MFR (
g / 10min, 230 ° C, 2.16kg load)
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
Meet.

The propylene polymer (A) is a syndiotactic propylene polymer (A1) that satisfies the following requirement (g) or an isotactic propylene polymer (A2) that satisfies the following requirement (h): May be.
(G): Syndiotactic pentad fraction (rrrr) measured by ¹³ C-NMR method
The fraction) is 85% or more, and the melting point (Tm) measured by DSC is 145 ° C. or more.
(H): Isotactic pentad fraction (mmmm) measured by ¹³ C-NMR method
The fraction) is 85% or more.

  Moreover, the pellet which consists of said propylene-type polymer composition (X) may be sufficient.

  The film or sheet of the present invention is excellent in adhesiveness or tackiness, and is excellent in transparency, heat resistance, and flexibility. The film or sheet is also useful for use in a laminate. These films or sheets are also used for bonding or sticking.

Hereinafter, the present invention will be specifically described.
In addition, the measuring method which prescribes | regulates a physical property is later mentioned in an Example.
In the film and sheet of the present invention, propylene-derived structural units are 50 mol% (the total of propylene-derived structural units and optional structural units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%). And a graft-modified propylene resin satisfying the following requirement (z):
The following requirements (1) to (3) are satisfied:
(Z) The graft-modified propylene resin is obtained by graft-modifying a propylene resin with a polar monomer, and the graft amount of the polar monomer is 0.02% by weight or more and 10% by weight with respect to 100% by weight of the graft-modified propylene resin. Is
(1) The needle entry temperature (TMA temperature) is 120 ° C. or higher.
(2) Flexible Young's modulus (YM) is 1 to 500 MPa.
(3) The internal haze of the film or sheet is 0.1% to 50%.

The propylene-based resin is a resin containing 50 mol% or more of a structural unit derived from propylene (here, the total of propylene and an optional component of an α-olefin having 2 to 20 carbon atoms is 100 mol%). In calculating the proportion of the structural unit derived from propylene, the grafted polar monomer is excluded from the denominator. (1) Needle entry temperature (TMA temperature)
The needle entry temperature of the film or sheet of the present invention is 120 ° C. or higher, preferably 120 ° C. to 170 ° C., more preferably 125 ° C. to 170 ° C.

Within this range, the heat resistance is particularly excellent.
(2) Young's modulus (YM, hereinafter also referred to as flexibility)
The flexibility of the film or sheet of the present invention is 1 to 500 MPa, preferably 1 to 450 MPa, more preferably 5 to 400 MPa. Excellent flexibility in this range. In addition, since it is flexible, it has excellent adhesion and stickiness to the substrate.
(3) Haze of film or sheet The haze of the film or sheet of the present invention is 0.1% to 50% or less, preferably 0.1% to 35%, more preferably 0.5% to 20%. In this range, the transparency is excellent. (4) Graft amount of polar monomer The propylene resin is graft-modified with a polar monomer, and the graft amount of the polar monomer is 0.02 wt% or more and 10 wt% or less with respect to 100 wt% of the graft-modified propylene resin, Preferably it is 0.05 weight% to 8 weight%, More preferably, it is 0.1 weight% to 5 weight%. In this range, the adhesiveness is excellent.

  Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, chlorides. Examples thereof include vinyl and carbodiimide compounds.

  As the polar monomer, an unsaturated carboxylic acid or a derivative thereof is particularly preferable. Examples of the unsaturated carboxylic acid or a derivative thereof include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.

Specific examples of the compound include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid ^TM (endocis-bicyclo [2.2.1] hept-5 Unsaturated carboxylic acids such as -ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters and the like. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

  These unsaturated carboxylic acids and / or derivatives thereof can be used singly or in combination of two or more. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used.

The modification is obtained by graft polymerizing a polar monomer to the object to be modified. When grafting such a polar monomer as described above to the object to be modified, the polar monomer is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight per 100 parts by weight of the object to be modified. used. This graft polymerization is usually carried out in the presence of a radical initiator.

As the radical initiator, an organic peroxide or an azo compound can be used.
The radical initiator can be used as it is mixed with the modified substance and the polar monomer, but can also be used after being dissolved in a small amount of an organic solvent. Any organic solvent that can dissolve the radical initiator can be used without particular limitation.

Further, when the polar monomer is graft-polymerized on the object to be modified, a reducing substance may be used. When a reducing substance is used, the graft amount of the polar monomer can be improved.
Graft modification of the object to be modified with a polar monomer can be performed by a conventionally known method. For example, the object to be modified is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution. The reaction can be carried out preferably by reacting at a temperature of 80 to 190 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours.

  In addition, a modified propylene polymer composition can also be produced by reacting an object to be modified with a polar monomer using an extruder or the like. This reaction is carried out at a temperature of, for example, 160 to 300 ° C., preferably 180 to 250 ° C., usually for 0.5 to 10 minutes when the object to be modified containing the propylene polymer (A) component is modified. Is desirable.

  Further, when the film or sheet is composed of the propylene polymer composition (X) described later, the modification may be blended with the component (BB) after graft modification of the component (A) alone, (B) You may graft-modify, after mixing a component and making it a composition.

  The modification amount (the graft amount of the polar monomer) of the modified product thus obtained is usually 0.02 to 10% by weight when the propylene resin constituting the film or sheet is 100% by weight.

  When the content of the polar monomer is within the above range, the film or sheet of the present invention can be used in a polar group-containing resin (for example, polyester, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, nylon, EVA, PVA, PS, PVC, etc.) show high adhesive strength.

  The film or sheet of the present invention is a propylene / α-polymer selected from a specific graft-modified propylene polymer (AA) and a specific propylene / α-olefin copolymer (B) and / or a graft-modified product (B1) thereof. It preferably consists of a propylene-based polymer composition (X) comprising an olefin copolymer (BB).

(AA) Graft-modified propylene polymer (A) as a raw material will be described.
(A) Propylene polymer The propylene polymer (A) has a melting point (Tm) determined by DSC of 140 ° C or higher, preferably 145 ° C or higher, more preferably 150 ° C to 170 ° C. To do. If it exists in this range, it can be set as the film or sheet | seat excellent in heat resistance.

The measurement by a differential scanning calorimeter (DSC) is performed as follows, for example. About 5 mg of sample is packed in a special aluminum pan, and DSCPyris1 or DSC manufactured by PerkinElmer
7 to 30 ° C. to 200 ° C. at 320 ° C./min, held at 200 ° C. for 5 minutes, then lowered from 200 ° C. to 30 ° C. at 10 ° C./min, and further at 30 ° C. for 5 minutes. After holding, the melting point (Tm) is obtained from the endothermic curve when the temperature is raised at 10 ° C./min.

When a plurality of peaks are detected during DSC measurement, the temperature at the peak detected on the highest temperature side is defined as the melting point (Tm). In the present invention, the propylene polymer (A) has a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR method of 85% or more and a melting point (measured by DSC) In one preferred embodiment, the propylene polymer (A1) has a Tm) of 145 ° C. or higher.

In the present invention, the propylene polymer) (A) is a propylene polymer (A2) having an isotactic pentad fraction (mmmm fraction) of 85% or more as measured by ¹³ CNMR. Is another preferred embodiment.
(A1) Propylene-based polymer The propylene-based polymer (A1) may be a homopolypropylene, a propylene / α-olefin (excluding propylene) random copolymer having 2 to 20 carbon atoms, or propylene. Although it may be a block copolymer, it is preferably a homopolypropylene or a propylene-alpha-olefin random copolymer having 2 to 20 carbon atoms. Particularly preferred is a copolymer of propylene and ethylene or an α-olefin having 4 to 10 carbon atoms, and a copolymer of propylene, ethylene and an α-olefin having 4 to 10 carbon atoms. Particularly preferred from the viewpoint of heat resistance.

Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene,
1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Examples include octadecene and 1-eicosene. The structural unit derived from propylene is usually in an amount exceeding 90 mol%, preferably 91 mol, with respect to 100 mol% in total of the structural units derived from an α-olefin having 2 to 20 carbon atoms (including propylene). More than% is included. In other words, the propylene-based polymer (A1) of the present invention usually has a propylene-derived constitutional unit in an amount of more than 90 mol% and 100 mol% or less, and an α-olefin having 2 to 20 carbon atoms (excluding propylene). ) In an amount of 0 mol% or more and less than 10 mol% (wherein the propylene-derived structural unit and an α-olefin having 2 to 20 carbon atoms (
(Excluding propylene) and the total of the structural units derived from 100 mol%), in particular, the structural units derived from propylene are contained in an amount of 91 mol% or more and 100 mol% or less, and α −2 to 20 carbon atoms. It is preferable to contain a structural unit derived from olefin (excluding propylene) in an amount of 0 mol% to 9 mol%.

When the propylene polymer (A) is a propylene / α-olefin random copolymer, 0.3 to 7 mol of a structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is used. %, Preferably 0.3 to 6 mol%, more preferably 0.3 to 5 mol%.

  The propylene polymer (A) used in the present invention has a syndiotactic pentad fraction (rrrr fraction, pentad syndiotacticity) measured by NMR method of 85% or more, preferably 90% or more. The propylene polymer (A) having a rrrr fraction in this range is preferably 93% or more, more preferably 94% or more, and is excellent in moldability, heat resistance and transparency, and is a crystalline polypropylene. The characteristics are favorable and preferable. The upper limit of the rrrr fraction is not particularly limited, but is 100% or less, and usually 99% or less, for example.

This syndiotactic pentad fraction (rrrr fraction) is measured as follows.
The rrrr fraction is derived from Prrrr in the NMR spectrum (absorption intensity derived from the methyl group of the third unit in a site where five units of propylene units are continuously syndiotactically bonded) and Pw (derived from all methyl groups of the propylene unit). The following formula (absorption intensity)
1).

rrrr fraction (%) = 100 × Prrrr / Pw (1)
The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And 13C-NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 10,000 times or more.

  The intrinsic viscosity [η] of the propylene polymer (A1) measured in decalin at 135 ° C. is 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g. More preferably 0.50 to 8.00 dL / g, still more preferably 0.95 to 8.00 dL / g, particularly preferably 1.00 to 8.00, and still more preferably 1.40 to 8.00 dL / g. It is desirable to be in the range of 1.40 to 5.00 dL / g. The propylene polymer (A1) having such an intrinsic viscosity [η] value exhibits good fluidity, is easy to be blended with other components, and a molded product having excellent mechanical strength can be obtained from the obtained composition. There is a tendency to be obtained.

Further, the propylene polymer (A1) has a melting point (Tm) obtained by differential scanning calorimetry (DSC) measurement of 145 ° C. or higher, preferably 147 ° C. or higher, more preferably 150 ° C. or higher, particularly preferably. It is 155 degreeC or more, Most preferably, it is 156 degreeC or more. The upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower, for example. Furthermore, the heat of fusion (ΔH
) Is 40 mJ / mg or more, preferably 45 mJ / mg or more, more preferably 50 mJ / mg or more, still more preferably 52 mJ / mg or more, and particularly preferably 55 mJ / mg or more.

  The differential scanning calorimetry is performed, for example, as follows. About 5.00 mg of sample is packed in a special aluminum pan, heated to 320 ° C./min from 30 ° C. to 200 ° C. using DSCPyris 1 or DSC 7 manufactured by Perkin Elmer, and held at 200 ° C. for 5 minutes. The temperature is lowered to 30 ° C. at 10 ° C./min, held at 30 ° C. for 5 minutes, and then the melting point (Tm) and the heat of fusion (ΔH) are determined from the endothermic curve when the temperature is raised at 10 ° C./min. When a plurality of peaks are detected during DSC measurement, the peak detected on the highest temperature side is defined as the melting point (Tm).

  The syndiotactic propylene polymer (A1) having a melting point (Tm) in this range is preferable because it is excellent in moldability, heat resistance and mechanical properties, and has good properties as crystalline polypropylene. A propylene polymer (A1) having a melting point (Tm) in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.

Propylene polymer (A1), when differential scanning calorimetry (DSC) isothermal crystallization temperature T _iso obtained in measurement, the crystallization half-time in the isothermal crystallization temperature T _iso was t _1/2,
110 ≦ T _iso ≦ 150 (℃)
Satisfies the following formula (Eq-1) in the range of

Preferably, the following formula (Eq-2) is satisfied,

More preferably, the following formula (Eq-3) is satisfied.

The half crystallization time (t _1/2 ) obtained by isothermal crystallization measurement is the DSC in the isothermal crystallization process
When the area between the calorie curve and the baseline is defined as the total calorific value, it is the time when the calorific value reaches 50%. [Refer to New Polymer Experiment Laboratory 8 Polymer Properties (Kyoritsu Publishing Co., Ltd.)]
The half crystallization time (t _1/2 ) is measured as follows. About 5 mg of a sample is packed in a special aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by PerkinElmer, and held at 200 ° C. for 5 minutes, then the temperature (200 ° C. ) To each isothermal crystallization temperature is obtained from a DSC curve obtained by lowering the temperature at 320 ° C./min and maintaining the isothermal crystallization temperature. Here, the half crystallization time (t _1/2 ) is obtained as isothermal crystallization process start time (time when the isothermal crystallization temperature is reached from 200 ° C.) t = 0. The propylene polymer (A1) used in the present invention is t _1/2 as described above.
However, when crystallization does not occur at a certain isothermal crystallization temperature, for example, 110 ° C., several measurements are made at an isothermal crystallization temperature of 110 ° C. or less for convenience, and semi-crystallization is performed from the extrapolated value. _{Find the} time (t _1/2 ).

The propylene polymer (A) satisfying the above (Eq-1) has remarkably superior moldability as compared with existing ones. Here, excellent moldability means that when molding such as injection, inflation, blow, extrusion, or press is performed, the time from solidification to solidification is short. Moreover, such a propylene polymer (A) is excellent in molding cycle property, shape stability, long-term productivity, and the like.

A propylene polymer (A) satisfying the above (Eq-1) can be produced by using a catalyst system as described later and setting the polymerization conditions as described later.
As a preferred embodiment of the propylene polymer (A), in addition to the preferred embodiment (satisfying ΔH ≧ 40 mJ / mg and satisfying (Eq-1)), the following requirement (n-decane soluble part) The aspect which satisfy | fills quantity) simultaneously is mentioned.

The propylene-based polymer (A1) has an n-decane soluble part amount of 1 (wt%) or less, preferably 0.8 (wt%) or less, more preferably 0.6 (wt%) or less. Is desirable. The amount of the n-decane soluble part is an index closely related to the blocking characteristics of the propylene polymer (A) or a molded product obtained therefrom, and the fact that the amount of the n-decane soluble part is usually small means that the amount of low crystalline component is low. Means less. That is, the propylene polymer (A1) that also satisfies this requirement (the amount of n-decane soluble part) has very good anti-blocking properties.

Accordingly, one of the most preferred embodiments of the propylene polymer (A1) is a syndiotactic pentad that contains a constituent unit derived from propylene in an amount exceeding 90 mol% and is measured by ¹³ C-NMR method. The fraction (rrrr fraction) is 85% or more, the melting point (Tm) determined by DSC is 145 ° C. or more, the heat of fusion (ΔH) is 40 mJ / mg or more, and the formula (Eq-1) is It is a propylene polymer satisfying and having an n-decane soluble part amount of 1 wt% or less.

In producing the propylene polymer (A1) used in the present invention,
(I) a bridged metallocene compound represented by the general formula [1];
(II) (II-1) organoaluminum oxy compounds,
(II-2) a polymerization catalyst (cat-) comprising: a compound that reacts with the bridged metallocene compound (A) to form an ion pair; and (II-3) at least one compound selected from organoaluminum compounds. 1) or a polymerization catalyst (cat-2) in which the catalyst (cat-1) is supported on a particulate carrier is preferably used, but the polymer produced is a requirement as a propylene polymer (A1). As long as the above conditions are satisfied, the catalyst for producing the propylene-based polymer (A1) is not limited to the catalyst.

In the general formula [1], R ¹ , R ² , R ³ and R ⁴ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group, and R ² and R ³ are bonded to each other to form a ring. R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R ¹² are selected from hydrogen, hydrocarbon groups and silicon-containing groups, and the two groups R ⁷ and R ¹⁰ are not hydrogen atoms, Selected from a hydrocarbon group and a silicon-containing group, which may be the same or different from R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² In the combination of one or more selected adjacent groups, the adjacent groups may be bonded to each other to form a ring.

R ¹⁷ and R ¹⁸ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon atom-containing group, which may be the same or different from each other, and the substituents may be bonded to each other to form a ring. Good.

  M is Ti, Zr or Hf, Y is carbon, Q is the same or different combination from halogens, hydrocarbon groups, anionic ligands, and neutral ligands that can coordinate with lone pairs. And j is an integer from 1 to 4.

(I) Bridged Metallocene Compound Specific examples of the bridged metallocene compound represented by the general formula [1] (also referred to as “component (I)” in the present specification) are shown below.

Cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl)
Zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6
-Ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl) Fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) ) Zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n- Chirumechiren (
Cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,3 , 6,7-tetra-tert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorene Nyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

Di-n-butylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) ( 2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-di tert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2 , 7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfur Oleenyl) zirconium dichloride, Isobutylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-dinaphthyl -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl ) Zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride [others include 1,3-diphenylisopropylidene (cyclopentadienyl) ) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, also abbreviated for the following], dibenzylmethylene (cyclopentadienyl (2,7-di (2,7 4,6-trimethylphenyl) -3,6-di-t ert-Butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,3,6,7-tetratert -Butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene ( Cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluore Nyl) zirconium dichloride,

Diphenethylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6- Ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-) Ethyl) methylene Clopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3 , 6-Ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di ( (Cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, J Tilmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (Biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

(Benzyl) (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadiene) Enyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Cyclopropylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadiene) Enyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7- Dimethyl-3, 6-di-tert-
(Butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ( 2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) Zirconium dichloride,

Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-
Dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, di-n-butyl Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di ( Trimethylsilyl) -butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di (trimethylsilyl) -butylfluorenyl) zirconium dichloride, dibenzylmethylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-diphenyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl -3,6-diphenyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (Cyclopentadienyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butyl Fluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, Di (m-chlorophenyl) methylene Lopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromo Phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7-Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl Fluorenyl) zirconium dichloride,

Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2 , 7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene Ropentajieniru) (2,7-dimethyl-3,6-di-tert- butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-
Butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3) , 6-Ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Chirufuruoreniru) zirconium dichloride, and the like can be exemplified.

  Furthermore, the compounds described above in which “zirconium” is changed to “hafnium” or “titanium”, “dichloride” is “difluoride”, “dibromide”, “diaiodide”, “dichloride” is “dimethyl” or “methyl”. Examples include metallocene compounds converted to “ethyl”.

  The bridged metallocene compound (I) can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include the production methods described in WO 2001/27124 and WO 2004/087775 by the present applicant.

The above bridged metallocene compound (I) can be used alone or in combination of two or more.
(II-1) Organoaluminum oxy compounds
As the organoaluminum oxy compound (also referred to herein as “component (II-1)”) used for the production of the propylene polymer (A), a conventionally known aluminoxane can be used as it is. Specifically, the following general formula [2] and / or general formula [3]

(In the above formula [2], R is each independently a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.)
(In the above formula [3], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.)
In particular, a methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with some organoaluminum compounds.

In the present invention, a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can be used. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. An organoaluminum oxy compound that is insoluble or sparingly soluble.

  Examples of the organoaluminum oxy compound include modified methylaluminoxane represented by the following general formula [4].

(In the formula [4], R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more.)
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [4] is generally called MMAO. Such MMAOs can be prepared by the methods listed in US4960878 and US5041584. In addition, Tosoh Finechem Co., Ltd. and the like are commercially produced under the names MMAO and TMAO where R is an isobutyl group prepared using trimethylaluminum and triisobutylaluminum. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, the MMAO is insoluble in benzene such as the compounds represented by the above formulas [2] and [3]. Unlike insoluble aluminoxane, it dissolves in aliphatic hydrocarbons and alicyclic hydrocarbons.

  Furthermore, as an organoaluminum oxy compound, an organoaluminum oxy compound containing boron represented by the following general formula [5] can be exemplified.

(In the formula [5], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and may be a hydrogen atom, a halogen atom or a carbon atom having 1 to 10 carbon atoms. Indicates a hydrogen group.)
(II-2) A compound that reacts with the bridged metallocene compound (a) to form an ion pair. It reacts with the bridged metallocene compound (I) used in the production of the syndiotactic propylene polymer (A1) to form an ion pair. The compound (II-2) to be formed (hereinafter sometimes referred to as “ionic compound” or “component (II-2)”) is disclosed in JP-A-1-501950 and JP-A-1-503636. Lewis acids, ionic compounds, borane compounds and the like described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Examples include carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

The ionic compound preferably employed in the present invention is a compound represented by the following general formula [6].

In the formula [6], examples of R ^{e +} include H ⁺ , a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal. R ^{f to} R ⁱ may be the same as or different from each other, and are organic groups, preferably aryl groups.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like. Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis ( o-Tolyl) borate, tri (n-butyl) ammonium tetrakis (
Pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis ( 3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n -Butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate Dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis ( 4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, dioctadecylmethylammonium and the like.

Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5- Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, etc. .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, an ionic compound disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can be used without limitation.
The ionic compound (II-2) as described above can be used as a mixture of two or more.

(II-3) Organoaluminum compound As the organoaluminum compound used in the production of the syndiotactic propylene polymer (A1) (also referred to herein as “component (II-3)”), for example, the following general formula An organoaluminum compound represented by [7], a complex alkylated product of a Group 1 metal represented by the following general formula [8] and aluminum, and the like can be exemplified.

R ^a _m Al (OR ^b ) _n H _p X _q ... [7]
(In the formula [7], R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.)
Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum;
Tri-branched alkyl aluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum
Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z
(Wherein x, y and z are positive numbers and z ≦ 2x) and the like, alkenyl aluminum such as isoprenyl aluminum;
Alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
General formula Ra _2.5 Al (ORb) _0.5
A partially alkoxylated alkylaluminum having an average composition represented by:
Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

M ² AlR ^a ₄ ... [8]
(In the formula [8], M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

A compound similar to the compound represented by the general formula [8] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. As such a compound, specifically, (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) A
and l (C ₂ H ₅ ) ₂ .

As the organoaluminum compound (II-3), trimethylaluminum and triisobutylaluminum are preferably used from the viewpoint of easy availability. Moreover, each said component can also be carry | supported and used for a particulate carrier.
(III) Carrier The carrier used as necessary (also referred to as “component (III)” in this specification) is an inorganic or organic compound, and is a granular or particulate solid.

Among these, as the inorganic compound, a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable. Specific examples of porous oxides include SiO ₂ and Al _2.
O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these, eg natural or synthetic zeolites, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —
TiO ₂ —MgO or the like can be used. Of these, SiO ₂ and / or A
Those having l ₂ O ₃ as a main component are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used has a particle size of 3 to 300 μm, more preferably 10 to 300 μm, and even more preferably 20 to 200 μm. Surface area of 50 to 1000 m ² / g, preferably 100
It is desirable that the pore volume be in the range of -700 m ² / g and the pore volume be in the range of 0.3-3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained therein can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3-5 cc / g, as measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain. The clay and clay mineral are also preferably subjected to chemical treatment.

  As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using ion exchangeability. Such a bulky ion plays a role of a column supporting the layered structure and is usually called a pillar. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Guest compounds that intercalate include TiCl4, Z
Cationic inorganic compounds such as rCl4, Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (O
Metal alkoxides such as R) ₃ (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^And metal hydroxide ions such as ⁺ . These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolysis of metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers. Of these, clays and clay minerals are preferred, and montmorillonite, vermiculite, pectolite, teniolite and synthetic mica are particularly preferred.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  When ion exchange layered silicate is used, in addition to its function as a carrier, it can also reduce the amount of organoaluminum oxy compounds such as alkylaluminoxane by utilizing its ion exchange properties and layer structure. Is possible. The ion-exchange layered silicate is naturally produced mainly as a main component of clay mineral, but is not limited to a natural product, and may be a synthetic product. Specific examples of clay, clay mineral, and ion-exchange layered silicate include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, teniolite, synthetic mica, synthetic hectorite, and the like.

Examples of the organic compound include granular or fine particle solids having a particle size in the range of 3 to 300 μm, preferably 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene or vinylcyclohexane or styrene is used. (Co) polymer produced as the main component, or polar functional groups obtained by copolymerizing or graft polymerizing polar monomers such as acrylic acid, acrylic acid ester, maleic anhydride, etc. to these polymers Examples thereof include polymers or modified products. These particulate carriers can be used alone or in combination of two or more.

Further, the olefin polymerization catalyst used in the production of the syndiotactic propylene polymer (A1) may contain a specific organic compound component (IV) as described later, if necessary, together with the above components. .
(IV) Organic Compound Component In the present invention, the organic compound component (also referred to as “component (IV)” in the present specification) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. . Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

Method for producing syndiotactic propylene polymer (A1)
In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding component (I) alone to the polymerization vessel.
(2) A method in which component (I) and component (II) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (I) supported on carrier (III) and component (II) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (II) supported on carrier (III) and component (I) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which component (I) and component (II) are supported on a carrier (III) is added to a polymerization vessel.

  In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance. In each of the above methods (4) and (5) in which component (II) is supported, unsupported component (II) may be added in any order as necessary. In this case, the components (II) may be the same or different.

  In addition, the solid catalyst component in which component (I) is supported on component (III) and the solid catalyst component in which component (I) and component (II) are supported on component (III) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

The propylene polymer (A) comprises propylene and at least one olefin selected from α-olefins (excluding propylene) having 2 to 20 carbon atoms in the presence of the olefin polymerization catalyst as described above. It can be obtained by polymerization or copolymerization.

The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also.
Using the olefin polymerization catalyst as described above, propylene and α-
In the polymerization with at least one olefin selected from olefins (excluding propylene), the component (I) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 mol per liter of reaction volume. Used in such an amount as to be ^-2 mol.

  Component (II-1) has a molar ratio [(II-1) / M] of component (II-1) and all transition metal atoms (M) in component (I) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (II-2) has a molar ratio [(II-2) / M] of component (II-2) to transition metal atom (M) in component (I) of usually 1 to 10, preferably It is used in such an amount as to be 1-5. Component (II-3) has a molar ratio [(II-3) / M] of the aluminum atoms in component (II-3) to the total transition metals (M) in component (I) of usually 10 to 10. The amount used is 5000, preferably 20-2000.

  When component (II) is component (II-1), component (IV) has a molar ratio [(IV) / (II-1)] of usually 0.01 to 10, preferably 0.1 to 5. When the component (II) is the component (II-2), the molar ratio [(IV) / (II-2)] is usually 0.01 to 10, preferably 0.1 to 5. When the component (II) is the component (II-3), the molar ratio [(IV) / (II-3)] is usually 0.01 to 2, preferably 0.005 to It is used in such an amount that it becomes 1.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually −50 to
It is +200 degreeC, Preferably it is the range of 0-170 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (II) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

The olefin supplied to the polymerization reaction is at least one olefin selected from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). Examples of the α-olefin having 4 to 20 carbon atoms include linear or branched α-olefins having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as 1-butene, 2-butene, and 1-pentene. 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, -Octadecene, 1-eicosen, etc.
(A2) Propylene polymer The propylene polymer (A2) has an isotactic pentad fraction (mmmm fraction) measured by ¹³ C-NMR method of 85% or more, preferably 90% or more, more preferably Is a propylene polymer (A2) of 95% or more (hereinafter sometimes referred to as “isotactic polypropylene”).

The isotactic polypropylene is a polypropylene having an isotactic pentad fraction measured by NMR method of 0.9 or more, preferably 0.95 or more.
The isotactic pentad fraction (mmmm) indicates the proportion of isotactic linkage in pentad units in the molecular chain measured using ¹³ C-NMR method, and includes 5 propylene monomer units. This is the fraction of propylene monomer units at the center of the chain that are continuously meso-bonded. Specifically, it is a value calculated as a fraction of the mmmm peak in the total absorption peak in the methyl carbon region observed in the ¹³ C-NMR spectrum.

In addition, this isotactic pentad fraction (mmmm) is measured as follows.
The mmmm fractions are Pmmmm in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously isotactically bonded) and P _W (total methylation of propylene units). It is calculated | required by following formula (3) from the absorption intensity of the absorption intensity derived from a group.

mmmm fraction = Pmmmm / P _W (3)
The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And ¹³ C-NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 10,000 times or more.

  Examples of the isotactic polypropylene (A) include a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms other than propylene. Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples thereof include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like, and ethylene or α-olefin having 4 to 10 carbon atoms is preferable.

  These α-olefins may form a random copolymer with propylene or a block copolymer. The structural unit derived from these α-olefins may be contained in polypropylene in a proportion of 40 mol% or less, preferably 20 mol% or less.

  Isotactic polypropylene (A) has a melt flow rate (MFR) of 0.01 to 1000 g / 10 minutes, preferably 0.05 to 500 g measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D 1238. It is desirable to be in the range of / 10 minutes.

Such isotactic polypropylene (A) includes, for example, (a) a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (b) an organoaluminum compound, and (c) an electron donor. It can manufacture by superposing | polymerizing using the Ziegler catalyst system which becomes. The same can be obtained by using a metallocene catalyst.
Graft Modification The (AA) graft-modified propylene polymer (A) of the present invention can be produced by graft-modifying (A). Examples of the polar monomer, radical initiator, and graft modification method that can be used at the time of graft modification include the same as those described in the section of the graft-modified propylene resin. In graft modification of (A), the component (A) alone may be subjected to graft modification, or the component (A) and the component (B) may be melt-kneaded and then subjected to graft modification.

  The amount of grafting to (A) can be determined as appropriate, but the amount of modification of the modified product (AA) (the graft amount of the polar monomer) is usually 0.1 when the modified product (AA) is 100% by weight. It is desirable that the content is -20% by weight, preferably 0.2-15% by weight, more preferably 0.2-10% by weight.

(BB) Propylene / α-olefin copolymer (B) and / or pro
Graft-modified propylene / α-olefin copolymer obtained by graft-modifying pyrene / α-olefin copolymer (B) with a polar monomer
(B) used as a raw material is demonstrated.
Propylene / α-olefin copolymer (B)
The propylene / α-olefin copolymer (B) has 30 structural units derived from propylene.
-90 mol% (however, the total of the structural units derived from propylene in the copolymer (B) and the structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) is 100 mol%. ) And containing structural units derived from at least one olefin selected from α-olefins (excluding propylene) having 2 to 20 carbon atoms in an amount of 10 to 70 mol%, and JIS K The MFR measured at 230 ° C. and 2.16 kg load in accordance with -6721 is in the range of 0.01-100 g / 10 min, and the following requirement (b-1) or (b-2)
1) or more.
(B-1): The syndiotactic triad fraction (rr) measured by ¹³ C-NMR method is 60% or more.
(B-2): Intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and MFR (g / 10 min) measured at 230 ° C. 2.16 kgf load according to JIS K-6721 Satisfies the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
In the present invention, a propylene / α-olefin copolymer having various physical properties within the above range (
B) is used without any particular limitation. As the propylene / α-olefin copolymer (B), for example, a structural unit derived from propylene is 30 to 90 mol%, preferably 40 to 90 mol%, more preferably 50-90 mol%, C2-C20 α-olefin (excluding propylene) is 10-70 mol%, preferably 10-60 mol%, more preferably 10-50 mol%
The propylene / C2-C20 α-olefin copolymer (excluding propylene) and the constituent units derived from propylene are contained in an amount of 30 to 90 mol%, preferably 40 to 90 mol%. Is contained in an amount of 50 to 90 mol%, more preferably 51 to 90 mol%,
The structural unit derived from ethylene and the structural unit derived from an α-olefin having 4 to 20 carbon atoms are combined in a total of 10 to 70 mol% (wherein the structural unit derived from propylene, the structural unit derived from ethylene, and the carbon number of 4 to 20). Of the α-olefin-derived structural unit is 100 mol%), preferably 10 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 10 to 49 mol%. The copolymer containing in the quantity of is mentioned.

In the case of propylene / ethylene / α-olefin copolymer having 4 to 20 carbon atoms, the proportion of structural units derived from ethylene is P _E (mol%), and the proportion of structural units derived from α-olefins having 4 to 20 carbon atoms is When P _HAO is specified, a copolymer _satisfying P _E ≦ P _HAO is more preferable. These two modes are excellent in transparency and flexibility, and are preferable from the viewpoint of vibration damping, scratch resistance, and wear resistance.

In the case of the syndiotactic propylene polymer (A1), in the propylene / α-olefin copolymer (B1), for example,
In the propylene / ethylene copolymer, the number of structural units derived from propylene is preferably 60 to 90 mol%, more preferably 70 to 90 mol%, and the number of structural units derived from ethylene is preferably 10 to 40. It is contained in an amount of mol%, more preferably in an amount of 10 to 30 mol%.

Further, in the α-olefin / ethylene copolymer having 4 to 20 carbon atoms, the structural unit derived from propylene is preferably in an amount of 84 to 41 mol%, more preferably in an amount of 78 to 43 mol%, and even more. Preferably, the amount of structural units derived from an α-olefin having 4 to 20 carbon atoms (hereinafter sometimes referred to as HAO) in an amount of 72 to 50 mol% is preferably 15 to 39 mol%, more preferably 20 It is contained in an amount of ˜39 mol%, more preferably 25 to 35 mol%. HAO is preferably 1-butene. The number of structural units derived from ethylene is preferably 1 to 20 mol%, more preferably 2 to 18 mol%, and even more preferably 3 to 15 mol%.

In the case of the isotactic propylene polymer (A2), for example,
In the α-olefin / ethylene copolymer having 4 to 20 carbon atoms, the structural unit derived from propylene is preferably 84 to 41 mol%, more preferably 78 to 43 mol%, and even more preferably. The number of structural units derived from HAO in an amount of 72-50 mol% is preferably 15-39 mol%, more preferably 20-39 mol%, and even more preferably 25-35 mol%. contains. HAO is preferably 1-butene. The number of structural units derived from ethylene is preferably 1 to 20 mol%, more preferably 2 to 18 mol%, and even more preferably 3 to 15 mol%.

Examples of the α-olefin having 2 to 20 carbon atoms (excluding propylene) include ethylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned, especially ethylene, 1-butene, 1-hexene,
4-Methyl-1-pentene and 1-octene are preferred.

  The MFR of the propylene / α-olefin copolymer (B) used in the present invention measured at 230 ° C. under a 2.16 kg load in accordance with JIS K-6721 is preferably 0.01 to 100 g / 10 min. Is preferably in the range of 0.05 to 50 g / 10 min, and more preferably in the range of 0.1 to 10 g / 10 min. When (B) is modified, it is molded to be in the range of 0.1 to 500 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes, and more preferably 0.1 to 50 g / 10 minutes. From the viewpoint of sex.

The propylene / α-olefin copolymer (B) used in the present invention satisfies at least one of the following (b-1) and (b-2).
(B-1) Syndiotactic triad fraction (rr fraction, measured by NMR method)
Triad syndiotacticity) is 60% or more.
(B-2) Intrinsic viscosity [η] (dL / g) measured in decalin at 135 ° C. and the MFR (
g / 10 min, 230 ° C., 2.16 kg load) satisfy the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
First, the requirement (b-1) will be described.
(B-1) Syndiotactic triad fraction (rr fraction, triad syndiotacticity) measured by ¹³ C-NMR method is 60% or more, preferably 70% or more, more preferably 75% or more And the rr fraction is in this range.
The olefin copolymer (B) is preferable because it has good compatibility with the syndiotactic propylene polymer (A).

The polymer satisfying (b-1) can be obtained, for example, by copolymerizing propylene and α-olefin in the presence of a catalyst capable of producing syndiotactic polypropylene. May be manufactured.

  The rr fraction is derived from Prr in the NMR spectrum (absorption intensity derived from the methyl group of the second unit in a site where three units of propylene units are continuously syndiotactically bonded) and Pw (derived from all methyl groups of the propylene unit). It is calculated | required by following formula (4) from the absorption intensity of absorption intensity).

rr fraction (%) = 100 × Prr / Pw (4)
Here, mr-derived absorption (of 3 units of propylene units, absorption derived from at least both syndiotactic and isotactic bonds, used for determination of Pmr (absorption intensity)), rr-derived absorption (propylene Absorption derived from the methyl group of the second unit at the site where 3 units are continuously syndiotactically bonded, used for determination of Prr (absorption intensity)), or absorption derived from mm (3 units of propylene units are consecutive) If the absorption derived from the methyl group of the second unit at the site where the isotactic bond is made, and Pmm (absorption intensity)) and the absorption derived from the comonomer overlap, the contribution of the comonomer component is not subtracted. Calculate as is.

Specifically, among the descriptions of how to obtain the “syndiotacticity parameter (SP value)” described in [0018] to [0031] of JP-A-2002-097325, [00
18] to [0023], and the calculation is performed by calculating from the integrated intensity of the signals in the first region, the second region, and the third region according to the above equation (2).

Further, in the present invention, the rr1 value is obtained particularly according to the method for obtaining the “syndiotacticity parameter (SP value)” described in JP-A-2002-097325, [0018] to [0031]. More preferably, the value is 60% or more, preferably 65% or more, more preferably 70% or more. In other words, in the calculation of the rr value, the rr1 value is the absorption of mr (absorption derived from at least both syndiotactic and isotactic bonds out of 3 units of propylene units, determination of Pmr (absorption intensity)). Used for determination of absorption, Prr (absorption intensity) derived from the methyl group of the second unit at a site where 3 units of propylene units are continuously syndiotactically bonded, or derived from mm Absorption (absorption derived from the methyl group of the second unit at the site where 3 units of propylene units are isotactically bonded, intensity used for determination of Pmm (absorption intensity)) and absorption derived from the comonomer In the case of overlap, the contribution of the comonomer component is subtracted.

In the measurement of the rr value and the rr1 value, the NMR measurement is performed, for example, as follows. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And 13C-NMR measurement is performed at 120 degreeC using the JEOL GX-400 type | mold NMR measuring apparatus. The number of integration is 8,000 times or more.

Next, requirement (b-2) will be described.
(B-2): The propylene / α-olefin copolymer (B) used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. and 2.16 kg at 230 ° C. in accordance with JIS K-6721. The MFR measured with the load satisfies the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
More preferably 1.80 × MFR ^(−0.20) ≦ [η] ≦ 2.50 × MFR ^(−0.19)
The propylene / α-olefin copolymer (B) satisfying this relational expression is preferable because it has good compatibility with the syndiotactic propylene polymer (A).

The propylene / α-olefin copolymer (B) satisfying the above formula can be obtained, for example, by copolymerizing propylene and α-olefin with a catalyst capable of producing syndiotactic propylene. You may manufacture using a catalyst. Such a material is preferable because it has good compatibility with the syndiotactic propylene polymer (A).

The propylene / α-olefin copolymer satisfying (b-2) exhibits the same [η] and a large MFR as compared with the conventional isotactic propylene-based copolymer.
As described in Macromolecules 31, 1335-1340 (1998), the molecular weight between the entanglement points of isotactic propylene (reported as Me = 6900 (g / mol) in the paper) and the syndiotactic propylene This is due to the difference in molecular weight between entanglement points (reported as Me = 2170 (g / mol) in the paper). That is, it is considered that the same [η] has a syndiotactic structure, so that the number of entanglement points increases with respect to the material having the isotactic structure, and the MFR increases.

As described above, the (B) propylene / α-olefin copolymer satisfying at least one of (b-1) and (b-2) is a propylene / α-olefin copolymer having an isotactic structure. A polymer having a stereoregularity different from a coalescence is considered to have a syndiotactic structure. For this reason, the propylene / α-olefin copolymer (B) is considered to have good compatibility with the component (A).

The intrinsic viscosity [η] measured in 135 ° C. decalin of the propylene / α-olefin copolymer (B) is 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g, more preferably 0.5. It is desirable to be -7.0 dL / g.

The propylene / α-olefin copolymer (B) preferably has a crystallinity measured by X-ray diffraction of 20% or less, more preferably 0 to 15%.
This propylene / α-olefin copolymer (B) has a single glass transition temperature, and the glass transition temperature (Tg) obtained by differential scanning calorimetry (DSC) measurement is usually 0 ° C. or lower. It is preferable. The propylene / α-olefin copolymer (B) is excellent in cold resistance and low temperature characteristics when the glass transition temperature (Tg) is within the above range.

  The differential scanning calorimetry is performed, for example, as follows. About 10.00 mg of the sample is packed in a special aluminum pan, and the temperature is increased from 30 ° C. to 200 ° C. at 200 ° C./min using a DSCRDC220 manufactured by Seiko Instruments Inc. After holding at 200 ° C. for 5 minutes, from 200 ° C. The temperature is lowered to −100 ° C. at 10 ° C./min, held at −100 ° C. for another 5 minutes, and then the glass transition temperature (Tg) is determined from the endothermic curve when the temperature is raised at 10 ° C./min.

Further, the molecular weight distribution (Mw / Mn, polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) of the propylene / α-olefin copolymer (B) measured by GPC is preferably 3.5 or less. Preferably it is 3.0 or less, More preferably, it is 2.5 or less.

The propylene / α-olefin copolymer (B) used in the present invention is:
(I ′) a bridged metallocene compound represented by the following general formula [9];
(II) (II-1) organoaluminum oxy compound,
(II-2) a compound that reacts with the bridged metallocene compound (I ′) to form an ion pair,
and
(II-3) selected from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) in the presence of an olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds Although it can manufacture by superposing | polymerizing with an at least 1 sort (s) of olefin, as long as the requirements as a propylene alpha-olefin copolymer (B) are satisfy | filled, a manufacturing method is not limited to this.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are atoms or groups selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group, and each is the same) But it can be different,
R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group,
R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group,
R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms at the same time (ie, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms at the same time),
R ² and R ³ may combine with each other to form a ring,
Adjacent groups among R ^{5 to} R ¹² may be bonded to each other to form a ring.

R ¹³ and R ¹⁴ are an aryl group having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkylaryl group having 6 to 40 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and a 7 to 40 carbon atom. Fluoroalkylaryl group, C6-C20 chloroaryl group, C7-C40 chloroalkylaryl group, C6-C20 bromoaryl group, C7-C40 bromoalkylaryl group, C6 Selected from -20 iodoaryl groups and 7-40 carbon atoms iodoalkylaryl groups, which may be the same or different,
At least one of R ¹³ and R ¹⁴ is an aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, a chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl group having 6 to 20 carbon atoms, A bromoalkylaryl group having 7 to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms, an iodoalkylaryl group having 7 to 40 carbon atoms and a fluoroalkylaryl group having 7 to 40 carbon atoms;
M is Ti, Zr or Hf,
Y is carbon or silicon;
Q is selected from halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or nonconjugated diene, anionic ligand and neutral ligand capable of coordinating with a lone electron pair in the same or different combinations. ,
j is an integer of 1-4. ).

Specific examples of the bridged metallocene compound represented by the general formula [9] (also referred to as “component (I ′)” in the present specification) are shown below, but the scope of the present invention is particularly limited thereby. It is not a thing. Here, octamethyloctahydrodibenzofluorene refers to the structure represented by the formula [10], octamethyltetrahydrodicyclopentafluorene refers to the structure represented by the formula [11], and dibenzofluorene refers to the formula [12] ] Is shown.

Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) ( 2,7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) ( 2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-di tert-Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Di (m-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-bromophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Di (p-iodophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (3,6-di tert-Butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-iodophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (
Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (
Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-
Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,

Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (
Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (
Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-
Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,

Di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (
Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, Di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Nyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl)
Zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert -Butylfluorenyl) zirconium dichloride,

Di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (
Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, Di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Nyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl)
Zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert -Butylfluorenyl) zirconium dichloride,

Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl)
Zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydro Dibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzo Fluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) Nyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2, 7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorene Nyl) zirconium dichloride,

Di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium Dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (dibenzofluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopent Dienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert -Butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) Zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,

Di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (
Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (3
, 5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydro Dicyclopentafluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl)
Zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloro Methyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclo Pentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (2, 3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (4-chloronaphthyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (3-chloronaphthyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (5-chloronaphthyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, phenyl (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) Len (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7 -Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-di tert-Butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,

Naphtyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,

Naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, naphthyl (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) Len (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7 -Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-di tert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,

(p-Tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl) ) (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zyl Nium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p- Chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) ) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6, 7-tetra-tert-butylfluorenyl) zirconium dichloride,

(p-Tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl) ) (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zyl Nium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m- Chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) ) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6, 7-tetra-tert-butylfluorenyl) zirconium dichloride,
(p-Tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) ) Methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydro (Dibenzofluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (p-tolyl) (m -Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) ) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- ( Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl)- 3,6-di-tert-
(Butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, etc. .

  Furthermore, the compounds described above in which “zirconium” is changed to “hafnium” or “titanium”, “dichloride” is “difluoride”, “dibromide”, “diaiodide”, “dichloride” is “dimethyl” or “methyl”. Similarly, the metallocene compound represented by “ethyl” is a metallocene compound represented by the general formula [9].

  The (a) bridged metallocene compound can be produced by referring to a known method. Examples of known production methods include the production methods described in the pamphlet of WO04 / 029062 by the present applicant.

The above metallocene compounds can be used singly or in combination of two or more. The organoaluminum oxy compound (II-1) used for the production of the propylene / α-olefin copolymer (B) is an organoaluminum oxy compound (II-) used for the production of the syndiotactic propylene polymer (A). The same as 1) is used.

As the compound (II-2) which forms an ion pair by reacting with the bridged metallocene compound (I ′) used in the production of the propylene / α-olefin copolymer (B), the above syndiotactic propylene polymer ( The same compound (II-2) that reacts with the bridged metallocene compound (I) used in the production of A1) to form an ion pair is used.

The organoaluminum compound (II-3) used in the production of the propylene / α-olefin copolymer (B) is an organoaluminum compound (II-3) used in the production of the syndiotactic propylene polymer (A1). ) Is used.

Moreover, each said component can also be carry | supported and used for a particulate carrier. The same carrier as that used in the production of the syndiotactic propylene polymer (A1) is used as necessary.
Method for Producing Propylene / α-Olefin Copolymer (B) In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.

A method in which component (I ′) and component (II) are added to the polymerization vessel in any order. In the above method, at least two or more of the catalyst components may be contacted in advance.
When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (I ′) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 1 per liter of the reaction volume.
Used in such an amount as to be 0 ^-2 mol.

Component (II-1) has a molar ratio [(II-1) / M] of component (II-1) to all transition metal atoms (M) in component (I ′) of usually 0.01-5. It is used in such an amount that it becomes 1,000, preferably 0.05 to 2,000. Component (II-2) includes an aluminum atom in component (II-2) and component (I ′
) In the molar ratio [(II-2) / M] with all transition metals (M) in the range of 1 to 1,000, preferably 1 to 500. Component (II-3) includes component (II-3) and component (I ′
) In the molar ratio [(II-3) / M] to the transition metal atom (M) is usually 1 to 10,000, preferably 1 to 5,000.

The propylene / α-olefin copolymer (B) is at least one selected from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) in the presence of the olefin polymerization catalyst as described above. The olefin is usually copolymerized in the liquid phase. In this case, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. Specific examples of the hydrocarbon medium include those described above. Copolymerization can be carried out by either a batch method or a continuous method.

Examples of α-olefins that can be used for polymerization include ethylene, 1-butene, 1-
Pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. α-olefin is a single type,
Or it can use in combination of 2 or more types.

  When the copolymerization is carried out by a batch method using an olefin polymerization catalyst, the concentration of the metallocene compound in the polymerization system is usually from 0.00005 to 1 mmol, preferably from 0.0001 to 0, per liter of polymerization volume. Used in an amount of 50 mmol.

The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1.
5 hours.

The propylene and at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are obtained as propylene / α-olefin copolymers (B) having the above specific composition. To the polymerization system in such amounts. In the copolymerization, a molecular weight regulator such as hydrogen can be used.

When propylene and at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are copolymerized as described above, propylene · α-
The olefin copolymer (B) is usually obtained as a polymerization solution containing the olefin copolymer (B). This polymerization solution is treated by a conventional method to obtain a propylene / α-olefin copolymer (B).

  In this copolymerization reaction, the temperature is usually 40 to 200 ° C., preferably 40 ° C. to 180 ° C., more preferably 50 ° C. to 150 ° C., and the pressure exceeds 0 to 10 MPa, preferably 0.5 to It is carried out under the condition of 10 Mpa, more preferably 0.5-7 Mpa.

Graft modified (B1)
In the production of (B1) which is the graft modified product of (B) used in the present invention, polar monomers, radical initiators, graft modification methods, etc. that can be used for graft modification are described in the section of graft modified propylene resin. The same can be mentioned. As a production method, the component (B1) alone can be graft-modified, but it is preferable to form a composition with the component (A) and the component (B) and then graft-modify it.

The amount of grafting is not particularly limited. For example, the amount of grafting of (B1) can be determined as appropriate, but the amount of modification of the modified product (B1) (the graft amount of the polar monomer) is usually 100% by weight of the modified product (B1). When it is, it is usually 0.1 to 20% by weight, preferably 0.2 to 15% by weight, and more preferably 0.2 to 10% by weight.
(X) Propylene polymer composition The propylene polymer composition (X) according to the present invention comprises (AA) 10 to 95 parts by weight of the graft-modified propylene polymer, preferably 15 to 90 parts by weight, (BB) The propylene / α-olefin copolymer (B) and / or the graft-modified propylene / α-olefin copolymer (B1) contains 90 to 5 parts by weight, preferably 85 to 10 parts by weight. It is desirable.
The propylene-based polymer composition (X) of the present invention has performances such as transparency, heat resistance, flexibility, scratch resistance, vibration damping properties, and wear resistance, and is compatible or bonded with other materials. In addition, since the content of the polar monomer, for example, unsaturated carboxylic acid and / or derivative thereof is in the above range, the propylene-based polymer composition (X) of the present invention can be obtained. High adhesion strength to polar group-containing resins (for example, polyester, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, nylon, EVA, PVA, PS, PVC, etc.). It also exhibits good adhesion to polyolefins such as polypropylene, α-olefin / cyclic olefin copolymer, cyclic olefin ring-opening polymer or hydrogenated product thereof, poly-4-methyl-1-pentene, and polyethylene.

  In addition, the propylene polymer composition (X) in which at least a part of the present invention is graft-modified has other polymers such as olefin-based thermoplastic resins and olefins as long as the properties of the modified product are not impaired. A system elastomer etc. can be mix | blended. Their blending may be in the graft modification step or after modification. When determining whether it is a graft-modified propylene-based resin, it is determined including these olefin-based thermoplastic resins and olefin-based elastomers.

In the propylene-based polymer composition (X) according to the present invention, a weather resistance stabilizer, heat resistance stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, Additives such as a nucleating agent, a lubricant, a pigment, a dye, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant may be blended as necessary. For example, one or more resins (C) selected from the group consisting of a rosin resin, a terpene resin and a petroleum resin in order to increase adhesiveness
May be added. Among these, examples of rosin resins include natural rosin, polymerized rosin, modified rosin and rosin derivatives modified with maleic acid, fumaric acid, (meth) acrylic acid, and the like. Examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof. Furthermore, these hydrogenated substances can also be mentioned.

  Examples of terpene resins include resins comprising α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, etc., and α-pinene, β-pinene, limonene, dipentene, etc. An aromatic modified terpene resin obtained by polymerizing an aromatic monomer such as Moreover, these hydrogenated substances can also be mentioned.

The petroleum resin includes, for example, an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and a copolymer petroleum resin thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And a C9 fraction copolymer), a coumarone indene resin containing styrene, indene, coumarone, other dicyclopentadiene, etc. of the tar naphtha fraction, p-tert-butylphenol and Examples thereof include alkylphenol resins typified by condensates of acetylene, xylene resins obtained by reacting o-xylene, p-xylene or m-xylene with formalin.

  In addition, one or more resins (C) selected from the group consisting of rosin resins, terpene resins and petroleum resins, which may be used in the present invention, are hydrogenated in order to have excellent weather resistance and discoloration resistance. Derivatives are preferred. The softening point of the resin (C) by the ring and ball method is preferably in the range of 40 to 180 ° C. The number average molecular weight (Mn) molecular weight measured by GPC of the resin (C) is preferably in the range of about 100 to 10,000.

A commercially available product may be used as one or more resins (C) selected from the group consisting of rosin resins, terpene resins and petroleum resins, which may be used in the present invention.
One or more resins selected from the group consisting of these rosin resins, terpene resins and petroleum resins may contain a total of 0.1 to 50 parts by weight with respect to 100 parts by weight of the propylene polymer composition (X). it can.

Moreover, you may add a coupling agent further with respect to the propylene-type polymer composition (X) used by this invention. The coupling agent is usually blended mainly for the purpose of improving the adhesion to glass, plastic and the like. In the present invention, the coupling agent can be used without particular limitation as long as it can improve the adhesion between the film or sheet of the present invention and other layers such as glass and polyester resin. And chrome coupling agents are preferably used. In particular, a silane coupling agent (silane coupling agent) is preferably used.

Known silane coupling agents can be used, and there are no particular restrictions, but specific examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxy-ethoxysilane), and γ-glycidoxypropylate. Lipitry methoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like can be used.

The compounding quantity of a silane coupling agent is 0.1-5 weight part normally with a silane coupling agent with respect to 100 weight part of propylene polymer compositions (X), Preferably it is 0.1-3 weight part. It is preferable that the amount of the coupling agent is in the above range since the adhesiveness is sufficiently improved and the transparency and flexibility of the film are not adversely affected.

In order to further improve the moldability of the propylene-based polymer composition (X) according to the present invention, that is, to increase the crystallization temperature and increase the crystallization speed, a nucleating agent which is a specific optional component may be included. In this case, for example, the nucleating agent is dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di-). tert-butylphenyl) sodium phosphate, pimelic acid and its salt, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, etc., and the amount is not particularly limited, but is 0 with respect to 100 parts by weight of the propylene polymer composition. About 0.1 to 1 part by weight is preferred. There is no restriction | limiting in particular in a mixing | blending timing, It can add during superposition | polymerization, after superposition | polymerization, or a shaping | molding process.
Production Method of Propylene Polymer Composition (X) The propylene polymer composition (X) as described above may be prepared by various known methods such as slurry phase, solution phase or A method of multistage polymerization in the gas phase in a continuous or batch manner, a method of mixing with a Henschel mixer, V-blender, riboblender, tumbler blender, etc., or after mixing, a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. Then, after melt-kneading, it can be produced by employing a method of granulating or pulverizing.

Alternatively, (A) and (B) may be preliminarily melt-kneaded to form a composition, followed by graft modification.
By pelletizing the composition of the present invention, the adhesive composition can be easily handled. Furthermore, it becomes possible to knead and use in a multi-resin.

  Examples of the shape of the propylene-based polymer composition (X) pellet include a spherical shape, a cylindrical shape, a lens shape, and a cubic shape. After the propylene-based polymer composition (X) is uniformly melt-mixed and extruded with an extruder, spherical, cylindrical, and lens-shaped pellets are obtained by hot cutting or strand cutting. In this case, the cutting may be performed either in water or in an air stream such as air. The cubic pellets can be obtained by, for example, uniformly mixing, forming into a sheet shape with a roll or the like, and using a sheet pelletizing machine. As for the size, the length of the longest part of the pellet is preferably 3 cm or less. In the case of pellets larger than this, the weighing error may increase.

  The pellet of the propylene-based polymer composition (X) is one in which one or more of calcium carbonate, barium sulfate, silica, talc, stearic acid and polyolefin powder are dusted on the surface of the pellet. May be. In this case, it is preferable from the viewpoint of suppressing the bridging phenomenon in the pellet when the mutual attachment is further pressed or taken out from a silo or the like. The required amount of dusting may be added depending on the size and shape of the pellet, but it is usually added in an amount of 0.05 to 3 parts by weight based on the resin composition pellet.

Description of base material Examples of base materials include α-olefin (co) polymers having 2 to 20 carbon atoms (for example, ethylene homopolymer, ethylene / carbon number 3 to 20 α-olefin copolymer, propylene homopolymer). , Propylene / C2-C20 α-olefin copolymer (excluding propylene, etc.), polar group-containing polymer (for example, α-olefin / polar group-containing vinyl monomer copolymer, aromatic vinyl) Compound (co) polymer, polyester, polyamide, polycarbonate, etc.), metal, vapor-deposited film, paper, and the like.

Production method of film or sheet It can be produced by a usual method. For example, the film or sheet made of the olefin resin composition of the present invention is a film or sheet produced from the olefin resin composition of the present invention by a method such as a T-die molding method, an inflation molding method, or a lamination molding method. It is not limited to these methods. Moreover, the film or sheet | seat which consists of an olefin resin composition of this invention may be used by a single layer, and may be laminated | stacked with another resin layer. Further, the film or sheet of the present invention may be stretched at least in a uniaxial direction, or may be stretched in a biaxial direction.

The thickness of the film or sheet is, for example, usually 1 μm to 1000 μm, preferably 10 μm to 500 μm. 1 μm to 200 μm is preferable for adhesion, and 1 for adhesion.
It is preferably μm to 200 μm.

Manufacturing method of laminated body The film or sheet of the present invention may be subjected to surface treatment such as corona treatment.
Specific examples of the laminate having the layer (X) made of the film or sheet made of the propylene-based resin of the present invention include the following structures:
A laminate in which a layer (X) comprising the film or sheet is laminated on a substrate,
A multilayer laminate in which a substrate is laminated on the layer (X) comprising the film or sheet, and the layer (X) comprising the film or sheet is further laminated thereon;
A multilayer laminate in which a layer (X) composed of the film or sheet is laminated on a substrate, and further a substrate is laminated on the substrate or layer (X) composed of the film or sheet / substrate / the film Or various structures, such as the multilayer laminated body laminated | stacked in order of layer (X) / base material which consists of a sheet | seat, are mentioned.

  In the above illustration, when two or more layers (X) composed of a film or a sheet are included, the layers (X) composed of a film or a sheet may be the same or different. Moreover, when it has two or more base material layers, base material layers may be the same or different.

As the laminate, at least the surface of the layer (X) composed of a film or a sheet is one of preferred embodiments since the transparency of the layer (X) can be exhibited.
Examples of the base material include PET, polycarbonate, α-olefin / cyclic olefin copolymer, ring-opening polymer of cyclic olefin or hydrogenated product thereof, poly-4-methyl-1-pentene, and syndiotactic PP. When using as a base material, it is excellent in transparency.

  The film or sheet and the laminate having the film or sheet include shrink film, wrap film, beverage bottle, food packaging, transparent substrate, masking film, laminate (including glass), reflective film, dicing film, automobile Skin material, damping material, soundproofing material, solar cell sealing material, radiation resistant film, gamma ray resistant film, protective film, adhesive tape, adhesive tape, touch panel, operation panel (base, switch / button), laminated glass interlayer , Touch panel (base), liquid crystal display, stationery, etc.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples at all.

The analysis method used in the present invention is as follows.
[1] Amount of n-decane soluble component (Dsol) at room temperature 200 ml of n-decane was added to 20 cm × 20 cm of the monolayer film of the present invention and dissolved by heating at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter referred to as “n-decane insoluble component: Dinsol”) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the component dissolved in n-decane (this is referred to as “precipitate (A)”). The precipitate (A) and acetone were separated by filtration, and the precipitate (A) was dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble component was determined by the following formula.

n-decane soluble component amount (% by weight) = [precipitate (A) weight / sample weight] × 100
[2] Mw / Mn measurement (Mw: weight average molecular weight, Mn: number average molecular weight)
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as an antioxidant, moving at 1.0 ml / min, sample concentration 15 mg / 10 mL, sample injection volume 500 micron A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

  Converted to PP using a general calibration method. The Mark-Houwink coefficients of PS and PP are the values described in J. Polym. Sci., Part A-2, 8, 1803 (1970) and Makromol. Chem., 177, 213 (1976), respectively. It was.

[3] Melting point (Tm)
Using a DSCPyris 1 or DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20
ml / min), a sample of about 5 mg was heated to 200 ° C. and held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 5 minutes, the melting point was calculated from the peak of the crystal melting peak when the temperature was raised to 200 ° C. at 10 ° C./min, and the heat of fusion was calculated from the integrated value of the peaks.

In addition, in the propylene-type composition described in this-application Example, when several peaks were observed, the peak of the highest temperature side was made into Tm.
[4] Intrinsic viscosity [η]
Intrinsic viscosity [η]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of polymer powder, pellets or resin mass is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η _sp is measured in the same manner. This dilution operation is further repeated twice, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity (see the following formula).

[Η] = lim (η _sp / C) (C → 0)
[5] Propylene unit concentration (Sp), ethylene unit concentration (SE), and α-olefin unit concentration (Sα) having 4 to 10 carbon atoms
Quantification of ethylene, propylene, and α-olefin content was measured as follows using a JNM GX-500 type NMR measuring apparatus manufactured by JEOL Ltd. A 0.35 g sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. This solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is charged into an NMR tube having an inner diameter of 10 mm, and ¹³ C-NMR measurement is performed at 120 ° C. The number of integration is 10,000 times or more. The composition of ethylene, propylene and α-olefin was quantified by the obtained NMR spectrum.

[6] MFR (melt flow rate)
Based on JIS K-6721, it measured with the load of 2.16kgf at 230 degreeC.
[7] Young's modulus of the press sheet (= tensile modulus)
In accordance with JIS K6301, JIS No. 3 dumbbells were punched out and used as evaluation samples. The sample was measured under the conditions of 23 ° C. with a span interval of 30 mm and a tensile speed of 30 mm / min.
[7] Press sheet TMA
In accordance with JIS K7196, using a 1 mm thick test piece, a pressure of ² kg / cm ² was applied to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min.
° C).

[8] Haze measurement Further, using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. with the pellets set at 190 ° C., 10M
Form a 1.0 mm thick sheet with Pa pressure (spacer shape; 200 x 200 x 1.0 mm), and compress it with a pressure of 10 MPa using another Kamito Metal Industries hydraulic hot press set at 20 ° C. The sample for measurement was prepared by cooling with. The hot plate was a 5 mm thick SUS plate. The above-mentioned 200 × 200 × 1.0 mm thick press sheet was produced.

  Further, the press sheet was sandwiched between biaxially stretched PET films (trade name; Lumirror) manufactured by Toray Industries, Inc., and bonded for 1 minute at a pressure of 0.1 MPa using a hydraulic hot press machine manufactured by Shindo Metal Industry Co., Ltd. set at 180 ° C. . Using another hydraulic heat press machine manufactured by Shinfuji Metal Industry Co., Ltd., set to 20 ° C., the sample for measurement was prepared by cooling for 5 minutes without losing pressure. The hot plate was a 5 mm thick SUS plate.

The cut Haze of the film was measured.
It was measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.
[8] Evaluation of film adhesion Using a hydraulic hot press machine manufactured by Shindo Metal Industry Co., Ltd., in which the pellets were set at 190 ° C., 10M
Form a 1.0 mm thick sheet with Pa pressure (spacer shape; 200 x 200 x 1.0 mm), and compress it with a pressure of 10 MPa using another Kamito Metal Industries hydraulic hot press set at 20 ° C. The sample for measurement was prepared by cooling with. The hot plate was a 5 mm thick SUS plate. The above-mentioned 200 × 200 × 1.0 mm thick press sheet was produced.

  In addition, the press sheet was sandwiched between biaxially stretched PET films (trade name; Lumirror) manufactured by Toray Industries, Inc. and bonded for 1 minute at a pressure of 0.1 MPa using a hydraulic hot press machine manufactured by Shindo Metal Industry Co., Ltd. set at 180 ° C. . Using another hydraulic heat press machine manufactured by Shinfuji Metal Industry Co., Ltd., set to 20 ° C., the sample for measurement was prepared by cooling for 5 minutes without losing pressure. The hot plate was a 5 mm thick SUS plate.

The sample was subjected to a T-type peel test.
The strip was cut into a 100 mm × 10 mm strip (50 mm × 10 mm of the portion to be adhered to the pet), and a T-type peel test was performed at a tensile speed of 300 mm / min using an Instron tensile tester INSTRONON 1123.

Adhesion evaluation criteria;
○: Base material destruction (adhesion layer destruction or base material breakage)
Δ: Interfacial elongation peeling ×: peeling Details of the examples are shown below.

<Example of catalyst synthesis>
<Synthesis Example 1>
Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride was produced by the method described in Synthesis Example 3 of JP-A No. 2004-189666.

<Synthesis Example 2>
Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was prepared as follows.
(Step 1) Synthesis of 2,7-Dibromo-3,6-di-tert-butyl-fluorene In a nitrogen stream, 170 mL of propylene carbonate was added to 15.22 g (54.7 mmol) of 3,6-di-tert-butylfluorene. Stirring was performed. To this solution, 20.52 g (115 mmol) of N-bromosuccinimide was added. Stirring was carried out at 80 ° C. for 5 hours. After natural cooling, the reaction solution was added to 800 mL of water. The mixture was stirred at room temperature for 15 minutes and filtered using a Kiriyama funnel. The obtained white yellow powder was washed 5 times with 10 mL of ethanol. A mixed solution of hexane and a small amount of dichloromethane was added to the white yellow powder and heated to 60 ° C. to completely dissolve the powder. -2
Allowed to stand at 0 ° C. overnight. The precipitated crystals were washed 3 times with 5 mL of hexane to obtain the target product as a white yellow powder (yield 21.16 g, yield 76%).
¹ H NMR (270 MHz, CDCl ₃ ): δ 1.60 (s, tBu (Flu), 18H), 3.75 (s, Flu-9H, 2H), 7.73
(s, Flu, 2H), 7.81 (s, Flu, 2H).
MS (FD): M / z 436 (M ⁺ ).
(Step 2) Synthesis of 3,6-Di-tert-butyl-2,7-diphenyl-fluorene Under a nitrogen stream, 8.15 g (18.7 mmol) of 2,7-dibromo-3,6-di-tert-butylfluorene, To 1.08 g (0.93 mmol) of Pd (PPh ₃ ) was added 120 mL of anhydrous DME,
Stirring was carried out at room temperature for 20 minutes. To this solution was added a solution of 5.01 g (41.1 mmol) of phenylboric acid in 20 mL of ethanol. The flask containing phenylboric acid was washed twice with 4 mL of ethanol and added. After stirring at room temperature for 20 minutes, 2.0 mo
37.4 mL (74.8 mmol) of 1 / L aqueous sodium carbonate solution was added. Heating under reflux was performed for 18 hours. After natural cooling, the reaction was terminated with 1N hydrochloric acid in an ice bath. Ether was added for liquid separation, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off and separation by silica gel chromatography was performed. A mixed solution of hexane and a small amount of dichloromethane was added to the obtained white yellow powder, and heated to 60 ° C. to completely dissolve it. After leaving still at room temperature for 1 hour, it left still at -20 degreeC for 13 hours. The precipitated crystals were washed 3 times with 10 mL of hexane to obtain the desired product as a white powder (yield 4.36 g, yield 54%).
¹ H NMR (270 MHz, CDCl ₃ ): δ 1.29 (s, tBu (Flu), 18H), 3.78 (s, Flu-9H, 2H), 7.16 (s, Flu, 2H), 7.34 (br, PhFlu, 10H), 7.97 (s, Flu, 2H).
MS (FD): M / z 430 (M ⁺ ).
(Step 3) Synthesis of 6,6-dibenzylfulvene In a nitrogen atmosphere, 8.0 g (121.0 mmol) of cyclopentadiene and 100 mL of dehydrated THF were added to a 500 mL three-necked flask and stirred. This mixed solution was cooled in an ice bath, and 80 mL (125.6 mmol) of a hexane solution of n-butyllithium having a concentration of 1.57 mol / L.
l) was added. Thereafter, the mixture was stirred at room temperature for 3 hours, and the resulting white slurry was cooled in an ice bath. Then, 25.0 g (118.0 mmol) of 1,3-diphenyl-2-propanone was added to dehydrated THF50.
A solution dissolved in ml was added. The mixture was then stirred at room temperature for 12 hours, and the resulting yellow solution was quenched with saturated aqueous NH ₄ Cl. Hexane 100mL was added and the soluble part was extracted, and this organic phase was dried with magnesium sulfate after washing | cleaning with water and a saturated salt solution. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a yellow solid (yield 3.7 g, yield 12%).
¹ H NMR (270 MHz, CDCl ₃ ): δ 3.69 (s, PhCH ₂ , 4H), 6.60-6.72 (m, Cp, 4H), 7.13-7.32 (m, PhCH ₂ , 10H).
(Step 4) Synthesis of (PhCH ₂ ) ₂ C (Cp) (3,6-tBu ₂ -2,7-Ph ₂ -Flu) 3,6-Di-tert-butyl-2,7-diphenyl under nitrogen flow 40 mL of anhydrous THF was added to 1.60 g (3.71 mmol) of -fluorene and stirred. The solution was cooled in an ice bath and 1.56M
2.65 mL (4.13 mmol) of n-butyllithium in hexane was added. Stir at room temperature for 2 hours. The obtained red solution was cooled to −78 ° C. with a dry ice-methanol bath, and 2 solutions of 1.06 g (4.10 mmol) of 6,6-dibenzylfulvene in 20 mL of THF were added.
Added dropwise over 0 minutes. Thereafter, the mixture was stirred for 18 hours while gradually warming to room temperature. To the resulting black-red solution, 60 mL of 1N hydrochloric acid was added to terminate the reaction. 80 mL of ether was added to carry out liquid separation, and a soluble part was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The target product was obtained as a white yellow powder by evaporating the solvent and purifying by silica gel chromatography (yield 0.59 g, yield 23%).
¹ H NMR (270 MHz, CDCl ₃ ): δ 1.25 (s, tBu (Flu), 18H), 2.66 (br, CpH, 1H), 3.22 (br, CH ₂ Ph, 4H), 4.41 (br, Flu- 9H, 1H), 5.85-6.51 (m, Cp, 4H), 6.82-7.40 (m, Ph (Flu) and CH ₂ Ph and Flu, 22H), 7.67 (s, Flu, 2H).
MS (FD): M / z 688 (M ⁺ ).
(Step 5) Synthesis of (PhCH ₂ ) ₂ C (Cp) (3,6-tBu ₂ -2,7-Ph ₂ -Flu) ZrCl _{2 In} a nitrogen atmosphere, add (PhCH ₂ ) ₂ C (Cp) to a 100 mL Schlenk tube ) (3,6-tBu ₂ -2,7-Ph ₂ -Flu) 0
. 59 g (0.855 mmol) and anhydrous diethyl ether 40 mL were added and stirred. This mixed slurry solution was cooled in an ice bath, 1.21 mL (1.88 mmol) of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L was added, and the mixture was stirred for 45 hours while gradually warming to room temperature. The red reaction solution was cooled (−78 ° C.) with a dry ice / methanol bath, and 0.200 g (0.858 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 42 hours while gradually warming to room temperature to obtain a red-orange suspension.

The solvent was dried under reduced pressure, dissolved in hexane in a glove box, washed with hexane through a glass filter packed with celite, and the orange powder not dissolved in hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off, washed with diethyl ether / cold pentane, and dried to obtain the desired product as an orange powder (yield 515 mg, 71%).
¹ H NMR (270 MHz, CDCl ₃ ): δ 1.30 (s, tBu (Flu), 18H), 3.82 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 3.93 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 5.80 (t, J = 2.6 Hz, Cp, 2H), 6.25 (t, J = 2.6 Hz, Cp, 2H), 6.97-7.34 (m, Ph (Flu) and CH ₂ Ph, 20H ), 7.37 (s, Flu, 2H), 8.32 (s, Flu, 2H).
MS (FD): M / z 848 (M ⁺ ).
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was prepared by the following method.

<Synthesis Example 3>
Synthesis of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (i) Synthesis of 6,6-di (p-chlorophenyl) fulvene Reaction vessel equipped with a dropping funnel Under nitrogen atmosphere, 40 ml of dehydrated tetrahydrofuran and 2.15 ml (25.9 mmol) of cyclopentadiene were added, and 18.0 ml (28.5 mmol) of a hexane solution of 1.58 mol / L n-butyllithium was cooled while cooling this solution to 0 ° C.
Was slowly added dropwise and stirred. Thereafter, a solution obtained by dissolving 5.00 g (19.9 mmol) of 4,4′-dichlorobenzophenone in 30 ml of dehydrated tetrahydrofuran was added to the dropping funnel, and the solution was slowly added dropwise while cooling to 0 ° C., followed by returning to room temperature and stirring for one day. This reaction solution was extracted with diethyl ether, the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the separated organic phase was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered off. The solvent of the filtrate was distilled off under reduced pressure using a rotary evaporator. Purification was performed on a silica gel column to obtain the desired product (yield 3.37 g, yield 57%). The target product was identified by ¹ H-NMR.
¹ H NMR spectrum (270 MHz, CDCl ₃ , TMS): δ 6.21-6.24 (m, 2H), 6.60-6.63 (m, 2H), 7.23 (d, 2H, J = 8.1 Hz), 7.37 (d, 2H , J = 8.6 Hz).
(Ii) Synthesis of octamethyloctahydrodibenzofluorene In a 500 ml three-necked flask equipped with a nitrogen-filled three-way cock, dropping funnel and magnetic stirrer, 9.72 g (58.6 mmol) of fluorene and 2,5-dimethyl were added. -19.6 g (134 mmol) of -2,5-hexanediol was added at room temperature. After adding 85 ml of dehydrated dichloromethane and stirring with a magnetic stirrer, the mixture was cooled to −8 ° C. with an ice bath. To this, 38.9 g (292 mmol) of crushed anhydrous aluminum chloride was added over 70 minutes, followed by stirring at 0 ° C. for 2 hours, further removing the ice bath and stirring at room temperature for 19 hours. After confirming disappearance of fluorene by GC, the black brown solution was quenched by pouring into 150 ml of ice water. After extraction of soluble components with 500 ml of diethyl ether, the organic layer was neutralized with a saturated aqueous solution of sodium bicarbonate and washed with water. The separated organic phase was dried over anhydrous magnesium sulfate, the magnesium sulfate was filtered off, and the solvent of the filtrate was distilled off under reduced pressure using a rotary evaporator. The residue was transferred onto a Kiriyama funnel, washed with hexane 10 ml × 6 times, and then dried under reduced pressure to obtain the desired product (yield 12.0 g).
Yield 53%). The object was identified by ¹ H-NMR and FD-MS spectra.

¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.3 (s, 12H), 1.4 (s, 12H), 1.7 (s, 8H), 3.8 (s, 2H), 7.4 (s, 2H ), 7.6 (s, 2H).
MS (FD): M / z 386 (M ⁺ ).
(Iii) Synthesis of di (p-chlorophenyl) cyclopentadienyl (octamethyloctahydrodibenzofluorenyl) methane In a reaction vessel equipped with a dropping funnel, 40 ml of dehydrated tetrahydrofuran and the octamethyloctahydrodibenzofluorene were added in a nitrogen atmosphere. 2.35 g (6.08 mmol) was added, and while cooling this solution to 0 ° C., 4.62 ml (7.30 mmol) of a 1.58 mol / L n-butyllithium hexane solution was slowly added dropwise and stirred. To this solution, 1,3-dimethyl-
After adding 0.86 ml (7.90 mmol) of 2-imidazolidinone and stirring for 30 minutes, 2.00 g (6.68 mmol) of 6,6-di (p-chlorophenyl) fulvene was dissolved in 30 ml of dehydrated tetrahydrofuran in a dropping funnel. The solution was added dropwise slowly while cooling to -78 ° C., and stirred for one day while slowly returning to room temperature. This reaction solution was extracted with diethyl ether, the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the separated organic phase was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered off. The solvent of the filtrate was distilled off under reduced pressure using a rotary evaporator. After purification with a silica gel column, recrystallization was performed with toluene to obtain the desired product (yield 0.714 g, yield 17%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H NMR spectrum (270 MHz, CDCl ₃ , TMS): δ 0.94 (s, 6H), 1.14 (s, 6H), 1.27 (s, 12H), 1.62 (s, 8H), 3.06 (b, 2H), 5.30 (s, 1H), 6.38-6.50 (b, 3H), 7.00-7.29 (m, 8H)
FD-MS spectrum: m / z 684 (M ⁺ ).
(Iv) Synthesis of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride Under nitrogen atmosphere, 15 ml of dehydrated diethyl ether was added to di (p-chlorophenyl) cyclopentadienyl ( 428 mg (0.62 mmol) of octamethyloctahydrodibenzofluorenyl) methane was added, and 0.87 ml (1.37 mmol) of a 1.58 mol / L n-butyllithium hexane solution was slowly added dropwise while cooling the solution to 0 ° C. And stirred overnight. Then -78 ° C
While cooling, 224 mg (0.59 mmol) of zirconium tetrachloride / tetrahydrofuran complex (1: 2) was added and stirred overnight. After distilling off the volatile components of this slurry under reduced pressure, the residue was washed with 40 ml of dehydrated hexane, and the washing solution was separated by filtration. The hexane-dissolved portion of the filtrate was concentrated, and dehydrated hexane was added to the resulting solid and recrystallized to obtain the desired product (yield 90 mg, 18%). The target product was identified by ¹ H-NMR and FD-MS spectra.
¹ H NMR (Spectrum 270 MHz, CDCl ₃ ): δ 0.87 (s, 6H), 0.99 (s, 6H), 1.42 (s, 6H), 1.49 (s, 6H), 1.64-1.71 (m, 8H), 5.51-5.53 (m, 2H), 6.17 (s, 2H), 6.29-6.31 (m, 2H), 7.33 (dd, 2H, J = 2.16 Hz, 8.37 Hz), 7.46 (dd, 2H, J = 1.89 Hz , 8.64 Hz), 7.74 (dd, 2H,
J = 2.43 Hz, 8.1 Hz), 7.88 (dd, 2H, J = 2.16 Hz, 8.37 Hz), 8.08 (s, 2H)
FD-MS spectrum: m / z 844 (M ⁺ ).
<Synthesis Example 4>
Synthesis of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride (i) Preparation of 1-ethyl-3-tert-butylcyclopentadiene Synthesis Under a nitrogen atmosphere, a 300 ml three-necked flask equipped with a magnetic stirrer and a three-way cock was charged with 200 ml of dehydrated diethyl ether and 52 ml (154 mmol) of a 3.0M ethylmagnesium bromide diethyl ether solution. In an ice water bath, 17.8 g (129 mmol) of 3-tert-butylcyclopentenone was added dropwise over 1 hour. After stirring at room temperature for 20 hours, the reaction solution was poured into 100 ml of 2N hydrochloric acid. The organic layer was separated and the aqueous layer was extracted twice with 50 ml of ether. The obtained organic layers were combined and washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, and twice with saturated brine. It dried with magnesium sulfate and the solvent was distilled off. Thereafter, purification by column chromatography gave 20.2 g (GC purity 75%) of a pale yellow transparent liquid. The yield was 78%. Identification was performed by ¹ H-NMR spectrum. The measurement results are shown below.

¹ H-NMR spectrum (270 MHz, CDCl ₃ , TMS standard): δ / ppm 6.19 + 6.05 + 5.81 + 5.77 (m + m + m + m, 2H), 2.91 + 2.85 (m + m, 2H), 2.48− 2.27 (m, 2H), 1.15−1.08 (s + s + m, 12H)
(Ii) Synthesis of 3-tert-butyl-1-ethyl-6,6-diphenylfulvene In a 300 ml three-necked flask equipped with a magnetic stirrer and a three-way cock in a nitrogen atmosphere, 1-ethyl-3-tert-butylcyclo Pentadiene 5.11 g (23.9 mmol) (GC purity 75%) and THF 150 ml were charged. In a dry ice / methanol bath, 16 ml (25.2 mmol) of a 1.56 Mn-butyllithium hexane solution was slowly added dropwise, and then stirred at room temperature for 20 hours. To the resulting reaction solution, 3.1 ml (28.8 mmol) of 1,3-dimethyl-2-imidazolidinone was added, followed by charging with 5.3 g (28.8 mmol) of benzophenone and refluxing for 48 hours. Stir. The reaction solution was poured into 100 ml of 2N hydrochloric acid. The organic layer was separated and the aqueous layer was extracted twice with 50 ml of hexane. The organic layer was combined and washed with a saturated aqueous sodium hydrogen carbonate solution, water, and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. Thereafter, the product was purified by column chromatography to obtain 4.2 g of an orange solid. The yield was 56%. Identification was performed by ¹ H-NMR spectrum. The measurement results are shown below.
¹ H-NMR spectrum (270 MHz, CDCl ₃ , TMS standard): δ / ppm 7.2−7.4 (m, 10H), 6.3 (m, 1H), 5.7 (m, 1H), 1.70 + 1.85 (q, 2H) , 1.15 (s, 9H), 0.85 (t, 3H)
(Iii) Synthesis of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) A 200 ml three-necked flask equipped with a magnetic stir bar and a three-way cock was used. After sufficiently purging with nitrogen, 3.8 g of 2,7-di-tert-butylfluorene (13.7 mmol) was dissolved in 80 ml of dehydrated diethyl ether under a nitrogen atmosphere. Under an ice-water bath, 9.2 ml of n-butyllithium / hexane solution (1.56M: 14.3 mmol) was gradually added dropwise to this solution, and then stirred at room temperature for 100 hours. To this reaction solution was added 4.5 g of 3-tert-butyl-1-ethyl-6,6-diphenylfulvene (14.3 mmol), and the mixture was stirred for 30 hours under reflux. The reaction solution was poured into 100 ml of 2N aqueous hydrochloric acid solution in an ice bath, diethyl ether was added to separate the organic layer, and the aqueous layer was extracted twice with 50 ml of diethyl ether. The organic layer was combined and washed with a saturated aqueous sodium hydrogen carbonate solution, water, and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. Thereafter, the residue was purified by column chromatography to obtain 4.2 g of a white solid. The yield was 53%. Identification was performed by FD-mass spectrometry spectrum (FD-MS). The measurement results are shown below.

FD-MS: m / z = 592 (M ⁺ )
(Iv) Diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl)
Synthesis of (2,7-di-tert-butylfluorenyl) zirconium dichloride A 100 ml Schlenk flask equipped with a magnetic stirrer tip and a three-way cock was thoroughly purged with nitrogen, and 1.0 g of diphenylmethylene ( 3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) (1.68 mmol) was dissolved in 40 ml of dehydrated diethyl ether. To this solution, 2.2 ml (3.4 mmol) of a 1.56 M n-butyllithium hexane solution was gradually added dropwise in an ice bath, followed by stirring at room temperature for 28 hours. The reaction solution was sufficiently cooled in a dry ice / methanol bath, and 0.39 g of zirconium tetrachloride (1.68 mmol) was added. After stirring for 48 hours while gradually returning to room temperature, the solvent was distilled off under reduced pressure. The slurry was reslurried with hexane and filtered through a glass filter filled with diatomaceous earth. The brown solid on the filter was extracted with a small amount of dichloromethane and filtered. The solvent was distilled off under reduced pressure for each of the obtained hexane solution and dichloromethane solution. The dark orange solid was washed with a small amount of pentane and diethyl ether, respectively, and dried under reduced pressure to obtain 140 mg (0.186 mmol) of the target compound as an orange solid. Identification was performed by ¹ H-NMR spectrum and FD-mass spectrometry spectrum.
The measurement results are shown below.

¹ H-NMR spectrum (270 MHz, CDCl ₃ , TMS):
δ / ppm 7.90−8.07 (m, 5H), 7.75 (m, 1H), 7.15−7.60 (m, 8H), 6.93 (m, 1H),
6.15-6.25 (m, 2H), 5.6 (d, 1H), 2.05 + 2.25 (q, 2H),
0.95-1.15 (s + t + s, 30H).
FD-MS: m / z = 752 (M ⁺ ).
<Polymerization Example A-1>
Synthesis of Syndiotactic Propylene Polymer (A-1) A 1000-liter n-heptane was charged into a 3 m ³ internal reaction tank sufficiently purged with nitrogen, and a toluene solution of methylaluminoxane (Al = 1.53 mol) at room temperature. / L) to 610 ml
(0.93 mol) was added dropwise. On the other hand, a magnetic stirrer was placed in a 5-liter branch flask which had been sufficiently purged with nitrogen. To this was added 610 ml (0.93 mol) of a toluene solution of methylaluminoxane (Al = 1.53 mol / l) and then dibenzylmethylene. A toluene solution of 1.30 g (1.86 mmol) of (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride was added and stirred for 20 minutes. This solution was added to the reaction vessel and then hydrogen 3200 NL was fed at 19 N m ³ / h over 10 minutes. Thereafter, polymerization was started while supplying propylene at 65 kg / hr and hydrogen so that the gas phase concentration in the reaction vessel was 53 mol%. Propylene is continuously supplied in an amount of 65 kg / hr while maintaining a gas phase concentration of 53 mol% in a hydrogen reaction tank, polymerization is carried out at 25 ° C. for 4 hours, and then a small amount of diethylene glycol monoisopropyl ether is added for polymerization. Stopped. The obtained polymer was washed with 1.8 m ³ of heptane and dried under reduced pressure at 80 ° C. for 15 hours. As a result, 100 kg of polymer was obtained. The MFR is 2.4 (g / 10 min), the polymerization activity is 13.4 kg-PP / mmol-Zr · hr, and the obtained polymer [η] is 1.90 dl / g, Tm1 = 152 ° C. Tm2 = 158 ° C. and rrrr fraction = 94%. The physical properties are shown in Table 1.

<Polymerization Example A-2>
As the syndiotactic propylene polymer (A-2), total syndiotactic polypropylene (Finaplas1471 ^™ , MFR = 5.0 g / 10 min) was used. The physical properties are shown in Table 1.

<Polymerization Example A-3>
As the isotactic polypropylene polymer (A-3), an isotactic polypropylene (Prime Polypro ^™ : B205, MFR = 1.4 g / 10 min) manufactured by Prime Polymer Co., Ltd. was used. The physical properties are shown in Table 1.

<Polymerization example B-1>
Propylene / α-olefin copolymer (B-1)
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.67 MPa, the system pressure was adjusted to 1.37 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 10 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.37 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 90 g, MFR was 1.0 (g / 10 min), and [η] = 2.3 (dL / g) measured in 135 ° C. decalin. The rr value was 83.5%. Table 1 shows the measured physical properties of the obtained polymer. This operation was repeated to obtain a necessary amount of polymer, which was melt-kneaded and used in Examples described later.

<Polymerization example B-2>
Synthesis of propylene / α-olefin copolymer (B-2) After charging 1834 ml of dry hexane, 1-butene and 20 g of triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature. The temperature inside the polymerization apparatus was raised to 70 ° C., and the pressure inside the system was increased to 0.63 MPa with propylene, and then the system pressure was adjusted to 1.33 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 10 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.30 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 107 g, the MFR was 0.9 (g / 10 min), and [η] = 2.4 (dL / g) measured in 135 ° C. decalin. Met. Table 1 shows the measured physical properties of the obtained polymer. The rr value was 85.1%. This operation was repeated to obtain a necessary amount of polymer, which was melt-kneaded and used in Examples described later.

<Polymerization example B-3>
Synthesis of Propylene / α-Olefin Copolymer (B-3) After charging 833 ml of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol) into a 2000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature The internal temperature of the polymerization apparatus was raised to 60 ° C., and the pressure in the system was increased to 0.33 MPa with propylene, and then the system pressure was adjusted to 0.63 MPa with ethylene. Next, 0.002 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem Co.) in terms of aluminum are brought into contact with each other. The toluene solution was added to the polymerization vessel and polymerized for 20 minutes while maintaining the internal temperature at 60 ° C. and the internal pressure at 0.63 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 97 g, MFR was 1.0 (g / 10 min), and [η] = 2.3 (dL / g) measured in decalin at 135 ° C. Table 1 shows the measured physical properties of the obtained polymer.

[Example 1]
[Production of modified sPP]
To the syndiotactic polypropylene obtained in <Polymerization Example (A-1)>, 0.015 parts by weight of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as MAH), t-butyl peroxybenzoate (Nippon Yushi) A solution prepared by dissolving 0.015 part by weight of trade name Perbutyl Z) in acetone was dry blended. After that, using a twin-screw kneader (Technobel Co., Ltd., KZW15), the resin was extruded at a resin temperature of 180 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 25 g / min. An acid-modified syndiotactic polypropylene (hereinafter abbreviated as MAH-sPP) was obtained. The obtained MAH-sPP was dissolved in xylene, purified by reprecipitation in acetone, and the grafting amount of maleic anhydride was measured.
. It was 30% by weight. The MFR of this MAH-sPP was 91 g / 10 min. In the following, denatured
PP is a polymer (A-1G).

[Example 2]
<Syndiotactic polypropylene (A-1) 20 obtained in <Polymerization example (A-1)>
Parts by weight, and propylene / ethylene copolymer (B-1) 8 obtained in <Polymerization Example (B-2)> 8
0 part by weight, 0.1 part by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer, and 0.0050 weight of maleic anhydride Part and 0.0050 part by weight of t-butyl peroxybenzoate were blended. Using a Plavo twin screw extruder, granulation was carried out under the conditions of a preset temperature of 200 ° C., a resin extrusion rate of 40 g / min and 200 rpm to obtain a pellet sheet for measurement.

In addition, using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. with the pellet sheet set at 190 ° C,
A sheet of 1.0 mm thickness is formed at a pressure of 10 MPa (spacer shape; 200 × 200 × 1.0 mm), and compressed at a pressure of 10 MPa using another Kamito Metal Industries hydraulic hot press set at 20 ° C. The sample for measurement was prepared by cooling with. The hot plate was a 5 mm thick SUS plate. The above-mentioned 200 × 200 × 1.0 mm thick press sheet was produced.

In addition, the press sheet was sandwiched between biaxially stretched PET films (trade name; Lumirror) manufactured by Toray Industries, Inc. and bonded for 1 minute at a pressure of 0.1 MPa using a hydraulic hot press machine manufactured by Shindo Metal Industry Co., Ltd. set at 180 ° C. . A laminate for measurement was prepared by using another hydraulic heat press machine manufactured by Shinfuji Metal Industry Co., Ltd. set at 20 ° C. and cooled for 5 minutes without losing pressure. The hot plate was a 5 mm thick SUS plate. Table 2 shows the measurement results.
Shown in

[Example 3]
<Syndiotactic polypropylene (A-1) 40 obtained in <Polymerization example (A-1)>
Parts by weight, and propylene / ethylene copolymer (B-2) 6 obtained in <Polymerization Example (B-2)>
0 parts by weight, 0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer, and 0.0075 maleic anhydride Part and 0.0075 part by weight of t-butyl peroxybenzoate were blended. Using a Plavo twin screw extruder, granulation was carried out under the conditions of a preset temperature of 200 ° C., a resin extrusion rate of 40 g / min and 200 rpm to obtain a pellet sheet for measurement.

Pressing was performed in the same manner as in Example 2 to obtain a press sheet. The press sheet was bonded to a PET film. The measurement results are shown in Table 2.
[Example 4]
30 parts by weight of the modified syndiotactic polypropylene obtained in Example 1, 70 parts by weight of the propylene / ethylene copolymer (B-2) obtained in <Polymerization Example (A-1G)>, and a heat stabilizer 0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate was added. Using Pravo's twin screw extruder, set temperature 200 ° C,
Granulation was carried out at a resin extrusion rate of 40 g / min and 200 rpm to obtain a pellet sheet for measurement.

Pressing was performed in the same manner as in Example 2 to obtain a press sheet. The press sheet was bonded to a PET film. The measurement results are shown in Table 2.
[Example 5]
20 parts by weight of the modified syndiotactic polypropylene obtained in Example 1, 80 parts by weight of the propylene / butene / ethylene copolymer (B-3) obtained in <Polymerization Example (A-1G)>, and heat resistant stability As an agent, 0.1 part by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate was blended. Using a Plavo twin screw extruder, granulation was carried out under the conditions of a preset temperature of 200 ° C., a resin extrusion rate of 40 g / min and 200 rpm to obtain a pellet sheet for measurement.

Pressing was performed in the same manner as in Example 2 to obtain a press sheet. The press sheet was bonded to a PET film. The measurement results are shown in Table 2.
[ Reference Example 6]
And the prime Polymer Co. isotactic polypropylene (B205) 20 parts by weight, and <Polymerization Example (A-3)> In the obtained propylene-butene-ethylene copolymer (B-3) 80 parts by weight, heat stability As an agent, 0.1 part by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate was blended. Further, 0.0050 parts by weight of maleic anhydride and 0.0050 parts by weight of t-butyl peroxybenzoate were blended. Using a Plavo twin screw extruder, granulation was carried out under the conditions of a preset temperature of 200 ° C., a resin extrusion rate of 40 g / min and 200 rpm to obtain a pellet sheet for measurement.

Pressing was performed in the same manner as in Example 2 to obtain a press sheet. The press sheet was bonded to a PET film. The measurement results are shown in Table 2.
[Comparative Example 1]
Total Syndiotactic Polypropylene (A-2) (Finaplas1471 ^TM , M
FR = 5.0 g / 10 min.) 20 parts by weight, 80 parts by weight of the propylene / ethylene copolymer (B-2) obtained in <Polymerization Example (B-2)>, and maleic anhydride 0 0050 parts by weight and 0.0050 parts by weight of t-butyl peroxybenzoate were blended. Using a Plavo twin screw extruder, granulation was carried out under the conditions of a preset temperature of 200 ° C., a resin extrusion rate of 40 g / min and 200 rpm to obtain a pellet sheet for measurement.

Pressing was performed in the same manner as in Example 2 to obtain a press sheet. The press sheet was bonded to a PET film. The measurement results are shown in Table 2.
[Comparative Example 2]
Total Syndiotactic Polypropylene (A-2) (Finaplas1471 ^TM , M
FR = 5.0 g / 10 min.) 20 parts by weight and 80 parts by weight of the propylene / ethylene copolymer (B-2) obtained in <Polymerization Example (B-2)> were blended. Using a Plavo twin screw extruder,
Granulation was performed under the conditions of a preset temperature of 200 ° C., a resin extrusion rate of 40 g / min, and 200 rpm to obtain a measurement pellet sheet.
Pressing was performed in the same manner as in Example 2 to obtain a press sheet. The press sheet was bonded to a PET film. The measurement results are shown in Table 2.
[Polymerization Example AA-1]
(Synthesis of syndiotactic propylene polymer (AA-1))
To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branched flask with sufficient nitrogen substitution, to which was added 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), followed by dibenzylmethylene (cyclopentadiene). Enil) (3,6-
Di-tert-butylfluorenyl) zirconium dichloride in toluene solution 5.0 μmo
was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated to initiate polymerization. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. under normal pressure for 45 minutes, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 2.38 g of polymer was obtained. The polymerization activity is 0.63 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer is 1.9 dl / g, Tm1 = 152 ° C., Tm2 = 158 ° C., rrrr = 93.5% Met. This operation was repeated to obtain the required amount of polymer and used in the polymerization examples. Table 3 shows the physical properties of the polymer (AA-1).
(Syndiotactic propylene polymer (AA-2))
Total Syndiotactic Polypropylene (Finaplas1471 ^™ , MFR = 5.
0 g / 10 min) was used. Table 3 shows the physical properties of the polymer (AA-2).
[Polymerization Example AA-3]
(Synthesis of syndiotactic propylene polymer (AA-3))
According to the production method of Polymerization Example AA-1 except that hydrogen was further supplied to the polymerization system, the polymer had the same TMA softening temperature, rrrr fraction, and Mw / Mn as [AA], [η] = 1.4 dl
/ G syndiotactic propylene polymer (AA-3) (propylene homopolymer) was used. Table 4 shows the physical properties of the polymer (AA-3).
[Polymerization Example A-4]
(Synthesis of syndiotactic propylene polymer (AA-4))
According to the production method of Polymerization Example AA-1 except that hydrogen was further supplied to the polymerization system, the polymer had the same TMA softening temperature, rrrr fraction, and Mw / Mn as [AA], [η] = 1.2 dl
A propylene homopolymer of / g was used. Table 4 shows the physical properties of the polymer (AA-4). (Syndiotactic propylene polymer (AA-5))
Total Syndiotactic Polypropylene (Finaplas1571 ^™ , MFR = 9.
1 g / 10 min) was used. Table 4 shows the physical properties.
[Polymerization Example BB-1]
(Synthesis of propylene / α-olefin copolymer (BB-1))
After charging 8.3 ml of dry hexane, 1-butene and 120 g of triisobutylaluminum (1.0 mmol) into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, the temperature inside the polymerization apparatus was raised to 60 ° C. and propylene was used. After the pressure in the system was increased to 0.33 MPa, the system pressure was adjusted to 0.62 MPa with ethylene. Next, 0.002 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem Co.) in terms of aluminum are brought into contact with each other. The toluene solution was added to the polymerization vessel and polymerized for 20 minutes while maintaining the internal temperature at 60 ° C. and the internal pressure at 0.62 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 73 g and [η] = 2.1 (dL / g) measured in 135 ° C. decalin. The measured physical properties of the obtained polymer are shown in Table 3 [Polymerization Example BB-2].
(Propylene / α-olefin copolymer (BB-2))
After charging 8.3 ml of dry hexane, 1-butene and 120 g of triisobutylaluminum (1.0 mmol) into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, the temperature inside the polymerization apparatus was raised to 60 ° C. and propylene was used. After the pressure in the system was increased to 0.33 MPa, the system pressure was adjusted to 0.63 MPa with ethylene. Next, 0.002 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem Co.) in terms of aluminum are brought into contact with each other. The toluene solution was added to the polymerization vessel and polymerized for 20 minutes while maintaining the internal temperature at 60 ° C. and the internal pressure at 0.63 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 97 g, and [η] = 2.3 (dL / g) measured in 135 ° C. decalin. Table 3 shows the measured physical properties of the obtained polymer.
[Polymerization Example BB-3]
(Propylene / α-olefin copolymer (BB-3))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.67 MPa, the system pressure was adjusted to 1.37 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 10 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.37 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 90 g and [η] = 2.2 (dL / g) measured in 135 ° C. decalin. Table 3 shows the measured physical properties of the obtained polymer.
[Polymerization Example BB-4]
(Synthesis of propylene / α-olefin copolymer (BB-4))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) in a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 50 ° C., and the pressure inside the system was adjusted with propylene. After pressurizing to 0.67 MPa, the system pressure was adjusted to 1.37 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel, polymerized for 10 minutes while maintaining the internal temperature at 50 ° C. and the internal pressure at 1.37 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 78 g, [η] = 3.5 (dL / g) measured in decalin at 135 ° C., and the ethylene content measured by ¹³ C-NMR was 18 mol%. Table 4 shows the measured physical properties of the obtained polymer.
[Polymerization Example (BBB-1)]
(Synthesis of propylene / α-olefin copolymer (BBB-1))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.66 MPa, the system internal pressure was adjusted to 1.36 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 15 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.36 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 105 g, MFR was 0.7 (g / 10 min), and [η] = 2.5 (dL / g) measured in 135 ° C. decalin. Table 5 shows the measured physical properties of the obtained polymer. R
The r ₁ value was 78%.
[Polymerization Example (BBB-2)]
(Synthesis of propylene / α-olefin copolymer (BBB-2))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.64 MPa, the system internal pressure was adjusted to 1.34 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 15 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.34 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer is 109 g,
The MFR was 0.6 (g / 10 min), and [η] = 2.6 (dL / g) measured in decalin at 135 ° C. Table 5 shows the measured physical properties of the obtained polymer. R
The r ₁ value was 76%.
[Polymerization Example (BBB-3)]
(Synthesis of propylene / α-olefin copolymer (BBB-3))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.67 MPa, the system pressure was adjusted to 1.37 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 10 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.37 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 90 g, MFR was 1.0 (g / 10 min), and [η] = 2.3 (dL / g) measured in 135 ° C. decalin. Table 5 shows the measured physical properties of the obtained polymer. The rr ₁ value was 75%.
[Polymerization Example (BBB-4)]
(Synthesis of propylene / α-olefin copolymer (BBB-4))
In a 4000 ml polymerization apparatus sufficiently purged with nitrogen, 1834 ml of dry hexane, 20 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, and then the temperature inside the polymerization apparatus was raised to 70 ° C. with propylene. After pressurizing the system pressure to 0.63 MPa, the system pressure was adjusted to 1.33 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 10 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.33 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 102 g, the MFR was 1.0 (g / 10 min), and [η] = 2.3 (dL / g) measured in 135 ° C. decalin. Table 5 shows the measured physical properties of the obtained polymer. The rr ₁ value was 75%.

Details of the other components are as follows.
(Propylene polymer (D-1))
PP (F102W ^™ , MFR = 2.1 g / 10 min) manufactured by Prime Polymer
(Propylene polymer (D-2))
PP manufactured by Prime Polymer Co., Ltd. (J104W ^™ , MFR = 5.2g / 10min)
(Propylene polymer (D-3))
PP (B101 ^™ , MFR = 0.7 g / 10 min) manufactured by Prime Polymer
(Propylene polymer (D-4))
PP manufactured by Prime Polymer Co., Ltd. (J106G ^™ , MFR = 15.0 g / 10 min)
(Propylene polymer (D-5))
PP (J107G ^™ , MFR = 30.0 g / 10 min) manufactured by Prime Polymer Co., Ltd.
(Propylene polymer (D-6))
PP (J108M ^™ , MFR = 45.0g / 10min) manufactured by Prime Polymer
(Propylene polymer (D-7))
(Synthesis of propylene / ethylene / butene copolymer)
After charging 1834 ml of dry hexane, 1-butene and 110 g of triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 55 ° C. After pressurizing the system pressure to 0.58 MPa, the system pressure was adjusted to 0.75 MPa with ethylene. Subsequently, diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride synthesized in Synthesis Example 3 was 0.001 mmol and 0 in terms of aluminum. A toluene solution contacted with 3 mmol of methylaluminoxane (manufactured by Tosoh Finechem) was added to the polymerization vessel, and polymerization was performed for 25 minutes while maintaining the internal temperature at 55 ° C. and the internal pressure at 0.75 MPa with ethylene. Methanol was added to stop the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 120.2 g and MFR was 0.7 (g / 10 min).
(Propylene polymer (D-8))
Except for setting the polymerization temperature to 40 ° C., the ethylene content and the butene content were the same as those of the (D-7) produced according to the production conditions of the propylene polymer (D-7), and [η] = 4 A polymer having 0.0, Mw / Mn = 2.1 was used.
Table 6 shows the properties of the propylene polymers (D-1) to (D-8).

  Isotactic propylene polymers (D-1) to (D-8), (BB-1) to (BB-4), (BBB-1) to (BBB-4), (AA-1) to FIG. 2 shows a plot of (AA-5) MFR and [η]. It can be seen that the isotactic polymer and the polymer used in the present invention are distinguished by the formula (b-2).

  The film or sheet of the present invention is excellent in adhesiveness or tackiness, and is also excellent in transparency, heat resistance, and flexibility, and thus is used for adhesion or tackiness. Moreover, since the laminated body which consists of this film or sheet has the said characteristic, it is used for various uses.

FIG. 7 is a graph plotting the relationship between a specific isothermal crystallization temperature (T _iso ) and a half crystallization time (t _1/2 ) at the temperature for the syndiotactic propylene polymers described in the examples and comparative examples of the present invention. is there. In addition, the part enclosed with the thick line shows the area | region of the inequality (Eq-1) which is a preferable property of the syndiotactic propylene polymer (A) used for this invention. It is the figure which plotted the relationship between MFR and [(eta)] about the polymer applicable to (A) component or (B) component used for this invention, and an isotactic propylene-type polymer. In addition, the part enclosed with the thick line shows the area | region of (b-2) which is one of the preferable characteristics of (B) component of this invention, and a broken line shows the preferable range of (b-2).

Claims (3)

The propylene-derived structural unit is contained in an amount of 50 mol% or more (the total of the propylene-derived structural unit and the optional component derived from an α-olefin having 2 to 20 carbon atoms is 100 mol%), and the following requirements ( z) consisting of a graft-modified propylene resin satisfying
(Z) The graft-modified propylene resin is obtained by graft-modifying a propylene resin with a polar monomer, and the graft amount of the polar monomer is 0.02% by weight or more and 10% by weight with respect to 100% by weight of the graft-modified propylene resin. Ri der below,
The graft-modified propylene resin is
(AA) 10-40 parts by weight of a graft-modified propylene polymer obtained by graft-modifying with a polar monomer with respect to the syndiotactic propylene polymer (A1) satisfying the following requirements (a) and (c); ,
(BB) Graft modification obtained by graft modification with a polar monomer for propylene / α-olefin copolymer (B) and / or propylene / α-olefin copolymer (B) satisfying the following requirement (b) 90-60 parts by weight of the propylene / α-olefin copolymer (B1) (however, the sum of (AA) and (BB) is 100 parts by weight)
A propylene-based polymer composition (X) comprising:
(A) and (c): Melting point (Tm) measured by a differential scanning calorimeter (DSC) is 145 ° C. or higher, and 90 mol% of structural units derived from propylene (however, in the polymer (A)) The total of the structural units derived from propylene and the structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) which may be included as necessary is 100 mol%. And a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR method is 85% or more,
(B): 30 to 90 mol% of structural units derived from propylene (provided that the structural units derived from propylene in the copolymer (B) and α-olefins having 2 to 20 carbon atoms (excluding propylene) And a structural unit derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene). It is contained in an amount of 10 to 70 mol% (provided that the total of structural units derived from propylene and structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) is 100 mol%). In addition, the MFR measured at 230 ° C. under a 2.16 kg load in accordance with JIS K-6721 is in the range of 0.01 to 100 g / 10 min, and the following requirement (b-1) is satisfied. Satisfies any one or more of (b-2);
(B-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B-2): Intrinsic viscosity [η] (dL / g) measured in decalin at 135 ° C. and the above MFR (g / 10 minutes, 230 ° C., 2.16 kg load)
1.50 × MFR ^(−0.20) ≦ [η] ≦ 2.65 × MFR ^(−0.20) is satisfied,
A film or sheet characterized by satisfying the following requirements (1) to (3);
(1) The needle entry temperature (TMA temperature) is 120 ° C. or higher.
(2) Flexible Young's modulus (YM) is 1 to 500 MPa.
(3) The internal haze of the film or sheet is 0.1% to 50%.   A laminate having a layer comprising the film or sheet according to claim 1. A layer comprising the film or sheet of claim 1, the product Sotai of claim 2 and a base material that Yusuke at least in part adjacent structure.

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