The present invention is a propylene homopolymer compositions and methods of manufacturing that is suitable for capacitor films excellent in high-temperature voltage resistance, and to a capacitor film obtained by stretching them.

Background technique

[0002]

　Biaxially oriented polypropylene film, mechanical properties, heat resistance, transparency, chemical stability, is excellent in electric characteristics and the like, packaging applications, as well as the tape application, capacitors, electrical applications including battery separator It has been widely used in various fields. In particular, oriented polypropylene film capacitor is, not only the high voltage capacitor, switching power supplies, converters, noise filter capacitor, such as an inverter, it has also been used as a smoothing capacitor.

[0003]

　In these applications, miniaturization of the capacitor, higher capacity has been demanded. Also, hybrid car, when using capacitors in high output as electric automotive applications, transistors, since the temperature used in a large current circuit such as a capacitor is high, the withstand voltage in a high-temperature condenser sex is also being sought.

[0004]

　Miniaturization of the capacitor, due to the high capacity, it is effective to thin the film. However, the withstand voltage is significantly reduced and thinning the film, to breakdown under voltage capacitor film is low at the time of use capacitor. On the other hand, from the film processing surface, the film breakage tends to occur during processing of the thin film, the productivity is remarkably lowered.

[0005]

　Patent Document 1, MFR (Melt Flow Rate) of two different propylene homopolymer of the composition by voltage resistance obtained consisting of excellent ultra-thin roughening biaxially oriented polypropylene film is disclosed. Patent Documents 2 and 3, obtained in metallocene catalysts, having high stereoregularity, excellent propylene homopolymer of voltage resistance is disclosed. Patent Document 4, biaxially oriented polypropylene film capacitor using a polypropylene material resin having an adjusted Mw / Mn is disclosed. Patent Document 5, metallized film capacitor consisting of meso pentad fraction of different polypropylene is disclosed. Patent Document 6, a polypropylene resin and a molecular weight distribution 3 capacitor biaxially oriented polypropylene film mesopentad fraction of 30 ~ to 60% of the polypropylene resin with the following molecular weight distribution 5-10 are disclosed.

CITATION

Patent literature

[0006]

Patent Document 1: Japanese Unexamined Patent Publication No. 2010-254794
Patent Document 2: WO 2010/087328 Patent
Patent Document 3: Japanese Unexamined Patent Publication No. 2012-209541
Patent Document 4: WO 2012/099167 Patent
Patent Document 5: JP 2010-280795 JP
Patent Document 6: Japanese Unexamined Patent Publication No. 2014-205799

Summary of the invention

Problems that the Invention is to Solve

[0007]

　However, the film described in Patent Document 1 is excellent in handling properties of the film at the time of capacitor processing, is insufficient high-temperature voltage resistance. The film described in Patent Document 2, although the withstand voltage is high, thin biaxially oriented film in Patent Document 2 has not been obtained. Further, although obtained thin film in Patent Document 3, it is insufficient high-temperature voltage resistance. Further, the high temperature withstand voltage in Patent Document 4 is insufficient. Further, in the technology described in Patent Document 5, is insufficient voltage resistance because it contains a low meso pentad fraction polypropylene. Further, in the technology described in Patent Document 6, although the meso pentad fraction contains 60% of polypropylene resin stretchability of the film is improved, is insufficient high temperature withstand voltage for the withstand voltage is lowered. Therefore, it is easy to manufacture the thin film, and a capacitor film for a propylene homopolymer composition having excellent high-temperature voltage resistance of the film and the development of the capacitor film is desired.

[0008]

　The present invention is easy to manufacture the thin film, the capacitor film for propylene homopolymer compositions and methods of manufacturing excellent in high-temperature voltage resistance of the film, as well as an object to provide a capacitor film.

Means for Solving the Problems

[0009]

　The present invention includes the following items.

[0010]

　[1] following (A-i) ~ (A -iii) a propylene homopolymer having the characteristics of (A1) less than 1 wt% to 50 wt%, or less of (B-i) ~ (B -ii) more than 50% by weight of propylene homopolymer (B1) having a characteristic wherein 99 wt% or less (the propylene homopolymer (A1) and total 100 wt% of the propylene homopolymer (B1)),
(i) a melt flow rate (MFR) of a is 1.0 ~ 10.0g / 10
min, (ii) a capacitor film for a propylene homopolymer composition, wherein the chlorine content is not more than 2 mass ppm .
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0
℃, (a-iii) molecular weight distribution (Mw / Mn) as measured by GPC is less than
3.0, (B-I) 13 is mesopentad rate as measured by C-NMR (mmmm) 0.950 it is at
least, is (B-ii) the molecular weight was measured by GPC distribution Mw / Mn 3.0 or higher.

[0011]

　[2] the following (A-i) ~ (A -ii) a propylene homopolymer having the characteristics of (A2) less than 1 wt% to 50 wt%, or less of (B-i) ~ (B -iii) more than 50% by weight of propylene homopolymer (B2) having the properties comprising 99 wt% or less (the propylene homopolymer (A2) and total 100 wt% of the propylene homopolymer (B2)),
(i) a melt flow rate (MFR) of a is 1.0 ~ 10.0g / 10
min, (ii) a capacitor film for a propylene homopolymer composition, wherein the chlorine content is not more than 2 mass ppm .
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0 °
C., (Bs-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is the 0.950 or more,
a molecular weight distribution Mw / Mn measured by (B-ii) GPC 3.0 it is at
least, is (B-iii) a half-value width of the eluted peaks, measured by the Atsushi Nobori elution fractionation method (the TREF) is 4.0 ° C. or higher.

[0012]

　[3] The propylene homopolymer (A1) or the propylene homopolymer (A2) is a capacitor film for a propylene homopolymer composition according to [1] or [2] is produced using a metallocene catalyst.

[0013]

　[4] The propylene homopolymer (B1) or the propylene homopolymer (B2) is a capacitor film for a propylene homopolymer heavy according to any one of [1] to [3], which is produced using a Ziegler-Natta catalyst coalescence composition.

[0014]

　[5] [1] to a capacitor film for a propylene homopolymer composition according to any one of [4], the capacitor film thickness of 1 - 50 .mu.m.

[0015]

　Capacitor film according to [6] thickness is 50μm or less exceed 4 .mu.m [5 of 5].

[0016]

　[7] [1] to capacitor film obtained by stretching a capacitor film for a propylene homopolymer composition according stretching surface magnification (longitudinal × lateral area magnification) at 30 to 80 times in any one of [4].

[0017]

　Capacitor film according to any one of [8] is a capacitor separator film [5] - [7].

[0018]

　[9] using a metallocene catalyst, following the step of producing a propylene homopolymer (A1) having a (A-i) characteristic of ~ (A-iii),
　by using a Ziegler-Natta catalyst, the following ( a step of producing a propylene homopolymer (B1) having B-i) ~ properties of the (B-ii),
　the propylene homopolymer of less than 1 wt% 50 wt% and (A1), 50 mass% a step of mixing 99 wt% or less of the propylene homopolymer and (B1) a (the propylene homopolymer (A1) and total 100 wt% of the propylene homopolymer (B1)) beyond,
including a method of manufacturing a capacitor film for a propylene homopolymer
composition, (i) said a melt flow rate of the capacitor film for a propylene homopolymer composition (MFR) is 1.0 ~ 10.0g / 10 min,
(ii) the method for producing a capacitor film for a propylene homopolymer compositions chlorine content of the capacitor film for a propylene homopolymer composition is equal to or less than 2 mass ppm.
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0 ℃,
(a-iii) molecular weight distribution (Mw / Mn) as measured by GPC is less than
3.0, (B-I) 13 is mesopentad rate as measured by C-NMR (mmmm) 0.950 it is at
least, is (B-ii) the molecular weight was measured by GPC distribution Mw / Mn 3.0 or higher.

[0019]

　[10] using a metallocene catalyst, following the step of producing a propylene homopolymer (A2) having a (A-i) characteristic of ~ (A-ii),
　using a Ziegler-Natta catalyst, the following ( a step of producing a propylene homopolymer (B2) having B-i) ~ properties of (B-iii),
　the propylene homopolymer of less than 1 wt% 50 wt% and (A2), 50 wt% a step of mixing 99 wt% or less of the propylene homopolymer and (B2) a (the propylene homopolymer (A2) and total 100 wt% of the propylene homopolymer (B2)) beyond,
including a method of manufacturing a capacitor film for a propylene homopolymer
composition, (i) said a melt flow rate of the capacitor film for a propylene homopolymer composition (MFR) is 1.0 ~ 10.0g / 10 min,
(ii) the method for producing a capacitor film for a propylene homopolymer compositions chlorine content of the capacitor film for a propylene homopolymer composition is equal to or less than 2 mass ppm.
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0 °
C., (Bs-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is the 0.950 or
more, a molecular weight distribution Mw / Mn measured by (B-ii) GPC 3.0 it is at
least, is (B-iii) a half-value width of the eluted peaks, measured by the Atsushi Nobori elution fractionation method (the TREF) is 4.0 ° C. or higher.

Effect of the invention

[0020]

　According to the present invention, it is easy to manufacture the thin film, the capacitor film for propylene homopolymer compositions and methods of manufacturing excellent in high-temperature voltage resistance of the film, as well as to provide a capacitor film.

DESCRIPTION OF THE INVENTION

[0021]

　Capacitor film for propylene homopolymer composition according to the present invention (hereinafter referred to as propylene homopolymer composition), in order to satisfy the above requirements, propylene homopolymer heavy manufacturing the thin film is easy, and according to the present invention film obtained from a polymer composition is excellent in high-temperature voltage resistance, is suitable as a capacitor film. As described below, especially when the thickness of the capacitor film is in the present invention is greater than 4 .mu.m, particularly excellent in high-temperature voltage resistance.

[0022]

　Propylene homopolymer (B1) is a broad molecular weight distribution ((B-ii)). In some cases, the half-value width of the eluted peaks, measured by the TREF wide ((B-iii)). The crystal structure of the capacitor film comprising the composition to the containing propylene homopolymer of greater than 50 wt% (B1) is a relatively non-uniform, crystal size also increases, defects as a starting point of breakdown (for example, Boyd , the size of HiAkirabu) is considered large. On the other hand, high molecular weight component contained in the propylene homopolymer (B1) becomes the nucleating agent, it is expected that the crystallinity of the film is increased. The impact on the voltage resistance becomes small due to a defect in a relatively thick film, it influence of crystallinity of the entire film becomes larger than considered to contribute to the breakdown voltage is enhanced relatively.

[0023]

　On the other hand, the propylene homopolymer (A1) has a narrow half-value width of the eluted peaks, measured with TREF ((A-ii)), since narrower molecular weight distribution ((A-iii)), the crystal structure is uniform, crystalline size is reduced, it is considered a defect is reduced. Thus, by incorporating propylene homopolymer of less than 50 wt% (A1), without impairing the crystallinity of the film, uniformity of the crystalline structure is achieved, it is estimated that the withstand voltage is increased.

[0024]

　The following is a detailed description of the present invention. Incidentally, the propylene homopolymer (A1) and collectively (A2) "propylene homopolymer (A)", the propylene homopolymer (B1) together and the (B2) "propylene homopolymer (B) "and also shown.

[0025]

　
　propylene homopolymer composition according to the present invention, when a total of 100 wt% of the propylene homopolymer (A) and the propylene homopolymer (Bs), the propylene homopolymer (a) less than 1 wt% to 50 wt%, comprising the propylene homopolymer (B) to exceed 50 wt% 99 wt% or less. Propylene homopolymer composition according to the present invention, the propylene homopolymer (A) 1 to 40% by weight, preferably contains the propylene homopolymer (B) 60 to 99% by weight, the propylene homopolymer heavy polymer (a) 5 to 30 wt%, the propylene homopolymer is more preferred to contain 70 to 95% by weight (Bs), the propylene homopolymer (a) 10 ~ 25 wt%, the propylene homopolymer heavy and more preferably comprise coalescing (B) 75 ~ 90 wt%.

[0026]

　If the ratio is less than 1 wt% of the propylene homopolymer (A), there is no effect of containing propylene homopolymer (A), shows approximately equal properties as the propylene homopolymer (B) alone. Further, if the ratio of the propylene homopolymer (A) is 50 mass% or more, stretchability is lowered, a high temperature withstand voltage is lowered.

[0027]

　Wherein the proportion of the propylene homopolymer (A) is the reason why is not clear to decrease such is the high temperature voltage endurance at least 50 mass%, it is considered as follows. "Yamakita RyuTadashi, Tomio Ariyasu, the Institute of Electrical Engineers Journal A, 110 Vol., No. 11, pp. 817-823, 1990" to, it is reported that the breakdown voltage of spherulites than amorphous is large cage, indicating that high voltage resistance higher crystallinity. Meanwhile, the propylene homopolymer (A) is less high molecular weight components to the molecular weight distribution is narrow, oriented crystallization in the stretching process during film molding is insufficient. Therefore, crystallinity of the film is reduced, voltage resistance is presumed to have decreased as a result.

[0028]

　Requirement (i)]
　a propylene homopolymer composition according to the present invention has a melt flow rate (MFR, ASTM D1238,230 ℃, 2.16kg load) is the 1.0 ~ 10.0g / 10 min, preferably is 1.5 ~ 8.0g / 10 min, more preferably from 2.0 ~ 6.0g / 10 min, more preferably from 2.0 ~ 4.0g / 10 min.

[0029]

　If MFR is less than 1.0 g / 10 min, it is difficult to raw molded in the extruder and the chuck may come off and during the stretching occurs, desired film can not be obtained. In addition, when the MFR is more than 10.0g / 10 minutes, etc. film rupture occurs frequently during stretching of the film, the production of the film is greatly reduced. Incidentally, MFR is the MFR and the blending ratio of the propylene homopolymer (A) and the propylene homopolymer (B) by appropriately changing, it can be set within the above range.

[0030]

　Requirement (ii)]
　propylene homopolymer composition according to the present invention is a chlorine content of 2 ppm by mass or less (0 to 2 ppm by weight), is preferably more than 1.5 mass ppm, more preferably is less than or equal to 1 mass ppm. When the chlorine content is more than 2 mass ppm, not only the voltage resistance of the resulting film is reduced, long-term capacitor characteristics is also reduced. Electric field of chlorine ion the vicinity of the film inside at the time of use capacitor is locally increased, voltage resistance is understood to decline from there to insulation breakdown is likely to occur. Chlorine content, by or worked up or, a propylene homopolymer (B) increasing the amount of propylene homopolymer obtained with the metallocene catalyst to be described later (the A), by controlling in the above range can.

[0031]

　Further, the propylene homopolymer composition according to the present invention, 13 meso pentad fraction, as measured by C-NMR (mmmm) is preferably 0.940 or more, is 0.945 or more 0.995 or less it is more preferable. In the mesopentad fraction (mmmm) is less than 0.940, there is a case in which the high-temperature withstand voltage of the film is reduced. On the other hand, if the meso pentad fraction (mmmm) exceeds 0.995, the stress during stretching is increased, and when the film of the thin required for capacitor applications can not be obtained, a film having a uniform film thickness distribution there is a case that can not be obtained.

[0032]

　
　[Requirement (A-i)]
　The propylene homopolymer (A1) is 13 mesopentad fraction measured by C-NMR (nuclear magnetic resonance) (mmmm) is 0.930 or more, preferably at 0.935 or more 0.995 or less, more preferably 0.940 or more 0.995 or less, further preferably 0.945 or more 0.990 or less. The mmmm is less than 0.930 can not be obtained film having a desired voltage resistance. Incidentally, when the mmmm exceeds 0.995, the stress during stretching is increased, if the thin film required for capacitor applications and can not be obtained, no film having a uniform film thickness distribution is obtained is there.

[0033]

　Requirement (A-ii)]
　The propylene homopolymer (A1) is heated elution fractionation method using o- dichlorobenzene curve showing elution component amount with respect to the elution temperature measured by (TREF) (TREF elution curve) in, full width at half maximum of the elution peak is a is less than 4.0 ℃, preferably not more than 2.0 ℃ 3.8 ℃ or less, more preferably less than 3.6 ℃ 2.5 ℃ or more, more preferably 3.0 ℃ more than 3.5 ℃ is less than or equal to. If the full width at half maximum of the elution peak is greater than or equal to 4.0 ℃, reduced high-temperature withstand voltage of the film, considerably high temperature withstand voltage is lowered and in particular film becomes thinner. Half-width, that is, when the stereoregularity distribution is widened, in order to increase the melting point distribution becomes widely low melting point component of the film, resulting in the degree of crystallization of the high temperature it is presumed to be reduced.

[0034]

　Requirement (A-iii)]
　The propylene homopolymer (A1) has a molecular weight distribution measured by gel permeation chromatography (GPC) (Mw / Mn, the value obtained by dividing the number average molecular weight Mn of the weight average molecular weight Mw) of it is less than 3.0, preferably less than 2.0 to 3.0, more preferably less than 2.3 to 3.0, further preferably 2.5 or more 2.8 or less.

[0035]

　
　[Requirement (A-i) and requirements (A-ii)]
　The requirements (A-i) and requirements (A-ii), similarly to the propylene homopolymer (A1) it is.

[0036]

　
　The melt flow rate of the propylene homopolymer (A) (MFR) is not particularly limited, preferably 1 ~ 100g / 10 minutes, more preferably 1 ~ 50g / 10 min , and still more preferably 2 ~ 30g / 10 minutes, particularly preferably 3 ~ 10g / 10 min. If the MFR is less than 1 g / 10 min may gel produced inside the film. Further, in the case where the MFR exceeds 100 g / 10 min, like film breakage occurs during stretching, the productivity of the film may deteriorate.

[0037]

　The propylene homopolymer of (the A), . 13 C-NMR are determined from the spectrum, a heterologous binding to 2,1 based on insertion of propylene monomer in all propylene structural units ratio and 1,3-insertion based on heterogeneous binding of the sum of the proportions, preferably not more than 0.2 mol%, more preferably not more than 0.15 mol%, more preferably not more than 0.1 mol%. When該和exceeds 0.2 mol%, since the disturbance of the crystalline propylene homopolymer (A) increases, there is a case where crystal components contained in the resulting film is reduced, high temperature withstand voltage is lowered.

[0038]

　Chlorine content of the propylene homopolymer (A) is the chlorine content of the propylene homopolymer composition is not particularly limited as long as less than 2 mass ppm, preferably not more than 2 mass ppm, less 1.5 mass ppm and still more preferably, less is more preferably from 1 mass ppm.

[0039]

　
　[Requirement (B-i)]
　The propylene homopolymer (B1) is 13 mesopentad fraction measured by C-NMR (nuclear magnetic resonance) (mmmm) is 0.950 or more, preferably 0.950 or more 0.995 or less, more preferably 0.955 or more 0.995 or less, further preferably 0.960 or more 0.990 or less. The mmmm is less than 0.950 can not be obtained film having a desired voltage resistance. Incidentally, when the mmmm exceeds 0.995, the stress during stretching is increased, if the thin film required for capacitor applications and can not be obtained, no film having a uniform film thickness distribution is obtained is there.

[0040]

　Requirement (B-ii)]
　The propylene homopolymer (B1) has a molecular weight distribution measured by gel permeation chromatography (GPC) (Mw / Mn, the value obtained by dividing the number average molecular weight Mn of the weight average molecular weight Mw) of and 3.0 or more, preferably 3.0 or more 12.0 or less, more preferably 3.5 or more 12.0 or less, more preferably 6.0 or more 12.0 or less, particularly preferably it is 8.0 or 12.0 or less. If the molecular weight distribution is less than 3.0, the high-temperature withstand voltage of the thin film film is reduced.

[0041]

　
　[Requirements (B-i) and requirements (B-ii)]
　for requirements (B-i) and requirements (B-ii), similarly to the propylene homopolymer (B1) it is.

[0042]

　Requirement (B-iii)]
　The propylene homopolymer (B2) is heated elution fractionation method using o- dichlorobenzene curve showing elution component amount with respect to the elution temperature measured by (TREF) (TREF elution curve) in, full width at half maximum of the elution peak is not less 4.0 ℃ or more, preferably at 4.0 ℃ more than 6.0 ℃ or less, more preferably less than 5.5 ℃ 4.0 ℃ or more, more preferably 4.0 ℃ more than 4.5 ℃ is less than or equal to. If the half-width of the elution peak is less than 4.0 ° C., stretchability is insufficient. Incidentally, when the half width of the elution peak is more than 6.0 ° C., there are cases where high-temperature voltage resistance of the film is lowered.

[0043]

　
　but not limited to a melt flow rate (MFR) of the propylene homopolymer (Bs), preferably 0.5 ~ 10g / 10 minutes, more preferably 1 ~ 7g / 10 min, more preferably from 1.5 ~ 5 g / 10 min. If the MFR is less than 0.5 may gel is generated in the film. On the other hand, if the MFR is more than 10g / 10 minutes, in some cases the productivity of the film is lowered. Further, the film inside the crystal size does not become small at the time of stretching, there are cases where the effect of improving high-temperature voltage resistance by the film stretching is reduced.

[0044]

　Of the propylene homopolymer (B), 13 C-NMR obtained from the spectrum, heterogeneous bonds 2,1 based on the insertion of propylene monomer in all propylene structural unit rate and 1,3-insertion based on heterogeneous binding the sum of the proportions, preferably not more than 0.2 mol%, more preferably not more than 0.15 mol%, more preferably not more than 0.1 mol%. When該和exceeds 0.2 mol%, since the disturbance of the crystalline propylene homopolymer (B) is increased, there is a case where crystal components in the resulting film is reduced, high temperature withstand voltage is lowered.

[0045]

　Chlorine content of the propylene homopolymer (B) is the chlorine content of the propylene homopolymer composition is not particularly limited as long as less than 2 mass ppm, preferably not more than 2 mass ppm, less 1.5 mass ppm and still more preferably, less is more preferably from 1 mass ppm.

[0046]

　
　is not particularly limited production method of the propylene homopolymer (A), the propylene homopolymer from the viewpoint of high-temperature voltage resistance of (A), using a metallocene catalyst it is preferable to produce on. As the metallocene catalyst, a polymerization catalyst containing a metallocene compound having a cyclopentadienyl skeleton in the molecule is preferably used.

[0047]

　As the metallocene compound having a cyclopentadienyl skeleton in the molecule, can be exemplified the following formula metallocene compound represented by [the I], and crosslinked metallocene compound represented by the following formula [II]. Among these, crosslinked metallocene compound represented by the following formula [II] is preferably a said metallocene compound.

[0048]

[Formula 1]

[0049]

　In the formula [I] and [II], M represents a titanium atom, a zirconium atom or a hafnium atom. Q represents a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by lone pair. Cp 1 and Cp 2 is a cyclopentadienyl group or substituted cyclopentadienyl group capable of forming a sandwich structure together with M. Cp 1 and Cp 2 may be the same or different from each other. j is an integer of 1 to 4. When j is 2 or greater, Q is may be the same or different from each other.

[0050]

　The substituted cyclopentadienyl group, indenyl group, fluorenyl group, encompasses azulenyl group and been substituted these with one or more of the hydrocarbyl group, indenyl group, fluorenyl group, in the case of azulenyl group Shikupenta some of the double bonds of the unsaturated ring fused to the dienyl group may be hydrogenated.

[0051]

　In the formula [II], Y is a divalent C 1-20 carbon atoms hydrocarbon group, a divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, -Ge-, etc. divalent germanium-containing group, -Sn- 2 divalent tin-containing groups such as, -O -, - CO -, - S -, - SO -, - SO 2 -, - N (Ra) -, - P ( Ra) -, - P (O ) (Ra) -, - B (Ra) - or -Al (Ra) - show a. Ra is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom, one halogen atom or a nitrogen atom hydrocarbon group having 1 to 20 carbon atoms or two binding it is a nitrogen compound residue.

[0052]

　The polymerization catalyst containing the metallocene compound, the crosslinking metallocene compound represented by the following formula [III], as well as organometallic compounds, compounds capable of reacting with an organic aluminum oxy compound and a metallocene compound capable of forming an ion pair at least one compound selected from the group consisting of, a particulate carrier, if necessary, a metallocene catalyst comprising preferred.

[0053]

[Of 2]

[0054]

　In the formula [III], R 1 R from 14 are each independently a hydrogen atom, a hydrocarbon group or a silicon-containing group. R 1 from R 14 may be each the same or may be different.

[0055]

　Examples of the hydrocarbon group, a methyl group, an ethyl group, n- propyl group, an allyl group, n- butyl group, n- pentyl group, n- hexyl, n- heptyl, n- octyl group, n- nonyl group , straight-chain hydrocarbon group, such as n- decanyl group; an isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethyl propyl group, a 1,1-dimethylbutyl group, 1-methyl cyclopentyl; 1-propyl butyl group, 1,1-propyl butyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-branched hydrocarbon group, such as isopropyl-2-methylpropyl group , cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, a cyclic saturated hydrocarbon group such as an adamantyl group; a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a cyclic unsaturated hydrocarbon group such as an anthracenyl group ; benzyl group, cumyl group, 1,1-diphenylethyl group, a cyclic unsaturated substituted with a hydrocarbon group a saturated hydrocarbon group such as triphenylmethyl group; methoxy group, an ethoxy group, a phenoxy group, a furyl group, N- methyl amino group, N, N- dimethylamino group, N- phenylamino group, pyrryl group, such as heteroatom-containing hydrocarbon group such as a thienyl group.

[0056]

　Examples of the silicon-containing group, a trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, and the like.

[0057]

　Further, R 5 of 5 R from 12 adjacent substituents may be bonded to each other to form a ring.

[0058]

　Examples of such substituted fluorenyl group, benzofluorenyl group, dibenzo fluorenyl group, octahydrofluorenyl dibenzo fluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyl tetrahydrodicyclopentadiene fluorenyl group, etc. and the like.

[0059]

　R 1 , R 2 , R 3 and R 4 is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 2 and R 4 is more preferably is a hydrocarbon group having 1 to 20 carbon atoms. R 1 and R 3 are hydrogen atom, R 2 and R 4 and more preferably is a linear or branched alkyl group having 1 to 5 carbon atoms.

[0060]

　R 5 R from 12 is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms, may be exemplified hydrocarbon groups described above. Further, R . 7 and R . 11 is preferred it is not a both hydrogen atom, R . 6 , R . 7 , R 10 and R . 11 is more preferably not all hydrogen atoms.

[0061]

　Y is a Group 14 element, carbon, silicon, germanium is preferred, the carbon is more preferable.

[0062]

　R . 13 , R 14 is preferably is a hydrocarbon group having 1 to 20 carbon atoms, and more preferably an aryl group an alkyl group or a C 6-20 having 1 to 3 carbon atoms. R . 13 , R 14 as is, for example, methyl, ethyl, phenyl, tolyl group and the like are preferable. R 13 , R 14 , which may be the same or different from each other, may be bonded to each other to form a ring. Further, R . 13 , R 14 are, R 5 of 5 R from 12 adjacent substituents, or R, 1 from R 4 may be bonded to each other with the adjacent substituents to form a ring.

[0063]

　M is a transition metal of Group 4, it is preferable that a titanium atom, zirconium atom or hafnium atom.

[0064]

　Q is a halogen, a hydrocarbon group, and a neutral ligand capable of coordination with an anionic ligand or a lone pair of electrons. j is an integer of 1 to 4. When j is 2 or greater, Q is may be the same or different from each other.

[0065]

　Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The include hydrocarbon groups similar to the above specific examples of the hydrocarbon group.

[0066]

　Specific examples of the anionic ligand, methoxy, tert-butoxy, alkoxy groups such as phenoxy, acetate, carboxylate groups such as benzoate, and sulfonate groups such as mesylate and tosylate.

[0067]

　Specific examples of the neutral ligands capable of coordination by the lone electron pair, trimethylphosphine, triethylphosphine, triphenylphosphine, organic phosphorus compounds such as diphenyl methyl phosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2 ethers such as dimethoxyethane, and the like.

[0068]

　Q is preferably at least one of which is a halogen or an alkyl group.

[0069]

　The formula [III] bridged metallocene compound represented by, for example, WO 01/27124, WO 2014/050816, it can be exemplified compounds disclosed in WO 2014/050817 can. Preferred examples among these, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene -12 '- yl) (3-methyl -5-tert-butyl -1,2,3,3a- tetrahydro pentalene)] zirconium dichloride, [3- (1', 1 ', 4', 4 ', 7', 7 ', 10', 10'- octamethyl octahydro-dibenzo [b, h] fluorene-12'-yl) (3-phenyl -5-tert- butyl -1,2,3,3a- tetrahydrocannabinol pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) (1 - methyl-3-phenyl -5-tert-butyl -1,2,3,3a- tetrahydro pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7' , 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene-12'-yl) (1-phenyl-3-methyl -5-tert- butyl -1,2,3,3a- tetrahydrocannabinol pentalene )] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) (1-p-tolyl-3-methyl -5-tert-butyl -1,2,3,3a- tetrahydro pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) (1,3-dimethyl -5-tert-butyl -1,2,3,3a- tetrahydro pentalen)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene 12' yl) (1,3-diphenyl--5-tert-butyl -1,2,3,3a- tetrahydro pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7 ', 10', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) (1,3-diphenyl-1-methyl -5-tert-butyl -1,2,3,3a - tetrahydro pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene -12 '- yl) (1,3-di (p- tolyl) -1-methyl -5-tert- butyl -1,2,3,3a- tetrahydrocannabinol pentalene)] zirconium dichloride, [3- (1', 1 ', 4', 4 ', 7', 7 ', 10', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) (1,2,3,3a- tetrahydro pentalene) ] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) ( 1,1-dimethyl -5-tert-butyl -1,2,3,3a- tetrahydro pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene-12'-yl) (1,1-dimethyl-3-phenyl -5-tert- butyl -1,2,3,3a- tetrahydrocannabinol penta Ren)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl ) (1,1,3-trimethyl-5-trimethylsilyl -1,2,3,3a- tetrahydrocannabinol pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7 ', 10', 10'- octamethyl octahydro-dibenzo [b, h] fluorene-12'-yl) (1,1,3-trimethyl-5-ethyl -1,2,3,3a- tetrahydrocannabinol pentalene) ] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) ( 1,1,3-trimethyl -5-tert-butyl -1,2,3,3a- tetrahydro pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7 ', 10', 10'- octamethyl octahydro-dibenzo [b, h] fluorene-12'-yl) (1,1,3-triethyl-2-methyl-5-tert- butyl -1,2,3,3a - tetrahydro pentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene -12 '- yl) (1,1,3,5- tetramethyl -1,2,3,3a- tetrahydrocannabinol pentalene)] zirconium dichloride, and the like. The polymerization of olefins using the above metallocene compound, tends to affect the stereoregularity of the polymer polymerization temperatures. These metallocene compounds, exhibits a high stereospecificity in the polymerization of 3 or more α- olefins carbon tends to be able to give high stereoregularity of an olefin polymer at high polymerization temperature. Therefore, it can be considered a particularly preferred embodiment in terms of simplicity and production cost of the process.

[0070]

　These titanium derivatives, may be used hafnium derivatives. These may be using a kind, it may be used in combination of two or more thereof. However, metallocene compounds that can be used in the present invention is not intended to be limited to the above exemplified compounds.

[0071]

　Note that the position numbers used in the nomenclature of the compound, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h ] fluorenyl) (1,1,3-trimethyl -5-tert- butyl -1,2,3,3a- tetrahydrocannabinol pentalene)] zirconium dichloride, [1- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) (5-tert- butyl-1-methyl -3-an iso-propyl-1,2, 3,4 tetrahydro pentalene)] zirconium dichloride, and [8- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h ] fluorene-12'-yl) (2- (1-adamantyl) -8-methyl -3,3b, 4,5,6,7,7a, 8- octahydrocyclopenta [a] indene)] zirconium dichloride, taken as an example, each of the following formula [IV], shown in [VI], and [VII]. Note that the formula [VI] and [VII], shown for one of the optical isomers. Also it includes, although not particularly referred to the optical isomers, without departing from the scope of the present invention, all isomers.

[0072]

[Formula 3]

[0073]

[Of 4]

[0074]

[Of 5]

[0075]

　Used with the above formula [III] bridged metallocene compound represented by the organometallic compounds, organoaluminum oxy-compound, and reacted with the metallocene compound at least one selected from the group consisting of the compounds to form an ion pair compound (cocatalyst), the particulate carrier employed if necessary, can be used the present application WO01 / 27 124 and by persons, without limitation compounds disclosed in JP-a-11-315109.

[0076]

　How propylene homopolymer (A1) is controlled so as to satisfy the requirements (A-i) ~ (A-iii) simultaneously, the propylene homopolymer (A2) is the requirement (A-i) ~ (A-ii ) as a method for controlling so as to satisfy simultaneously, for example, using a catalyst as described above include a method of setting the polymerization conditions such as polymerization temperature appropriately.

[0077]

　Specific examples, as the catalyst [8- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene 12' yl) (2- (1-adamantyl) -8-methyl -3,3b, 4,5,6,7,7a, 8- octahydrocyclopenta [a] indene)] using a zirconium dichloride, the polymerization temperature 50 and ~ 90 ℃, preferably between 60 ~ 80 ℃, raw materials along with the supply of hydrogen, the supply amount of the hydrogen and 0.03 ~ 0.3mol%, preferably 0.06 ~ 0.21mol%, more preferably and a method to 0.07 ~ 0.18mol%.

[0078]

　Note that in the present application examples described below, as the metallocene compound [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluorene-12'-yl) (1,1,3-trimethyl -5-tert- butyl -1,2,3,3a- tetrahydrocannabinol pentalene)] zirconium dichloride, or [8- (1 ', 1' , 4 ', 4', 7 ', 7', 10 ', 10'- octamethyl octahydro-dibenzo [b, h] fluoren-12'-yl) (2- (1-adamantyl) -8-methyl-3 , 3b, 4,5,6,7,7a, 8- octahydrocyclopenta [a] indene)] zirconium dichloride, a cocatalyst as a, co-presence of methylaluminoxane solid catalyst and triethylaluminum supported on silica support in conduct prepolymerization followed but propylene homopolymer according to the present invention is prepared by carrying out the main polymerization composed of multiple stages, the present invention should not be construed as being in any way constrained to the condition.

[0079]

　
　method for producing the propylene homopolymer (B) is not particularly limited, the propylene homopolymer from the viewpoint of stretchability and (B), using a Ziegler-Natta catalyst it is preferable to produce on. For example, the propylene homopolymer (B) is solid titanium catalyst component (the I), Group 1 of the Periodic Table, an organic metal containing metal atom selected from Group 2 and 13 the group consisting of Group compound (II), it is preferably obtained by polymerization in the presence of an olefin polymerization catalyst comprising an electron donor (III), if necessary. Hereinafter is a detailed description of each component of the olefin polymerization catalyst.

[0080]

　
　The solid titanium catalyst component (I) is a titanium compound, a magnesium compound, a halogen, an electron donor (I), the cyclic ester compound (a) and the cyclic ester compound (b), it is preferable to contain a catalyst component (c) is optional in the electron donor (I). These compounds are, for example, in International Publication No. WO 2006/077945, WO 2006/077946, WO 2008/010459, WO 2009/069483, the compounds described in JP-A-7-109314 JP, etc. it can be exemplified.

[0081]

　
　As the titanium compound, for example, the following formula
　　Ti (OR) g X- 4-g
may be mentioned tetravalent titanium compounds represented by.

[0082]

　In the formula, R is a hydrocarbon group, X is a halogen atom, g is 0 ≦ g ≦ 4.

[0083]

　As the titanium compound, in particular, TiCl 4 , TiBr 4 titanium tetrahalides such as; Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 of 5 ) Cl 3 , Ti (O-n-C 4 H . 9 ) Cl 3 , Ti (OC 2 H 5 ) Br 3 , Ti (O-IsoC 4 H 9 ) Br 3 trihalogenated alkoxytitanium such as; Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2 dihalogenated alkoxy titanium such as; Ti (OCH 3 ) 3 Cl, Ti (O-N-C 4 H 9 ) 3 Cl, Ti (OC 2 H 5 ) 3 monohalogenated alkoxytitanium such as Br; Ti ( OCH 3 ) 4 , Ti (OC 2 H 5 of 5 ) 4 , Ti (OC 4 H . 9 ) 4 , Ti (O-2-ethylhexyl) 4 , etc. tetraalkoxytitanium such as and the like. Among these, as the titanium compound, preferably titanium tetrahalides, titanium tetrachloride is more preferable. These titanium compounds may be used in combination of two or more kinds thereof may be used alone.

[0084]

　
　Examples of the magnesium compounds, specifically, magnesium chloride, magnesium halide such as magnesium bromide; methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy alkoxy magnesium halides such as magnesium chloride; ethoxy magnesium, isopropoxy magnesium , butoxy magnesium, alkoxy magnesium such as 2-ethylhexoxide magnesium; aryloxy magnesium such as phenoxy magnesium; such as carboxylic acid salts of magnesium, such as magnesium stearate, and the like. Also it is used These magnesium compounds may be used in combination of two or more thereof. Further, these magnesium compounds, complex compounds with other metals, may be a mixture of double compounds or other metal compounds.

[0085]

　Among these, as the magnesium compound, magnesium compounds containing halogen are preferable, magnesium halide are more preferred, and magnesium chloride are more preferred. In addition, alkoxy magnesium such as ethoxy magnesium is also preferably used. Further, the magnesium compound, those derived from other substances, for example an organic magnesium compound such as Grignard reagent, titanium halide, silicon halide, be one obtained by contacting the halogenated alcohol it may be. For example, when combining the alkoxy magnesium and tetraalkoxytitanium is reacted and silicon tetrachloride as the halogenating agent, it is preferable that the magnesium halide.

[0086]

　
　said halogen, a is Ti (OR) an example of the titanium compound G X 4-G X of, such as halogen of magnesium halide, which is an example of the magnesium compounds. These halogens may be used singly or in combination of two or more.

[0087]

　
　Examples of the electron donor (I), may be used cyclic ester compound (a) and the cyclic ester compound (b), and a catalyst component (c) optionally.

[0088]

　
　cyclic ester compound (a), for example, can be exemplified compounds described in international Publication No. 2006/077945 Patent and WO 2009/069483.

[0089]

　The cyclic ester compound as (a) is a compound represented by the following formula (1a) is preferred.

[0090]

[Of 6]

[0091]

　In the formula (1a), n is an integer of 5-10, preferably of 5-7 integer, more preferably 6. Further, C a and C b represent carbon atoms.

[0092]

　A plurality of R 1 are each independently from 1 to 20 carbon atoms, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably a monovalent hydrocarbon of 4-6 is a group. As the hydrocarbon group, for example a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group , tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like. As the hydrocarbon group Of these, n- butyl group, an isobutyl group, a hexyl group, an octyl group are preferable, n- butyl group, an isobutyl group, from the viewpoint of producing a wide propylene block copolymer molecular weight distribution more preferable.

[0093]

　A plurality of R each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, in atom or a group of a halogen-containing group or a silicon-containing group is there. Further, at least one R is an atom or group other than a hydrogen atom. As the atom or group other than a hydrogen atom, preferably a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group of carbon number 1 to 20, for example a methyl group, an ethyl group, n- propyl group, iso- propyl group, n- butyl group, iso- butyl group, sec- butyl group, n- pentyl group, cyclopentyl, n- hexyl group, a cyclohexyl group, a vinyl group, a phenyl group, such as octyl group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, alicyclic hydrocarbon group, an aromatic hydrocarbon group. Of these, the hydrocarbon group of carbon number 1 to 20, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, n- propyl group, iso- propyl group, n- butyl group, iso- butyl group, sec- butyl group are more preferable.

[0094]

　Single bond in the cyclic skeleton (provided that C a -C a bond and C a -C b excluding bond) may be replaced with a double bond. That is, (when n is 6 ~ 10) C-C bonds in the cyclic skeleton, C a -C bond and C b -C bond may be replaced with a double bond.

[0095]

　As the compound represented by the formula (1a), in particular, 3,6-dimethylcyclohexane-1,2-dicarboxylic acid diisobutyl, 3,6-dimethyl-cyclohexane-1,2-dicarboxylic acid di n- hexyl, 3, 6-dimethyl cyclohexane-1,2-dicarboxylic acid di-n- octyl, 3-methyl-6-ethyl-cyclohexane-1,2-dicarboxylic acid diisobutyl, 3-methyl-6-ethyl-cyclohexane-1,2-dicarboxylic acid di-n - hexyl, 3-methyl-6-ethylcyclohexane-1,2-dicarboxylic acid di n- octyl, 3-methyl -6-n- propyl-1,2-dicarboxylic acid diisobutyl, 3-methyl -6-n- propyl-1,2-dicarboxylic acid di n- hexyl, 3-methyl -6-n- propyl-1,2-dicarboxylic acid di n- octyl, 3,6-diethyl-1,2-dicarboxylic acid diisobutyl , 3,6-diethyl cyclohexane-1,2-dicarboxylic acid di-n- hexyl, is 3,6-diethyl-1,2-dicarboxylic acid di-n- octyl preferable. These compounds can be prepared by using a Diels Alder reaction.

[0096]

　Cyclic ester compounds having a diester structure as described above in (a) is the cis isomers are present, such as transformers, has the effect of meeting the object of even the present invention have any structure, containing the trans isomer Write rate is high, not only the effect of broadening the molecular weight distribution is preferable because the stereoregularity of activity and the resulting polymer is higher tendency. The proportion of the trans form of the cis and trans form, preferably at least 51%, more preferably at least 55%, more preferably 60% or more, particularly preferably 65% ​​or more. The proportion of the trans form is more than 100%, preferably 90% or less, more preferably 85% or less, more preferably 79% or less.

[0097]

　
　a cyclic ester compound (b), for example, WO 2006/077946, are exemplified compounds described in International Publication No. 2009/069483 can.

[0098]

　Examples of the cyclic ester compound (b), a compound having a cycloalkane-1,2-dicarboxylic acid diester structure or a cycloalkene-1,2-dicarboxylic acid diester structure represented by the following formula (2a) is preferred.

[0099]

[Chemical Formula 7]

[0100]

　In the formula (2a), n is an integer of 5-10, preferably of 5-7 integer, more preferably 6. Further, C a and C b represent carbon atoms.

[0101]

　A plurality of R 1 are each independently from 1 to 20 carbon atoms, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably a monovalent hydrocarbon of 4-6 is a group. As the hydrocarbon group, for example a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group , tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like. Viewpoint Among them, as the hydrocarbon group, n- butyl group, an isobutyl group, a hexyl group, an octyl group are preferable, n- butyl group, isobutyl group, capable of producing a wide propylene block copolymer molecular weight distribution more from the preferred.

[0102]

　Single bond (except C in the cyclic skeleton A -C A bond and C A -C B except the binding. That is, C-C A bond, C-C B if the bond and C-C bond (n 6 to 10 )) may be replaced with a double bond.

[0103]

　Among them, the compound represented by the formula (2a), cyclohexane-1,2-dicarboxylic acid diisobutyl cyclohexane-1,2-dicarboxylic acid dihexyl, cyclohexane-1,2-dicarboxylic acid di heptyl, cyclohexane 1,2-dicarboxylic acid dioctyl, cyclohexane-1,2-dicarboxylic acid di-2-ethylhexyl is preferable. Not only high catalytic performance, these compounds because the relatively inexpensive to manufacture by using a Diels Alder reaction.

[0104]

　Cyclic ester compounds having a diester structure as described above in (b) is cis, the isomers of transformer or the like is present, has the effect of meeting the object of even the present invention have any structure. The proportion of the trans form of the cis and trans form, preferably at least 51%, more preferably at least 55%, more preferably 60% or more, particularly preferably 65% ​​or more. The proportion of the trans form is more than 100%, preferably 90% or less, more preferably 85% or less, more preferably 79% or less. The reason is not clear, the variations described below stereoisomers, are presumed to be in the region suitable for broad molecular weight distribution of.

[0105]

　In particular, the formula (2a) when cyclohexane-1,2-dicarboxylic acid diester is n = 6 in, it is preferable that the purity of the trans-isomer is within the above range. If the purity of the trans form is less than 51%, it may have a wide molecular weight distribution of the effect, activity and stereospecificity, etc. becomes insufficient. Further, the purity of the trans form it may become insufficient effect of weight, the broad molecular weight distribution of 79%. On the other hand, if the purity of the range of the trans form, advantageous for both the effect of broadening the molecular weight distribution of the resulting polymer, and a high stereoregularity of activity and the resulting polymer of the catalyst at a high level such is often.

[0106]

　The cyclic ester compound (a) may be used singly or may be used in combination of two or more. Further, the cyclic ester compound (b) may be used singly or may be used in combination of two or more.

[0107]

　Ratio of the cyclic ester compound (a) and the cyclic ester compound (b) and the cyclic ester compound to the sum of (a) (cyclic ester compound (a) / (cyclic ester compound (a) + cyclic ester compound (b) ) × 0.89 (mol%)) is preferably at least 10 mol%, more preferably at least 30 mol%, more preferably at least 40 mol%, particularly preferably at least 50 mol%. The proportion is preferably 99 mol% or less, more preferably 90 mol% or less, more preferably 85 mol% or less, particularly preferably 80 mol% or less.

[0108]

　The solid titanium catalyst component (I) also have low content of the solid titanium catalyst component (I) a cyclic ester compound in (a), wide very molecular weight distribution, the propylene polymer having high stereoregularity it can be given in high activities. The cause of this effect is unknown, the present inventors have presumed as follows.

[0109]

　The cyclic ester compound (a) has a very large variation of the three-dimensional structure capable of forming as compared with the cyclic ester compound (b) by the presence of substituent R. Is Consequently, becomes dominant influence of the cyclic ester compound (a) the molecular weight distribution, considered the annular ratio of the ester compound (a) can give propylene polymers of very broad molecular weight distribution even at low . On the other hand, because the relatively structure resembles the cyclic ester compound (a) and the cyclic ester compound (b), the activity, for the basic performance such as stereoregularity hardly affect the effect of mutual compound ( If the structure using different compounds, or that the activity and stereoregularity or the like is rapidly changing, there are many cases in which the effect of one compound becomes dominant).

[0110]

　Further, the cyclic hydrocarbon structure, chair, it is known to form a variety of three-dimensional structures such as boat type. In addition, when having a cyclic hydrocarbon structure substituents, variations of the three-dimensional structure that can be taken is further increased. Further, of the carbon atoms forming the cyclic skeleton of the cyclic ester compound, an ester group (COOR 1 group) carbon atoms are bonded with an ester group (COOR 1 is bonded between the groups) other carbon atoms bonded if a single bond, a variation of the three-dimensional structure that can be taken is spread. That can take this colorful three-dimensional structure, leading to the formation of a variety of active species on the solid titanium catalyst component (I). As a result, production is performed the polymerization of propylene using a solid titanium catalyst component (I), it may be to produce the propylene polymer of various molecular weights at a time, i.e. a wide propylene block copolymer molecular weight distribution can do.

[0111]

　The cyclic ester compound (a) and (b), solid titanium catalyst component (I) may be formed in the process of preparing. For example, in preparing the solid titanium catalyst component (the I), a cyclic ester compound (a) and (b) the corresponding carboxylic anhydride and carboxylic acid dihalide, and a corresponding alcohol is the step of substantially contacting by providing, it may contain cyclic ester compound (a) and (b) the solid titanium catalyst component (I).

[0112]

　
　As the catalyst component (c), for example, ether compounds described in JP-A-7-109314 discloses such or can be exemplified polyvalent carboxylic acid ester.

[0113]

　Among these, compounds having two or more ether linkages through a plurality of atoms as (c1), 1,3- diethers are preferable, and 2- isopropyl-2-isobutyl-1,3-dimethoxypropane, 2, 2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1, 3-dimethoxypropane is more preferable.

[0114]

　Furthermore, among these compounds, examples of the polyvalent carboxylic acid esters, aromatic polycarboxylic acid esters are preferred, phthalic acid esters are more preferred.

[0115]

　The catalyst component is an electron donor component (c), while maintaining high catalytic activity, effect and to improve the stereoregularity of the resulting polymer, effect and to control the composition distribution of the resulting copolymer, the catalyst particles indicating, for example, flocculant effect of controlling the particle shape and particle size. Further, the cyclic ester compound (a) and (b) is considered to further also has the effect of controlling the molecular weight distribution.

Claim 1]

　The following (A-i) ~ propylene homopolymer (A1) less than 1 wt% to 50 wt% having the characteristics of (A-iii), the following characteristics of (B-i) ~ (B -ii) and a propylene homopolymer (B1) exceeds 50 mass% with containing 99 wt% or less (the propylene homopolymer (A1) and total 100 wt% of the propylene homopolymer
(B1)), (i) the melt flow rate (MFR) of a is 1.0 ~ 10.0g / 10
min, (ii) a capacitor film for a propylene homopolymer composition, wherein the chlorine content is not more than 2 mass ppm.
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0
℃, (a-iii) molecular weight distribution (Mw / Mn) as measured by GPC is less than
3.0, (B-I) 13 is mesopentad rate as measured by C-NMR (mmmm) 0.950 it is at
least, is (B-ii) the molecular weight was measured by GPC distribution Mw / Mn 3.0 or higher.

[Claim 2]

　The following (A-i) ~ propylene homopolymer (A2) less than 1 wt% to 50 wt% having the characteristics of (A-ii), the following characteristics of (B-i) ~ (B -iii) and a propylene homopolymer (B2) exceeds 50 mass% with containing 99 wt% or less (the propylene homopolymer (A2) and total 100 wt% of the propylene homopolymer
(B2)), (i) the melt flow rate (MFR) of a is 1.0 ~ 10.0g / 10
min, (ii) a capacitor film for a propylene homopolymer composition, wherein the chlorine content is not more than 2 mass ppm.
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0 °
C., (Bs-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is the 0.950 or more,
a molecular weight distribution Mw / Mn measured by (B-ii) GPC 3.0 it is at
least, is (B-iii) a half-value width of the eluted peaks, measured by the Atsushi Nobori elution fractionation method (the TREF) is 4.0 ° C. or higher.

[Claim 3]

　The propylene homopolymer (A1) or the propylene homopolymer (A2) is a capacitor film for a propylene homopolymer composition according to claim 1 or 2 are produced using a metallocene catalyst.

[Claim 4]

　The propylene homopolymer (B1) or the propylene homopolymer (B2) is a capacitor film for a propylene homopolymer composition according to any one of claims 1 to 3 which is produced using a Ziegler-Natta catalyst.

[Claim 5]

　A capacitor film for a propylene homopolymer composition according to any one of claims 1 to 4, the capacitor film thickness of 1 ~ 50μm.

[6.]

　Capacitor film according to claim 5 thickness is 50μm or less beyond 4 .mu.m.

[7.]

　Capacitor film obtained by stretching a capacitor film for a propylene homopolymer composition according at a draw surface magnification (longitudinal × lateral area magnification) 30 to 80 times in any one of claims 1-4.

[8.]

　Capacitor film according to any one of claims 5 to 7, which is a capacitor separator film.

[9.]

　Using a metallocene catalyst, the following (A-i) ~ a step of producing a propylene homopolymer (A1) having the characteristics of (A-iii),
　by using a Ziegler-Natta catalyst, the following (B-i ) - (a step of producing a propylene homopolymer (B1) having the characteristics of B-ii),
　the propylene homopolymer of less than 1 wt% 50 wt% and (A1), 99 exceed 50% wt% or less of the propylene homopolymer (B1) and the steps of (total 100 wt% of the propylene homopolymer (A1) and the propylene homopolymer (B1)) is mixed with
a capacitor film comprising a method of manufacturing a propylene homopolymer
composition, (i) a melt flow rate of the capacitor film for a propylene homopolymer composition (MFR) is the 1.0 ~ 10.0g / 10
min, (ii) method for producing a propylene homopolymer composition capacitor film characterized in that chlorine content of the capacitor film for a propylene homopolymer composition is not more than 2 mass ppm.
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0 ℃,
(a-iii) molecular weight distribution (Mw / Mn) as measured by GPC is less than
3.0, (B-I) 13 is mesopentad rate as measured by C-NMR (mmmm) 0.950 it is at
least, is (B-ii) the molecular weight was measured by GPC distribution Mw / Mn 3.0 or higher.

[10.]

　Using a metallocene catalyst, the following (A-i) ~ a step of producing a propylene homopolymer (A2) having the characteristics of (A-ii),
　using a Ziegler-Natta catalyst, the following (B-i ) - (a step of producing a propylene homopolymer (B2) having the characteristics of B-iii),
　the propylene homopolymer of less than 1 wt% 50 wt% and (A2), 99 exceed 50% wt% or less of the propylene homopolymer (B2) and the steps of (total 100 wt% of the propylene homopolymer (A2) and the propylene homopolymer (B2)) mixing the
capacitor film comprising a method of manufacturing a propylene homopolymer
composition, (i) a melt flow rate of the capacitor film for a propylene homopolymer composition (MFR) is the 1.0 ~ 10.0g / 10
min, (ii) method for producing a propylene homopolymer composition capacitor film characterized in that chlorine content of the capacitor film for a propylene homopolymer composition is not more than 2 mass ppm.
(The A-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is 0.930 or
more, the half width of the eluted peaks, measured with (A-ii) Atsushi Nobori elution fractionation method (TREF) 4. is less than 0 °
C., (Bs-i) . 13 meso pentad fraction measured by C-NMR (mmmm) is the 0.950 or
more, a molecular weight distribution Mw / Mn measured by (B-ii) GPC 3.0 it is at
least, is (B-iii) a half-value width of the eluted peaks, measured by the Atsushi Nobori elution fractionation method (the TREF) is 4.0 ° C. or higher.