JP5181104B2 - Propylene block copolymer - Google Patents

Description

  The present invention relates to a propylene-based block copolymer excellent in flexibility, transparency, heat resistance, low-temperature impact resistance, and stress relaxation properties.

  Conventionally, soft polyvinyl chloride (hereinafter referred to as soft PVC) has been used for various film applications such as surface protective film, dicing film, wrap film, shrink film, sealant film, adhesive tape, marking film, agricultural film, and medical film. Have been widely used in terms of price, secondary processability and quality stability. However, since it contains a lot of plasticizers, the use of soft PVC is not preferable in the food or medical field. Particularly in recent years, environmental problems such as recycling have been regarded as important, and the use of soft PVC containing chlorine is regarded as a problem in all fields.

  For this reason, recently, development of a film using a polyolefin resin as an alternative material for the soft PVC has been actively carried out. Examples of the raw material of the film using such a polyolefin resin include polypropylene, low density polyethylene, high density polyethylene, and linear low density polyethylene.

  Among these, since the polyethylene film has a low melting point, the polyethylene film has the disadvantages of poor heat resistance and inferior stress relaxation properties.

  Polypropylene films are insufficient in flexibility and low temperature impact resistance because polypropylene is crystalline. Therefore, in order to generally obtain flexibility, there is a method of adding a soft polymer such as ethylene-propylene rubber (hereinafter referred to as EPR) or ethylene-propylene terpolymer (hereinafter referred to as EPDM) to polypropylene. According to the method, although the flexibility and impact resistance at low temperature can be improved, it is white or milky white, and since it is inferior in stress relaxation, it should be used as a film material that requires transparency and stress relaxation. I couldn't.

  Therefore, the development of a material having excellent properties such as flexibility, impact resistance at low temperature, and the like, which are possessed by a mixture of polypropylene and the above EPR and EPDM, and excellent in transparency and stress relaxation properties is an issue. Yes.

In order to solve the above problems, Patent Document 1 discloses that a propylene-based block copolymer having a specific composition manufactured using a titanium-based catalyst exhibits good flexibility, low-temperature impact resistance, and is transparent. And excellent stress relaxation properties. However, the block copolymer obtained by the above method is not yet satisfactory in terms of low-temperature impact resistance, transparency, and stress relaxation properties, and further improvements have been desired.
Japanese Patent Application Laid-Open No. 07-300548

  Accordingly, an object of the present invention is to provide a propylene-based block copolymer excellent in flexibility, transparency, heat resistance, low-temperature impact resistance, and stress relaxation properties.

As a result of intensive studies to achieve the above object, the present inventors have found that in the presence of a catalyst composed of a metallocene compound, an aluminoxane compound and / or a non-coordinating ion compound exhibiting at least two different stereospecificities. , the found that successful the copolymer component of the polypropylene component and the propylene and ethylene with the development of each stepwise specific amount produced block copolymer, such a block copolymer, satisfy all of the above objects Completed the invention.

That is, the present invention is a copolymer component of the polypropylene component and the propylene and ethylene with the presence of a catalyst comprising a metallocene compound showing at least two different stereospecificity and aluminoxane compound and / or a non-coordinating ionic compound Are produced in stages, and are composed of a polypropylene component and a copolymer component of propylene and ethylene, and are eluted at a temperature up to 80 ° C. by a temperature-temperature elution fractionation method using an o-dichlorobenzene solvent. Ingredients account for 40-99% by weight of the total, and components eluting at a temperature of 80 ° C. or higher are measured at 60-1% by weight of the total, at 230 ° C. under a load of 2.16 kg according to ASTM-D1238. A propylene-based block copolymer having a melt flow rate of 0.01 to 50 g / 10 min is provided .
In addition, the present invention is composed of a polypropylene component and a copolymer component of propylene and ethylene, and the components eluting at a temperature up to 80 ° C. by the temperature rising elution fractionation method using an o-dichlorobenzene solvent are entirely contained. The component that elutes at a temperature of 40 to 99% by weight and at a temperature of 80 ° C. or higher is 60 to 1% by weight of the total, and has a melt flow rate measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM-D1238. Provided is a propylene-based block copolymer of 0.01 to 50 g / 10 min.
The present invention provides a film formed by molding the above polypropylene-based block copolymer.

  The propylene block copolymer of the present invention in which the crystallinity distribution measured by the TREF method takes a specific form is excellent in flexibility, transparency, heat resistance, low temperature impact resistance, and stress relaxation.

  The present invention will be described in detail below.

Propylene block copolymer of the present invention is composed of a polypropylene component, a copolymer component of propylene and ethylene Len.

And propylene to the polypropylene component, the ratio of the copolymer component of ethylene Len, by elution component weight determined from the elution curve by o- temperature rise elution fractionation using dichlorobenzene as a solvent (hereinafter referred to as TREF) method Can be identified.

That is, the polypropylene component mainly comprises an elution component at 80 ° C. or higher in the elution curve by the TREF method. Further, the copolymer component of propylene and ethylene Len consists components eluted at temperatures up to mainly 80 ° C..

  Here, the TREF method is a method described in detail in, for example, Journal of Applied Polymer Science; Applied Polymer Symposium 45, 1-24 (1990). That is, a high-temperature polymer solution is introduced into a column packed with a diatomaceous earth filler, and the column temperature is gradually lowered to cause crystallization from a highly crystalline component in order on the filler surface. This is a method of separating the eluted polymer components by gradually elevating the components so as to elute them in order from components having low crystallinity. By this method, the crystalline distribution of the polymer can be measured.

In the present invention, flexibility is the effect of the present invention, low-temperature impact resistance, heat resistance, transparency, is characterized of excellent stress relaxation properties, and polypropylene component, propylene and the component ratio of the copolymer component of ethylene Len The ratio of the eluted components (crystallinity distribution) measured by the TREF method that indirectly represents is extremely important.

In the propylene-based block copolymer of the present invention, the elution component at 80 ° C. or higher (hereinafter referred to as a high temperature elution component) preferably has a propylene unit content of 97 to 100% by weight. Specifically, the high temperature eluting component, a propylene homopolymer, or a main component of propylene monomer units is 3 wt% consisting of ethylene Len or less, preferably 1.5 wt% or less, more preferably A random copolymer of 1% by weight or less is preferable because heat resistance is improved.

  In the propylene-based block copolymer of the present invention, the proportion of the high temperature eluting component is 1 to 60% by weight, preferably 3 to 40% by weight, and more preferably 5 to 30% by weight. That is, when the ratio of the high temperature eluting component is lower than 1% by weight, the heat resistance is deteriorated, and when it is 60% by weight or more, the flexibility and transparency are remarkably deteriorated.

In the propylene block copolymer of the present invention, components eluted at temperatures up to 80 ° C. (hereinafter, referred to as low-temperature eluting component) is preferably a copolymer of propylene and ethylene Len.

Further, a copolymer of the propylene and ethylene Len, flexible products, low-temperature impact resistance, transparency, in order to effectively impart stress relaxation properties, formed by random copolymerization of propylene and ethylene Len A copolymer is preferred.

  In the propylene-based block copolymer of the present invention, the amount of the low temperature elution component is 40 to 99% by weight, preferably 60 to 97% by weight, and more preferably 70 to 95% by weight. When the medium-low temperature elution component is less than 40% by weight, the product has poor flexibility and transparency. Further, when the amount of the low temperature elution component is more than 99% by weight, the heat resistance is deteriorated.

Ethylene Ren unit content in the low-temperature eluting component, flexibility, transparency, heat resistance, low-temperature impact resistance, it is preferred that the stress relaxation properties 4-50 wt% In consideration of. Furthermore 5-20 wt%, more preferably predominantly low-crystalline propylene copolymer containing ethylene lens unit 6 to 15 wt%.

  Further, the propylene block copolymer of the present invention has a glass transition temperature (Tg) of a toluene soluble content at a temperature of −40 ° C., preferably −20 ° C. or less, in order to improve transparency and low temperature impact resistance. Is more preferably −25 ° C. or lower, more preferably −30 ° C. or lower, and a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the toluene-soluble component is 50,000 g / mol or higher, Preferably, it is 70,000 g / mol or more, more preferably 90,000 g / mol, and the toluene-soluble component whose molecular weight is 10,000 g / mol or less is measured at a temperature of −40 ° C. It is more preferably 10% by weight or less of the amount, more preferably 7% by weight or less, and further preferably 5% by weight or less. In the present invention, the glass transition temperature of the -40 ° C. toluene-soluble component is measured by dynamic thermomechanical measurement (DMA).

  Further, the propylene-based block copolymer of the present invention has a toluene-soluble content measured at a temperature of −40 ° C. for improving low-temperature impact resistance, 5 to 30% by weight, preferably 7 to 27% by weight, Furthermore, it is more preferable that it is 10-25 weight%.

  The propylene-based block copolymer of the present invention is not particularly limited as long as it satisfies the above-described configuration. For example, the propylene-based block copolymer is measured by a differential scanning calorimeter (hereinafter referred to as DSC) of the high temperature elution component. The melting point is 120 to 170 ° C., preferably 125 to 165 ° C., and more preferably 130 to 155 ° C. in order to improve transparency and heat resistance of the product film.

  Further, the molecular weight distribution dispersity (Mw / Mn) measured by gel permeation chromatography (GPC) of the propylene-based block copolymer of the present invention is 5 or less, preferably for improving the blocking resistance of the film product. Is preferably 4.5 or less, more preferably 4 or less.

  The intrinsic viscosity [η] measured using an Ubbelohde viscometer in tetralin at 135 ° C. is 0.5 to 5.0 dl / g, preferably 0.8, in order to improve the molding processability or the blocking resistance of the product. It is 5 to 3.0 dl / g, more preferably 0.8 to 2.0 dl / g.

  Further, the propylene block copolymer of the present invention has a melt flow rate measured under a load of 2.16 kg at 230 ° C. in accordance with ASTM-D1238. Minutes, preferably 0.1-30 g / 10 min, more preferably 0.5-20 g / 10 min are suitable.

  Furthermore, the calorific value of the endothermic peak measured by DSC is preferably 80 mJ / mg or less, preferably 70 mJ / mg or less, more preferably 50 mJ / mg or less in order to improve the transparency of the product.

Propylene resin composition of the present invention, as a resin component, in addition to the copolymer component of the polypropylene component and the propylene and ethylene Ren described above, in a range not impairing the effect of the propylene resin composition of the present invention, for example 5 Another α-olefin polymer may be contained as a component in the range of not more than% by weight. Examples of the α-olefin include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4- Methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-octadecene, 1-eicosene and the like can be exemplified.

  The propylene-based block copolymer of the present invention comprises at least two metallocene compounds having different stereospecificities (hereinafter abbreviated as component [I]), aluminoxane compounds and / or non-coordinating ionized compounds (hereinafter referred to as components [II] ] Can be obtained by stepwise production of the polypropylene component (A) and the copolymer component (B).

  In the present invention, as the at least two different stereospecific metallocene compounds, a metallocene compound having isospecificity and a metallocene compound having low stereospecificity or essentially no stereospecificity are preferably used. The metallocene compound having isospecificity gives a crystalline polymer when propylene is polymerized, and the [mm] triad fraction of the resulting polymer, which is an index of stereospecificity, is 0.6 or more, preferably 0.8. It is preferably 7 or more, more preferably 0.8 or more. In addition, the metallocene compound having low stereospecificity or essentially no stereospecificity gives an amorphous polymer when propylene is polymerized, and the [mm] triad fraction is less than 0.6, preferably , 0.5 or less, more preferably 0.4 or less.

[Mm] Triad fraction is A. A value calculated by isolating the three consecutive monomers in the polymer molecular chain using the method described in Macromolecules, 6, 925 (1973) by Zambelli et al., Ie, ¹³ C-NMR. It is.

As the metallocene compound having isotactic stereospecificity, known compounds can be used without any limitation. Among them, a chiral racemic compound represented by the following general formula (1) can be preferably used.
^{_{Q (C 5 H 4-m}} R 1 m) (C 5 H 4-n R 2 n) MX 1 X 2 (1)
(In the formula, M represents a transition metal atom of Group IVb of the periodic table. (C ₅ H _4-m R ¹ _m ) and (C ₅ H _4-n R ² _n ) are substituted cyclopentadienyl groups. M and n are integers of 1 to 3, and R ¹ and R ² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, Or a hydrocarbon group which is bonded to two carbon atoms on the cyclopentadienyl ring to form one or more hydrocarbon rings which may be substituted with a hydrocarbon group, Q is (C ₅ H _4-m R ¹ _m ) and (C ₅ H _4-n R ² _n ) are crosslinkable groups, and are divalent hydrocarbon groups, unsubstituted silylene groups, or hydrocarbon-substituted silylene groups. .X ¹ and X ² are the same or different and have good hydrogen, halogen or hydrocarbon Are shown.)
More preferably, in the above formula (1), M is a zirconium or hafnium atom, R ¹ and R ² are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and X ¹ and X ² are the same or different halogens. A chiral racemic metallocene compound in which an atom or a hydrocarbon group and Q is a hydrocarbon-substituted silylene group is preferred.
^{_{(C 5 H 4-m R}} 1 m) and ^{_{(C 5 H 4-n R}} 2 n) , specifically 2-methyl - include benzindenyl group.

  Specific components [I] are exemplified by rac-dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene (2,4- Dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′trimethylcyclo Pentadienyl) zirconium dichloride, rac-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4′5 ′, 5′-trimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylenebis (2-Methyl-indenyl) zirconium dichloride rac-diphenylsilylenebis (2-methyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-indenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-Methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, ac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl Rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-isopropyl) Indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl) -4-Isopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium Dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis ( 2-Methyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dichloride, rac-dimethylsilyl Bis (2-methyl-4-t-butylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4- Phenylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-Methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4- Phthylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2 -Methyl-benzindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-benzindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-benzindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-benzindenyl) Zirconium dimethyl etc. are mentioned.

  Moreover, the compound which replaced said zirconium with hafnium is also used suitably.

  As the metallocene compound having low stereospecificity or essentially no stereospecificity, a known compound can be used without any limitation. ) Zirconium dichloride, ethylenebis (fluorenyl) zirconium dichloride, and the like can be used.

  Among them, meso-dimethylsilylenebis (2-methyl-benzindenyl) zirconium dichloride, meso-dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride, meso-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride Dimethylsilylene (bisfluorenyl) zirconium dichloride and ethylenebis (fluorenyl) zirconium dichloride can be suitably used.

  A compound in which the above zirconium is replaced with hafnium can also be used.

  The ratio of the metallocene compound having isospecificity [I] and the metallocene compound having low or no stereospecificity is limited as long as the resulting block copolymer satisfies the requirements of the present invention. The mixing ratio (molar ratio) between the metallocene compound having isospecificity and the metallocene compound having low stereospecificity or essentially no stereospecificity is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 80/20.

  As the aluminoxane compound and / or the non-coordinating ionized compound component [II], known compounds can be used without any limitation. The aluminoxane compound and the non-coordinating ionized compound component may be used alone or in combination. As the aluminoxane compound, an aluminum compound represented by the general formula (2) or (3) is preferable.

一般式（３）または（４）において、Ｒ^３は炭素数が、１〜６、好ましくは１〜４のアルキル基であり、メチル基、エチル基、プロピル基、ブチル基、イソブチル基が挙げられる。これらのうち特に好ましいのはメチル基であり、一部炭素数２〜６のアルキル基を含んでいてもよい。ｍは、４〜１００の整数であり、好ましくは、６〜８０、特に好ましくは１０〜６０である。

In the general formula (3) or (4), R ³ is an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. . Among these, a methyl group is particularly preferable, and a part of the alkyl group having 2 to 6 carbon atoms may be included. m is an integer of 4 to 100, preferably 6 to 80, particularly preferably 10 to 60.

  The production method of the above aluminoxane compound may be any of various known methods, for example, a method of reacting trialkylaluminum directly with water in a hydrocarbon solvent, copper sulfate hydrate having crystal water, aluminum sulfate Examples thereof include a method of reacting moisture adsorbed in a hydrocarbon solvent with trialkylaluminum using hydrate, water-containing silica gel or the like.

  As the non-coordinating ionizable compound, known compounds are used without particular limitation, and in particular, an ionized compound containing a boron atom can be preferably used.

  Specific examples of ionized compounds containing boron atoms include Lewis acids containing boron atoms and ionic compounds containing boron atoms.

  Examples of the Lewis acid containing a boron atom include a compound represented by the general formula (4).

BR ⁴ ₃ (4)
In the above general formula, R ⁴ is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group or the like.

  Specific examples of the compound represented by the general formula include trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, and tris (4-fluoromethylphenyl). Examples include borane, tris (pentafluorophenyl) borane, tris (p-tolyl) borane, tris (o-tolyl) borane, and tris (3,5-dimethylphenyl) borane. Of these, tris (pentafluorophenyl) borane is preferably used.

  The ionic compound containing boron is a salt of a cationic compound and an anionic compound containing boron, and is a trialkyl-substituted ammonium salt, N, N-dialkylanilinium salt, dialkylammonium salt, triaryl phosphor. Examples thereof include nium salts. Examples of trialkyl-substituted ammonium salts include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium. Tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p -Trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like, and N, N-dialkylanilinium salts N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron and the like. And dialkylammonium salts include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Triarylphosphonium salts include triphenylphosphonium tetra ( Phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) boron and the like.

  Furthermore, as the ionic compound containing boron, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate Can also be mentioned.

  Of these, triphenylcarbonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferably used.

  The amount of component [I] and component [II] used is arbitrary, but the amount of component [II] used when an aluminoxane compound is used for component [II] (the molar amount of Al atoms in component [II]) ) Is preferably 0.1 to 100,000 mol, more preferably 1 to 50,000 mol, and still more preferably 10 to 30,000 mol with respect to 1 mol of the transition metal in component [I]. is there. The amount of component [II] used (mol amount of boron atom in component [II]) when a non-coordinating ionized compound is used as component [II] is 1 mol of transition metal in component [I]. The amount is preferably 0.01 to 10,000 mol, more preferably 0.1 to 5,000 mol, and still more preferably 1 to 3,000 mol.

Component [I] and the component compounds in the presence of a catalyst consisting of [II] the polypropylene component (A) and propylene having at least two non-conjugated vinyl groups and a copolymer component of ethylene-les emission (B) Can be used in combination with an organoaluminum compound (hereinafter abbreviated as component [III]) as necessary. Component [III] is a compound represented by general formula (5).

AlR ⁵ _m X ³ _3-m (5)
(In the formula, R ⁵ represents a hydrocarbon group such as an alkyl group having 1 to 10 carbon atoms or an aryl group, or an alkoxy group. X ³ represents a halogen atom. (It is an integer.)
Specific examples of the compound represented by the above general formula include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. Trialkylaluminums such as tri-n-decylaluminum, diethylaluminum monochloride, diethylaluminum monobromide, dialkylaluminum monohalides such as diethylaluminum monofluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride Alkyl aluminum halides, diethyl aluminum monoethoxide, ethyl aluminum Alkoxy aluminum such as Mujietokishido like. Among these, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum are preferably used.

  The amount of component [III] used is not particularly limited, but is generally 1 to 50,000 mol, preferably 5 to 10,000 mol, per 1 mol of transition metal atom in component [I]. is there. More preferably, it is 10-5,000 mol.

  Component [I] and / or component [II] can also be used by being supported on a particulate carrier (hereinafter abbreviated as component [IV]). When the catalyst component is supported on the carrier, the particle properties of the resulting polymer are improved, and process compatibility in resin production, such as prevention of polymerization scale in the reactor, can be greatly improved.

  As the fine particle carrier, those having a function as a carrier are used without limitation, and inorganic oxides are particularly preferable.

Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, or a mixture thereof, for example, SiO ₂ —Al ₂ O ₃ , SiO _{2 -MgO, SiO 2 -TiO 2, SiO} 2 -V 2 O 5, SiO 2 -Cr 2 O 3, etc. SiO ₂ -TiO 2 -MgO can be suitably used. Among these, a carrier containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component is more preferable.

  The inorganic fine particle carrier is usually used after being fired at 150 to 1000 ° C, preferably 200 to 800 ° C.

  The properties of the carrier vary depending on the type and production method, but the particle size of the carrier preferably used in the present invention is generally 0.1 to 500 μm, preferably 1 to 200 μm, more preferably 10 to 100 μm. When the particle size is small, the produced particles become a finely divided polymer, and when the particle size is too large, the particles become coarse and difficult to handle the powder.

The pore volume of these carriers is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. The pore volume can be measured by a BET method or a mercury intrusion method.

The specific surface area of these carriers is usually 50 to 1000 m ² / g, preferably 100 to 700 m ² / g.

  The amount of component [I] used relative to 1 g of component [IV] is 0.005 to 1 mmol, preferably 0.05 to 0.5 mmol in terms of transition metal atoms. Further, when an aluminoxane compound is used as component [II], the amount of the aluminoxane compound used relative to component [I] is converted to 1 mol of transition metal atoms in component [I] in terms of the molar amount of Al atoms. It is 1-200 mol with respect to it, Preferably it is 15-150 mol.

  When the non-coordinating ionized compound is used, the amount of the non-coordinating ionized compound used relative to the component [I] is converted to the molar amount of boron atoms in the non-coordinating ionized compound, and the component [I] It is 0.1-20 mol with respect to 1 mol of transition metal atoms in it, Preferably it is 1-15 mol.

  In order to obtain the obtained polymer with more excellent particle properties, the following method can also be employed.

  That is, olefin prepolymerization is first performed in the presence of the component [I], the component [II], the component [IV], and, if necessary, the component [III]. The amount of the component [III] used in the prepolymerization is not particularly limited, but is generally 1 to 50,000 mol, preferably 5 to 10, mol per 1 mol of the transition metal atom in the component [I]. 000 mol. More preferably, it is 10-5,000 mol. Each of the above components used in the prepolymerization may be added sequentially one by one, or a mixture may be added all at once. Preferably, a method of bringing the components [I] and [II] into contact with the catalyst component [IV] in advance is employed. More preferably, after the component [II] is supported on the catalyst component [IV], the method of supporting the component [I] is effective for obtaining a block copolymer with a more excellent bulk specific gravity.

  Examples of the olefin used in the prepolymerization include ethylene; propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 4,4-dimethyl-1-pentene. 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and other α-olefins; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5 , 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like. Furthermore, styrene, dimethylstyrenes, allyl norbornane, allylbenzene, allylnaphthalene, allyltoluenes, vinylcyclopentane, vinylcyclohexane, vinylcyclopeptane, diene, and the like can be used. Preferably, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4 -Methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, cyclopentene, vinylcyclohexane, particularly preferred Are ethylene, propylene, 1-butene, 1-heptene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene.

  The prepolymerization is preferably carried out by substantially homopolymerization of 95 mol% or more of olefin.

  The polymerization amount of the olefin initially applied in the prepolymerization of the present invention is 0.1 to 1000 g, preferably 1 to 50 g, per 1 g of the catalyst formed from the catalyst components [I], [II] and [IV]. Choose from a range.

  In addition, as a particularly preferred embodiment of the prepolymerization, in the prepolymerization described above, first, in the presence of each component of [I], [II], [IV] and optionally [III], Propylene is prepolymerized as one prepolymerization to obtain a first prepolymerization catalyst, and then a second prepolymerization of 1-butene is further carried out stepwise in the presence of the first prepolymerization catalyst and component [III]. The method is preferably used.

  The amount of component [III] used in each prepolymerization is not particularly limited, but is generally 1 to 50,000 moles, preferably 5 to 10 moles per mole of transition metal atoms in component [I]. 1,000 moles. More preferably, it is 10-5,000 mol. After obtaining the first prepolymerization catalyst by the above-mentioned prepolymerization of propylene, it is usually desirable to remove unreacted propylene and the component [III] used as necessary by washing and then subject to the subsequent second prepolymerization. .

  In each prepolymerization stage, it is preferable to carry out substantially homopolymerization of propylene and 1-butene of 95 mol% or more, preferably 98 mol% or more.

  The polymerization amount of propylene initially applied in the prepolymerization is from 0.1 to 1000 g, preferably from 1 to 10 g, per 1 g of the catalyst formed from the catalyst components [I], [II] and [IV]. The polymerization amount of 1-butene to be performed next is selected in the range of 0.1 to 1000 g, preferably 1 to 500 g, per 1 g of the catalyst formed from the catalyst components [I], [II] and [III]. Good. The ratio of the propylene polymerization amount to the 1-butene polymerization amount is preferably in the range of 0.001 to 100, preferably 0.005 to 10 in terms of the weight ratio of propylene polymerization amount / 1-butene polymerization amount.

For the prepolymerization, it is usually preferable to apply slurry polymerization, and as the solvent, saturated aliphatic hydrocarbons or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene may be used alone, or a mixed solvent thereof may be used. it can. The first and second prepolymerization temperatures are preferably −20 to 100 ° C., particularly preferably 0 to 60 ° C., and each stage of the prepolymerization may be performed under different temperature conditions. The prepolymerization time may be appropriately determined according to the prepolymerization temperature and the polymerization amount in the prepolymerization, and the pressure in the prepolymerization is not limited, but in the case of slurry polymerization, generally from atmospheric pressure to 5 kg / cm. It is about ² .

  Each preliminary polymerization may be carried out by any of batch, semi-batch and continuous methods.

  After completion of each prepolymerization, it is preferable to wash saturated aliphatic hydrocarbons or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene alone or with a mixed solvent thereof. 5-6 times are preferable.

  The polymerization conditions are not particularly limited as long as the effect of the present invention is recognized, but the following conditions are generally preferred.

The polymerization of the polypropylene component is propylene alone or a propylene in the range satisfying the requirements of the present invention may be carried out by feeding a mixture of ethylene Ren. The polymerization temperature in the polymerization of the polypropylene component is 0 to 100 ° C, preferably 20 to 80 ° C.

  In the polymerization, hydrogen can be allowed to coexist as a molecular weight regulator. In addition, any method such as slurry polymerization, gas phase polymerization, solution polymerization or the like using the monomer itself used for polymerization as a solvent may be used. Considering the simplicity of the process and the reaction rate, and the particle properties of the copolymer to be produced, slurry polymerization using propylene itself as a solvent is a preferred form.

  The polymerization method may be any of batch, semi-batch and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different conditions such as hydrogen concentration and polymerization temperature.

Following polymerization for obtaining the polypropylene component, the random copolymer of propylene and ethylene Len is performed. Random copolymer of propylene and ethylene Len, in the case of slurry polymerization of propylene itself as a solvent by feeding ethylene gas subsequent to the propylene polymer, also in the case of gas phase polymerization mixture of propylene and ethylene Len This is done by supplying gas.

The random copolymerization of propylene and ethylene Len of the invention it is preferable to carry out the random copolymerization of one stage following the propylene polymer can also be prepared by changing the feed concentration of ethylene Ren in multiple stages. The polymerization temperature for a random copolymer of propylene and ethylene Len, 0 to 100 ° C., preferably, it is preferred to employ the range of 20 to 80 ° C.. Further, if necessary, hydrogen can be used as a molecular weight regulator, and the polymerization can be carried out by changing the hydrogen concentration at that time in multiple steps or continuously.

Propylene and random copolymerization batch of ethylene Ren, semi-batch, may be any method of continuous, it may be performed separately polymerized in multiple stages. Further, the polymerization in this step may employ any method of slurry polymerization, gas phase polymerization, and solution polymerization.

  After completion of the main polymerization, the monomer can be evaporated from the polymerization system to obtain the propylene resin of the present invention. This propylene resin can be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.

  You may add commercially available additives, such as antioxidant, a heat stabilizer, and a chlorine scavenger, to the propylene-type resin composition of this invention. In this case, these additives may be mixed with the resin composition and then pelletized with an extruder. In addition to the above additives, an organic peroxide may also be added for thermal decomposition, and the molecular weight may be adjusted within a range that satisfies the requirements of the present invention.

  The propylene-based block copolymer of the present invention is excellent in flexibility and transparency, and is suitable as a film, particularly a soft film, because it exhibits excellent low-temperature impact resistance and stress relaxation properties that have not been conventionally achieved. The use of the film is not particularly limited and is used for packaging applications such as food, clothing, stationery and sundries. Among these uses, it has excellent low-temperature impact resistance and can be suitably used particularly for food applications. .

  As a method for forming the propylene-based block copolymer into a film, a known film forming method can be adopted without any particular limitation. The molding temperature at that time is preferably 200 to 300 ° C., preferably 220 to 270 ° C., considering the occurrence of melt fracture, film moldability, thermal degradation of the resin, and the like. As a method for forming the film, any forming method such as a non-stretched film using a T-die, a uniaxially stretched film, a biaxially stretched film, or calendar molding or inflation molding can be used.

  In the present invention, the film does not have a strict meaning particularly regarding the thickness, and is a generic name including a sheet, and usually about 10 to 1000 μm is preferably used.

  The polypropylene-based block copolymer may be used as a single layer film, or may be used by laminating other resins. The layer structure is not particularly limited, and may be a surface layer or an inner layer. There are no particular restrictions on the resin used for lamination, but ethylene resins such as propylene resin, high density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, etc. Etc. Further, the film surface can be subjected to corona treatment.

  Furthermore, since the propylene-based block copolymer obtained by the present invention is excellent in flexibility, transparency, heat resistance, low-temperature impact resistance, and stress relaxation properties, various fields in which conventional thermoplastic elastomers are used. Can be suitably used. For example, bumpers, mat guards, and lamp packings for automobile parts in the injection molding field, and various packings, ski shoes, grips, and roller skates in the household appliance field. On the other hand, in the extrusion molding field, various automotive interior materials, home appliances and electric wire materials, various insulating sheets, cord coating materials, and waterproof sheets, waterproofing materials, joint materials, stretch films for packaging, etc. it can.

  The molding method is not particularly limited, and can be suitably used for various applications by any molding method such as extrusion molding, injection molding, press molding, and vacuum molding.

  When molding, various stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, anti-aggregation agents, lubricants, plasticizers, pigments, inorganic or organic fillers can be blended. Illustrative of these additives are 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 4,4 '-Butylidenebis (6-t-butyl-m-cresol), tocophenols, ascorbic acid, dilauryl thiodipropionate, phosphate stabilizer, fatty acid monoglyceride, N, N- (bis-2-hydroxyethyl) Alkylamine, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydro Talcite, talc, clay, plaster, glass fiber, titania, calcium carbonate, carbon Rack, petroleum resins, polybutene, waxes, synthetic or natural rubber.

  Furthermore, other resins can be added to the polypropylene resin composition of the present invention within a range that does not significantly affect the characteristics of the present invention. For example, 90% mol or more of propylene and α-olefin other than propylene, for example, 1 mol or more of 10 mol% such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene Random copolymer, high density polyethylene (HDPE), low density polyethylene (LDPE), linear polyethylene (LLDPE) by copolymerization of ethylene and C4 to C10, ethylene vinyl acetate copolymer (EVA), ethylene Polyethylene resins such as methyl methacrylate copolymer (EMMA), ethylene / propylene copolymer (EPR, EPDM), ethylene / butene-1 copolymer (EBM), propylene / butene-1 copolymer (PBM), etc. Olefin soft resin, styrene-butadiene block copolymer (SBR), petroleum resin Those pen resin or the like known hydrogenated product thereof can be used without restriction.

  In the present invention, the polypropylene-based resin composition to be used is obtained by mixing and melt-kneading after blending the above raw materials and the like as necessary. Although the method of melt kneading is not particularly limited, for example, it may be carried out at a temperature of 160 to 300 ° C., preferably 180 to 270 ° C. using a screw extruder, a Banbury mixer, a mixing roll, or the like. Moreover, this melt-kneading can also be performed under inert gas flow, such as nitrogen gas. A known mixing device such as a tumbler or a Henschel mixer can be used without any limitation before the melt-kneading.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples.

  In addition, the measuring method of the various physical properties of the polymer obtained in the following Examples and Comparative Examples is as follows.

(1) Melt flow rate (abbreviated as MFR)
Conforms to ASTM D1238.

(2) Bulk density Conforms to ASTM D1895.

(3) Melting point Using DSC-6200R manufactured by Seiko Electronics Co., Ltd., about 5 mg of sample was packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, held at 200 ° C. for 5 minutes, and then to 20 ° C./minute to room temperature. It was determined from the endothermic curve when the temperature was lowered and then raised at 10 ° C./min.

(4) Ethylene content It calculated from the ¹³ C-NMR spectrum measured using JEOL GSX-270.

(5) Molecular weight distribution It developed by column GMH6HT (made by Tosoh Corporation) using 150C type gel permeation chromatography (GPC) made by Waters. The molecular weight distribution (Mw / Mn) was determined from the ratio of the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

(6) TREF (temperature rising elution fractionation) elution curve Measurement was performed under the following conditions using an automatic TREF device (SSC-7300, ATREF) manufactured by Senshu Kagaku.

Solvent: Orthodichlorobenzene Flow rate: 150 ml / hour Temperature rising rate: 4 ° C./hour Detector: Infrared detector Measurement wave number: 3.41 μm
Column: “Packed column 30Φ” manufactured by Senshu Scientific Co., Ltd., 30 mmΦ × 300 mm
Concentration: 1g / 120ml
Injection volume: 100ml
In this case, after introducing the sample solution into the column at 145 ° C., the sample solution is gradually cooled to −10 ° C. at a rate of 2 ° C./hour to adsorb the sample polymer on the surface of the filler, and at the same time the solvent starts to flow. The polymer concentration eluted at each temperature by raising the temperature under the above conditions was measured with an infrared detector to obtain an elution temperature-elution amount curve.

(7) Transparency (haze value)
Conforms to JIS K6714.

(8) Flexural modulus It conformed to ASTM D-790.

(9) Vicat softening temperature Measured under the condition of a load of 250 g according to JIS K7206.

(10) Glass transition temperature (Tg)
Using a DMS-200 manufactured by Seiko Electronics Co., Ltd., measuring viscoelasticity at a measurement temperature of −100 ° C. to 200 ° C. and a temperature increase rate of 2 ° C./min with a sample having a width of 5 mm and a thickness of 0.5 mm. The peak top temperature of tan δ was defined as Tg.

(11) Izod impact strength Based on JIS 7105, it was measured with notches at temperatures of 23 ° C. and −40 ° C.

(12) Soluble amount of toluene at −40 ° C. After 1 g of polymer was added to 100 ml of toluene and heated to 100 ° C. while stirring, stirring was further continued for 30 minutes to completely dissolve the polymer. Left in the room for 6 hours. The precipitate was filtered off in a -40 ° C constant temperature room, and the toluene solution was completely evaporated to obtain a soluble component.

−40 ° C. toluene soluble content (wt%) = (toluene soluble content (g) / polymer 1 g) × 100
It is represented by

(13) Stress relaxation property A test piece cut out in a strip shape from a film having a thickness of 150 μm is stretched by 10% and held for 5 minutes. The value of the stress after 5 minutes is measured and obtained from the relationship with the maximum stress at the time of stretching according to the following formula.

Stress relaxation value (%) = (maximum stress value−stress value after 5 minutes) / maximum stress value × 100
Example 1
[Preparation of supported metallocene catalyst]
Silica gel support methylaluminoxane (MAO on SiO _2, Uittoko Co., 25 wt% -Al product) 10 g to rac- dimethylsilylene bis - (2-methyl - benzindenyl) zirconium dichloride a toluene solution of 70 ml (0.005 mmol / ml toluene solution) And 30 ml of a toluene solution of meso-dimethylsilylenebis- (2-methyl-benzindenyl) zirconium dichloride (0.005 mmol / ml toluene solution) were added and stirred at room temperature for 30 minutes.

  Next, the reaction mixture was filtered, and the resulting solid was washed twice with 50 ml of toluene and dried under reduced pressure to obtain a metallocene catalyst supported on silica gel. 0.045 mmol of metallocene was supported per gram of catalyst.

[polymerization]
(First stage, polymerization of propylene)
600 kg of propylene was inserted into a polymerization tank having an internal volume of 2 m ³ and 612 mmol of triisobutylaluminum was introduced. Thereafter, the internal temperature of the polymerization tank was raised to 55 ° C. Next, 5 g of the metallocene catalyst supported on the silica gel was charged. Subsequently, the internal temperature of the polymerization tank was raised to 60 ° C., and polymerization was performed for 70 minutes.

(Later, copolymerization of propylene and ethylene)
After the previous polymerization, ethylene gas was supplied in a gas phase concentration to a concentration of 16 mol%, and further copolymerization was carried out for 70 minutes while supplying the ethylene gas phase concentration so as to be kept constant. After the completion of the polymerization, unreacted propylene was purged, followed by drying at 50 ° C. for 1 hour to obtain 141 kg of a white granular polymer.

  When the elution component of 80 ° C. or higher and the elution component of lower than 80 ° C. separated by TREF of the obtained polymer were analyzed, the melting point of the component of 80 ° C. or higher was 146 ° C.

  Furthermore, the elution component below 80 ° C. had an ethylene content of 12.5 wt%, and no melting point peak was detected by DSC. Further, the toluene soluble content measured at −40 ° C. was 18.4 wt%, the Tg was −49.7 ° C., the Mw was 125,000, and the components below 10,000 were 3.5% by weight. It was.

  The melting point and ethylene content of the TREF-eluting component of the polymer obtained in Table 1, the amount of the TREF-eluting component, the amount of the soluble component of -40 ° C. toluene, Tg, Mw, the amount of the component having a molecular weight of 10,000 or less, MFR, molecular weight distribution, The bulk density is shown.

[Evaluation of the physical properties]
To 100 parts by weight of the obtained polymer, 0.1 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant and 0.05 part by weight of calcium stearate as a chlorine scavenger are added. After mixing for 5 minutes, extrusion was performed at 230 ° C. using an extrusion granulator having a screw diameter of 65 mmΦ, and pellets were granulated to obtain raw material pellets, which were subjected to physical property measurement. The haze value is a value of a 3 mm thick test piece for transparency evaluation obtained by injection molding. The results are shown in Table 2.

Example 2
The same procedure as in Example 1 was performed except that the polymerization time in the former stage of Example 1 was 20 minutes and the polymerization time in the latter stage polymerization was 120 minutes. The results are shown in Tables 1 and 2.

Example 3
The same procedure as in Example 1 was performed except that the polymerization time in the former stage of Example 1 was 80 minutes and the polymerization time in the latter stage polymerization was 60 minutes. The results are shown in Tables 1 and 2.

Example 4
The same procedure as in Example 1 was performed except that the polymerization time in the former stage of Example 1 was 90 minutes and the polymerization time in the latter stage polymerization was 50 minutes. The results are shown in Tables 1 and 2.

Example 5
In the preparation of the supported metallocene catalyst of Example 1, 15 ml (0.005 mmol / ml toluene solution) of rac-dimethylsilylenebis- (2-methyl-benzindenyl) zirconium dichloride and meso-dimethylsilylenebis- (2- Example 1 except that the toluene solution of methyl-benzindenyl) zirconium dichloride was 85 ml (0.005 mmol / ml toluene solution), the polymerization time in the former stage was 80 minutes, and the polymerization time in the latter stage polymerization was 60 minutes. went. The results are shown in Tables 1 and 2.

Example 6
In the preparation of the supported metallocene catalyst of Example 1, 85 ml (0.005 mmol / ml toluene solution) of rac-dimethylsilylenebis- (2-methyl-benzindenyl) zirconium dichloride and meso-dimethylsilylenebis- (2- The same procedure as in Example 1 except that the toluene solution of methyl-benzindenyl) zirconium dichloride was 15 ml (0.005 mmol / ml toluene solution), the polymerization time in the former stage was 60 minutes, and the polymerization time in the latter stage polymerization was 80 minutes. went. The results are shown in Tables 1 and 2.

Example 7
In the preparation of the supported metallocene catalyst of Example 1, 5 ml (0.005 mmol / ml toluene solution) of rac-dimethylsilylenebis- (2-methyl-benzindenyl) zirconium dichloride and meso-dimethylsilylenebis- (2- Example 1 except that the toluene solution of methyl-benzindenyl) zirconium dichloride was 95 ml (0.005 mmol / ml toluene solution), the polymerization time in the former stage was 90 minutes, and the polymerization time in the latter stage polymerization was 50 minutes. went. The results are shown in Tables 1 and 2.

Example 8
In the preparation of the supported metallocene catalyst of Example 1, 95 ml (0.005 mmol / ml toluene solution) of rac-dimethylsilylenebis- (2-methyl-benzindenyl) zirconium dichloride and meso-dimethylsilylenebis- (2- Example 1 except that the toluene solution of methyl-benzindenyl) zirconium dichloride was 5 ml (0.005 mmol / ml toluene solution), the polymerization time in the former stage was 50 minutes, and the polymerization time in the latter stage polymerization was 90 minutes. went. The results are shown in Tables 1 and 2.

Example 9
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 80 minutes, the gas phase ethylene concentration in the latter stage polymerization was 18.6 mol%, and the polymerization time was 60 minutes. The results are shown in Tables 1 and 2.

Example 10
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 90 minutes, the gas phase ethylene concentration in the latter stage polymerization was 24.8 mol%, and the polymerization time was 50 minutes. The results are shown in Tables 1 and 2.

Example 11
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 100 minutes, the gas phase ethylene concentration in the latter stage polymerization was 39.2 mol%, and the polymerization time was 40 minutes. The results are shown in Tables 1 and 2.

Reference example 1
The polymerization time was 60 minutes in the former stage of Example 1, the gas phase ethylene concentration in the latter stage polymerization was 7.1 mol%, and liquefied butene-1 was added to 5.0 mol% in the gas phase butene-1 concentration. The same operation as in Example 1 was performed except that the time was 80 minutes. The results are shown in Tables 1 and 2.

Example 13
[Preparation of supported catalyst metallocene catalyst]
The same operation as in Example 1 was performed.

[Preliminary polymerization]
In a 1 L autoclave subjected to N ₂ substitution, 200 ml of purified heptane, 50 mmol of triisobutylaluminum, and 5 mmol of the supported metallocene catalyst component were charged in terms of Zr atoms, and then 1 g of propylene was added to 5 g of 1 g of the supported metallocene catalyst component. The polymer was introduced into the reactor continuously for a period of time and subjected to prepolymerization. The temperature during this period was maintained at 15 ° C.

After 1 hour, the introduction of propylene was stopped, and the inside of the reactor was sufficiently replaced with N ₂ . The solid component of the resulting slurry was washed 6 times with purified heptane.

[polymerization]
The same procedure as [Polymerization] in Example 1 was performed using the above prepolymerization catalyst. The results are shown in Table 1.

[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.

Example 14
[Preparation of supported catalyst metallocene catalyst]
The same operation as in Example 1 was performed.

[Preliminary polymerization]
In a 1 L autoclave subjected to N ₂ substitution, 200 ml of purified heptane, 50 mmol of triisobutylaluminum, and 5 mmol of the supported metallocene catalyst component were charged in terms of Zr atom, and then 1 g of propylene was added to 1 g of the supported metallocene catalyst component. The polymer was introduced into the reactor continuously for a period of time and subjected to prepolymerization.

The temperature during this period was maintained at 15 ° C. After 1 hour, the introduction of propylene was stopped, and the inside of the reactor was sufficiently replaced with N ₂ . The solid component (first prepolymerization catalyst) of the obtained slurry was washed 6 times with purified heptane.

Further, this first prepolymerized catalyst was charged into a 1 L autoclave with N ₂ substitution, and after adding 200 ml of purified heptane and 50 mmol of triisobutylaluminum, 1-butene was 20 g with respect to 1 g of the supported metallocene catalyst component. Thus, it was continuously introduced into the reactor for 1 hour and subjected to prepolymerization. The temperature during this period was maintained at 15 ° C.

  The solid part of the obtained slurry was washed 6 times with purified heptane to obtain a prepolymerized catalyst comprising a metallocene-containing polyolefin.

[polymerization]
It carried out similarly to [Polymerization] of Example 1 using the above-mentioned prepolymerization catalyst.

  The results are shown in Table 1.

[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.

Example 15
[polymerization]
(First stage, polymerization of propylene)
450 g of propylene was charged into an autoclave having an internal volume of 2 L, and 1 ml of a toluene solution of methylaluminoxane (PMAO-S, manufactured by Tosoh Akzo Co., Ltd., 3.1 mmol-Al / ml) was introduced. Thereafter, the internal temperature of the autoclave was raised to 55 ° C. Next, 0.5 ml of a pre-activated toluene solution of methylaluminoxane (PMAO-S, manufactured by Tosoh Akzo Co., Ltd., 3.1 mmol-Al / ml) and rac-dimethylsilylenebis- (2-methyl-benzindenyl) were preliminarily activated at room temperature for 15 minutes. ) A total amount of 0.07 mg of zirconium dichloride and 0.03 mg of meso-dimethylsilylenebis- (2-methyl-benzindenyl) zirconium dichloride was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was performed for 70 minutes.

(Later, copolymerization of propylene and ethylene)
After the previous polymerization, ethylene gas was supplied to the concentration of 16.0 mol% at a gas phase concentration, and further, copolymerization was performed for 70 minutes while supplying the gas phase concentration of ethylene to be kept constant. After the completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 180 g of a white block polymer. The results are shown in Table 1.

[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.

Example 16
In the preparation of the supported metallocene catalyst of Example 1, 70 ml (0.005 mmol / ml toluene solution) of rac-dimethylsilylenebis- (2-methyl-benzindenyl) zirconium dichloride and bis (cyclopentadienyl) titanium dichloride were used. The toluene solution was 30 ml (0.005 mmol / ml toluene solution), the polymerization time in the former stage was 80 minutes, and the polymerization time in the latter stage was 60 minutes. The results are shown in Tables 1 and 2.

Comparative Example 1
In [Polymerization] of Example 1, the same procedure as in Example 1 was performed except that the polymerization time of the former stage was 10 minutes and the polymerization time of the latter stage was 110 minutes. The results are shown in Tables 1 and 2.

Comparative Example 2
In [Polymerization] of Example 1, the same procedure as in Example 1 was performed except that the polymerization time at the former stage was 120 minutes and the polymerization time at the latter stage was 20 minutes. The results are shown in Tables 1 and 2.

  The propylene-based block copolymer of the present invention can be suitably used as a polyolefin flexible film in various fields where conventional polyolefin films are used, and a resin film other than polyolefin such as a flexible PVC film is used. The present invention can also be suitably used in the fields that are used.

  For example, surface protective film, protective film for vehicle, dicing film, decorative film, wrap film, shrink film, stretch film, pallet stretch film, film for sealant, heat welding film, heat bonding film, patch film, banco base film , Label film, building material film, building material skin film, stationery film, adhesive base film, adhesive tape, binding tape, masking tape, display tape, packaging film, packaging tape, electrical insulation tape, marking film It can be used for agricultural films, house films, medical films, medical adhesive tapes, infusion bags, surgical tapes, and the like.

  Further, it is suitably used in various fields where conventional thermoplastic elastomers are used.

It is a flowchart which shows the typical polymerization method of this invention. It is a flowchart which shows the typical polymerization method of this invention.

Claims (12)

Following formula
Q (2-methyl-benzindenyl) ₂ MX ¹ X ² (1)
(In the formula, M represents a zirconium atom or a hafnium atom. Q is a group capable of cross-linking 2-methyl-benzindenyl group and 2-methyl-benzindenyl group, which is a divalent hydrocarbon group, unsubstituted. A silylene group or a hydrocarbon-substituted silylene group, X ¹ and X ² may be the same or different and each represents a hydrogen, halogen, or hydrocarbon group.) A metallocene compound and an aluminoxane compound exhibiting at least two different stereospecificities , comprising a metallocene compound having low specificity or essentially no stereospecificity in a mixing ratio (molar ratio) of 5/95 to 95/5 , and Copolymer component of polypropylene component, propylene and ethylene in the presence of a catalyst comprising a non-coordinating ionic compound Ingredients that are produced in stages, and are composed of a polypropylene component and a copolymer component of propylene and ethylene, and are eluted at temperatures up to 80 ° C. by temperature-temperature elution fractionation using an o-dichlorobenzene solvent. 40 to 99% by weight of the total, and the component that elutes at a temperature of 80 ° C. or higher is 60 to 1% by weight of the total, and the melt is measured at 230 ° C. under a load of 2.16 kg according to ASTM-D1238. A propylene-based block copolymer having a flow rate of 0.01 to 50 g / 10 min. In the formula (1), R ¹ And R ² Are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and X ¹ And X ² 2. The propylene-based block copolymer according to claim 1, which is a chiral racemic metallocene compound in which are the same or different halogen atoms or hydrocarbon groups, and Q is a hydrocarbon-substituted silylene group. The chiral racemic metallocene compound comprises rac-dimethylsilylene bis (2-methyl-benzindenyl) zirconium dichloride, rac-diphenylsilylene bis (2-methyl-benzindenyl) zirconium dichloride, rac-dimethylsilylene bis (2-methyl-). The propylene-based block copolymer according to claim 2, selected from the group consisting of benzindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-benzindenyl) zirconium dimethyl, and a compound in which zirconium of the above compound is replaced with hafnium. Coalescence . The metallocene compound having low stereospecificity or essentially no stereospecificity is a meso-type compound of the metallocene compound having isospecificity; bis (cyclopentadienyl) titanium dichloride, dimethylsilylene (bisfluorenyl) zirconium The propylene-based block copolymer according to any one of claims 1 to 3, which is selected from the group consisting of dichloride and ethylenebis (fluorenyl) zirconium dichloride; and a compound obtained by replacing zirconium in the compound with hafnium . The mixing ratio (molar ratio) of the metallocene compound having isospecificity and the metallocene compound having low stereospecificity or essentially no stereospecificity is 10/90 to 90/10 . The propylene-based block copolymer according to any one of the above.   6. The ethylene monomer unit in a component eluting at a temperature of 80 ° C. or higher by a temperature rising elution fractionation method using the o-dichlorobenzene solvent is 3% by weight or less. The propylene-based block copolymer described in 1.   7. The ethylene monomer unit in a component eluted at a temperature up to 80 ° C. by a temperature rising elution fractionation method using the o-dichlorobenzene solvent is 4 to 50 wt%. The propylene-based block copolymer according to item.   The propylene-based block according to claim 7, wherein the ethylene monomer unit is 4 to 15% by weight in a component eluted at a temperature up to 80 ° C by a temperature-temperature elution elution fractionation method using the o-dichlorobenzene solvent. Copolymer.   (1) Glass transition temperature (Tg) is −20 ° C. or lower, and (2) Weight average molecular weight (Mw) by gel permeation chromatography is 50,000 g / min. The propylene according to any one of claims 1 to 8, wherein a component having a molecular weight of 10,000 or more and (3) a molecular weight of 10,000 g / mol or less is 10% by weight or less of a toluene soluble amount measured at a temperature of -40 ° C. Block copolymer.   The propylene-based block copolymer according to any one of claims 1 to 9, wherein the toluene-soluble component measured at a temperature of -40 ° C is 5 to 30% by weight of the whole.   The film formed by shape | molding the propylene-type block copolymer of any one of Claims 1-10.   The film according to claim 11, which is a surface protective film.

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