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WO2024210117A1 - Composition de polymère à base de propylène, film, et film multicouche - Google Patents

Composition de polymère à base de propylène, film, et film multicouche Download PDF

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Publication number
WO2024210117A1
WO2024210117A1 PCT/JP2024/013567 JP2024013567W WO2024210117A1 WO 2024210117 A1 WO2024210117 A1 WO 2024210117A1 JP 2024013567 W JP2024013567 W JP 2024013567W WO 2024210117 A1 WO2024210117 A1 WO 2024210117A1
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Prior art keywords
propylene
mass
olefin copolymer
less
based polymer
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English (en)
Japanese (ja)
Inventor
一輝 波戸
友章 水川
知也 村上
大貴 近藤
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Prime Polymer Co Ltd
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Prime Polymer Co Ltd
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Priority to JP2025513141A priority Critical patent/JPWO2024210117A1/ja
Priority to KR1020257023779A priority patent/KR20250123893A/ko
Priority to CN202480013073.6A priority patent/CN120693368A/zh
Publication of WO2024210117A1 publication Critical patent/WO2024210117A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to a propylene-based polymer composition, a film, and a multilayer film.
  • Patent Document 1 also discloses an unstretched polypropylene film with particularly excellent rigidity that uses a specific propylene-based polymer.
  • the present invention aims to provide a propylene-based polymer composition capable of forming a film having a well-balanced and excellent rigidity and TD tensile strength compared to conventionally known propylene-based polymer compositions, a film having the above-mentioned physical properties, and a multilayer film having the above-mentioned film.
  • the present invention relates to, for example, the following [1] to [7].
  • [1] A propylene- ⁇ -olefin copolymer (A) having an intrinsic viscosity [ ⁇ ] of 10 dl/g or more and 15 dl/g or less as measured in a tetralin solvent at 135° C.
  • the propylene-based polymer (B) includes a propylene- ⁇ -olefin copolymer (B-1) having an intrinsic viscosity [ ⁇ ] of 0.5 dl/g or more and 2 dl/g or less, a content of structural units derived from ⁇ -olefins (excluding propylene) of 0.1 mol% or more and 10 mol% or less, and a molecular weight distribution (Mw/Mn (Mn is number average molecular weight, Mw is weight average molecular weight)) of 10 or more and 100 or less, and a propylene-based polymer (B-2) having an intrinsic viscosity [ ⁇ ] of 0.5 dl/g or more and 5 dl/g or less, a content of structural units derived from ⁇ -olefins (excluding propylene) of 1 mol% or more and 9 mol% or less, and a molecular weight distribution (Mw/Mn (Mn is number average molecular weight
  • a film comprising the propylene polymer composition according to any one of [1] to [5] above.
  • the propylene-based polymer composition of the present invention can be suitably produced into a film having a good balance between rigidity and TD tensile strength, as well as into a multilayer film having the film.
  • FIG. 2 is a diagram showing the balance of physical properties in the examples of the present invention and some comparative examples, when the comonomer content of the propylene-based polymer (B-2) is 8.5 mol %.
  • the propylene polymer composition of the present invention contains a propylene/ ⁇ -olefin copolymer (A) and a propylene polymer (B) which will be described below.
  • the propylene/ ⁇ -olefin copolymer (A) and the propylene-based polymer (B) described below may each contain one type of polymer or two or more types of polymers, unless otherwise specified.
  • the intrinsic viscosity [ ⁇ ] of the propylene/ ⁇ -olefin copolymer (A) measured in a tetralin solvent at 135° C. is in the range of 10 dl/g or more and 15 dl/g or less, preferably 10 dl/g or more and 13 dl/g or less, and more preferably 10.5 dl/g or more and 11.5 dl/g or less.
  • intrinsic viscosity [ ⁇ ] measured at 135°C in tetralin solvent
  • the rigidity of the film obtained from the propylene-based polymer composition is good.
  • the intrinsic viscosity [ ⁇ ] is equal to or lower than the upper limit, the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the propylene- ⁇ -olefin copolymer (A) is a copolymer of propylene and an ⁇ -olefin (excluding propylene).
  • the ⁇ -olefin include ⁇ -olefins having 2 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene.
  • ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene are preferred.
  • the ⁇ -olefins can be used alone or in combination.
  • the propylene/ ⁇ -olefin copolymer (A) may be a random copolymer or a block copolymer, but is more preferably a random copolymer in that it has excellent transparency and a good balance between rigidity and TD tensile strength.
  • the content of the structural units derived from an ⁇ -olefin (excluding propylene) in the propylene- ⁇ -olefin copolymer (A) is 0.1 mol % or more and 6.0 mol % or less, preferably 0.5 mol % or more and 5.5 mol % or less, and more preferably 1.0 mol % or more and less than 5.0 mol %, assuming that the total content of the structural units derived from propylene and the structural units derived from an ⁇ -olefin (excluding propylene) is 100 mol %.
  • the content can be measured by 13 C-NMR.
  • the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the amount of structural units derived from ⁇ -olefin is equal to or less than the upper limit, the rigidity of the film obtained from the propylene-based polymer composition is good.
  • the polymerization of propylene with the ⁇ -olefin can be carried out by a known method such as slurry polymerization, bulk polymerization, etc. It is also preferable to use a catalyst for producing polypropylene, which will be described later.
  • the propylene- ⁇ -olefin copolymer (A) is preferably produced by bulk polymerization of the raw material monomers in the absence of hydrogen, at a polymerization temperature of preferably 20 to 80°C, more preferably 40 to 70°C, and at a polymerization pressure of generally normal pressure to 9.8 MPa, preferably 0.2 to 4.9 MPa.
  • Propylene- ⁇ -olefin copolymer (A) can be produced by the above-mentioned method, but for example, propylene- ⁇ -olefin copolymer (A) and propylene- ⁇ -olefin copolymer (B-1) described below can also be produced in one polymerization system or two or more polymerization systems.
  • a propylene-based polymer containing a relatively high molecular weight propylene- ⁇ -olefin copolymer (A) and a relatively low molecular weight propylene- ⁇ -olefin copolymer (B-1) can be obtained by two or more multi-stage polymerizations.
  • the propylene/ ⁇ -olefin copolymer containing the propylene/ ⁇ -olefin copolymer (A) and the propylene/ ⁇ -olefin copolymer (B-1) is also referred to as the propylene/ ⁇ -olefin copolymer (C).
  • propylene- ⁇ -olefin copolymer (C) for example, a method in which propylene and an ⁇ -olefin are polymerized in a multi-stage polymerization of two or more stages in the presence of a catalyst for producing polypropylene, which will be described later, is preferred.
  • this method involves polymerizing propylene in the first polymerization stage substantially in the absence of hydrogen to produce a propylene- ⁇ -olefin copolymer (A) having a relatively high molecular weight, and then producing a propylene- ⁇ -olefin copolymer (B-1) having a relatively low molecular weight in the second and subsequent polymerization stages.
  • A propylene- ⁇ -olefin copolymer
  • B-1 propylene- ⁇ -olefin copolymer having a relatively low molecular weight
  • the production order (polymerization order) of the propylene/ ⁇ -olefin copolymer (A) and the propylene/ ⁇ -olefin copolymer (B-1) is preferably such that in the first stage, a relatively high molecular weight propylene/ ⁇ -olefin copolymer (A) is produced substantially in the absence of hydrogen, and then in the second stage or later, a relatively low molecular weight propylene/ ⁇ -olefin copolymer (B-1) is produced, for example, in the presence of hydrogen.
  • the production order can be reversed, but in order to produce a relatively low molecular weight propylene/ ⁇ -olefin copolymer (B-1) in the first stage and then produce a relatively high molecular weight propylene/ ⁇ -olefin copolymer (A) in the second stage or later, it is necessary to remove as much of the molecular weight regulator such as hydrogen contained in the reaction product of the first stage before the start of polymerization in the second stage or later, which makes the polymerization apparatus complex and makes it difficult to increase the intrinsic viscosity [ ⁇ ] in the second stage or later.
  • the molecular weight regulator such as hydrogen contained in the reaction product of the first stage before the start of polymerization in the second stage or later
  • the polymerization of each stage in the multi-stage polymerization can be carried out continuously or batchwise, but it is preferable to carry out the polymerization in the batchwise manner.
  • the residence time distribution can cause compositional unevenness between the polymer particles, which can increase fish eyes (FE).
  • FE fish eyes
  • by polymerizing in the batchwise manner it is possible to obtain a propylene- ⁇ -olefin copolymer (C) with low FE. Therefore, by adopting the batchwise method, it is possible to obtain a film with low FE, despite the use of a high molecular weight propylene- ⁇ -olefin copolymer (A).
  • a catalyst for producing polypropylene (hereinafter, also simply referred to as "catalyst") that can be used in the production of the propylene/ ⁇ -olefin copolymer (A) can be formed, for example, from a solid catalyst component containing magnesium, titanium, and a halogen as essential components, an organometallic compound catalyst component such as an organoaluminum compound, and an electron-donor compound catalyst component such as an organosilicon compound.
  • the catalyst components that can be used include the following:
  • the support constituting the solid catalyst component is preferably a support obtained from metallic magnesium, an alcohol, and a halogen and/or a halogen-containing compound.
  • the metallic magnesium in granular, ribbon, powdered, etc. form can be used.
  • the metallic magnesium does not have a coating such as magnesium oxide formed on the surface.
  • the alcohol it is preferable to use a lower alcohol having 1 to 6 carbon atoms, and in particular, when ethanol is used, a carrier that significantly improves the expression of catalytic performance is obtained.
  • the amount of alcohol used is preferably 2 to 100 moles, more preferably 5 to 50 moles, per mole of metallic magnesium.
  • One or more types of alcohol can be used.
  • halogen chlorine, bromine, and iodine are preferred, and iodine is more preferred.
  • halogen-containing compound MgCl2 and MgI2 are preferred.
  • the amount of halogen or halogen-containing compound used is usually 0.0001 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more of halogen atom or halogen atom in the halogen-containing compound per gram atom of metallic magnesium.
  • the halogen and halogen-containing compound can each be used one or more kinds.
  • a method for obtaining a carrier by reacting metallic magnesium with an alcohol and a halogen and/or halogen-containing compound is, for example, to react metallic magnesium with an alcohol and a halogen and/or halogen-containing compound under reflux (e.g., about 79°C) until no hydrogen gas is generated (usually 20 to 30 hours).
  • the reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.
  • the obtained support When used for the synthesis of a solid catalyst component, it may be used after drying, or after filtering and washing with an inert solvent such as heptane.
  • the carrier obtained is nearly granular, and has a sharp particle size distribution. Furthermore, the variation in particle size is very small even when each particle is examined.
  • the sphericity (S) represented by the following formula (I) is less than 1.60, particularly less than 1.40, and the particle size distribution index (P) represented by the following formula (II) is less than 5.0, particularly less than 4.0.
  • E1 represents the contour length of the projection of a particle
  • E2 represents the perimeter of a circle equal to the projected area of the particle.
  • D90 refers to the particle size corresponding to a mass cumulative fraction of 90%.
  • the mass sum of the particle group smaller than the particle size represented by D90 is 90% of the total mass sum of all particles.
  • D10 refers to the particle size corresponding to a mass cumulative fraction of 10%.
  • the solid catalyst component is usually obtained by contacting the support with at least a titanium compound.
  • the contact with the titanium compound may be carried out in multiple batches.
  • titanium compounds include titanium compounds represented by the general formula (III).
  • X 1 is a halogen atom, and particularly preferably a chlorine atom
  • R 1 is a hydrocarbon group having 1 to 10 carbon atoms, and preferably a linear or branched alkyl group ; When present, they may be the same or different from one another and n is an integer from 0 to 4.
  • titanium compounds include Ti(O-i -C3H7 ) 4 , Ti(O- C4H9 ) 4 , TiCl(O- C2H5 ) 3 , TiCl (O-i - C3H7 ) 3 , TiCl (O- C4H9 ) 3 , TiCl2 ( O - C4H9 ) 2 , TiCl2 (O-i - C3H7 ) 2 and TiCl4 , with TiCl4 being preferred.
  • the titanium compounds can be used alone or in combination.
  • the solid catalyst component is usually obtained by further contacting the carrier with an electron donor compound.
  • An example of the electron donor compound is di-n-butyl phthalate.
  • One or more types of electron donor compounds can be used.
  • a halogen-containing silicon compound such as silicon tetrachloride can be brought into contact with the support.
  • a halogen-containing silicon compound such as silicon tetrachloride can be brought into contact with the support.
  • One or more halogen-containing silicon compounds can be used.
  • the solid catalyst component can be prepared by a known method.
  • an inert hydrocarbon such as pentane, hexane, heptane or octane is used as a solvent, and the carrier, electron donor compound and halogen-containing silicon compound are added to the solvent, followed by adding the titanium compound while stirring.
  • 0.01 to 10 moles, preferably 0.05 to 5 moles of the electron donor compound are added per mole of carrier in terms of magnesium atoms
  • 1 to 50 moles, preferably 2 to 20 moles of the titanium compound are added per mole of carrier in terms of magnesium atoms, and the contact reaction is carried out at 0 to 200°C for 5 minutes to 10 hours, preferably at 30 to 150°C for 30 minutes to 5 hours.
  • the solid catalyst component may also be a component obtained by contacting a liquid magnesium compound with a liquid titanium compound in the presence of an electron donor compound.
  • the contact with the liquid titanium compound may be carried out in multiple batches.
  • the liquid magnesium compound can be obtained, for example, by contacting a known magnesium compound with an alcohol, preferably in the presence of a liquid hydrocarbon medium, to form a liquid.
  • the magnesium compound include magnesium halides such as magnesium chloride and magnesium bromide.
  • the alcohol include aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and 2-ethylhexyl alcohol.
  • the liquid hydrocarbon medium include hydrocarbon compounds such as heptane, octane, and decane.
  • the amount of alcohol used in preparing the liquid magnesium compound is usually 1.0 to 25 moles, preferably 1.5 to 10 moles, per mole of the magnesium compound.
  • One or more types of liquid magnesium compounds can be used.
  • the liquid titanium compound may be the titanium compound represented by the general formula (III) described above.
  • the amount of the liquid titanium compound used per mole of magnesium atom (Mg) contained in the liquid magnesium compound is usually 0.1 to 1000 moles, preferably 1 to 200 moles.
  • One or more types of liquid titanium compounds may be used.
  • the electron donor compound examples include dicarboxylic acid ester compounds such as phthalic acid esters, acid anhydrides such as phthalic anhydride, organic silicon compounds such as dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, and cyclohexylmethyldimethoxysilane, polyethers, acid halides, acid amides, nitriles, and organic acid esters.
  • the amount of the electron donor compound used per mole of magnesium atom (Mg) contained in the liquid magnesium compound is usually 0.01 to 5 moles, and preferably 0.1 to 1 mole.
  • One or more types of electron donor compounds can be used.
  • the temperature during contact is usually from -70 to 200°C, preferably from 10 to 150°C.
  • organometallic compound catalyst component is preferably an organoaluminum compound, for example, a compound represented by the general formula (IV):
  • R 2 is an alkyl group, a cycloalkyl group or an aryl group having 1 to 10 carbon atoms
  • X 2 is a halogen atom or an alkoxy group, preferably a chlorine atom or a bromine atom
  • n is 1 to It is an integer number 3.
  • organoaluminum compounds include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum monoethoxide, and ethylaluminum sesquichloride.
  • the organoaluminum compounds can be used alone or in combination.
  • the amount of the organometallic compound catalyst component used is usually 0.01 to 20 moles, preferably 0.05 to 10 moles, per mole of titanium atom in the solid catalyst component.
  • the electron donor compound to be supplied to the polymerization system is preferably an organosilicon compound, such as dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diethylaminotriethoxysilane, diisopropyldimethoxysilane, or cyclohexylisobutyldimethoxysilane.
  • organosilicon compound such as dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diethylaminotriethoxysilane, diisopropyldimethoxysilane, or cyclohexylisobutyldimethoxysilane.
  • the organosilicon compounds can be used alone or in combination.
  • the amount of the electron donor compound used is usually 0.01 to 20 moles, preferably 0.1 to 5 moles, per mole of titanium atom in the solid catalyst component.
  • the solid catalyst component is preferably used for polymerization after pretreatment such as preliminary polymerization.
  • an inert hydrocarbon such as pentane, hexane, heptane, or octane is used as a solvent, and the solid catalyst component, the organometallic compound catalyst component, and, if necessary, the electron donor compound component are charged into the solvent, and propylene is supplied while stirring to cause a reaction.
  • Propylene is preferably supplied under a propylene partial pressure higher than atmospheric pressure, and pretreatment is preferably performed at 0 to 100° C. for 0.1 to 24 hours. After completion of the reaction, it is preferable to wash the pretreated product using an inert hydrocarbon such as n-hexane or n-heptane.
  • the intrinsic viscosity [ ⁇ ] of the propylene polymer (B) is in the range of 0.5 dl/g to 5 dl/g, preferably 0.5 dl/g to 3 dl/g, more preferably 0.5 dl/g to 2 dl/g.
  • the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the intrinsic viscosity [ ⁇ ] is equal to or lower than the upper limit, the fluidity of the propylene-based polymer composition is high and the moldability is good.
  • the propylene polymer (B) is a copolymer of propylene and an ⁇ -olefin (excluding propylene).
  • the ⁇ -olefin include ⁇ -olefins having 2 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene.
  • ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene are preferred.
  • the ⁇ -olefins can be used alone or in combination.
  • the ⁇ -olefin (excluding propylene) content of the propylene polymer (B) is preferably from 1 mol % to 10 mol %, more preferably from 5 mol % to 8.5 mol %.
  • the method for producing the propylene polymer (B) is not particularly limited, and for example, the propylene polymer (B) can be produced by copolymerizing propylene and an ⁇ -olefin using a Ziegler-Natta catalyst or a metallocene catalyst, and a commercially available propylene polymer can be used as the propylene polymer (B).
  • the propylene polymer (B) preferably contains a propylene- ⁇ -olefin copolymer (B-1) and a propylene polymer (B-2).
  • the intrinsic viscosity [ ⁇ ] of the propylene/ ⁇ -olefin copolymer (B-1) is in the range of 0.5 dl/g or more and 2 dl/g or less, preferably 0.5 dl/g or more and 1.5 dl/g or less, and more preferably 0.7 dl/g or more and 1.2 dl/g or less.
  • the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the intrinsic viscosity [ ⁇ ] is equal to or lower than the upper limit, the fluidity of the propylene-based polymer composition is high and the moldability is good.
  • Propylene- ⁇ -olefin copolymer (B-1) is a copolymer of propylene and ⁇ -olefin (excluding propylene).
  • ⁇ -olefins include ⁇ -olefins having 2 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene.
  • ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene are preferred.
  • One or more types of ⁇ -olefins can be used.
  • the content of the structural units derived from an ⁇ -olefin (excluding propylene) in the propylene- ⁇ -olefin copolymer (B-1) is 0.1 mol % to 10 mol %, preferably 0.1 mol % to 10 mol %, more preferably 0.1 mol % to 6 mol %, assuming that the sum of the content of the structural units derived from propylene and the content of the structural units derived from an ⁇ -olefin is 100 mol %.
  • the content can be measured by 13 C-NMR.
  • the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the amount of structural units derived from ⁇ -olefin is equal to or less than the upper limit, the rigidity of the film obtained from the propylene-based polymer composition is good.
  • the molecular weight distribution (Mw/Mn) of the propylene- ⁇ -olefin copolymer (B-1), measured by the method employed in the examples described below, is 10 to 100, preferably 10 to 50, and more preferably 10 to 20.
  • Mn is the number average molecular weight
  • Mw is the weight average molecular weight.
  • Mw/Mn When Mw/Mn is equal to or greater than the lower limit, dispersibility with the propylene- ⁇ -olefin copolymer (A) is good, and a film with low FE can be produced.
  • Mw/Mn is equal to or less than the upper limit, the propylene-based polymer composition contains less oligomer components, suppressing smoke generation during molding and stickiness of the film.
  • the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the propylene/ ⁇ -olefin copolymer (B-1) can be produced by the method described in the section on the production method of the propylene/ ⁇ -olefin copolymer (A) above.
  • the propylene- ⁇ -olefin copolymer (B-1) is preferably produced by polymerizing the raw material monomers in the presence of hydrogen as a molecular weight regulator under conditions of a polymerization temperature of preferably 20 to 80°C, more preferably 40 to 70°C, and a polymerization pressure of generally normal pressure to 9.8 MPa, preferably 0.2 to 4.9 MPa.
  • the intrinsic viscosity [ ⁇ ] of the propylene polymer (B-2) is in the range of 0.5 dl/g to 5 dl/g, preferably 0.5 dl/g to 3 dl/g, more preferably 1 dl/g to 2 dl/g.
  • the melt tension of the propylene-based polymer composition is high, and the film moldability and the TD tensile strength of the film obtained from the propylene-based polymer composition are good.
  • the intrinsic viscosity [ ⁇ ] is equal to or lower than the upper limit, the fluidity of the propylene-based polymer composition is high, and the moldability is good.
  • the propylene-based polymer (B-2) is a copolymer of propylene and an ⁇ -olefin (excluding propylene).
  • the ⁇ -olefin include ⁇ -olefins having 2 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene.
  • ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene are preferred.
  • One or more types of ⁇ -olefins can be used.
  • the content of the structural units derived from an ⁇ -olefin (excluding propylene) in the propylene-based polymer (B-2) is 1 mol % to 9 mol %, preferably 3 mol % to 9 mol %, and more preferably 5 mol % to 9 mol %, assuming that the sum of the content of the structural units derived from propylene and the content of the structural units derived from an ⁇ -olefin is 100 mol %.
  • the content can be measured by 13 C-NMR.
  • the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the amount of structural units derived from ⁇ -olefin is equal to or less than the upper limit, the rigidity of the film obtained from the propylene-based polymer composition is good.
  • the Mw/Mn of the propylene polymer (B-2) is 2 or more and less than 10, preferably 3 or more and less than 10, and more preferably 4 or more and less than 10.
  • Mw/Mn When Mw/Mn is equal to or greater than the lower limit, the fluidity is good and the resin pressure during molding can be suppressed. When Mw/Mn is equal to or less than the upper limit, the oligomer components in the propylene-based polymer composition are reduced, smoke generation during molding and stickiness of the film can be suppressed, and the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the method for producing the propylene-based polymer (B-2) is not particularly limited.
  • the propylene-based polymer (B-2) can be produced by copolymerizing propylene and an ⁇ -olefin using a Ziegler-Natta catalyst or a metallocene catalyst.
  • a commercially available polypropylene-based polymer can be used.
  • the propylene/ ⁇ -olefin copolymer (C) contains the propylene/ ⁇ -olefin copolymer (A) and the propylene/ ⁇ -olefin copolymer (B-1).
  • the mass fraction of the propylene- ⁇ -olefin copolymer (A) is 5% by mass or more and 50% by mass or less, and the mass fraction of the propylene-based polymer (B-1) is 50% by mass or more and 95% by mass or less, where the total mass fraction of the propylene- ⁇ -olefin copolymer (A) and the propylene- ⁇ -olefin copolymer (B-1) is 100% by mass.
  • the mass fraction of the propylene- ⁇ -olefin copolymer (A) is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and the mass fraction of the propylene-based polymer (B-1) is preferably 60% by mass or more and 90% by mass or less, more preferably 65% by mass or more and 85% by mass or less.
  • the mass fractions of the propylene/ ⁇ -olefin copolymer (A) and the propylene/ ⁇ -olefin copolymer (B-1) are within the ranges, the dispersibility of the propylene/ ⁇ -olefin copolymer (C) and the propylene-based polymer (B-2) is good, and the film obtained from the propylene-based polymer composition has a well-balanced and excellent stiffness and TD tensile strength.
  • the propylene/ ⁇ -olefin copolymer (C) can be produced by the method described in the production conditions section for the propylene/ ⁇ -olefin copolymer (A).
  • the propylene polymer composition of the present invention may contain additives such as weathering stabilizers, heat stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, decomposition agents, pigments, dyes, nucleating agents, plasticizers, hydrochloric acid absorbers, antioxidants, crosslinking agents, crosslinking accelerators, reinforcing agents, fillers, softeners, processing aids, activators, moisture absorbents, adhesives, flame retardants, and release agents, within the scope of the present invention.
  • additives such as weathering stabilizers, heat stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, decomposition agents, pigments, dyes, nucleating agents, plasticizers, hydrochloric acid absorbers, antioxidants, crosslinking agents, crosslinking accelerators, reinforcing agents, fillers, softeners, processing aids, activators, moisture absorbents, adhesives, flame
  • the propylene polymer composition according to the present invention contains the propylene/ ⁇ -olefin copolymer (A) and the propylene polymer (B).
  • the mass fraction of the propylene- ⁇ -olefin copolymer (A) is 0.1% by mass or more and 8% by mass or less, and the mass fraction of the propylene-based polymer (B) is 92% by mass or more and 99.9% by mass or less, where the sum of the mass fractions of the propylene- ⁇ -olefin copolymer (A) and the propylene-based polymer (B) is 100% by mass.
  • the mass fraction of the propylene- ⁇ -olefin copolymer (A) is preferably 0.5% by mass or more and 7% by mass or less, more preferably 0.5% by mass or more and 6% by mass or less, and the mass fraction of the propylene-based polymer (B) is preferably 93% by mass or more and 99.5% by mass or less, more preferably 94% by mass or more and 99.5% by mass or less.
  • the film obtained from the propylene-based polymer composition has a good balance between rigidity and TD tensile strength.
  • the melting point of the propylene polymer composition measured under the conditions employed in the examples described below, is 110°C or higher and 150°C or lower, preferably 115°C or higher and 150°C or lower, and more preferably 120°C or higher and 150°C or lower.
  • the melting point is equal to or higher than the lower limit, the rigidity of the film obtained from the propylene-based polymer composition is good.
  • the melting point is equal to or lower than the upper limit, the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the content of the structural units derived from ⁇ -olefins (excluding propylene) in the propylene-based polymer composition is 1 mol % to 10 mol %, preferably 3 mol % to 9 mol %, and more preferably 5 mol % to 8 mol %, based on 100 mol % of the total structural units of the polymer in the composition.
  • the content can be measured by 13C -NMR.
  • the TD tensile strength of the film obtained from the propylene-based polymer composition is good.
  • the amount of structural units derived from ⁇ -olefin is equal to or less than the upper limit, the rigidity of the film obtained from the propylene-based polymer composition is good.
  • the melt flow rate (MFR) of the propylene polymer composition measured at 230°C under a load of 2.16 kg is 1 g/10 min or more and 10 g/10 min or less, preferably 2 g/10 min or more and 9 g/10 min or less, and more preferably 4 g/10 min or more and 7 g/10 min or less.
  • the MFR of the propylene-based polymer composition When the MFR of the propylene-based polymer composition is equal to or higher than the lower limit, the fluidity of the propylene-based polymer composition is high and the moldability is good. When the MFR of the propylene-based polymer composition is equal to or lower than the upper limit, the TD tensile strength is good.
  • the propylene-based polymer composition according to the present invention may also contain the propylene- ⁇ -olefin copolymer (A) and the propylene- ⁇ -olefin copolymer (B-1) containing the propylene- ⁇ -olefin copolymer (C), and the propylene-based polymer (B-2).
  • the intrinsic viscosities [ ⁇ ] of the propylene- ⁇ -olefin copolymer (B-1) and the propylene polymer (B-2) contained in the propylene polymer composition preferably satisfy the relationship (the intrinsic viscosity [ ⁇ ] of the copolymer (B-1)) ⁇ (the intrinsic viscosity [ ⁇ ] of the polymer (B-2)) and the difference between the two intrinsic viscosities [ ⁇ ] is 3 dl/g or less.
  • surface roughness (poor appearance) is less likely to occur during film formation.
  • the film made of the composition containing the propylene- ⁇ -olefin copolymer (A) and the propylene-based polymer (B) or the composition containing the propylene- ⁇ -olefin copolymer (A), the propylene- ⁇ -olefin copolymer (B-1), and the propylene-based polymer (B-2) may be surface-treated from the viewpoint of improving printability, improving adhesion, and improving adhesion to an adhesive. Specifically, surface treatments such as corona treatment, flame treatment, plasma treatment, primer coat treatment, and ozone treatment (also referred to as "surface activation treatments") may be performed.
  • the composition of the present invention requires only a small amount of energy output for surface treatment, and the surface treatment can be efficiently performed in a short time.
  • the mass fraction of the propylene- ⁇ -olefin copolymer (C) is 1% by mass or more and 30% by mass or less, and the mass fraction of the propylene-based polymer (B-2) is 70% by mass or more and 99% by mass or less, where the total mass fraction of the propylene- ⁇ -olefin copolymer (C) and the propylene-based polymer (B-2) is 100% by mass.
  • the mass fraction of the propylene-based polymer (C) is preferably 1% by mass or more and 25% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and the mass fraction of the propylene-based polymer (B-2) is preferably 75% by mass or more and 99% by mass or less, more preferably 80% by mass or more and 99% by mass or less.
  • the film obtained from the propylene-based polymer composition has a good balance between rigidity and TD tensile strength.
  • the propylene polymer composition of the present invention can be produced by blending the above-mentioned components.
  • the components may be blended sequentially in any order, or may be mixed simultaneously.
  • a multi-stage mixing method may be employed in which some components are mixed and then other components are mixed.
  • a propylene- ⁇ -olefin copolymer (C) containing a relatively high molecular weight propylene- ⁇ -olefin copolymer (A) and a relatively low molecular weight propylene- ⁇ -olefin copolymer (B-1) obtained by two or more multi-stage polymerization can be mixed with a propylene-based polymer (B-2) to produce a propylene-based polymer composition, and additives may be added as necessary.
  • the components can be mixed or melt-kneaded simultaneously or sequentially using a mixing device such as a Banbury mixer, single-screw extruder, twin-screw extruder, or high-speed twin-screw extruder.
  • a mixing device such as a Banbury mixer, single-screw extruder, twin-screw extruder, or high-speed twin-screw extruder.
  • the polymer temperature during melt-kneading is usually 180 to 280°C, preferably 180 to 260°C.
  • the propylene-based polymer composition may contain at least one structural unit derived from biomass-derived propylene or ⁇ -olefin.
  • the same type of monomer constituting the polymer may be only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers.
  • the biomass-derived monomer is a monomer obtained from any renewable natural raw material, such as a plant-derived or animal-derived raw material including fungi, yeast, algae, and bacteria, and its residue, and contains about 1 ⁇ 10 ⁇ 12 of 14 C isotope as carbon and has a biomass carbon concentration (pMC) of about 100 (pMC) measured in accordance with ASTM D6866.
  • Biomass-derived propylene and ⁇ -olefins can be obtained, for example, by a conventionally known method. It is preferable that the propylene-based polymer composition contains a structural unit derived from a biomass-derived monomer from the viewpoint of reducing the environmental load (mainly reducing greenhouse gases).
  • the polymer production conditions such as the polymerization catalyst, polymerization process, and polymerization temperature
  • the polymer production conditions are the same, even if the raw material monomer contains a biomass-derived monomer, the molecular structure, other than the inclusion of 14C isotopes at a ratio of about 1 ⁇ 10 -12 to 1 ⁇ 10 -14 , is the same as that of a propylene- ⁇ -olefin copolymer made of a fossil fuel-derived monomer. Therefore, the performance is said to be the same.
  • the propylene-based polymer composition may contain at least one structural unit derived from chemically recycled propylene or ⁇ -olefin.
  • the same type of monomer constituting the polymer may be only chemically recycled monomer, only fossil fuel-derived monomer, or may contain chemically recycled monomer and fossil fuel-derived monomer and/or biomass-derived monomer.
  • Chemically recycled propylene and ⁇ -olefin may be obtained by a conventionally known method, for example. It is preferable that the propylene-based polymer composition contains a structural unit derived from chemically recycled monomer from the viewpoint of reducing the environmental load (mainly reducing waste).
  • the chemically recycled monomer is a monomer obtained by depolymerizing or pyrolyzing a polymer such as waste plastic back to a monomer unit such as propylene, and a monomer produced using the monomer as a raw material. Therefore, if the polymer production conditions such as the polymerization catalyst, polymerization process, and polymerization temperature are the same, the molecular structure is the same as that of a propylene- ⁇ -olefin copolymer made of a fossil fuel-derived monomer. Therefore, the performance is said to be the same.
  • molded products can be obtained by molding the polypropylene polymer composition of the present invention according to known molding techniques.
  • molding techniques include film molding, sheet molding, calendar molding, compressed air molding, vacuum molding, pipe molding, profile extrusion molding, blow molding, laminate molding, injection molding, injection stretch blow molding, compression molding, injection compression molding, etc.
  • the film of the present invention is formed from the propylene-based polymer composition of the present invention.
  • the thickness of the film of the present invention is usually less than 200 ⁇ m, preferably 10 to 150 ⁇ m, and more preferably 15 to 100 ⁇ m. Since the film of the present invention has excellent rigidity, it is easy to make it thinner.
  • film manufacturing methods include extrusion molding methods such as the T-die method and inflation method, compression molding, calendar molding, and casting.
  • Film formation can be carried out, for example, as follows.
  • the components constituting the propylene-based polymer composition may be directly charged into a hopper or the like of a film forming machine, or the components may be mixed in advance using a ribbon blender, Banbury mixer, Henschel mixer, super mixer, or the like, or may be melt-kneaded using a kneader such as a single-screw or twin-screw extruder or roll to obtain a propylene-based polymer composition, which is then molded into a film.
  • a kneader such as a single-screw or twin-screw extruder or roll
  • the above components are fed into an extruder and melt-kneaded at a temperature usually between 180 and 280°C, preferably between 200 and 270°C, and then extruded into a film from the die lip of a T-die.
  • the molten film is cooled and taken up by a take-up machine such as a nip roll to obtain the film.
  • Methods for cooling the molten film include, for example, cooling using rolls and air cooling using the air knife method or air chamber method, narrow pressure cooling using the polishing roll method, swing roll method, belt casting method, etc., and contact cooling using a refrigerant such as water cooling.
  • the resulting film can be subjected to the film treatment methods typically used in film molding, such as corona discharge treatment and liquid coating treatment.
  • the multilayer film of the present invention has the film of the present invention.
  • the multilayer film may be a multilayer film having two or more layers of the film of the present invention, or may be a multilayer film having one or more layers of the film of the present invention and one or more other layers. By making it a multilayer structure, it is possible to impart various functions to the film. Methods that can be used in this case include a co-extrusion method and an extrusion coating method.
  • Other layers include, for example, a barrier layer for gases such as water vapor and oxygen, a sound absorbing layer, a light shielding layer, an adhesive layer, a pressure sensitive adhesive layer, a colored layer, a conductive layer, and a layer containing recycled resin.
  • gases such as water vapor and oxygen
  • an adhesive layer such as water vapor and oxygen
  • a pressure sensitive adhesive layer such as water vapor and oxygen
  • a colored layer such as a conductive layer
  • a layer containing recycled resin included in the other layers
  • materials for forming the other layers include an olefin polymer composition other than the propylene polymer composition, a gas barrier resin composition, and an adhesive resin composition.
  • the film and multilayer film of the present invention can be used as a packaging film in a wide range of packaging fields, such as packaging various foods such as fresh foods such as vegetables and fish, dried foods such as snacks and noodles, and water-based foods such as soups and pickles; packaging medical products such as medical products in various forms such as tablets, powders, and liquids, and medical peripheral materials; and packaging various electrical devices such as cassette tapes and electrical parts.
  • packaging various foods such as fresh foods such as vegetables and fish, dried foods such as snacks and noodles, and water-based foods such as soups and pickles
  • packaging medical products such as medical products in various forms such as tablets, powders, and liquids, and medical peripheral materials
  • packaging various electrical devices such as cassette tapes and electrical parts.
  • the mass fractions of the propylene-based polymer obtained in the first stage (corresponding to the propylene- ⁇ -olefin copolymer (A)) and the propylene-based polymer obtained in the second stage (corresponding to the propylene- ⁇ -olefin copolymer (B-1)) were determined from the amount of reaction heat generated during polymerization.
  • Comonomer content of propylene- ⁇ -olefin copolymer (B-1) ⁇ mass fraction of propylene- ⁇ -olefin copolymer (B-1) comonomer content of propylene- ⁇ -olefin copolymer (C) ⁇ mass fraction of propylene- ⁇ -olefin copolymer (C) - comonomer content of propylene- ⁇ -olefin copolymer (A) ⁇ mass fraction of propylene- ⁇ -olefin copolymer (A)
  • the comonomer content, intrinsic viscosity [ ⁇ ] and Mw/Mn of the propylene- ⁇ -olefin copolymer (A) were determined from the measured values of the propylene- ⁇ -olefin copolymer (A) polymerized under the same conditions as in the first stage.
  • melt flow rate (g/10 min) was measured in accordance with JIS-K7210 at a measurement temperature of 230° C. and a load of 2.16 kgf (21.2 N).
  • Mw/Mn The average molecular weight (number average molecular weight Mn, weight average molecular weight Mw) was obtained by gel permeation chromatography (GPC) using the following apparatus and conditions, and the molecular weight distribution (Mw/Mn) was calculated.
  • the Mw/Mn of the propylene/ ⁇ -olefin copolymer (B-1) was calculated by preparing a GPC chart of the propylene/ ⁇ -olefin copolymer (B-1) using the difference between the GPC chart of the propylene/ ⁇ -olefin copolymer (C) and the GPC chart of the propylene/ ⁇ -olefin copolymer (A).
  • GPC measurement device Gel permeation chromatograph HLC-8321 GPC/HT type (Tosoh Corporation) Analysis equipment: Data processing software Empower 3 (Waters) Measurement conditions Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (Both are 7.5mm ID x 30cm, manufactured by Tosoh Corporation) Column temperature: 140 ° C.
  • the crystalline melting point was determined by measuring under the following measurement conditions using a differential scanning calorimeter (DSC, manufactured by PerkinElmer (Diamond DSC)) in accordance with JIS-K7121.
  • DSC differential scanning calorimeter
  • the apex of the endothermic peak in the fourth step when the measurement was performed under the following measurement conditions was defined as the crystalline melting point (Tm).
  • Tm crystalline melting point
  • Tm crystalline melting point
  • Measurement environment Nitrogen gas atmosphere
  • Sample amount 5 mg
  • Sample shape Press film (formed at 230°C, thickness 400 ⁇ m)
  • Sample pan Flat-bottomed aluminum sample pan.
  • First step Heat from 30°C to 230°C at 50°C/min. Hold for 10 minutes.
  • Second step Decrease temperature to 30° C. at 10° C./min.
  • Third step Hold at 30° C. for 1 minute.
  • Fourth step Ramp to 230° C. at 10° C./min.
  • the tensile elastic modulus (MPa) was measured according to the method of JIS K7161. The measurement was performed at 23°C in the extrusion direction (MD) and the direction perpendicular to the MD (TD). The higher the tensile elastic modulus, the higher the rigidity.
  • the obtained prepolymerization catalyst was resuspended in purified heptane to adjust the total heptane weight to 140 mL.
  • a prepolymerization catalyst slurry was obtained in which 3.0 g of propylene was polymerized per 1 g of the solid titanium catalyst component.
  • the system was thoroughly purged with nitrogen. After completing the nitrogen purge, 1.5 kg of propylene, 35 NL of hydrogen, and 2.0 g of ethylene were charged in that order, and the temperature was raised to 50°C with thorough stirring, and polymerization was carried out for 120 minutes. The system was then depressurized and the polymer was recovered. (End of second-stage polymerization). The obtained polymer was dried under reduced pressure at 80°C for 6 hours, yielding 317.7 g of powder-like random propylene polymer.
  • the proportion of the propylene-based polymer (A) produced in the first polymerization stage in the propylene-based polymer was 23 mass%
  • the proportion of the propylene-based polymer (B-1) produced in the second polymerization stage was 77 mass%
  • the intrinsic viscosity [ ⁇ ] was 0.68 dl/g
  • the comonomer content was 1.1 mol%
  • Mw/Mn was 10.2, all of which were calculated from the mass balance.
  • the treated solid catalyst component was fed to a 200-liter polymerization apparatus equipped with a stirrer at a rate of 3 mmol/hr calculated as titanium atoms in the components, triethylaluminum at 4 mmol/kg-PP, and dicyclopentyldimethoxysilane at 1 mmol/kg-PP, respectively, and propylene, ethylene, 1-butene, and hydrogen were reacted at a polymerization temperature of 80° C. and a polymerization pressure (total pressure) of 28 kgf/cm 2 G.
  • the feed rates of ethylene, 1-butene, and hydrogen were adjusted so as to obtain the desired ethylene and 1-butene contents and MFR.
  • the composition analysis values (gas chromatography analysis) of the gas part in the polymerization apparatus showed that the ethylene concentration was 3.5 mol%, the 1-butene concentration was 4.9 mol%, and the hydrogen concentration was 2.5 mol%.
  • the propylene-ethylene-1-butene copolymer thus obtained was mixed with 2000 ppm of Irganox 1010 (BASF), 2000 ppm of Irgaphos 168 (BASF), and 1000 ppm of Sandstab P-EPQ (Clariant Japan) as antioxidants, and 1000 ppm of calcium stearate as a neutralizing agent, and then melt-kneaded in a twin-screw extruder to obtain pelletized propylene-ethylene-1-butene random copolymer.
  • Irganox 1010 BASF
  • Irgaphos 168 BASF
  • Sandstab P-EPQ Sandstab P-EPQ
  • Example 1 A 25 ⁇ m-thick film made of a propylene-based polymer composition was produced under the following conditions using 5% by mass of the propylene- ⁇ -olefin copolymer obtained in Production Example 1 and 95% by mass of the propylene-ethylene-1-butene random copolymer obtained in Production Example 4.
  • T-die film-making machine Model: GT-25-A, manufactured by Plastics Engineering Research Institute Co., Ltd.
  • Screw diameter 25 mm
  • L/D 24 Screw rotation speed: 100 rpm
  • Example 3 The physical properties of the film are shown in Table 3. [Examples 2 to 4, Comparative Examples 1 to 3] A film was produced in the same manner as in Example 1, except that the blending composition was changed as shown in Table 3.

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Abstract

L'invention fournit une composition de polymère à base de propylène qui permet de former un film présentant un excellent équilibre entre rigidité et résistance à la traction dans une direction verticale (TD) vis-à-vis d'une direction extrusion (MD) lors du moulage. Plus précisément, l'invention concerne une composition de polymère à base de propylène qui comprend : un copolymère propylène・α－oléfine (A) de viscosité intrinsèque ［η］ comprise entre １０ et １５ｄｌ／ｇ, et comprenant ０,１% en moles ou plus à ６,０% en moles ou moins d'une unité structurale dérivée d'une α－oléfine (à l'exclusion d'un propylène) ; et un polymère à base de propylène (B) de viscosité intrinsèque ［η］ comprise entre ０,５ et ５ｄｌ／ｇ. La fraction en masse dudit copolymère (A) est comprise entre ０,１ et ８% en masse, et la fraction en masse dudit polymère (B) est comprise entre ９２ et ９９,９% en masse pour 100% en masse au total dudit copolymère (A) et dudit polymère (B).
PCT/JP2024/013567 2023-04-03 2024-04-02 Composition de polymère à base de propylène, film, et film multicouche Pending WO2024210117A1 (fr)

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JPS6058459A (ja) * 1983-09-08 1985-04-04 Mitsui Toatsu Chem Inc ポリプロピレン樹脂組成物
JPH09208761A (ja) * 1996-02-02 1997-08-12 Tokuyama Corp ポリオレフィン系樹脂組成物
WO1998006781A1 (fr) * 1996-08-09 1998-02-19 Chisso Corporation Composition a base de polypropylene, procede de production et catalyseur permettant sa polymerisation
JP2005146160A (ja) * 2003-11-18 2005-06-09 Sumitomo Chemical Co Ltd プロピレン系重合体、その重合体を含むポリプロピレン系樹脂組成物、および、その組成物からなる射出成形体
JP2006045268A (ja) * 2004-07-30 2006-02-16 Japan Polypropylene Corp ポリプロピレン系樹脂被覆用発泡体
JP2008037908A (ja) * 2006-08-02 2008-02-21 Japan Polypropylene Corp オレフィン（共）重合体組成物の製造方法及びそれに用いる予備活性化触媒の製造方法
JP2008163320A (ja) * 2006-12-05 2008-07-17 Prime Polymer:Kk プロピレン系樹脂組成物およびプロピレン系樹脂発泡成形体
JP2021024641A (ja) * 2019-08-08 2021-02-22 三井化学株式会社 延伸容器

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021025142A1 (fr) 2019-08-08 2021-02-11 株式会社プライムポリマー Composition de polymère à base de propylène, film non étiré et stratifié

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6058459A (ja) * 1983-09-08 1985-04-04 Mitsui Toatsu Chem Inc ポリプロピレン樹脂組成物
JPH09208761A (ja) * 1996-02-02 1997-08-12 Tokuyama Corp ポリオレフィン系樹脂組成物
WO1998006781A1 (fr) * 1996-08-09 1998-02-19 Chisso Corporation Composition a base de polypropylene, procede de production et catalyseur permettant sa polymerisation
JP2005146160A (ja) * 2003-11-18 2005-06-09 Sumitomo Chemical Co Ltd プロピレン系重合体、その重合体を含むポリプロピレン系樹脂組成物、および、その組成物からなる射出成形体
JP2006045268A (ja) * 2004-07-30 2006-02-16 Japan Polypropylene Corp ポリプロピレン系樹脂被覆用発泡体
JP2008037908A (ja) * 2006-08-02 2008-02-21 Japan Polypropylene Corp オレフィン（共）重合体組成物の製造方法及びそれに用いる予備活性化触媒の製造方法
JP2008163320A (ja) * 2006-12-05 2008-07-17 Prime Polymer:Kk プロピレン系樹脂組成物およびプロピレン系樹脂発泡成形体
JP2021024641A (ja) * 2019-08-08 2021-02-22 三井化学株式会社 延伸容器

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