WO1997044389A1 - Composition de resine polypropylenique - Google Patents

Composition de resine polypropylenique Download PDF

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Publication number
WO1997044389A1
WO1997044389A1 PCT/JP1997/001691 JP9701691W WO9744389A1 WO 1997044389 A1 WO1997044389 A1 WO 1997044389A1 JP 9701691 W JP9701691 W JP 9701691W WO 9744389 A1 WO9744389 A1 WO 9744389A1
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WO
WIPO (PCT)
Prior art keywords
phenoxy
titanium dichloride
tert
butyl
methyl
Prior art date
Application number
PCT/JP1997/001691
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English (en)
Japanese (ja)
Inventor
Yasuhito Ijichi
Hidetake Hozumi
Original Assignee
Sumitomo Chemical Company, Limited
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Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO1997044389A1 publication Critical patent/WO1997044389A1/fr

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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
    • 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
    • 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 polypropylene resin composition. More specifically, the present invention relates to a polypropylene resin composition having excellent flexibility, heat resistance, and scratch resistance, and having high tensile elongation. Background art
  • polypropylene-based resins are widely used in the fields of home appliances, automobile parts, and miscellaneous goods.
  • the polypropylene resin used in these fields is required to have excellent flexibility, heat resistance, and scratch resistance, and to have high tensile elongation. Is being transformed. Under such circumstances, conventional polybroylene-based resins have not always been satisfactory.
  • a composition mainly comprising 10 to 90% by weight of boiling butane-soluble polypropylene and 90 to 10% by weight of boiling heptane-insoluble polypropylene is disclosed. Fairness 7—1 1 9 2 9 2 publication).
  • the polybrobylene resin composition was not satisfactory in the effect of softening.
  • the problem to be solved by the present invention is to provide a polypropylene resin composition having excellent flexibility, heat resistance and scratch resistance, and having high bow and elongation. Disclosure of the invention
  • the present invention relates to an amorphous polypropylene resin having ( ⁇ ) a crystalline polypropylene resin component of 5 to 95% by weight and ( ⁇ ) an ⁇ -hexane insoluble content at a temperature of 25 ° C. of not more than double S%.
  • a polypropylene-based resin composition containing 5 to 5% by weight of a resin component ⁇ Brief description of drawings
  • FIG. 1 is a graph (DSC chart) showing the relationship between the differential heat and temperature of the amorphous polypropylene prepared in Reference Example 1 as measured by a differential scanning calorimeter.
  • FIG. 2 is a DSC chart of amorphous polypropylene prepared in Reference Example 2.
  • the component (A) of the present invention is a crystalline polypropylene resin, which is a homopolymer of propylene or propylene and a small amount of ethylene or / and a mono-olefin having a carbon number of 4 or more (preferably 4 to 12). It is sometimes simply referred to as "Hiseki Refin.")
  • the copolymerization ratio of ethylene and / or one-year-old olefin having 4 or more carbon atoms in the copolymer is generally 10% by weight or less in total, preferably 0.5 to 7% by weight.
  • the copolymerization ratio of ethylene and / or one-year-old olefin having 4 or more carbon atoms in the copolymer is generally 1 to 40% by weight in total, preferably 1 to 25% by weight.
  • the content is more preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight.
  • These polypropylene polymers may be a combination of two or more polymers.
  • As an index of the crystallinity of polypropylene for example, melting point, heat of crystal fusion, etc. are used, and the melting point is 120 ° C. to 1 ⁇ 6 ° C., and the heat of crystal fusion is 6 ° J / g to l 2 OJ / g. It is preferably within the range. If the melting point of the crystal is too low or the heat of fusion is too low, the heat resistance of the material will be poor.
  • a Ziegler-Natta type catalyst using a combination of a so-called titanium-containing solid transition metal component and an organometallic component, particularly, a titanium or magnesium transition metal component is used.
  • a solid component or titanium trichloride containing an electron donating compound as an optional component and halogen as an essential component and using a catalyst in which an organometallic component is an aluminum compound, slurry polymerization, gas phase polymerization, bulk polymerization,
  • One-stage or multi-stage propylene homopolymerization by a polymerization method such as solution polymerization or a combination thereof may be used to obtain a propylene homopolymer, or propylene and ethylene or Examples of the method include a method of obtaining a propylene copolymer by co-polymerizing a single olefin having 4 to 12 carbon atoms, more preferably ethylene in one or more stages. Note that commercially available products may be used.
  • the component (B) of the present invention is an amorphous polypropylene resin having an n-hexane insoluble content of 2% by weight or less at a temperature of 25 ° C., and is a homopolymer of propylene.
  • the component (B) has an n-hexane insoluble content at a temperature of 25 ° C of 2% by weight or less, preferably 1% by weight or less. If the insoluble content is excessive, the flexibility of the amorphous polypropylene may be insufficient, the flexibility of the blend composition with the crystalline polypropylene may be insufficient, or the scratch resistance may be poor. is there.
  • the method for measuring the insoluble content is as follows.
  • n—hexane insoluble part (wt%) 100 (Z-Y) / X
  • the component (B) is preferably an amorphous polypropylene-based resin having neither a crystal melting peak nor a crystallization peak of 1 J ng or more as measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the component (B) preferably has a molecular weight distribution nonuniformity index Mw / Mn (Mw represents a weight average molecular weight and Mn represents a number average molecular weight) of 5 or less. If the index is too large, the low molecular weight component also increases, and the tensile elongation of the blend composition with the crystalline polypropylene may decrease, or the molded product may become sticky due to bleeding of the low molecular weight component.
  • the molecular weight distribution was measured by a gel permeation chromatography (GPC) method (Waters, 150CV ALC / GPC). The elution temperature was 140 ° C, the column used was Showa Denko's Sho X Packed Column AT-806 M / S 8mm0x250mm (2 pieces), and the molecular weight standard was polystyrene (Tosoichisha, molecular weight 68-8 , 400,000). Using the obtained polystyrene-converted weight average molecular weight (Mw) and number average molecular weight (Mn), this ratio (Mw / Mn) was taken as the molecular weight distribution non-uniformity index.
  • GPC gel permeation chromatography
  • the intrinsic viscosity [] of the amorphous polypropylene as the component (B) was measured in xylene at 70 ° C. using an Ubbelohde viscometer. Samburu dissolved 30 Omg in 100 ml xylene to prepare a 3 mg / ml solution. The solution was further diluted to 1/2, 1/3, 1/5 and measured in a constant temperature water bath at 70 ° C ( ⁇ 0.1 ° C). The measurement was repeated three times at each concentration, and the obtained values were averaged and used.
  • the component (B) is an amorphous polypropylene-based resin obtained by polymerizing propylene, preferably using a meta-mouth catalyst.
  • a meta-open-chain catalyst a meta-open-chain transition metal complex represented by the following chemical formula (1) can be exemplified.
  • M represents a transition metal element of Group 4 of the periodic table of the elements
  • Cp represents cyclopentenyl genenyl, substituted cyclopentyl genenyl, indenyl, substituted indenyl, fluorenyl or substituted fluorenyl.
  • A represents an element.
  • B represents an element of Group 14 of the Periodic Table of the elements.
  • X 1 and X 2 represent a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms.
  • a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an amide group having 1 to 20 carbon atoms. may be different.
  • ⁇ ⁇ 6 represents a hydrogen atom, a halogen atom, a hydrocarbon group having a carbon number of 1 to 2 0, a halogenated hydrocarbon group having a carbon number of 1 to 2 0, the number 1 to 2 0 carbon atoms
  • Represents an alkoxy group, an amide group having 1 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, and Al may be the same or different, it may be further formed them optionally bonded to ring.
  • transition metal complex examples include, for example, methylene (cyclopentagenenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (cyclopentenyl) (3-tert-butyl-2-phenoxy).
  • Titanium dichloride methylene (cyclopentagenenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentagenenyl) (3-phenyl-2-phenoxy) titanium Dichloride, methylene (cyclopentenyl) (3-tert-butyldimethylsilyl-1-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentenyl) (3-trimethylsilyl-1-5-methyl-2-phenoxy) ) Titanium dichloride, methylene (six Lopene genil) (3-tert-butyl-5-methoxy-2-phenoxy) Titanium dichloride, methylene (cyclopentene genil) (3-tert-butyl Titanium 5-chloro-2-phenoxy titanium dichloride, methylene (methylcyclopentenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentenyl) (3-tert- But
  • n-Propylcyclopentenyl isopropylcyclopentenyl, sec-butylcyclopentenyl, isobutylcyclopentenyl, tert-butyldimethylsilylcyclopentagenenyl, phenylcyclopentenyl, methylindenyl, Compound in which 2-phenyl has been changed to phenylindenyl, 2-phenyl has been changed to 3-phenyl-2-phenoxy, 3-trimethylsilyl-1-phenoxy, 3-tert-butyldimethylsilyl-12 Compounds with Lucyl, Diphenylsilyl, Dimethoxysilyl, Titanium with Zirconium, Hafnium, Chloride with Bromide, Iodide, Dimethylamide, Getylamide, n-Butoxide, Isopropoxide B in the general formula (1) such as the compounds are transition metal complexes is a Group 14 atoms of the Periodic Table of the Elements other than carbon atoms
  • the transition metal complex represented by the general formula (1) and the compound (X) described below or the compound (Y) can be added and used in an arbitrary order during the polymerization.
  • a reaction product obtained by bringing these compounds into contact in advance may be used.
  • (X) used in the present invention a known organic aluminum compound can be used.
  • (XI) - general formula E 'organoaluminum Miniumu compound represented by a Al Z 3 _ a
  • ( X2) - general formula ⁇ _A1 (E 2) one 0- ⁇ circular having a structure represented by b Aluminoxane and (X3) —general formula E 3 ⁇ -A1 (E 3 ) -0- ⁇
  • a linear aluminoxane having a structure represented by C A1 E 3 2 (where, EE 2, E 3 is a hydrocarbon group having 1-8 carbon atoms, all of E all E 2 beauty all E 3 is Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different, a is a number of 0 ⁇ a ⁇ 3, and b is 2 And c represents an integer of 1 or more.) Or a mixture of two or three of them.
  • E 2 and E 3 in the linear aluminoxane having the formula (X3) include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal benzyl group, a neopentyl group, and the like. Can be exemplified.
  • b is an integer of 2 or more
  • c is an integer of 1 or more
  • E 2 and E 3 are a methyl group or an isobutyl group
  • b is 2 to 40
  • c is 1 to 40.
  • the above aluminoxanes are made by various methods. There are no particular restrictions on the method. Instead, it may be made according to a known method. For example, a solution in which a trialkylaluminum (for example, trimethylaluminum, etc.) is dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water.
  • a trialkylaluminum for example, trimethylaluminum, etc.
  • a suitable organic solvent benzene, aliphatic hydrocarbon, etc.
  • a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt containing water of crystallization for example, copper sulfate hydrate or the like
  • a metal salt containing water of crystallization for example, copper sulfate hydrate or the like
  • the compound ( ⁇ ) includes (Y1) —a boron compound represented by the general formula BQ'Q 2 ⁇ ! 3 ; and (Y2) —a boron compound represented by the general formula Z + (BQiQSQSQ 4 ) — things, (Y3) - general formula (L one H) + (BQ iQSQSQ 4) - one of boron compound represented by the used.
  • Formula BQiQZQ boron compound represented by 3 in (Y 1) B is a boron atom in the trivalent valence state
  • Qi ⁇ Q 3 is a halogen atom, 1-20 hydrocarbon group containing a carbon atom
  • a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or containing 2 to 20 carbon atoms Are 2-substituted amino groups, which may be the same or different.
  • Preferred Qi ⁇ Q 3 is a halogen atom, 1-20 hydrocarbon group containing a carbon atom, a halogenated hydrocarbon group containing 1-20 carbon atoms.
  • Lewis acids (Y1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-tetrafluorophenyl) ) Borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) porane, phenylbis (pentafluorofluorophenyl) borane Su (Penyu fluorophenyl) borane.
  • Z + iBQ ′ QSQSQ 4 ) — examples include Z + which is an inorganic cation, a phenocenium cation, and an alkyl-substituted ferrocene cation.
  • Z + which is an inorganic cation, a phenocenium cation, and an alkyl-substituted ferrocene cation.
  • Zion which is an organic cation such as thione and silver cation, includes a triphenylmethyl cation.
  • (BQ'Q 2 Q 3 Q 4 ) includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5) —Tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate and the like.
  • L is a neutral Lewis base
  • (L—H) + is a Bronsted acid.
  • B is a boron atom in a trivalent valence state
  • Q to Q are the same as Q to Q in (Y 1) above.
  • Specific examples of the compound represented by the general formula (L—H) + (BQ′Q 2 Q 3 Q 4 ) — include a Bronsted acid (L-H) +, a trialkyl-substituted ammonium, N , N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like, and (BQ i QSQSQ 4 ) — includes the same as described above.
  • the method for producing the component (B) includes, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; aromatic hydrocarbons such as benzene and toluene; and halogenated compounds such as methylene dichloride.
  • Solvent polymerization using a hydrocarbon as a solvent, slurry polymerization, gas-phase polymerization in a gaseous monomer, and the like are possible, and both continuous polymerization and batch polymerization are possible.
  • the polymerization temperature is preferably ⁇ 50 ° C. to 200 ° C., particularly preferably ⁇ 20 ° C.
  • the polymerization pressure is preferably normal pressure to 60 kg / cm 2 G.
  • the polymerization time is appropriately determined depending on the type of the catalyst used and the reaction apparatus, but can range from 1 minute to 20 hours.
  • a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.
  • component (A) is 90 to 20% by weight and component (B) is 10 to 80% by weight, more preferably component (A) is 70 to 30% by weight and component (B) is 30 to 70% by weight. You. If the component (A) is too small (the component (B) is too large), the fluidity will decrease, and the molding If the component (A) is too large (the component (B) is too small), the flexibility or the scratch resistance is poor.
  • polypropylene resin composition of the present invention in addition to the essential components (A) and (B), other rubber components such as ethylene-propylene copolymer rubber, ethylene-propylene Non-conjugated gen copolymer rubber, ethylene-butene-11 copolymer rubber, polybutadiene, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, styrene-butadiene random copolymer Combined rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, partially hydrogenated styrene-butadiene random copolymer rubber, styrene-isoprene block copolymer rubber, partially hydrogenated styrene-isoprene block copolymer rubber Etc.
  • ethylene-propylene copolymer rubber ethylene-propylene Non-con
  • a peroxide if necessary.
  • an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a pigment, a filler, and a flame retardant may be added.
  • Examples of the method for obtaining the polypropylene resin composition of the present invention include a method in which each component is melt-kneaded using a twin-screw extruder, a Banbury mixer, or the like.
  • the polypropylene-based resin composition of the present invention can be optimally used for home electric appliances, automobile parts, miscellaneous goods, etc. by utilizing its excellent characteristics.
  • a 2-liter separable flask reactor was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and the pressure was reduced.
  • One liter of dried toluene was introduced into the flask as a polymerization solvent.
  • 8 NL / min of propylene was continuously fed at normal pressure, and the solvent temperature was 30 ° C. .
  • Triisobutylaluminum hereinafter
  • TIBA Triisobutylaluminum
  • Cyclopentadienyl System 0.005 mmol of landichlorotitanium was added to the polymerization vessel. Fifteen seconds after that, triphenylcarboditetrakis (pentafluorophenyl) 0.05 mmol was added to the polymerization tank, and polymerization was started. As a result of polymerization for 30 minutes, 43.9 g of propylene was obtained.
  • Type * o Cl C-2 Amount WtA U ⁇ U 50 50 Shiki says Rebeak Book 4 Yes Yes Hardness no no n Ao 96 93 N 3 1 U 00 ⁇ 00 o4 00 Flexural modulus kgf / cm 2 1550 2060 3280 4110 4700 Tensile strength kgf / cm 2 81 95 57 99 129 Tensile elongation 560 640 10 250 20 Scratch depth am 32 28 121 117 70 Haze (two t)% 94 97 89 97 91
  • B-3 Acrylic polypropylene Sumitic SK-11C (Sumitomo Chemical Co., Ltd.) Polymerized by a Ziegler's Natta-type catalyst using a combination of a titanium-containing solid transition metal component and an organometallic component It is.
  • the melt viscosity measured at 170 ° C. using a B-type viscometer is 300 to 5000 cps.
  • Crystal peak presence of crystal melting peak and crystallization beak as measured by differential scanning calorimetry (DSC).
  • EPR Ethylene propylene rubber
  • Tuffma I S 4030 (Mitsui Petrochemicals) Propylene content-63 wt%, viscosity of MU (ML
  • +4 121 ° C) 48
  • EBR Ethylene butene rubber
  • Esplen SPO N0394 Suditomo Chemical
  • Butene content 17 wt%, 230 ° C, 2.16 kg load MI is 7.3 (g / 10 min)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine polypropylénique comprenant 5 à 95 % en poids d'un composant (A) constitué d'une résine propylénique cristalline et 95 à 5 % en poids d'un composant (B) constitué d'une résine polypropylénique non cristalline contenant des insolubles n-hexane ne représentant pas plus de 2 % en poids, mesurés à une température de 25 °C. La composition présente une excellente flexibilité, une excellente résistance à la chaleur et une excellente résistance à l'abrasion, elle présente également un allongement en traction élevé.
PCT/JP1997/001691 1996-05-22 1997-05-20 Composition de resine polypropylenique WO1997044389A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP12717996A JPH09309982A (ja) 1996-05-22 1996-05-22 ポリプロピレン系樹脂組成物
JP8/127179 1996-05-22

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WO1997044389A1 true WO1997044389A1 (fr) 1997-11-27

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0842939A1 (fr) * 1995-07-14 1998-05-20 Sumitomo Chemical Company, Limited Complexe a base de metal de transition, procede de preparation dudit complexe, catalyseur de polymerisation pour des olefines le contenant et procede de production de polymeres d'olefines
EP0842955A2 (fr) * 1996-11-15 1998-05-20 Sumitomo Chemical Company, Limited Copolymère de propylène-1-butène
EP0931814A1 (fr) * 1998-01-21 1999-07-28 Fina Research S.A. Polyoléfines et leur utilisation
US6326086B1 (en) * 1997-07-22 2001-12-04 Nissha Printing Co., Ltd. Sheet for molded-in foil decoration and method of producing molded resin having molded-in foil decoration by using the sheet
US6866938B2 (en) 1997-07-22 2005-03-15 Nissha Printing Co., Ltd. Foil-detecting sheet and method of producing a foil-decorated resin article using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69941039D1 (de) 1998-06-25 2009-08-06 Idemitsu Kosan Co Propylenpolymer und Zusammensetzung damit, Formobjekt und Laminat damit sowie Verfahren zur Herstellung von Propylenpolymer und einer Zusammensetzung damit
JP2000072950A (ja) * 1998-09-02 2000-03-07 Chisso Corp 高発色性ポリプロピレン系組成物
JP2006083327A (ja) * 2004-09-17 2006-03-30 Sumitomo Chemical Co Ltd オレフィン系樹脂組成物
US20070267059A1 (en) * 2004-12-28 2007-11-22 Dupont-Mitsui Polychemicals Co., Ltd. Encapsulating Material for Solar Cell
JP2006328306A (ja) * 2005-05-30 2006-12-07 Asahi Kasei Chemicals Corp オレフィン系重合体組成物
KR101200696B1 (ko) 2007-12-27 2012-11-12 미쓰이 가가쿠 가부시키가이샤 프로필렌계 중합체 조성물
US8765872B2 (en) 2008-07-10 2014-07-01 Mitsui Chemicals, Inc. 4-methyl-1-pentene polymer, resin composition containing 4-methyl-1-pentene polymer, masterbatch thereof, and formed product thereof
TWI472537B (zh) 2008-07-10 2015-02-11 Mitsui Chemicals Inc 4-methyl-1-pentene-based polymer and a resin composition containing 4-methyl-1-pentene-based polymer and its masterbatch and the molded product

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0314851A (ja) * 1989-03-23 1991-01-23 Idemitsu Petrochem Co Ltd 軟質ポリプロピレン樹脂組成物
JPH07206921A (ja) * 1994-01-25 1995-08-08 Tonen Corp 結晶性ポリプロピレン

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0314851A (ja) * 1989-03-23 1991-01-23 Idemitsu Petrochem Co Ltd 軟質ポリプロピレン樹脂組成物
JPH07206921A (ja) * 1994-01-25 1995-08-08 Tonen Corp 結晶性ポリプロピレン

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6329478B1 (en) 1995-07-14 2001-12-11 Sumitmo Chemical Company, Limited Transition metal complex, process for producing the same, olefin polymerization catalyst containing the transition metal complex and process for producing olefin polymers
EP1498178A3 (fr) * 1995-07-14 2005-02-09 Sumitomo Chemical Company, Limited Complexe à base de metal de transition, procédé de préparation dudit complexe, catalyseur de polymerisation pour des olefines le contenant et procédé de production de polymeres d'olefines
EP1498178A2 (fr) * 1995-07-14 2005-01-19 Sumitomo Chemical Company, Limited Complexe à base de metal de transition, procédé de préparation dudit complexe, catalyseur de polymerisation pour des olefines le contenant et procédé de production de polymeres d'olefines
EP0842939A4 (fr) * 1995-07-14 2000-04-12 Sumitomo Chemical Co Complexe a base de metal de transition, procede de preparation dudit complexe, catalyseur de polymerisation pour des olefines le contenant et procede de production de polymeres d'olefines
EP0842939A1 (fr) * 1995-07-14 1998-05-20 Sumitomo Chemical Company, Limited Complexe a base de metal de transition, procede de preparation dudit complexe, catalyseur de polymerisation pour des olefines le contenant et procede de production de polymeres d'olefines
EP0842955A2 (fr) * 1996-11-15 1998-05-20 Sumitomo Chemical Company, Limited Copolymère de propylène-1-butène
EP0842955A3 (fr) * 1996-11-15 1998-07-15 Sumitomo Chemical Company, Limited Copolymère de propylène-1-butène
US6326086B1 (en) * 1997-07-22 2001-12-04 Nissha Printing Co., Ltd. Sheet for molded-in foil decoration and method of producing molded resin having molded-in foil decoration by using the sheet
US6866938B2 (en) 1997-07-22 2005-03-15 Nissha Printing Co., Ltd. Foil-detecting sheet and method of producing a foil-decorated resin article using the same
US6348272B1 (en) 1998-01-21 2002-02-19 Fina Research, S.A. Polyolefins and uses thereof
WO1999037711A3 (fr) * 1998-01-21 2000-03-16 Fina Research Polyolefines et leurs utilisations
EP0931814A1 (fr) * 1998-01-21 1999-07-28 Fina Research S.A. Polyoléfines et leur utilisation
US6881493B2 (en) 1998-01-21 2005-04-19 Atofina Research S.A. Polyolefins and uses thereof

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