WO2004018557A1 - Compositions de poly-$g(a)-olefines et leur procede de production - Google Patents

Compositions de poly-$g(a)-olefines et leur procede de production Download PDF

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Publication number
WO2004018557A1
WO2004018557A1 PCT/JP2003/010513 JP0310513W WO2004018557A1 WO 2004018557 A1 WO2004018557 A1 WO 2004018557A1 JP 0310513 W JP0310513 W JP 0310513W WO 2004018557 A1 WO2004018557 A1 WO 2004018557A1
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Prior art keywords
modified
polymer
component
weight
polypropylene resin
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PCT/JP2003/010513
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English (en)
Japanese (ja)
Inventor
Rikuo Onishi
Yasuhisa Sugita
Ryoichi Tsunori
Tomio Tatsumi
Toshiya Abiko
Takenori Fujimura
Shinichi Yukimasa
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Idemitsu Petrochemical Co., Ltd.
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Priority claimed from JP2002241732A external-priority patent/JP4167028B2/ja
Priority claimed from JP2002241731A external-priority patent/JP4167027B2/ja
Priority claimed from JP2002259198A external-priority patent/JP4172971B2/ja
Priority claimed from JP2002296463A external-priority patent/JP4172985B2/ja
Application filed by Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO2004018557A1 publication Critical patent/WO2004018557A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention 1 relates to an ⁇ -olefin polymer having 2 to 20 carbon atoms, an organic silicon compound, and an ⁇ -modified with a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule.
  • the present invention relates to an a-olefin polymer composition obtained by mixing (reacting) an -olefin polymer and a method for producing the same.
  • the present invention 2 relates to an ⁇ -olefin polymer having 2 to 20 carbon atoms containing an organic silicon compound, and a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule.
  • the present invention relates to an ⁇ -olefin polymer composition obtained by mixing (reacting) a modified hypoolefin polymer having 2 to 20 carbon atoms and a method for producing the same.
  • the present invention 3 relates to a modified polypropylene resin composition and a method for producing the same.
  • the present invention 4 relates to a method for producing a modified -olefin polymer composition.
  • polyolefin melt tension has been improved with the aim of improving formability, but these have only been achieved through complex processes or the use of special equipment.
  • Methods for improving the melt tension of polyolefin include: (1) an electron beam crosslinking method of polypropylene (JP-A-62-121704, JP-A-2-695333, etc.), (2) Cross-linked polio using olefin-non-conjugated gen copolymer A method for forming a refin (Japanese Patent Application Laid-Open Nos. Hei 5-194659, Japanese Patent Application Laid-Open No. Hei 7-209628), and a method for coexisting ultra-high molecular weight polyethylene in polypropylene No. 200-017-224).
  • the method (1) requires special equipment for electron beam crosslinking, the method (2) requires the use of a special non-conjugated gen that is not industrially produced, and the method (3) requires a special spare. Neither can be said to be highly versatile in that a polymerization step is required.
  • the purpose of the present invention namely, to improve the melt tension, is different from the purpose, and as a technique mainly for imparting chemical properties such as adhesiveness, paintability, hydrophilicity, etc.
  • Several patents have been filed for the reaction of a silane coupling agent with a modified polyolefin, and for the reaction product thereof (Japanese Patent Application Laid-Open No. 59-184,272; Publication No. 0 149 49, Japanese Unexamined Patent Application Publication No. Hei 5-111264, Japanese Unexamined Patent Application Publication No. 2000-265365, etc.).
  • Japanese Patent Application Laid-Open No. Hei 1-150149 and Japanese Patent Laid-Open Publication No. Hei 5-112694 disclose a composition comprising a simple combination of a modified polyolefin and an alkoxyaminosilane.
  • a simple combination of a modified polyolefin and an alkoxyaminosilane there is a possibility that the gelation may partially proceed without increasing the melt tension.
  • Japanese Patent Application Laid-Open No. 59-184,272 discloses a technique in which a modified polyolefin and a silane compound are blended, and further an unmodified polyolefin is blended. There is no description or suggestion about the modified ⁇ -olefin polymer.
  • Japanese Patent Application Laid-Open No. 2001-226655 discloses a reaction between a carboxylic acid-modified polymer, an amine compound having an alkoxysilyl group and a carbonyl compound.
  • a one-pack type cross-linking composition in which a product is dissolved in an organic solvent and an ordinary thermoplastic resin is added is disclosed.
  • composition of the one-part type which is different from the composition of the invention, which is usually solid.
  • Japanese Patent Application Laid-Open No. 2002-5188573 discloses a silane-cured thermoplastic elastomer obtained by reacting a rubber or a thermoplastic resin obtained by graphitizing or copolymerizing a carboxylic anhydride with an aminosilane.
  • a toma composition is disclosed wherein the gel content is between 10 and 50% by weight.
  • Japanese Patent Application Laid-Open No. 201-2265355 describe a silane cup made of an alkoxyaminosilane compound or the like for the purpose of improving the adhesive property, coatability, printability, hydrophilicity and other chemical properties of polyolefin.
  • the reaction of a ring agent with a modified polyolefin and the reactants thereof are disclosed.
  • Japanese Patent Application Laid-Open No. 59-184432 discloses a composition in which a modified polyolefin and a silane compound are blended, and further a non-modified polyolefin is blended.
  • JP-A-Heisei 501-4949, JP-A-Heisei 4-344,106, JP-A-Heisei 5-11 JP-A-26-94 and JP-A-2001-22653 are not aimed at improving the physical properties of polyolefins.
  • the purpose is to improve the physical properties of polyolefin
  • the modified polyolefin contains a large amount of a modifying agent (for example, an acid).
  • a modifying agent for example, an acid
  • the present inventions 1 and 2 have been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a hoolefin polymer composition which has no gelation, has an increased melt tension, and has greatly improved moldability, and a method for producing the same. It is.
  • the third object of the present invention is to provide a modified polypropylene resin composition having an excellent balance between melt tension and fluidity, and a method for producing the same.
  • the present invention 4 is a modified one-year-old refining paper having an excellent balance between melt tension and fluidity. It is an object of the present invention to provide a method for producing a polymer composition.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, using general-purpose equipment, an organic silicon compound and a compound containing an ethylenic double bond and a polar group in the same molecule Mixing (reaction) with an acid-modified ⁇ -olefin polymer, preferably a high molecular weight modified with a polar group derived from a polymer, to form a component capable of highly dispersing an organic silicon compound. It has been found that by performing the reaction in an ⁇ -olefin polymer having the following properties, the generation of gel is suppressed, the melt tension is increased, and an ⁇ -olefin polymer composition having significantly improved moldability can be obtained. The invention has been completed.
  • X is a polar group, preferably a substituent containing a group capable of reacting with a carboxylic acid or its anhydride
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n represents an integer of 1 to 3
  • m represents an integer of 0 to 2
  • (n + m) 1 to 3.
  • the silicon compound derived from the organic silicon compound (B1) is 0.000
  • X in the general formula (1) is one or more substituents selected from substituents including an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the average particle size of the ( ⁇ ) component is 50-20 ° 0 ⁇ , and the bulk specific gravity is 0.2- 0. a 6 gZc ni 3, ⁇ - Orefuin polymer composition according to the above 7.
  • the present inventors used a general-purpose facility and prepared an ⁇ -olefin polymer in which an organic silicon compound was dispersed, and a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule.
  • X is a polar group, preferably a substituent containing a group capable of reacting with a carboxylic acid or its anhydride
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n represents an integer of 1 to 3
  • m represents an integer of 0 to 2
  • (n + m) 1 to 3.
  • the intrinsic viscosity [] measured in tetralin at 135 ° C is in the range of 0.7 to 5 dl / g. 100 parts by mass of an ⁇ -olefin polymer having 2 to 20 carbon atoms, and (CI) A polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule, preferably an acid derived from an unsaturated carboxylic acid and / or an anhydride thereof, 0.001 to 1 mass 0 / 0 Intrinsic viscosity measured in tetralin at 135 ° C [ ⁇ ] Force S 0.7 d 1 Modified by a polar group having 2 to 20 carbon atoms with a carbon content of 1 g or more, preferably acid The modified ⁇ -olefin polymer is obtained by mixing (contacting) 0.1 to 30 parts by mass, and has a melt tension ( ⁇ ), melt
  • X in the general formula (1) is one or more substituents selected from substituents including an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the component has a mesopentad fraction [mmmm] of 97 mol% or more.
  • the component is obtained by supplying the organic silicon compound represented by the general formula (1) to a drying step and a transferring step in the production of a propylene polymer or a 1-butene polymer, or a molding step of the polymer. 2.
  • the present inventors have found that a composition obtained by mixing a polypropylene resin having a specific polar group, a silane coupling agent and an antioxidant exhibits a high melt tension, and completed the present invention. I came to.
  • melt tension ( ⁇ ⁇ ) and melt rate (M l) obtained by mixing the following components (C 2) and ( ⁇ ) are MT / 7 X (M l) — ° ⁇ 8 >
  • a modified polypropylene resin composition that satisfies the relationship 1 and has a paraxylene-insoluble component amount (G value) of 1% by weight or less at 130 ° C.
  • a phosphorus-based and / or phenolic antioxidant (D) is further mixed by mixing 0.05 to 1 part by weight.
  • a phosphorus-based and / or phenolic antioxidant (D) is further mixed by mixing 0.05 to 1 part by weight.
  • Polypropylene resin (C 2) The modified polypropylene resin composition according to the above 1, which is a mixture of the following (C 3) and (C 5) or the following (C 4) and (C 5).
  • the melting enthalpy of the unmodified polypropylene resin (C 4) measured by differential scanning calorimetry (DSC) is 100 J / g or less, and the mesopentad fraction determined by 13 C-NMR measurement 5.
  • modified polypropylene resin composition according to the above item 5, wherein the molar ratio of the polar group to the polymer chain of the modified polypropylene resin (C5) is 0.8 to 2.
  • X is a substituent containing a functional group capable of reacting with the polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n is 1-3
  • 8. The modified polypropylene resin composition according to the above 7, wherein in the general formula (1): is a substituent containing an amino group.
  • Silane coupling agent ( ⁇ ) contains 10 to 100,000 ppm, phosphorus-based and ⁇ Z or phenol-based antioxidants (D) F 500-: L0, OOO ppm
  • the silane coupling agent (B), the phosphorus-based and Z- or phenol-based antioxidants (D), and the following polypropylene-based resin (C3) or (C4) are mixed, and 100 parts by weight of the mixture is obtained.
  • a method for producing a modified polypropylene resin composition comprising mixing 0.1 to 3 parts by weight of the following modified polypropylene resin (C5).
  • (C5) A modified polypropylene resin containing 0.001 to 1% by weight of the polar group, and having an intrinsic viscosity of 0.7 d1 Zg or more measured at 135 ° C in tetralin.
  • the polypropylene-based resin (C 3) or (C 4) is mixed, and the silane coupling agent (B) is reacted with the following modified polypropylene-based resin (C 5).
  • a method for producing a modified polypropylene resin composition comprising mixing 0.1 to 30 parts by weight of a reactant.
  • the modified polypropylene resin is an intrinsic viscosity measured in tetralin is 0. 7 d 1 / g or more
  • the present inventors have found that when an ⁇ -olefin polymer is mixed with a mixture of a specific modified ⁇ -olefin polymer and a silane coupling agent, a composition exhibiting high melt tension can be efficiently obtained. This led to the completion of the present invention.
  • A An intrinsic polymer having an intrinsic viscosity of 0.7 to 5.0 d 1 / g, measured in tetralin at 135 ° C, having 2 to 20 carbon atoms. 2. modified a- melt tension (MT) of Orefuin polymer composition and Merutofu port one rate (MI) i MT / 7 X (MI) - met ° ⁇ 8> 1 relationship One or, 1 30 ° 2.
  • Modified a-olefin polymer (C 6) Production of modified a-olefin polymer composition according to 1 above, which is a modified S, modified propylene (co) polymer or modified 1-butene (co) polymer Method.
  • Silane coupling agent (B) 1 The process for producing a modified a-olefin polymer composition according to the above 1 or 2, which is an organosilicon compound represented by the general formula (1).
  • X is a substituent containing a functional group capable of reacting with the polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n is 1-3
  • m is 0- 2 represents an integer
  • (n + m) 1 to 3.
  • the present invention provides:
  • X is a substituent containing a group capable of reacting with a polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n 1-3
  • m 0-2.
  • (n + m) 1 to 3.)
  • X is a substituent containing a group capable of reacting with a polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n 1-3
  • m 0-2.
  • (n + m) 1 to 3.
  • an organosilicon compound represented by the following formula: (A) an intrinsic viscosity [] measured in tetralin at 135 ° C in the range of 0.7 to 5 dl Zg; 100 parts by mass of a monoolefin polymer having 2 to 20 carbon atoms and 0.01 to 1 parts by mass of a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule. %, And the intrinsic viscosity [ ⁇ ] measured in tetralin at 135 ° C is 0.7 dl Zg or more.
  • melt tension ( ⁇ ) and melt flow rate (M l) is, MT / 7 X (MI) -. 0 8> to satisfy the first relation
  • X in the general formula (1) is one or more substituents selected from a substituent containing an amino group, a hydroxyl group, an epoxy group, and an isocyanate group. Composition.
  • the preparation of a mixture of the component (A) and the component (B1) is carried out in a drying step and a transporting step in the production of a propylene polymer or a 1-butene polymer, or in a molding step of the polymer. 3.
  • melt tension (MT) and menoleto flow rate (Ml) obtained by mixing the following components (C2) and (B) are MT / 7 X (Ml) — 0 ⁇ 8
  • a modified polypropylene resin composition that satisfies the relationship of 1 and has a paraxylene-insoluble component amount (G value) of 1 ° C or less at 130 ° C. . (C 2) ethylenic double bond and 1 X 1 0- 6 ⁇ 0 polarity base that - derived polar group to a compound containing in the same molecule 2 5 wt% comprising polypropylene resins: 1 00 parts by weight
  • Polypropylene resin (C2) the modified polypropylene according to 16 or 17 above, which is a mixture of (C3) and (C5) below, or a mixture of (C4) and (C5) below -Based resin composition.
  • the melting enthalpy of the unmodified polypropylene resin (C 4) measured by differential scanning calorimetry (DSC) is 100 J / g or less, and 13 C—N MR was measured.
  • Silane coupling agent (B) force S, (B 1) The modified polypropylene resin according to the above 16 or 17, which is an organic silicon compound represented by the general formula (1).
  • X is a substituent containing a functional group capable of reacting with the polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n is 1-3
  • m is 0- 2 represents an integer
  • (n + m) 1 to 3.
  • silane coupling agent (B) is included in the range of 10 to 10,000 ppm and the phosphorus and / or phenolic antioxidant (D) in the range of 500 to L0, OOO p pm Coupling agent (B), phosphorus and / or phenolic antioxidant (D), and the following polypropylene resin (C3) or
  • Phosphorus and / or phenolic antioxidant so that the phosphorus and / or phenolic antioxidant (D) is contained at 500 to 10,000 ppm
  • a method for producing a modified polypropylene resin composition comprising mixing 0.1 to 30 parts by weight of the reactant with 0 part by weight.
  • a method for producing a modified a-olefin polymer composition which comprises mixing to give a force S, OZl 00 to 99/1.
  • Modified a-olefin polymer melt tension ( ⁇ ) and Merutofu the low rate of the composition (M l) is met MT / 7 X (M l) 10. 8> the one relationship, and 1 3 0.
  • the amount of paraxylene-insoluble components (G value) in C is 1 weight.
  • Modified haloolefin polymer (C6) Force The method for producing the modified ⁇ -olefin polymer composition according to the above item 26 or 27, which is a modified propylene (co) polymer or a modified 1-butene (co) polymer .
  • silane coupling agent ( ⁇ ) Force S, (B1) Modified ⁇ -olefin polymer composition according to the above 26 or 27, which is an organic silicon compound represented by the general formula (1) Method of manufacturing a product.
  • X is a substituent containing a functional group capable of reacting with the polar group
  • Y is a hydrocarbon.
  • FIG. 1 is a diagram showing the compositions of Examples 20 to 35, Comparative Examples 6 to 9, and Reference Examples 1 to 8 and the relationship between ⁇ I and ⁇ of the calculated values.
  • FIG. 2 shows Examples 36 to 44, Comparative Examples 10 to 13, Undenatured ⁇ _; 3 is a diagram showing the compositions of Reference Examples 1 to 8 and the relationship between ⁇ I and ⁇ of the calculated values.
  • FIG. 3 shows the compositions of Examples 45 to 62, Comparative Examples 14 to: 18 and native ⁇ ⁇ _ 5 to 8, Reference Examples 1 to 8 and the relationship between ⁇ I and ⁇ of the calculated values.
  • Examples of the ⁇ -olefin polymer having 2 to 20 carbon atoms which is the component (II) of the present invention 1 and 2, include a high-density polyethylene, a low-density polyethylene, a propylene polymer, a propylene-based copolymer, and a 1-butene polymer. Coalesce, 1-butene copolymer, higher haloolefin polymer having 5 to 20 carbon atoms, and the like. Preferred are a propylene polymer and a 1-butene polymer.
  • the intrinsic viscosity [] measured in tetralin at 135 ° C. is 0.7 to 5 d 1 / g, preferably 1.0 to 3. 10513
  • the intrinsic viscosity [77] is less than 0.7 d 1 / g, mechanical properties such as flexural modulus, flexural strength, and Izod impact strength of the a-olefin polymer compositions of the present inventions 1 and 2 decrease. However, if it exceeds 5 d 1 / g, the moldability will decrease.
  • the shape of the ⁇ -olefin polymer of the present invention 1 is preferably a powder shape or a flake shape.
  • the component organosilicon compound can be easily and highly dispersed in the ⁇ -olefin polymer composition.
  • a powdery ⁇ -olefin polymer having a high surface area is preferred.
  • the particle size of the flake-shaped a-olefin polymer is from 200 to 2000 ⁇ m, preferably from 200 to 150 ⁇ m.
  • the average particle size of the powdery haeofin polymer is from 50 to 2000 ⁇ ; preferably from 200 to 150 ⁇ m.
  • the average particle size is less than 50 m, the supply of the haloolefin polymer during melt kneading becomes unstable due to clogging and the like, and if the average particle size exceeds 200 ⁇ m, the ⁇ -olefin polymer There is a possibility that the dispersion of the organosilane compound therein cannot be sufficiently performed, and that the supply of the one-year-old refin polymer becomes unstable.
  • the bulk specific gravity is 0.2 to 0.6 g / cm 3 , and preferably 0.30 to 0.55 g / cm. It is.
  • ⁇ - Orefin polymer of the present invention 1 and 2 when the propylene polymer and 1 one heptene polymer, its Mesopentatsu de fraction [mmmm] is preferably not 9 7 mol% or more.
  • the mesopentad fraction [mmmm] refers to the 13 C— proposed by A. Zambelli, et al., In “Macromolecules, 6, 9, 25 (1973)”. It means the isotactic fraction in pentad units in a propylene polymer molecule measured by NMR spectrum.
  • 1-butene polymer as in the case of propylene polymer, it means the isotactic fraction in pentad units in 1-butene polymer molecule measured by 13 C-NMR spectrum. I do.
  • X is a substituent containing a group capable of reacting with the polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n 1-3
  • m 0-2.
  • (n + m) 1 to 3.
  • X is preferably at least one substituent selected from substituents including an amino group, a hydroxyl group, an epoxy group and an isocyanate group, and particularly preferably a substituent including an amino group.
  • R is preferably an alkyl group having 1 to 6 carbon atoms, and (n + m) is 1 to T / JP2003 / 010513
  • organic silicon compound examples include, for example, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminobutyritol (methoxyethoxy) silane, 3-aminopropylmethyldiethoxysilane , 3-aminopropino reethoxymethoxysilane, 4-aminobutyltriethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 31 (1-aminopropoxy) 1,3,3-dimethyl-1-propionyltrimethoxysilane, methyltris (2-aminoethoxy) silane, 2- (2-aminoethylthioethyl) ethoxymethylsilane, 3- [2 — (2-aminoe
  • the addition amount is less than 0.01 part by mass, the melt tension of the ⁇ -olefin polymer composition will not be improved, and if it exceeds 1 part by mass, the improvement in the melt tension commensurate with the cost increase will not be observed.
  • the content of the organic silicon compound of the present invention 2 is 0.001 to 1 part by mass, preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the ⁇ -olefin polymer.
  • the melt tension of the ⁇ -olefin polymer composition will not be improved, and if it is more than 1 part by mass, no improvement in the melt tension corresponding to the cost increase will be observed.
  • the ⁇ -olefin polymer of the component ( ⁇ ) containing the organic silicon compound of the component (B 1) of the present invention 2 is, for example, an ⁇ -olefin polymer of the component ( ⁇ ) and an organic cage compound of the component ( ⁇ 1). It can be produced by melt-kneading elemental compounds.
  • melt kneading method examples include (1) a method of passing a dry mixture of a monoolefin polymer and an organic silicon compound through an extruder, and (2) a method of adding an organic silicon compound to an ⁇ -olefin polymer of the extruder.
  • the melt-kneading temperature is generally from 170 to 300 ° C, preferably from 180 to 250 ° C.
  • the melt-kneading (residence) time is from 10 seconds to 120 seconds.
  • melt-kneading it is preferable to keep it under an inert gas atmosphere.
  • steam may be added or volatile components may be removed under reduced pressure.
  • a single screw extruder, a twin screw extruder, or the like is used as the molding machine.
  • twin-screw extruder 20 mm ⁇ Laboplastomill, 3 5 ⁇ ⁇ (Toshiba Machine twin screw extruder).
  • the component (A) can be efficiently produced.
  • Examples of the olefin polymer modified with a polar group having 2 to 20 carbon atoms of the component (C1) of the present invention 1 and 2 include, for example, high-density polyethylene, low-density polyethylene, propylene polymer, and propylene-based copolymer. And modified polymers of unsaturated carboxylic acids and / or anhydrides thereof, such as 1-butene polymers, 1-butene copolymers and higher haloolefin polymers having 5 to 20 carbon atoms.
  • ⁇ -olefin polymer a propylene polymer and a 1-butene polymer are preferable.
  • the intrinsic viscosity [ ⁇ ] measured in tetralin at 135 ° C. is 0.7 d 1 / g or more, preferably 0.7 to 5 d 1 / g, more preferably 0.8 to 3 deciliters Zg.
  • the intrinsic viscosity [] is less than 0.7 dl / g, a component effective for developing the melt tension of the ⁇ -olefin polymer composition is efficiently generated. If it exceeds 5 dl / g, miscibility with the a-olefin polymer of the component (A) containing the organic silicon compound of the component (B 1) tends to be poor, and the by-product of the gel tends to occur.
  • the effective components for the development of the melt tension include the high molecular weight of ⁇ -olefin formed by the reaction of the polar group-modified monoolefin polymer with the organic silicon compound and the water crosslinking reaction which is considered to occur subsequently.
  • Polymers and haloolefin polymers having a long-chain branched or star-shaped structure are conceivable.
  • the content of the polar group derived from the compound containing the ethylenic double bond and the polar group of the present invention 1 and 2 in the same molecule is 0.001 to 1% by mass, preferably 0.01% by mass. ⁇ 0.5 mass. / 0 .
  • the above-mentioned melt-tension-generating component is generated by the reaction with the organic silicon compound or the reaction with the organic silicon compound contained in the component (II). If the content exceeds 1% by mass, a three-dimensional network structure (gel component) tends to be produced as a by-product in addition to the melt tension developing component due to the reaction with the organic silicon compound.
  • the amount of the a-olefin polymer modified with a polar group is 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the ⁇ -olefin polymer. It is.
  • the amount is less than 0.1 part by mass, the amount of the melt tension generating component is reduced, and it is difficult to achieve a sufficient effect.
  • the amount of the three-dimensional network structure which is considered to be a by-product of the process, increases, and molding defects, appearance defects, etc. tend to occur.
  • the proportion of the high-refined polymer modified with the polar group in the composition is increased, and the cost is increased.
  • the ⁇ -olefin polymer modified with the polar group of the component (C 1) according to the first and second aspects of the present invention preferably further satisfies the following (1) to (3).
  • the melt tension cannot be sufficiently improved, and if it exceeds 3.0, the generation of a three-dimensional network structure increases, which may cause problems such as poor molding and poor appearance.
  • 3 1 value is the number average molecular weight Mn [gel permeation chromatography to Nkuroma chromatograph (GP C) Method] chain number of the calculated ⁇ - Orefuin polymer from (mol / g) and the polar group content (mol / g) means that a compound containing one molecule of an ethylenic double bond and a polar group in one molecule per chain of ⁇ -olefin polymer is added when this value is 1. Become.
  • MwZMn exceeds 2.5, the homogeneity of the molecular weight of the polymer modified with a polar group is reduced (components having different molecular weights are mixed), and the melt tension generated by the reaction with the organic silicon compound is reduced.
  • the improving component also becomes non-uniform, making it difficult to achieve a stable melt tension improving effect.
  • Examples of the polar group derived from the compound containing an ethylenic double bond and a polar group in the same molecule used for modifying the -olefin polymer of the present invention 1 and 2 include a carboxylic acid group, a carboxylic anhydride group, and a carboxylic acid.
  • these compounds include carboxylic acid anhydrides, esters, halides, amides, imides and salts. 3 Of these, unsaturated dicarboxylic acids or their anhydrides are preferred.
  • unsaturated mono- or dicarboxylic acids include acrylic acid, methacrylic acid, maleic acid, endo-bicyclo [2.2.1] 1-heptene-1,2,3-dicarboxylic acid (endic acid), fumaric acid , Tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid and the like.
  • unsaturated carboxylic acid derivatives include maleenyl chloride, maleimide, maleic anhydride, endic anhydride, methyl acrylate, acrylic amide, methyl methacrylate, glycidyl methacrylate, methacrylic amide, and anhydride.
  • examples include citraconic acid, itaconic anhydride, nadic anhydride, monomethyl maleate, dimethyl maleate, monomethyl fumarate, dimethyl fumarate and the like.
  • acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred, and maleic anhydride is more preferred.
  • the amount of the compound containing an ethylenic double bond and a polar group in the same molecule is 0.1 to 10 parts by mass, preferably 0.2 to 100 parts by mass of the ⁇ -olefin polymer. ⁇ 2 parts by weight is good.
  • the amount of the compound used is less than 0.1 part by mass, the addition amount of the compound containing an ethylenic double bond and a polar group in the same molecule is small, and the 1 value may be less than 0.5. is there.
  • a compound containing an unreacted ethylenic double bond and a polar group in the same molecule that causes odor for example, unsaturated rubonic acid and / or anhydride thereof will be added.
  • a radical initiator is usually used for the modification of the a-olefin polymer of the present invention 1 or 2 with a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule.
  • radical initiators of the present invention 1 and 2 include butylperoxide, a, ⁇ -bis (t-butylpentanoloxy) diisopropinolebenzene, benzoinolenolenoxide, dichlorenbenzoenolenolenoxide, and dicuminolate.
  • Preferred radical initiators include 2,5-dimethyl-1,2,5-di (t-butynolenoleoxy) hexine-13, dicaminolenoreoxide, hi, hibis (t-butylperoxy) diisopropylbenzene, 5-dimethinolee 2,5-di (t-butylperoxy) hexane;
  • the amount of the radical initiator to be used is 0.01 to 1 part by mass, preferably 0.05 to 0.25 part by mass, per 100 parts by mass of the olefin polymer.
  • Weight average molecular weight (Mw) / number average molecular weight (Mn) may exceed 2.5.
  • the intrinsic viscosity [] of the ⁇ -olefin polymer modified with a polar group becomes less than 0.7 d 1 Zg, and the amount of components having a molecular weight of 10,000 or less exceeds ⁇ ⁇ 5 mass%. May be.
  • the method for producing the ⁇ -olefin polymer modified with the polar group of the present invention 1 and 2 includes, for example, ⁇ ; -olefin polymer, a radical initiator, unsaturated carboxylic acid and ⁇ or anhydride thereof.
  • a method of blending and melt-kneading is exemplified.
  • the ⁇ -olefin polymer modified with the polar group of the present invention 1 contains irganox 101 0 [tetrakis (methylene-3- (3,, 5 ′)-diene) as long as the effect of the present invention is not impaired.
  • t-Ptinolate 1 '-(hydroxyphenyl) propionate) methane irgafos 16 8 [tris (2,4-di-t-butyl: nyl) phosphite] and antioxidants as described below
  • Conventional additives such as neutralizing agents such as calcium stearate and the like can be further added.
  • the melting and kneading temperature of the present inventions 1 and 2 is generally 170 to 300 ° C, preferably 180 to 250 ° C. 3 Melt kneading (residence) time is 10 seconds to 120 seconds.
  • melt-kneading it is preferable to keep it under an inert gas atmosphere.
  • steam may be added or volatile components may be removed under reduced pressure.
  • a single screw extruder, a twin screw extruder, or the like is used as the molding machine.
  • twin-screw extruder examples include a 20 mm ⁇ laboplast mill, 35 ⁇ (Toshiba Machine twin-screw extruder) and the like.
  • the ⁇ -olefin polymer modified with the polar group melt-kneaded is then subjected to the following treatment (1), treatment (2), or treatment (2).
  • treatment (1), treatment (2), or treatment (2) the content of a polar group derived from a compound containing an unreacted ethylenic double bond and a polar group in the same molecule can be reduced.
  • the one-year-old olefin polymer composition of the present invention 1 comprises 100 parts by mass of the monoolefin polymer of the component ( ⁇ ), 0.001 to 1 part by mass of the organosilicon compound of the component ( ⁇ 1), and (C 1) Hyolephine polymer modified with the polar group of the component 0: It can be obtained by contacting! To 30 parts by mass.
  • the ⁇ -age olefin polymer composition of the present invention 1 further satisfies the following items (1) to (3).
  • the silicon compound derived from the organic silicon compound of ( ⁇ 1) component is 0.0 0.01 to :! Mass%
  • MT c [unit: g] 7 X (MI) _.
  • ⁇ 8 means from equation (3) that the melt tension is 7 times the melt tension of the olefin polymer.
  • the MT value means the melt tension level at which various physical properties due to the improvement of the melt tension are sufficiently exhibited, and the moldability, mainly the drawdown property of blow molding and thermoforming, and the pinch-off property and the like. It also serves as an index for high-speed moldability during film formation.
  • the ⁇ -olefin polymer composition of the present invention 2 comprises 100 parts by mass of a component (II) of a haloolefin polymer containing an organic silicon compound as a component (B 1) and 100 parts by mass of a component (C 1). It is obtained by mixing (reacting) 0.1 to 30 parts by mass of a olefin polymer modified with a polar group, and has a melt tension ( ⁇ ), a melt flow rate (Ml) force, MT / 7 x ( MI)-° ⁇ 8 > 1. ,
  • the amount of the component insoluble in paraxylene at 130 ° C. is preferably less than 1% by mass.
  • the component amount (G value) insoluble in paraxylene at 130 ° C was adopted.
  • Methods for obtaining the a-olefin polymer compositions of the present inventions 1 and 2 include a melt-kneading method, a reaction method in a solution, and the like. And a melt-kneading method.
  • the conditions for the melt-kneading method include, for example, the following conditions.
  • the melt-kneading temperature is from 80 to 350 ° C, preferably from 130 to 250 ° C.
  • the melting and kneading time is 1 second to 6 hours, preferably 30 seconds to 3 hours.
  • a single screw extruder, a twin screw extruder, or the like is used as the molding machine.
  • twin-screw extruder examples include a 20 mm ⁇ laboratory blast mill, 35 mm ⁇ i> TEM (Toshiba Machine twin-screw extruder) and the like.
  • the organic silicon compound as the component (B 1) is sufficiently dispersed in advance in the ⁇ -olefin polymer as the component (A).
  • the ⁇ -olefin polymer composition obtained by dispersing the component (B 1) into the component (II) under the temperature condition equal to or lower than the melting point of the component (II) and then reacting the component (C 1) is more preferable.
  • an ⁇ -olefin polymer of the component ( ⁇ ) containing the organic silicon compound of the component (B1) is produced in the first half of the extruder, and in the latter half thereof. It is also possible to knead the o-olefin polymer modified with the polar group of the component (C1).
  • antioxidants can be added to the ⁇ -olefin polymer compositions of the present inventions 1 and 2 as long as the effects of the present invention are not impaired.
  • examples of the antioxidants of the present inventions 1 and 2 include phenol-based, zeolite-based, and phosphorus-based antioxidants.
  • phenolic antioxidants examples include 2,6-di-tert-butyl-1- ⁇ -talesol, butylated hydroxy-sonoré, 2,6-di-tert-butynole 4-ethylphenol, and stearyl-1 ⁇ - (3,5-di- t-puchiru 4-h 10513 Monophenolic antioxidants, such as droxyphenyl) propionate, 2,2'-methylenebis (4-methynole-6-t-p-tinolephenenole), 2,2'-methylenebis (4-ethynole-one 6-t-ptinolef) Enolole), 4,4, -thiobis (3-methyl-6-t-butynolephenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1,1] -Dimethyl-2-[[ ⁇ - (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy]
  • zeotype antioxidants examples include dilauryl-1,3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-1,3,3′-thiodipropionate, and the like.
  • Phosphorus-based antioxidants include triphenyl phosphite, diphenylisodesinolephosphite, phenyleisoisodecinolephosphite, 4,4'-butylidene-bis (3-methyl-6-t- Butylpyruditridecyl) phosphite, cyclic neopentanetetraylbis (octadecyl phosphite), tris (noylphenyl) phosphite, tris (mono) 3 or dinoyurphenyl) phosphite, disodecylpentaerythritol diphosphite, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -19,10-dihydro-19-oxa 1 10—Phosphaphenanthrene 1 10—Oxide, 10 0—Dexyloxy 9, 10 0—Dihydro 9 9
  • the compounding amount of the antioxidant is preferably in the range of 100 to 100,000 mass ppm with respect to the total amount of the components (A), (Bl) and (C1).
  • it is 1000 to 5000 mass ppm.
  • the MI and MT may not be stable. Even if the amount exceeds 10,000 mass parts per million, an effect commensurate with cost cannot be obtained.
  • the antioxidant it is preferable to mix both a phosphorus antioxidant and a phenolic antioxidant.
  • additives such as a neutralizing agent such as calcium stearate can be further added.
  • the polypropylene resin (C 2) is a compound containing a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule (hereinafter, referred to as a modifier).
  • the amount 0/0 preferably, 2X1 0- 5 ⁇ 0. 1 5 wt 0/0, more preferably, not particularly limited as long as it is 5x1 0- 5 '0 0 weight 0/0 containing polypropylene resin.
  • the content of the polar base is 1 xl 0 - If less than 6 wt 0/0, Shirankappuri down the reaction does not proceed too much and grayed agent (B), the melt tension of the composition is difficult to increase. On the other hand, if the content exceeds 0.25% by weight, the composition gels, and conversely, the melt tension of the composition decreases, and the heat resistance and mechanical properties decrease.
  • the content of the polar group can be determined by forming a polypropylene resin (C 2) into a film and measuring the Fourier transform infrared absorption spectrum using the film.
  • the polypropylene resin is a propylene homopolymer, or a random copolymer, a block copolymer, a graft copolymer, or a mixture thereof of propylene and a one-year-old olefin (eg, ethylene, 1-butene, etc.).
  • a one-year-old olefin eg, ethylene, 1-butene, etc.
  • propylene homopolymer is preferred.
  • the polar group of the polypropylene resin (C 2) may be a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule used for modifying the monoolefin polymer of the present inventions 1 and 2. The same can be mentioned.
  • the modifier used in the present invention 3 is not particularly limited, and examples thereof include the same modifiers as those of the present inventions 1 and 2.
  • Such a polypropylene resin (C 2) can be produced, for example, by melt-kneading a polar group-free polypropylene resin, a radical initiator, and the above-mentioned modifier.
  • the conditions such as the blending conditions and the reaction conditions can be appropriately adjusted so that the ratio of the polar group is lxlO 16 to 0.25% by weight.
  • radical initiator of the present invention 3 include the same radical initiators as those of the present inventions 1 and 2.
  • polypropylene resin (C 2) a polypropylene resin not containing a polar base (an unmodified polypropylene resin) and a polar base are used.
  • a mixture with a containing polypropylene resin (modified polypropylene resin) can also be used.
  • the ratio of the polar group in the modified polypropylene resin and the mixing ratio of these are appropriately determined so that the ratio of the polar group contained in the mixture finally becomes 1 ⁇ 10 16 to 0.25% by weight. Can be adjusted.
  • polypropylene resin (C2) preferably, the following (C3) and (C5), or the mixture of the following (C4) and (C5) is used.
  • the melt flow rate is preferably from 0.01 to: 100 g / l 0 min, more preferably from 0.1 to 50 g / 10 min, even more preferably from 1 to 20 g / l.
  • the melting point is preferably between 145 and 170.
  • C more preferably an unmodified polypropylene resin at 150-170 ° C
  • the methanol flow rate is preferably from 0.01 to: 100 g / 10 minutes, more preferably from 0.1 to 50 gZ10 minutes, and still more preferably from 1 to 20 g. / 1 0 minutes, 13 C-NMR was measured to seek the main Sopenta' de fraction ([mmmm]) force S, preferably, 40-9 0 mol%, more preferably, 60-8 0 mol 0 / 0 unmodified polypropylene resin
  • the content of (C 5) polarity base is preferably 0.00 1-1 wt%, good Ri preferably 0. 0 1 to 0.5 wt 0/0, 1 3 5 ° C, Tetorari Intrinsic viscosity measured in solution is preferably 0.7 dl, g or more, more preferably 0.7 to 5.0 dl / g, and still more preferably 0.8 to 3.0 dl / g.
  • the unmodified polypropylene resin (C4) used here is an unmodified soft polypropylene resin.
  • the reaction between the modified polypropylene resin (C5) and the silane coupling agent (B) (the formation of a melt tension developing component) 2003/010513 reaction), and will be performed in the unmodified polypropylene resin (C3) or (C4).
  • a component effective for improving the melt tension can be uniformly distributed in the unmodified resin.
  • melt flow ratio of the unmodified polypropylene resins (C3) and (C4) is less than 0.01 g / 10 minutes, the moldability of the resin composition may be reduced.
  • the heat resistance of the polypropylene resin may be impaired.
  • the content of the polar group was 0.001% by weight. If the ratio is less than / 0, there is a possibility that the effect of improving the melt tension is not so much exhibited.
  • the intrinsic viscosity is less than 0.7 d 1 / g, there is a possibility that a component having a property effective for the development of melt tension may not be efficiently generated, or that the melt tension of the obtained resin composition may lower the melt tension. There is.
  • the unmodified polypropylene resin (C5) has a melting enthalpy measured by a differential scanning calorimeter (DSC) of preferably lOOJZg or less, more preferably 90JZg or less. Above 100 jZg, flexibility may be impaired.
  • DSC differential scanning calorimeter
  • the mesopentad fraction ([mmm m] and [rrrr]) force determined by measuring 13 C-NMR, preferably ([rrrr] Z 1— [mmm m]) ⁇ 20% Fulfill.
  • This value is more preferably 20 to 30%.
  • the pentad fractions [mm mm] and [rrrr] are as shown in A. Zambelli 1 S, Macromolecules, Vol. 6, 9 proposed in 2 page 5 (1 9 7 3), respectively taste Thanked Mesopenta' de fraction and racemic pair Nta' de fraction in Penta' degrees polypropylene molecular chain as determined from 1 3 C one NMR spectrum .
  • the polar base may be too small and the melting tension of the resin composition may not be improved.
  • the molecular chain may be cut too much and the intrinsic viscosity may decrease.
  • the amount of the modified polypropylene resin (C5) is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight of the unmodified polypropylene resin (C3) or (C4). , 1 to 20 parts by weight.
  • the amount is less than 0.1 part by weight, the polar base in the polypropylene resin (C 3) may be too small.
  • Such unmodified polypropylene resins (C 3) and (C 4) can be appropriately polymerized by a known method.
  • the modified polypropylene resin (C5) can be produced by the same method as described above.
  • the silane coupling agent (B) of the present invention 3 is not particularly limited, but is preferably (B1) an organic silicon compound represented by the general formula (1).
  • X is a substituent containing a functional group capable of reacting with the polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • 11 is 1-3
  • m is 0- 2 represents an integer
  • (n + m) 1 to 3.
  • organosilicon compound represented by the general formula (1) are as described in the present inventions 1 and 2.
  • the blending amount of the silane coupling agent (B) is as follows. 2) 0.001 to 1 part by weight, preferably 0.1 to 0.5 part by weight, per 100 parts by weight.
  • the amount is less than 0.001 part by weight, the effect of improving the melt tension is reduced.
  • melt tension may decrease.
  • antioxidant (D) of the present invention 3 examples include tris (2,4-di-t-butylphenyl) phosphite (Circa succinoreti ⁇ ilgafos 1668 (trade name) manufactured by Chemika Norez).
  • Pentaerythri-tono-resin phosphite made by Adeki-A-Igas Co., Ltd., PEP-36 (trade name)
  • 4,4,1-biphenyl phosphine Phosphorus antioxidants such as acid tetrakis (2,4-di-tert-butylphenyl) (manufactured by Clearant Japan, S ande Stab P—E.PQ (trade name)) and tetrakis (methylene _ 3 -— (3'5, 1-t, 1-hydroxyl-hydroxy-2-propionate) Propionate) Methane (manufactured by Ciba-Susio-Noretti Chemicals, Inc., Irganox 101 (trade name)), Tetrakis [methylene One 3— (3,5'-di-t-butyl-1-4'-hydroxyphenyl)] propionat
  • Irganox 110 and Irgafos 168 are preferred.
  • the phosphorus-based and phenol-based antioxidants may be used alone or in combination of two or more.
  • antioxidants may be used in combination.
  • the amount of the antioxidant (D) to be blended is 0.1 to 0.5 part by weight, preferably 0.1 to 0.5 part by weight, per 100 parts by weight of the polypropylene resin (C 2). .
  • the amount is less than 0.05 part by weight, quality may be reduced during processing and storage of the polypropylene resin.
  • the cost may increase.
  • melt tension (MT) and the melt flow ratio (Ml) satisfy the relationship of MT / 7 X (Ml) "° ⁇ 8 > 1.
  • This ratio is preferably a value greater than 2.
  • a composition satisfying this relationship is superior to a conventional polypropylene-based resin in that it exhibits high fluidity while maintaining a high melt tension.
  • This relationship is based on the fact that the component generated by the reaction between the modified polypropylene resin (C4) and the silane coupling agent ( ⁇ ) contributes to the improvement of ⁇ (structure having a high molecular weight and a branched structure). It is established when it becomes.
  • the molecular weight of the modified polypropylene resin (C 4) is extremely small (for example, [77] is 0.19), the relationship of the formula can be satisfied because the molecular weight of the branched structure formed is low. No enhancement component is formed. Further, when the polarity base Z polymer chains of the modified polypropylene resin (C 4) (] 3 2 value) is significantly higher (e.g., but 1 2), the three-dimensional network structure does not stop in the formation of branched structures It is believed that the reaction proceeds until formation. The network structure thus formed is merely a gel component, and does not work as an improving component.
  • modified polypropylene resin (C4) be uniformly dispersed (sufficiently compatible) in the unmodified polypropylene resin (C2, C3).
  • the molecular weight of the modified polypropylene resin (C 4) is significantly different from the molecular weight of the unmodified polypropylene resin (C 2, C 3) or when the polarity of the modified polypropylene resin (C 4) is extremely high. (e.g., if the amount of the acid is 4 by weight. / 0 and significantly higher), the phase for solubility is significantly decreased, uniform dispersion of the in ⁇ improve Ingredient unmodified polypropylene resin (C 2, C 3) Is obstructed, and the relation of the expression cannot be satisfied.
  • ⁇ value can be adjusted freely.
  • the modified polypropylene resin composition of the present invention 3 has a paraxylene-insoluble component amount (G value) at 130 ° C. of 1% by weight or less.
  • G value is the amount of gelled component with ultra-high molecular weight, and G value is 1 weight. /. If it exceeds, the appearance may be poor when the composition is molded.
  • G value 1 weight 0 /. If it exceeds, reduce Blend amount and the amount of acid-modified polypropylene (C 4), reducing the amount of the silane coupling agent (B), also of the modified polypropylene (C 4); 8 binary By reducing the value, the G value can be reduced to 1% by weight or less.
  • composition of the present invention 3 may contain, if necessary, a nucleating agent, an antioxidant, an ultraviolet absorber, an external lubricant, a plasticizer, an antistatic agent, a coloring agent, a flame retardant, a flame retardant auxiliary, and other additives.
  • a thermoplastic resin or the like can be appropriately compounded.
  • nucleating agent examples include aluminum di (pt-butylbutylate) and other metal salts of carboxylic acids, methylenebis (2,4-di-t-butylphenol) acid phosphate sodium and others Metal salts of phosphoric acid, talc, phthalocyanine derivatives and the like.
  • plasticizer examples include polyethylene glycol, polyamide oligomer, ethylene bisstearamide, estenolate phthalonate, polystyrene oligomer, polyethylene wax, mineralolae inole, and silicone oil.
  • flame retardant examples include brominated polystyrene, brominated syndiotactic polystyrene, and brominated polyphenylene ether.
  • flame retardant aid examples include antimony trioxide and other antimony compounds.
  • thermoplastic resins may be used alone or in a combination of two or more.
  • composition of the present invention can be produced by mixing the following (C 2) and (B) or the following (C 2), (B) and (D).
  • (C 2) 1 ⁇ 10 6 to 0.25 weight of a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule.
  • / 0 including polypropylene resin 100 parts by weight
  • melt kneading method a melt kneading method, a solution mixing method, and the like can be cited, but the melt kneading method is preferable in consideration of economic efficiency.
  • the melt-kneading method it is preferable to disperse the silane coupling agent (B) in the polypropylene resin (C 2) in advance.
  • the mixing of the components is preferably performed at 80 to 350 ° C, more preferably 130 to 250 ° C, preferably for 1 second to 6 hours, more preferably 30 seconds to 3 hours.
  • the polypropylene resin (C2) can be produced by mixing the following (C2) and (C4) or the following (C4) and (C5).
  • (C4) a modified polypropylene resin containing 0.001-1% by weight of the polar group and having an intrinsic viscosity of 0.7 d 1 / g or more measured at 135 ° C. in tetralin; : 0.1 to 30 parts by weight
  • composition of the present invention 3 is preferably produced by the following method.
  • modified polypropylene resin (C4) is mixed with 100 parts by weight of the mixture.
  • a phosphorus-based and / or phenol-based antioxidant (D) is contained so that the phosphorus-based and / or phenol-based antioxidant (D) is contained in an amount of 500 to 100,000 ppm, preferably 1,000 to 5,000 ppm.
  • D) is mixed with a polypropylene resin (C 2) or (C 3).
  • silane coupling agent (B) is reacted with the modified polypropylene resin (C4).
  • composition of the present invention 3 has a high melt tension, it is possible to greatly improve the moldability of the polypropylene resin.
  • composition of the present invention can be molded by sheet molding, film molding, thermoforming, foam molding, blow molding, or other molding methods. This is effective when performing professional molding or foam sheet molding, which was difficult to mold.
  • composition of the present invention is very versatile because it can be easily produced with existing production equipment.
  • the molded article of the composition of the present invention can be used for various general-purpose trays, interior materials for automobiles, and the like.
  • a method for producing the modified o-olefin polymer composition of the present invention 4 will be described.
  • the composition does not exhibit a desired melt tension.
  • the silane coupling agent ( ⁇ ) when the amount exceeds 0.5 parts by weight, the silane coupling agent ( ⁇ ) is not effectively used, and the production cost is increased.
  • the mixing method of each component is not particularly limited, and includes, for example, a melt mixing method and a solution mixing method.
  • the melt mixing method is preferable in view of economy.
  • the modified a-olefin polymer (C 6) and the silane coupling agent (B) are preferably melt-mixed.
  • the modified monoolefin polymer (C 6) and the silane coupling agent (B) are melt-mixed, and the melt mixture [(B) + (C 6)] and ⁇ -olefin polymer ( ⁇ ) is melt-mixed.
  • the mixing temperature of the modified hypoolefin polymer (C 6) and the silane coupling agent IJ ( ⁇ ) is preferably 160 to 300 ° C., more preferably 200 to 250 ° C., and the mixing time Is preferably 1 second to 10 minutes, more preferably 30 seconds to 4 minutes. 03010513
  • the mixing conditions of the mixture [(B) + (C 6)] and the ⁇ -olefin polymer ( ⁇ ) are not particularly limited, but preferably the same temperature and time as described above.
  • the modified ⁇ -olefin polymer (C 6) is an ⁇ -olefin polymer having 2 to 20 carbon atoms modified by a compound containing an ethylenic double bond and a polar group in the same molecule (hereinafter referred to as a “modifier”). It is united.
  • Modified ⁇ - Orefuin polymer (C 6) is containing chromatic of the polar base from denaturant, 0.0 0 1 to 0.4 wt 0/0, preferably 0.0 1 to 0.4 weight 0/0, more preferably 0.0 3 to 0.3 wt%.
  • the composition does not exhibit a desired melting tension.
  • composition gels and the G value is 1% by weight. / 0 will be exceeded.
  • the content of the polar group can be determined by forming a modified ⁇ -olefin polymer (C 6) into a film and measuring the Fourier transform infrared absorption spectrum using the film.
  • Examples of the polar group of the modified ⁇ -olefin polymer (C 6) of the present invention 4 include the same polar groups as those of the present invention 1 and 2.
  • the modifier used in the present invention 4 is not particularly limited, and examples thereof include the same modifiers as those used in the present invention 1 and 2.
  • the modified ⁇ - olefin polymer (C 6) of the present invention 4 was prepared at 135 ° C.
  • Intrinsic viscosity ([77]) measured in a solution, 0.9 to 5.0 d 1 Zg, preferably: 9 to 3.5 dl Zg, more preferably 1.0 to 2 5 d 1 / g.
  • composition gels and the G value exceeds 1% by weight.
  • the modified olefin polymer (C 6) has a weight average molecular weight and a number average molecular weight (Mw / Mn) of 3 or less, preferably 2.5 or less.
  • Mw and Mn can be measured by gel permeation chromatography (GPC).
  • the modified ⁇ -refined polymer (C 6) has a molar ratio ( ⁇ 3 value) between the polar group and the polymer chain of 0.1 to 3.0, preferably 0.5 to 3.0. Preferably, it is 0.5 to 2.0.
  • 3 3 value means a ratio of the calculated from ⁇ measured by GP C method (C 6) polymer strand number (mol Zg) and a polar base (mol / g), the value is 1 In this case, one molecule of the modifying agent is added per one polymer chain.
  • a modified olefin polymer (C 6) can be produced, for example, by melt-kneading a one-year-old olefin polymer having 2 to 30 carbon atoms, a radical initiator and the above-mentioned modifier.
  • the conditions such as the blending conditions and the reaction conditions are determined based on the polar base content of (C 6), [77], MwZMn and
  • the ( ⁇ ) ⁇ -olefin polymer having 2 to 20 carbon atoms of the present invention 4 includes, for example, ethylene (co) polymer, propylene (co) polymer, 1-butene
  • a propylene (co) polymer or 1-butene (co) polymer is preferred.
  • These polymers can be appropriately polymerized by a known method.
  • radical initiator of the present invention 4 examples include the same radical initiators as those of the present inventions 1 to 3.
  • the preferred modified olefin polymer (C 6) used in the present invention 4 is a maleic anhydride-modified propylene (co) polymer and a maleic anhydride-modified 1-butene (co) polymer.
  • the silane coupling agent ( ⁇ ) of the present invention 4 is not particularly limited, but is preferably ( ⁇ 1) an organic silicon compound represented by the general formula (1).
  • X is a substituent containing a functional group capable of reacting with the polar group
  • Y is a hydrocarbon group, a hydrogen atom or a halogen atom
  • R is a hydrocarbon group
  • n is 1-3
  • organosilicon compound represented by the general formula (1) are as described in the present inventions 1 and 2.
  • the modified propylene polymer (C 6) and the silane coupling agent (B) are mixed under the above-mentioned conditions to obtain a mixture which is a component effective for the development of a melting tension. [(B) + (C6)] can be obtained efficiently.
  • the detailed mechanism by which the mixture [(B) + (C6)] is produced is unknown, but is presumed as follows.
  • the mixture [(B) + (C 6)] is presumed to be a branched, cross-linked or ultra-high molecular weight ⁇ -olefin polymer centered on a silicon atom.
  • the graft structure is formed by the reaction with the amino group of (B), and the methoxy group derived from (B) of this structure is condensed to form a mixture [(B) + (C 6)]. It is estimated to generate.
  • the a-olefin polymer (A) of the present invention 4 is an a-olefin polymer having 2 to 20 carbon atoms, and the [ ⁇ ] force s measured at 135 ° C in tetralin is 0.7. 5.5.0 d 1 / g, preferably 0.9-3.5 d 1 / g, more preferably 1.0-2.5 d I Zg.
  • the moldability of the composition will decrease.
  • ⁇ -olefin polymer ( ⁇ ) those similar to the raw materials for producing the modified ⁇ -olefin polymer (C 6) can be used.
  • These polymers can be appropriately polymerized by a known method.
  • a phosphorus-based and / or phenol-based antioxidant is further mixed with the modified ⁇ -olefin polymer (C 6) and the silane coupling agent ( ⁇ ).
  • an antioxidant of the present invention 4 include the same phosphorus antioxidants and phenolic antioxidants as those of the present inventions 1 to 3.
  • an antioxidant, a nucleating agent, an antioxidant, an ultraviolet absorber, an external lubricant, a plasticizer, an antistatic agent, a coloring agent, a flame retardant, a flame retardant auxiliary, and the like , Or a thermoplastic resin or the like can be appropriately mixed.
  • Specific examples of the nucleating agent, plasticizer, flame retardant and flame retardant auxiliary of the present invention 4 include the same nucleating agent, plasticizer, flame retardant and flame retardant auxiliary as those of the present invention 3. These additives and thermoplastic resins may be used alone or in a combination of two or more.
  • the modified ⁇ -refined polymer composition obtained by the production method of the present invention 4 preferably has a melt tension ( ⁇ ), a melt flow rate (Ml), and MT / I (MI) —. ⁇ Satisfies the relationship 8 > 1.
  • This ratio is more preferably a value greater than 2.
  • a composition satisfying this relationship is superior to a conventional ⁇ -olefin polymer composition in that it exhibits good fluidity while maintaining a high melt tension.
  • the modified ⁇ -refined polymer composition obtained by the production method of the present invention is 130.
  • the amount of paraxylene-insoluble component (G value) of C is preferably 1% by weight or less, more preferably 0.5% by weight or less.
  • the G value is the amount of the gelled component with an ultrahigh molecular weight. If the G value exceeds 1% by weight, the physical properties of the composition are reduced due to the occurrence of multiple gels.
  • the modified ⁇ -olefin polymer composition obtained by the production method of the present invention has a high melt tension, it is possible to greatly improve the moldability of the ⁇ -olefin polymer.
  • This composition can be molded by sheet molding, film molding, thermoforming, foam molding, blow molding, or other molding methods. This is effective when performing blow molding and sheet molding, which was difficult.
  • the molded article of this composition can be used for various general-purpose trays, interior materials for automobiles, and the like.
  • the production method of the present invention can be easily carried out with an existing production apparatus, and is not limited to a modified polyolefin polymer, and produces a composition using another modified thermoplastic resin (for example, polycarbonate or the like). It is very versatile because it can be applied to any situation.
  • the required amount of the relatively expensive silane coupling agent can be reduced, which is economical in terms of manufacturing cost.
  • the physical properties of the present invention were measured according to the following methods.
  • RI detector for liquid chromatogram WATERS 1 50C measurement conditions
  • Solvent 90: 1 0 (volume ratio) of 1, 2, 4-trichlorobenzene and heavy benzene
  • Pulse repetition time 4 seconds
  • the measurement was performed at a measurement temperature of 230 ° C and a load of 2.16 kg according to JIS-K7210.
  • the measurement was performed using a Capillograph 1C manufactured by Toyo Seiki Co., Ltd. at a measurement temperature of 230 ° C and a take-up speed of 3.lm / min.
  • the obtained para-xylene solution was quickly filtered through a 400-mesh stainless steel wire gauze, and then the wire gauze was vacuum-dried at 90 ° C for 4 hours, weighed, and the mass of the components that did not pass through the wire gauze was determined. 1 The amount of paraxylene insoluble part at 30 ° C was determined.
  • the particles were classified using sieves having different meshes, and the particle size at 50% by mass was defined as the average particle size.
  • the temperature of the solution was raised to 80 ° C., followed by 77 milliliters of titanium tetrachloride dropwise added thereto, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a contact operation.
  • a stainless steel autoclave with an internal volume of 10 liters with a stirrer was thoroughly dried, replaced with nitrogen, and dehydrated with 6 liters of heptane, 12.5 millimoles of triethylamine, 12.5 millimoles of dicyclopentyldimethoxysilane 0.3 milliliters Remol was added.
  • the catalytic activity per 1 g of the solid catalyst was 33.1 kg / g-cat. ⁇ 3 hr in 3 hours of polymerization.
  • the propylene polymer used as the raw material of the component (C 1) was synthesized in the same manner as in the above (3) propylene polymerization in the synthesis of the component (A) except that hydrogen was not added.
  • the intrinsic viscosity [77] of the obtained propylene polymer was 7.65 (11 ⁇ ).
  • Acetone (0.5 kg) and heptane (0.7 kg) were added to the obtained pellet-like sample (1 kg), and the mixture was heated and stirred at 85 ° C. for 2 hours (implemented in a pressure vessel). After the same operation, the pellets were collected with a wire mesh, and then immersed in 1.5 kg of acetone for 15 hours.
  • pellets were collected with a wire mesh, air-dried, and vacuum-dried at 80 ° C for 6 hours and at 130 ° C for 6 hours.
  • the characteristics of the maleic anhydride-modified propylene polymer are shown below.
  • component (A) 380 g of the above-mentioned propylene polymer powder, and as the component (B1), 0.995 g of 3-aminopropyltriethoxysilane (APTES), and ilganox 1010 were added. 0.24 g, ilgafoss 1 6 8 was added and 0.5 g of calcium stearate was added, and 0.2 g of calcium stearate was added.
  • APTES 3-aminopropyltriethoxysilane
  • the value of MTc is a calculated value obtained from Equation (3).
  • the value of MTZMTC of the obtained propylene polymer composition was as high as 2.0.
  • a propylene polymer composition was prepared in the same manner as in Example 1 except that the amount of the component (C 1) was changed.
  • the value of MT / MTc of the obtained propylene polymer composition showed a high value of 1.5 to 2.7.
  • Example 1 (3) In the synthesis of the component (A) in Example 1 (3), in the propylene polymerization, a propylene polymer composition was prepared in the same manner as in Example 1 except that the component (A) having a different intrinsic viscosity was used under different hydrogen conditions. Was prepared.
  • the bulk specific gravity of the polymer powder ranged from 0.36 to 0.39 g / cm 3 .
  • the value of MT / MTc of the obtained propylene polymer and composition was as high as 1.6 to 2.7.
  • Example 1 In the synthesis of component (A) in Example 1 (3) In the propylene polymerization, titanium trichloride and getyl aluminum The same procedure as in Example 1 was repeated except that the following components were used and the component (A) was synthesized under the conditions of (2) prepolymerization and (3) propylene polymerization. Was prepared.
  • the value of MT / MTc of the obtained propylene polymer composition was as high as 2.1.
  • a stainless steel autoclave with an internal volume of 10 liters equipped with a stirrer was sufficiently dried, and after purging with nitrogen, 6 liters of dehydrated heptane was added, and nitrogen in the system was replaced with propylene.
  • a propylene polymer composition was prepared in the same manner as in Example 1, except that the component (B1) was not used.
  • the value of MTZMTc of the obtained propylene polymer composition was as low as 0.6.
  • a propylene polymer composition was prepared in the same manner as in Example 1 except that the component (C 1) was not used.
  • the value of MTZMTc of the obtained propylene polymer composition was as extremely low as 0.5.
  • Example 1 A propylene polymer was prepared in the same manner as in Example 1 except that the component (C 1) having a different intrinsic viscosity and a different maleic anhydride content was obtained by changing the amount of peroxide used during the synthesis of the component. A coalescing composition was prepared.
  • the value of MTZMTc of the obtained propylene polymer composition showed a high value of 1.7 to 3.2.
  • the resulting propylene polymer composition had many gels and could not be measured for MI and MT.
  • Example 1 was repeated except that the component (C1) of Example 1 was replaced with a commercially available modified propylene polymer (manufactured by Sanyo Chemical Co., Umex 1010) having a low intrinsic viscosity and a high maleic anhydride content. Similarly, a propylene polymer composition was prepared.
  • a commercially available modified propylene polymer manufactured by Sanyo Chemical Co., Umex 1010 having a low intrinsic viscosity and a high maleic anhydride content.
  • Umex 1010 commercially available modified propylene polymer having a low intrinsic viscosity and a high maleic anhydride content.
  • a propylene polymer composition was prepared.
  • the value of MTZMTc of the obtained propylene polymer composition was as low as 0.4.
  • Example 1 The procedure was performed in the same manner as in Example 1, except that a commercially available modified propylene polymer (manufactured by Toyo Kasei Co., Ltd., Toyo Tack H 1 000 P) having a low intrinsic viscosity and a high maleic anhydride content was used instead of the component (C 1) in Example 1.
  • a propylene polymer composition was prepared in the same manner as in Example 1.
  • the value of MTZMTc of the obtained propylene polymer composition was as low as 0.4.
  • a propylene polymer composition was prepared in the same manner as in Example 1 except that the amount of the component (B1) was changed.
  • the value of MT / MTc of the obtained propylene polymer composition showed a high value of 2.7 to 3.0.
  • Example 19 10513 A propylene polymer composition was prepared in the same manner as in Example 1 except that 3-aminopropyl trimethoxysilane (APTMS) was used instead of APTES.
  • APITMS 3-aminopropyl trimethoxysilane
  • the value of MT / MTc of the obtained propylene polymer composition was 1.2.
  • the component (A), the component (B1) and the component (C1) were simultaneously blended and melted and kneaded, but the components (A) and (B1) were sufficiently blended. Thereafter, the same results as in the case of blending and melt-kneading the component (C 1) were obtained.
  • This powdery mixture was melt-mixed at 230 ° C. using a 20-millimeter twin screw extruder to obtain a propylene polymer pellet containing 300,000 ppm of APTES.
  • Table 2 shows the physical property values of the obtained propylene polymer composition.
  • the value of MTc is a calculated value obtained from Equation (3).
  • the values of MI and MT of the obtained propylene polymer composition were 5.1 g / 10 minutes and 4.2 g, respectively.
  • This MT value was 2.2 times the MTc value obtained by the relational expression (3) between Ml and MT.
  • a propylene polymer composition was prepared in the same manner as in Example 20, except that the content of the organic silicon compound in the component (A) was changed by changing the blending amount of ATES. Table 2 shows the results.
  • the ratio of M I ZMT values of the obtained propylene polymer composition showed a high value of 2.9 to 3.8.
  • the ratio of M I / MT of the obtained propylene polymer composition showed a high value of 1.8 to 3.0.
  • Propylene was prepared in the same manner as in Example 20 except that no organic silicon compound was added.
  • a ren polymer composition was prepared.
  • the ratio of the values of M I ZMT of the obtained propylene polymer composition was 0.6, an extremely low value.
  • a propylene polymer composition was prepared in the same manner as in Example 20, except that the component (C 1) was not used.
  • the ratio of the values of M I / MT of the obtained propylene polymer composition showed an extremely low value of 0.5.
  • a propylene polymer composition was prepared in the same manner as in Example 20, except that the maleic anhydride content of the component (C 1) was changed.
  • the ratio of M I / MT values of the obtained propylene polymer composition was as high as 1.9 to 3.7.
  • a propylene polymer composition was prepared in the same manner as in Example 20, except that the amount of the component (C 1) was changed.
  • the ratio of M I ZMT values of the obtained propylene polymer composition showed a high value of 1.7 to 3.0.
  • Propylene was used in the same manner as in Example 20 except that a commercially available modified propylene polymer having a low intrinsic viscosity and a high content of maleic anhydride (Umettas 110, manufactured by Sanyo Chemical Co., Ltd.) was used as the component (C 1). A polymer composition was prepared. Table 2 shows the results.
  • the ratio of M I ZMT values of the obtained propylene polymer composition was extremely low, 0.4.
  • Example 20 As in Example 20, except that a commercially available modified propylene polymer (manufactured by Toyo Kasei Co., Ltd., Toyo Tack H 1 000 P) having a low intrinsic viscosity and a high maleic anhydride content was used as the component (C 1). A propylene polymer composition was prepared. Table 2 shows the results.
  • the ratio of M I / MT values of the obtained propylene polymer composition showed an extremely low value of 0.3.
  • Table 3 shows the measurement results of the MI and MT of the propylene polymer.
  • the Ml ZMT c ratio showed an extremely low value of 0.3 to 0.5.
  • a stainless steel autoclave with an internal volume of 10 liters equipped with a stirrer was sufficiently dried, purged with nitrogen, and then added with 6 liters of dehydrated heptane, 12.5 millimoles of triethylamine, and 2.5 millimoles of dicyclopentyldimethoxysilane.
  • propylene was introduced with stirring.
  • the catalytic activity per 1 g of the solid catalyst component was 9.8 kg / g-cat. ⁇ 3 hr in 3 hours of polymerization.
  • This polymer exhibited the following properties.
  • the heating and stirring were performed in a pressure vessel.
  • the pellet was collected with a wire mesh and immersed in 1.5 kg of acetone for 15 hours.
  • This polymer exhibited the following properties.
  • the powder blend was melt-kneaded at 230 ° C. using a 20 mm twin screw extruder to produce a polymer composition.
  • Table 4 shows the measurement results of various physical properties.
  • This powder blend was melt-kneaded at 230 ° C. using a 20 mm twin-screw extruder to produce a polymer composition.
  • Table 4 shows the measurement results of various physical properties.
  • the powder blend was melt-kneaded at 230 ° C. using a 20 mm twin screw extruder to produce a polymer composition.
  • Table 4 shows the measurement results of various physical properties.
  • a polymer composition was obtained in the same manner as in Example 36 except that acid-modified PP_2 was used instead of acid-modified PP-1.
  • Table 4 shows the measurement results of various physical properties.
  • a polymer composition was obtained in the same manner as in Example 36 except that acid-modified PP-3 was used instead of acid-modified PP-1.
  • Table 4 shows the measurement results of various physical properties.
  • a polymer composition was obtained in the same manner as in Example 36, except that APTES was not used.
  • Table 4 shows the measurement results of various physical properties.
  • Example 36 maleic anhydride having a modification rate of 4.2 wt%, an intrinsic viscosity of 0.19 d 1 Z g, a polar group Z polymer chain: 2.10 instead of the acid-modified PP-1 was used.
  • a polymer composition was obtained in the same manner as in Example 36, except that a modified propylene polymer (Yumettasu 110 (trade name) manufactured by Sanyo Chemical Industries, Ltd.) (acid-modified PP-4) was used.
  • a modified propylene polymer (Yumettasu 110 (trade name) manufactured by Sanyo Chemical Industries, Ltd.) (acid-modified PP-4) was used.
  • Table 4 shows the measurement results of various physical properties.
  • Example 36 maleic anhydride having a modification rate of 4.1 wt%, an intrinsic viscosity of 0.56 d1 Zg, and a polar group / polymer chain of 12.0 instead of the acid-modified PP-1
  • a polymer composition was obtained in the same manner as in Example 36, except that a modified propylene polymer (manufactured by Toyo Kasei Co., Ltd., Toyo Tac 100 P (trade name)) (acid-modified PP-5) was used.
  • Table 4 shows the measurement results of various physical properties.
  • Example 36 To 800 g of the native PP-1 used in Example 36, 2.0 g of APTES, 0.40 g of irganox, 0.148 g of irganox, 168: 1.12 g of irgafos, calcium stearate: 0.4 g was added and thoroughly blended. This powder blend was melt-kneaded at 230 ° C using a 20 mm twin-screw extruder to produce a polypropylene pellet containing 2,500 ppm of APTES and 2,000 ppm of antioxidant. .
  • this pellet 380 g of this pellet and 20 g of the acid-modified PP-1 pellet were mixed and melt-kneaded at 230 ° C. using a 20 mm twin-screw extruder to produce a polymer composition.
  • Table 4 shows the measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 41 except that the amount of APTES used in Example 41 was changed to 1 g.
  • Table 4 shows the measurement results of various physical properties.
  • Example 41 a polymer composition was produced in the same manner as in Example 41, except that the acid-modified PP_2 used in Example 39 was used instead of the acid-modified PP-1.
  • Table 4 shows the measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 41 except that the acid-modified PP-1 was not used.
  • Table 4 shows the measurement results of various physical properties.
  • Table 4 shows the measurement results of various physical properties.
  • Example 36-44 Comparative Examples 10-13, Unmodified P P— :! ⁇ 3 and Reference Examples
  • FIG. 2 shows the relationship between M I and MT of the compositions 1 to 8.
  • compositions of the examples have higher melt tension, show better fluidity, and are more practical than the compositions of the comparative examples.
  • a 10 liter stainless steel autoclave with a stirrer was thoroughly dried and purged with nitrogen, then 2 kg of propylene, 6 mmol of triethylaluminum, 2.4 mmol of CHMDS, and 1-aryl-1-3 , 4—Dimethoxy 0.48 millimoles of benzene (ADMB) was added, and the temperature was raised to 65 ° C.
  • irganox 101 0.06 parts by weight
  • irgafos 168 0.14 parts by weight
  • calcium stearate 0.05 parts by weight
  • Parhexin 25 B / 40 0.035 parts by weight was added and thoroughly blended.
  • This powder blend was melt-kneaded at 180 ° C using a 20 mm twin-screw extruder to produce an unmodified propylene polymer (unmodified PP-5) pellet.
  • Table 5 shows the physical properties of the obtained polymer pellet.
  • This powder blend was melt-kneaded at 180 ° C using a 20 mm twin screw extruder.
  • the heating and stirring were performed in a pressure vessel. After the operation was completed, the pellet was collected and immersed in 1.5 kg of acetone for 15 hours.
  • Table 5 shows the physical properties of this polymer.
  • Table 5 shows the physical properties of this polymer.
  • Table 5 shows the physical properties of this polymer.
  • Table 5 shows the physical properties of this polymer.
  • Table 5 shows the physical properties of this polymer.
  • Table 5 shows the physical properties of this polymer.
  • Unmodified PP synthesized in Production Example 2 (4) —5 pellets of ground product: 380 g, APTE S: 1.0 g, Acid-modified PP synthesized in Production Example 3—20 g And blended well.
  • This powder blend was melt-kneaded at 230 ° C. using a 20 mm twin screw extruder to produce a polymer composition.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • Example 45 the amount of the acid-modified PP-7 was changed to 10 g (Example 461), 30 g (Example 47) and 40 g (Example 48) by adding unmodified PP-7.
  • Polymer was prepared in the same manner as in Example 45, except that the compounding amount of 5 was changed to 390 g (Example 46), 370 g (Example 47), and 360 g (Example 48). A composition was produced.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer was prepared in the same manner as in Example 45 except that the amount of APTE S was changed to 0.3 g (Example 49) and 0.6 g (Example 50) in Example 45.
  • a composition was prepared.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • Example 45 a polymer composition was produced in the same manner as in Example 45, except that the unmodified PP-6 synthesized in Production Example 4 was used instead of the unmodified PP-5.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • Example 45 the unmodified PP-7 synthesized in Production Example 5 was used instead of the unmodified PP-5, and the acid-modified PP-8 synthesized in Production Example 6 was used instead of the acid-modified PP-7.
  • a polymer composition was prepared in the same manner as in Example 45 except that the polymer composition was used. Was manufactured.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • Example 10 the unmodified PP-5 synthesized in Production Example 7 was used in place of the unmodified PP-5, and the acid-modified PP-9 synthesized in Production Example 8 was replaced with the acid-modified PP-7 in place of the acid-modified PP-7. Except for using, a polymer composition was produced in the same manner as in Example 10.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 45 except that APTES was not used in Example 45.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 45 except that the acid-modified PP-7 was not used.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 45 except that acid-modified PP-4 was used in place of acid-modified PP-7.
  • Table 5 shows the manufacturing conditions and measurement results of various physical properties.
  • Unmodified PP-5 pellets 100 parts by weight, irganox 101: 0.03 parts by weight, irgafos 168: 0.07 parts by weight, stearic acid strength: 0.025 parts by weight, APTE S: 0.25 parts by weight was added, and the mixture was melt-kneaded at 230 ° C. using a 20 mni twin screw extruder to produce pellets containing 2,500 ppm of APTE S.
  • Table 6 shows the manufacturing conditions and measurement results of various physical properties.
  • Example 54 Except that the amount of the acid-modified PP-7 used in Example 54 was changed to 3 parts by weight (Example 55), 8 parts by weight (Example 56), and 12 parts by weight (Example 57). A polymer composition was produced in the same manner as in Example 54.
  • Table 6 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer was prepared in the same manner as in Example 54 except that a pellet containing 800 ppm of APTES (Example 58) and a pellet containing 1,600 ppm (Example 59) were used. A composition was prepared.
  • Table 6 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 54, except that in place of the unmodified PP-5, the unmodified PP-6 synthesized in Production Example 4 was used.
  • Table 6 shows the manufacturing conditions and measurement results of various physical properties.
  • Example 6 1 In Example 54, the unmodified PP-7 synthesized in Production Example 5 was used instead of the unmodified PP-5, and the acid-modified PP-8 synthesized in Production Example 6 was used instead of the acid-modified PP-7. Except for using, a polymer composition was produced in the same manner as in Example 54.
  • Table 6 shows the manufacturing conditions and measurement results of various physical properties.
  • Example 54 the unmodified PP-5 synthesized in Production Example 7 was used instead of the unmodified PP-5, and the acid-modified PP-9 synthesized in Production Example 8 was used instead of the acid-modified PP-7. Except for using, a polymer composition was produced in the same manner as in Example 54.
  • Table 6 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 54, except that the acid-modified PP-7 was not used.
  • Table 6 shows the manufacturing conditions and measurement results of various physical properties.
  • a polymer composition was produced in the same manner as in Example 54, except that the acid-modified PP-7 was used instead of the acid-modified PP-7.
  • FIG. 3 shows the relationship between M I and M T for the compositions of Examples 45 to 62, Comparative Examples 14 to 18, Native PP-5 to 8, and Reference Examples 1 to 8.
  • compositions of the examples have higher melt tension, show better fluidity, and are more practical than the compositions of the comparative examples.
  • Resin compositions of the examples have higher melt tension, show better fluidity, and are more practical than the compositions of the comparative examples.
  • MAH - unmodified polypropylene G4
  • MAH-modified polypropylene (C5) modification rate Ml (mmmm) lOO X rrrr / ⁇ ⁇ APTES B) antioxidant base / formulation (wt%)
  • Type (g / 10 min) (moles 0 / 0) (1-mmmm) (l / g) 3 Yes (D) Content Type (dl / g) Polymer chain (weight
  • Example 54 5.24 X 10 "" 3 native ⁇ -5 6.5 69.2 20.5 76.2 2500 2000 acid-modified PP - 7 0.11 1.34 1.1
  • Example 55 3.20 X 10- 3 unmodified ro-ro -5 6.5 69.2 20.5 76.2 2500 2000 acid ⁇ pp- 7 0.11 1.34 1.1
  • example 56 8.15 x 10- 3 unmodified [rho [rho one 5 6.5 69.2 20.5 76.Zeta 2500 2000 acid-modified PP- 7 0.11 1.34 1.1 example 57 t.t8 ⁇ 0 ⁇ 3 native ⁇ -5 6.5 ⁇ 69.2 20.5 76.2 2500 2000 acid-modified PP- 7 0.11 1.34 1.1 1 example 58 5.24 X 10 one 3 native ⁇ -5 6.5 69.2 20.5 76.2 800 2000 acid-modified PP - 7 0.11 1.34 1.1 example 59 5.24 X 10 one 3 native ⁇ -5 6.5 69.2 20.5 7
  • mmmm mesopentad (molar fraction)
  • mr racemic pentad (molar fraction)
  • D irganox 1010 + irgafoss 168
  • the temperature of the solution was raised to 80 ° C., followed by dropwise addition of 77 milliliters of titanium tetrachloride, followed by stirring at an internal temperature of 125 ° C. for 2 hours to perform a contact operation.
  • propylene was introduced with stirring.
  • the catalytic activity per gram of the solid catalyst component was 9.8 kg / g-cat. ⁇ 3 hr in 3 hours of polymerization.
  • the pellet was filtered off, air-dried, and vacuum-dried at 90 ° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer (acid-modified PP-10).
  • Table 7 shows the physical property values of this polymer.
  • Example 9 a maleic anhydride-modified propylene polymer (acid-modified PP_1 1) was obtained in the same manner as in Example 9 except that the amount of maleic anhydride used was changed to 1.2 parts by weight. Was.
  • Table 7 shows the physical property values of this polymer. .
  • Table 7 shows the physical property values of this polymer.
  • Production Example 9 Except that in Example 4 (4), the amount of maleic anhydride used was changed to 1.2 parts by weight, and the amount of perhexin 25 B / 40 was changed to 0.2 part by weight, Production Example 9 In the same manner as described above, a maleic anhydride-modified propylene polymer (acid-modified PP-14) was obtained.
  • Table 7 shows the physical property values of this polymer.
  • the temperature was maintained at 20 ° C, and propylene was introduced with stirring.
  • a stainless steel autoclave with an internal volume of 10 liters equipped with a stirrer was sufficiently dried and purged with nitrogen. Then, 6 liters of dehydrated heptane was added, and nitrogen in the system was replaced with propylene.
  • the entire contents were transferred to a filtration tank equipped with a filter, and the temperature was raised to 85 ° C to perform solid-liquid separation.
  • the catalytic activity per gram of solid catalyst was 4.2 kg / g—cat. * 7.5 hr in 7.5 hours of polymerization.
  • the pellets were collected with a wire mesh and immersed in 100 parts by weight of acetone for 15 hours.
  • pellets are collected with a wire mesh, air-dried, and then vacuum-dried at 80 ° C for 6 hours and at 130 ° C for 6 hours to obtain a maleic anhydride-modified propylene polymer (acid-modifiable PP-15).
  • Table 7 shows the physical property values of this polymer.
  • Table 7 shows the physical property values of this polymer.
  • Preparation Example 14 (3) the maleic anhydride-modified propylene polymer (acid-modified) was prepared in the same manner as in Preparation Example 14 except that the amount of the protein toxin 25 B / 40 was changed to 0.1 part by weight. PP-1 7) was obtained.
  • Table 7 shows the physical property values of this polymer.
  • Table 7 shows the physical property values of this polymer.
  • a propylene polymer (unmodified PP) was obtained in the same manner as in Production Example 9 except that maleic anhydride was not used in Production Example 9 (4).
  • Table 7 shows the physical property values of this polymer.
  • Table 7 shows the physical property values of this composition.
  • Example 63 the amounts of APTE S were changed to 0.025 parts by weight (Example 64), 0.01 parts by weight (Example 65), and 0.1 parts by weight (Example A propylene polymer composition was produced in the same manner as in Example 63, except that 66) and 0.2 parts by weight (Example 67) were used.
  • Table 7 shows the physical property values of these compositions.
  • a propylene polymer composition was produced in the same manner as in Example 63 except that 3-aminopropyltrimethoxysilane (APTMS) was used instead of APTES.
  • APITMS 3-aminopropyltrimethoxysilane
  • Table 7 shows the physical property values of this composition.
  • a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-11 synthesized in Production Example 10 was used instead of the acid-modified PP-10 in Example 63. Manufactured.
  • Example 63 propylene was prepared in the same manner as in Example 63, except that the acid-modified PP-12 synthesized in Production Example 11 was used instead of the acid-modified PP-10. A polymer composition was produced.
  • Table 7 shows the physical property values of this composition.
  • a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-13 synthesized in Production Example 12 was used instead of the acid-modified PP-10 in Example 63. Manufactured.
  • Table 7 shows the physical property values of this composition.
  • a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP_14 synthesized in Production Example 13 was used instead of the acid-modified PP-10 in Example 63. Manufactured.
  • Table 7 shows the physical property values of this composition.
  • a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-15 synthesized in Production Example 14 was used instead of the acid-modified PP-10 in Example 63. Manufactured.
  • Table 7 shows the physical property values of this composition.
  • a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-16 synthesized in Production Example 15 was used instead of the acid-modified PP-10 in Example 63. Manufactured.
  • Table 7 shows the physical property values of this composition.
  • Example 63 a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP- 17 synthesized in Production Example 16 was used instead of the acid-modified PP-10. Manufactured. Table 7 shows the physical property values of this composition.
  • a propylene polymer composition was produced in the same manner as in Example 63 except that APTES was not used.
  • Table 7 shows the physical property values of this composition.
  • a propylene polymer composition was produced in the same manner as in Example 63 except that the unmodified PP synthesized in Comparative Production Example 1 was used in place of the acid-modified PP-10 in Example 63. .
  • Table 7 shows the physical property values of this composition.
  • Example 6 Example 6 was repeated except that in place of the acid-modified PP-10, Toyo Tac 100 P (trade name, manufactured by Toyo Gosei Co., Ltd.) was used as the maleic anhydride-modified propylene polymer. A propylene polymer composition was produced in the same manner as in 3.
  • Table 7 shows the physical property values of this composition.
  • Example 6 Example 6 was repeated except that Eunox 110 (trade name, manufactured by Sanyo Chemical Co., Ltd.) was used as the maleic anhydride-modified propylene polymer in place of the acid-modified PP-10.
  • a propylene polymer composition was produced in the same manner as in 3.
  • Table 7 shows the physical property values of this composition.
  • Table 7 shows the physical property values of this composition.
  • Example 76 except that the homopolypropylene Z composition (weight ratio) was changed to 40/60 (Example 77) and 60/40 (Example 77), respectively, A propylene polymer composition was produced in the same manner as in Example 76. Table 7 shows the physical property values of this composition. '' Example 7 9
  • a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-18 synthesized in Production Example 17 was used instead of the acid-modified PP-10 in Example 63. Was manufactured.
  • Table 7 shows the physical property values of this composition.
  • Example 79 Same as Example 79 except that the homopolypropylene composition (weight ratio) in Example 79 was changed to 80Z20 (Example 80) and 70/30 (Example 81), respectively. To produce a propylene polymer composition.
  • Table 7 shows the physical property values of this composition. Table tied o
  • the amount is based on 100 parts by weight of the maleic anhydride-modified propylene polymer (# 6).
  • an ⁇ -olefin polymer composition is obtained in which the generation of gel is suppressed, the melt tension is increased, and the moldability is greatly improved.
  • the third aspect of the present invention it is possible to provide a modified polypropylene pyrene-based resin composition excellent in balance between melt tension and fluidity, and a method for producing the same.
  • the # 1 method for producing a modified phosphorescent polymer pirates having an excellent melting balance and excellent bacterial balance it is possible to use the # 1 method for producing a modified phosphorescent polymer pirates having an excellent melting balance and excellent bacterial balance.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de poly-α-oléfine qui est obtenue par mélange de (A) une poly-α-oléfine, (B1) un composé organosilicone et (C) une poly-α-oléfine modifiée dont un substituant réagit avec un groupe polaire et dont la viscosité intrinsèque est de 0,7 dl/g au minimum, ladite composition pouvant être également obtenue par mise en contact mutuel des composants (A), (B1) et (C). L'invention concerne également une composition de résine polypropylène modifiée qui est obtenue par mélange de (C2) une résine de polypropylène présentant un groupe polaire et (B) un agent de couplage silane, dont la tension en fusion et l'indice de fluidité sont spécifiés et qui présente une teneur en p-xylène non soluble de 1 % en poids au maximum. L'invention concerne en outre un procédé de production desdites compositions de poly-α-oléfines modifiées, qui se caractérise en ce qu'on mélange un mélange constitué de (C6) une poly-α-oléfine modifiée dont la viscosité intrinsèque, le rapport Mw/Mn et la teneur en groupes polaires sont spécifiés et (B) un agent de couplage silane avec (A) une poly-α-oléfine présentant une viscosité intrinsèque de 0,7 à 5,0 dl/g pour un rapport pondéral (A) / [(B) + (C)] de 0/100 à 99/1.
PCT/JP2003/010513 2002-08-22 2003-08-20 Compositions de poly-$g(a)-olefines et leur procede de production WO2004018557A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2002/241731 2002-08-22
JP2002241732A JP4167028B2 (ja) 2002-08-22 2002-08-22 α−オレフィン重合体組成物及びその製造方法
JP2002/241732 2002-08-22
JP2002241731A JP4167027B2 (ja) 2002-08-22 2002-08-22 α−オレフィン重合体組成物及びその製造方法
JP2002/259198 2002-09-04
JP2002259198A JP4172971B2 (ja) 2002-09-04 2002-09-04 変性ポリプロピレン系樹脂組成物及びその製造方法
JP2002296463A JP4172985B2 (ja) 2002-10-09 2002-10-09 変性α−オレフィン重合体組成物の製造方法
JP2002/296463 2002-10-09

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JP6720913B2 (ja) * 2017-04-18 2020-07-08 信越化学工業株式会社 不飽和結合含有ビスシリル化合物およびその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09227733A (ja) * 1996-02-22 1997-09-02 Idemitsu Petrochem Co Ltd 防水シート
JP2001064332A (ja) * 1999-07-13 2001-03-13 Clariant Gmbh 水性ポリマー分散液、その製造法及び使用法
JP2002518573A (ja) * 1998-06-22 2002-06-25 クロンプトン・コーポレーション シラン硬化熱可塑性エラストマー

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09227733A (ja) * 1996-02-22 1997-09-02 Idemitsu Petrochem Co Ltd 防水シート
JP2002518573A (ja) * 1998-06-22 2002-06-25 クロンプトン・コーポレーション シラン硬化熱可塑性エラストマー
JP2001064332A (ja) * 1999-07-13 2001-03-13 Clariant Gmbh 水性ポリマー分散液、その製造法及び使用法

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