WO2007069760A1 - Composition de resine de polyolefine, corps moule obtenu a partir de cette composition et procede de fabrication de cette composition de resine de polyolefine - Google Patents

Composition de resine de polyolefine, corps moule obtenu a partir de cette composition et procede de fabrication de cette composition de resine de polyolefine Download PDF

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Publication number
WO2007069760A1
WO2007069760A1 PCT/JP2006/325142 JP2006325142W WO2007069760A1 WO 2007069760 A1 WO2007069760 A1 WO 2007069760A1 JP 2006325142 W JP2006325142 W JP 2006325142W WO 2007069760 A1 WO2007069760 A1 WO 2007069760A1
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component
weight
parts
polyolefin resin
resin composition
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PCT/JP2006/325142
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English (en)
Japanese (ja)
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Yoshiaki Oobayashi
Katsuhisa Kitano
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Sumitomo Chemical Company, Limited
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Priority to CN2006800528389A priority Critical patent/CN101374902B/zh
Publication of WO2007069760A1 publication Critical patent/WO2007069760A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers

Definitions

  • a polyolefin resin composition a molded article comprising the same,
  • the present invention relates to a polyolefin resin composition and a molded product thereof. Furthermore, in addition to a good appearance and excellent mechanical strength, it also has long-term durability in an environment affected by oxygen, heat, and light, especially excellent light stability over a long period of time.
  • the present invention relates to a polyolefin resin composition and a molded product thereof. Light
  • Polyolefin resins are excellent in mechanical strength, B heat resistance, moldability, chemical resistance, etc., and are relatively inexpensive polymer materials, so they are widely used in various fields such as injection molded products.
  • Japanese Patent Application Laid-Open No. 2004-1499 discloses a polypropylene resin pellet for use in a vehicle front structure, as a means for improving the durability of the vehicle front structure in a metal contact environment. Describes glass fiber reinforced polypropylene resin pellets containing specific amounts of deactivators, phenolic antioxidants, thio antioxidants, hindered amine light stabilizers, phosphorus antioxidants, and UV absorbers. ing.
  • 2004-197068 discloses a polyolefin resin composition used for injection-molded products, which is a means for maintaining the mechanical strength of the polyolefin resin composition at a practical level and improving durability. It contains modified polyolefin and filler, the content of the filler is in a certain range, the amount of graft modification of the modified polyolefin resin is in a certain range, and its melt flow rate is in a certain range A polyolefin resin composition is described.
  • the object of the present invention is a polyolefin resin that has excellent appearance and excellent mechanical strength, as well as long-term durability in an environment affected by oxygen, heat, and light, and in particular, excellent light stability over a long period of time. It is to provide a composition and its molded product.
  • the present invention includes components (A) 39.5 to 98.5 parts by weight, component (B) 0.5 to 10 parts by weight, component (C) ′ 1 to 60 parts by weight, A polyolefin resin composition comprising (D) 0.05 to 1 part by weight, component (E) 0.05 to 1 part by weight, and component (F) 0.00 1 to 10 parts by weight
  • the total amount of components (A), (B) and (C) is 100 parts by weight).
  • Component (B) The amount of graft modification obtained by graft modification of a polyolefin resin using a modifier selected from unsaturated carboxylic acid and unsaturated carboxylic acid derivative is 0.5 to 10% by weight. Yes, melt flow rate measured at a temperature of 2 30 and a load of 2 1.2 N is 2
  • R ′ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • this invention provides the preferable method for manufacturing the said polyolefin resin composition. Best mode for carrying out
  • Component (A) is a polyolefin resin, which is a resin obtained by polymerizing at least one olefin.
  • olefins include ethylene, propylene, and ⁇ -'olefins having 4 to 12 carbon atoms.
  • Examples of ⁇ -olefins having 4 to 12 carbon atoms include 1-butene, 2-methyl-1_propene, 2-methyl-1-butene, 3-methyl_1-butene, 1-hexene, 2 —Ethyl— 1-butene, 2, 3—dimethyl-1-butene, 2-methyl—1-pentene, 3 _methyl— 1 _pentene, 4 monomethyl _1--pentene, 3,3-dimethyl-1-butene, 1 —Heptene, Methyl _ 1 Monohexene, .Dimethyl _ 1 Pentene, Ethyl 1 i-Pentene, Trimethyl 1-Butene, Methyl Ethyl— 1-Butene, 1-Octene, Methyl 1 _Pentene, Ethyl 1 1-hexene, dimethyl 1-hexene, propyl 1-heptene, methyl edil-1 1 heptene, ⁇
  • component (A) examples include polyethylene resin, polypropylene resin, polybutene resin, and blends thereof. Polypropylene resin is preferred.
  • polyethylene resin examples include an ethylene homopolymer, an ethylene- ⁇ -aged refin copolymer, and the like.
  • ⁇ -olefin as a constituent monomer of the ethylene- ⁇ -year-old olefin copolymer, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.
  • Examples of the ethylene- ⁇ -olefin copolymer include ethylene 1-1-butene copolymer, ethylene_1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer. Etc.
  • the polyethylene resin may be one kind of polymer or a mixture of two or more kinds of polymers.
  • Examples of the polypropylene resin include propylene homopolymer, propylene monoethylene random copolymer, propylene monoalpha-olefin random copolymer, propylene-ethylene-alpha-olefin copolymer, propylene homopolymer component or mainly propylene.
  • a copolymer component (hereinafter referred to as the polymer component (I)) and at least one monomer selected from ethylene and ⁇ -olefin and propylene.
  • a propylene-based block copolymer comprising a polymer component (hereinafter referred to as polymer component ( ⁇ )).
  • These polypropylene resins may be used alone or in combination of two or more.
  • ⁇ -Olefin as a constituent monomer of polypropylene resin is preferably 1-butene, 1 monopentene, 1-hexene, 4_methyl-1 monopentene, 1-octene, 1-decene, more preferably 1 — Butene, 1-hexene, 1-octene.
  • propylene- ⁇ -olefin fin random copolymer examples include propylene mono-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, and the like.
  • propylene / ethylene / ⁇ -year-old refin copolymers examples include propylene / ethylene / l-butene copolymer, propylene / ethylene / l-hexene copolymer, and propylene / ethylene-1-octene copolymer. Is mentioned. .
  • the comonomer content in the propylene-based copolymer that is, the ethylene content in the propylene-ethylene random copolymer, the ⁇ -sulfine content in the propylene- ⁇ -olefin random copolymer, propylene-ethylene
  • the total content of ethylene and ⁇ -olefin in the monoolefin copolymer is usually from 0.1 to 30% by weight, and preferably from 0.1 to 20% by weight. However, 'the total amount of the copolymer is 100% by weight.
  • the polymer component (I) of the propylene-based block copolymer is a copolymer component mainly composed of propylene
  • the polymer component (I) includes ethylene and an ⁇ having 4 to 12 carbon atoms. — Containing structural units derived from at least one olefin selected from olefins, and the content thereof is usually from 0 to 30% by weight.
  • the copolymer component mainly composed of propylene as the polymer component ( ⁇ ) include propylene-ethylene copolymer component, propylene-1-butene copolymer component, propylene-1-hexene copolymer A coalescence component etc. are mentioned.
  • Examples of the polymer component (II) of the propylene-based block copolymer include propylene monoethylene copolymer component, propylene monoethylene monobutene copolymer component, propylene-ethylene-1-hexene copolymer Examples thereof include a blending component, a propylene / ethylene / l-octene copolymer component, a propylene / l-butene copolymer component, a propylene / l-hexene copolymer component, and a propylene / l-octene copolymer component.
  • the content of structural units derived from at least one olefin selected from ethylene and ⁇ -olefin having 4 to 12 carbon atoms contained in the polymer component (II) is usually 1 to 80. % By weight, preferably 20 to 70% by weight, more preferably 30 to 60% by weight. However, the total amount of the polymer component (II) is 100% by weight.
  • the content of the polymer component in the propylene-based block and copolymer. (II) is usually 1 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 40%. % By weight.
  • propylene-based block copolymer examples include: (propylene)-(propylene-ethylene) copolymer, (propylene) 1 (propylene-ethylene-1 1-butene) copolymer, (propylene) 1 (propylene-ethylene 1) 1-hexene) copolymer, (propylene) 1 (propylene-1-butene) copolymer, (propylene) 1 (propylene-1 1-hexene) copolymer, (propylene-1 ethylene) 1 (propylene-1 (Ethylene) Copolymer, (Propylene-Ethylene) One (Propylene-Ethylene-1, 1-Butene) Copolymer, (Propylene-Ethylene-1)-(Propylene-Ethylene-1-Hexene) Copolymer, (Propylene-Ethylene)- (Propylene-1-butene) Copolymer, (Propylene-Ethylene
  • Preferred polypropylene resins as the component (A) are propylene homopolymer, propylene-ethylene random copolymer, propylene 1-butene random copolymer, propylene-ethylene 1-1-butene copolymer, the polymer component (I) and the above A propylene block copolymer comprising a polymer component (II).
  • the crystallinity of the resin can be appropriately determined according to the quality required for the resin composition of the present invention and the quality required for a molded product obtained by molding the resin composition. good.
  • the crystallinity of a polypropylene resin can be expressed by its melting temperature (melting point) and stereoregularity.
  • melting point melting point
  • stereoregularity As an index of stereoregularity, a isotactic index, a syndiotactic index, and the like are known.
  • stereoregularity is expressed using a isotactic index. Iso evening click ticks index, A. Z ambel 1 i et al method published by (M acromo 1 ecu 1 es Vol. 6, No.
  • the isotactic index of the polypropylene resin is determined as the area fraction of mmmm peaks in the total absorption peak in the methyl carbon region of the 13 C—NMR spectrum.
  • a low isotactic index indicates low crystallinity, while a high isotactic index indicates high crystallinity.
  • Component (A) can be produced by a known polymerization method using a known polymerization catalyst.
  • the polymerization catalyst include a catalyst system comprising a radical initiator, a Ziegler catalyst system, a Ziegler-Natta catalyst system, a transition metal compound of Group 4 of the periodic table having a cyclopentenyl ring and an alkylaluminoxane. Transition gold of the periodic table group 4 with the cyclopentenyl ring And a catalyst system comprising a compound which reacts with a genus compound to form an ionic complex and an organoaluminum compound, and a supported catalyst system in which the catalyst component is supported on an inorganic compound or an organic compound carrier.
  • a prepolymerized catalyst prepared by prepolymerizing ethylene or ⁇ -aged refin in the presence of the above catalyst system can also be used.
  • the above catalyst system include, for example, Japanese Patent Application Publication No. 61-2-2186600, Japanese Patent Application Laid-Open No. 5-1: 194.
  • Examples of the polymerization method include bulk polymerization, solution polymerization, slurry polymerization, and gas phase polymerization.
  • Bulk polymerization is a method in which liquid olefin is used as a medium at the polymerization temperature
  • solution polymerization or slurry polymerization is a method such as propane, butane, isobutane, pentane, hexane, heptane, and octane.
  • the polymerization is carried out in an active hydrocarbon solvent
  • the gas phase polymerization is a method in which a gaseous monomer is used as a medium and the gaseous monomer is polymerized in the medium.
  • polymerization methods may be either batch type or continuous type, and these polymerization methods may be arbitrarily combined. From the viewpoint of being industrial and economical, it is preferably a continuous gas phase polymerization method, or a bulk polymerization one gas phase polymerization method in which a bulk polymerization method and a gas phase polymerization method are continuously performed.
  • the component ( ⁇ ) may be produced in one stage, or may be produced in two or more stages.
  • the propylene-based block copolymer comprising a polymer component (I) and a polymer component (II) is preferably prepared by producing the polymer component (I) and the polymer component (II). It can be produced by a multi-stage polymerization method having at least two stages. Examples of the multistage polymerization method include a polymerization method described in JP-A Nos. 5-19494 and 8-202-1269. Various conditions for polymerization, such as polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc., can be arbitrarily changed as appropriate in order to produce the desired component (i).
  • component ( ⁇ ) is optionally added to component ( ⁇ ) to remove residual solvent contained in component ( ⁇ ) and ultra-low molecular weight oligomers produced as a by-product during production. ) May be dried at a temperature below that at which it melts. Examples of the drying method include the method described in Japanese Patent Application Laid-Open No. 5-5-7 5 4 10 and Japanese Patent No. 2 5 6 5 7 5 3.
  • the melt flow rate (MFR) of the component ( ⁇ ) is usually from 0.01 to 400 g / 10 min. From the viewpoint of the mechanical strength and production stability of the resin composition, it is preferably l It is ⁇ 400 gZ10 minutes, more preferably 5 to 200 g / 10 minutes, and even more preferably 10 to 150 gZ10 minutes. Note that M FR is a value measured with 2 30 and 2 1.2 N loads according to ASTM D 1 2 3 8.
  • Component (A) includes modified polyolefin resin as component (B) described later, that is, polyolefin modified with a modifier selected from unsaturated carboxylic acid and derivatives of unsaturated carboxylic acid. Absent.
  • Component (B) is a modified polyolefin resin, which is a modified polyolefin resin obtained by graft modification of a polyolefin resin with a modifying agent selected from unsaturated carboxylic acid and unsaturated carboxylic acid derivatives.
  • component (A) A resin different from the polyolefin resin is selected.
  • Component (B) acts to improve the dispersibility of the fibrous filler (component (C)) in the polyolefin composition and the adhesive strength at the interface between component (A) and component (C) ′.
  • the unmodified polyolefin resin that is the raw material of component (B) may be the same as or different from the polyolefin resin of component (A).
  • the amount of the part derived from the modifying agent in the component (B) is 0.5 to 10% by weight of the component (B).
  • the ratio of the weight of the portion derived from the modifying agent introduced into the polyolefin resin by graft modification to the weight of the modified polyolefin resin produced is referred to as the graph modification amount of the modified polyolefin resin.
  • the amount of graft modification is preferably 0.5 to 8% by weight, more preferably 0.5 to 5% by weight.
  • the graft modification amount of the modified polyolefin resin is determined from the intensity of absorption resulting from the structure derived from the modifier introduced by graft modification in the infrared absorption spectrum of the modified polyolefin resin.
  • the unsaturated carboxylic acid and unsaturated carboxylic acid derivative used as a modifier in the production of component (B) are selected from at least one unsaturated group (i), a carboxyl group, and a group derived from a carboxyl group.
  • unsaturated group (i) a carboxyl group
  • a group derived from a carboxyl group a group derived from a carboxyl group.
  • the compound (1) having at least one kind of group ( ⁇ ) and a structure change due to dehydration reaction, etc. in the production process and at least the i-type unsaturated group (i), carboxyl group and carboxyl group
  • Examples thereof include a compound (2) that can be converted into a structure having at least one group (ii) selected from derived groups.
  • Examples of the saturated net group (1) include a carbon-carbon double bond or a carbon-carbon triple bond.
  • An unsaturated carboxylic acid derivative a compound that can be dehydrated in the step of graphing on a polyolefin resin to produce an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative, and the like.
  • the unsaturated carboxylic acid include maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid.
  • Examples of the unsaturated carboxylic acid derivative include maleic anhydride, itaconic anhydride, and acrylic acid.
  • unsaturated carboxylic acids and unsaturated carboxylic acid derivatives acrylic acid, glycidyl ester of methacrylic acid, and maleic anhydride are preferred.
  • Examples of the compound that produces an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative by dehydration in the process of graphing on the polyolefin resin include citrate and malic acid.
  • the melt flow rate (MFR) of the component (B) is usually from 20 to 190 g / 10 minutes, preferably from 20 to 150 g l 0 minutes, more preferred Or 2 ⁇ 0 to 100 g and 10 minutes, and more preferably 2 to 70 g / 10 minutes.
  • the MFR is a value measured with a 2.3 0 ⁇ , 21.2 N load according to ASTM D 1 2 38.
  • the component (B) can be produced by a method in which a modifier is graphed using an organic peroxide on an unmodified polyolefin resin.
  • organic peroxide examples include alkyl peroxides, diacyl peroxides, peroxide esters, and peroxide ⁇ -bonates.
  • alkyl peroxides include dic, milperoxide, di-tert-butyl peroxide, di-tert-butyl milperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxide).
  • Examples include triethyl-3,6,9-trimethyl-1,4,7_-lipaxonan.
  • diacyl peroxides include benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, and the like.
  • peroxide esters examples include 1,1,3,3-tetramethylbutyl carboxyneodecanoate, ⁇ -cumylperoxyneodecanoate, and tert-butylperoxyneodecanoate.
  • Tert-butyl peroxyneohe tert _ butyl peroxybivalate, tert _ hexyl peroxybivalate, 1, 1, 3, 3-tetramethylbutyl carboxy-2-ethyl KEY NO ", tert-milperoxy 2-ethyl, ruhexanoate, tert-butyl peroxy-2-ethyl hexanoe, tert-butyl carboxyisopropylate
  • component (B) For the production of component (B), various mixing methods used for mixing resins or resins and solid or liquid additives can be applied. Preferably, there is a method in which all of each component or some of each component is combined and mixed separately to form a uniform mixture, and then the mixture is melt-kneaded. Examples of a method for obtaining a uniform mixture include a method of uniformly mixing with a mixer such as a Henschel mixer or a ribbon printer. Examples of the melt kneading method include a method using a Banbury mixer, a plast mill, a Brabender plastograph, a single screw or a twin screw extruder, and the like.
  • the temperature of the kneading part of the kneader is determined from the viewpoint of the amount of graft modification achieved and the prevention of decomposition of the polyolefin resin. It is 5 0 to 3.0 0 ° C, and preferably 1 0 0 to 2 5 0.
  • the temperature of the kneading part of the kneader can be divided into two stages, for example, the first half and the second half, and the temperature in the second half can be set higher than the first half. From the viewpoint of preventing the decomposition of the polyolefin resin, it is 0.1 to 30 minutes, and particularly preferably 0.5 to 5 minutes.
  • a known additive generally added to the polyolefin resin such as an antioxidant or a neutralizing agent, may be blended.
  • -Component (C) is one kind of fibrous filler or a combination of two or more kinds of fibrous fillers, and acts to improve the mechanical strength of the polyolefin resin.
  • Component (C) includes, for example, glass fiber, calcium silicate fiber, calcium titanate fiber, carbon fiber, polyester fiber, metal fiber, aromatic polyamide fiber, bamboo fiber, cellulose fiber, kenaf fiber, And vinylon fiber. Glass fiber is preferable.
  • the shape and size of the component (C) are appropriately determined according to the ease of handling of the component (C) in the production process of the polyolefin resin composition and the appearance and mechanical strength of the molded product made of the polyolefin resin composition.
  • the average fiber diameter of the component (C) may be arbitrarily adjusted with synthetic powder or the like.
  • the fibrous filler of component (C) may be bundled with a sizing agent.
  • the sizing agent include polyolefin resin, polyurethane resin, polyester resin, acrylic resin, epoxy resin, starch, vegetable oil and the like. Is mentioned.
  • Component (C) is treated with a surface treatment agent to improve wettability and adhesion between the polyolefin resin (component (A)) and the modified polyolefin resin (component (B)). May be.
  • the surface treatment agent include silane coupling agents, titanate coupling agents, aluminum coupling agents, chromium coupling agents, zirconium force coupling agents, borane coupling agents, and the like.
  • Silane-based coupling agents and titanate-based coupling agents are preferably silane-based coupling agents.
  • Silane coupling agents include, for example, tri!: Toxisilane, vinyl squirrel (3-methoxyethoxy) silane, alpha-methacryloxypropyl trimethoxysilane, alpha-glycidoxypropyl trimethylsilane, ⁇ - ( 3 ,.
  • Ethyltrimethoxysilane ⁇ - / 3- (aminoethyl) -aminopropyl trimethoxysilane, ⁇ —) 3- (aminoethyl) -7 ”-amino
  • Examples thereof include propylmethyldimethoxysilane, aminopropyltriethoxysilane, 2-phenylaminopropyltrimethoxysilane, mercaptopropyl trimethoxysilane, and chloropropyltrimethoxysilane.
  • a surface treating agent for example, aqueous solution method, an organic solvent method, a spray method and the like.
  • the component (C) When the component (C) is mixed with other components, the component (C) may be, for example, a mouth bing, a strand, a chopped strand, a pulverized product in a fibrous form called milled fiber or powder, etc. Can be used.
  • the weight average fiber diameter of component (C) is Preferably 5 to 50 m, more preferably 8 to 40 m, and further Preferably, it is 15 to 30 / im.
  • the weight average fiber length of component (C) is at least 1 mm, preferably 1 to 5 Omm, more preferably 2 to 3 Omm.
  • the average fiber diameter of the component (C) is determined by the measurement method described in JP-A-2006-193735, that is, the measurement method by image analysis processing of the fiber observed with a microscope. Specifically, a glass fiber scanning electron microscope (SEM) photograph (magnification: 200x magnification) is analyzed using an image processing device (for example, “Luzex AP” manufactured by Nireco Corporation) The average value of the fiber diameter is obtained with the number of data n being 300 or more. This is the average fiber diameter of component (C). In addition, both image data make object the image of the fiber cross section which the fiber image
  • Ingredient (D) is a hindered amine light stabilizer of 100 or more. More specifically, the hindered amine light stabilizer of component (D) is a light stabilizer having a 2, 2, 6, 6-teramethylpiperine skeleton in the molecule. Component (D) may be a single hindered amine light stabilizer or a combination of two or more hindered amine light stabilizers.
  • the component (D) hindered amine light stabilizer has a molecular weight of 1 000 or more. Yes, preferably 1 000 to 1 0000, more preferably 1 500 to 5000. If the molecular weight of component (D) is less than 1 000, light stability may be insufficient.
  • Component (D) is preferably hydrogen bonded to the nitrogen atom of the 2, 2, 6, 6-tetramethyl-4-piperidyl group from the viewpoint of the mechanical strength of the polyolefin resin composition and the light stability.
  • component (D) for example, a compound represented by the following structural formula (d-1) (for example, trade name: Syar soap UV-3529, manufactured by CYTEC J APAN; molecular weight: about 1700),
  • Examples include compounds represented by the following structural formula (d-4) (for example, ADK STAB LA-63, manufactured by AD EKA Corporation; molecular weight: about 2000).
  • a compound having a molecular weight of 100 or more represented by the above structural formula (d_3) is preferable.
  • Component (E) is a benzoate compound represented by the following general formula (I).
  • R 1 represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • examples of the alkyl group having 1 to 30 carbon atoms in R ′ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group Tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, lauryl group, myristyl group, palmityl group, Stearyl group, behenyl group, triacontyl group, monyuyl group, eicosyl group and the like can be mentioned.
  • the alkyl group is preferably an alkyl group having 14 to 3 carbon atoms, and particularly preferably an alkyl group having 16 to 28 carbon atoms.
  • the aryl group having 6 to 30 carbon atoms as R 1 include an aryl group and an aryl group having a substituent bonded to an aromatic ring.
  • Preferred as an aryl group having a substituent bonded to the aromatic ring is one or two substituents bonded to the aromatic ring, and the substituent is bonded to the 2-position and / or 4-position of the aromatic ring. It is an allyl group.
  • Examples of the substituent bonded to the aromatic ring include an alkyl group, an alkenyl group, a hydroxyl group, and an amino group. It is preferably an alkyl group, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably an alkyl group having 1 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec monobutyl group, tert-butyl group, pentyl group, isopentyl group, and Examples include xyl group, heptyl group, octyl group, isooctyl group and the like.
  • 'Component (E) includes, for example, myristyl-3,5-tert-butyl-4-hydroxybenzoate, lauryl-1,5-tert-butyl-4-hydroxybenzoate, no, luminyl-3,5-tert —Butyl 4-hydroxybenzoate, stearyl— 3, 5— tert-butyl — 4-hydroxybenzoate, beneux 3, 5- tert-butyl—4-hydroxybenzoate, monyu nilu 3, 5-tert-butyl-4-hydroxybenzoate, 2-methyl-phenyl 3-, 5--di-tert-butyl-4-hydroxybenzoate, 2-ethylrofurenyl- 3, 5, 5-di tert-butyl-4-hydroxybenzoate , 2 — n-propyl monophenyl 3, 5—di _ tert-petite 4 ⁇ hydroxybenzoate, 2— ⁇ f propyl monophenyl—3; 5 _
  • the component (F) is a white pigment having a Mohs hardness of 1 to 6, and the Mohs hardness is measured by a method in accordance with British Standard B S 6 4 3 1.
  • the Mohs hardness of the component (F) is preferably 5 or less, more preferably 4 or less.
  • the fibrous filler (component (C)) may break, and the resulting polyolefin resin composition may not have sufficient mechanical strength.
  • Component (F) includes, for example, barium sulfate (Mohs's hardness:
  • Zinc sulfide is preferred as the component (F).
  • Zinc sulfide may be surface-treated with a different white pigment to protect its surface.
  • the polyolefin resin composition of the present invention may contain one or more colorants other than the component (F).
  • colorants include carbon black such as furnace black, channel black, acetylene black, lamp black, iron black, petal, titanium oxide, cadmium red, cadmium yellow, ultramarine, cobalt blue, titanium.
  • Inorganic pigments such as yellow, red lead, yellow lead, and blue, quinacridone, polyazo yellow, anthraquinone yellow, polyazo red, azore yellow, peri.lene, phthalocyanine green, phthalocyanine blue, Organic pigments such as Renon Yellow are listed.
  • each of component (A), component (B), component (C), component (D), component (E) and component (F) in the polyolefin resin composition of the present invention is as follows: Component (A) 39. '5 to 98.5 parts by weight, component (B) 0.5 to 10 parts by weight, component (C) 1 to 60 parts by weight, component (D) 0.05 to 1 part by weight, ⁇ component (E) 0. 05 to 1 part by weight, and component (F) 0.001 to 10 parts by weight, where the total amount of component (A), component (B) and component (C) is 100 parts by weight.
  • the content of component (B) is preferably 0.5 to 7 parts by weight, more preferably 0.5 to 5% by weight.
  • the content of the component (, B) is less than 0. '. 5 parts by weight, the dispersibility of the component (C) may be insufficient, and the component (C) and the component (A) Adhesiveness is weak, and improvement of the mechanical strength of the molded product may be insufficient. If it exceeds 10 parts by weight, the molding processability of the polyolefin resin composition may be deteriorated, and the mechanical strength of the molded product may be impaired.
  • the content of component (C) is preferably 5 to 60 parts by weight, more preferably 5 to 45 parts by weight, and still more preferably 10 to 45 parts by weight. When the content of component (C) exceeds 60 parts by weight, it may be difficult to produce a polyolefin resin composition or to mold the resin composition.
  • the ratio of the weight of the component (C) to the weight of the component ((C) / (B)) in the polyolefin resin composition of the present invention is preferably from the viewpoint of mechanical strength and light stability. 100-1 to 5-1, more preferably 50 / 1-10.
  • the content of each of component (D), component (E), and component (F) is as follows: component (D) 0.05 to: Parts by weight, component (E) 0.05 to 1 part by weight, and component (F) 0.001 to 10 parts by weight.
  • the content of component (D) is preferably 0.05 to 0.5, 6 parts by weight, and more preferably 0.1 to 0.4 parts by weight.
  • component (D) is less than 0.05 parts by weight, the light stability is insufficient, and the molded product may crack, resulting in decreased gloss or discoloration. If the amount exceeds 1 part by weight, the light stabilizer may bleed out during storage or use of the composition or its molded product, and the surface of the product may be whitened or discolored to yellow or red. Sometimes.
  • the content of component (E) is preferably 0.05 to 0.6 parts by weight, and more preferably Q. 1 to 0.4 parts by weight. If the content of component (E) is less than 0.05 parts by weight, the light stability is insufficient, and the appearance of the product may crack, resulting in a decrease in gloss or discoloration.
  • the surface of the product may be whitened or discolored to yellow or red due to bleed out of component (C) during storage or use of the product.
  • the ratio of the weight of component (D) to the weight of component (E) ((D) / (E)) is preferably 8Z1 ⁇ 1Z2 from the viewpoint of light stability. Preferably, it is 5Zl to l / 2, and more preferably 5 / l to lZl.
  • the component (E) and the component (D) in combination the light resistance of the polyolefin resin composition can be improved.
  • the discoloration of the product can be prevented by reducing the content of the light stabilizer (component (D)).
  • the content of the component (F) is 0.001 to 10 parts by weight as described above, and within this range, the mechanical properties and appearance of the molded product made of the polyolefin resin composition are not impaired.
  • the hue required for the product can be obtained.
  • the content of component (F) is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.
  • the content of such a colorant is the sum of the components (A), (B) and (C). From the viewpoint of colorability, appearance of a molded product obtained from the composition, and economical efficiency, it is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight.
  • the polyolefin resin composition of the present invention can be produced by a method of melt-kneading component (A), component (B), component (C), component (D), component (E), and component (F).
  • a method of melt-kneading component (A), component (B), component (C), component (D), component (E), and component (F) For example, a method of melting and kneading the respective components at once, a method of adding and melting the respective components in any order, and melt melting and kneading the respective components separately in any combination
  • Two or more kinds of mixtures can be prepared in advance, and the obtained mixtures can be combined and melt-kneaded.
  • a method for producing a polyolefin resin composition by melt-kneading the following mixture (1), mixture (ii) and mixture (iii).
  • Mixture (iii) Mixture prepared by melt-kneading component (A) 3 to 9.0 parts by weight and component (F) 10 to 70 parts by weight:
  • the total amount of component (A), component (B) and component (C) is 100 parts by weight, and component (D) 0.05 to 1 weight f3 ⁇ 4 and component (E) 0 05 ⁇ :! Part by weight and component (F) 0.001 to 10 parts by weight are blended.
  • the total amount of component (A), component (B) and component (C) is 100 parts by weight with respect to T, component (D) 0.05 to 1 part by weight, and component (E ) 0.
  • the polyolefin resin composition of the present invention is produced by melt-kneading the resin components obtained by previously melt-kneading each of the above components in any combination, a resin obtained by previously melt-kneading in any combination What is necessary is just to prepare suitably content of each component contained in a component so that content of each component contained in the polyolefin resin composition of this invention may become predetermined content.
  • preferred shapes of the mixtures (i) to (iv) obtained by melt-kneading include powder, beads, granules, and pellets.
  • the component (F) or other colorant and mixture) are directly It may be melt kneaded.
  • these components can be blended when the mixture (i) is prepared.
  • component (F) and other colorants are smoothly contained in mixture (i), and component (F) and other colorants are easily dispersed in mixture (i) and contained in mixture (i).
  • the following process pigment and the mixture (i) are preferably melt-kneaded.
  • the processed pigment is obtained by combining or kneading a white pigment (component (F)) and other colorants and a dispersant.
  • the dispersant is preferably wax, modified wax, metal sarcophagus, low molecular weight polyethylene, or low molecular weight polypropylene. These may be used alone, or at least two of them may be used in combination.
  • the dispersant may contain a plasticizer.
  • a mixer such as a super mixer, a tumbler, or a heating roll is used. Further, a mass batch obtained by diluting the processed pigment with a vehicle and the mixture (i) may be melt-kneaded.
  • the vehicle is preferably a polyolefin resin and may be the same as the component (A) used in the present invention. More preferably, it is a polyolefin resin whose melting temperature is lower than the melting temperature of the component (A) used in the present invention and whose viscosity at the time of melting is lower than the viscosity at the time of melting the component (A).
  • a manufacturing method of the master batch a method of melt kneading the processed pigment and the vehicle using a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, etc. can be used. .
  • the content of the white pigment (component (F)) and other colorants contained in the masterbatch may be appropriately determined. Usually, it is 10 to 70% by weight, preferably 10 to 50% by weight, and more preferably 10 to 30% by weight. However, the total amount of the master batch is 100% by weight.
  • the polyolefin resin composition of the present invention may contain one or more additives.
  • additives include neutralizers, antioxidants, nucleating agents, crystallization accelerators, clearing agents, antifoaming agents, flame retardants, flame retardant aids, dispersants, antistatic agents, and processing aids.
  • Agents, lubricants, antibacterial agents, plasticizers, foaming agents and the like it is preferable that a neutralizing agent and Z or an antioxidant are contained.
  • the polyolefin resin composition of the present invention can contain one or more neutralizing agents, and preferably, a neutralizing agent having excellent dispersibility is used.
  • the average particle size of the neutralizing agent is preferably from 0.01 to 10 m, more preferably from 0.01 to 5 m, and even more preferably from the viewpoint of dispersibility into the polyolefin resin. 0 1 to 1 111.
  • Examples of such a neutralizing agent include higher fatty acid metal stalagmites and hydrated talcite.
  • Metal stalagmites of higher fatty acids include calcium myristate, calcium stearate, calcium palmitate, 12-'calcium hydroxystearate, magnesium myristate, magnesium stearate, magnesium palmitate, 12-hydroxy magnesium stearate Lithium myristate, lithium stearate, lithium palmitate, 12-hydroxylithium stearate, zinc myristate, zinc stearate, zinc palmitate, zinc 12-hydroxystearate, aluminum myristate, stearic acid Examples thereof include aluminum, aluminum palmitate, and 12-hydroxyaluminum stearate.
  • hydrotalcites the following hydrated talcite is preferable.
  • the polyolefin resin composition of the present invention can contain one or more antioxidants.
  • the antioxidant a known antioxidant is used, and examples thereof include phenolic antioxidants, phosphorus antioxidants, phenol antioxidants, hydroxylamine antioxidants, benzofuranone compounds, and the like. Can be mentioned.
  • phenolic antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, tetrakis [methylene-3 (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] Methane, Octa. Decyl— 3— (3, 5—Di-tert-butyl-
  • phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and distearyl pentaerythritol!
  • Ludiphosphite bis (2,4-di-tert-butylphenyl) Penyuerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythri I ⁇
  • One diphosphite ⁇ bis ( 2,6-di-tert-butyl-4-methylphenyl) Pennyl erythritol phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4: —Diphenylene diphosphonate, 2, 2 '—Methylenebis (4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, 2 ,.
  • thio antioxidants examples include dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3 'monodipropionate, distearyl 3,3' —Thiodipropionate, laurylstearyl 3, 3 ′ —Thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), bis [2-methyl-4 -— (3 _n-alkyl (12 to 12 carbon atoms) 14 alkyl) thiopropionyloxy) — 5-tert-butylphenyl] sulfide and the like.
  • hydroxylamine-based antioxidants examples include hydroxyamine-based compounds represented by the following general formula (II).
  • R 2 and R 3 each represent an alkyl group having 12 to 30 carbon atoms.
  • the hydroxylamine compound represented by the above formula (II) has a polyolefin resin heated or heated. It is a compound that suppresses thermal oxidative degradation of polyolefin resins by forming nitroxy radicals in reactions that are degraded by oxygen.
  • alkyl group having 12 to 30 carbon atoms examples include: ⁇ -decyl group, tetradecyl group, pentadecyl 3 ⁇ 4, hexadecyl group, heptadecyl group, octadecyl group, notidecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl A tetradecyl group, a hexadecyl group, an octadecyl group, an icosyl group, and a docosyl group.
  • benzofurason compounds include 5, 7-di-tert-petityl 3- (3,4-dimethylphenyl) 1 3 H-benzofuran 1-one, 5, 7-di tert-butyl-3 1 ( 3,5-dimethylphenyl) — H-benzofuran 1_one, 5, 7-di-tert-butyl-3— (3, 4, 5-trimethylphenyl) — 3H-benzofuran-2-one, 5, 6, 7—G ⁇ 6 1 ”1; —Butyl-3- (3,4-dimethylphenyl) _ 3H—Benzofuran 2 _one, 5, 7-Di-tert-butyl— 3— (4— Methylphenyl): — 3H—Benzofuran 1_one, 5— tert-butyl— 3— (3,4-dimethylphenyl) —3H—benzofuran —2—one, 5, 7—di-tert-petitu 3— (3,
  • the form of the additive may be powder or granule.
  • the particle diameter of the granular additive is preferably in the range of 0.3 to 10 mm.
  • the content of these additives is usually 0.001 to 5 parts by weight, preferably 0.001 to 5 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). 3 parts by weight, more preferably 0.001 to 1 part by weight, still more preferably 0.01 to 1 part by weight.
  • the polyolefin resin composition of the present invention may contain one or more resins in addition to the component (A) and the component (B).
  • Such resins include ethylene- ⁇ -olefin-based elastomers, polystyrenes (eg polystyrene, poly ( ⁇ -methylstyrene), poly ( ⁇ -methylstyrene), AS resin (acrylonitrile Z styrene copolymer resin). ), ABS (acrylonitrile tributadiene / styrene copolymer) resin, AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, ACS.
  • polystyrenes eg polystyrene, poly ( ⁇ -methylstyrene), poly ( ⁇ -methylstyrene)
  • AS resin acrylonitrile Z styrene copolymer resin
  • ABS acrylonitrile tributadiene / styrene copolymer
  • AAS special acrylic rubber / acrylonitrile / styrene copolymer
  • the method of incorporating component (C) into component ( ⁇ ) and ⁇ or component ( ⁇ ) is A method in which the component ( ⁇ ) and the component ( ⁇ ) are contained without breaking is preferable.
  • the Plutrus-Yon method Japanese Patent Laid-Open Nos. 3-121146 and 3. — 2 7 2 8 30) and the like.
  • the pultrusion method is basically a method in which a continuous fiber bundle is drawn and impregnated with resin.
  • the fiber bundle is placed in the crosshead.
  • a method using a crosshead described in Japanese Patent Application Laid-Open No. 3-27 2 8 30 is preferable.
  • the resin impregnation operation in these pultrusion methods may be performed in one step, or may be performed in two or more steps.
  • Examples of the shape of the polyolefin resin composition of the present invention include a strand shape, a sheet shape, a flat plate shape, and a pellet shape obtained by cutting a strand into an appropriate length.
  • the shape of the polyolefin resin composition applied to the injection molding method is preferably a pellet having a length of 1 to 5 O mm from the viewpoint of the mechanical strength of the obtained molded product and the production stability during molding. .
  • the molded product of the present invention is a molded product obtained by molding the polyolefin resin composition of the present invention.
  • Examples of the method for producing a molded article of the present invention include, for example, an injection molding method, a press molding method, a vacuum molding method, a foam molding method, and an extrusion molding method that are usually used industrially.
  • a molding method in which the same type of polyolefin resin as the polyolefin resin composition of the present invention or another resin is bonded, a method of coextrusion molding, and the like are also included.
  • the molded article of the present invention is preferably an injection molded article obtained by an injection molding method.
  • Examples of the injection molding method include known molding methods that are usually used industrially. For example, an injection molding method, an injection foam molding method, a supercritical injection foam molding method, an ultra-high speed injection molding method, an injection.
  • Compression molding method gas assist injection molding method, sandwich molding method, sandwich Examples thereof include a foam molding method and an insert-sert molding method.
  • the weight average fiber length of the fibers contained in the molded product is preferably 1 mm or more.
  • a polyolefin resin group having excellent long-term durability in an environment affected by oxygen, heat, and light, in particular, excellent light stability over a long period of time. Compositions and ⁇ -molded products can be obtained.
  • Applications of the molded article of the present invention include, for example, automobile materials, household electrical appliance materials, ⁇ equipment materials, building materials, drainage equipment, toilet evening materials, various tanks, containers, and sheets.
  • automotive materials include interior parts such as door trims, villas, instrument panels, consoles, rocker panels, armrests, door inner panels, spare tire covers, door knobs, bumpers, boilers, fenders, sides. Steps, doors, exterior parts such as outer panels, other parts such as air intake ducts, coolant reserve tanks, raje evenings, reserve tanks, window washer tanks, fender liners, fans, etc.
  • home appliance materials include washing machine materials, dryer materials, vacuum cleaner materials, rice cooker materials, warmer materials, dishwasher materials, and air cleaner materials.
  • Media related materials include magnetic recording media and optical recording media 'cases, personal computer parts, printers and copy parts.
  • Building materials include frames that harden concrete and wall materials.
  • Examples of drainage facilities include pipes and pump parts.
  • the use of the molded article of the present invention is preferably an automobile material, a household appliance material, a building material, a drainage facility, or a container.
  • Polyolefin resin (component (A)), modified polyolefin resin (component (B)), fibrous filler (component (C)), hindered amine light stabilizer (component (D)) used in Examples and Comparative Examples Benzoate compounds (component (E)) and white pigment (component (F)) are shown below.
  • Component (A) Polyolefin resin
  • a maleic anhydride modified product of a propylene- (ethylene-propylene) block copolymer produced by the method described in JP-A-2002-308947 was used.
  • the physical properties of this modified block copolymer are shown below.
  • the long fiber-containing polyolefin resin composition was produced by performing the method described in JP-A-3-121146 at an impregnation temperature of 270 and a take-up speed of 33 ft. Minutes.
  • Benzoate compounds of the following structural formula (trade name: Sumisorp 400, Sumitomo Chemical (manufactured by ffi; chemical name: 2, 4-ji tert-butyl-phenol 3, 3,5-di-tert-butyl-4 hydroxybenzoate) )
  • the measurement of the isotactic index of the polyolefin resin was carried out using a 13 C—N MR spectrum measuring device AM400 manufactured by BRUKER.
  • test piece The molded product for evaluation (test piece) was injection-molded from the obtained long fiber pellets using the following Nippon Steel Works molding machine under the following conditions. -[Molding machine manufactured by Nippon Steel Works]
  • the tensile strength was measured according to AS TM D 638 under the following conditions. Measurement temperature: 23 ° C
  • the bending strength was measured according to AS TM D 790 under the following conditions.
  • I ZOD impact strength was measured in accordance with ASTM D 256 under the following conditions.
  • Test specimen dimensions 5 OmmX 5 OmmX 3 mm (thickness)
  • Test time 300 hours or ⁇ 00 hours
  • the surface glossiness of the test piece before irradiation treatment described in the previous section (6-1) and the surface brightness of the test piece after irradiation treatment were measured to determine the gloss retention.
  • the surface gloss was measured according to JISZ 8741 (1 997) using a precision gloss meter (GM-3D, angle 60 °) manufactured by Murakami Color Research Laboratory. The higher the surface gloss retention, the better the light stability.
  • test piece after the irradiation treatment described in the previous section (6-1) was observed with an optical microscope (100 magnifications) for any abnormal appearance such as cracks. '
  • glass fiber having a glass fiber content of 40% by weight A pellet (9 mm in length) of the containing polyolefin resin composition (GFPP-1) was prepared. At this time, the impregnation temperature was 270, and the take-up speed was 33 ⁇ / min.
  • the content of each component in the resin composition (GFPP-1) is shown below.
  • P-Pyrene homopolymer (A-1) 48 parts by weight
  • ⁇ -Pyrene homopolymer (A-2) 10 parts by weight.
  • -Modified pro Soku copolymer (B_l): 2 parts by weight
  • Fibrous filler (C-1) ' 40 parts by weight (The total amount of (A-1), ( ⁇ -2), ( ⁇ -1) and (C-1)) is 100 parts by weight. ) Phenolic antioxidants (G-1): 0.1 part by weight
  • Phosphorus antioxidant (G-2) 0.1 part by weight
  • Propylene-ethylene random copolymer powder (A-4) and (F-1) Zinc sulfide is melt-kneaded.
  • F-1) Colorant-containing masterbatch with a zinc sulfide content of 21% by weight (MB-3) pellets were produced. However, as pigments other than zinc sulfide, quinacridone, isoindolinone compound, carbon black (furnace black), and metal stone-based dispersant were blended.
  • Glass fiber-containing polyolefin resin composition (GFPP-1), light stabilizer-containing master patch (MB-1), benzoate-containing matrix X-batch (MB-2), and colorant-containing mass-batch (MB-3) was melt-kneaded to produce a polyolefin resin composition.
  • the total amount of light stabilizer-containing masterbatch (MB-1), benzoate compound-containing masterbatch (MB-2), and colorant-containing masterbatch (MB-3) is contained in GFP P-1
  • the total amount of (A 1), (A-2), (B-1), and (C 1) was 100 parts by weight, and was 3 parts by weight, 1 part by weight, and 2 parts by weight.
  • the composition of the polyolefin resin composition produced is shown in Table 1. (4-2) Fabrication and evaluation of injection molded products
  • a molded article (test piece) for measuring physical properties comprising the polyolefin resin composition obtained above was produced.
  • the obtained molded article was measured for physical properties and subjected to a light stability test (600 hours). The results are shown in Table 1. ,
  • a light-stabilizer-containing masterbatch (MB-1 ′) was prepared.
  • a polyolefin resin composition was produced by the same method as described in Example 1 except that this master batch (MB-1 ′) was used as a light stabilizer-containing master batch. Further, a molded article (test piece) made of the same composition was prepared, and the physical properties were measured and the light stability test (600 hours) was performed. The results are shown in Table 1.
  • a master batch containing benzoate compound (MB-2 ') was prepared. As described in Example 1, except that the masterbatch (MB-1 ') was used as a light stabilizer-containing masterbatch, and the masterbatch (MB-2') was used as a benzoate compound-containing masterbatch.
  • a polyolefin resin composition was produced by a method similar to the above method. Furthermore, a molded product (test piece) made of the same composition was prepared, and the physical properties were measured and the light stability test (600 hours) was performed. The result is not ⁇ 1.
  • Example 1 except that the above-mentioned master batch (MB—1 ′ ′) was used as the master batch containing light stabilizer, and the master batch (MB—2 ′ ′) was used as the master batch containing benzoate compound.
  • a polyolefin resin composition was produced by the same method as described in 1. Further, a molded article (test piece) made of the same composition was prepared, and its physical property measurement and light stability test (600 hours) were performed. The results are shown in Table 1.
  • GFPP P-1 glass fiber-containing polyolefin resin composition
  • MB-1 light stabilizer-containing masterbatch
  • MB-2 benzoic compound-containing masterbatch
  • resin composition A polyolefin resin composition was produced in the same manner as described in Example 1 except that GFPP-2), masterbatch (MB-1 ') and masterbatch (MB-2') were used. did.
  • a molded product (test piece) made of the same composition was produced, and its physical properties were measured and a light stability test (300 hours) was performed. The results are shown in Table 2.
  • Example 4 the light stabilizer-containing masterbatch and the benzoic compound-containing masterbatch used were not used, and (A) the polyolefin resin described in Example 4 and (B) the modified resin were used.
  • a resin composition containing a polyolefin resin, (C) a fibrous filler, and (G) an antioxidant, and a light stabilizer (D-2) and a benzoate series are produced simultaneously with the step of producing the resin composition.
  • a polyolefin resin composition and a molded article (test piece) comprising the same were prepared in the same manner as described in Example 4 except that compound (E_2) was added, and the physical properties were measured and the light stability test (300 Time). The results are shown in Table 2. The amount of each component of the resin composition was adjusted in the same manner as in Example 4. ''
  • the light stabilizer (D-1) contained in the light stabilizer-containing masterbatch (MB-1) used in Example 1 was used for the pellet (GF P P_ 1) of the long-fiber-containing polyolefin resin composition described in Example 1. — 1) 0.3 parts by weight was changed to light stabilizer (D—3) D. 14 parts by weight and contained in the master compound-containing batch (M 1 2) used in Example 1.
  • An article and a molded article (test piece) comprising the same were prepared and subjected to physical property measurement and light stability test (600 hours). The results are shown in Table 3.
  • Polyolefins were prepared in the same manner as described in Example 1 except that zinc sulfide (F-1) contained in the colored master batch used in Comparative Example 2 was changed to titanium oxide (F-2). A resin composition was produced. Furthermore, a molded article (test piece) comprising the same composition was prepared, and the physical properties were measured and the light stability test (600 hours) was performed. The results are shown in Table 3.
  • Examples 1 to 3 have a good appearance and excellent light-resistant stability over a long period of time.
  • Example 4 and Example S have a good appearance and excellent mechanical strength, and also have excellent light resistance over a long period of time.
  • This is a polyolefin resin composition obtained by melt-kneading a pellet of a polyolefin resin composition containing long fibers, a master batch containing a light stabilizer and a master batch containing a benzoate compound. High strength, bending strength, and high impact strength, high gloss retention, and excellent light stability. Comparative Examples 1 to 3 in which a light stabilizer having a molecular weight of 100 or more was not used have insufficient light stability over a long period of time.

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Abstract

L’invention concerne une composition de résine de polyoléfine contenant de 39,5 à 98,5 parties en poids du composant (A) défini ci-dessous, de 0,5 à 10 parties en poids du composant (B) défini ci-dessous, de 1 à 60 parties en poids du composant (C) défini ci-dessous, de 0,05 à 1 partie en poids du composant (D) défini ci-dessous, de 0,05 à 1 partie en poids du composant (E) défini ci-dessous et de 0,001 à 10 parties en poids du composant (F) défini ci-dessous (à condition que le total des composants (A), (B) et (C) représente 100 parties en poids). Composant (A) : une résine de polyoléfine Composant (B) : une résine de polyoléfine modifiée obtenue par modification par greffage d’une résine de polyoléfine en utilisant un agent de modification choisi parmi des acides carboxyliques insaturés et des dérivés d’acide carboxylique insaturé, la quantité de modification par greffage étant comprise entre 0,5 et 10 % en poids et le débit de masse fondue, mesuré avec une charge de 21,2 N et une température de 230 ˚C, étant compris entre 20 et 190 g/10 min Composant (C) : des charges fibreuses Composant (D) : un photostabilisant à base d’amine empêchée ayant une masse moléculaire supérieure ou égale à 1 000 Composant (E) : un composé de benzoate représenté par une formule structurale spécifique Composant (F) : un pigment blanc ayant une dureté de Mohs comprise entre 1 et 6
PCT/JP2006/325142 2005-12-14 2006-12-12 Composition de resine de polyolefine, corps moule obtenu a partir de cette composition et procede de fabrication de cette composition de resine de polyolefine WO2007069760A1 (fr)

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EP2436721A1 (fr) * 2009-05-29 2012-04-04 Prime Polymer Co., Ltd. Composition de résine renforcée de fibres longues et objet moulé fait de celle-ci
WO2016002192A1 (fr) * 2014-06-30 2016-01-07 三井化学株式会社 Composition de résine pour matériau réfléchissant, et panneau réfléchissant la comprenant
CN113692424A (zh) * 2019-01-23 2021-11-23 美利肯公司 热塑性组合物
CN114381234A (zh) * 2021-12-31 2022-04-22 佛山南宝高盛高新材料有限公司 一种防水的超低温冷冻品专用标签胶及其制备方法

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