US20060231972A1 - Method for producing polyolefin-polyamide resin composition - Google Patents

Method for producing polyolefin-polyamide resin composition Download PDF

Info

Publication number
US20060231972A1
US20060231972A1 US10/543,019 US54301905A US2006231972A1 US 20060231972 A1 US20060231972 A1 US 20060231972A1 US 54301905 A US54301905 A US 54301905A US 2006231972 A1 US2006231972 A1 US 2006231972A1
Authority
US
United States
Prior art keywords
component
melting point
polyamide
polyolefin
kneading
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/543,019
Other languages
English (en)
Inventor
Norishige Kawaguchi
Masashi Yamaguchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Assigned to UBE INDUSTRIES, LTD. reassignment UBE INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YAMAGUCHI, MASASHI, KAWAGUCHI, NORISHIGE
Publication of US20060231972A1 publication Critical patent/US20060231972A1/en
Priority to US12/708,066 priority Critical patent/US20100140833A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B29C48/83—Heating or cooling the cylinders
    • B29C48/832—Heating
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; 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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a method of manufacturing polyolefin-polyamide resin composition suitably available in materials for reinforcing rubbers and resins.
  • glass fibers or inorganic fillers are combined. Although the combination of these materials may provide improvements in stiffness, elastic modulus, strength, and creep-resistance, it worsens appearances of moldings and results in heavy moldings.
  • JP-A 7-238189 and JP-A 9-59431 disclose composition, which comprise thermoplastic polyamide fiber dispersed as fine fiber in a matrix of polyolef in and rubber-like polymer. These composition can be improved in mechanical property when a rubber is combined.
  • the rubber to be combined is limited, however, and maybe gelled while kneading. In particular, it has a trend in easily gelling at higher temperatures, which may prevent expression of original properties such as strength, elongation, and elastic modulus.
  • Japanese patent publication No. JP-A 63-75108 discloses a multi-component fiber as a basic component for leather, in which a boundary between gathered inner and outer layers has a specific range.
  • Japanese patent publication No. JP-A 54-73921 discloses a polyamide ultra-thin fiber with a thickness of 0.1 denier, which is derived from a mixed high-speed spun strand produced by mixed high-speed spinning of polyamide and subjected to solvent removing polystyrene and polyethylene glycol.
  • JP-A 3-279419, JP-A 4-272222 and JP-A4-281015 disclose lightweight composite fiber, which cause no peeling at the interface between polypropylene and polyamide. They have an object to improve dye-affinity of polypropylene using core sheathe strands. These methods and strands have an object to obtain an ultra-thin strand with a thickness of 0.1-1 denier (d) by extracting through a small bore spinning nozzle, high-speed spinning, solvent processing, and melting. Accordingly, they are poor in productivity and can not be regarded as economical processes. In addition, these strands are continuous strands of ultra-thin strands and excellent materials for fabrics and synthetic leathers with nice luster and feeling. When they are filled and kneaded in a rubber or resin, however, they are hardly dispersed by kneading because they are continuous strands.
  • Japanese patent publication No. JP-A 11-106570 describes a polyolefin-polyamide resin composition, in which fine polyamide strands with an average strand diameter of 0.2-0.6 ⁇ m are uniformly dispersed in a polyolef in matrix and the polyolef in is bonded to the strand at the interface.
  • the polyolefin-polyamide resin composition can be produced in the form of pellets and accordingly has easy dispersibility and reinforcing ability when it is kneaded in a rubber or resin.
  • JP-A 11-106570 is produced by melting and kneading, extruding, and drafted drawing or rolling (a) a polyolefin, (b) a polyamide, and (c) a silane coupling agent to disperse the polyamide (b) in the form of strands with an average strand diameter of 1 ⁇ m or less in the polyolefin (a) to finish the composition in the form of pellets.
  • an antioxidant of pentaerithritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is added.
  • an antioxidant with a melting point of 110° C. is employed.
  • Such the antioxidant with a low melting point can not function sufficiently while kneading and reacting in a biaxial extruder. Therefore, gelation of polyolefin (decomposition when polypropylene is employed) occurs and causes scorches in the extruder, resulting in a small amount of discharge and a large amount of strand cut. It is also required to frequently clean a device for removing scorches from the extruder, which causes a problem associated with impossibility of long-time running and extremely bad productivity. In particular, cleaning for removal of scorches requires decomposition of devices such as the extruder and exerts a large influence on productivity.
  • the present invention has an object to provide a method of manufacturing polyolefin-polyamide resin composition, which method has a large amount of discharge and is capable of long-time running and excellent in productivity.
  • the present invention provides a method of manufacturing polyolefin-polyamide resin composition, comprising melting and kneading, extruding, and drafted drawing or rolling (a) a polyolef in, (b) a polyamide, (c) a silane coupling agent, (d) a first antioxidant with a melting point of 70-170° C., and (e) a second antioxidant with a melting point of 180-300° C., preferably 200-300° C., more preferably 200-290° C. to disperse the polyamide (b) in the form of fiber with an average fiber diameter of 1 ⁇ m or less in the polyolef in (a) to finish the composition in the form of pellets.
  • the two antioxidants of components (d) and (e) are combined.
  • This combination can provide a method of manufacturing polyolefin-polyamide resin compositions, which method has a large amount of discharge and is capable of long-time running and excellent in productivity.
  • the component (a) is a polyolefin, preferably, with a melting point falling within 80-250° C.
  • a melting point falling within 80-250° C.
  • those having a Vicat softening point of 50° C. or higher, more preferably 50-200° C. may be employed.
  • Such suitable examples include homopolymers or copolymers of an olefin having 2-8 carbon atoms; and copolymers of an olefin having 2-8 carbon atoms with an aromatic vinyl compound such as styrene, chlorostyrene, and a-methyl styrene; copolymers of an olefin having 2-8 carbon atoms with a vinyl acetate; copolymers of an olefin having 2-8 carbon atoms with an acrylic acid or an ester thereof; copolymers of an olefin having 2-8 carbon atoms with a methacrylic acid or an ester thereof; and copolymers of an olef in having 2-8 carbon atoms with a vinyl silane compound, which are suitably employed.
  • high density polyethylene low density polyethylene; linear low density polyethylene; polypropylene; ethylene-propylene block copolymers; ethylene-propylene random copolymers; poly 4-methylpentene-1; polybutene-1; polyhexene-1; ethylene-vinylacetatecopolymers; ethylene-vinyl alcohol copolymers; ethylene-acrylic acid copolymers; ethylene-methyl acrylate copolymers; ethylene-ethyl acrylate copolymers; ethylene-propyl acrylate copolymers; ethylene-butyl acrylate copolymers; ethylene-2-ethylhexyl acrylate copolymers; ethylene-hydroxyethyl acrylate copolymers; ethylene-vinyl trimethoxysilane copolymers; ethylene-vinyl triethoxysilane copolymers; ethylene-vinylsilanecopolymers; ethylene-styrene copo
  • polyolefin of component (a) include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-vinyl acetate copolymers (EVA), ethylene-ethyl acrylate copolymers (EEA), and ethylene-vinyl alcohol copolymers.
  • most preferable examples have a melt flow index (MFI) of 0.2-50g/10 min and may be employed individually or in combination of two or more.
  • the component (b) is a thermoplastic polyamide having an amide group in the main chain (hereinafter referred to as polyamide), with a melting point falling within 135-350° C. and higher than the melting point of the polyolefin of component (a), preferably with a melting point of 160-265° C.
  • polyamide thermoplastic polyamide having an amide group in the main chain
  • Such the component (b) includes as a preferable example a polyamide that provides tough fiber by extruding and drawing.
  • polyamide examples include nylon 6; nylon 66; nylon 6-nylon 66 copolymers; nylon 610; nylon 612; nylon 46; nylon 11; nylon 12; nylon MXD6; condensation polymers of xylylenediamine and adipic acid; condensation polymers of xylylenediamine and pimelic acid; condensation polymers of xylylenediamine and suberic acid; condensation polymers of xylylenediamine and azelaic acid; condensation polymers of xylylenediamine and sebacic acid; condensation polymers of tetramethylenediamine and terephthalic acid; condensation polymers of hexamethylenediamine and terephthalic acid; condensation polymers of octamethylenediamine and terephthalic acid; condensation polymers of trimethylhexamethylenediamine and terephthalic acid; condensation polymers of decamethylenediamine and terephthalic acid; condensation polymers of undecamethylenediamine and terephthalic
  • polyamide examples include nylon 6 (PA6), nylon 66 (PA66), nylon 12 (PA12), and nylon 6-nylon 66 copolymers, which may be employed individually or in combination of two or more.
  • these polyamides may have a molecular weight ranging between 10,000-200,000.
  • silane coupling agent of component (c) examples include vinyl methoxy silane; vinyl triethoxy silane; vinyl tris( ⁇ -methoxyethoxy) silane; vinyl triacetyl silane; ⁇ -methacryloxy propyl trimethoxy silane; ⁇ -(3,4-epoxy cyclohexyl) ethyl trimethoxy silane; ⁇ -grycidoxy propyl trimethoxy silane; ⁇ -grycidoxy propyl methyl dimethoxy silane; ⁇ -grycidoxy propyl methyl diethoxy silane; ⁇ -grycidoxy propyl ethyl dimethoxy silane; ⁇ -grycidoxy propyl ethyl diethoxy silane; N- ⁇ -(aminoethyl) aminopropyl trimethoxy silane; N- ⁇ -(aminoethyl) aminopropyl triethoxy silane; N- ⁇ -(aminoeth
  • the silane coupling agent of component (c) is contained within a range of 0.1-5.5 weight parts, more preferably 0.2-3.0 weight parts, on the basis of 100 weight parts of the components (a) and (b).
  • An amount of the silane coupling agent less than 0.1 weight part can not yield a high-strength composition.
  • An amount of the silane coupling agent more than 5.5 weight parts can not yield a composition excellent in elastic modulus.
  • An amount of the silane coupling agent less than 0.1 weight % yields only a low-strength composition because a strong bond can not be formed between the component (a) and the component (b).
  • An amount of the silane coupling agent more than 5.5 weight % yields only a composition with poor elastic modulus as well because the component (b) can not turn in excellent fine fiber.
  • an organic peroxide may be used together.
  • the use of the organic peroxide together promotes the reaction of the component (a) with the silane coupling agent because a radical is formed in the molecular chain of the component (a) and reacts with the silane coupling agent.
  • the usage of the organic peroxide is 0.01-1.0 weight part on the basis of 100 weight parts of the component (a).
  • Preferably available organic peroxides have such a half value period temperature for minute that is a temperature equal to higher one of the melting point of the component (a) and the melting point of the component (c), or within a temperature range about 30° C. higher than this temperature. Specifically, those having a half-life temperature per minute falling within 110-200° C. may be employed preferably.
  • organic peroxide examples include di- ⁇ -cumyl peroxide; 1,1-di-t-butylperoxy-3,3,5-trimethyl cyclohexane; 1,1-di-t-butylperoxy cyclohexane; 2,2-di-t-butylperoxy butane; n-butyl 4,4-di-t-butylperoxy valerinate; 2,2-bis-(4,4-di-t-butylperoxy cyclohexane)propane; 2,2,4-trimethyl pentylperoxy neodecanate; ⁇ -cumylperoxy neodecanate; t-butylperoxy neohexanate; t-butylperoxy pivalate; t-butylperoxy acetate; t-butylperoxy laurate; t-butylperoxy benzoate; and t-butylperoxy isophthlate.
  • preferably available ones have such a half-life temperature per minute that is equal to a melting and kneading temperature or within a temperature range about 30° C. higher than this temperature, specifically a half-life temperature per minute falling within 80-260° C.
  • the first antioxidant of component (d) has a melting point of 70-170° C.
  • Examples include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-yl amino)phenol; 2,2′-methylene bis(4-methyl-6-t-butylphenol); 4,4′-thiobis(3-methyl-6-t-butylphenol); 2-[1-(2-hydroxy-3,5-di-t-pentyl phenyl)ethyl]-4,6-di-t-pentylphenylacryl; and 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methyl benzyl)-4-methylphenylacryl.
  • the first antioxidant of component (d) is contained within a range of 0.01-5 weight
  • the second antioxidant of component (e) has a melting point of 180-300° C., preferably200-300° C., and more preferably 200-290° C.
  • Examples include 4,4′-butylidene bis(3-methyl-6-t-butylphenol); 2-mercaptobenzoimidazole; 3,3′,3′′,5,5′,5′,5′′-hexa-t-butyl-a,a′a′′-(mesitylene-2,4,6-tiryl)tri-p-cresol; 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2 ,4,6(1H,3H,5H)-trione; tri-(3,5-di-t-butyl-4-hydroxy benzyl)-isocyanurate; 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butyl phenyl)butane; 4,4′-butylidene bis(
  • two antioxidants are employed as the components (d) and (e).
  • the antioxidant or component (e) is employed.
  • the method of manufacturing polyolef in-polyamide resin composition according to the present invention may comprise a first step of melting and kneading the polyolefin of component (a), the silane coupling agent of component (c), the first antioxidant of component (d), and the second antioxidant of component (e) for chemical modification; a second step of melting and kneading the polyamide of component (b) at a melting point of the component (b) or higher into the component (a) chemically modified in the first step; a third step of melting and kneading the polyamide of component (b) for chemical modification at the melting point of the component (b) or higher into the component (a) chemically modified in the first step and extruding a product; a fourth step of drafted drawing or rolling the extruded product molten and kneaded and chemically modified in the third step, at a temperature higher than a melting point of the component (a) and lower than the melting point of the component (b); and
  • the melting and kneading temperature is preferably above the melting point of the component (a), and more preferably 30° C. higher than the melting point. Melting and kneading at a temperature 30° C. higher than the melting point can chemically modify it through reaction with the silane coupling agent of component (c). Melting and kneading can be performed in a device usually employed for kneading a resin or rubber. Such devices include a Banbury mixer, a kneader, a kneader/extruder, an open roll, a uniaxial kneader, and a biaxial kneader. The biaxial kneader is most preferable among these devices because it is capable of melting and kneading continuously in a short time.
  • the melting and kneading temperature is preferably above the melting point of the component (b), and more preferably 10° C. higher than the melting point. If the melting and kneading temperature is lower the melting point of the component (b), it can not be kneaded and dispersed in the form of fiber. Accordingly, melting and kneading is performed at a temperature higher than the melting point, and more preferably at a 20° C. higher temperature.
  • the kneaded product obtained at the step of extruding is extruded preferably through a spinning nozzle, an inflation die or a T-die. It is required to implement both spinning and extruding at a temperature higher than the melting point of the component (b). Specifically, it is implemented at a temperature higher than the melting point of the component (b), preferably a temperature range 30° C. higher than this temperature. Even if melting and kneading is performed at a temperature lower than the melting point of the component (b) in this step, the kneaded product is not structured to contain fine particles of the component (b) dispersed in a matrix of the component (a). Therefore, even spinning and drawing such the kneaded product can not turn the component (b) in fine fiber.
  • the extruded product is spun in the form of a string or yarn through continuous processes of cooling and drawing or rolling.
  • the processes of cooling and drawing or rolling are implemented at a temperature 10° C. lower than the melting point of the component (b). More preferably, drawing and rolling can form much tougher fiber and accordingly exert the property as a fiber-reinforcing resin composition.
  • Drawing or rolling is implemented, for example, by extruding the kneaded product through a spinning nozzle to spin it in the form of a string or yarn, and drafted winding it around a bobbin. Alternatively, it may be implemented by a method of cutting it into pellets.
  • “Drafted” is herein defined as determination of a winding speed higher than a spinning nozzle speed. A ratio of the winding speed to the spinning nozzle speed (draft ratio) is determined preferably within 1.5-100, more preferably within 2-50, and most preferably within 3-30.
  • pelletizing allows for uniform kneading even if a resin or rubber component is added. Therefore, preferably pellets may be employed as the polyolefin-polyamide resin composition.
  • the use of the resin composition in the form of pellets allows the resin composition to be kneaded together with an elastomer uniformly to easily produce a reinforced elastomer composition with fine fiber uniformly dispersed therein.
  • the first through third steps are described separately on a step basis.
  • the use of a biaxial kneader having first through five inlets capable of supplying the components (a), (b), (c), (d) and (e) therethrough, and having first through five kneading belts corresponding to the inlets allows processing in a batch through continuous processes. To do so, the method becomes an economic, stable and safe method of manufacturing.
  • adjuvant such as carbon black, white carbon, active calcium carbonate, ultra particulate magnesium silicate, high styrene resin, phenol resin, lignin, modified melamine resin, coumarone indene resin, and oil resin; various fillers such as calcium carbonate, basic magnesium carbonate, clay, zinc flower, silious earth, recycled rubber, powdered rubber, and ebonite powder; stabilizer such as amine-aldehydes, amine-ketons, amines, phenols, imidazoles, sulfur-containing antioxidants, and phosphorous-containing antioxidants; and various pigment may be added appropriately.
  • pellets are collected for one minute at a hopper chute opening of a pelletizer and weighted. This operation is repeated three times and an average thereof is calculated as an amount of discharge.
  • a continuous running time is defined as a period after the time of supplying a silane modified polyolefin and a polyamide into a biaxial extruder (the beginning of running) until collection of products becomes impossible because of many occurrences of strand cut.
  • Part of strands is collected every two hours after the beginning of running and measured by a caliper.
  • the extruded strands may be cut by a tensile force while drafted drawing.
  • the number of cut strands is evaluated by a ratio to the time.
  • the size of gums formed at the spinning nozzle is visually observed every 0.5 hour after the beginning of running.
  • the biaxial extruder After completion of continuous running, the biaxial extruder is dismantled to visually identify the state of scorch in the barrel and on the screw.
  • a percentage of (Amount of Produced Polyolefin-Polyamide Resin Composition) to (Total Amount of Prepared Silane Modified Polyolefin+Polyamide) from the beginning to the ending of continuous running is calculated as a yield.
  • An amount of products produced from the beginning to the ending of daily continuous running is measured as a production.
  • silane modified polyethylene 50 weight parts of nylon 6 [1030B available from Ube Industries, Ltd having a melting point of 215-225° C.] as the component (b) are supplied in a biaxial extruder. They are kneaded for reaction at 240° C., extruded, then cooled in air, drawn with drawing rolls at a draft ratio of 7, and 1.5 times stretched between 5-inch rolls at room temperature for pelletization.
  • the pelletized shape has a diameter of 1 mm and a length of 3 mm.
  • Hot toluene is applied to the produced pellets to solve out polyethylene. No insolubles clings around the agitating fan, and the suspension is found uniform. The insoluble content is observed through a scanning electron microscope and found in the form of fine fiber with adiameter of 0.3 ⁇ m. Amount of Discharge, Continuous Running Time, Uniformity of Strand Diameter, Cut of Strand, Generation of Gum, Scorch in Extruder, Yield, and Daily Production at the time are shown in Table 1.
  • Example 1 Amount of Discharge 50 50 20 (Kg/hr) Continuous Running Time 24 or more 24 or more 8 (hr) Uniformity of Strand Uniform Uniform Non-uniform Diameter Cut of Strand Extremely Little Many little Generation of Gum Extremely Little Much little Scorch in Extruder Free Free Present Yield (%) 98 96 80 Daily Production 1176 1152 108
  • a 2-mercaptobenzoimidazole As the component (e), 0.5 weight part of a 2-mercaptobenzoimidazole [Sumilizer MB available from Sumitomo Chemical Industry having a melting point of 285° C.] is employed instead of 4,4′-butylidene bis(3-methyl-6-t-butylphenol).
  • the kneading and reacting temperature in the biaxial kneader is set at 300° C. With these exceptions, a polyolefin-polyamide resin composition is produced in the same manner as in Example 1. Amount of Discharge, Continuous Running Time, Uniformity of Strand Diameter, Cut of Strand, Generation of Gum, Scorch in Extruder, Yield, and Daily Production at the time are shown in Table 1.
  • the component (e) is not added as the antioxidant and only 1.0 weight part of the antioxidant of component (d) is added. With this exception, a polyolef in-polyamide resin composition is produced in the same manner as in Example 1. Amount of Discharge, Continuous Running Time, Uniformity of Strand Diameter, Cut of Strand, Generation of Gum, Scorch in Extruder, Yield, and Daily Production at the time are shown in Table 1.
  • Examples 1 and 2 with the component (e) added as the antioxidant result in little strand cut, large amounts of discharge, and free from scorch in the extruder compared to Comparative Example 1 with the component (e) not added. Accordingly, it is possible to extremely reduce cleanings inside the extruder to remove scorches, resulting in a long-time running, a larger yield, and a very greater daily production.
  • the component (d) is not added as the antioxidant and only 1.0 weight part of the antioxidant of component (e) is added.
  • a Banbury mixer is employed in kneading and reacting at 170° C. and a uniaxial kneader is then employed in pelletizing in the same manner as in Example 1. In this case, however, it is not possible to perform stable continuous pelletizing to produce a polyolefin-polyamide resin composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
US10/543,019 2003-12-26 2004-11-09 Method for producing polyolefin-polyamide resin composition Abandoned US20060231972A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/708,066 US20100140833A1 (en) 2003-12-26 2010-02-18 Method of manufacturing polyolefin-polyamide resin composition

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2003-432281 2003-12-26
JP2003432281 2003-12-26
PCT/JP2004/016577 WO2005065908A1 (ja) 2003-12-26 2004-11-09 ポリオレフィン−ポリアミド樹脂組成物の製造方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/708,066 Continuation US20100140833A1 (en) 2003-12-26 2010-02-18 Method of manufacturing polyolefin-polyamide resin composition

Publications (1)

Publication Number Publication Date
US20060231972A1 true US20060231972A1 (en) 2006-10-19

Family

ID=34746858

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/543,019 Abandoned US20060231972A1 (en) 2003-12-26 2004-11-09 Method for producing polyolefin-polyamide resin composition
US12/708,066 Abandoned US20100140833A1 (en) 2003-12-26 2010-02-18 Method of manufacturing polyolefin-polyamide resin composition

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/708,066 Abandoned US20100140833A1 (en) 2003-12-26 2010-02-18 Method of manufacturing polyolefin-polyamide resin composition

Country Status (8)

Country Link
US (2) US20060231972A1 (ja)
EP (1) EP1704977A4 (ja)
JP (1) JP4285482B2 (ja)
KR (1) KR20070003804A (ja)
CN (1) CN1898070A (ja)
CA (1) CA2551289A1 (ja)
MY (1) MY136861A (ja)
WO (1) WO2005065908A1 (ja)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150361615A1 (en) * 2014-06-12 2015-12-17 Edward J. Negola Dyed Olefin Yarns And Textile Fabrics Using Such Yarns
US9918905B1 (en) 2016-10-13 2018-03-20 Stanley Howard Medication container with smart cap

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130043613A1 (en) * 2009-11-17 2013-02-21 Shinya Kawasoe Method for Producing Polyolefin Microporous Membrane
DE112013006962B4 (de) * 2013-04-19 2023-06-15 Mitsubishi Electric Corporation Verfahren zum Herstellen eines Formproduktes aus silanvernetztem Polyethylenharz, Verfahren zum Herstellen eines stabförmigen Formproduktes und Vorrichtung zu dessen Herstellung

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5424104A (en) * 1990-11-30 1995-06-13 Mitsui Petrochemical Industries, Ltd. Thermoplastic resin composition and use thereof
US6596198B1 (en) * 2000-04-28 2003-07-22 Albemarle Corporation Additive system for polymers in pellet form which provides proportioned stabilization and internal mold release characteristics

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5853953A (ja) * 1981-09-28 1983-03-30 Motoo Takayanagi 炭化水素系重合体組成物
EP0265070B1 (en) * 1986-09-26 1991-10-09 Ube Industries, Ltd. Fiber-reinforced rubber composition and production process and use thereof
JP2823036B2 (ja) * 1992-08-20 1998-11-11 矢崎総業株式会社 コネクタ
JP3454481B2 (ja) * 1993-02-08 2003-10-06 出光石油化学株式会社 ポリオレフィン樹脂組成物
JP3543011B2 (ja) * 1993-04-27 2004-07-14 出光石油化学株式会社 ポリオレフィン樹脂組成物
JP3326957B2 (ja) * 1994-03-01 2002-09-24 宇部興産株式会社 繊維強化熱可塑性組成物及びその製造方法
US6207737B1 (en) * 1994-03-14 2001-03-27 Ppg Industries Ohio, Inc. Glass fiber sizing, sized glass fibers and polyolefin reinforced articles
JPH0827305A (ja) * 1994-07-13 1996-01-30 Fuji Photo Film Co Ltd 写真感光材料の包装材料用着色マスターバッチ樹脂組成物及びその製造方法並びに写真感光材料用包装材料及びその製造方法
JP3120711B2 (ja) * 1995-08-21 2000-12-25 宇部興産株式会社 繊維強化熱可塑性樹脂組成物の製造法
JP3661736B2 (ja) * 1997-09-30 2005-06-22 宇部興産株式会社 ポリオレフィン−ポリアミド樹脂組成物の製造方法
JPH11181162A (ja) * 1997-12-24 1999-07-06 Ube Ind Ltd 高溶融張力ポリオレフィン組成物とその製造法
JPH11209535A (ja) * 1998-01-27 1999-08-03 Ube Ind Ltd ポリアミド繊維強化熱可塑性エラストマー組成物とその製造法
US6376057B1 (en) * 1998-11-19 2002-04-23 Fuji Photo Film, Co., Ltd. Packaging material for photographic photosensitive material
US6433102B1 (en) * 1998-12-04 2002-08-13 Nippon Zeon Co., Ltd. Hydrogenated polymers, resin composition, and process for producing substrate for information-recording medium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5424104A (en) * 1990-11-30 1995-06-13 Mitsui Petrochemical Industries, Ltd. Thermoplastic resin composition and use thereof
US6596198B1 (en) * 2000-04-28 2003-07-22 Albemarle Corporation Additive system for polymers in pellet form which provides proportioned stabilization and internal mold release characteristics

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150361615A1 (en) * 2014-06-12 2015-12-17 Edward J. Negola Dyed Olefin Yarns And Textile Fabrics Using Such Yarns
US9918905B1 (en) 2016-10-13 2018-03-20 Stanley Howard Medication container with smart cap

Also Published As

Publication number Publication date
MY136861A (en) 2008-11-28
EP1704977A1 (en) 2006-09-27
KR20070003804A (ko) 2007-01-05
US20100140833A1 (en) 2010-06-10
JP4285482B2 (ja) 2009-06-24
CA2551289A1 (en) 2005-07-21
EP1704977A4 (en) 2010-10-27
CN1898070A (zh) 2007-01-17
JPWO2005065908A1 (ja) 2007-07-26
WO2005065908A1 (ja) 2005-07-21

Similar Documents

Publication Publication Date Title
EP2872568B1 (en) Olefin-maleic anhydride copolymer compositions and uses thereof
CN1191303C (zh) 含纤维增强材料的聚烯烃组合物以及使用该组合物的纤维增强树脂模塑制品
JP3216428B2 (ja) 長繊維強化ポリマーアロイ樹脂組成物
US6521693B2 (en) Long fiber-reinforced polypropylene resin composition and molded article
JPWO2007097184A1 (ja) ガラス繊維強化熱可塑性樹脂組成物および成形品
US20060167158A1 (en) Resin composition for coating electric wire and electric wire using the same
WO2005092814A1 (ja) チョップドストランドの製造方法
US20100140833A1 (en) Method of manufacturing polyolefin-polyamide resin composition
KR101996094B1 (ko) 성형 조성물
JP3661736B2 (ja) ポリオレフィン−ポリアミド樹脂組成物の製造方法
US10273348B2 (en) Glass fiber-reinforced polyamide 66 resin composition with high tensile strength and method of manufacturing the same
KR100730421B1 (ko) 폴리올레핀 수지조성물 및 그 제조 방법
JP2007245517A (ja) 樹脂塊状物およびその製造方法
CN113563716B (zh) 手机玻璃屏幕边缘抛光用抛光丝材料及其制备方法和应用
JPH11255987A (ja) ポリオレフィン樹脂組成物、成形用材料、成形品の成形方法および成形品
JPH11302464A (ja) ポリアミド繊維強化ポリオレフィン樹脂組成物とその製 造方法
JP2004058481A (ja) リサイクル樹脂製品の製造方法及び自動車用樹脂部品
JP3120711B2 (ja) 繊維強化熱可塑性樹脂組成物の製造法
KR102020606B1 (ko) 내후성이 우수한 장섬유 강화 열가소성 수지 조성물 및 이를 포함하는 성형품
JP2001234076A (ja) 有機繊維樹脂組成物及びその利用
JP2022039310A (ja) 繊維強化ポリアミド樹脂組成物成形品
CN116829640A (zh) 玻璃纤维强化丙烯系树脂组合物
TW200530334A (en) Method for producing polyolefin-polyamide resin composition
JP2006096966A (ja) 長繊維強化熱可塑性樹脂構造体とその成形体及びその製造方法
JP2013119561A (ja) ポリオレフィン樹脂組成物ペレットおよびその製造方法、ならびにそれを成形してなる成形体

Legal Events

Date Code Title Description
AS Assignment

Owner name: UBE INDUSTRIES, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KAWAGUCHI, NORISHIGE;YAMAGUCHI, MASASHI;REEL/FRAME:016437/0615;SIGNING DATES FROM 20050803 TO 20050809

STCB Information on status: application discontinuation

Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION