WO2015098867A1 - ポリオレフィン用加工助剤、及び、ポリオレフィン組成物 - Google Patents
ポリオレフィン用加工助剤、及び、ポリオレフィン組成物 Download PDFInfo
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- WO2015098867A1 WO2015098867A1 PCT/JP2014/083958 JP2014083958W WO2015098867A1 WO 2015098867 A1 WO2015098867 A1 WO 2015098867A1 JP 2014083958 W JP2014083958 W JP 2014083958W WO 2015098867 A1 WO2015098867 A1 WO 2015098867A1
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- density polyethylene
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Definitions
- the present invention relates to a processing aid for polyolefins and a polyolefin composition containing the same. More specifically, the present invention relates to a composition containing a processing aid that can be suitably used for processing a melt processable polymer.
- melt-processable polymer composition In the processing of a melt processable polymer, it is necessary to extrude and process at a high speed in order to improve productivity and reduce costs.
- the melt-processable polymer composition always has a critical shear rate, and when this rate is exceeded, a state called a melt fracture becomes rough, and a good molded product cannot be obtained.
- a method of improving these problems achieving a higher extrusion speed without generating melt fracture and improving the extrusion characteristics, there is a method of forming at a higher molding temperature.
- Patent Document 1 discloses a method for producing an extrudable composition, i) 121 ° C. measured by ASTM D-1646 based on the total weight of the extrudable composition. 0.001 to 10 weight percent of a first fluoroelastomer having a first Mooney viscosity ML (1 + 10) at ii) measured by ASTM D-1646, based on the total weight of the extrudable composition Mixing together 0.001-10 weight percent of a second fluoroelastomer having a second Mooney viscosity ML (1 + 10) at 121 ° C. and iii) a non-fluorinated melt processable polymer, A method is disclosed wherein the difference between the first and second Mooney viscosities is at least 15.
- Patent Document 2 also includes a step of forming a melt-processable polymer composition comprising a melt-processable thermoplastic host polymer and an effective amount of a processing additive composition containing a specific multimode fluoropolymer.
- a method is disclosed that includes mixing a processing additive composition and a host polymer for a time sufficient to blend them and melt processing the polymer composition.
- Patent Document 3 discloses an extrudable composition comprising a thermoplastic hydrocarbon polymer, a poly (oxyalkylene) polymer, and a fluorocarbon polymer.
- Patent Document 4 discloses a resin blend containing a metallocene-catalyzed linear low-density polyethylene resin and a low-density polyethylene resin, a fluoroelastomer having a Mooney viscosity ML (1 + 10) at 121 ° C. of 30 to 60, an interface agent, An extrudable composition is disclosed.
- Patent Document 5 discloses a processing aid containing a fluorine-containing polymer having an acid value of 0.5 KOH mg / g or more.
- Patent Document 6 describes the case of crystallinity. 2 to 95 parts by weight of a fluorocarbon copolymer that is in a molten state at a temperature at which the hardly melt-processable polymer is melt-processed, and in the case of being amorphous, , Tetrafluoroethylene homopolymer or copolymer of tetrafluoroethylene and a monomer copolymerizable with tetrafluoroethylene, wherein the molar ratio of fluorine atom to hydrogen atom is at least 1: 1, and hardly melt-processed
- a processing aid composition for difficult-to-melt processable polymers which essentially contains 98 to 5 parts by weight of a copolymer that is solid at the temperature at which the soluble polymer is melt-process
- Patent Document 7 in the molding process of low-temperature decomposable engineering plastics, the molding processability can be improved by reducing the extrusion pressure and the extrusion torque, the melting point is 200 ° C. or less, and the decomposition temperature is 300 ° C. or less.
- a low temperature decomposable engineering plastic and at least one atom selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom and a fluorine atom bonded to a non-terminal carbon atom constituting the main chain
- a low-temperature-decomposable engineering plastic resin composition obtained by blending a fluorine-containing resin composed of a fluorine-containing polymer having substantially no polar functional group having reactivity with the low-temperature-decomposable engineering plastic.
- the present invention provides a processing aid for polyolefin that can eliminate the melt fracture generated at the start of molding in a short time even when a polyolefin that is a melt processable polymer is extruded at a high speed.
- a polyolefin composition comprising such a polyolefin processing aid and a specific polyolefin is provided.
- the processing aid is dispersed in the form of particles in the polyolefin, and the average dispersed particle size of the processing aid in the polyolefin is 10 ⁇ m or less, It has also been found that the melt fracture can be eliminated in the same time as the prior art. In this way, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly by including a processing aid for polyolefins containing perfluoroelastomer and a specific polyolefin.
- the present invention is selected from the group consisting of low-density polyethylene, linear low-density polyethylene, high-density polyethylene, metallocene-catalyzed linear low-density polyethylene, polypropylene, and polyvinyl chloride, characterized by comprising a perfluoroelastomer A processing aid for polyolefins used to extrude at least one polyolefin produced.
- CF 2 CFO (CF 2 CF (Y) O) m (CF 2) n F (Wherein Y represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4).
- a copolymer with at least one fluoromonomer is preferred.
- the perfluoroelastomer is tetrafluoroethylene and general formula (8):
- CF 2 CF—ORf 81 (Wherein Rf 81 represents a perfluoroalkyl group having 1 to 8 carbon atoms) and is preferably a copolymer with a fluoromonomer.
- the perfluoroelastomer is preferably a copolymer of tetrafluoroethylene and perfluoro (methyl vinyl ether).
- the polyolefin processing aid of the present invention is further selected from the group consisting of silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, polyether polyols, amine oxides, carboxylic acids, aliphatic esters, and poly (oxyalkylenes). It is preferable to contain 1 to 99% by weight of at least one surfactant.
- the present invention also relates to a polyolefin processing aid and a composition comprising a polyolefin, wherein the polyolefin processing aid includes a perfluoroelastomer, and the polyolefin includes a low density polyethylene, a linear low density polyethylene, A polyolefin composition characterized by being at least one selected from the group consisting of high-density polyethylene, metallocene-catalyzed linear low-density polyethylene, polypropylene and polyvinyl chloride.
- CF 2 CFO (CF 2 CF (Y) O) m (CF 2) n F (Wherein Y represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4).
- a copolymer with at least one fluoromonomer is preferred.
- the perfluoroelastomer is tetrafluoroethylene and general formula (8):
- CF 2 CF—ORf 81 (Wherein Rf 81 represents a perfluoroalkyl group having 1 to 8 carbon atoms) and is preferably a copolymer with a fluoromonomer.
- the perfluoroelastomer is preferably a copolymer of tetrafluoroethylene and perfluoro (methyl vinyl ether).
- the polyolefin processing aid is further selected from the group consisting of silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, polyether polyols, amine oxides, carboxylic acids, aliphatic esters and poly (oxyalkylenes). It is preferable to contain 1 to 99% by weight of at least one interfacial agent.
- the content of the polyolefin processing aid is preferably 0.0005 to 10% by weight based on the total weight of the composition. The present invention is described in detail below.
- the present invention is selected from the group consisting of low density polyethylene, linear low density polyethylene, high density polyethylene, metallocene catalyzed linear low density polyethylene, polypropylene and polyvinyl chloride, characterized in that it comprises a perfluoroelastomer A processing aid for polyolefins used to extrude at least one polyolefin. Therefore, even when a polyolefin composition obtained by adding the processing aid for polyolefin of the present invention to a specific polyolefin is extruded at a high shear rate, the melt fracture generated at the start of molding can be eliminated in a short time. it can.
- the perfluoroelastomer refers to a fluoropolymer containing 96 to 100 mol% of polymerized units based on perfluoromonomer and 0 to 4 mol% of polymerized units based on a monomer providing a crosslinking site, based on all polymerized units.
- the perfluoroelastomer is preferably amorphous. “Amorphous” means that the magnitude of the melting peak ( ⁇ H) appearing in DSC measurement (temperature rising temperature 10 ° C./min) is 2.0 J / g or less.
- the fluoromonomer constituting the perfluoroelastomer preferably has at least one double bond.
- the fluoromonomer is preferably a perfluoromonomer.
- CF 2 CFO (CF 2 CF (Y) O) m (CF 2) n F (Wherein Y represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4). It is preferable that there is at least one.
- fluoromonomer represented by the general formula (8) examples include perfluoro (alkyl vinyl ether) (PAVE). Among them, perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether), and perfluoro At least one selected from the group consisting of fluoro (propyl vinyl ether) is preferred, and perfluoro (methyl vinyl ether) is more preferred.
- CF 2 CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 F
- CF 2 CFO (CF 2 CF (CF 3 ) O) 2 (CF 2 ) 3 F
- CF 2 ⁇ CFO (CF 2 CF (CF 3 ) O) 2 (CF 2 ) 2 F are preferably at least one selected from the group consisting of F.
- the perfluoroelastomer may be obtained by polymerizing the perfluoromonomer and a monomer that gives a crosslinking site.
- CX 3 2 CX 3 -R f 121 CHR 121 X 4
- X 3 is a hydrogen atom, a fluorine atom or CH 3
- R f 121 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group
- R 121 Is a hydrogen atom or CH 3
- X 4 is an iodine atom or a bromine atom
- CX 3 2 CX 3 -R f 131 X 4 (Wherein X 3 is a hydrogen atom, fluorine atom or CH 3 , R f 131 is a fluoroalkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group
- Formula (14) CF 2 ⁇ CFO (CF 2 CF (CF 3 ) O) m (CF 2 ) n —X 5 (Wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X 5 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH 2 I).
- m is an integer of 0 to 5
- n is an integer of 1 to 3
- X 6 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH 2 OH.
- X 3 is preferably a fluorine atom.
- R f 121 and R f 131 are preferably perfluoroalkylene groups having 1 to 5 carbon atoms.
- R 121 is preferably a hydrogen atom.
- CF 2 CFOCF 2 CF ( CF 3) OCF 2 CF 2 CN
- CF 2 CFOCF 2 CF (CF 3) OCF 2 CF 2 COOH
- CF 2 CFOCF 2 CF (CF 3) OCF 2 CF 2 CH 2 I
- CF 2 CFOCF 2 CF 2 CH 2 I
- CH 2 CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CN
- CH 2 CFCF 2 OCF (CF 3) CF 2 OCF (CF 3 ) COOH
- CH 2 CFCF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) CH 2 OH
- CH 2 CHCF 2 CF 2 I
- the perfluoroelastomer is preferably obtained by polymerizing only the perfluoromonomer or only the perfluoromonomer and the monomer that gives a crosslinking site.
- the perfluoroelastomer particles can be produced by polymerizing only the perfluoromonomer, or only the perfluoromonomer and the monomer providing the crosslinking site.
- CF 2 CFO (CF 2 CF (Y) O) m (CF 2) n F (Wherein Y represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4).
- a copolymer with at least one fluoromonomer is preferred.
- perfluoroelastomer examples include perfluororubbers containing TFE, for example, a fluoromonomer copolymer represented by TFE / general formula (8), (10) or (11), and TFE / general formula (8), (10 ) Or (11) is preferably at least one selected from the group consisting of a fluoromonomer / monomer copolymer that provides a crosslinking site.
- the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, and still more preferably 55 to 70/30 to 45.
- a monomer copolymer giving a TFE / PAVE / crosslinking site it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), more preferably 55 to 79. 9/20 to 44.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
- a fluoromonomer copolymer represented by the general formula (8), (10) or (11) having 4 to 12 carbon atoms preferably 50 to 90/10 to 50 (mol%). More preferably, it is 60 to 88/12 to 40, and still more preferably 65 to 85/15 to 35.
- the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.
- the monomer that gives the crosslinking site is as described above.
- Examples of the perfluoroelastomer include TFE / fluoromonomer copolymer represented by the general formula (11), TFE / fluoromonomer represented by the general formula (11) / monomer copolymer that provides a crosslinking site, TFE / general It is at least one selected from the group consisting of a fluoromonomer copolymer represented by formula (8) and a fluoromonomer represented by TFE / general formula (8) / a monomer copolymer that provides a crosslinking site. It is more preferable.
- perfluoroelastomer examples include perfluoroelastomers described in International Publication No. 97/24381, Japanese Examined Patent Publication No. 61-57324, Japanese Examined Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Can do.
- the perfluoroelastomer is more preferably a fluoromonomer copolymer represented by TFE / general formula (8).
- the perfluoroelastomer may contain two or more kinds, but preferably contains only a fluoromonomer copolymer represented by TFE / general formula (8), and further includes TFE / perfluoro ( It is preferably a copolymer with (methyl vinyl ether).
- the perfluoroelastomer is selected from the group consisting of —CONH 2 , —OCOOR (R represents an alkyl group having 1 to 6 carbon atoms), —CH 2 OH, —COF and —COOH at the end of the main chain. It is preferable to have at least one kind of group. Since the perfluoroelastomer has such a functional group at the end of the main chain, the affinity between the metal surface of the die and the processing aid is improved, so the pressure drop rate when used as a processing aid is high. Improves and increases the pressure drop.
- the said functional group can be introduce
- R in the group represented by —OCOOR represents an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. . More preferred are a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.
- the perfluoroelastomer may have a cross-linked site, but if the cross-linked site is present, it will gel and lead to molding failure (for example, generation of fish eyes in a molded product). It is preferable that the unit is not included.
- the monomer unit composition of the perfluoroelastomer can be measured by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
- the perfluoroelastomer is a suspension polymerization, a solution polymerization, an arbitrary monomer that becomes a polymerization unit of the perfluoroelastomer, a polymerization initiator, a chain transfer agent, a surfactant, and an aqueous medium. It can be produced by a known polymerization method such as emulsion polymerization. In the above polymerization, the conditions such as temperature and pressure, the polymerization initiator and other additives can be appropriately set according to the composition and amount of the desired perfluoroelastomer.
- a preferable polymerization method includes emulsion polymerization using a surfactant.
- a wide range of emulsifiers can be used for the emulsion polymerization. From the viewpoint of suppressing the chain transfer reaction to the emulsifier molecules occurring during the polymerization, salts of carboxylic acids having a fluorocarbon chain or a fluoropolyether chain. Is desirable.
- the amount of the emulsifier used is preferably about 0.05 to 2% by weight, more preferably 0.2 to 1.5% by weight of the added water.
- the perfluoroelastomer is a perfluoroelastomer aqueous dispersion produced by emulsion polymerization or the like
- the perfluoroelastomer is preferably particulate.
- the perfluoroelastomer particles in the aqueous dispersion preferably have a volume average particle diameter of 0.1 to 700 nm.
- the perfluoroelastomer particles having a volume average particle diameter in the above range can be stably present in the aqueous dispersion.
- the volume average particle diameter of the perfluoroelastomer particles is more preferably 1 nm or more, further preferably 10 nm or more, more preferably 400 nm or less, and further preferably 200 nm or less.
- the volume average particle diameter is measured by a dynamic light scattering method.
- the aqueous dispersion obtained by polymerization was diluted 10-fold with pure water to prepare an aqueous dispersion for particle diameter measurement, and ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) was used at 25 ° C. for a total of 70 times.
- Measure with Solvent The refractive index of water is 1.3328, and the viscosity of the solvent is 0.8878. Let the average value of volume distribution be a volume average particle diameter.
- the perfluoroelastomer particles contained in the aqueous dispersion of perfluoroelastomer may be coagulated to remove the contained water by drying to obtain a perfluoroelastomer powder or crumb.
- the coagulation may be performed by a known method such as adding an inorganic salt such as aluminum sulfate or an inorganic acid, applying a mechanical shearing force, or freezing the dispersion.
- the drying is not particularly limited as long as it can remove moisture without degrading the perfluoroelastomer itself, but a method of usually performing the drying at 50 to 150 ° C. for 5 to 100 hours can be mentioned.
- the drying may be performed under vacuum or with hot air under normal pressure.
- the perfluoroelastomer has a glass transition temperature of preferably ⁇ 70 ° C. or higher, more preferably ⁇ 50 ° C. or higher, and further preferably ⁇ 30 ° C. or higher in view of excellent dispersibility in polyolefin. preferable. Further, it is preferably 5 ° C. or less, more preferably 0 ° C. or less, and further preferably ⁇ 3 ° C. or less from the viewpoint that a desired effect can be obtained even when molding a polyolefin at a low temperature.
- the glass transition temperature is obtained by using a differential scanning calorimeter (Mettler Toledo, DSC822e) to obtain a DSC curve by raising the temperature of 10 mg of the sample at 10 ° C./min. It can be determined as the temperature indicating the midpoint of the two intersections of the extension of the line and the tangent at the inflection point of the DSC curve.
- the perfluoroelastomer preferably has a Mooney viscosity ML 1 + 20 at 170 ° C. of 10 or more, more preferably 40 or more, and even more preferably 50 or more from the viewpoint of good heat resistance. Moreover, it is preferable that it is 150 or less at a point with favorable workability, and it is more preferable that it is 120 or less.
- the Mooney viscosity can be measured according to JIS K6300 at 100 ° C. or 170 ° C. using a Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.
- the content of the perfluoroelastomer is preferably 1 to 100% by weight in the processing aid.
- the polyolefin processing agent of the present invention may contain an anti-sticking agent. By including the anti-adhesive agent, the perfluoroelastomer can be prevented from adhering.
- the anti-sticking agent is preferably an inorganic compound powder.
- a powder of an inorganic compound exemplified by a filler, a colorant, an acid acceptor and the like is preferable.
- the anti-sticking agent for example, those usually used as fillers, colorants, acid acceptors and the like can be used.
- the filler include barium sulfate, calcium carbonate, graphite, talc, and silica.
- the colorant include metal oxides such as titanium oxide, iron oxide, and molybdenum oxide.
- the acid acceptor include magnesium oxide, calcium oxide, lead oxide and the like.
- the anti-sticking agent is preferably the filler. Especially, it is more preferable that the anti-adhesion agent is at least one selected from the group consisting of talc, silica and calcium carbonate.
- the anti-sticking agent is preferably a powder having an average particle size of 0.01 ⁇ m or more and 50 ⁇ m or less.
- the average particle diameter of the powder is more preferably 0.05 ⁇ m or more and 30 ⁇ m or less, and further preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
- the average particle size of the anti-sticking agent is a value measured in accordance with ISO 13320-1.
- the anti-sticking agent may be subjected to a surface treatment with a coupling agent as required.
- the content of the anti-sticking agent is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, and still more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the perfluoroelastomer.
- 1 type may be sufficient as the said sticking
- the processing aid for polyolefins of the present invention may also contain an interfacial agent.
- an interfacial agent is a compound having a lower melt viscosity than the perfluoroelastomer at the molding temperature.
- the interfacial agent is preferably a compound that has a lower melt viscosity than the melt processable resin at the molding temperature and can wet the surface of the perfluoroelastomer.
- the interfacial agent is at least one selected from the group consisting of silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, polyether polyols, amine oxides, carboxylic acids, aliphatic esters, and poly (oxyalkylenes).
- a compound is preferred. Of these, poly (oxyalkylene) is more preferable.
- the poly (oxyalkylene) is preferably polyethylene glycol.
- the number average molecular weight of polyethylene glycol is preferably 50 to 20000, more preferably 1000 to 15000, and still more preferably 2000 to 9500.
- the number average molecular weight of polyethylene glycol is a value obtained by calculation from a hydroxyl value measured in accordance with JIS K0070.
- the aliphatic polyester is preferably polycaprolactone.
- the number average molecular weight of the polycaprolactone is preferably 1000 to 32000, more preferably 2000 to 10,000, and still more preferably 2000 to 4000.
- the content of the interfacial agent is preferably 1 to 99% by weight in the processing aid, more preferably 5 to 90% by weight, still more preferably 10 to 80% by weight, and particularly preferably 20 to 70% by weight.
- the content of the interfacial agent is preferably 50% by weight or more, more preferably more than 50% by weight.
- the processing aid of the present invention preferably contains only a fluoroelastomer when the molding temperature is high (about 280 ° C. or higher), and includes a fluoroelastomer and an interfacial agent when the molding temperature is about 250 ° C. or lower. Those are preferred.
- the processing aid containing the perfluoroelastomer When the processing aid containing the perfluoroelastomer is added to a specific polyolefin described later, the processing aid is dispersed in the specific polyolefin in the form of particles, and the average dispersed particle diameter of the processing aid in the polyolefin Is 10 ⁇ m or less, and the melt fracture can be eliminated in a time equivalent to that of the prior art.
- a polyolefin composition characterized in that it is at least one selected from the group consisting of high-density polyethylene, metallocene-catalyzed linear low-density polyethylene, polypropylene, and polyvinyl chloride is also one aspect of the present invention.
- Polyolefin in the polyolefin composition of the present invention includes low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), metallocene catalyzed linear low density polyethylene (mLLDPE), polypropylene (PP) and It is at least one selected from the group consisting of polyvinyl chloride (PVC).
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- HDPE high density polyethylene
- mLLDPE metallocene catalyzed linear low density polyethylene
- PP polypropylene
- It is at least one selected from the group consisting of polyvinyl chloride (PVC).
- PVC polyvinyl chloride
- polyethylene and polypropylene are more preferable, and polyethylene is more preferable.
- the polyolefin preferably has a melt processing temperature of 100 to 350 ° C.
- the polyolefin may have crystallinity or may not have crystallinity.
- the polyolefin When the polyolefin has crystallinity, it preferably has a melting point of 80 to 300 ° C, more preferably a melting point of 100 to 200 ° C.
- the polyolefin having no crystallinity is preferably one having a processing temperature substantially equal to that of a polyolefin having a crystallinity and a melting point range.
- the melting point of the polyolefin having crystallinity can be measured with a DSC apparatus.
- the polyolefin can be synthesized by a conventionally known method or the like according to each type.
- the polyolefin may be powder, granules, pellets, etc., but in the polyolefin composition of the present invention, the polyolefin can be efficiently melted and the processing aid for polyolefins can be dispersed. It is preferable that
- the polyolefin composition of the present invention is one in which a processing aid for polyolefin is dispersed in the form of fine particles in the polyolefin.
- a processing aid for polyolefin is dispersed in the form of fine particles in the polyolefin.
- the polyolefin composition of the present invention has an average dispersed particle size in the polyolefin of a processing aid for polyolefins of 10 ⁇ m or less.
- a processing aid for polyolefin for polyolefins
- the average dispersed particle size of the polyolefin processing aid is preferably 7 ⁇ m or less, and more preferably 5 ⁇ m or less. More preferably, it is 3 ⁇ m or less.
- the lower limit of the average dispersed particle size is not particularly limited, but may be 0.1 ⁇ m.
- the average dispersed particle size of the processing aid for polyolefin is obtained by observing the polyolefin composition of the present invention with a confocal laser microscope or by forming an ultrathin section from a press sheet or pellet prepared from the polyolefin composition of the present invention. It can be obtained by cutting out, observing the ultrathin section with a transmission electron microscope or a reflection optical microscope, and binarizing the obtained image with an optical analyzer.
- the polyolefin composition of the present invention may be blended with other components, if necessary, together with the polyolefin processing aid and polyolefin.
- the other components include ultraviolet absorbers; flame retardants; reinforcing materials such as glass fibers and glass powders; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; Pigment such as carbon black; Conductive agent such as carbon black; Impact resistance improver such as rubber; Antioxidant such as hindered phenol and phosphorus; Nucleating agent such as metal salt and sorbitol acetal; Additives described in the positive list established as a voluntary standard by the council can be used.
- the content of the processing aid for polyolefin is preferably 0.0005 to 10% by weight based on the total weight of the composition.
- the polyolefin composition of the present invention can be used as a molding material for obtaining a molded product. It can also be prepared and used as a master batch for auxiliaries.
- the content of the processing aid for polyolefin in the polyolefin composition of the present invention is preferably 0.001 to 7% by weight, and preferably 0.0025 to 5% by weight, based on the total weight of the composition. Is more preferable.
- the weight percentage ratio of the perfluoroelastomer to the polyolefin is preferably 1 to 0.00005% by weight. More preferably, it is 0.5 to 0.0001% by weight, and still more preferably 0.2 to 0.005% by weight.
- the masterbatch for processing aids prepared from the polyolefin composition of the present invention can be suitably used as a processing aid for molding a polyolefin.
- the processing aid for polyolefin is evenly dispersed in the polyolefin.
- the processability of polyolefin can be improved, such as a decrease in pressure.
- polystyrene resin As said polyolefin, the thing similar to the above-mentioned polyolefin can be mentioned, Especially, it is preferable that they are polyethylene and a polypropylene, and it is more preferable that it is polyethylene.
- the processing aid masterbatch is not limited in the form of powder, granules, pellets, etc., but the polyolefin processing aid of the present invention is held in a finely dispersed state in the polyolefin.
- a pellet obtained by melt-kneading is preferable.
- the melt kneading temperature is preferably performed at an extrusion temperature higher than the melting point of the perfluoroelastomer.
- the extrusion temperature is preferably higher than the melting point, and more preferably higher than the melting point by 10 ° C. or higher.
- the perfluoroelastomer preferably has a weight% ratio of the perfluoroelastomer to polyolefin of 0.05 to 10% by weight from the viewpoint of easy melt molding. More preferably, it is 1 to 5% by weight.
- the master batch for processing aid may be formed by blending other components with the processing aid for polyolefin and the polyolefin, if necessary. It does not specifically limit as said other component, For example, the thing similar to the other component contained in the composition of this invention mentioned above is mentioned.
- the processing aid masterbatch can be obtained by kneading the perfluoroelastomer and optionally the other components added to the polyolefin described above at a temperature of 100 to 350 ° C.
- a polyolefin processing aid for molding a polyolefin, and a composition containing polyolefin, wherein the polyolefin processing aid includes a perfluoroelastomer, and the polyolefin includes low-density polyethylene is also a preferred embodiment of the present invention. one of.
- the present invention is also a molded article obtained by molding the above-described polyolefin composition of the present invention.
- the polyolefin composition of the present invention may be prepared in advance and charged into a molding machine, and melted, extruded, etc., or the perfluoroelastomer, the polyolefin and other components may be molded as desired. It may be one that is simultaneously charged into a machine and melted, extruded, or the like, or the above processing aid masterbatch and polyolefin are simultaneously charged into a molding machine to be melted and extruded. .
- the molding of the polyolefin composition is not particularly limited, and examples thereof include extrusion molding, injection molding, blow molding, etc. Among them, in order to effectively exhibit the molding processability, extrusion molding is used. preferable.
- the various conditions relating to the molding are not particularly limited, and can be appropriately set according to the composition and amount of the polyolefin composition to be used, the shape and size of the desired molded product, and the like.
- the molding temperature at the time of molding is generally not less than the melting point of the polyolefin in the polyolefin composition of the present invention and less than the lower one of the decomposition temperatures of the perfluoroelastomer and the polyolefin, It is in the range of ⁇ 350 ° C. In the case of extrusion molding, the molding temperature may be referred to as extrusion temperature.
- the polyolefin composition of the present invention can eliminate the melt fracture generated at the start of molding in a short time even when extruded at a high speed, and a processing aid that is a perfluoroelastomer is specified. Since the melt fracture can be eliminated in a time equivalent to that of the prior art by adding a small amount to the polyolefin, the molding can be performed at a high temperature and at a high speed. For example, it is possible to mold at a molding temperature of 280 ° C. or higher, or to mold at a shear rate of 800 to 2500 sec ⁇ 1 .
- a step of obtaining a polyolefin composition by mixing the perfluoroelastomer and the polyolefin and a step of obtaining a molded product by molding the polyolefin composition at 220 ° C. or higher.
- the manufacturing method is also one aspect of the present invention.
- the polyolefin composition is molded at a shear rate of 800 to 2500 sec ⁇ 1 in the step of obtaining the molded product.
- a manufacturing method can be expected to improve productivity because molding is performed at high speed.
- the step of obtaining the polyolefin composition in the above production method it is preferable to obtain a composition by mixing so that the weight percent ratio of the perfluoroelastomer to the polyolefin is 0.0001 to 1 weight percent.
- the molded article of the present invention can be formed into various shapes such as a sheet shape; a film shape; a rod shape; a pipe shape;
- the use of the molded article is not particularly limited and depends on the type of polyolefin to be used.
- the molded article is suitably used for those that are mainly required to have mechanical properties such as mechanical properties and surface properties.
- Examples of the use of the molded product include various films, bags, covering materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded products. .
- composition containing the processing aid for polyolefin of the present invention has the above-described configuration, even when the polyolefin, which is a melt-processable polymer, is extruded at a high speed, the melt fracture generated at the start of molding is reduced for a short time. Can be eliminated.
- FIG. 1 is a graph showing changes in die pressure over time in extrusion of Example 1 and Comparative Examples 2 and 5.
- FIG. 2 is a graph showing changes in die pressure over time in extrusion of Examples 10 to 13 and Comparative Examples 6 to 8.
- FIG. 3 is a graph showing changes in die pressure over time in extrusion of Examples 14 to 16 and Comparative Examples 9 to 11.
- FIG. 4 is a graph showing changes in die pressure with time in extrusion of Examples 14, 17 to 20 and Comparative Examples 9 to 12.
- FIG. 5 is a graph showing changes in die pressure with time in extrusion of Examples 21 to 23 and Comparative Example 13.
- FIG. 6 is a graph showing changes in die pressure with time in extrusion of Examples 24 to 26 and Comparative Example 14.
- FIG. 7 is a graph showing changes in die pressure with time in extrusion of Examples 27 to 29 and Comparative Example 15.
- Mooney viscosity (ML 1 + 20 ) The measurement was performed at 170 ° C. according to JIS K 6300-1.
- melt fracture disappearance time Extrude until the pressure stabilizes with only the polyolefin with melt fracture occurring on the entire surface. When the subsequent screw is visible, materials of each composition such as processing aids are put into the hopper. The time when the melt fracture disappeared and the entire surface of the molded article became smooth was defined as the melt fracture disappearance time. The disappearance of the melt fracture was performed visually and by palpation. Note that, as a result of visual inspection and palpation, the entire surface is not a glossy smooth surface from which melt fracture has disappeared, but is entirely or partially wavy striped, and is referred to as “shark skin” in this specification. .
- the fluorine-containing polymers PFEL1 to PFEL9 used in Examples 1 to 24 are shown in Table 1 using a method substantially similar to the polymerization of Examples in WO01 / 023470 and WO99 / 50319. It is manufactured with the composition shown.
- a mixture of the produced fluorine-containing polymer and an anti-sticking agent so that the fluorine-containing polymer / the anti-sticking agent (weight ratio) was 90/10 was used as a processing aid.
- the anti-sticking agent a premixed mixture of talc, silica and calcium carbonate was used.
- the fluoropolymer PFEL4 + PEG used in Example 25 and the fluoropolymer PFEL7 + PEG used in Example 26 the fluoropolymer / polyethylene glycol (weight ratio) is 1/1 relative to the produced fluoropolymer.
- a mixture of polyethylene glycol number average molecular weight: 8675 was used as a processing aid.
- the fluorine-containing polymer FKM (fluororubber) used in Comparative Examples 2, 6, and 9 was produced with the composition shown in Table 2 using a method substantially the same as the polymerization of Examples in Japanese Patent No. 5140902. It is a thing.
- processing aids were prepared by mixing the produced fluoropolymer with an anti-sticking agent so that the fluoropolymer / anti-sticking agent (weight ratio) was 90/10. Used as. The same anti-sticking agent as in Example 1 was used.
- the FKM + PEG of Comparative Examples 3, 7, and 10 is PEG so that the FKM / PEG (weight ratio) is 1/2 with respect to the fluoropolymer FKM (fluororubber) used in Comparative Examples 2, 6, and 9.
- a mixture of was used as a processing aid.
- the same PEG as in Example 25 was used.
- the fluorine-containing polymer PVDF used in Comparative Example 4 is Neoflon VDF VP-825 manufactured by Daikin Industries, Ltd.
- the fluorine-containing polymer (tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] / vinylidene fluoride [VDF] copolymer) used in Comparative Examples 5, 8, and 11 to 15 is disclosed in Japanese Patent No. 4834971, US Patent. It was manufactured with the composition shown in Table 2 using a method substantially similar to the polymerization of the examples in Japanese Patent No. 6277919B1. In Comparative Examples 5, 8, and 11 to 15, this fluoropolymer was used as a processing aid.
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- VDF vinylidene fluoride copolymer
- the above-mentioned processing aid is mixed with linear low density polyethylene (manufactured by EXXON MOBIL, LLDPE 1002YB) so that the processing aid is 5% by weight with respect to the total weight of the linear low density polyethylene and the processing aid, and further oxidized. 0.1% by weight of the inhibitor was mixed and charged into a twin screw extruder (Toyo Seiki Seisakusho Co., Ltd., Laboplast Mill 30C150 Screw L / D25), and pellets containing processing aids at a screw speed of 80 rpm. Obtained.
- linear low density polyethylene manufactured by EXXON MOBIL, LLDPE 1002YB
- the pellets containing the obtained processing aid are mixed by tumbling, and the above pellets are obtained except that the screw speed is 100 rpm.
- a master batch containing a processing aid and a processing aid and a polyolefin was obtained.
- the temperature conditions in extrusion are as follows. Conditions: cylinder temperature 150, 170, 180, die temperature 180 ° C An ultrathin section was cut out from the obtained pellet, observed with a microscope using a reflection optical microscope, and the obtained image was binarized with an optical analyzer. As a result, it was confirmed that the processing aid was dispersed finely in the linear low density polyethylene in the obtained pellet. And as a result of calculating
- Example 1 A master batch containing a processing aid (PFEL 1 to 9+ anti-sticking agent) formed in a linear low density polyethylene (manufactured by EXXON MOBIL, LLDPE 1201XV) with the above twin screw extruder is combined with a linear low density polyethylene and a master batch.
- the master batch is added so as to be 1% by weight with respect to the total weight, mixed by tumbling, and added to a single screw extruder (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm).
- extrusion was performed at a cylinder temperature of 180 to 200 ° C., a die temperature of 200 ° C., and a screw rotation speed of 30 rpm, and a change in the die pressure was observed for 60 minutes. Thereafter, the change in the die pressure was observed for 10 minutes by changing to a screw rotation speed of 10 rpm, 15 minutes by changing to 80 rpm, and further changing to 5 rpm for 120 minutes.
- Tables 1 and 2 show the compositions of the fluoropolymers used in Examples and Comparative Examples.
- Table 3 shows the extrusion evaluation results in Examples 1 to 9 and Comparative Examples 1 to 5. Furthermore, the time-dependent change of the die pressure in extrusion of Example 1 and Comparative Examples 2 and 5 is shown in FIG.
- Table 4 shows the shear rate calculated from the following mathematical formula.
- Example 10 The master batch containing the processing aid used in Example 1 was added to the linear low density polyethylene (manufactured by EXXON MOBIL, LLDPE 1201XV), and the master batch was 1 with respect to the total weight of the linear low density polyethylene and the master batch. It added so that it might become weight%, and it mixed by the tumbling.
- the linear low density polyethylene manufactured by EXXON MOBIL, LLDPE 1201XV
- the obtained master batch-containing linear low density polyethylene was uniaxially extruded (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm), cylinder temperature 170 to 200 ° C., die temperature 200 ° C., screw Extrusion was performed at a rotational speed of 80 rpm, and changes in the die pressure and melt fracture were observed.
- Example 11 The master batches containing processing aids used in Example 1 were added so as to be 0.05, 0.02, and 0.01% by weight based on the total weight of the linear low density polyethylene and the master batch, respectively. Except for the above, extrusion evaluation was performed in the same manner as in Example 10.
- Table 5 shows the evaluation results of Examples 10 to 13 and Comparative Examples 6 to 8.
- FIG. 2 shows the change over time in the die pressure in the extrusion of Examples 10 to 13 and Comparative Examples 6 to 8.
- processing aid additive concentration is the ratio of processing aid to the total weight of the linear low density polyethylene and the master batch.
- Example 10 the pressure dropped by 3.1 MPa within 10 minutes after the start of adding the master batch, and the melt fracture disappeared completely.
- the amount of pressure drop decreased as the processing aid addition concentration decreased, but the melt fracture completely disappeared within 70 minutes after the addition even at the addition concentration of 5 ppm.
- Comparative Example 6 the extrusion pressure was increased by 0.5 MPa.
- Comparative Example 7 stable extrusion could not be performed.
- Comparative Example 8 the pressure was reduced by 1.6 MPa. In Comparative Examples 6 to 8, the melt fracture did not disappear even after 70 minutes from the start of the addition of the master batch.
- Extrusion evaluation 3 (Examples 14, 15, and 16) Extrusion evaluation was performed in the same manner as Extrusion Evaluation 2 except that the master batch containing the processing aid used in Examples 1, 4, and 5 was used, the cylinder temperature was 210 to 240 ° C., and the die temperature was 240 ° C. The shear rate calculated from the mathematical formula 1 was about 1,200 sec ⁇ 1 .
- Table 6 shows the evaluation results and the like in Examples 14 to 16 and Comparative Examples 9 to 11. Further, FIG. 3 shows changes with time of the die pressure in the extrusion of Examples 14 to 16 and Comparative Examples 9 to 11.
- Example 17 to 20 The master batches containing processing aids used in Example 14 are 0.2, 0.1, 0.05, and 0.02% by weight based on the total weight of the linear low density polyethylene and the master batch, respectively. Extrusion evaluation was performed in the same manner as in Example 15 except that the addition was performed as described above. (Comparative Example 12) Extrusion was carried out in the same manner as in Comparative Example 11 except that the master batch containing the processing aid used in Comparative Example 11 was added to 0.2% by weight based on the total weight of the linear low density polyethylene and the master batch. Evaluation was performed.
- Table 7 shows the evaluation results and the like in Examples 14 and 17 to 20 and Comparative Examples 9 to 12.
- FIG. 4 shows changes in die pressure over time in extrusion of Examples 14, 17 to 20 and Comparative Examples 9 to 12.
- Example 21 Extrusion evaluation was carried out in the same manner as Extrusion Evaluation 2 except that the master batch containing the processing aid used in Example 4 was used, the cylinder temperature was 250 to 280 ° C., and the die temperature was 280 ° C. The shear rate calculated from the mathematical formula 1 was about 1,190 sec ⁇ 1 .
- Example 22 Example except that the masterbatch containing the processing aid used in Example 21 was added to 0.2% and 0.1% by weight with respect to the total weight of the linear low density polyethylene and the masterbatch, respectively. Extrusion evaluation was performed in the same manner as in No. 21.
- Table 8 shows the evaluation results in Examples 21 to 23 and Comparative Example 13.
- FIG. 5 shows the change over time in the die pressure in the extrusion of Examples 21 to 23 and Comparative Example 13.
- the obtained master batch-containing linear low density polyethylene was uniaxially extruded (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm), cylinder temperature 190 to 220 ° C, die temperature 220 ° C, screw Extrusion was performed at a rotational speed of 70 rpm, and changes in the die pressure and melt fracture were observed.
- the shear rate calculated from the mathematical formula 1 was about 2,500 sec ⁇ 1 .
- Table 9 shows the evaluation results in Examples 24 to 26 and Comparative Example 14.
- FIG. 6 shows changes in the die pressure over time in the extrusion of Examples 24 to 26 and Comparative Example 14.
- Example 6 ⁇ Evaluation 2 at ultra-high shear rate> (Examples 27 to 29)
- the master batch containing the processing aids used in Example 4 was divided into the master batch with respect to the total weight of the linear low density polyethylene and the master batch. It added so that it might become 1, 0.1 and 0.05 weight%, and it mixed by the tumbling.
- the obtained masterbatch-containing linear low density polyethylene was uniaxially extruded (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm), cylinder temperature 210-240 ° C, die temperature 240 ° C, screw Extrusion was performed at a rotational speed of 70 rpm, and changes in the die pressure and melt fracture were observed.
- the shear rate calculated from the mathematical formula 1 was about 2,400 sec ⁇ 1 .
- Table 10 shows the evaluation results in Examples 27 to 29 and Comparative Example 15.
- FIG. 7 shows changes with time of the die pressure in extrusion in Examples 27 to 29 and Comparative Example 15.
- polyolefin processing aid and polyolefin composition of the present invention have the above-described configuration, for example, various films, bags, covering materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline It can be used in a wide range of fields such as tanks and other industrial molded products.
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Abstract
Description
これらの不具合を改善し、メルトフラクチャーを発生させずに、より速い押出速度を達成して、押出し特性を向上させる方法として、成形温度をより高温にして成形する方法がある。しかしながら、高温成形することにより、溶融加工性ポリマーの熱分解により成形品の機械特性低下、成形品の着色などの問題がある上に、溶融加工性ポリマーの溶融粘度が低下することにより冷却固化する前に垂れや変形が発生し、成形品の寸法精度が損なわれる問題もある。
更に、そのようなポリオレフィン用加工助剤と特定のポリオレフィンとを含むポリオレフィン組成物を提供する。
このように、パーフルオロエラストマーを含むポリオレフィン用加工助剤と特定のポリオレフィンとを含むものとすることによって、上記課題を見事に解決することができることに想到し、本発明に到達した。
上記パーフルオロエラストマーは、テトラフルオロエチレンと、へキサフルオロプロピレン、一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマー、
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)で表されるフルオロモノマー、及び、
一般式(11):CF2=CFO(CF2CF(Y)O)m(CF2)nF
(式中、Yはフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)で表されるフルオロモノマーからなる群より選択される少なくとも1種のフルオロモノマーとの共重合体であることが好ましい。
上記パーフルオロエラストマーは、テトラフルオロエチレンと
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマーとの共重合体であることが好ましい。
上記パーフルオロエラストマーは、テトラフルオロエチレンとパーフルオロ(メチルビニルエーテル)との共重合体であることが好ましい。
本発明のポリオレフィン用加工助剤は、更に、シリコーン-ポリエーテルコポリマー、脂肪族ポリエステル、芳香族ポリエステル、ポリエーテルポリオール、アミンオキシド、カルボン酸、脂肪族エステル及びポリ(オキシアルキレン)からなる群より選択される少なくとも1種の界面剤を1~99重量%含むことが好ましい。
上記パーフルオロエラストマーは、テトラフルオロエチレンと、へキサフルオロプロピレン、
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマー、
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)で表されるフルオロモノマー、及び、
一般式(11):CF2=CFO(CF2CF(Y)O)m(CF2)nF
(式中、Yはフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)で表されるフルオロモノマーからなる群より選択される少なくとも1種のフルオロモノマーとの共重合体であることが好ましい。
上記パーフルオロエラストマーは、テトラフルオロエチレンと
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマーとの共重合体であることが好ましい。
上記パーフルオロエラストマーは、テトラフルオロエチレンとパーフルオロ(メチルビニルエーテル)との共重合体であることが好ましい。
上記ポリオレフィン用加工助剤は、更に、シリコーン-ポリエーテルコポリマー、脂肪族ポリエステル、芳香族ポリエステル、ポリエーテルポリオール、アミンオキシド、カルボン酸、脂肪族エステル及びポリ(オキシアルキレン)からなる群より選択される少なくとも1種の界面剤を1~99重量%含むことが好ましい。
上記ポリオレフィン用加工助剤の含有量は、組成物の全重量に対して0.0005~10重量%であることが好ましい。
以下に本発明を詳細に説明する。
このため、本発明のポリオレフィン用加工助剤を特定のポリオレフィンに添加したポリオレフィン組成物を高剪断速度で押出成形した場合であっても、成形開始時に発生するメルトフラクチャーを短時間で消失させることができる。
テトラフルオロエチレン〔TFE〕、
へキサフルオロプロピレン〔HFP〕、
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマー、
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)で表されるフルオロモノマー、及び、
一般式(11):CF2=CFO(CF2CF(Y)O)m(CF2)nF
(式中、Yはフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)で表されるフルオロモノマー
からなる群より選択される少なくとも1種であることが好ましい。
一般式(12):CX3 2=CX3-Rf 121CHR121X4
(式中、X3は、水素原子、フッ素原子又はCH3、Rf 121は、フルオロアルキレン基、パーフルオロアルキレン基、フルオロ(ポリ)オキシアルキレン基又はパーフルオロ(ポリ)オキシアルキレン基、R121は、水素原子又はCH3、X4は、ヨウ素原子又は臭素原子である)で表されるフルオロモノマー、
一般式(13):CX3 2=CX3-Rf 131X4
(式中、X3は、水素原子、フッ素原子又はCH3、Rf 131は、フルオロアルキレン基、パーフルオロアルキレン基、フルオロポリオキシアルキレン基又はパーフルオロポリオキシアルキレン基、X4は、ヨウ素原子又は臭素原子である)で表されるフルオロモノマー、
一般式(14):CF2=CFO(CF2CF(CF3)O)m(CF2)n-X5
(式中、mは0~5の整数、nは1~3の整数、X5は、シアノ基、カルボキシル基、アルコキシカルボニル基、ヨウ素原子、臭素原子、又は、-CH2Iである)で表されるフルオロモノマー、及び、
一般式(15):CH2=CFCF2O(CF(CF3)CF2O)m(CF(CF3))n-X6
(式中、mは0~5の整数、nは1~3の整数、X6は、シアノ基、カルボキシル基、アルコキシカルボニル基、ヨウ素原子、臭素原子、又は-CH2OHである)で表されるフルオロモノマー、及び、
一般式(16):CR162R163=CR164-Z-CR165=CR166R167
(式中、R162、R163、R164、R165、R166及びR167、は、同一又は異なって、水素原子又は炭素数1~5のアルキル基である。Zは、直鎖又は分岐状で酸素原子を有していてもよい、炭素数1~18のアルキレン基、炭素数3~18のシクロアルキレン基、少なくとも部分的にフッ素化している炭素数1~10のアルキレン基若しくはオキシアルキレン基、又は、
-(Q)p-CF2O-(CF2CF2O)m(CF2O)n-CF2-(Q)p-
(式中、Qはアルキレン基またはオキシアルキレン基である。pは0または1である。m/nが0.2~5である。)で表され、分子量が500~10000である(パー)フルオロポリオキシアルキレン基である。)で表されるモノマー
からなる群より選択される少なくとも1種であることが好ましい。
テトラフルオロエチレン〔TFE〕と、
へキサフルオロプロピレン〔HFP〕、
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマー、
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)で表されるフルオロモノマー、及び、
一般式(11):CF2=CFO(CF2CF(Y)O)m(CF2)nF
(式中、Yはフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)で表されるフルオロモノマーからなる群より選択される少なくとも1種のフルオロモノマーとの共重合体であることが好ましい。
これらの組成の範囲を外れると、ゴム弾性体としての性質が失われ、樹脂に近い性質となる傾向がある。
また、上記パーフルオロエラストマーは、2種以上を含むものであってもよいが、TFE/一般式(8)で表されるフルオロモノマー共重合体のみ含むことが好ましく、さらに、TFE/パーフルオロ(メチルビニルエーテル)との共重合体であることが好ましい。
なお、重合時に用いる重合開始剤又は上記官能基を側鎖に有する単量体を適宜選択することにより、上記官能基をパーフルオロエラストマーに導入することができる。
上記重合において、温度、圧力等の各条件、重合開始剤やその他の添加剤は、所望のパーフルオロエラストマーの組成や量に応じて適宜設定することができる。
上記水性分散液中のパーフルオロエラストマー粒子は、体積平均粒子径が0.1~700nmであることが好ましい。体積平均粒子径が上記範囲にあるパーフルオロエラストマーの粒子は、水性分散体中に安定して存在することができる。
パーフルオロエラストマー粒子の体積平均粒子径は、1nm以上であることがより好ましく、10nm以上であることが更に好ましく、400nm以下であることがより好ましく、200nm以下であることが更に好ましい。
上記凝析は、硫酸アルミニウム等の無機塩又は無機酸を添加したり、機械的な剪断力を与えたり、分散液を凍結させる等の公知の方法で行うとよい。
上記乾燥は、パーフルオロエラストマー自体を劣化させることなく水分を除去できる方法であれば、特に限定されないが、通常50℃~150℃で5~100時間かけて行う方法が挙げられる。上記乾燥は、真空下で行ってもよいし、常圧下で熱風で行ってもよい。
固着防止剤を含むことにより、パーフルオロエラストマーの固着を抑制することができる。
上記固着防止剤としては、例えば、充填剤、着色剤、受酸剤等として通常用いられているものを用いることができる。
上記充填剤としては、硫酸バリウム、炭酸カルシウム、グラファイト、タルク、シリカ等が挙げられる。
上記着色剤としては、酸化チタン、酸化鉄、酸化モリブデン等の金属酸化物が挙げられる。
上記受酸剤としては、酸化マグネシウム、酸化カルシウム、酸化鉛等が挙げられる。
上記固着防止剤は、必要に応じてカップリング剤などで表面処理を施されたものであってもよい。
上記固着防止剤は、1種であってもよいし、2種以上であってもよい。
上記パーフルオロエラストマーと界面剤を併用することにより、パーフルオロエラストマーの加工助剤としての性能を更に向上させることができる。
上記界面剤は、成形温度において上記パーフルオロエラストマーより低い溶融粘度を有する化合物である。上記界面剤は、後述するポリオレフィン組成物中に含まれる場合、成形温度において溶融加工性樹脂よりも低い溶融粘度を有し、パーフルオロエラストマーの表面を濡らすことができる化合物であることが好ましい。
ポリエチレングリコールの数平均分子量は、JIS K0070に準拠して測定される水酸基価より計算して求めた値である。
そのような、上述のポリオレフィン用加工助剤、及び、ポリオレフィンを含む組成物であって、上記ポリオレフィン用加工助剤は、パーフルオロエラストマーを含み、上記ポリオレフィンは、低密度ポリエチレン、線状低密度ポリエチレン、高密度ポリエチレン、メタロセン触媒型線状低密度ポリエチレン、ポリプロピレン及びポリ塩化ビニルからなる群より選択される少なくとも1種であることを特徴とするポリオレフィン組成物もまた、本発明の一つである。
上記ポリオレフィンとしては、なかでも、ポリエチレン、ポリプロピレンがより好ましく、ポリエチレンが更に好ましい。
結晶性を有するポリオレフィンの融点は、DSC装置により測定することができる。
上記ポリオレフィンは、粉末、顆粒、ペレット等であってよいが、本発明のポリオレフィン組成物においては、上記ポリオレフィンを効率的に溶融させ、上記ポリオレフィン用加工助剤を分散させることができる点で、ペレットであることが好ましい。
ポリオレフィン用加工助剤の平均分散粒子径としては、7μm以下であることが好ましく、より好ましくは5μm以下である。更に好ましくは3μm以下である。
平均分散粒子径の下限は特に限定されないが0.1μmであってよい。
上記その他の成分としては、例えば、紫外線吸収剤;難燃剤;ガラス繊維、ガラス粉末等の補強材;ミネラル、フレーク等の安定剤;シリコーンオイル、二硫化モリブデン等の潤滑剤;二酸化チタン、弁柄等の顔料;カーボンブラック等の導電剤;ゴム等の耐衝撃性向上剤;ヒンダートフェノール系、リン系等の酸化防止剤;金属塩、ソルビトールのアセタール等の造核剤;その他のポリオレフィン等衛生協議会で自主基準として制定されているポジティブリストに記載の添加剤等を用いることができる。
上記その他の成分としては特に限定されず、例えば、上述した本発明の組成物に含まれるその他の成分と同様のものが挙げられる。
上記成形は、本発明のポリオレフィン組成物を予め調製して成形機に投入し、溶融、押出等を行うものであってもよいし、上記パーフルオロエラストマー、上記ポリオレフィンおよび所望によりその他の成分を成形機に同時に投入し、溶融、押出等を行うものであってもよいし、上記加工助剤用マスターバッチとポリオレフィンとを成形機に同時に投入し、溶融、押出等を行うものであってもよい。
上記成形の際の成形温度としては、一般に、本発明のポリオレフィン組成物におけるポリオレフィンの融点以上、且つ、上記パーフルオロエラストマー及び上記ポリオレフィンの各分解温度のうち低い方の温度未満の温度で行い、100~350℃の範囲である。
上記成形温度は、押出成形の場合、押出温度ということがある。
上記成形品の用途としては特に限定されず、用いるポリオレフィンの種類によるが、例えば、機械的性質をはじめとする力学的性質や表面性を主として強く要求されるもの等に好適に用いられる。
1.共重合組成
19F-NMR(Bruker社製、AC300P型)を用いて測定した。
ASTM D 3159に準拠して測定した。
PVDFのMFR測定 240℃ 49N
TFE/HFP/VdFのMFR測定 265℃ 49N
JIS K 6300-1に準拠して、170℃で測定した。
DSC装置(セイコー社製)を用い、10℃/分の速度で昇温したときの融解熱曲線における極大値に対応する温度を融点とした。
ポリオレフィンのみで、全面にメルトフラクチャーが発生している状態で圧力が安定するまで押出を行い、その後のスクリューが見えた時点で加工助剤等の各組成の材料をホッパーに投入してその時点を0とし、メルトフラクチャーが消え成形品の全面が平滑になった時間をメルトフラクチャー消失時間とした。メルトフラクチャーの消失は目視および触診により行った。
なお、目視および触診の結果、表面全体がメルトフラクチャーの消失した光沢のある平滑面ではなく、全体あるいは部分的に波打った縞状である状態を、本明細書中、「サメ肌」と呼ぶ。
後述する押出評価では、押出圧力が初期の加工助剤の入っていない線状低密度ポリエチレンだけの圧力(初期圧力)から、加工助剤の効果が発揮されて低下し、その後、ほぼ一定の圧力で安定する(安定圧力)。上記初期圧力と安定圧力の差を降下圧力量とした。また、上記安定圧力に到達するまでの時間を安定圧力到達時間とした。
実施例1~24で用いた含フッ素ポリマーPFEL1~PFEL9は、国際公開第01/023470号及び国際公開第99/50319号における実施例の重合と実質的に同様の方法を用いて、表1に示す組成にて製造されたものである。実施例においては、この製造された含フッ素ポリマーに、固着防止剤を、含フッ素ポリマー/固着防止剤(重量比)が90/10となるように混合したものを加工助剤として用いた。
固着防止剤は、タルク、シリカ、炭酸カルシウムを予め混合したものを用いた。
実施例25で用いた含フッ素ポリマーPFEL4+PEG、実施例26で用いた含フッ素ポリマーPFEL7+PEGは、それぞれ製造された含フッ素ポリマーに対して、含フッ素ポリマー/ポリエチレングリコール(重量比)が1/1となるように、ポリエチレングリコール(数平均分子量:8675)を混合したものを加工助剤として用いた。
比較例2、6、9で用いた含フッ素ポリマーFKM(フッ素ゴム)は、特許第5140902号公報における実施例の重合と実質的に同様の方法を用いて、表2に示す組成にて製造されたものである。比較例2、6、9においては、この製造された含フッ素ポリマーに、固着防止剤を、含フッ素ポリマー/固着防止剤(重量比)が90/10となるように混合したものを加工助剤として用いた。固着防止剤は、実施例1と同様のものを用いた。
比較例3、7、10のFKM+PEGは、比較例2、6、9で用いた含フッ素ポリマーFKM(フッ素ゴム)に対して、FKM/PEG(重量比)が1/2となるように、PEGを混合したものを加工助剤として用いた。PEGは、実施例25と同様のものを用いた。
比較例4で用いた含フッ素ポリマーPVDFは、ダイキン工業株式会社製ネオフロンVDF VP-825である。
比較例5、8、11~15で用いた含フッ素ポリマー(テトラフルオロエチレン[TFE]/ヘキサフルオロプロピレン[HFP]/ビニリデンフルオライド[VDF]共重合体)は、特許第4834971号公報、米国特許第6277919B1号公報における実施例の重合と実質的に同様の方法を用いて、表2に示す組成にて製造されたものである。比較例5、8、11~15においては、この含フッ素ポリマーを加工助剤として用いた。
線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1002YB)に、線状低密度ポリエチレンと加工助剤との合計重量に対して、上記加工助剤が5重量%となるように混合し、さらに酸化防止剤を0.1重量%混合し、二軸押出機(株式会社東洋精機製作所製、ラボプラストミル30C150 スクリューのL/D25)に投入し、スクリュー回転数80rpmで加工助剤を含有するペレットを得た。マスターバッチ中の加工助剤の分散均一性を向上させるために、得られた加工助剤を含有するペレットをタンブリングにて混合し、スクリュー回転数を100rpmにしたこと以外は、上記ペレットを得るときと同条件で、加工助剤とポリオレフィンとからなる加工助剤入りマスターバッチを得た。
押出における温度条件は以下の通りである。
条件:シリンダー温度150、170、180、ダイ温度180℃
得られたペレットから超薄切片を切り出し、反射型光学顕微鏡にて顕微鏡観察を行い、得られた画像を光学解析装置にて二値化処理した。その結果、得られたペレットにおいて加工助剤は線状低密度ポリエチレン中に微粒子状に分散していることが確認された。そして、二値化処理画像からその平均分散粒子径を求めた結果、得られたペレットはいずれも5μm以下であった。
(実施例1~9)
線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1201XV)に、上記二軸押出機にて成形した加工助剤(PFEL1~9+固着防止剤)入りマスターバッチを、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、上記マスターバッチが1重量%になるように添加し、タンブリングにて混合し、一軸押出機(HAAKE社製、Rheomex OS、L/D:33、スクリュー径:20mm)にて、シリンダー温度180~200℃、ダイ温度200℃、スクリュー回転数30rpmにて押出を行い60分間ダイ圧力の変化を観察した。その後、スクリュー回転数10rpmに変更して10分間、80rpmに変更して15分間、さらに5rpmに変更して120分間それぞれダイ圧力の変化を観察した。
上記線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1201XV)のみを一軸押出機にて押出を行った以外は、実施例1~9と同様にして押出評価を行った。
上記線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1201XV)に、上記二軸押出機にて成形した加工助剤(表3記載)入りマスターバッチを、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、上記マスターバッチが1重量%になるように添加し、タンブリングにて混合した以外は、比較例1と同様にして押出評価を行った。
TFE:テトラフルオロエチレン
PMVE:CF2=CFOCF3
CNVE:CF2=CFOCF2CF(CF3)OCF2CF2CN
VDF:ビニリデンフルオライド
HFP:ヘキサフルオロプロピレン
固:固着防止剤
γ:剪断速度(sec-1)
Q:押出量(kg/hr)
R:ダイの直径(mm)
(実施例10)
線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1201XV)に、実施例1で用いた加工助剤入りマスターバッチを、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、マスターバッチが1重量%になるように添加し、タンブリングにて混合した。得られたマスターバッチ入り線状低密度ポリエチレンを一軸押出機(HAAKE社製、Rheomex OS、L/D:33、スクリュー径:20mm)にて、シリンダー温度170~200℃、ダイ温度200℃、スクリュー回転数80rpmにて押出を行い、ダイ圧力とメルトフラクチャーの変化を観察した。
実施例1で用いた加工助剤入りマスターバッチをそれぞれ、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、0.05、0.02、0.01重量%になるように添加した以外は実施例10と同様にして押出評価を行った。
比較例2、3、5で用いた加工助剤入りマスターバッチを用いた以外は、実施例10と同様にして押出評価を行った。
(実施例14、15、16)
実施例1、4、5で用いた加工助剤入りマスターバッチを用い、シリンダー温度を210~240℃、ダイ温度を240℃とした以外は押出評価2と同様にして押出評価を行った。数1の数式より算出される剪断速度は、約1,200sec-1であった。
比較例2、3、5で用いた加工助剤入りマスターバッチを用いた以外は、実施例14~16と同様にして押出評価を行った。
実施例14で用いた加工助剤入りマスターバッチをそれぞれ、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、0.2、0.1、0.05、0.02重量%になるように添加した以外は実施例15と同様にして押出評価を行った。
(比較例12)
比較例11で用いた加工助剤入りマスターバッチを線状低密度ポリエチレンとマスターバッチとの合計重量に対して、0.2重量%になるように添加した以外は比較例11と同様にして押出評価を行った。
(実施例21)
実施例4で用いた加工助剤入りマスターバッチを用い、シリンダー温度を250~280℃、ダイ温度を280℃とした以外は押出評価2と同様にして押出評価を行った。数1の数式より算出される剪断速度は、約1,190sec-1であった。
実施例21で用いた加工助剤入りマスターバッチをそれぞれ、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、0.2、0.1重量%になるように添加した以外は実施例21と同様にして押出評価を行った。
比較例5で用いた加工助剤入りマスターバッチを用いた以外は、実施例21と同様にして押出評価を行った。
(実施例24~26)
線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1201XV)に、PFEL7+固着防止剤、PFEL4+PEG、PFEL7+PEGをそれぞれ加工助剤に用いたマスターバッチを、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、マスターバッチが1重量%になるように添加し、タンブリングにて混合した。得られたマスターバッチ入り線状低密度ポリエチレンを一軸押出機(HAAKE社製、Rheomex OS、L/D:33、スクリュー径:20mm)にて、シリンダー温度190~220℃、ダイ温度220℃、スクリュー回転数70rpmにて押出を行い、ダイ圧力とメルトフラクチャーの変化を観察した。数1の数式より算出される剪断速度は、約2,500sec-1であった。
比較例5で用いた加工助剤入りマスターバッチを用いた以外は、実施例24と同様にして押出評価を行った。
(実施例27~29)
線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1201XV)に、実施例4で用いた加工助剤入りマスターバッチを、線状低密度ポリエチレンとマスターバッチとの合計重量に対して、マスターバッチがそれぞれ1、0.1、0.05重量%になるように添加し、タンブリングにて混合した。得られたマスターバッチ入り線状低密度ポリエチレンを一軸押出機(HAAKE社製、Rheomex OS、L/D:33、スクリュー径:20mm)にて、シリンダー温度210~240℃、ダイ温度240℃、スクリュー回転数70rpmにて押出を行い、ダイ圧力とメルトフラクチャーの変化を観察した。数1の数式より算出される剪断速度は、約2,400sec-1であった。
比較例5で用いた加工助剤入りマスターバッチを用いた以外は、実施例27と同様にして押出評価を行った。
Claims (11)
- パーフルオロエラストマーを含むことを特徴とする、低密度ポリエチレン、線状低密度ポリエチレン、高密度ポリエチレン、メタロセン触媒型線状低密度ポリエチレン、ポリプロピレン及びポリ塩化ビニルからなる群より選択される少なくとも1種のポリオレフィンを押出成形するために用いるポリオレフィン用加工助剤。
- パーフルオロエラストマーは、
テトラフルオロエチレンと、
へキサフルオロプロピレン、
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマー、
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)で表されるフルオロモノマー、及び、
一般式(11):CF2=CFO(CF2CF(Y)O)m(CF2)nF
(式中、Yはフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)で表されるフルオロモノマー
からなる群より選択される少なくとも1種のフルオロモノマーとの共重合体である請求項1記載のポリオレフィン用加工助剤。 - パーフルオロエラストマーは、
テトラフルオロエチレンと
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマーとの共重合体である請求項1又は2記載のポリオレフィン用加工助剤。 - パーフルオロエラストマーは、テトラフルオロエチレンとパーフルオロ(メチルビニルエーテル)との共重合体である請求項1、2又は3記載のポリオレフィン用加工助剤。
- 更に、シリコーン-ポリエーテルコポリマー、脂肪族ポリエステル、芳香族ポリエステル、ポリエーテルポリオール、アミンオキシド、カルボン酸、脂肪族エステル及びポリ(オキシアルキレン)からなる群より選択される少なくとも1種の界面剤を1~99重量%含む請求項1、2、3又は4記載のポリオレフィン用加工助剤。
- ポリオレフィン用加工助剤、及び、ポリオレフィンを含む組成物であって、
前記ポリオレフィン用加工助剤は、パーフルオロエラストマーを含み、
前記ポリオレフィンは、低密度ポリエチレン、線状低密度ポリエチレン、高密度ポリエチレン、メタロセン触媒型線状低密度ポリエチレン、ポリプロピレン及びポリ塩化ビニルからなる群より選択される少なくとも1種である
ことを特徴とするポリオレフィン組成物。 - パーフルオロエラストマーは、
テトラフルオロエチレンと、
へキサフルオロプロピレン、
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマー、
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)で表されるフルオロモノマー、及び、
一般式(11):CF2=CFO(CF2CF(Y)O)m(CF2)nF
(式中、Yはフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)で表されるフルオロモノマー
からなる群より選択される少なくとも1種のフルオロモノマーとの共重合体である請求項6記載のポリオレフィン組成物。 - パーフルオロエラストマーは、
テトラフルオロエチレンと
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマーとの共重合体である請求項6又は7記載のポリオレフィン組成物。 - パーフルオロエラストマーは、テトラフルオロエチレンとパーフルオロ(メチルビニルエーテル)との共重合体である請求項6、7又は8記載のポリオレフィン組成物。
- ポリオレフィン用加工助剤は、更に、シリコーン-ポリエーテルコポリマー、脂肪族ポリエステル、芳香族ポリエステル、ポリエーテルポリオール、アミンオキシド、カルボン酸、脂肪族エステル及びポリ(オキシアルキレン)からなる群より選択される少なくとも1種の界面剤を1~99重量%含む請求項6、7、8又は9記載のポリオレフィン組成物。
- ポリオレフィン用加工助剤の含有量が、組成物の全重量に対して0.0005~10重量%である請求項6、7、8、9又は10記載のポリオレフィン組成物。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108430732A (zh) * | 2015-12-02 | 2018-08-21 | 阿科玛法国公司 | 用于聚烯烃的挤出剂 |
WO2018199034A1 (ja) * | 2017-04-28 | 2018-11-01 | Agc株式会社 | ポリテトラフルオロエチレン水性分散液 |
WO2019130975A1 (ja) * | 2017-12-26 | 2019-07-04 | ダイキン アメリカ インコーポレイティッド | 電線、電線の製造方法及びマスターバッチ |
CN114573929A (zh) * | 2022-03-15 | 2022-06-03 | 湖南省希润弗高分子新材料有限公司 | 一种聚烯烃用助剂组合物 |
Families Citing this family (2)
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WO2018005817A1 (en) * | 2016-07-01 | 2018-01-04 | Daikin America, Inc. | Thermoplastic and fluoropolymer blend and extruded products |
CN116217781A (zh) * | 2023-04-26 | 2023-06-06 | 山东惠畅新材料有限公司 | 一种含氟聚合物加工助剂ppa及其制备方法 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6157324B2 (ja) | 1981-10-22 | 1986-12-06 | Daikin Kogyo Co Ltd | |
JPH0270737A (ja) | 1988-04-15 | 1990-03-09 | Minnesota Mining & Mfg Co <3M> | 押出可能な熱可塑性炭化水素ポリマー組成物 |
US5013792A (en) | 1990-01-04 | 1991-05-07 | E. I. Du Pont De Nemours And Company | Processing aid for polymers |
JPH0481608B2 (ja) | 1983-06-23 | 1992-12-24 | Ii Ai Deyuhon De Nimoasu Ando Co | |
JPH0513961B2 (ja) | 1985-03-28 | 1993-02-23 | Daikin Ind Ltd | |
WO1997024381A1 (fr) | 1995-12-28 | 1997-07-10 | Daikin Industries, Ltd. | Copolymeres elastiques contenant du fluor, composition durcissable les contenant et materiau d'etancheite prepare a l'aide de ces copolymeres |
WO1999050319A1 (fr) | 1998-03-25 | 1999-10-07 | Daikin Industries, Ltd. | Procede de reduction de la teneur en metal d'un fluoroelastomere |
WO2001023470A1 (fr) | 1999-09-30 | 2001-04-05 | Daikin Industries, Ltd. | Composition elastomere transparente |
US6277919B1 (en) | 1999-05-13 | 2001-08-21 | Dyneon Llc | Polymer processing additive containing a multimodal fluoropolymer and melt processable thermoplastic polymer composition employing the same |
WO2003044088A1 (fr) | 2001-11-21 | 2003-05-30 | Daikin Industries, Ltd. | Composition a base de resine plastique d'ingenierie decomposable a basse temperature et procede de production d'un objet moule a partir de cette composition |
JP2005508429A (ja) * | 2001-11-08 | 2005-03-31 | デュポン ダウ エラストマーズ エルエルシー | 溶融加工性ポリマー用の加工助剤 |
JP2007510003A (ja) | 2003-08-20 | 2007-04-19 | デュポン パフォーマンス エラストマーズ エルエルシー | メタロセン触媒型線状低密度ポリエチレンポリマーのための加工助剤 |
WO2011025052A1 (en) | 2009-08-27 | 2011-03-03 | Daikin Industries, Ltd. | Processing additive, molding composition, masterbatch of processing additive and molding article |
JP4834971B2 (ja) | 2004-04-07 | 2011-12-14 | ダイキン工業株式会社 | 含フッ素エラストマー重合体の製造方法 |
JP5140902B2 (ja) | 1999-11-09 | 2013-02-13 | ダイキン工業株式会社 | 加硫可能な含フッ素エラストマー組成物 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009155357A (ja) * | 2006-04-18 | 2009-07-16 | Daikin Ind Ltd | 加工助剤及び成形用組成物 |
US11274172B2 (en) * | 2009-08-27 | 2022-03-15 | Daikin Industries, Ltd. | Processing additive, molding composition masterbatch of processing additive and molding article |
-
2014
- 2014-12-22 EP EP14874641.5A patent/EP3067390A4/en not_active Withdrawn
- 2014-12-22 WO PCT/JP2014/083958 patent/WO2015098867A1/ja active Application Filing
- 2014-12-22 US US15/104,632 patent/US20160311954A1/en not_active Abandoned
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6157324B2 (ja) | 1981-10-22 | 1986-12-06 | Daikin Kogyo Co Ltd | |
JPH0481608B2 (ja) | 1983-06-23 | 1992-12-24 | Ii Ai Deyuhon De Nimoasu Ando Co | |
JPH0513961B2 (ja) | 1985-03-28 | 1993-02-23 | Daikin Ind Ltd | |
JPH0270737A (ja) | 1988-04-15 | 1990-03-09 | Minnesota Mining & Mfg Co <3M> | 押出可能な熱可塑性炭化水素ポリマー組成物 |
US5013792A (en) | 1990-01-04 | 1991-05-07 | E. I. Du Pont De Nemours And Company | Processing aid for polymers |
WO1997024381A1 (fr) | 1995-12-28 | 1997-07-10 | Daikin Industries, Ltd. | Copolymeres elastiques contenant du fluor, composition durcissable les contenant et materiau d'etancheite prepare a l'aide de ces copolymeres |
WO1999050319A1 (fr) | 1998-03-25 | 1999-10-07 | Daikin Industries, Ltd. | Procede de reduction de la teneur en metal d'un fluoroelastomere |
US6277919B1 (en) | 1999-05-13 | 2001-08-21 | Dyneon Llc | Polymer processing additive containing a multimodal fluoropolymer and melt processable thermoplastic polymer composition employing the same |
JP2002544358A (ja) | 1999-05-13 | 2002-12-24 | ダイネオン エルエルシー | マルチモードフルオロポリマーを含むポリマー加工用添加剤およびこれを用いた溶融加工可能な熱可塑性ポリマー組成物 |
WO2001023470A1 (fr) | 1999-09-30 | 2001-04-05 | Daikin Industries, Ltd. | Composition elastomere transparente |
JP5140902B2 (ja) | 1999-11-09 | 2013-02-13 | ダイキン工業株式会社 | 加硫可能な含フッ素エラストマー組成物 |
JP2005508429A (ja) * | 2001-11-08 | 2005-03-31 | デュポン ダウ エラストマーズ エルエルシー | 溶融加工性ポリマー用の加工助剤 |
JP4181042B2 (ja) | 2001-11-08 | 2008-11-12 | デュポン パフォーマンス エラストマーズ エルエルシー | 溶融加工性ポリマー用の加工助剤 |
WO2003044088A1 (fr) | 2001-11-21 | 2003-05-30 | Daikin Industries, Ltd. | Composition a base de resine plastique d'ingenierie decomposable a basse temperature et procede de production d'un objet moule a partir de cette composition |
JP2007510003A (ja) | 2003-08-20 | 2007-04-19 | デュポン パフォーマンス エラストマーズ エルエルシー | メタロセン触媒型線状低密度ポリエチレンポリマーのための加工助剤 |
JP4834971B2 (ja) | 2004-04-07 | 2011-12-14 | ダイキン工業株式会社 | 含フッ素エラストマー重合体の製造方法 |
WO2011025052A1 (en) | 2009-08-27 | 2011-03-03 | Daikin Industries, Ltd. | Processing additive, molding composition, masterbatch of processing additive and molding article |
Non-Patent Citations (1)
Title |
---|
See also references of EP3067390A4 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108430732A (zh) * | 2015-12-02 | 2018-08-21 | 阿科玛法国公司 | 用于聚烯烃的挤出剂 |
CN108430732B (zh) * | 2015-12-02 | 2020-04-28 | 阿科玛法国公司 | 用于聚烯烃的挤出剂 |
WO2018199034A1 (ja) * | 2017-04-28 | 2018-11-01 | Agc株式会社 | ポリテトラフルオロエチレン水性分散液 |
JPWO2018199034A1 (ja) * | 2017-04-28 | 2020-03-12 | Agc株式会社 | ポリテトラフルオロエチレン水性分散液 |
JP7116048B2 (ja) | 2017-04-28 | 2022-08-09 | Agc株式会社 | ポリテトラフルオロエチレン水性分散液 |
WO2019130975A1 (ja) * | 2017-12-26 | 2019-07-04 | ダイキン アメリカ インコーポレイティッド | 電線、電線の製造方法及びマスターバッチ |
JPWO2019130975A1 (ja) * | 2017-12-26 | 2020-10-22 | ダイキン アメリカ インコーポレイティッドDaikin America,Inc. | 電線、電線の製造方法及びマスターバッチ |
JP7181228B2 (ja) | 2017-12-26 | 2022-11-30 | ダイキン アメリカ インコーポレイティッド | 電線、電線の製造方法及びマスターバッチ |
CN114573929A (zh) * | 2022-03-15 | 2022-06-03 | 湖南省希润弗高分子新材料有限公司 | 一种聚烯烃用助剂组合物 |
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