WO2016027702A1 - 加工助剤 - Google Patents
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- WO2016027702A1 WO2016027702A1 PCT/JP2015/072507 JP2015072507W WO2016027702A1 WO 2016027702 A1 WO2016027702 A1 WO 2016027702A1 JP 2015072507 W JP2015072507 W JP 2015072507W WO 2016027702 A1 WO2016027702 A1 WO 2016027702A1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- 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
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- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
Definitions
- the present invention relates to a processing aid, a molding composition, a master batch for a processing aid, and a molded article.
- melt processable resin composition In the processing of a melt processable resin, it is necessary to extrude and process at a high speed in order to improve productivity and reduce costs.
- the melt processable resin composition always has a critical shear rate, and if this rate is exceeded, a state called a melt fracture becomes rough, and a good molded product cannot be obtained.
- 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 a processing aid mixed with a thermoplastic hydrocarbon polymer comprising a copolymer of a fluorinated olefin monomer and a substantially non-fluorinated hydrocarbon olefin monomer.
- melt fracture can be eliminated in a shorter time, and the extrusion pressure can be reduced to produce a molded article having a good appearance. Processing aids are still in demand today.
- the present invention can eliminate melt fracture generated when extruding a melt processable resin at a high shear rate in a short time, can greatly reduce the extrusion pressure, and has a good appearance.
- An object of the present invention is to provide a processing aid that can produce a molded product.
- the present invention is a processing aid characterized by comprising a polymer containing an elastomeric fluorine-containing polymer segment and a non-elastomeric fluorine-containing polymer segment.
- the elastomeric fluorine-containing polymer segment includes vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, vinylidene Fluoride / tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, vinylidene fluoride / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer, tetrafluoroethylene At least selected from the group consisting of: / propylene copolymer and tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer It is preferably a
- the non-elastomeric fluorine-containing polymer segment includes tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, ethylene / tetrafluoroethylene / other monomer (a) copolymer, vinylidene fluoride.
- the polymer is preferably a block polymer or a graft polymer.
- the processing aid preferably contains 1 to 99% by mass of an interfacial agent.
- the interfacial agent is at least one compound 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 poly (oxyalkylene), more preferably polyethylene glycol.
- the anti-sticking agent is preferably at least one selected from the group consisting of talc, silica and calcium carbonate.
- the present invention is a master batch for a processing aid comprising the above processing aid and a melt processable resin, wherein the polymer in the processing aid has a total mass of 0. It is also a master batch for processing aids characterized by being more than 1% by mass and not more than 20% by mass.
- the melt processable resin is preferably a polyolefin resin.
- the present invention is a molding composition comprising the above processing aid and a melt processable resin, wherein the polymer in the above processing aid has a total mass of 0. It is also a molding composition characterized by being 0001 to 10% by mass.
- the melt processable resin is preferably a polyolefin resin.
- the present invention is also a molded article formed by molding the molding composition described above.
- the processing aid of the present invention can eliminate the melt fracture generated when the melt processable resin is extruded at a high shear rate in a short time, can greatly reduce the extrusion pressure, and has a good appearance. Molded articles can be manufactured. It can also be expected to suppress the accumulation of die build-up at the tip of the discharge nozzle of the die of the extruder.
- 6 is a graph showing changes in die pressure with time in extrusion of Examples 1 to 3 and Comparative Examples 1 to 4.
- 6 is a graph showing changes in die pressure with time in extrusion of Example 4 and Comparative Examples 5 to 8.
- 6 is a graph showing changes in die pressure with time in extrusion of Example 5 and Comparative Examples 9-12.
- 6 is a graph showing changes in die pressure with time in extrusion of Example 6 and Comparative Examples 13 to 16.
- the processing aid of the present invention comprises a polymer containing an elastomeric fluorine-containing polymer segment and a non-elastomeric fluorine-containing polymer segment.
- the elastomeric fluorine-containing polymer segment preferably includes a VDF unit or a TFE unit, and more preferably includes a VDF unit.
- the VDF unit is preferably 30 to 85 mol%, more preferably 50 to 80 mol%, based on all monomer units constituting the elastomeric fluorine-containing polymer segment.
- the TFE unit is preferably 45 to 90 mol% with respect to all monomer units constituting the elastomeric fluorine-containing polymer segment when the elastomeric fluorine-containing polymer segment does not contain a VDF unit. More preferably, it is 55 to 70 mol%.
- the elastomeric fluorine-containing polymer segment includes VDF / HFP copolymer, VDF / TFE / HFP copolymer, VDF / TFE / 2,3,3,3-tetrafluoro-1-propene copolymer, VDF / PAVE.
- VDF / TFE / PAVE copolymer VDF / HFP / PAVE copolymer, VDF / CTFE copolymer, VDF / 2,3,3,3-tetrafluoro-1-propene copolymer, TFE It is preferably a segment composed of at least one elastomeric fluorine-containing polymer selected from the group consisting of a / propylene copolymer and a TFE / PAVE copolymer.
- the VDF / HFP copolymer preferably has a VDF / HFP composition of (45 to 85) / (55 to 15) (mol%), more preferably (50 to 80) / (50 to 20). (Mol%), more preferably (60-80) / (40-20) (mol%).
- the VDF / TFE / HFP copolymer preferably has a VDF / TFE / HFP composition of (30 to 80) / (4 to 35) / (10 to 35) (mol%).
- VDF / TFE / 2,3,3,3-tetrafluoro-1-propene copolymer the composition of VDF / TFE / 2,3,3,3-tetrafluoro-1-propene is (30 to 80) / (4-35) / (10-35) (mol%) is preferred.
- the VDF / PAVE copolymer preferably has a VDF / PAVE composition of (65 to 90) / (35 to 10) (mol%).
- the VDF / TFE / PAVE copolymer preferably has a VDF / TFE / PAVE composition of (40 to 80) / (3 to 40) / (15 to 35) (mol%).
- the VDF / HFP / PAVE copolymer preferably has a VDF / HFP / PAVE composition of (65 to 90) / (3 to 25) / (3 to 25) (mol%).
- the VDF / CTFE copolymer preferably has a VDF / CTFE composition of (30 to 90) / (70 to 10) (mol%).
- the composition of the VDF / 2,3,3,3-tetrafluoro-1-propene copolymer is (30 to 90) / Those of (70 to 10) (mol%) are preferred.
- the TFE / propylene copolymer preferably has a TFE / propylene composition of (45 to 90) / (55 to 10) (mol%).
- the TFE / PAVE copolymer preferably has a TFE / PAVE composition of (65 to 90) / (35 to 10) (mol%).
- the elastomeric fluorine-containing polymer segment is preferably a segment composed of a copolymer containing VDF units, among which a VDF / HFP copolymer, a VDF / HFP / TFE copolymer, VDF / 2, 3, At least one elastomer selected from the group consisting of 3,3-tetrafluoro-1-propene copolymer and VDF / TFE / 2,3,3,3-tetrafluoro-1-propene copolymer More preferably, the segment is made of a segmented fluoropolymer, and the segment is made of at least one elastomeric fluoropolymer selected from the group consisting of a VDF / HFP copolymer and a VDF / HFP / TFE copolymer. More preferably.
- the elastomeric fluorine-containing polymer segment preferably has a Mooney viscosity ML (1 + 10) of 10 to 100.
- the Mooney viscosity ML (1 + 10) is more preferably 20 or more, further preferably 30 or more, more preferably 80 or less, and further preferably 60 or less.
- the Mooney viscosity ML (1 + 10) can be measured according to ASTM D-1646 at 121 ° C. using a Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.
- the elastomeric fluorine-containing polymer segment preferably has a glass transition temperature of ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, further preferably ⁇ 50 ° C. or higher, and more preferably 5 ° C. or lower. It is preferably 0 ° C. or lower, more preferably ⁇ 3 ° C. or lower.
- 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 non-elastomeric fluorine-containing polymer segments are tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], trifluoroethylene, hexafluoroisobutylene.
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- CTFE chlorotrifluoroethylene
- VDF vinyl fluoride
- VDF trifluoroethylene, hexafluoroisobutylene.
- CH 2 CZ 1 (CF 2 ) n Z 2 (wherein Z 1 is H or F, Z 2 is H, F or Cl, and n is an integer of 1 to 10).
- the non-elastomeric fluorine-containing polymer segment preferably includes a VDF unit, a TFE unit, or a CTFE unit, and more preferably includes a VDF unit or a TFE unit.
- the VDF unit is preferably 20 to 100 mol%, more preferably 40 to 100 mol%, based on all monomer units constituting the non-elastomeric fluorine-containing polymer segment.
- the TFE unit is preferably 20 to 100 mol%, more preferably 40 to 100 mol%, based on all monomer units constituting the non-elastomeric fluorine-containing polymer segment.
- the non-elastomeric fluorine-containing polymer segment includes TFE / HFP copolymer, TFE / ethylene copolymer, ethylene / TFE / other monomer (a) copolymer, VDF / TFE copolymer, polytetrafluoro Ethylene [PTFE], polychlorotrifluoroethylene [PCTFE], polyvinylidene fluoride [PVDF], VDF / HFP copolymer, VDF / CTFE copolymer, polyvinyl fluoride, CTFE / TFE copolymer, CTFE / ethylene
- the segment is preferably a segment composed of at least one non-elastomeric fluorine-containing polymer selected from the group consisting of a copolymer and a TFE / PAVE copolymer.
- the other monomer (a) is preferably a monomer copolymerizable with TFE and ethylene.
- HFP pentafluoropropylene, 3,3,3-trifluoropropylene-1,2-trifluoro Methyl-3,3,3-trifluoropropylene-1, PAVE, (perfluoroalkyl) ethylene, and CH 2 ⁇ CX— (CF 2 ) n Z (wherein X and Z are the same or different; It represents a hydrogen atom or a fluorine atom, and n is an integer of 2 to 8.
- (Perfluoroalkyl) ethylene includes (perfluorobutyl) ethylene, (perfluorohexyl) ethylene and the like.
- Examples of CH 2 ⁇ CX— (CF 2 ) n Z include CH 2 ⁇ CFCF 2 CF 2 CF 2 H, CH 2 ⁇ CFCF 2 CF 2 CF 2 CF 2 H, and the like.
- the TFE / ethylene copolymer preferably has a TFE / ethylene composition of (20 to 90) / (80 to 10) (mol%), more preferably (37 to 85) / (63 to 15). (Mol%), more preferably (38 to 80) / (62 to 20) (mol%).
- composition of ethylene / TFE / other monomer (a) is preferably (79.9-10) / (20-89.9) / (0.1-14) (mol%), more preferably Is (62.9-15) / (37-84.9) / (0.1-10) (mol%), more preferably (61.8-20) / (38-79.8) / (0 .2-8) (mol%).
- the VDF / TFE copolymer preferably has a VDF / TFE composition of (0.1 to 99.9) / (99.9 to 0.1) (mol%), more preferably (10 to 90) / (90 to 10) (mol%).
- the VDF / HFP copolymer preferably has a VDF / HFP composition of (70 to 99.9) / (30 to 0.1) (mol%), more preferably (85 to 99.9). / (15 to 0.1) (mol%).
- the VDF / CTFE copolymer preferably has a VDF / CTFE composition of (70 to 99.9) / (30 to 0.1) (mol%), more preferably (85 to 99.9). / (15 to 0.1) (mol%).
- the non-elastomeric fluorine-containing polymer segment is, among others, TFE / ethylene copolymer, ethylene / TFE / other monomer (a) copolymer, PVDF, VDF / TFE copolymer, CTFE / ethylene copolymer. More preferably, it is a segment composed of at least one non-elastomeric fluorine-containing polymer selected from the group consisting of a coalescence and a CTFE / ethylene / other monomer (a) copolymer.
- the non-elastomeric fluorine-containing polymer segment not only exerts an effect in extrusion molding at a high shear rate, but can also exert an effect in extrusion molding at a low shear rate. Therefore, PVDF, VDF / HFP copolymer, A segment composed of at least one non-elastomeric fluorine-containing polymer selected from the group consisting of a VDF / CTFE copolymer and a VDF / TFE copolymer is preferable.
- the polymer may be a block polymer or a graft polymer.
- the block polymer may have the formula: Q-[(AB -...) I] n (Wherein Q is a residue obtained by removing an iodine atom from an iodide compound, A, B,... Are polymer chain segments (however, at least one of them is an elastomeric fluorine-containing polymer segment, at least one Is a non-elastomeric fluorine-containing polymer segment.), I is an iodine atom liberated from an iodide compound, and n is the number of bonds of Q).
- the block polymer has, as essential components, a chain composed of at least two polymer chain segments and a residue obtained by removing at least one iodine atom from an iodine atom and an iodide compound bonded to both ends thereof.
- Examples of the iodide compound include monoiodoperfluoromethane, 2-iodo-1-hydroperfluoroethane, 2-iodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,3-diiodoperfluoropropane, Examples include 2-chloro-1,3-diiodoperfluoropropane, 2,4-dichloro-1,5-diiodoperfluoropentane, 4-iodoperfluorobutene-1.
- block polymer examples include (elastomeric fluorine-containing polymer segment)-(non-elastomeric fluorine-containing polymer segment), (elastomeric fluorine-containing polymer segment)-(non-elastomeric fluorine-containing polymer segment)-( And a polymer containing (non-elastomeric fluorine-containing polymer segment)-(elastomeric fluorine-containing polymer segment)-(non-elastomeric fluorine-containing polymer segment).
- a known method can be employed. For example, an elastomeric fluorine-containing polymer in which an iodine atom is bonded to at least one terminal by radical polymerization of a fluoromonomer in the presence of an iodide compound. And a step of radically polymerizing a fluoromonomer in the elastomeric fluorine-containing polymer to obtain a polymer containing an elastomeric fluorine-containing polymer segment and a non-elastomeric fluorine-containing polymer segment. If necessary, a polymer containing a third segment can be obtained by further radical polymerization of a fluoromonomer with the polymer.
- the production methods described in Japanese Patent Publication Nos. 62-21805 and 63-59405 can also be employed.
- graft polymer a step of producing an elastomeric fluorine-containing polymer that becomes a trunk polymer by radical copolymerization of a fluoromonomer and a monomer having a double bond and a peroxide bond in the molecule, and the elastomer
- examples thereof include polymers obtained by a production method including a step of graft polymerization of a fluoromonomer in the presence of a functional fluorine-containing polymer.
- Examples of the monomer having both a double bond and a peroxide bond in the molecule include t-butyl peroxy methacrylate, di (t-vinyl peroxy) fumarate, t-butyl peroxycrotonate, t-butyl peroxyallyl carbonate, t- Hexyl peroxyallyl carbonate, 1,1,3,3-tetramethyl peroxyallyl carbonate, t-butyl peroxymethallyl carbonate, 1,1,3,3-tetramethylbutyl peroxymethallyl carbonate, p-menthane peroxyallyl carbonate, and p-menthane peroxymethallyl carbonate.
- the ratio of the elastomeric fluorine-containing polymer segment (SS) to the sum of the elastomeric fluorine-containing polymer segment (SS) and the non-elastomeric fluorine-containing polymer segment (HS) is 1 to It is preferably 99, more preferably 50 or more, still more preferably 60 or more, still more preferably 90 or less, and even more preferably 80 or less. If the proportion of the elastomeric fluoropolymer segment is too large, the extrusion pressure at a high shear rate may not be reduced sufficiently. If the proportion of the non-elastomeric fluoropolymer segment is too large, the extrusion rate at a low shear rate may be insufficient. The extrusion pressure may not be reduced sufficiently
- the polymer preferably has a melting point of 120 to 280 ° C, more preferably 140 ° C or higher, further preferably 160 ° C or higher, more preferably 270 ° C or lower, more preferably 230 ° C or lower. More preferably it is.
- the melting point is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].
- the polymer preferably has a melt flow rate (MFR) of 0.1 to 80 g / 10 min.
- MFR melt flow rate
- the MFR is more preferably 0.5 or more, further preferably 1 or more, more preferably 50 or less, and further preferably 30 or less.
- the above MFR is measured at an appropriate temperature according to the melting point of the non-elastomeric fluorine-containing polymer segment.
- the non-elastomeric fluorine-containing polymer segment is an ethylene / TFE / other monomer (a) copolymer, It can be measured at 230 ° C. at 250 ° C. with polyvinylidene fluoride [PVDF].
- the processing aid of the present invention also includes an interfacial agent, which is one of preferred forms.
- an interfacial agent which is one of preferred forms.
- the interfacial agent is contained in a molding composition to be described later, the interfacial agent is preferably a compound that has a melt viscosity lower than that of the melt processable resin at the molding temperature and can wet the surface of the polymer.
- the interfacial agent and the melt processable resin are different compounds.
- the interfacial agent is at least one interface 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 that it is an agent. These interfacial agents have a lower melt viscosity than the polymer. For this reason, when the polymer and the interfacial agent are mixed, the surface of the polymer can be wetted and functions sufficiently as an interfacial agent. More preferably, it is poly (oxyalkylene).
- 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 mass in the processing aid, more preferably 5 to 90% by mass, still more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. Moreover, it is preferable that content of the said interface agent is 50 mass% or more, and it is more preferable to exceed 50 mass%.
- the processing aid of the present invention may contain an anti-sticking agent. By including an anti-adhesive agent, it is possible to suppress the adhesion of the polymer.
- 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 polymer.
- 1 type may be sufficient as the said sticking
- the processing aid of the present invention may contain additives such as antioxidants, ultraviolet absorbers, flame retardants and the like as necessary in addition to the above components.
- the molding composition of the present invention comprises a melt processable resin and the above-described processing aid of the present invention.
- the melt processable resin means a polymer that can measure the melt flow at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.
- the melt processable resin is not particularly limited, and is preferably a resin containing no fluorine.
- polyolefin resin such as polyethylene and polypropylene
- polyamide [PA] resin such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon MXD6
- polyethylene terephthalate [PET] polybutylene terephthalate Polyester
- PBT polyethylene terephthalate
- PET polybutylene terephthalate Polyester
- PBT polyarylate, aromatic polyester (including liquid crystal polyester), polycarbonate [PC], etc .
- polyacetal [POM] resin polyphenylene oxide [PPO], modified polyphenylene ether, polyether ether ketone [PEEK], etc.
- Polyether resin such as polyamino bismaleimide [PAI] resin; Polysulfone such as polysulfone [PSF] and polyethersulfone [PES] System resin; ABS resin, poly-4-methylpentene -1 (TPX resins) other vinyl polymers such as polyphenylene sulfide [PPS], polyketone sulfide, polyether imide, polyimide [PI] and the like.
- the nylon MXD6 is a crystalline polycondensate obtained from metaxylenediamine [MXD] and adipic acid.
- melt-processable resins polyolefin resins and / or PA resins are preferable, and polyolefin resins are more preferable.
- the melt processable resin in the molding composition is preferably a thermoplastic resin from the viewpoint of easy melt molding.
- the melt processable resin may be used alone or in combination of two or more.
- the melt processable resin preferably has a melt processing temperature of 100 to 350 ° C.
- the melt processable resin may have crystallinity or may not have crystallinity.
- the melt processable resin When the melt processable resin has crystallinity, it preferably has a melting point of 80 to 300 ° C, more preferably a melting point of 100 to 200 ° C.
- the melt-processable resin having no crystallinity preferably has a processing temperature substantially equal to that of a melt-processable resin that is crystalline and has a melting point range.
- the melting point of the melt-processable resin having crystallinity can be measured with a DSC apparatus.
- the melt processable resin can be synthesized by a conventionally known method or the like according to each type.
- the melt processable resin may be powder, granules, pellets, etc., but in the obtained molding composition, the melt processable resin can be efficiently melted and the processing aid can be dispersed. A pellet is preferable.
- the polymer is preferably 0.0001 to 10% by mass of the total mass of the processing aid and the melt processable resin comprising the polymer.
- the polymer is more preferably 0.001% by mass or more, more preferably 5% by mass or less, and more preferably 0.5% by mass of the total mass of the processing aid and the melt-processable resin comprising the polymer. % Or less is more preferable.
- the molding composition may be prepared by adding the processing aid of the present invention itself to the melt processable resin, or in addition to the melt processable resin as a master batch for a processing aid described later. It may be prepared.
- the molding composition of the present invention may be blended with other components, if necessary, together with the processing aid and the melt processable resin.
- Examples of the other components include reinforcing materials such as glass fiber and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and petals; carbon black and the like.
- Conductive agent of rubber such as rubber; Antioxidant such as hindered phenol and phosphorus; Nucleating agent such as metal salt and acetal of sorbitol; Other voluntary standards established by the Sanitation Council for Polyolefins, etc. Additives described in the positive list can be used.
- the master batch for processing aid of the present invention comprises the processing aid of the present invention described above and a melt processable resin.
- the master batch for processing aid of the present invention can be suitably used as a processing aid when molding a melt processable resin.
- the master batch for processing aid of the present invention is a polymer in which the above polymer is uniformly dispersed in the melt processable resin, it can be added during molding of the melt processable resin to reduce extrusion torque, extrusion pressure, etc. Can be improved.
- melt processable resin examples include those similar to the above-described melt processable resin, and among them, a polyolefin resin is preferable, and polyethylene is more preferable.
- the master batch for processing aids of the present invention may be of any form such as powder, granules, pellets, etc., but the polymer is held in a finely dispersed state in the melt processable resin. Pellets obtained by melt kneading are preferred.
- the polymer exceeds 0.1% by mass of the total mass of the processing aid and the melt-processable resin made of the polymer in terms of facilitating melt molding, and 20 It is preferable that it is below mass%.
- 0.3% by mass of the total mass is a more preferable lower limit
- 0.6% by mass is a further preferable lower limit
- 10% by mass is a more preferable upper limit.
- the master batch for a processing aid of the present invention may be formed by blending other components with the processing aid and the melt processable resin as necessary.
- the other components are not particularly limited, and examples thereof include those described in the molding composition of the present invention.
- the master batch for a processing aid of the present invention can be obtained by kneading a processing aid and optionally adding other components to a melt processable resin at a temperature of 100 to 350 ° C. From the viewpoint of dispersibility of the polymer, a polymer obtained by kneading, at this temperature, a material prepared by adding the above-mentioned processing aid prepared in advance to a melt-processable resin is preferable.
- the molded article of the present invention is formed by molding the molding composition of the present invention described above.
- the molding may be performed by preparing the molding composition of the present invention in advance and feeding it into a molding machine, and performing melting, extrusion, or the like, or molding the above-mentioned processing aid and melt-processable resin.
- the above-mentioned master batch for processing aid and the melt-processable resin may be simultaneously added to the molding machine for melting, extruding, etc. May be.
- the molding of the molding 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 included. Is preferred.
- the various conditions relating to the molding are not particularly limited, and can be appropriately set according to the composition and amount of the molding composition to be used, the shape and size of the desired molded product, and the like.
- the molding temperature is generally not less than the melting point of the melt-processable resin in the molding composition and less than the lower one of the decomposition temperatures of the processing aid and the melt-processable resin. 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 present invention is also a method for extruding a molding composition, comprising the steps of obtaining a molding composition by adding the processing aid to a melt processable resin, and extruding the molding composition. .
- 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 melt processable resin used. For example, it is suitably used for mechanical properties and other mechanical properties that are mainly strongly required. .
- Examples of the use of the molded article include various films, bags, covering materials, tableware such as beverage containers, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded articles.
- Copolymer composition 19 F-NMR manufactured by Bruker, AC300P type was used for measurement.
- 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. At that time, 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 extrusion pressure is reduced from the pressure of the linear low-density polyethylene containing only the initial processing aid (initial pressure), and the effect of the processing aid is exhibited. Stable at a constant pressure (stable pressure). The difference between the initial pressure and the stable pressure was taken as the pressure drop. If the pressure was not stable within the set time, the difference between the initial pressure and the end time was taken as the pressure drop.
- the processing aids used in Examples 1-3 were prepared by the following method. Fluorine-containing polymer using the polymerization method of Examples 1 and 2 described in JP-B-63-59405 and the polymerization method of Examples described in JP-B-6-21805 1-3 were produced. The compositions of the fluoropolymers 1 to 3 are shown in Table 1. Further, talc (Luzenac, Jetfine 1A), silica (GRACE, SYLOBLOC 45H), and calcium carbonate (Shiraishi Kogyo Co., Ltd., Brilliant 1500) are set to have a mass ratio of 3/6/2. An anti-sticking agent was prepared by mixing. Next, any one of the fluoropolymers 1 to 3 and the anti-sticking agent were mixed so that the mass ratio was 90/10 to obtain a processing aid.
- the processing aid used in Comparative Example 1 was prepared by the following method.
- the processing aid used in Comparative Example 2 was prepared by the following method.
- the above FKM and polyethylene glycol (manufactured by DOW CHEMICAL, CARBOWAX TM SENTRY TM POLYETHYLENE GLYCOL 8000 GRANULAR, hereinafter referred to as “PEG”) were mixed so as to have a mass ratio of 1/2 to obtain a processing aid. .
- PVDF1 a PVDF homopolymer (melting point 159 ° C., MFR 4.4) (hereinafter referred to as “PVDF1”) produced by a known emulsion polymerization method was used as a processing aid.
- PVDF2 modified PVDF (HFP 4.5 mol%, melting point 144 ° C., MFR 1.1) (hereinafter referred to as “PVDF2”) produced by a known emulsion polymerization method was used as a processing aid.
- Linear low density polyethylene (EXXON MOBIL, LLDPE 1002YB) is mixed with the above processing aid to 5% by weight with respect to the total weight of the linear low density polyethylene and processing aid, and further IRGANOX B225 (manufactured by BASF) is mixed by 0.1% by weight and charged into a twin-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd., Laboplast Mill 30C150 screw L / D), and processing aid is added at a screw speed of 80 rpm. A contained pellet was obtained.
- 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. Under the same conditions, a master batch containing a processing aid and a processing aid and a polyolefin was obtained.
- the temperature conditions in extrusion of the fluoropolymers 1 and 2 are as follows. Condition 1: Cylinder temperature 150 ° C, 250 ° C, 250 ° C, die temperature 180 ° C (2) Temperature conditions in extrusion of the fluoropolymer 3, FKM, and FKM + PEG are as follows.
- Condition 2 Cylinder temperature 150 ° C, 170 ° C, 180 ° C, die temperature 180 ° C (3) The temperature conditions in the extrusion of PVDF1 and PVDF2 are as follows.
- Condition 3 Cylinder temperature 150 ° C, 180 ° C, 190 ° C, die temperature 180 ° C
- Example 1 A master batch containing 5% by weight of a fluoropolymer 1 in linear low density polyethylene (EXXON MOBIL, LLDPE 1201XV) is 1 weight based on the total weight of the linear low density polyethylene and the master batch. % And mixed by tumbling.
- the obtained master batch-containing linear low density polyethylene was subjected to a cylinder temperature of 210 to 240 ° C. using a single screw extruder (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm ⁇ ⁇ 40 mmL). Extrusion was performed at a die temperature of 240 ° C. and a screw rotation speed of 80 rpm, and changes in the die pressure and melt fracture were observed.
- Example 2 Extrusion evaluation was performed in the same manner as in Example 1 except that a master batch containing 5% by weight of the fluoropolymer 2 was added.
- Example 3 Extrusion evaluation was performed in the same manner as in Example 1 except that a master batch containing 5% by weight of the fluoropolymer 3 was added.
- Example 1 Extrusion evaluation was performed in the same manner as in Example 1 except that a master batch containing 5% by weight of FKM was added.
- Example 2 Extrusion evaluation was performed in the same manner as in Example 1 except that a master batch containing 5% by weight of FKM + PEG was added.
- Example 3 Extrusion evaluation was performed in the same manner as in Example 1 except that a master batch containing 5% by weight of PVDF1 was added.
- Example 4 Extrusion evaluation was performed in the same manner as in Example 1 except that a master batch containing 5% by weight of PVDF2 was added.
- Table 2 shows the evaluation results and the like in Examples 1 to 3 and Comparative Examples 1 to 4.
- FIG. 1 shows the change over time in the die pressure in the extrusion of Examples 1 to 3 and Comparative Examples 1 to 4.
- the shear rate calculated from the following formula 1 was about 1,200 sec ⁇ 1 .
- the processing aids used in Examples 1 to 3 have a large effect of improving moldability in molding at a high shear rate.
- Example 4 The master batch used in Example 1 was added to linear low-density polyethylene (manufactured by EXXON MOBIL, LLDPE 1201XV) at 1% by weight based on the total weight of the linear low-density polyethylene and the master batch. The mixture was mixed by tumbling, and the cylinder temperature was 210 to 240 ° C. in a single screw extruder (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm ⁇ ⁇ 40 mmL). Extrusion was performed at a die temperature of 240 ° C. and a screw rotation speed of 10 rpm, and changes in the die pressure and melt fracture were observed.
- HAAKE Rheomex OS
- L / D 33
- screw diameter 20 mm
- die diameter 2 mm ⁇ ⁇ 40 mmL
- Comparative Example 5 Extrusion evaluation was performed in the same manner as in Example 4 except that the master batch used in Comparative Example 1 was added.
- Table 3 shows the evaluation results in Example 4 and Comparative Examples 5 to 8. Further, FIG. 2 shows the change over time of the die pressure in the extrusion of Example 4 and Comparative Examples 5 to 8.
- Equation 1 the shear rate calculated from Equation 1 was about 130 sec ⁇ 1 .
- Example 4 the pressure dropped by 3.0 MPa within 15 minutes after the start of the masterbatch addition, and the melt fracture disappeared completely within 60 minutes.
- Comparative Examples 5 and 6 there was almost no pressure drop (a pressure drop ⁇ P), and the melt fracture did not disappear completely even after 70 minutes from the start of the masterbatch addition.
- Comparative Examples 7 and 8 the melt fracture disappeared completely within 60 minutes, but almost no pressure drop (drop pressure ⁇ P) was observed as in Comparative Examples 5 and 6.
- Example 5 The master batch used in Example 1 was added to high-density polyethylene (SABIC, Vestolene A 6060R black) so that the master batch was 1% by weight based on the total weight of the high-density polyethylene and the master batch.
- the mixture was tumbled and mixed with a single screw extruder (manufactured by HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm ⁇ ⁇ 40 mmL), cylinder temperature 170 to 200 ° C., die temperature 200 Extrusion was performed at 10 ° C. and a screw rotation speed of 10 rpm, and changes in the die pressure were observed. Melt fracture did not occur under the molding conditions performed.
- Comparative Example 9 Extrusion evaluation was performed in the same manner as in Example 5 except that the master batch used in Comparative Example 1 was added.
- Table 4 shows the evaluation results and the like in Example 5 and Comparative Examples 9 to 12.
- FIG. 3 shows the change with time of the die pressure in the extrusion of Example 5 and Comparative Examples 9-12.
- Equation 1 the shear rate calculated from Equation 1 was about 130 sec ⁇ 1 .
- Example 5 has a larger pressure drop (a pressure drop ⁇ P) than Comparative Examples 9 to 12, and is effective even when high-density polyethylene is molded at a low temperature and a low shear rate.
- Example 6 The master batch used in Example 1 was added to high-density polyethylene (SABIC, Vestolene A 6060R black) so that the master batch was 1% by weight based on the total weight of the high-density polyethylene and the master batch. The mixture was mixed by tumbling, and the cylinder temperature was 200 to 230 ° C. and the die temperature was 230 with a single screw extruder (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm ⁇ ⁇ 40 mmL). Extrusion was performed at 10 ° C. and a screw rotation speed of 10 rpm, and changes in the die pressure were observed. Melt fracture did not occur under the molding conditions performed.
- SABIC high-density polyethylene
- Table 5 shows the evaluation results and the like in Example 5 and Comparative Examples 13 to 16.
- FIG. 4 shows the change over time of the die pressure in the extrusion of Example 6 and Comparative Examples 13 to 16.
- Equation 1 the shear rate calculated from Equation 1 was about 130 sec ⁇ 1 .
- Example 6 the pressure drop (the pressure drop ⁇ P) is larger than those in Comparative Examples 13-16.
- the fluoropolymer 1 exhibits a workability improving effect in a molding temperature range employed in molding at a low shear rate selected when molding a high-density polyethylene large-diameter pipe.
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Abstract
Description
VDF/HFP共重合体としては、VDF/HFPの組成が、(70~99.9)/(30~0.1)(モル%)のものが好ましく、より好ましくは(85~99.9)/(15~0.1)(モル%)である。
VDF/CTFE共重合体としては、VDF/CTFEの組成が、(70~99.9)/(30~0.1)(モル%)のものが好ましく、より好ましくは(85~99.9)/(15~0.1)(モル%)である。
(式中、Qはアイオダイド化合物からヨウ素原子を除いた残基、A、B、・・・はそれぞれポリマー鎖セグメント(ただし、そのうちの少なくとも一つはエラストマー性含フッ素ポリマーセグメントであり、少なくとも一つは非エラストマー性含フッ素ポリマーセグメントである。)、Iはアイオダイド化合物から遊離したヨウ素原子、nはQの結合手の数を表わす。)で示されるものが好ましい。上記ブロックポリマーは、少なくとも2種のポリマー鎖セグメントからなる連鎖と、その両末端に結合した、ヨウ素原子及びアイオダイド化合物から少なくとも1個のヨウ素原子を除いた残基を必須成分としてなることが好ましい。
また、上記界面剤の含有量は、50質量%以上であることが好ましく、50質量%を超えることがより好ましい。
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。
上記溶融加工性樹脂としては、なかでも、ポリオレフィン樹脂及び/又はPA樹脂が好ましく、ポリオレフィン樹脂がより好ましい。
上記溶融加工性樹脂は、粉末、顆粒、ペレット等であってよいが、得られる成形用組成物において、上記溶融加工性樹脂を効率的に溶融させ、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。
上記ポリマーは、該ポリマーからなる加工助剤及び溶融加工性樹脂の合計質量の0.001質量%以上であることがより好ましく、また、5質量%以下であることがより好ましく、0.5質量%以下であることが更に好ましい。
本発明の成形用組成物は、上記加工助剤及び上記溶融加工性樹脂とともに、必要に応じて、その他の成分を配合したものであってもよい。
上記その他の成分としては特に限定されず、例えば、本発明の成形用組成物において説明したものが挙げられる。
上記成形は、本発明の成形用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、上述の加工助剤と溶融加工性樹脂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し、上述の加工助剤用マスターバッチと溶融加工性樹脂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。
上記成形温度は、一般に、成形用組成物における溶融加工性樹脂の融点以上、且つ、上記加工助剤及び上記溶融加工性樹脂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、用いる溶融加工性樹脂の種類によるが、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。
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。
含フッ素ポリマー2、3は250℃にて98N、含フッ素ポリマー1は230℃にて98N、PVDF1は230℃にて198N、PVDF2は230℃にて98N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。
設定時間内で、圧力が安定しない場合は、初期圧力と終了時間の圧力の差を降下圧力量とした。
実施例1~3で使用する加工助剤を次の方法で調製した。
特公昭63-59405号公報に記載の実施例1及び2の重合方法、並びに、特公昭62-21805号公報に記載の実施例の重合方法と実質的に同様の方法を用いて、含フッ素ポリマー1~3を製造した。含フッ素ポリマー1~3の組成を表1に示す。
また、タルク(Luzenac社製、Jetfine 1A)、シリカ(GRACE社製、SYLOBLOC 45H)、及び、炭酸カルシウム(白石工業株式会社製、Brilliant 1500)を、質量比が3/6/2となるように混合して、固着防止剤を調製した。
次に、含フッ素ポリマー1~3のいずれかと固着防止剤とを、質量比が90/10となるように混合して、加工助剤とした。
TFE:テトラフルオロエチレン
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
特許第5140902号公報に記載の実施例の重合方法と実質的に同様の方法を用いて、VDF/HFP共重合体〔FKM〕(VDF/HFP=78/22mol%、ムーニー粘度40)を製造した。
また、タルク(Luzenac社製、Jetfine 1A)、シリカ(GRACE社製、SYLOBLOC 45H)、及び、炭酸カルシウム(白石工業株式会社製、Brilliant 1500)を、質量比が3/6/2となるように混合して、固着防止剤を調製した。
次に、上記FKMと固着防止剤とを、質量比が90/10となるように混合して、加工助剤とした。
特許第5140902号公報に記載の実施例の重合方法と実質的に同様の方法を用いて、VDF/HFP共重合体〔FKM〕(VDF/HFP=78/22mol%、ムーニー粘度40)を製造した。
上記FKMとポリエチレングリコール(DOW CHEMICAL社製、CARBOWAXTM SENTRYTM POLYETHYLENE GLYCOL 8000 GRANULAR、以下「PEG」と称する。)とを、質量比が1/2となるように混合して、加工助剤とした。
比較例4では、公知の乳化重合方法によって製造された変性PVDF(HFP4.5mol%、融点144℃、MFR1.1)(以下、「PVDF2」とする)を加工助剤として使用した。
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IRGANOX B225(BASF社製)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/D)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。
(1)含フッ素ポリマー1、2の押出における温度条件は、以下の通りである。
条件1:シリンダー温度150℃、250℃、250℃、ダイ温度180℃
(2)含フッ素ポリマー3、FKM、FKM+PEGの押出における温度条件は、以下の通りである。
条件2:シリンダー温度150℃、170℃、180℃、ダイ温度180℃
(3)PVDF1、PVDF2の押出における温度条件は、以下の通りである。
条件3:シリンダー温度150℃、180℃、190℃、ダイ温度180℃
(実施例1)
線状低密度ポリエチレン(EXXON MOBIL社製、LLDPE 1201XV)に、含フッ素ポリマー1を5重量%含むマスターバッチを、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、ダイ径:2mmφ×40mmL)にて、シリンダー温度210~240℃、ダイ温度240℃、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。
含フッ素ポリマー2を5重量%含むマスターバッチを添加した以外は実施例1と同様にして押出評価を行った。
含フッ素ポリマー3を5重量%含むマスターバッチを添加した以外は実施例1と同様にして押出評価を行った。
FKMを5重量%含むマスターバッチを添加した以外は実施例1と同様にして押出評価を行った。
FKM+PEGを5重量%含むマスターバッチを添加した以外は実施例1と同様にして押出評価を行った。
PVDF1を5重量%含むマスターバッチを添加した以外は実施例1と同様にして押出評価を行った。
PVDF2を5重量%含むマスターバッチを添加した以外は実施例1と同様にして押出評価を行った。
γ:剪断速度(sec-1)
Q:押出量(kg/hr)
R:ダイの直径(mm)
(実施例4)
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、ダイ径:2mmφ×40mmL)にて、シリンダー温度210~240℃、ダイ温度240℃、スクリュー回転数10rpm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。
比較例1で用いたマスターバッチを添加した以外は実施例4と同様にして押出評価を行った。
比較例2で用いたマスターバッチを添加した以外は実施例4と同様にして押出評価を行った。
比較例3で用いたマスターバッチを添加した以外は実施例4と同様にして押出評価を行った。
比較例4で用いたマスターバッチを添加した以外は実施例4と同様にして押出評価を行った。
(実施例5)
高密度ポリエチレン(SABIC社製、VestolenA 6060R ブラック)に、実施例1で用いたマスターバッチを、高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、ダイ径:2mmφ×40mmL)にて、シリンダー温度170~200℃、ダイ温度200℃、スクリュー回転数10rpmにて押出を行い、ダイ圧力の変化を観察した。
実施した成形条件では、メルトフラクチャーは発生しなかった。
比較例1で用いたマスターバッチを添加した以外は実施例5と同様にして押出評価を行った。
比較例2で用いたマスターバッチを添加した以外は実施例5と同様にして押出評価を行った。
比較例3で用いたマスターバッチを添加した以外は実施例5と同様にして押出評価を行った。
比較例4で用いたマスターバッチを添加した以外は実施例5と同様にして押出評価を行った。
(実施例6)
高密度ポリエチレン(SABIC社製、VestolenA 6060R ブラック)に、実施例1で用いたマスターバッチを、高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、ダイ径:2mmφ×40mmL)にて、シリンダー温度200~230℃、ダイ温度230℃、スクリュー回転数10rpmにて押出を行い、ダイ圧力の変化を観察した。
実施した成形条件では、メルトフラクチャーは発生しなかった。
比較例1で用いたマスターバッチを添加した以外は実施例6と同様にして押出評価を行った。
比較例2で用いたマスターバッチを添加した以外は実施例6と同様にして押出評価を行った。
比較例3で用いたマスターバッチを添加した以外は実施例6と同様にして押出評価を行った。
比較例4で用いたマスターバッチを添加した以外は実施例6と同様にして押出評価を行った。
Claims (15)
- エラストマー性含フッ素ポリマーセグメントと非エラストマー性含フッ素ポリマーセグメントを含むポリマーからなることを特徴とする加工助剤。
- エラストマー性含フッ素ポリマーセグメントは、
ビニリデンフルオライド/ヘキサフルオロプロピレン共重合体、
ビニリデンフルオライド/テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体、
ビニリデンフルオライド/パーフルオロ(アルキルビニルエーテル)共重合体、
ビニリデンフルオライド/テトラフルオロエチレン/パーフルオロ(アルキルビニルエーテル)共重合体、
ビニリデンフルオライド/ヘキサフルオロプロピレン/パーフルオロ(アルキルビニルエーテル)共重合体、
ビニリデンフルオライド/クロロトリフルオロエチレン共重合体、
テトラフルオロエチレン/プロピレン共重合体、及び、
テトラフルオロエチレン/パーフルオロ(アルキルビニルエーテル)共重合体
からなる群より選択される少なくとも1種のエラストマー性含フッ素ポリマーからなるセグメントである請求項1記載の加工助剤。 - 非エラストマー性含フッ素ポリマーセグメントは、
テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体、
テトラフルオロエチレン/エチレン共重合体、
エチレン/テトラフルオロエチレン/他の単量体(a)共重合体、
ビニリデンフルオライド/テトラフルオロエチレン共重合体、
ポリテトラフルオロエチレン、
ポリクロロトリフルオロエチレン、
ポリビニリデンフルオライド、
ビニリデンフルオライド/ヘキサフルオロプロピレン共重合体、
ビニリデンフルオライド/クロロトリフルオロエチレン共重合体、
ポリフッ化ビニル、
クロロトリフルオロエチレン/テトラフルオロエチレン共重合体、
クロロトリフルオロエチレン/エチレン共重合体、及び、
テトラフルオロエチレン/パーフルオロ(アルキルビニルエーテル)共重合体
からなる群より選択される少なくとも1種の非エラストマー性含フッ素ポリマーからなるセグメントである請求項1又は2記載の加工助剤。 - ポリマーは、ブロックポリマー又はグラフトポリマーである請求項1、2又は3記載の加工助剤。
- 界面剤を1~99質量%含む請求項1、2、3又は4記載の加工助剤。
- 界面剤は、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、脂肪族エステルおよびポリ(オキシアルキレン)からなる群から選択される少なくとも一種の化合物である請求項5記載の加工助剤。
- 界面剤は、ポリ(オキシアルキレン)である請求項5又は6記載の加工助剤。
- 界面剤は、ポリエチレングリコールである請求項5、6又は7記載の加工助剤。
- ポリマー100質量部に対して1~30質量部の固着防止剤を含む請求項1、2、3、4、5、6、7又は8記載の加工助剤。
- 固着防止剤は、タルク、シリカおよび炭酸カルシウムからなる群から選択される少なくとも1種である請求項9記載の加工助剤。
- 請求項1、2、3、4、5、6、7、8、9又は10記載の加工助剤と、溶融加工性樹脂とからなる加工助剤用マスターバッチであって、
ポリマーが、該ポリマー及び溶融加工性樹脂の合計質量の0.1質量%を超え、且つ20質量%以下であることを特徴とする加工助剤用マスターバッチ。 - 溶融加工性樹脂は、ポリオレフィン樹脂である請求項11記載の加工助剤用マスターバッチ。
- 請求項1、2、3、4、5、6、7、8、9又は10記載の加工助剤と、溶融加工性樹脂とからなる成形用組成物であって、
ポリマーが、該加工助剤及び溶融加工性樹脂の合計質量の0.0001~10質量%であることを特徴とする成形用組成物。 - 溶融加工性樹脂は、ポリオレフィン樹脂である請求項13記載の成形用組成物。
- 請求項13又は14記載の成形用組成物を成形してなることを特徴とする成形品。
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CN106661163B (zh) * | 2014-08-21 | 2020-04-14 | 大金工业株式会社 | 加工助剂 |
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