WO2012018140A1 - Procédé de mesure de la densité de réticulation d'un article moulé en mousse polymère thermoplastique réticulée et article moulé en mousse réticulée - Google Patents

Procédé de mesure de la densité de réticulation d'un article moulé en mousse polymère thermoplastique réticulée et article moulé en mousse réticulée Download PDF

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Publication number
WO2012018140A1
WO2012018140A1 PCT/JP2011/068210 JP2011068210W WO2012018140A1 WO 2012018140 A1 WO2012018140 A1 WO 2012018140A1 JP 2011068210 W JP2011068210 W JP 2011068210W WO 2012018140 A1 WO2012018140 A1 WO 2012018140A1
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crosslinked
ethylene
molded article
foamed molded
thermoplastic polymer
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PCT/JP2011/068210
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English (en)
Japanese (ja)
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勝大 山田
博 豊田
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住友化学株式会社
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Priority to CN201180037887.6A priority Critical patent/CN103068893B/zh
Publication of WO2012018140A1 publication Critical patent/WO2012018140A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/122—Soles
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/248—Measuring crosslinking reactions
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/0058—Kind of property studied
    • G01N2203/0092—Visco-elasticity, solidification, curing, cross-linking degree, vulcanisation or strength properties of semi-solid materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/02—Details not specific for a particular testing method
    • G01N2203/022—Environment of the test
    • G01N2203/0222—Temperature

Definitions

  • the present invention relates to a method for measuring the crosslinking density of a thermoplastic polymer crosslinked foamed molded article, and a crosslinked foamed molded article having a crosslinking density calculated by the measuring method of a certain value or more.
  • Crosslinked foamed molded articles made of thermoplastic polymers are widely used for daily goods, flooring materials, sound insulation materials, heat insulating materials and the like.
  • a cross-linked foamed molded article made of an ethylene polymer is used for footwear members (outer sole (lower bottom), midsole (upper bottom), insole (sole), etc.)).
  • the crosslinked foamed molded product made of an ethylene polymer include a crosslinked foamed molded product obtained by crosslinking and foaming an ethylene-vinyl acetate copolymer as described in JP-B-3-2657, and JP-A-2005-314638.
  • cross-linked foamed molded product obtained by cross-linking and foaming an ethylene- ⁇ -olefin copolymer as described in Japanese Patent Publication No. JP-A.
  • crosslinking density is known as one of the elements that greatly affect various physical properties of the crosslinked foamed molded article.
  • the crosslinking density is also referred to as an effective network chain concentration, and represents the number of cross-linking points between the polymers constituting the crosslinked foamed molded product contained in the unit weight of the foamed molded product.
  • a method for measuring the cross-linking density of a vulcanized rubber cross-linked foamed molded article for example, a method described in JP-A-2007-238783 is known.
  • two or more solid bodies that is, non-foamed molded bodies, which are the same type of polymer as the foamed molded body whose crosslink density is to be measured and have different crosslinking densities, are used.
  • the crosslink density of each solid body is calculated in advance by using equilibrium swelling, and the relaxation times of the solid bodies for which the crosslink density has been calculated are measured by a pulse nuclear magnetic resonance (NMR) apparatus. From the above, a calibration curve of the same kind of polymer is prepared. Next, the relaxation time in the foam molded article is measured by the pulse nuclear magnetic resonance (NMR) apparatus, and the crosslinking density of the foam molded article is calculated based on the calibration curve.
  • NMR pulse nuclear magnetic resonance
  • FIG. 1 is a diagram showing a correlation between compression set and gel fraction of a crosslinked foamed molded article.
  • FIG. 2 is a diagram showing the correlation between the compression set of the crosslinked foamed molded article and the crosslinking density measured by the method of the present invention.
  • the present inventor used a stress relaxation behavior obtained by compressively deforming a cross-linked foam molded article to be measured, thereby forming a cross-linked foam molded article made of a thermoplastic polymer. A method for accurately measuring the crosslink density of was found. In addition, the present inventors have found that a crosslinked foamed molded article having a crosslinking density calculated by the above measurement method exceeding a certain value is suitable as a member for shoes.
  • the first of the present invention is a cross-linked foamed molded product made of an ethylene polymer, which is subjected to compression deformation under the conditions of a measurement temperature of 60 ° C., a compression strain of 50%, and a measurement time of 1800 seconds.
  • the stress relaxation of the crosslinked foamed molded article is measured, and the crosslinked density determined using the relaxation elastic modulus obtained from the stress relaxation measurement is 0.30 mol / kg or more, and the crosslinked foamed molded article made of an ethylene polymer is used.
  • the second of the present invention is a member for shoes comprising the above-mentioned crosslinked foamed molded article.
  • the third aspect of the present invention is a method for measuring the crosslinking density of a thermoplastic polymer crosslinked foamed molded article, Heating the thermoplastic polymer cross-linked foam to a predetermined temperature; A pressure is applied to the crosslinked foamed molded product made of a thermoplastic polymer maintained at a predetermined temperature to compressively deform the crosslinked foamed molded product, and while maintaining the amount of compressive strain of the crosslinked foamed molded product to be constant, Measuring stress relaxation; A step of obtaining relaxation elastic modulus Gc from stress relaxation, where Gc is the elastic modulus when the stress of the crosslinked foamed molded article becomes constant, Calculating the crosslinking density of the crosslinked foamed thermoplastic polymer from the Gc by the following formula.
  • n Gc / RT n: Crosslink density
  • R Gas constant
  • T Measurement temperature
  • Method of measuring crosslinking density of the crosslinked foamed molded article of the present invention is a method of calculating from the relaxation modulus of the crosslinked foamed molded article when obtained by compression deformation of the cross-linked foamed molded article. Specifically, it has a compressible mechanism such as a tensile tester with a compression function and a rotary viscometer with a compression function, and the stress at the time of compression of a cross-linked foamed molded article using an apparatus that can obtain stress data. Measure relaxation. For example, an apparatus equipped with a stress sensor that can measure compressive stress, a parallel plate-shaped jig that sandwiches the sample, an oven that heats the sample, and a position sensor that can measure the amount of compressive strain is used.
  • the shape of the sample is preferably a plate shape having parallel planes that can uniformly contact the jig surface.
  • the thickness of the sample in the range that can be sandwiched in the jig can be freely set, and preferably 0.1 mm ⁇ 50 mm, more preferably 1 mm ⁇ 20 mm.
  • the shape of the sample on the surface in contact with the jig is preferably a point-symmetric shape such as a circle, square, or equilateral triangle.
  • the area of the sample on the surface in contact with the jig is preferably equal to or slightly larger than the area of the jig.
  • the sample is sandwiched between the jig so that the center of the surface where the sample contacts the jig and the center of the jig coincide.
  • a sample sandwiched between jigs is placed in an oven, and the sample is heated to the measurement temperature.
  • the measurement temperature can be freely set as long as the shape of the sample can be maintained.
  • the measurement temperature is preferably a temperature at which 1% to 100% compressive strain can be applied to the sample.
  • the amount of compressive strain applied to the sample is determined by the material, shape, and measurement temperature of the sample.
  • the amount of compressive strain is defined by the following equation.
  • the amount of compressive strain applied to the sample may be a non-linear region, that is, a region where the viscosity of the sample changes according to the amount of compressive strain when the amount of compressive strain applied to the sample is changed.
  • the amount of compressive strain applied to the sample is preferably 1% to 100%, more preferably 10 to 100%.
  • the stress relaxation of the sample is measured while keeping the amount of compressive strain applied to the sample constant.
  • the measurement time may be a time until the stress of the crosslinked foamed molded article disappears and the stress of the crosslinked foamed molded article becomes substantially constant, or a longer time.
  • the calculation method of the crosslinking density used in the present invention is as follows. The relaxation elastic modulus Gc when the stress of the crosslinked foamed molded product is attenuated and the stress of the crosslinked foamed molded product becomes substantially constant is obtained, and the crosslinking density n of the crosslinked foamed molded product is calculated using the following formula.
  • the measuring method of the present invention can also be applied to a crosslinked foamed product made of an ethylene polymer, which has conventionally been difficult to accurately measure the crosslinking density.
  • a crosslinked foamed product made of an ethylene polymer, which has conventionally been difficult to accurately measure the crosslinking density.
  • the method of measuring crosslinking density of the crosslinked foamed molded body formed by using a high-pressure low-density polyethylene and / or ethylene - ⁇ - olefin copolymer it is preferred.
  • Crosslinked foamed molded article which is capable of measuring the cross-linking density in the method of the present invention may be a cross-linked foamed molded article crosslinked in any way.
  • Examples of the crosslinking method include electron beam crosslinking and a method of crosslinking a polymer with an organic peroxide.
  • the measurement method of the present invention is suitable for the measurement of the crosslinking density of a crosslinked foamed molded product obtained by crosslinking a polymer with an organic peroxide.
  • Crosslinked foamed molded article of the present invention is mainly composed of ethylene-based polymer, the crosslinking density is 0.30 mol / kg or more cross-linked foamed molded article.
  • the crosslinking density of the crosslinked foamed molded product is the compression modulus of the crosslinked foamed molded product obtained under the conditions of a measurement temperature of 60 ° C., a compression strain of 50%, and a measurement time of 1800 seconds.
  • the crosslink density is preferably 0.30 mol / kg or more.
  • the ethylene polymer in the present invention is an ethylene- ⁇ -olefin copolymer, a high-pressure method low-density polyethylene, or a mixture thereof.
  • the ethylene- ⁇ -olefin copolymer is a copolymer containing a monomer unit based on ethylene and a monomer unit based on an ⁇ -olefin.
  • ⁇ -olefin examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4 -Methyl- 1-hexene etc. are mention
  • the ⁇ -olefin is preferably an ⁇ -olefin having 3 to 20 carbon atoms, more preferably an ⁇ -olefin having 4 to 8 carbon atoms, and still more preferably 1-butene or 1-hexene. , 1-octene and 4-methyl-1-pentene.
  • Examples of the ethylene- ⁇ -olefin copolymer include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-4-methyl-1-pentene copolymer, and an ethylene-1-octene copolymer.
  • Examples thereof include a polymer, an ethylene-1-butene-1-hexene copolymer, an ethylene-1-butene-4-methyl-1-pentene copolymer, and an ethylene-1-butene-1-octene copolymer.
  • a copolymer having a monomer unit based on ethylene and a monomer unit based on an ⁇ -olefin having 6 to 8 carbon atoms specifically, Ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, and ethylene-1-butene-1-octene copolymer.
  • the content of monomer units based on ethylene is usually 80 to 98% by weight when the total weight of the ethylene- ⁇ -olefin copolymer is 100% by weight.
  • the density of the ethylene polymer is usually 860 to 945 kg / m. 3 It is.
  • the density is preferably 865 kg / m from the viewpoint of increasing the rigidity of the crosslinked foamed molded article. 3 Or more, more preferably 870 kg / m 3 Or more, more preferably 900 kg / m 3 That's it.
  • 940 kg / m. 3 It is as follows.
  • the melt flow rate (MFR; unit is g / 10 minutes) of the ethylene polymer is 0.01 to 3.0 g / 10 minutes.
  • An MFR is preferably 0.01 g / 10 min or more because a foamed molded article having a high foaming ratio is obtained and foam moldability is also improved.
  • MFR is preferably not more than 3.0 g / 10 min, more preferably not more than 2.5 g / 10 min.
  • the MFR is measured by the A method according to JIS K7210-1995 under conditions of a temperature of 190 ° C. and a load of 21.18N.
  • an ethylene polymer previously blended with about 1000 ppm of an antioxidant is used.
  • the ethylene-based copolymer used in the present invention preferably has a flow activation energy (Ea) of 40 kJ / mol or more from the viewpoint of making the cell properties uniform in the crosslinked foamed molded article and improving the appearance.
  • Ea is preferably 50 kJ / mol or more, more preferably 55 kJ / mol or more.
  • the flow activation energy (Ea) is a master curve showing the dependence of the melt complex viscosity (unit: Pa ⁇ sec) at 190 ° C. on the angular frequency (unit: rad / sec) based on the temperature-time superposition principle.
  • the shift factor (a T ) And a numerical value calculated by the Arrhenius equation and obtained by the following method.
  • melt complex viscosity-angular frequency curve of the ethylene- ⁇ -olefin copolymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. T, unit: ° C.
  • melt complex viscosity is Pa ⁇ sec.
  • the unit of the angular frequency is rad / sec.), Based on the temperature-time superposition principle, for each melt complex viscosity-angular frequency curve at each temperature (T), Shift factor (a) at each temperature (T) obtained when superimposed on the melt complex viscosity-angular frequency curve of the coalesced T ) Is obtained, and each of the temperature (T), from a shift factor (aT) at each temperature (T), by the method of least squares [ln (a T )] And [1 / (T + 273.16)] are calculated. Next, Ea is obtained from the slope m of the linear expression and the following expression (II).
  • the logarithmic curve has an angular frequency a for each curve. T Double the melt complex viscosity to 1 / a T Move twice.
  • the formula (I) in the minimum square method is usually 0.99 or more.
  • the melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1. It is performed under the conditions of 5 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec.
  • the measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.
  • the molecular weight distribution (Mw / Mn) of the ethylene-based polymer is preferably 3 or more, more preferably 5 or more, from the viewpoint of improving the moldability. Moreover, from a viewpoint of raising impact strength, Preferably it is 25 or less, More preferably, it is 20 or less, More preferably, it is 15 or less.
  • the molecular weight distribution (Mw / Mn) is a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).
  • Mw and Mn are gel permeation chromatograph (GPC). ) Method. Moreover, as measurement conditions of GPC method, the following conditions can be mention
  • Apparatus Waters 150C manufactured by Waters
  • Separation column TOSOH TSKgelGMH6-HT (3) Measurement temperature: 140 ° C
  • Carrier Orthodichlorobenzene (5) Flow rate: 1.0 mL / min (6) Injection volume: 500 ⁇ L (7) Detector: differential refraction (8)
  • HMw-Index High Molecular Index
  • Aw weight average molecular chain length
  • HMw-Index (%) (Component ratio of LogAw> 4.5 or more) / (Component ratio of LogAw> 4.0 or more) ⁇ 100 More HMw-Index is high, can mean that higher proportions of the molecular chain component weight with high molecular weight, achieve a high crosslinking density crosslinked foamed molded article.
  • Examples of the method for producing an ethylene- ⁇ -olefin copolymer used for obtaining a crosslinked foamed product made of an ethylene polymer of the present invention having a crosslinking density of 0.30 mol / kg or more include an alkylene group and a silylene group.
  • a metallocene complex having a ligand in which two (substituted) indenyl groups are bonded to each other by a bridging group for example, a metallocene catalyst using ethylenebis (1-indenyl) zirconium diphenoxide as a catalyst component, and ethylene and ⁇ -olefin And a method of copolymerizing with.
  • a metallocene catalyst using ethylenebis (1-indenyl) zirconium diphenoxide as a catalyst component
  • ethylene and ⁇ -olefin ethylene and ⁇ -olefin
  • a promoter component that activates the metallocene complex is used.
  • the promoter component include organic aluminum oxy compounds, boron compounds, and organic zinc compounds. These promoter components are preferably used by being supported on a particulate carrier.
  • a porous material is preferable, and SiO 2 , Al 2 O 3 , MgO, ZrO 2 TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 Inorganic oxides such as; clays and clay minerals such as smectite, montmorillonite, hectorite, laponite, saponite; organic polymers such as polyethylene, polypropylene, styrene-divinylbenzene copolymer, etc. are used.
  • the 50% volume average particle diameter of the particulate carrier is usually 10 to 500 ⁇ m, and the 50% volume average particle diameter is measured by a light scattering laser diffraction method or the like.
  • the fine particle carrier has a pore volume of usually 0.3 to 10 ml / g, and the pore volume is mainly measured by a gas adsorption method (BET method).
  • the specific surface area of the particulate carrier is usually 10 to 1000 m. 2 / G, and the specific surface area is mainly measured by a gas adsorption method (BET method).
  • the following promoter support (A) and an alkylene group or a silylene group are used.
  • a polymerization catalyst obtained by contacting a metallocene complex (B) having a ligand in which two (substituted) indenyl groups are bonded by a bridging group with an organoaluminum compound (C) ethylene and an ⁇ -olefin Can be used.
  • the cocatalyst carrier (A) is composed of component (a) diethylzinc, component (b) two types of fluorinated phenol, component (c) water, component (d) inorganic particulate carrier and component (e) 1,1. , 1,3,3,3-hexamethyldisilazane (((CH 3 ) 3 Si) 2 NH) is a carrier obtained by contact.
  • the fluorinated phenol of component (b) include pentafluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol, 2,4,6-trifluorophenol and the like.
  • pentafluorophenol / 3,4,5-trifluorophenol pentafluorophenol / 2,4,6-trifluorophenol, pentafluorophenol / 3,5-difluoro
  • pentafluorophenol / 3,4,5-trifluorophenol pentafluorophenol / 3,4,5-trifluorophenol
  • pentafluorophenol / 3,5-difluoro A combination of phenol and the like can be mentioned, and a combination of pentafluorophenol / 3,4,5-trifluorophenol is preferable.
  • the molar ratio of the fluorinated phenol having a large number of fluorine and the fluorinated phenol having a small number of fluorine is usually 20/80 to 80/20.
  • the inorganic compound particles of component (d) are preferably silica gel.
  • the amount of each component used is not particularly limited, but the molar ratio of each component used is the component (a) diethyl.
  • the molar ratio of zinc: component (b) 2 types of fluorinated phenol: component (c) water 1: x: y, x and y preferably satisfy the following formula.
  • ⁇ 1 X in the above formula is preferably a number from 0.01 to 1.99, more preferably a number from 0.10 to 1.80, and still more preferably a number from 0.20 to 1.50. Most preferably, the number is 0.30 to 1.00.
  • the amount of component (d) inorganic fine particle carrier used for component (a) diethyl zinc is included in the particles obtained by contacting component (a) diethyl zinc and component (d) inorganic fine particle carrier.
  • the amount of zinc atoms derived from the component (a) diethylzinc is preferably 0.1 mmol or more and 0.5 to 20 mmol in terms of the number of moles of zinc atoms contained in 1 g of the obtained particles. It is more preferable that
  • the amount of component (e) trimethyldisilazane used for component (d) inorganic particulate carrier is such that component (e) trimethyldisilazane is 0.1 mmol or more per gram of component (d) inorganic particulate carrier.
  • the amount is preferably 0.5 to 20 mmol, and more preferably 0.5 to 20 mmol.
  • Preferred examples of the metallocene complex (B) having a ligand in which two (substituted) indenyl groups are bonded by a bridging group such as an alkylene group or a silylene group include ethylenebis (1-indenyl) zirconium diphenoxide. .
  • the organoaluminum compound (C) is preferably triisobutylaluminum or trinormaloctylaluminum.
  • the amount of the metallocene complex (B) used is preferably 5 ⁇ 10 to 1 g of the promoter support (A). -6 ⁇ 5 ⁇ 10 -4 mol.
  • the amount of organoaluminum compound (C) used is 1 to 2000 in terms of the ratio (Al / M) of the number of moles of aluminum atoms in the organoaluminum compound (C) to the number of moles of metal atoms in the metallocene complex (B).
  • the promoter support (A) and the metallocene complex (B) are optionally added. It is good also as a polymerization catalyst which makes an electron-donating compound (D) contact an organic aluminum compound (C).
  • a small amount of olefin is polymerized (hereinafter referred to as prepolymerization) using a solid catalyst component in which a promoter component is supported on a particulate carrier. )) Obtained by polymerizing a small amount of olefin using a co-polymerized solid component, for example, a co-catalyst carrier, a metallocene complex, and a co-catalyst component (such as an alkylating agent such as an organoaluminum compound).
  • a co-polymerized solid component for example, a co-catalyst carrier, a metallocene complex, and a co-catalyst component (such as an alkylating agent such as an organoaluminum compound).
  • a method in which ethylene and an ⁇ -olefin are copolymerized using a polymerization solid component as a catalyst component or a catalyst is preferable.
  • a polymerization solid component as a catalyst component or a catalyst.
  • triethylaluminum as a promoter component in order to increase HMw-Index and further improve compression set performance.
  • the olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene and cyclohexene. These can be used alone or in combination of two or more.
  • the content of the prepolymerized polymer in the prepolymerized solid component is usually 0.1 to 500 g, preferably 1 to 200 g, per 1 g of the solid catalyst component.
  • the preliminary polymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method.
  • catalyst components such as a promoter carrier, a metallocene complex, and other promoter components (such as an alkylating agent such as an organoaluminum compound) into a polymerization reactor for performing prepolymerization, nitrogen, argon, or the like is usually used.
  • the polymerization temperature in the prepolymerization is usually a temperature lower than the melting point of the prepolymerized polymer, preferably 0 to 100 ° C, more preferably 10 to 70 ° C.
  • the solvent include hydrocarbons having 20 or less carbon atoms.
  • saturated aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane, octane, decane, etc .; aromatic hydrocarbons such as benzene, toluene, xylene, etc., which are used alone Alternatively, two or more kinds are used in combination.
  • a method for producing an ethylene- ⁇ -olefin copolymer a continuous polymerization method involving the formation of particles of an ethylene- ⁇ -olefin copolymer is preferable.
  • a continuous gas phase polymerization method for example, a continuous gas phase polymerization method, a continuous slurry polymerization method, a continuous bulk weight It is a legal method, preferably a continuous gas phase polymerization method.
  • the gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion.
  • a stirring blade may be installed in the reaction vessel.
  • an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is usually used.
  • the high-pressure low-density polyethylene is generally a tank-type reactor or a tubular reactor, and a free radical generator such as an organic oxide or oxygen is used.
  • a resin produced by polymerizing ethylene under a polymerization pressure of 100 to 300 MPa and a polymerization temperature of 130 to 300 ° C. can be used.
  • MFR can also be adjusted by using hydrocarbons such as hydrogen, methane, and ethane as molecular weight regulators.
  • the same method as the conventional method for producing a crosslinked foamed molded product of ethylene-vinyl acetate copolymer or high-pressure low-density polyethylene can be used.
  • a foaming agent is blended into an ethylene polymer, and this is uniformly mixed using a ribbon blender or the like, and the resulting mixture is substantially decomposed by an extruder or a calender roll.
  • the composition is filled into a mold by an injection molding machine or the like, foamed in a pressurized (holding) / heated state, and then cooled to take out a crosslinked foamed molded product, or (3) an ethylene polymer.
  • foam The mixture obtained by uniformly mixing using a ribbon blender or the like is melt-kneaded with an extruder or a calender roll at a temperature and pressure at which the foaming agent is not substantially decomposed, and formed into a sheet shape. Examples thereof include a method in which a sheet-like molded body is put in a mold, foamed in a pressurized (holding) / heated state with a pressure press or the like, and then cooled to take out a crosslinked foamed molded body.
  • the composition is further injected into the mold under conditions where the foaming agent and the crosslinking agent are not substantially decomposed, and the foaming agent and the crosslinking agent are decomposed in the mold, for example, a temperature of about 130 to 200 degrees.
  • a method (injection foaming method) in which the resin is crosslinked and foamed while maintaining the above can also be mentioned.
  • foaming agent examples include a thermally decomposable foaming agent having a decomposition temperature equal to or higher than the melting temperature of the ethylene polymer.
  • a thermally decomposable foaming agent having a decomposition temperature equal to or higher than the melting temperature of the ethylene polymer.
  • azodicarbonamide or sodium hydrogen carbonate is preferable.
  • the foaming agent include compounds mainly composed of urea; metal oxides such as zinc oxide and lead oxide; higher fatty acids such as salicylic acid and stearic acid; and metal compounds of the higher fatty acids.
  • the amount of the foaming aid used is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, with the total of the foaming agent and the foaming aid being 100% by weight.
  • ionizing radiation is used as a method for crosslinking an ethylene polymer
  • ⁇ rays, ⁇ rays, neutrons, electron beams, and the like can be used.
  • the irradiation amount is preferably in the range of 5 to 20 Mrad.
  • a crosslinking agent is used as a method for crosslinking the ethylene polymer, an organic peroxide having a decomposition temperature equal to or higher than the flow start temperature of the ethylene polymer is suitable.
  • dicumyl peroxide 1,1-ditertiary butyl peroxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-ditertiary butyl peroxyhexane, 2,5-dimethyl-2 , 5-ditertiary butyl peroxyhexyne, ⁇ , ⁇ -ditertiary butyl peroxyisopropylbenzene, tertiary butyl peroxyketone, tertiary butyl peroxybenzoate, and the like.
  • the blending ratio of the crosslinking agent is usually 0.02 to 3 parts by weight, preferably 0.05 to 1.5 parts by weight, with the total amount of the resin components being 100 parts by weight.
  • the temperature at which the cross-linking agent does not substantially decompose is a temperature not higher than the one-hour half-life temperature of the cross-linking agent.
  • the 1-hour half-life temperature of a crosslinking agent is described in MSDS etc. of this crosslinking agent.
  • the crosslinked foamed molded article of the present invention comprises a heat stabilizer, weathering agent, lubricant, antistatic agent, filler and pigment (metal oxide such as zinc oxide, titanium oxide, calcium oxide, magnesium oxide, silicon oxide; magnesium carbonate, Various additives such as carbonates such as calcium carbonate; fiber materials such as pulp) may be included.
  • a resin such as an ethylene-unsaturated ester copolymer, high-density polyethylene, polypropylene, polybutene, or rubber may be included.
  • the cross-linked foamed molded product of the present invention or the compression-crosslinked foamed molded product to be described later is used for a shoe sole or a shoe sole member, it is often necessary to adhere to other members such as rubber and a vinyl chloride sheet.
  • an ethylene-unsaturated ester copolymer such as a vinyl copolymer in combination with the ethylene polymer.
  • the proportion is 100 parts by weight of the ethylene polymer, and the ethylene-unsaturated ester copolymer is based on 100 parts by weight of the polymer.
  • the combined amount is preferably 25 to 900 parts by weight, and more preferably 40 to 400 parts by weight.
  • the pressure-crosslinking foaming method which is one of the methods for producing a crosslinked foamed molded product, will be described.
  • An ethylene polymer, a crosslinking agent, a foaming agent, and the like are melt-kneaded at a temperature at which both components of the crosslinking agent and the foaming agent are not substantially decomposed to produce a foaming resin composition.
  • the foaming resin composition is filled into a mold and 50 kg / cm.
  • a cross-linked foamed molded article can be obtained by heating at a temperature equal to or higher than the decomposition temperature of the foaming agent and higher than the decomposition temperature of the cross-linking agent while being pressurized.
  • the clamping pressure of the mold is 50 to 300 kgf / cm 2
  • the pressure holding time is preferably about 10 to 60 minutes.
  • the crosslinked foamed molded product of the present invention may be a compression crosslinked foamed molded product obtained by further compression molding the crosslinked foamed molded product. Compression molding is usually 130-200 ° C, 30-200 kg / cm 2 The process is carried out under the condition of 5 to 60 minutes while applying the above load.
  • a compression-crosslinked foamed molded article is more suitable for a midsole, which is a kind of footwear member.
  • the crosslinked foamed molded article of the present invention may be used after being cut into a desired shape, or may be used after being buffed.
  • the crosslinked foamed article of the present invention preferably has a foaming ratio of 4 to 20 times.
  • the surface hardness is preferably in the range of 30-80 in Shore C method hardness.
  • the crosslinked foamed molded article of the present invention may be laminated with other layers to form a multilayer laminate.
  • the material constituting the other layers includes vinyl chloride resin material, styrene copolymer rubber material, olefin copolymer rubber material (ethylene copolymer rubber material, propylene copolymer rubber material, etc.), natural A leather material, an artificial leather material, a cloth material, and the like can be mentioned, and at least one kind of material is used as these materials.
  • Examples of a method for producing these multilayer laminates include a method in which the crosslinked foamed molded product of the present invention and another layer formed separately are bonded by heat bonding or a chemical adhesive.
  • Known chemical adhesives can be used. Of these, urethane chemical adhesives and chloroprene chemical adhesives are particularly preferable.
  • an undercoat agent called a primer may be applied in advance at the time of bonding with these chemical adhesives.
  • a crosslinked foamed molded article it is known that the crosslinking density is closely related to compression set. In general, the higher the crosslink density, the lower the compression set of the crosslinked foamed molded product.
  • the crosslinked foamed molded article of the present invention exhibits a good compression set because of its high crosslinking density. Compression set is an index that shows how much the foamed molded body has recovered from compression after being compressed for a certain period of time under certain conditions, released from compression and left for a certain period of time. Emphasized as an indicator of fatigue resistance.
  • the crosslinked foamed molded article of the present invention preferably has a compression set of 30 to 65% when the hardness of the crosslinked foamed molded article is 50 by the Shore C method. Therefore, for example, the crosslinked foamed molded article of the present invention can be suitably used as a member of footwear such as shoes and sandals in a single layer or multilayer form. Examples of the footwear member include a midsole, an outer sole, an insole and the like. In addition to the footwear member, the crosslinked foamed molded article of the present invention is also used for building materials such as a heat insulating material and a cushioning material.
  • HMw-Index (%) (Component ratio of LogAw> 4.5 or more) / (Component ratio of LogAw> 4.0 or more) ⁇ 100 It means that the higher the HMw-Index, the higher the proportion of the molecular chain component amount having a high molecular weight.
  • Appearance of crosslinked foamed molded product (unit: none) The beauty of the appearance of the obtained cross-linked foamed molded article was determined visually. Judgment was performed in the following three stages.
  • the mixture was stirred at 5 ° C for 1.5 hours, then heated to 40 ° C, stirred at 40 ° C for 2 hours, further heated to 80 ° C, and stirred at 80 ° C for 2 hours. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. Then, 3 liters of toluene was added and stirred at 95 ° C. for 2 hours. The solid component was allowed to settle, and when the interface between the precipitated solid component layer and the upper slurry portion was seen, the upper slurry portion was removed.
  • the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant.
  • the average polymerization time was 4 hours.
  • the obtained polymer powder is fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C.
  • an ethylene-1-hexene copolymer hereinafter referred to as PE (1) was obtained.
  • the molecular weight distribution (Mw / Mn) of PE (1) was 6.9, and HMw-Index was 11.4%.
  • Table 1 shows the physical properties of PE (1).
  • “Cermic CE” ADCA type chemical foaming agent” 4.2 parts by weight and 0.7 parts by weight of dicumyl peroxide were kneaded at a roll temperature of 120 ° C. using a roll kneader. Kneading was performed for 5 minutes to obtain a resin composition. The resin composition is filled into a 13 cm ⁇ 13 cm ⁇ 2.0 cm mold, and the temperature is 165 ° C., the time is 30 minutes, and the pressure is 200 kg / cm. 2
  • a cross-linked foamed molded article (1) was obtained by pressure-crosslinking foaming under the conditions of Table 3 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results.
  • Example 2 Pressure cross-linked foaming Except for changing the amount of the chemical foaming agent to 2.2 parts by weight, a crosslinked foamed molded article (2) was obtained by kneading and pressure-crosslinking foaming under the same conditions as in Example 1. Table 3 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results.
  • Example 3 (1) Production of ethylene- ⁇ -olefin copolymer Using the prepolymerized catalyst component (1) obtained in Example 1, copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus to obtain a polymer powder.
  • the polymerization temperature was 84 ° C.
  • the polymerization pressure was 2 MPa
  • the hydrogen molar ratio to ethylene was 0.38%
  • the 1-hexene molar ratio to the total of ethylene and 1-hexene was 2.0%.
  • ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant.
  • the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant.
  • the average polymerization time was 4 hours.
  • the obtained polymer powder is fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C.
  • an ethylene-1-hexene copolymer hereinafter referred to as PE (2)
  • Mw / Mn The molecular weight distribution (Mw / Mn) of PE (2) was 6.8, and HMw-Index was 11.4%. Table 1 shows the physical properties of PE (2).
  • Example 1 (1) To the toluene slurry obtained in Example 1 (1) above, 4.98 kg of a 32.0 wt% diethylzinc hexane solution as the compound (a) was added and stirred. Then, after cooling to 5 ° C., 2.66 kg of a 3,4,5-trifluorophenol toluene solution prepared as a compound (b) at a concentration of 35.4 wt% was added, and the temperature of the reactor contents was adjusted to 5 ⁇ 3. It was added dropwise over 60 minutes while maintaining the temperature. The molar ratio y of the compound (b) to the compound (a) corresponds to 0.49. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour.
  • the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant.
  • the average polymerization time was 4 hours.
  • the obtained polymer powder is fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C.
  • an ethylene-1-hexene copolymer hereinafter referred to as PE (3) was obtained.
  • the molecular weight distribution (Mw / Mn) of PE (3) was 4.8, and HMw-Index was 17.9%.
  • Table 1 shows the physical properties of PE (3).
  • Pressure cross-linked foaming PE (3) 60 parts, EVA 40 parts, heavy calcium carbonate 10 parts, stearic acid 1.0 part, zinc oxide 1.0 part, chemical foaming agent 2.2 part, The resin composition was obtained by kneading 0.7 parts by weight of mill peroxide using a roll kneader under conditions of a roll temperature of 120 ° C. and a kneading time of 5 minutes.
  • the resin composition is filled into a 13 cm ⁇ 13 cm ⁇ 2.0 cm mold, and the temperature is 165 ° C., the time is 30 minutes, and the pressure is 200 kg / cm. 2
  • a cross-linked foamed molded article (4) was obtained by pressure-crosslinking foaming under the following conditions. Table 4 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results. Comparative Example 1 (1) Preparation of promoter support Silica heated by a nitrogen-replaced stirrer at 300 ° C.
  • the obtained solid component was washed 6 times with 2 liters of toluene. Thereafter, 2 liters of toluene was added to form a slurry, which was allowed to stand overnight.
  • To the slurry obtained above 0.27 liter of diethyl zinc in hexane (diethyl zinc concentration: 2 mol / liter) was added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.05 kg of pentafluorophenol and 0.09 liter of toluene was added dropwise over 60 minutes while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C.
  • the mixture is allowed to stand, and the solid component is allowed to settle.
  • the upper slurry portion is removed, and then the remaining liquid components are removed with a filter.
  • 3 liters of toluene was added and stirred at 95 ° C. for 2 hours.
  • the solid component was allowed to settle, and when the interface between the precipitated solid component layer and the upper slurry portion was seen, the upper slurry portion was removed.
  • the mixture is allowed to stand to precipitate the solid component.
  • the polymerization conditions were a polymerization temperature of 80 ° C., a polymerization pressure of 2 MPa, a hydrogen molar ratio to ethylene of 1.6%, and a 1-hexene molar ratio to the total of ethylene and 1-hexene of 1.5%.
  • ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant.
  • the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant.
  • the average polymerization time was 4 hours.
  • the obtained polymer powder is fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C.
  • an ethylene-1-hexene copolymer hereinafter referred to as PE (4)
  • the results of physical property evaluation of the obtained copolymer are shown in Table 1.
  • the molecular weight distribution (Mw / Mn) of PE (4) was 8.8, and HMw-Index was 5.4%.
  • Table 2 shows the physical properties of PE (4).
  • a cross-linked foamed molded article (5) was obtained by pressure-crosslinking foaming under the conditions described above.
  • Table 4 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results.
  • Comparative Example 2 (1) Pressure cross-linked foaming 40 parts by weight of ethylene-1-hexene copolymer (Sumikacene E FV401 manufactured by Sumitomo Chemical Co., Ltd., hereinafter PE (5), physical properties are shown in Table 2), 60 parts by weight of EVA, 10 parts by weight of heavy calcium carbonate, stearin 1.0 parts by weight of acid, 1.0 part by weight of zinc oxide, 2.6 parts by weight of chemical foaming agent, and 0.7 parts by weight of dicumyl peroxide were mixed at a roll temperature of 120 ° C.
  • the resin composition was obtained by kneading under a condition of kneading time of 5 minutes.
  • the resin composition is filled into a 13 cm ⁇ 13 cm ⁇ 2.0 cm mold, and the temperature is 165 ° C., the time is 30 minutes, and the pressure is 200 kg / cm. 2
  • a cross-linked foamed molded article (6) was obtained by pressure-crosslinking foaming under the conditions described above.
  • Table 4 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results.
  • a cross-linked foamed molded article (7) was obtained by pressure-crosslinking foaming under the conditions described above.
  • Table 5 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results.
  • Comparative Example 4 (1) Pressure cross-linked foaming 60 parts by weight of ethylene-1-hexene copolymer (Sumikacene E FV403 manufactured by Sumitomo Chemical Co., Ltd., hereinafter PE (6), physical properties are shown in Table 2), 40 parts by weight of EVA, 10 parts by weight of heavy calcium carbonate, stearin 1.0 parts by weight of acid, 1.0 part by weight of zinc oxide, 2.6 parts by weight of chemical foaming agent, and 0.7 parts by weight of dicumyl peroxide were mixed at a roll temperature of 120 ° C.
  • a cross-linked foamed molded article (8) was obtained by pressure-crosslinking foaming under the conditions of Table 5 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results.
  • Comparative Example 5 Pressure cross-linked foaming EVA 100 parts by weight, heavy calcium carbonate 10 parts by weight, stearic acid 1.0 part by weight, zinc oxide 1.0 part by weight, chemical foaming agent 2.6 parts by weight, dicumyl peroxide 0.7 part by weight Were kneaded under the conditions of a roll temperature of 120 ° C. and a kneading time of 5 minutes using a roll kneader to obtain a resin composition. The resin composition is filled into a 13 cm ⁇ 13 cm ⁇ 2.0 cm mold, and the temperature is 165 ° C., the time is 30 minutes, and the pressure is 200 kg / cm.
  • a crosslinked foamed molded article (9) was obtained by pressure-crosslinking foaming under the following conditions.
  • Table 5 shows the physical property evaluation results of the obtained cross-linked foamed molded article, and the cross-linking density and gel fraction evaluation results.
  • the crosslink density of a cross-linked foamed molded article made of a polyethylene polymer can be calculated easily and accurately.
  • the accuracy of the crosslink density measured by the method of the present invention is that, as shown in FIGS. 1 and 2, the correlation with the compression set of the foamed molded product is one of known methods for identifying effective network chain structures. It is clear from the fact that the crosslink density measured by the method of the present invention is better than the gel fraction.
  • the crosslink density of a cross-linked foamed molded article made of a thermoplastic polymer can be accurately measured.
  • the measuring method of the present invention is suitable for measuring the crosslinking density of a crosslinked foamed product made of an ethylene polymer, which has conventionally been difficult to accurately measure the crosslinking density.
  • the crosslinked foamed molded product made of an ethylene polymer of the present invention has a high crosslinking density and excellent compression set performance, and is suitable as a member for shoes.

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Abstract

La présente invention concerne un article moulé en mousse polymère éthylénique réticulée. L'article moulé en mousse polymère éthylénique réticulée a une densité de réticulation de 0,30 mol/kg ou plus telle que déterminée en utilisant un module de relaxation basé sur une mesure de relaxation des contraintes obtenue par mesure de la relaxation des contraintes de l'article moulé en mousse réticulée lorsque l'article moulé en mousse réticulée est soumis à une déformation par compression dans des conditions d'une température de mesure de 60°C, d'une contrainte de compression de 50 %, et d'une durée de mesure de 1 800 secondes. La présente invention concerne en outre un procédé de mesure de la densité de réticulation d'un article moulé en une mousse polymère thermoplastique réticulée, le procédé comprenant : une étape consistant à chauffer l'article moulé en mousse polymère thermoplastique réticulée à une température prédéterminée ; une étape consistant à appliquer une pression à l'article moulé en mousse polymère thermoplastique réticulée, qui est maintenu à la température prédéterminée, de manière à induire une déformation par compression de l'article moulé en mousse réticulée, et à mesurer la relaxation des contraintes de l'article moulé en mousse réticulée alors que la contrainte de compression de l'article moulé en mousse réticulée est maintenue à un niveau constant ; une étape consistant à déterminer un module de relaxation (Gc) en se basant sur la relaxation des contraintes ; et une étape consistant à calculer la densité de réticulation de la mousse polymère thermoplastique réticulée à partir du Gc en utilisant la formule suivante dans laquelle Gc est le module d'élasticité lorsque la contrainte de l'article moulé en mousse réticulée est à un niveau constant : n = Gc/RT (n : densité de réticulation, R : constante de gaz, T : température de mesure).
PCT/JP2011/068210 2010-08-06 2011-08-03 Procédé de mesure de la densité de réticulation d'un article moulé en mousse polymère thermoplastique réticulée et article moulé en mousse réticulée WO2012018140A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112557438A (zh) * 2020-11-11 2021-03-26 南方电网科学研究院有限责任公司 一种高压交流电缆绝缘用预交联料存储寿命检测方法
EP3855157A1 (fr) * 2020-01-21 2021-07-28 Samsung Electronics Co., Ltd. Appareil et procédé de mesure de densité de réticulation in situ et produit réticulé et son procédé de formation

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9874530B2 (en) * 2014-09-11 2018-01-23 Sumitomo Rubber Industries, Ltd. Method of measuring crosslink densities in sulfur-containing polymer composite material
CN104483235A (zh) * 2014-12-05 2015-04-01 浙江万马高分子材料有限公司 检测超高压电缆用可交联乙烯系聚合物链结构的方法
AU2015418967B2 (en) * 2015-12-28 2019-09-19 Asics Corporation Shock absorbing material, shoe sole member, shoe, and protective equipment for sports
JP2018080298A (ja) * 2016-11-18 2018-05-24 三和化工株式会社 ポリオレフィン系発泡体の製造方法、ポリオレフィン系発泡体
JP6487591B1 (ja) * 2017-09-07 2019-03-20 旭化成株式会社 超高分子量エチレン系重合パウダー、及び、超高分子量エチレン系重合パウダーを用いた成型体
KR102384286B1 (ko) 2018-06-22 2022-04-06 주식회사 엘지화학 폴리프로필렌 수지의 물성 평가 방법, 폴리프로필렌 부직포의 제조 방법, 및 폴리프로필렌 부직포
CN110308061B (zh) * 2019-08-14 2020-04-21 清华大学 基于三维结构的材料弹性模量和密度的测量方法和系统

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03213515A (ja) * 1990-01-18 1991-09-18 Kanebo Ltd 耐熱ポリウレタン弾性糸
JP2007238783A (ja) * 2006-03-09 2007-09-20 Mitsui Chemicals Inc 発泡体
JP2010077421A (ja) * 2008-08-29 2010-04-08 Sumitomo Chemical Co Ltd 架橋発泡成形用樹脂組成物、架橋発泡成形体および架橋発泡成形体の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5167742B2 (ja) * 2006-09-29 2013-03-21 住友化学株式会社 加圧発泡成形用樹脂組成物、加圧発泡成形体、加圧発泡成形体の製造方法、履き物用部材および履き物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03213515A (ja) * 1990-01-18 1991-09-18 Kanebo Ltd 耐熱ポリウレタン弾性糸
JP2007238783A (ja) * 2006-03-09 2007-09-20 Mitsui Chemicals Inc 発泡体
JP2010077421A (ja) * 2008-08-29 2010-04-08 Sumitomo Chemical Co Ltd 架橋発泡成形用樹脂組成物、架橋発泡成形体および架橋発泡成形体の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
THE SOCIETY OF POLYMER SCIENCE, NYUMON KOBUNSHI TOKUSEI KAISEKI, 10 June 1984 (1984-06-10), JAPAN, pages 199 - 209 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3855157A1 (fr) * 2020-01-21 2021-07-28 Samsung Electronics Co., Ltd. Appareil et procédé de mesure de densité de réticulation in situ et produit réticulé et son procédé de formation
US11692920B2 (en) 2020-01-21 2023-07-04 Samsung Electronics Co., Ltd. Apparatus and method for measuring in-situ crosslink density and crosslinked product and method of forming the same
CN112557438A (zh) * 2020-11-11 2021-03-26 南方电网科学研究院有限责任公司 一种高压交流电缆绝缘用预交联料存储寿命检测方法
CN112557438B (zh) * 2020-11-11 2022-05-20 南方电网科学研究院有限责任公司 一种高压交流电缆绝缘用预交联料存储寿命检测方法

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