WO2017170481A1 - Résine à base de polypropylène modifié et procédé de production de résine à base de polypropylène modifié - Google Patents

Résine à base de polypropylène modifié et procédé de production de résine à base de polypropylène modifié Download PDF

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WO2017170481A1
WO2017170481A1 PCT/JP2017/012533 JP2017012533W WO2017170481A1 WO 2017170481 A1 WO2017170481 A1 WO 2017170481A1 JP 2017012533 W JP2017012533 W JP 2017012533W WO 2017170481 A1 WO2017170481 A1 WO 2017170481A1
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polypropylene resin
modified polypropylene
extruder
modified
mass
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PCT/JP2017/012533
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English (en)
Japanese (ja)
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皓平 田積
道弘 林
哲朗 田井
翔太 遠藤
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積水化成品工業株式会社
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Priority to JP2018508032A priority Critical patent/JPWO2017170481A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms

Definitions

  • the present invention relates to a modified polypropylene resin and a method for producing the modified polypropylene resin.
  • polypropylene resins have been used as raw materials for various molded articles because of their excellent mechanical properties and chemical resistance.
  • a foam molded product obtained by thermoforming a polypropylene resin foam sheet is known.
  • this polypropylene resin foam sheet one having a single foam layer or one having a laminated structure in which a foam layer and a non-foam layer are laminated is known.
  • the term “foamed sheet” is used in the narrow sense and used in the former sense, and the latter is referred to as “laminated foamed sheet” or the like.
  • foam sheets and laminated foam sheets are conventionally produced by extrusion foaming, but polypropylene resins generally have crystallinity, so the viscosity and melt tension at the time of melting tend to be insufficient, and the foamed state is good. It is difficult to get things.
  • Patent Document 1 describes a method for obtaining a modified polypropylene resin having a property that the elongational viscosity measured in a molten state rapidly increases as the amount of strain increases (also referred to as “strain hardening”). Has been.
  • the modified polypropylene resin as described above exhibits a high melt tension at the time of heat melting, but may not exhibit sufficient fluidity.
  • An object of the present invention is to provide a modified polypropylene resin which exhibits high melt tension at the time of heat melting and exhibits high fluidity.
  • the present invention is a modified polypropylene resin which is a reaction product of a polypropylene resin and an aromatic vinyl monomer and has a higher melt tension than the polypropylene resin
  • the polypropylene resin Provides a modified polypropylene resin having a melt mass flow rate of 4.0 g / 10 min or more measured at a temperature of 230 ° C. and a nominal load of 2.16 kg.
  • the present invention provides a method for producing a modified polypropylene resin, in which an aromatic vinyl monomer is reacted with a polypropylene resin to produce a modified polypropylene resin having a higher melt tension than the polypropylene resin.
  • a process for producing a modified polypropylene resin using a polypropylene resin exhibiting a melt mass flow rate of 4.0 g / 10 min or more under the measurement conditions of a temperature of 230 ° C. and a nominal load of 2.16 kg is provided as the polypropylene resin. To do.
  • FIG. 1 is a schematic cross-sectional view of a laminated foamed sheet using a modified polypropylene resin according to an embodiment. Schematic showing the equipment structure for manufacturing the laminated foam sheet.
  • FIG. 3 is a detailed view of a broken line A portion in FIG. 2. The schematic perspective view which showed the instruments for measuring a gel fraction.
  • FIG. 1 is a schematic cross-sectional view of a polypropylene resin foam sheet. As shown in FIG. And foam layers 20 and 20 '.
  • a polypropylene resin foam sheet having one or more foamed layers and one or more non-foamed layers including the one shown in FIG. 1 and a polypropylene system having two or more foamed layers are included.
  • the resin foam sheet is referred to as a “laminated foam sheet” and is distinguished from a polypropylene resin foam sheet having a single foam layer. Therefore, in the following, unless otherwise specified, the term “laminated foam sheet” means that having a laminated structure as shown in FIG. 1, and the term “foam sheet” means a single foam layer. It is used as a term to mean the sheet.
  • the laminated foam sheet 1 includes the foam layer 10 and the non-foam layers 20 and 20 '.
  • the foam layer 10 is formed of a foam sheet produced by an extrusion foaming method.
  • the non-foamed layers 20 and 20 ′ are formed of a resin film produced by an extrusion method.
  • the laminated foam sheet 1 is a co-extruded product of the foam layer 10 and the non-foam layers 20 and 20 ′. That is, the laminated foamed sheet 1 is extruded in a state in which a polypropylene resin composition for producing an extruded foamed sheet and an extruded film is laminated in a confluence mold, and these are laminated and integrated from one die slit. It has been made.
  • the foamed layer 10 and the non-foamed layers 20, 20 ′ are formed of a polypropylene resin composition containing a modified polypropylene resin.
  • the first polypropylene resin composition that forms the foam layer 10 includes a modified polypropylene resin, and is further expanded. Contains ingredients for.
  • the second polypropylene resin composition that forms the non-foamed layers 20 and 20 ' also contains a modified polypropylene resin.
  • the first polypropylene resin composition that forms the foamed layer 10 and the second polypropylene resin composition that forms the non-foamed layers 20 and 20 ' are different even if they contain the same modified polypropylene resin. May be.
  • the modified polypropylene resin of this embodiment is produced by a specific modified polymer manufacturing method. First, the modified polypropylene resin and the production method thereof will be described.
  • the modified polypropylene resin of the present embodiment is a resin composition containing (A) a polypropylene resin, (B) an organic peroxide, and (C) an aromatic vinyl monomer (hereinafter also referred to as “raw material composition”). It was obtained by reacting.
  • the modified polypropylene-based resin of the present embodiment it is preferable to employ a resin whose phase angle obtained by frequency dispersion dynamic viscoelasticity measurement at 200 ° C. is 30 ° or more and 70 ° or less at a frequency of 0.01 Hz. In frequency dispersion dynamic viscoelasticity measurement, the influence of the viscosity term tends to appear in the low frequency region.
  • the modified polypropylene resin of the present embodiment has a small phase angle in the low frequency region and is less likely to cause “slip” between molecules. Therefore, the modified polypropylene resin of the present embodiment exhibits a moderate elongation when foamed to form a foamed layer, and it is possible to suppress the bubble film from becoming rapidly thinner as the bubble grows. Therefore, film breakage (bubble breakage) is prevented, which is advantageous for obtaining a foam sheet having a low open cell ratio.
  • the non-foamed layer is subject to a phenomenon such as tearing or opening due to stretching (hereinafter referred to as “resin running out”), and the foamed layer is exposed on the surface of the non-foamed layer. It is also advantageous to suppress the draw down when being extruded in a state of being formed and laminated and integrated from the die slit.
  • the phase angle is obtained as follows. (How to find the phase angle)
  • the dynamic viscoelasticity measurement is performed with a viscoelasticity measuring device PHYSICA MCR301 (manufactured by Anton Paar) and a temperature control system CTD450.
  • the modified polypropylene resin used as a sample is pressed under a condition of heating at a temperature of 200 ° C. for 5 minutes with a hot press machine to produce a disk sample having a diameter of 25 mm and a thickness of 3 mm.
  • the sample is set on a plate of a viscoelasticity measuring apparatus heated to a measurement temperature (200 ° C.), and heated and melted for 5 minutes in a nitrogen atmosphere.
  • the interval is crushed to 2.0 mm with a parallel plate having a diameter of 25 mm, and the resin protruding from the plate is removed. Furthermore, after reaching the measurement temperature ⁇ 1 ° C, after heating for 5 minutes, the strain is 5%, the frequency is 0.01 to 100 (Hz), the number of measurement points is 21 (5 points / digit), and the measurement temperature is 200 ° C. Then, dynamic viscoelasticity measurement is performed to measure the phase angle ⁇ (°). Measurement starts from the high frequency side (100 Hz). Then, the phase angle ⁇ at a frequency of 0.01 Hz is obtained.
  • the modified polypropylene resin not only exhibits the above phase angle.
  • at least one of the first polypropylene resin composition and the second polypropylene resin composition preferably both, exhibit a phase angle of 30 ° to 70 ° at a temperature of 200 ° C. and a frequency of 0.01 Hz. preferable.
  • the modified polypropylene resin contained in the first polypropylene resin composition and the second polypropylene resin composition is modified so as to exhibit a higher melt tension than the starting material (A) polypropylene resin. It is. Whether or not the modified polypropylene resin exhibits a higher melt tension than the polypropylene resin used as a raw material can be determined by comparing the melt tension at a temperature of 230 ° C., for example. Since a general polypropylene resin has a melt tension of less than 5 cN at 230 ° C., the melt tension measured at 230 ° C. is a value of 6 cN or more, as compared with the starting material (A) polypropylene resin. Those exhibiting can be regarded as modified polypropylene resins.
  • the modified polypropylene resin preferably has a melt tension at 230 ° C. of 6 cN or more, more preferably a melt tension at 230 ° C. of 10 cN or more, and a melt tension at 230 ° C. of 15 cN or more. Is particularly preferred. However, if the melt tension of the modified polypropylene resin is excessively high, the load on the extruder may be increased when the first polypropylene resin composition or the second polypropylene resin composition is extruded. Therefore, the value at 230 ° C. is preferably 30 cN or less, and more preferably 28 cN or less.
  • the melt tension is measured using a twin-bore capillary rheometer Rheological 5000T (manufactured by Chiast, Italy). That is, after filling the measurement sample resin in a 15 mm diameter barrel heated to the test temperature and preheating for 5 minutes, the piston descending speed from the capillary die (diameter 2.0 mm, length 20 mm, inflow angle flat) of the above measuring device While holding (0.1546 mm / s) constant and extruding into a string, the string was passed through a tension detection pulley located 27 cm below the capillary die, and then using a winding roll, The winding speed is gradually increased at an initial speed of 8.7 mm / s and an acceleration of 12 mm / s 2 , and the average of the maximum value and the minimum value immediately before the string-like material is cut is defined as the melt tension of the sample. . When there is only one maximum point on the tension chart, the maximum value is taken as the melt tension.
  • the modified polypropylene-based resin is melted in order to reduce the load on the extruder during extrusion, to exhibit good foamability in the foamed layer 10, and to prevent the non-foamed layers 20 and 20 'from being out of resin. It is preferable that a mass flow rate (MFR) shows a predetermined value. More specifically, the modified polypropylene resin preferably has an MFR of 0.5 g / 10 min or more, more preferably 0.7 g / 10 min or more, and particularly preferably 1.0 g / 10 min or more. preferable. In forming a foamed layer having excellent closed cell properties (low open cell rate), the MFR of the modified polypropylene resin is preferably 0.7 g / 10 min or more.
  • the MFR of the modified polypropylene resin is preferably 5.0 g / 10 min or less. More preferably, it is 0 g / 10 min or less.
  • the MFR of the modified polypropylene resin can be measured based on the method B of JIS K7210: 1999 “Plastics—Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics”. It can be measured at a temperature of 230 ° C. and a nominal load of 2.16 kg. More specifically, MFR is measured as follows. When the measurement object is a pellet, it is used as it is as a measurement sample.
  • the foam sheet is pelletized using a pelletizer “Hand Truda Model PM-1” manufactured by Toyo Seiki Seisakusho Co., Ltd. as a measurement sample.
  • the cylinder temperature at the time of producing a pellet from a foam sheet using a pelletizer shall be 220 degreeC, and the waiting time from a sample filling to the start of extrusion shall be 2.5 minutes.
  • the melt mass flow rate (MFR) is a semi-auto melt indexer 2A manufactured by Toyo Seiki Seisakusho Co., Ltd. Method Measured by “b) Method of measuring time for piston to move a predetermined distance” described in method B.
  • the measurement conditions are a sample amount of 3 to 8 g, a preheating time of 270 seconds, a load hold time of 30 seconds, a test temperature of 230 ° C., a test load of 21.18 N, and a piston moving distance (interval) of 4 mm.
  • the number of tests is 3 times, and the average value is the value of melt mass flow rate (g / 10 min).
  • the starting material (A) polypropylene resin preferably has a predetermined melting property.
  • (A) Polypropylene resin is a polymer obtained by polymerizing a propylene monomer.
  • Examples of the (A) polypropylene resin to be contained in the raw material composition for obtaining the modified polypropylene resin include a homopolymer of a propylene monomer and a copolymer of a propylene monomer and another monomer.
  • the content of propylene monomer is preferably 50% by mass or more, and the content of propylene monomer is more preferably 80% by mass or more. The content of is particularly preferably 90% by mass or more.
  • the copolymerization may be random copolymerization or block copolymerization.
  • the component other than the propylene monomer is preferably at least one selected from the group consisting of an ethylene monomer and an ⁇ -olefin monomer having 4 to 8 carbon atoms.
  • -More preferably one or more of butene monomers.
  • polypropylene resins include propylene homopolymers, propylene random polymers, and propylene block polymers.
  • the polypropylene resin is preferably a homopolymer of a propylene monomer, and is preferably a propylene homopolymer.
  • the modified polypropylene resin In order for the modified polypropylene resin to exhibit a high MFR value, it is preferable to employ (A) a polypropylene resin that exhibits a high MFR.
  • Polypropylene resin used as a general foam sheet forming material has an MFR of about 1 g / 10 min or less, but as a polypropylene resin as a starting material for the modified polypropylene resin, melt mass flow rate (MFR) is 4 It is preferable that it is 0.0 g / 10 min or more.
  • MFR of the polypropylene resin is more preferably 4.0 g / 10 min or more and 20.0 g / 10 min or less, and particularly preferably 7.0 g / 10 min or more and 18.0 g / 10 min or less.
  • the first polypropylene resin showing an MFR of 4.0 g / 10 min or more and the second polypropylene resin having an MFR of less than 4.0 g / 10 min are used in combination. It is preferable.
  • the first polypropylene resin is preferably selected from those showing an MFR of 4.0 g / 10 min or more and 20 g / 10 min or less, although it shows an MFR of 7.0 g / 10 min or more and 18.0 g / 10 min or less. More preferably, it is selected from among them.
  • the second polypropylene resin having an MFR lower than that of the first polypropylene resin is preferably selected from those showing an MFR of 0.1 g / 10 min or more and less than 4.0 g / 10 min. More preferably, it is selected from those showing an MFR of 10 min or more and less than 4.0 g / 10 min.
  • the first polypropylene resin and the second polypropylene resin can be blended so that the mass ratio (first PP / second PP) is 90/10 to 10/90, for example.
  • the mixed resin obtained by mixing the plurality of polypropylene resins preferably has an MFR of 4.0 g / 10 min or more.
  • the MFR of the mixed resin is, for example, blending a polypropylene resin in the same proportion as that contained in the starting material, and melt-mixing the blended polypropylene resin to prepare a measurement sample. It can be determined by measuring.
  • the raw material composition has a mass percentage of the first polypropylene resin in the total value of the mass of the first polypropylene resin and the mass of the second polypropylene resin, a 1 (%), the second polypropylene
  • the mass percentage of the system resin is a 2 (%), the melt mass flow rate value of the first polypropylene resin is A 1 (g / 10 min), and the melt mass flow rate value of the second polypropylene resin is A 2 ( g / 10 min), it is preferable that at least the following relational expression (x) is satisfied.
  • the modified polypropylene resin of this embodiment uses a polypropylene resin having a high MFR as a starting material, excellent strain curability can be exhibited even after passing through an extruder.
  • the laminated foamed sheet not only has the strain-hardening property in the initial state of the modified polypropylene resin, but also can be in a good foamed state because the modified polypropylene-based resin exhibits strain-hardening properties even after passing through the extruder. .
  • the modified polypropylene resin exhibits strain-hardening properties when measured at a constant strain rate of 200 ° C. and a constant strain rate of 1.0 / sec after passing through an extruder,
  • the measurement result of uniaxial extensional viscosity is expressed by a logarithmic graph in which the axis is the logarithm of the amount of strain ( ⁇ ) (log ( ⁇ )) and the vertical axis is the logarithm of the extensional viscosity ( ⁇ ) (log ( ⁇ ))
  • the slope of the graph within the range of the strain amount of 1 to 3 is 1.0 or more.
  • the slope of the graph within the range of strain 1 to 3 in principle means that the graph is linearly approximated by the least square method between strains 1 to 3. This means the slope of this straight line.
  • the graph ends between strains 1 and 3 due to cutting of the stretched resin before the strain amount becomes 3 exceptionally, from the strain amount 1 to the above graph A straight line approximation is performed up to the end point by the least square method, and the gradient is determined as “the gradient of the graph within the range of strain 1 to 3”.
  • the slope of the graph shown by the modified polypropylene resin of this embodiment is preferably 1.1 or more, and more preferably 1.2 or more.
  • the slope of the graph is usually 4 or less, preferably 3 or less, more preferably 2.5 or less, and still more preferably 1.6 or less.
  • the term “after passing through an extruder” in the present specification means a state after being extruded by “Lab Plast Mill (trade name)” manufactured by Toyo Seiki Seisakusho Co., Ltd. More specifically, the main screw (model: 4M150) manufactured by Toyo Seiki Seisakusho is equipped with a single screw extruder (model: D2020 (caliber: 20mm, L / D: 20), standard screw (one full flight). ))) Is attached, and the temperatures of the three zones of the single screw extruder are set to 210 ° C., 190 ° C., and 190 ° C. in order from the upstream side to the downstream side in the extrusion direction, and the tip mold temperature is set to 180 ° C.
  • the rotation speed of the screw is fixed so that the discharge amount becomes 1 kg / h, and the state after passing through the “lab plast mill” is referred to as “after passing through the extruder” in this specification. It is determined as a state.
  • the measurement of the uniaxial extensional viscosity was performed by supplying the modified polypropylene resin to the “laboplast mill” set as described above and extruding it into a strand shape, and water at 20 ° C. was added to the strand-shaped sample. It can be obtained by passing through a 1 m water tank and cooling, cutting the cooled sample to produce a rod-shaped pellet having a length of about 4 mm.
  • the value of the uniaxial elongation viscosity after passing through the extruder of the modified polypropylene resin can be measured.
  • the value of the uniaxial elongation viscosity of the modified polypropylene resin after passing through the extruder can be measured under the following conditions.
  • the uniaxial elongation viscosity can be measured under the following conditions.
  • ⁇ Uniaxial elongation viscosity measurement conditions Uniaxial extensional viscosity measurement is performed with a viscoelasticity measuring apparatus “PHYSICA MCR301” (manufactured by Anton Paar) and a temperature control system “CTD450”.
  • the modified polypropylene resin to be measured is pressed with a hot press machine at a temperature of 190 ° C. for 5 minutes to produce a strip sample having a width of 10 mm and a thickness of about 0.8 mm.
  • this strip-shaped sample is cut out to have a length of 20 to 25 mm to obtain a test piece.
  • a test piece is set on a uniaxial extensional viscosity measuring jig (SER2) heated to 200 ° C., and after waiting for 10 seconds at a temperature of 200 ° C. ⁇ 0.5 ° C. in a nitrogen atmosphere, strain is applied.
  • the uniaxial extensional viscosity is measured at a speed of 1.0 / sec.
  • the measurement point interval is set to “obtain measurement point interval logarithmically”, and the start is 0.01 sec and the end is 26 sec.
  • the measurement point is 200.
  • the measurement results are as follows: the vertical axis is the common logarithm value (log ( ⁇ )) of elongational viscosity ( ⁇ : Pa ⁇ s), and the horizontal axis is the common logarithm value (log ( ⁇ )) of strain ( ⁇ : s / s).
  • the graph is a logarithmic axis graph. Is linearly approximated by the method of least squares, and the inclination of the approximated straight line is obtained.
  • modified polypropylene resin in which the slope in the uniaxial elongation viscosity graph is 1.0 or more after passing through the extruder include those having a branched structure in the molecular chain. That is, the modified polypropylene resin before passing through the extruder (hereinafter also referred to as “initial-mPP”) has a branched molecular structure in this embodiment.
  • the “initial-mPP” those having a large number of branches and being easily entangled with molecular chains are preferable.
  • a modified polypropylene resin with few branches is easily entangled by molecular chains due to shear applied in the extruder, and the strain hardenability after passing through the extruder is likely to be greatly reduced as compared with that before passing through the extruder. If an attempt is made to produce a laminated foam sheet by an extrusion foaming method using this type of modified polypropylene resin, the strain-hardening property of the modified polypropylene resin is already lost when it is extruded from the die slit, and good foaming is achieved. There is a possibility that a laminated foam sheet in a state cannot be obtained.
  • a modified polypropylene resin having a large number of branches and easily forming entanglement of molecular chains can maintain good strain hardening even after extrusion.
  • a high MFR as described above is used as a polypropylene resin having a linear molecular structure (hereinafter also referred to as “linear PP”) used as a starting material. It is advantageous to employ what is shown.
  • the main chain of the linear PP is cleaved by ⁇ -cleavage, and the cleaved molecules are bonded to other molecules to form long chain branches. Therefore, if the linear PP used as the starting material for the modified polypropylene resin has a large molecular weight, if a large amount of vinyl monomer or radical generator is added, the melt viscosity of the resin becomes too high and the number of branches may be increased too much. It may not be possible. On the other hand, a linear PP having a low molecular weight and a high MFR does not increase until the melt viscosity becomes a practical problem even if many branches are introduced. Therefore, in order to obtain a modified polypropylene-based resin exhibiting good strain hardening even after passing through the extruder, it is preferable to employ linear PP having a high MFR as a starting material.
  • the MFR of the polypropylene resin used as a starting material for the modified polypropylene resin is more preferably 5.0 g / 10 min or more, and even more preferably 7.0 g / 10 min or more.
  • the MFR of the polypropylene resin is preferably 20.0 g / 10 min or less, and more preferably 18.0 g / 10 min or less.
  • the MFR of the polypropylene resin (A), which is the starting material of the modified polypropylene resin, is JIS K7210: 1999 “Plastic / thermoplastic melt mass flow rate (MFR) and melt, similarly to the MFR of the modified polypropylene resin. Based on Method B of “Volume Flow Rate (MVR) Test Method”, measurement can be performed under conditions of a temperature of 230 ° C. and a nominal load of 2.16 kg.
  • the modified polypropylene-based resin after passing through an extruder, has a uniaxial elongational viscosity of 0.25 or more when measured at a temperature of 180 ° C. and a strain rate of 0.1 to 8.5 (sec ⁇ 1 ). It is preferable to show a branching index (MBI).
  • MBI branching index
  • the multi-branch index is a semi-logarithmic graph in which the horizontal axis is the logarithm of the strain rate (v) (log (v)) and the vertical axis is the strain hardening degree (SHI). This means the slope of the graph when the measurement result is expressed.
  • the strain hardening degree (SHI) is a logarithmic graph in which the horizontal axis is the logarithm of the strain amount ( ⁇ ) (log ( ⁇ )) and the vertical axis is the logarithm of the extensional viscosity ( ⁇ ) (log ( ⁇ )).
  • the “slope of the graph” when obtaining the multi-branch index (MBI) and the strain hardening degree (SHI) means the slope of this straight line when linearly approximated by the method of least squares.
  • the modified polypropylene resin of this embodiment when the uniaxial extensional viscosity is measured at a temperature of 180 ° C. and a strain rate of 0.1 to 8.5 (sec ⁇ 1 ) after passing through an extruder, any rate is obtained. It is preferable to employ a material exhibiting strain hardening property. Further, the multi-branch index (MBI) of the modified polypropylene resin is usually 0.6 or less, and preferably 0.5 or less.
  • Uniaxial extensional viscosity measurement when determining the strain hardening degree (SHI) can be carried out using a viscoelasticity measuring device “PHYSICA MCR301” (manufactured by Anton Paar) and a temperature control system “CTD450”.
  • PHYSICA MCR301 manufactured by Anton Paar
  • CCD450 temperature control system
  • the modified polypropylene resin to be measured is pressed at a temperature of 220 ° C. for 6 minutes with a hot press machine to produce a strip-shaped sample having a width of 10 mm and a thickness of about 0.8 mm.
  • this strip-shaped sample is cut out to have a length of 20 to 25 mm to obtain a test piece.
  • a test piece is set on a uniaxial extensional viscosity measuring jig (SER2) heated to 180 ° C., and after waiting for 10 seconds under a nitrogen atmosphere at 180 ° C. ⁇ 0.5 ° C., strain is applied.
  • the measurement point interval is set to “obtain measurement point interval logarithmically”, and the start is 0.01 sec and the end is 26 sec.
  • the measurement point is 200.
  • the multi-branch index (MBI) can be obtained as follows. First, in the graph in which the horizontal axis is the logarithm of log strain ( ⁇ : s / s) (log ( ⁇ )) and the vertical axis is the logarithm of extension viscosity ( ⁇ : Pa ⁇ s) (log ( ⁇ )), The measurement result of the uniaxial extensional viscosity carried out at a strain rate of 0.1 (s ⁇ 1 ) is represented. The graph is linearly approximated by a least square method between the strain amount 1 and the strain amount 3, and the slope (degree of strain hardening ( SHI 0.1 )) is determined.
  • the strain rate was then changed to 0.3 (s ⁇ 1 ), 1.0 (s ⁇ 1 ), 3.0 (s ⁇ 1 ), and 8.5 (s ⁇ 1 ), respectively, and the above Measurements are made to determine the strain hardening degree (SHI 0.3 , SHI 1.0 , SHI 3.0 , SHI 8.5 ) for each.
  • the above results are plotted on a graph in which the vertical axis is the strain hardening degree (SHI) and the horizontal axis is the logarithm of the strain rate (log (v)).
  • the polypropylene resin used as a starting material is preferably one having a relatively low molecular weight and high melt mass flow rate (MFR). That is, the melt mass flow rate (MFR) of the polypropylene resin used as a starting material is preferably 4.0 g / 10 min or more in order to obtain a modified polypropylene resin exhibiting a multi-branch index as described above. It is more preferably 0.0 g / 10 min or more, and further preferably 7.0 g / 10 min or more.
  • the MFR of the polypropylene resin is preferably 20.0 g / 10 min or less, and more preferably 18.0 g / 10 min or less.
  • the modified polypropylene-based resin not only exhibits the above multi-branching index (MBI) but also can reduce the gel content because the starting material has a high MFR.
  • MBI multi-branching index
  • the gel contained in the modified polypropylene resin may cause coarse bubbles to be formed in the foamed layer, or cause the resin to run out or form minute protrusions in the non-foamed layer.
  • the modified polypropylene resin of the present embodiment uses a plurality of polypropylene resins having different MFRs as a starting material as described above, so that the gel fraction value is, for example, 1.0% by mass or less.
  • the value of the gel fraction can be 0.6% by mass or less, particularly preferably 0.3% by mass or less.
  • a mesh wire net containing a sample is placed on the slat and 80 ml of xylene is added. After stirring for 3 hours at 130 ° C. and 80 rpm using a heating and agitation driver apparatus (Aswan HDBS-6), the 200-mesh wire mesh in the tall beaker was taken out with tweezers and washed in 80 mL of xylene heated to 130 ° C. Remove deposits on the side of the wire mesh. Thereafter, the resin insoluble matter on the wire mesh is naturally dried in a draft to evaporate xylene, and finally the resin insoluble matter is dried together with the wire mesh at 120 ° C. for 2 hours in a constant temperature dryer.
  • the amount of gel contained in the modified polypropylene resin is not limited to using a plurality of polypropylene resins having different MFR as a starting material, but also a monomer that reacts with the starting material and a radical that reacts the monomer with the polypropylene resin. It can also be reduced by selecting the type of generator and limiting the amount.
  • an organic peroxide is used as the radical generator, and an aromatic vinyl monomer is used as the monomer.
  • the (B) organic peroxide of this embodiment has a hydrogen abstraction ability with respect to a polypropylene resin, and is not particularly limited.
  • hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxide examples thereof include oxydicarbonate, peroxyketal, and ketone peroxide.
  • hydroperoxide examples include permethane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.
  • dialkyl peroxide examples include dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3. .
  • peroxy ester examples include t-butyl peroxy 2-ethylhexyl carbonate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxybenzoate, t-butyl peroxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, 2,5-dimethyl2,5-di (benzoylperoxy) hexane, and t-butylperoxyisopropyl monocarbonate Etc.
  • diacyl peroxide examples include dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, and di (3-methylbenzoyl) peroxide.
  • peroxydicarbonate examples include di (2-ethylhexyl) peroxydicarbonate and diisopropyl peroxydicarbonate.
  • the organic peroxide (B) in this embodiment is preferably a peroxyester, diacyl peroxide, or peroxydicarbonate.
  • the organic peroxide preferably has a structure represented by the following general formula (X).
  • R 1 represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted alkoxy group
  • R 2 represents a monovalent organic group
  • R 1 when “R 1 ” is an alkoxy group, “R 1 ” is an alkyl group having a branched structure having 3 to 8 carbon atoms (for example, isopropyl, t-butyl, An alkoxy group in which an oxygen atom is bonded to t-hexyl, 2-ethylhexyl and the like is preferable.
  • R 1 is other than an alkoxy group having an oxygen atom bonded to 2-ethylhexyl
  • the oxygen atom is preferably bonded to a secondary carbon or a tertiary carbon, and is represented by the following general formula (Y) It preferably has a structure.
  • R 11 and R 12 are either a methyl group, the other is a hydrogen atom, and “R 14 ” represents a linear alkyl group having 1 to 6 carbon atoms; 13 "represents secondary carbon or tertiary carbon.)
  • R 1 is either a substituted or unsubstituted phenyl group
  • R 1 is an unsubstituted phenyl group or a substituted phenyl in which one hydrogen atom is substituted with a methyl group It is preferable that
  • R 2 also preferably has a bulky structure such as branched alkyl or phenyl. Specifically, it preferably has a structure represented by the following general formula (Z).
  • R 21 in the formula represents either a linear alkyl group having 1 to 6 carbon atoms or a monovalent organic group having a phenyl group.
  • Examples of the organic peroxide having the structure represented by the general formula (X) include t-butyl peroxy 2-ethylhexyl carbonate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t -Hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, diisopropylperoxydicarbonate, etc. .
  • the content of the organic peroxide (B) relative to 100 parts by mass of the (A) polypropylene resin is 0.1 parts by mass or more and 1.5 parts by mass or less. Preferably there is.
  • the content of (B) organic peroxide when the content of (B) organic peroxide is too small, the reactivity of the raw material composition becomes low, so that a good modifying effect may not be exhibited.
  • the modified polypropylene resin of this embodiment if the content of (B) organic peroxide is excessive, the decomposition reaction of the polypropylene resin is likely to occur during melt-kneading, so the elastic component becomes small and good modification is achieved. The effect may not be demonstrated.
  • the raw material composition does not control the reaction conditions during melt-kneading with high accuracy.
  • a modified polypropylene resin having excellent melt tension can be produced.
  • the content of (B) organic peroxide with respect to 100 parts by mass of (A) polypropylene resin is 0.3.
  • the amount is preferably at least part by mass, and preferably at most 1.0 part by mass.
  • the (C) aromatic vinyl monomer is a component that acts as a crosslinking agent that chemically bonds to the (A) polypropylene resin to form a branched structure and to crosslink the polypropylene resins.
  • the (C) aromatic vinyl monomer to be contained in the raw material composition may be one type or two or more types.
  • aromatic vinyl monomer examples include styrene; methyl styrene such as o-methyl styrene, m-methyl styrene, p-methyl styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, dimethyl styrene, and trimethyl styrene; ⁇ -chlorostyrene.
  • the content of the aromatic vinyl monomer (C) in the raw material composition is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (A) polypropylene resin. If the content of the aromatic vinyl monomer (C) is too small in the modified polypropylene resin, there is a possibility that the branched and crosslinked structure is not sufficiently formed in the melt-kneading. In addition, if the content of the aromatic vinyl monomer (C) is too small, the decomposition of the resin by the peroxide is also insufficiently suppressed, so that a good reforming effect may not be exhibited.
  • the modified polypropylene resin tends to be unreacted with a part of the (C) aromatic vinyl monomer by melt kneading. Therefore, if the content of the aromatic vinyl monomer (C) is excessive, the modified polypropylene resin may contain a large amount of oligomers or may have a problem of cloudiness due to microphase separation or the like. . As a result, the influence of the elastic component is greatly reflected in the properties of the modified polypropylene resin, and the modified polypropylene resin is not good and may not exhibit a good modifying effect.
  • the quality of the aromatic vinyl monomer (C) in the raw material composition is 0.1 parts by mass or more and 10 parts by mass or less, the quality can be improved without controlling the reaction conditions at the time of melt-kneading with high accuracy.
  • Quality polypropylene resin can be produced.
  • the modified polypropylene resin thus obtained is effective for producing a laminated foam sheet having a foam layer having a low open cell ratio.
  • the raw material composition may contain a monomer other than the aromatic vinyl monomer.
  • the monomer include ethylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3,4-dimethyl-1-butene, ⁇ -olefin monomers such as heptene, 3-methyl-1-hexene, 1-octene and 1-decene; cycloolefin monomers such as cyclopentene and norbornene; 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, Diene monomers such as 1,4-hexadiene, methyl-1,4-hexadiene, 7-methyl-1,6-octadiene; chlorine-based monomers such as vinyl chloride and vinylidene chloride; acrylonitrile, acrylic acid, methacrylic acid, maleic acid, Ethyl acrylate, buty
  • the raw material composition preferably contains (D) a radical scavenger to control the reactivity.
  • (D) Use of the radical scavenger is effective for increasing the melt tension of the modified polypropylene resin. That is, the radical scavenger (D) is effective in obtaining a resin foam having a good appearance using a modified polypropylene resin.
  • the radical scavenger is capable of reacting with alkyl radical species.
  • the radical scavenger can be bonded to the aromatic vinyl monomer after being bonded to the alkyl radical.
  • a radical scavenger only 1 type may be used and 2 or more types may be used together.
  • radical scavenger examples include quinone compounds (quinones), naphthoquinone compounds (naphthoquinones), phenothiazine compounds (phenothiazines), and the like.
  • Examples of the quinone compound include p-benzoquinone, p-naphthoquinone, 2-t-butyl-p-benzoquinone, and 2,5-diphenyl-p-benzoquinone.
  • Examples of the naphthoquinone compound include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, vitamin K, and the like.
  • Examples of the phenothiazine compound include phenothiazine, bis- ( ⁇ -methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, and bis- ( ⁇ -dimethylbenzyl) phenothiazine.
  • the content of the (D) radical scavenger with respect to 100 parts by mass of the (A) polypropylene resin is preferably 0.005 parts by mass or more, more preferably 0.05 parts by mass or more. Further, the content of the (D) radical scavenger with respect to 100 parts by mass of (A) polypropylene resin is preferably 1 part by mass or less.
  • the content of the radical scavenger is not less than the lower limit and not more than the upper limit, the melt tension of the modified polypropylene resin is effectively increased, and the appearance of the foam is further improved.
  • an additive is suitably used according to various objectives, and is not specifically limited.
  • the additive include a weather resistance stabilizer, an antistatic agent, an antioxidant, a deodorant, a light stabilizer, a crystal nucleating agent, a pigment, a lubricant, imparting slipperiness or anti-blocking property.
  • examples thereof include a surfactant for the purpose of imparting, an inorganic filler, and a dispersibility improver for improving the dispersibility of the inorganic filler.
  • the dispersibility improver include higher fatty acids, higher fatty acid esters, and higher fatty acid amides.
  • the (E) additive may be contained in the raw material composition before melt-kneading or at the time of melt-kneading. In addition, the additive (E) may be added after melt-kneading and contained in the modified polypropylene resin. (E) As for an additive, only 1 type may be used and 2 or more types may be used together.
  • the organic peroxide is contained in an amount of 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the polypropylene resin, and the aromatic vinyl monomer
  • it can be easily obtained by melt-kneading a raw material composition containing 0.1 to 10 parts by mass of the aromatic vinyl monomer with respect to 100 parts by mass of the polypropylene resin.
  • the modified polypropylene resin according to the present embodiment is suitable for forming a foam molded article having a good appearance and excellent strength.
  • the modified polypropylene resin according to the present embodiment is foamed, it is difficult for foam breakage to occur inside, and it is possible to obtain a foamed molded article having a good appearance with a low open cell ratio.
  • the modified polypropylene resin according to the present embodiment has an advantage that a foamed sheet having a low open cell ratio is easily obtained.
  • the modified polypropylene resin according to the present embodiment has a low gel fraction and exhibits good flowability, and is suitable not only for forming a foam layer but also for forming a non-foam layer.
  • Method for producing modified polypropylene resin for example, (A) 100 parts by mass of polypropylene resin, (B) 0.1 to 1.5 parts by mass of organic peroxide, and (C) aromatic vinyl
  • a method of obtaining a modified polypropylene resin by melting and kneading a raw material composition containing 0.1 to 10 parts by mass of a monomer can be employed. At the time of melt kneading the raw material composition, it is preferable to control the heating temperature in order to bring the raw material composition into a good molten state. The raw material composition reacts by heating during melt kneading.
  • the organic peroxide generates a radical by the heating, and the radical attacks the hydrogen bonded to the tertiary carbon of the polypropylene resin to form an alkyl radical.
  • ⁇ -cleavage occurs and molecular cleavage of the polypropylene resin occurs, but in this embodiment, the aromatic vinyl monomer is bonded to the site to form a branched structure (crosslinked structure).
  • the aromatic vinyl monomer is obtained by mixing (A) a polypropylene resin and (B) an organic peroxide from the viewpoint of making the addition effect remarkable, and then obtaining the mixture. It is preferable to add to. However, (A) polypropylene resin, (B) organic peroxide, and (C) aromatic vinyl monomer may be mixed together.
  • (D) The radical scavenger may be added before (C) the aromatic vinyl monomer is added, or may be added after (C) the aromatic vinyl monomer is added, and mixed together with other components. May be.
  • the additive may be added before adding the (C) aromatic vinyl monomer, or may be added after adding the (C) aromatic vinyl monomer, and is mixed together with other components. May be.
  • melt kneading mixing of a raw material composition can be implemented using general apparatuses, such as a kneader, a Banbury mixer, and an extruder.
  • melt-kneading the raw material composition it is preferable to use an extruder.
  • the raw material composition is supplied to an extruder and subjected to a crosslinking reaction in the extruder to form a modified polypropylene resin, and the modified polypropylene resin is extruded from the extruder.
  • a modified polypropylene resin is efficiently obtained by continuously supplying the raw material composition to an extruder and continuously extruding the modified polypropylene resin from the extruder.
  • the extruder examples include a single screw extruder and a twin screw extruder.
  • the said extruder can be used for manufacture of a modified polypropylene resin as a single or a tandem-type extruder connected in plural.
  • a twin screw extruder is preferable from the viewpoint of further increasing dispersibility and reactivity of other components with respect to the polypropylene resin as the base resin.
  • carbon dioxide is supplied to an extruder, carbon dioxide is added to the kneaded material melt-kneaded, and the kneaded material added with carbon dioxide is further melt-kneaded for a certain period of time. It is preferable to discharge the gas containing carbon from the kneaded product.
  • a reaction step of reacting a polymer and a monomer by melt kneading and a carbon dioxide addition step of adding carbon dioxide to a kneaded product obtained by melt kneading in the reaction step It is preferable to carry out a degassing step of discharging a gas containing carbon dioxide from the kneaded material to which carbon dioxide has been added.
  • the carbon dioxide addition step is preferably carried out with the same extruder as the reaction step or another extruder connected to the extruder. That is, in the former case, for example, a carbon dioxide supply point is provided near the exit of the extruder, and (A) a polypropylene resin, (B) an organic peroxide, (C) upstream of the carbon dioxide supply point. ) It can be carried out using an extruder provided with a material supply point for a raw material composition such as an aromatic vinyl monomer.
  • a tandem extruder in which an upstream extruder and a downstream extruder are connected is used, a polypropylene resin is reformed in the upstream extruder, and carbon dioxide is added in the downstream extruder. And further melt kneading.
  • the degassing step may be performed simply by discharging the kneaded material from an extruder, and using an extruder provided with a vent mechanism, carbon dioxide is discharged from the kneaded material before discharging the kneaded material by the vent mechanism. You may make it discharge.
  • the carbon dioxide addition step and the degassing step the remaining monomer without being consumed in the reaction in the reaction step, the oligomer that is a decomposition product of the polymer, and the alcohol formed by decomposing the organic peroxide , Ketones and the like can be discharged together with carbon dioxide, and a modified polypropylene resin with reduced volatile organic substances can be obtained.
  • the modified polypropylene resin is preferably pelletized once for use in forming a foamed layer or a non-foamed layer. Therefore, in the method for producing a modified polypropylene resin according to the present embodiment, the kneaded material is extruded into a sheet shape or a strand shape from a die attached to the tip of the extruder, and then the modified polypropylene resin sheet or the modified polypropylene resin strand. It is preferable that the sheet or strand is pelletized with a pelletizer.
  • the MFR of the polypropylene resin used as a starting material for the modified polypropylene resin in order to obtain a uniform strand is more preferably 5.0 g / 10 min or more. Preferably, it is more preferably 7.0 g / 10 min or more.
  • the kneaded material is extruded into a strand shape from a die attached to the tip of the extruder, and the strand is intermittently cut at the outlet of the die to be pelletized. May be.
  • the method for producing a modified polypropylene resin of this embodiment since the kneaded material is discharged in a shape having a large specific surface area such as a sheet or a strand, in the method for producing a modified polypropylene resin of this embodiment, carbon dioxide and volatile organic matter are produced from this sheet or strand. Can be efficiently discharged, and a modified polypropylene resin with less volatile organic substances can be obtained. That is, the deaeration process in this embodiment can be performed by a method in which gas is discharged from the kneaded material by spontaneous release when the kneaded material is extruded from the extruder.
  • the carbon dioxide addition step is preferably carried out under conditions where carbon dioxide is in a supercritical state in that a modified polypropylene resin with reduced volatile organic substances is easily obtained. It is preferable to bring carbon into a supercritical state. At this time, when the amount of carbon dioxide added to the kneaded product is larger, the amount of volatile organic substances contained in the modified polypropylene resin can be reduced. However, excessive addition of carbon dioxide may cause foaming in the modified polypropylene resin sheet or the modified polypropylene resin strand in the deaeration process. The foamed modified polypropylene-based resin pellet can cause the formation of coarse bubbles in the foam layer when the laminated foam sheet is produced by the coextrusion method, or cause the resin to break in the non-foam layer.
  • the amount of carbon dioxide used in the carbon dioxide addition step is 1.0 part by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the produced modified polypropylene resin. More preferably, the content is 2.0 parts by mass or more and 3.0 parts by mass or less.
  • a mixed gas containing a small amount of a hydrocarbon having a carbon number of 5 or less such as methane, ethane, or propane, or nitrogen (for example, 95% by mass or more of CO 2 and 5% by mass or less).
  • the carbon dioxide addition step may be performed using a mixed gas containing other gas). When such a mixed gas is used, the ratio is preferably within the above range.
  • the carbon dioxide addition step may be performed after pelletization.
  • carbon dioxide after pelletization may be performed.
  • An addition step may be performed.
  • the carbon dioxide addition step for the pelletized modified polypropylene resin includes, for example, placing the modified polypropylene resin pellets in a pressure vessel and introducing carbon dioxide in a supercritical state into the pressure vessel. It can be carried out by such a method that the pellet is impregnated with carbon dioxide in a supercritical state.
  • the degassing step can be performed by discharging carbon dioxide from the pressure vessel after a predetermined time has elapsed, and reducing the pressure vessel to atmospheric pressure or lower as necessary.
  • the modified polypropylene resin thus obtained can be used as a raw material for the laminated foam sheet of the present embodiment (first polypropylene resin composition, second polypropylene resin composition) as it is or blended with other polymer components. ).
  • an unmodified polypropylene resin is preferable.
  • the polypropylene resin include those exemplified above as starting materials for the modified polypropylene resin.
  • a soft resin obtained by a multistage polymerization method is preferable.
  • the polypropylene resin includes a first stage in which homopolymerization of propylene or random copolymerization of propylene and ethylene, and ethylene and one or more ⁇ -olefins having 3 or more carbon atoms after the first stage. What is obtained through at least two steps of the second step of carrying out copolymerization is preferred.
  • the modified polypropylene resin and the other resin are, for example, 9: The mass ratio is preferably 1 to 1: 9 (modified polypropylene resin: other resin).
  • the first polypropylene resin composition and the second polypropylene resin composition are also subjected to frequency dispersion dynamics at 200 ° C. in the same manner as the modified polypropylene resin. It is preferable that the phase angle obtained by viscoelasticity measurement is 30 ° or more and 70 ° or less at a frequency of 0.01 Hz.
  • the melt mass flow rate (MFR1) of the first polypropylene resin composition and the melt mass flow rate (MFR2) of the second polypropylene resin composition may have the relationship shown in (y) below. preferable.
  • (MFR1) ⁇ (MFR2) (y) (Here, “MFR1” means the melt mass flow rate of the first polypropylene resin composition at a temperature of 230 ° C. and a nominal load of 2.16 kg, and “MFR2” means a temperature of 230 ° C. and a nominal load of 2 . Means the melt mass flow rate of the second polypropylene resin composition at 16 kg.)
  • the extrusion temperature In order to obtain a good laminated foam sheet by the coextrusion method, it is desirable to lower the extrusion temperature as much as possible from the viewpoint of reducing the open cell ratio. Since the first polypropylene resin composition contains a foaming agent when forming the foamed layer, the extrusion temperature can be lowered by utilizing the plasticizing effect of the foaming agent. On the other hand, since it is difficult to expect the second polypropylene resin composition used for forming the non-foamed layer to exhibit such an effect, it is difficult to lower the extrusion temperature.
  • melt mass flow rate (MFR1) of the first polypropylene resin composition and the melt mass flow rate (MFR2) of the second polypropylene resin composition are as described above. It is preferable to satisfy the relationship.
  • phase angle (PA1) of the first polypropylene resin composition In order to obtain a good laminated foam sheet by the coextrusion method, between the phase angle (PA1) of the first polypropylene resin composition and the phase angle (PA2) of the second polypropylene resin composition, It is preferable to have the relationship shown in the following (z). (PA1) ⁇ (PA2) (z) (Here, “PA1” means the phase angle at a frequency of 0.01 Hz of the first polypropylene resin composition obtained by frequency dispersion dynamic viscoelasticity measurement at 200 ° C., and “PA2” (It means the phase angle at a frequency of 0.01 Hz of the second polypropylene resin composition determined by frequency dispersion dynamic viscoelasticity measurement at 200 ° C.)
  • the first polypropylene resin composition containing the modified polypropylene resin can contain a foaming agent and a cell regulator necessary for forming the foamed layer, and the first polypropylene resin composition
  • a foamed layer can be formed by extrusion foaming a product.
  • the blowing agent include hydrocarbons such as propane, n-butane, i-butane, n-pentane, i-pentane, and cyclopentane, halides thereof, carbon dioxide gas, and nitrogen.
  • Examples of the air conditioner include talc, mica, silica, diatomaceous earth, aluminum oxide, titanium oxide, zinc oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, potassium carbonate, calcium carbonate, magnesium carbonate, Examples include inorganic compound particles such as potassium sulfate, barium sulfate and glass beads, and organic compound particles such as polytetrafluoroethylene.
  • azodicarbonamide, sodium hydrogen carbonate, a mixture of sodium hydrogen carbonate and citric acid, which also functions as a thermal decomposition type foaming agent, and the like can also be used as the bubble regulator.
  • the bubble regulator and the foaming agent do not need to be used singly and may be used in combination of two or more.
  • the second polypropylene resin composition containing the modified polypropylene resin also contains components necessary for forming the non-foamed layer, and the second polypropylene resin composition is used as the first polypropylene resin composition. It can be coextruded with the product to form a non-foamed layer.
  • FIG. 2 is a block diagram showing an example of a production apparatus used for producing a laminated foamed sheet, in which a first polypropylene resin composition containing a foaming agent is extruded and foamed from a circular die and second from the same circular die.
  • the polypropylene-based resin composition was extruded in a non-foamed state to form a cylindrical laminated foam in which the non-foamed layer overlapped on both sides of the foamed layer.
  • FIG. 3 is an enlarged cross-sectional view showing details of a portion indicated by a broken line circle A in FIG. 2, showing a state in which the cooled laminated foam is cooled and divided into two vertically and wound on a roll. Represents.
  • the manufacturing apparatus of the present embodiment includes a first extrusion line 70 for forming a foamed layer, a second extrusion line 80 for forming a non-foamed layer, and a first melt-kneaded in the first extrusion line 70.
  • the joining mold 90 has a resin flow path formed therein so that the first polypropylene resin composition and the second polypropylene resin composition are cylindrical, and the first polypropylene resin composition
  • the second polypropylene resin composition flows on both the inside and outside of the object.
  • the laminated foam sheet manufacturing apparatus includes a cooling device CR1 for air-cooling the laminated foam FB discharged from the circular die 100 in a cylindrical shape from the inside, and a predetermined diameter by expanding the diameter of the cylindrical laminated foam FB.
  • a winding roller 92 is provided for winding the strip-shaped laminated foamed sheet 1 after passing the plurality of rollers 91.
  • a modified polypropylene resin that exhibits a higher melt tension than a general polypropylene resin is used as a foam layer forming material, so that high discharge from the circular die 100 is achieved.
  • the cooling mandrel 200 can be expanded in diameter with a high blow-up ratio.
  • the modified polypropylene resin since the modified polypropylene resin is adopted as a material for forming the non-foamed layer, the non-foamed layer has a high follow-up property even when the foamed layer is extruded at a high speed and expanded at a high magnification. It is difficult to cause the resin to run out.
  • the resin temperature of the second polypropylene-based resin composition is preferably set to be somewhat higher in order to reduce the load on the extruder of the second extrusion line 80. If such conditions are set, the foamed layer that has been extruded and foamed is less likely to be cooled, so that the extrusion conditions are set such that bubble breakage is likely to occur in the foamed layer.
  • the laminated foam sheet has a low gel fraction of the modified polypropylene resin contained in the first polypropylene resin composition and a high MFR.
  • the laminated foam sheet reduces the load on the extruder of the second extrusion line 80 because there are few gels that are the starting points for the tearing of the foam film, and excellent extensibility is exhibited by the high MFR in the foam film.
  • the foamed layer can be in a dense and highly foamed state with closed cells.
  • the produced laminated foam sheet has excellent moldability in thermoforming and the like.
  • the resin of the non-foamed layer is likely to break at the boundary between the bottom surface and the side surface, but the laminated foam sheet is modified to a non-foamed layer.
  • Such a trouble is unlikely to occur because a modified polypropylene resin is included and the modified polypropylene resin exhibits a high MFR. That is, the laminated foam sheet is effective not only for improving the efficiency during production, but also for improving the yield of molded products.
  • the laminated foam sheet is preferably produced under conditions where the blow-up ratio is 1.8 or more, and more preferably produced under conditions where the blow-up ratio is 2.3 or more.
  • the blow-up ratio is a value (D / d) obtained from the diameter (D) of the cooling mandrel with respect to the diameter (d) of the circular discharge port of the circular die, and the diameter (d) of the discharge port of the circular die. ) Means the diameter of a circle passing through the inner edge of the discharge port.
  • the laminated foam sheet with a thin non-foamed layer is prone to resin breakage in the non-foamed layer.
  • the laminated foam sheet does not cause resin breakage even in such a case. It can be said that it is effective for conversion.
  • the laminated foam sheet preferably has a non-foam basis weight of 100 g / m 2 or less, and more preferably 50 g / m 2 or less.
  • the laminated foam sheet is usually produced so that the apparent density of the foam layer is 0.025 g / cm 3 or more and 0.5 g / cm 3 or less.
  • the apparent density of the laminated foam sheet is measured by the method described in JIS K7222: 1999 “Foamed Plastics and Rubber—Measurement of Apparent Density”, and specifically by the following method.
  • (Density measurement method) A sample of 100 cm 3 or more was prepared from the laminated foam sheet, and this sample was conditioned in JIS K7100: 1999 symbol 23/50, second grade environment for 16 hours, and then its dimensions and mass were measured to obtain an apparent density. Is calculated by the following equation.
  • Apparent density (g / cm 3 ) Sample mass (g) / Sample volume (cm 3 )
  • a “DIGIMATIC” CD-15 type manufactured by Mitutoyo Corporation can be used for measuring the dimensions of the sample.
  • the open cell ratio of the foamed layer is preferably 40% or less, and more preferably 30% or less.
  • the open cell ratio of the foam layer is measured by the following method. That is, a plurality of sheet-like samples having a length of 25 mm and a width of 25 mm are cut out from the laminated foam sheet, and the cut samples are overlapped so that there is no gap to obtain a measurement sample having a thickness of 25 mm. Is measured to 1/100 mm using “Digimatic Caliper” manufactured by Mitutoyo Corporation, and the apparent volume (cm 3 ) is obtained. Next, the volume (cm 3 ) of the sample for measurement is obtained by the 1-1 / 2-1 atmospheric pressure method using an air comparison type hydrometer 1000 type (manufactured by Tokyo Science).
  • the open cell ratio (%) is calculated from these obtained values and the following formula, and the average value of 5 tests is obtained.
  • the measurement is carried out in a JIS K7100-1999 symbol 23/50, second grade environment after conditioning for 16 hours in a JIS K7100-1999 symbol 23/50, second grade environment.
  • the air-comparing hydrometer corrects with a standard sphere (large 28.9 cc, small 8.5 cc).
  • Open cell ratio (%) 100 ⁇ (apparent volume ⁇ volume measured with air-based hydrometer) / apparent volume
  • the laminated foam sheet is useful as a foam molded article such as a buffer sheet as it is, and also as a raw material for a foam molded article provided with a three-dimensional shape by thermoforming or the like.
  • thermoforming include vacuum forming, pressure forming, vacuum / pressure forming, match mold forming, and press forming.
  • a container is preferable.
  • the foamed resin container thus produced is preferably used as various packaging containers because it is not only lightweight and high in strength, but also easily mass-produced.
  • the foamed resin container is preferably used for food packaging because it is excellent in heat insulation and the like.
  • a nonwoven fabric, metal foil, decorative paper, a printing film, or the like may be laminated on the surface of the foamed molded product depending on the application.
  • modified polypropylene resin is used as a forming material of a laminated foam sheet
  • the modified polypropylene resin of this invention can be used also for another use. That is, the present invention is not limited to the above examples.
  • Example 1 melt tension, MFR, phase angle>
  • the feed section was set to 170 ° C. and the subsequent temperature was set to 230 ° C., and the raw material composition was melt-kneaded in a twin-screw extruder under the conditions of a rotation speed of 120 rpm and a gear pump rotation speed of 25 rpm.
  • the melt-kneaded product was extruded in a strand form at a discharge rate of 45 kg / h from a die having a diameter of 2 mm and 9 holes attached to the tip.
  • the extruded strand-shaped melt-kneaded product was cooled by passing through a cooling water tank containing 30 ° C. water.
  • the cooled strand kneaded material was cut with a pelletizer to obtain pellets of a modified polypropylene resin.
  • Table 1 shows the results of the characteristic evaluation of the obtained modified polypropylene resin pellets.
  • Examples 2 to 7, Comparative Examples 1 to 10 A modified polypropylene resin was prepared in the same manner as described above except that the polypropylene resin used, the amount of styrene, and the amount of organic peroxide were changed as shown in the following table.
  • J105G”, “MA3H”, “MA3”, “J106”, “PM802A”, “PM900A”, “FY4”, “PL500A”, “E111G”, and “E200GP” are the following polypropylenes: It means a system resin.
  • the polypropylene resin used for the modification was a mixture of “PM802A” and “PM900A”.
  • the discharge amount from the die is made uniform when the modified polypropylene resin is produced.
  • the feed section is set to 170 ° C
  • the subsequent temperature is set to 230 ° C
  • the raw material composition is melted and kneaded in a twin-screw extruder under the conditions of a rotation speed of 120 rpm and a gear pump rotation speed of 25 rpm, and attached to the tip.
  • the melt-kneaded product was extruded in a strand shape from a die having a diameter of 2 mm, a land of 10 mm, and a number of holes of 9 at a discharge rate of 45 kg / h.
  • the extruded strand-shaped melt-kneaded product was cooled by passing through a cooling water tank containing 30 ° C. water.
  • a polypropylene resin composition containing a foaming agent was melt-kneaded by pressing into one extruder, and a first polypropylene resin composition for forming a foam layer was prepared in the extruder. Then, this 1st polypropylene resin composition is No.1. No. 1 extruder and No. 1 No. 2 through the transfer section connecting the extruder. 2 Flowed into the extruder. Then, this No.
  • the first polypropylene resin composition was uniformly cooled in the barrel of the two extruder, it was allowed to flow into the merging die.
  • the resin temperature at this time is 180 ° C.
  • the discharge rate from the 2 extruder was 30 kg / h.
  • the second polypropylene resin composition for the non-foamed layer includes the above-mentioned “modified PP-A” as the modified polypropylene resin, and the product name “Q100F” manufactured by Basell as the thermoplastic elastomer,
  • a polymer type antistatic agent containing a product name “Pelestat 230” (polyether-polypropylene block copolymer) manufactured by Sanyo Chemical Co., Ltd. was used.
  • a mixed raw material containing 74 parts by mass of the above-mentioned “modified PP-A”, 13 parts by mass of the thermoplastic elastomer, and 13 parts by mass of a polymer type antistatic agent is simply added with a diameter of 32 mm.
  • the mixture was supplied to a hopper of a shaft extruder, melted and kneaded, and then flowed into the joining die.
  • the discharge rate at this time was 3 kg / h.
  • the slit diameter of the first polypropylene resin composition and the second polypropylene resin composition joined by a joining die is 70 mm.
  • the circular die was fed and coextruded into a cylindrical shape from an annular discharge port (slit interval 0.4 mm) of the circular die.
  • the cylindrical foam with the non-foamed layer laminated on the foamed layer is cooled by a cooling mandrel, and then the cylindrical foam is cut by a cutter attached to the rear part of the cooling mandrel to form a long strip of laminated foam.
  • a sheet was prepared, and the laminated foam sheet was wound up at a take-up speed of 2.1 m / min. The average thickness of the laminated foam sheet at this time was 2.12 mm.
  • the modified polypropylene resin having excellent fluidity is useful for forming a laminated foam sheet having a low open cell ratio.
  • the feed section was set to 170 ° C. and the subsequent temperature was set to 230 ° C., and the raw material composition was melt-kneaded in a twin-screw extruder under the conditions of a rotation speed of 120 rpm and a gear pump rotation speed of 25 rpm.
  • the melt-kneaded product was extruded in a strand form at a discharge rate of 45 kg / h from a die having a diameter of 2 mm and 9 holes attached to the tip.
  • the extruded strand-shaped melt-kneaded product was cooled by passing through a cooling water tank containing 30 ° C. water.
  • the cooled strand kneaded product was cut with a pelletizer to obtain pellets of a modified polypropylene resin (modified PP-a).
  • melt tension As a sample, the pellet is used as it is.
  • the melt tension is measured using a twin-bore capillary rheometer Rheological 5000T (manufactured by Chiast, Italy). That is, after filling a measurement sample resin in a 15 mm diameter barrel heated to a test temperature (230 ° C.) and preheating for 5 minutes, the capillary die (2.0 mm diameter, 20 mm length, inflow angle flat) of the above measuring device While keeping the piston descending speed (0.1546 mm / s) constant and pushing it into a string shape, the string-like material is passed through a tension detection pulley located 27 cm below the capillary die, and then a winding roll The winding speed is gradually increased at an initial speed of 8.7 mm / s and an acceleration of 12 mm / s 2 , and the average of the maximum value and the minimum value immediately before the string-like material is cut is measured. Let melt tension. When there is only one
  • the modified PP-a pellets obtained above were supplied to this “lab plast mill” and extruded into a strand shape, and the strand-shaped extrudate was cooled by passing it through a water tank storing 20 ° C. cooling water. The cooled strand was cut and pelletized, and the uniaxial elongation viscosity (“slope of graph” at a strain of 1 to 3), MFR, and melt tension were measured again.
  • the first polypropylene resin composition was uniformly cooled in the barrel of the two extruder, it was allowed to flow into a confluence die.
  • the resin temperature at this time is 180 ° C.
  • the discharge rate from the 2 extruder was 30 kg / h.
  • the second polypropylene resin composition for the non-foamed layer includes the above-mentioned “modified PP-a” as a modified polypropylene resin, and the product name “Q100F” manufactured by Basell as a thermoplastic elastomer,
  • a polymer type antistatic agent containing a product name “Pelestat 230” (polyether-polypropylene block copolymer) manufactured by Sanyo Chemical Co., Ltd. was used.
  • a mixed raw material containing 74 parts by mass of the above-mentioned “modified PP-a”, 13 parts by mass of the thermoplastic elastomer, and 13 parts by mass of a polymer type antistatic agent is a single material having a diameter of 32 mm.
  • the mixture was supplied to a hopper of a shaft extruder, melted and kneaded, and then flowed into the joining die. The discharge rate at this time was 3 kg / h.
  • the foamed layer and the non-foamed layer are fed into the circular die having a slit diameter of 70 mm, and the first polypropylene resin composition and the second polypropylene resin composition joined by the joining die are fed into the circular die. It was produced by coextrusion into a cylindrical shape from an annular discharge port (slit spacing 0.4 mm). After this, the cylindrical foam with the non-foamed layer laminated on the foamed layer is cooled by a cooling mandrel, then the cylindrical foam is cut by a cutter attached to the rear of the cooling mandrel, and a long band-shaped resin foam is formed. The sheet (laminated foam sheet 1) was wound up at a take-up speed of 2.1 m / min. The average thickness of the resin foam sheet at this time was 2.18 mm.
  • Modified PP-b to Modified PP-f Laminated foam sheets 2 to 5
  • a modified polypropylene resin was prepared in the same manner as the modified PP-a except that the polypropylene resin used, the amount of styrene, and the amount of organic peroxide were changed as shown in Table 6 below, and various physical properties were investigated. . Further, using the obtained modified polypropylene resin, a laminated foam sheet was produced in the same manner as in the case of modified PP-a.
  • a laminated foam sheet was prepared using the modified PP-a and the modified PP-f. 39 parts by weight of “modified PP-a”, 55 parts by weight of a block PP commercially available from Nippon Polypro Co., Ltd. under the trade name “BC6C”, 6 parts by weight of a thermoplastic elastomer resin manufactured by Sun Allomer, A mixture was obtained by dry blending 1.5 parts by mass of a bubble regulator (“Fine Cell Master HCPO410K” manufactured by Dainichi Seika Kogyo Co., Ltd.). This mixture was mixed with No. 50 having a diameter of 50 mm. No. 1 extruder, No. 65 caliber No. No. of tandem type extruder with 2 extruders.
  • the first polypropylene resin composition was uniformly cooled in the barrel of the two extruder, it was allowed to flow into a confluence die.
  • the resin temperature at this time is 180 ° C.
  • the discharge rate from the 2 extruder was 30 kg / h.
  • the second polypropylene resin composition for the non-foamed layer includes the above-mentioned “modified PP-a” as a modified polypropylene resin, and the product name “Q100F” manufactured by Basell as a thermoplastic elastomer,
  • a polymer type antistatic agent containing a product name “Pelestat 230” (polyether-polypropylene block copolymer) manufactured by Sanyo Chemical Co., Ltd. was used.
  • a mixed raw material containing 74 parts by mass of the above-mentioned “modified PP-a”, 13 parts by mass of the thermoplastic elastomer, and 13 parts by mass of a polymer type antistatic agent is a single material having a diameter of 32 mm.
  • the mixture was supplied to a hopper of a shaft extruder, melted and kneaded, and then flowed into the joining die. Thereafter, a resin foam sheet (laminated foam sheet 6) was produced in the same manner as "Laminated foam sheet 1". The discharge rate at this time was 3 kg / h.
  • the modified PP-a was replaced with the modified PP-f to obtain a “laminated foam sheet 8”.
  • Table 7 shows the characteristics of the modified PP-a to the modified PP-e before passing through the extruder and after passing through the extruder.
  • Table 8 shows the characteristics of the foamed sheets produced using the modified PP-a to modified PP-f.
  • a modified polypropylene resin obtained by modifying a polypropylene resin having a high MFR exhibits a specific uniaxial elongation viscosity after passing through an extruder, and is suitable for applications where processing at a high shear rate is performed in a molten state. It turns out that it is a thing. From the above results, it can be seen that by using such a modified PP, a foam sheet in a good foamed state having high closed cell properties (low open cell ratio) can be obtained.
  • a foam sheet having a single layer structure was produced using the modified PP-a and the modified PP-f.
  • foam sheet (foam sheets 9, 10) 85 parts by mass of the obtained “modified PP”, a thermoplastic elastomer resin manufactured by Sun Allomer Co., Ltd., and 15 parts by mass of the trade name “Q100F” were dry blended to obtain a polymer mixture.
  • This polymer mixture was melt-kneaded with a chemical foaming agent ("Finecell Master HCPO410K” manufactured by Dainichi Seika Kogyo Co., Ltd.) in an extruder, and foamed while being extruded from a circular die attached to the tip of the extruder to produce a foamed sheet.
  • the characteristics of the foam sheet obtained using each modified PP are as follows.
  • a mold in which 22 truncated cones having a diameter of 10 mm (top surface) x a diameter of 35 mm (bottom surface) and different heights are arranged is used. Then, the mold surface temperature was adjusted to 50 ° C. to perform heat molding. The height of the 22 truncated cones is as shown in the table below.
  • the modified PP using a polypropylene resin having a high MFR as a starting material can form a resin foam having a high closed cell property (low open cell ratio) and good moldability (good elongation). It turns out that it is effective.
  • a modified polypropylene resin was produced in the same manner as the modified PP-a except that the polypropylene resin used, the amount of styrene, and the amount of organic peroxide were changed as shown in Table 12 below.
  • Four types (mPP1 to mPP4) of modified polypropylene resins having a multi-branch index before and after passing through the extruder as shown in Table 13 were prepared.
  • Table 13 shows the phase angle, MFR, and melt tension of the modified polypropylene resin.
  • mPP1 85 parts by mass of “mPP1” to “mPP4”, a thermoplastic elastomer resin manufactured by Sun Allomer, and 15 parts by mass of “Q100F” were dry-blended to obtain a polymer mixture.
  • This polymer mixture was melt kneaded with a chemical foaming agent ("Finecell Master HCPO410K” manufactured by Dainichi Seika Kogyo Co., Ltd.) with an extruder, foamed while being extruded from a circular die attached to the tip of the extruder, and shown in Table 14 below.
  • a foam sheet was prepared.
  • the characteristics of the resin foam sheet obtained using each mPP are as follows.
  • a flat rectangular test piece of 700 mm length ⁇ 1050 mm width was cut out from each produced foamed sheet. Then, a single molding machine (trade name “Unic Automatic Molding Machine FM-3A” manufactured by Tosei Sangyo Co., Ltd.) was prepared. The average temperature of the upper heater of this single molding machine was 274 ° C., the average temperature of the lower heater was 237 ° C., The upper atmosphere temperature was 192 ° C. and the lower atmosphere temperature was 185 ° C.
  • the modified PP exhibiting a specific multi-branch index after passing through the extruder is suitable for applications in which processing at a high shear rate is performed in a molten state. Moreover, it can be seen from the above results that a resin foam having high closed cell properties (low open cell ratio) and good moldability (good elongation) can be obtained by using such modified PP.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention traite le problème de l'obtention d'une résine à base de polypropylène modifié qui, lorsqu'elle est chauffée et fondue, présente une excellente aptitude à l'écoulement. Afin de résoudre le problème, la présente invention utilise, en tant que résine à base de polypropylène servant de matière première, une résine à base de polypropylène qui présente des propriétés de fusion/une viscoélasticité spécifiques.
PCT/JP2017/012533 2016-03-29 2017-03-28 Résine à base de polypropylène modifié et procédé de production de résine à base de polypropylène modifié WO2017170481A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020179792A1 (fr) * 2019-03-06 2020-09-10 キョーラク株式会社 Résine pour moulage par soufflage de mousse et procédé de production d'un article moulé par soufflage en mousse

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007887A1 (fr) * 1990-11-02 1992-05-14 Sumitomo Chemical Company, Limited Polymere de propylene modifie et composition de resine thermoplastique comprenant le polymere de propylene et un ether de polyphenylene
JPH09188728A (ja) * 1996-01-09 1997-07-22 Kanegafuchi Chem Ind Co Ltd 改質ポリプロピレン系樹脂およびその製法
JPH10298336A (ja) * 1997-04-23 1998-11-10 Kanegafuchi Chem Ind Co Ltd 改質ポリプロピレン系樹脂組成物からなる発泡体およびその製法
JP2008075076A (ja) * 2006-08-25 2008-04-03 Sekisui Plastics Co Ltd スチレン改質ポリプロピレン系樹脂粒子及びその発泡性樹脂粒子、それらの製造方法、予備発泡粒子及び発泡成形体
JP2012188642A (ja) * 2011-02-25 2012-10-04 Sekisui Plastics Co Ltd 改質ポリプロピレン系樹脂の予備発泡粒子および発泡成形体の製造方法
WO2016067814A1 (fr) * 2014-10-30 2016-05-06 積水化成品工業株式会社 Resine a base de polypropylene modifie, resine a base de polypropylene expanse, recipient constitue de resine expansee, et procede pour la production de resine a base de polypropylene modifie

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69419497T2 (de) * 1993-11-12 1999-12-23 Kanegafuchi Chemical Ind Polyolefinharzmischung

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007887A1 (fr) * 1990-11-02 1992-05-14 Sumitomo Chemical Company, Limited Polymere de propylene modifie et composition de resine thermoplastique comprenant le polymere de propylene et un ether de polyphenylene
JPH09188728A (ja) * 1996-01-09 1997-07-22 Kanegafuchi Chem Ind Co Ltd 改質ポリプロピレン系樹脂およびその製法
JPH10298336A (ja) * 1997-04-23 1998-11-10 Kanegafuchi Chem Ind Co Ltd 改質ポリプロピレン系樹脂組成物からなる発泡体およびその製法
JP2008075076A (ja) * 2006-08-25 2008-04-03 Sekisui Plastics Co Ltd スチレン改質ポリプロピレン系樹脂粒子及びその発泡性樹脂粒子、それらの製造方法、予備発泡粒子及び発泡成形体
JP2012188642A (ja) * 2011-02-25 2012-10-04 Sekisui Plastics Co Ltd 改質ポリプロピレン系樹脂の予備発泡粒子および発泡成形体の製造方法
WO2016067814A1 (fr) * 2014-10-30 2016-05-06 積水化成品工業株式会社 Resine a base de polypropylene modifie, resine a base de polypropylene expanse, recipient constitue de resine expansee, et procede pour la production de resine a base de polypropylene modifie

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020179792A1 (fr) * 2019-03-06 2020-09-10 キョーラク株式会社 Résine pour moulage par soufflage de mousse et procédé de production d'un article moulé par soufflage en mousse
JP2020143208A (ja) * 2019-03-06 2020-09-10 キョーラク株式会社 発泡ブロー成形用樹脂、発泡ブロー成形体の製造方法
JP7201910B2 (ja) 2019-03-06 2023-01-11 キョーラク株式会社 発泡ブロー成形用樹脂、発泡ブロー成形体の製造方法

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