WO2011065561A1 - 発泡性熱可塑性樹脂粒子とその製造方法 - Google Patents
発泡性熱可塑性樹脂粒子とその製造方法 Download PDFInfo
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- WO2011065561A1 WO2011065561A1 PCT/JP2010/071344 JP2010071344W WO2011065561A1 WO 2011065561 A1 WO2011065561 A1 WO 2011065561A1 JP 2010071344 W JP2010071344 W JP 2010071344W WO 2011065561 A1 WO2011065561 A1 WO 2011065561A1
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- 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
- C08J9/16—Making expandable particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/582—Component parts, details or accessories; Auxiliary operations for discharging, e.g. doors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/826—Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
- B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3461—Making or treating expandable particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2793/00—Shaping techniques involving a cutting or machining operation
- B29C2793/0027—Cutting off
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92971—Fluids, e.g. for temperature control or of environment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/345—Extrusion nozzles comprising two or more adjacently arranged ports, for simultaneously extruding multiple strands, e.g. for pelletising
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
- B29K2105/048—Expandable particles, beads or granules
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- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
Definitions
- the present invention relates to a method for producing expandable thermoplastic resin particles for producing expandable thermoplastic resin particles by a hot cut method, a method for producing thermoplastic resin foam particles, and a method for producing a thermoplastic resin foam molded article.
- the present invention claims priority based on Japanese Patent Application No. 2009-271985 filed in Japan on November 30, 2009, the contents of which are incorporated herein by reference.
- Patent Document 1 discloses a method for producing a foamed styrene polymer having a molecular weight Mw of more than 170000 g / mol, wherein a foaming agent-containing styrene polymer melt having a temperature of at least 120 ° C. has a pore diameter of 1.5 mm or less at the die outlet.
- a method of conveying through a die plate having a number of holes and then granulating the extrudate is disclosed.
- the paragraph [0021] states that “the die plate is heated at least to the temperature of the foaming agent-containing polystyrene melt.
- the temperature of the die plate is the blowing agent-containing polystyrene melt.
- the temperature is preferably in the range of 20 to 100 ° C. higher than the temperature of the product ”.
- Patent Document 2 discloses a method for producing foamable thermoplastic resin particles obtained by cutting a foaming agent-containing molten resin extruded from a die with a rotary cutter into resin particles, and using a die whose surface is thermally insulated, and a die surface And a method for producing expandable thermoplastic resin particles in which a rotary cutter is disposed in a non-contact state.
- the molten resin temperature and the die temperature it is described that both the molten resin temperature and the die temperature are set to 130 ° C. in Example 1, and in Example 2 and Comparative Example 1, the die temperature is set to 140 ° C. It is described that the temperature was set to ° C.
- Patent Document 3 discloses a method for producing foamable granules of a thermoplastic polymer, in which both polymer cutting granulation and granule cooling treatment are performed under a high pressure of 2 Bar or more.
- the production method of Patent Document 3 includes the following steps: a step of extruding a foaming agent-blended polymer from a die head part; immediately cutting the polymer with a die head, and taking out and cooling the resulting granule; Performing in a water bath or fluid maintained at a high temperature equal to or higher than the Tg value of the coalescence; the obtained granules are decooled at a temperature range of at least + 5 ° C which is the same value as the Tg value of the foamable polymer; A continuous process.
- the molten resin temperature and the die temperature only that the resin temperature is about 160 ° C. is described in Example 1, and the die temperature is not described.
- thermoplastic resin (A) and a foaming agent (B) are melt-kneaded (step 1), and the thermoplastic resin (A) and the foaming agent (B) are added from the extrusion holes of the die head.
- the molten kneaded product is discharged into a heated and pressurized liquid heated and pressurized to a temperature and pressure at which foaming does not occur, and immediately cut (step 2).
- a method for producing expandable thermoplastic resin particles is disclosed (step 4) after further heating (step 3) in the presence of a surfactant, followed by cooling and depressurization.
- the molten resin temperature and the die temperature only that the resin temperature is “150 ° C. immediately before the die portion” is described in Example 1, and the die temperature is not described. Absent.
- JP 2005-534733 A JP-A-6-31726 JP 59-221340 JP-A-9-221562
- Patent Documents 1 to 4 have the following problems.
- the die temperature is set to be higher than the molten resin temperature.
- coalescence of the resin particles that are extruded into the water from the small die holes and cut immediately thereafter is likely to occur. Therefore, there is a problem that the production yield of the expandable thermoplastic resin particles is deteriorated and it is difficult to manufacture high quality expandable thermoplastic resin particles.
- Patent Document 3 In the production methods described in Patent Document 3 and Patent Document 4, although the molten resin temperature is described, there is no description about the die temperature, and it is unclear whether the above-described problems of the prior art in Patent Documents 1 and 2 occur.
- Patent Literature 3 After the molten resin is cut in water, the obtained resin particles are cooled in the temperature range of the resin Tg value ⁇ 5 ° C. (Patent Literature 3). Then, the obtained resin particles are subjected to a post-process such as further heating under pressure and in the presence of a dispersant and / or a surfactant (Patent Document 4).
- the manufacturing facility is increased in size, the manufacturing process is increased, and the manufacturing cost is increased.
- the foamed thermoplastic resin particles obtained by cutting in water are not subjected to the “Step 3”, but are cooled with circulating water to recover the resin particles.
- the foamable thermoplastic resin particles obtained were flat and it was difficult to obtain spherical resin particles.
- the present invention has been made in view of the above circumstances, and in the production of expandable thermoplastic resin particles by the hot cut method, there is little coalescence of the obtained resin particles, and spherical and high-quality expandable heat can be obtained by simple manufacturing equipment and processes.
- An object is to provide a method capable of efficiently producing plastic resin particles.
- the present invention employs the following technique. That is, (1) The present invention includes a step of supplying a thermoplastic resin to a resin supply device equipped with a granulating die and melt-kneading the resin, A step of injecting a foaming agent into the thermoplastic resin while moving the thermoplastic resin toward the granulation die to form a foaming agent-containing resin; Cutting the foaming agent-containing resin discharged from a nozzle opened in the resin discharge surface of the granulation die in a cooling medium with a cutter to obtain expandable thermoplastic resin particles.
- a method for producing resin particles comprising: The temperature T1 of the foaming agent-containing resin in the granulation die and the temperature T2 of the granulation die satisfy T1> T2, and the flow rate L1 of the cooling medium and the foaming agent discharged from the nozzle
- the pressure of the cooling medium when the foaming agent-containing resin discharged from the nozzle is cut in a cooling medium by a cutter is 0. It is preferably 5 MPa or more.
- the cooling medium when the foaming agent-containing resin discharged from the nozzle is cut in a cooling medium by a cutter.
- the temperature is preferably within the range of 30 to 90 ° C.
- thermoplastic resin is a polystyrene resin
- temperature of the foaming agent-containing resin in the granulation die T1 is preferably in the range of 150 to 230 ° C.
- the coalesced particles in the foamable thermoplastic resin particles obtained are two or more
- the temperature T1, T2 and the ratio (L1 / L2) are preferably set so that the mixing ratio of the resin particles in a state where the resin particles are fused to each other is 1% by mass or less.
- the present invention also provides expandable thermoplastic resin particles obtained by the method for producing expandable thermoplastic resin particles described in (1) to (5) above.
- the present invention is manufactured by a hot cut method, and the mixing ratio of coalesced particles (wherein the coalesced particles are particles in which two or more resin particles are fused) is 1.
- an expandable thermoplastic resin particle having a mass% or less.
- the present invention provides a method for producing foamed thermoplastic resin particles, wherein the foamable thermoplastic resin particles described in (6) or (7) above are heated and pre-foamed to obtain thermoplastic resin foamed particles. To do.
- this invention provides the thermoplastic resin expanded particle obtained by the manufacturing method of the thermoplastic resin expanded particle as described in said (8).
- the present invention provides a method for producing a thermoplastic resin foam molded article, wherein the thermoplastic resin foam particles described in (9) above are subjected to in-mold foam molding to obtain a thermoplastic resin foam molded article.
- the present invention provides a thermoplastic resin foam molded article obtained by the method for producing a thermoplastic resin foam molded article according to (10).
- the temperature T1 of the foaming agent-containing resin in the granulation die and the temperature T2 of the granulation die are T1> T2.
- the ratio (L1 / L2) between the flow rate L1 of the cooling medium and the discharge amount L2 of the foaming agent-containing resin discharged from the nozzle is controlled to be in the range of 100 to 200, Thermoplastic resin particles are obtained.
- FIG. 1 and 2 are block diagrams showing an example of a granulating apparatus used in the production method of the present invention
- FIG. 2 is a side sectional view showing an example of the granulating die
- FIG. 3 is a die body of FIG.
- FIG. 4 is a side view showing the resin discharge surface
- FIG. 1 and 2 are block diagrams showing an example of a granulating apparatus used in the production method of the present invention
- FIG. 2 is a side sectional view showing an example of the granulating die
- FIG. 3 is a die body of FIG.
- FIG. 4 is a side view showing the resin discharge surface
- a granulating apparatus 100 is a granulating apparatus for granulating expandable thermoplastic resin particles by a hot cut method.
- the granulation apparatus 100 includes an extruder 2 (resin supply apparatus) having a granulation die 1 attached to the tip thereof, and a resin (in this embodiment, containing a foaming agent) discharged from the nozzle 15 of the granulation die 1.
- a cutter 3 for cutting the resin 20 is accommodated, and a chamber 4 for bringing a water flow into contact with the resin discharge surface 13 of the granulation die 1 is provided.
- the chamber 4 is connected to a pipe 5 for flowing a cooling medium such as circulating water (hereinafter referred to as water), and one end (upstream side of the chamber 4) of the pipe 5 is connected to the water pump 6. Connected to the water tank 7. The other end (downstream side of the chamber 4) of the pipe 5 is provided with a dehydration processing unit 8 that separates foamed thermoplastic resin particles from the circulating water and dehydrates and dries them.
- the expandable thermoplastic resin particles separated by the dehydration processing unit 8 and dehydrated and dried are sent to the container 9.
- Reference numeral 21 is a hopper, 22 is a blowing agent supply port, and 23 is a high-pressure pump.
- the side from which the resin is discharged is “front” and “front end”, and the opposite side is “rear” and “rear end” in the following description. Use.
- the granulation die 1 includes a die body 10 (also referred to as a die plate) and a die holder 11 fixed to the tip side (right side in the drawing) of the extruder 2.
- the die body 10 is fixed to the tip end side of the die holder 11 with a plurality of bolts 12.
- the die holder 11 is provided in communication with the cylinder of the extruder 2, and a rear end side flow path 11 a and a front end side flow path 11 b are formed in that order from the rear end side toward the front end side.
- the die body 10 is formed with a conical convex portion 10 a that protrudes rearward at the center of the rear end face.
- the conical convex portion 10a is inserted into the distal end side flow passage 11b of the die holder 11 with a predetermined gap. For this reason, the foaming agent-containing resin 20 that has passed through the rear end side flow passage 11a of the die holder 11 flows along the peripheral surface of the conical convex portion 10a in the front end side flow passage 11a, and is opened in the rear end face of the die body 10.
- the plurality of resin flow paths 14 (described later) communicate with each other.
- the die body 10 has a resin discharge surface 13 that comes into contact with the water flow at the tip surface thereof, and a plurality of resin flow paths 14 for transferring the foaming agent-containing resin 20 extruded from the extruder 2 toward the resin discharge surface 13.
- a plurality of nozzles 15 provided at the tips of the plurality of resin flow paths 14 and opening in the resin discharge surface 13, a heat insulating material 16 provided at the center position of the resin discharge surface 13, and extruded from the resin discharge surface 13.
- a cartridge heater 17 for heating the front end side of the resin discharge surface 13 and the resin flow path 14 at a position on the machine 2 side, and a short heater 18 for heating the rear end side of the resin flow path 14 are provided.
- the cartridge heater 17 and the short heater 18 can be appropriately selected and used from conventionally known cartridge heaters according to the size and shape of the die body 10.
- a heating wire (nichrome wire) wound around a rod-shaped ceramic is inserted into a pipe (heat-resistant stainless steel), and the gap between the heating wire and the pipe is highly thermally conductive and highly insulating.
- a bar heater with a high power density, which is encapsulated with an excellent material (MgO).
- the cartridge heater 17 and the short heater 18 may be a cartridge heater with two lead wires on one side or a cartridge heater (seeds heater) with one lead wire on each side, but with two lead wires on one side.
- a cartridge heater is preferred because it has a higher power density.
- the means for heating the die body 10 is not limited to rod heaters such as the cartridge heater 17 and the short heater 18, and a flow path for passing a heat transfer medium such as thermo oil is formed inside the die body 10.
- the die body 10 may be heated by the heated heat transfer medium.
- the heating means may be heating using only a bar heater, heating only a heat transfer medium, or heating using a bar heater and a heat transfer medium in combination.
- the resin discharge surface 13 of the die body 10 is provided with a heat insulating material 16 having a circular cross section at the center, and discharge ports of a plurality of nozzles 15 are provided along the concentric circles on the outer side in the radial direction of the heat insulating material 16.
- the central portion of the resin discharge surface 13 on which the heat insulating material 16 and the plurality of nozzles 15 are disposed is in contact with water inside the chamber 4.
- Each resin flow path 14 has a circular cross section, extends in a direction orthogonal to the resin discharge surface 13, and has a circumference (depicted on the resin discharge surface 13) around the central axis of the die body 10. Are arranged at regular intervals along the circumference.
- the plurality of resin flow paths 14 are provided at eight locations, and the central angle between the plurality of resin flow paths 14 adjacent in the circumferential direction of the circumference is 45 °. As described above, each resin flow path 14 communicates with the front end side flow path 11 b of the die holder 11.
- the plurality of nozzles 15 are arranged at predetermined intervals along the circumference drawn on the resin discharge surface 13.
- one nozzle 15 includes a nozzle unit in which a plurality of single nozzles 15a, 15b, 15c are arbitrarily arranged within the range of the cross-sectional shape of each resin flow path 14 (in the present invention, This is referred to as a “nozzle”).
- a method for arranging the single nozzles 15a, 15b, and 15c for example, a method in which a large number of nozzles are arranged on a plurality of small circles can be adopted. However, the arrangement is not limited to such an arrangement.
- the heat insulating material 16 is provided in the resin discharge surface 13 inside the circumference where the plurality of nozzles 15 are arranged, and the temperature of the die body 10 is lowered so that the heat of the die body 10 does not escape to the water in the chamber 4. Suppress.
- This heat insulating material 16 is water resistant and is preferably a heat insulating material having a structure with high surface hardness.
- a heat insulating material excellent in heat resistance and heat insulating performance that does not cause deformation or the like even when in contact with the high-temperature die body 10 is disposed, and this is waterproofed with a fluorine resin or the like excellent in heat insulating performance.
- a laminated type in which a material having a high surface hardness such as stainless steel or ceramic is laminated in order on the resin discharge surface 13 side can be used.
- Each of the cartridge heater 17 and the short heater 18 is a rod-shaped heater, and the cartridge heater 17 is located closer to the resin discharge surface 13 side than the short heater 18 in the distal end direction of the granulation die 1.
- the cartridge heaters 17 are arranged on both sides of the circumference of the circumference of the resin flow path 14, and are arranged in a state of crossing the circumference with the longitudinal direction directed in the radial direction of the circumference. In the vicinity, it has a function of heating the resin discharge surface 13, the nozzle 15, and the resin flow path 14.
- Each of the plurality of cartridge heaters 17 of the present embodiment is provided with a predetermined central angle (here, an angle of 45 °) in the circumferential direction. That is, the individual nozzles 15 are arranged so as to be sandwiched by the two cartridge heaters 17 and 17 from the circumferential direction of the circumference.
- the cartridge heater 17 is provided in the vicinity of the resin discharge surface 13, that is, within a predetermined heater depth range from the resin discharge surface 13 toward the extruder 2 side.
- the heater depth refers to the distance from the resin discharge surface 13 to the center of the cartridge heater 17 for surface heating (symbol L shown in FIG. 1).
- the heater depth is within a range that does not hinder the processing surface and durability of the die, and a smaller distance is preferable because the effect of suppressing nozzle clogging is increased. That is, the heater depth is preferably in the range of 10 to 50 mm. If it is less than 10 mm, the processed surface of the die and the durability may be hindered, and if it exceeds 50 mm, the nozzle clogging suppression effect may be reduced. A more preferable range is 15 to 30 mm.
- the diameter of the cartridge heater 17 is small as long as the heat generation capacity can be ensured because the cross-sectional area of the resin flow path can be increased, and the number of nozzles is increased.
- the diameter of the cartridge heater 17 is preferably 15 mm or less, but if it is less than 10 mm, the required heat generation capacity cannot be ensured and the heater becomes expensive, so the diameter is preferably 10 mm to 15 mm, more preferably 10 mm to 12 mm.
- the length of the cartridge heater 17 is determined from a position extending to the center side of the nozzle 15 arranged in the radial direction of the die body 10 (that is, a position where at least the tip of the cartridge heater 17 is on the center side of the nozzle 15). This is the position up to substantially the outer periphery of the die body 10.
- the short heaters 18 are arranged on the rear side with a predetermined interval with respect to each cartridge heater 17, the same number (eight) as the number of the cartridge heaters 17 is arranged, and have a function of heating the rear end side of the resin flow path 14. is doing.
- the length of the short heater 18 is shorter than that of the cartridge heater 17.
- the die holder 11 is provided with a temperature measuring body (not shown) such as a thermocouple for measuring the temperature of the foaming agent-containing resin 20 press-fitted from the tip of the extruder 2.
- the position of the temperature measuring body is provided at a position where the temperature of the foaming agent-containing resin 20 in the rear end side channel 11a of the die holder 11 can be measured.
- the reason why the position of the temperature measuring body is the position of the rear end side flow path 11a of the die holder 11 is that the front end side flow path 11b of the die holder 11, the resin flow path 14 of the die body 10 and the nozzle 15 of the die body 10 are This is because the flow path is too narrow and it is difficult to measure the resin temperature.
- the resin temperature measured by this temperature measuring element is referred to as “temperature T1 of the foaming agent-containing resin in the granulation die”.
- the die body 10 is provided with a temperature measuring element 19 (19A, 19B) (temperature sensor) such as a thermocouple. That is, the die body 10 can be adjusted in temperature by individually controlling the cartridge heater 17 and the short heater 18 on and off based on the measured temperatures of the temperature measuring elements 19. By adjusting the temperature of the die body 10, the resin temperature in the resin flow path 14 of the die body 10 and the nozzle 15 of the die body 10 can be adjusted.
- the position of the side warming body 19 is a central portion (8t / 10) excluding the rear end side (t / 10) and the front end side (t / 10) of the thickness t (reference sign t shown in FIG. 2) of the die body 10. ) At a position where the temperature can be measured.
- the side temperature body 19 is provided at a position that is 1 ⁇ 2 of the thickness t of the die body 10.
- the reason for setting the temperature measuring element 19 to the position excluding the rear end side (t / 10) and the front end side (t / 10) is that the heater and heat transfer medium are located at the rear end side and the front end side. This is because the heat hardly reaches and does not represent the temperature of the die body 10.
- tip (sensor part) of the side temperature body 19 is located in the vicinity of the resin flow path 14 of the die main body 10 (refer FIG. 3).
- the temperature measured by the temperature measuring element 19 is referred to as “temperature T2 of the granulation die”.
- the temperature of the heat transfer medium can be set to “the temperature T2 of the granulation die”.
- the discharge amount L2 of the blowing agent-containing resin 20 discharged from the nozzle 15 is stored in the container for 1 minute by separating the dehydrated and dried foamed thermoplastic resin particles separated in the dehydration processing unit 8, and the mass is measured by an electronic balance.
- the discharge amount per minute can be obtained.
- the discharge amount L2 per hour can be measured.
- symbol S indicates a sensing section for measuring the temperature and pressure (water pressure) of circulating water that is a cooling medium in the granulation apparatus 100.
- the water temperature and pressure of the circulating water can be measured using a conventionally known temperature measuring / side pressure device.
- the temperature of the circulating water is controlled by a heater or a cooler provided at an appropriate position in the circulating water supply path, and the pressure (water pressure) and the amount of water (cooling medium flow rate L1) are controlled by the pressure setting of the water supply pump 6.
- the extruder 2 (resin supply device) used in the granulating apparatus 100 shown in FIG. 1 can be appropriately selected and used according to the type of resin to be granulated from conventionally known various extruders.
- a screw is used.
- Either an extruder or an extruder that does not use a screw can be used.
- Examples of the extruder using a screw include a single-screw extruder, a multi-screw extruder, a vent-type extruder, and a tandem extruder.
- Examples of the extruder that does not use a screw include a plunger type extruder and a gear pump type extruder.
- any extruder can use a static mixer.
- an extruder using a screw is preferable from the viewpoint of productivity.
- the chamber 4 which accommodated the cutter 3 can also use the conventionally well-known chamber used in the hot cut method.
- the type of the thermoplastic resin is not limited, but as the thermoplastic resin, for example, polystyrene resin, polyethylene resin, polypropylene resin, polyester resin, vinyl chloride resin, ABS resin, AS resin, etc. are used alone. Alternatively, two or more types can be mixed and used. Furthermore, it is possible to use a recovered resin of a thermoplastic resin obtained after being used once as a resin product.
- polystyrene resins such as amorphous polystyrene (GPPS) and high impact polystyrene (HIPS) are preferably used.
- the thermoplastic resin is placed in an extruder 2 having a granulating die 1 attached to the tip. Is supplied from the hopper 21 and melted and kneaded. Next, while moving the thermoplastic resin toward the granulation die 1, the foaming agent is pressed into the thermoplastic resin from the foaming agent supply port 22 by the high-pressure pump 23, and the foaming agent and the thermoplastic resin are mixed. Thus, the foaming agent-containing resin 20 is formed. The foaming agent-containing resin 20 is sent from the tip of the extruder 2 through the die holder 11 to the resin flow path 14 of the die body 10 of the granulating die 1.
- the foaming agent-containing resin 20 sent through the resin flow path 14 is discharged from each nozzle 15 opened in the resin discharge surface 13 of the die main body 10, and the water in the chamber 4 (cooling medium) is rotated by the rotary blade of the cutter 3. It will be cut immediately.
- the temperature T1 of the foaming agent-containing resin 20 in the granulation die 1 and the temperature T2 of the granulation die 1 satisfy T1> T2.
- the ratio (L1 / L2) between the flow rate L1 of the cooling medium and the discharge amount L2 of the foaming agent-containing resin 20 discharged from the nozzle 15 is controlled to be in the range of 100 to 200, Expandable thermoplastic resin particles are obtained.
- T1 and T2 are suitably set according to the kind of thermoplastic resin used for granulation.
- T1 is preferably in the range of 150 to 230 ° C.
- a more preferable range of T1 of the polystyrene resin is 160 to 220 ° C., and a most preferable range is 170 to 210 ° C.
- T1 is preferably in the range of 130 to 210 ° C.
- a more preferable range of T1 of the polyethylene resin is 140 to 200 ° C., and most preferable is a range of 150 to 190 ° C.
- thermoplastic resin is a polypropylene resin
- T1 is preferably in the range of 180 to 270 ° C.
- a more preferable range of T1 of the polypropylene resin is 190 to 260 ° C., and most preferable is a range of 200 to 250 ° C.
- various thermoplastic resins can be used, but the most preferable resin is a polystyrene resin.
- T1 and T2 preferably satisfy the relationship of T1-5 (° C.) ⁇ T2 (° C.), and more preferably satisfy the relationship of T1-10 (° C.) ⁇ T2 (° C.).
- the aperture ratio of the nozzle is reduced in a short time, and the discharge amount per one nozzle that is opened increases, so that the particle diameter of the foamable thermoplastic resin particles obtained is increased or the particle diameter is not uniform. growing. Therefore, although not particularly limited, it is preferable to satisfy the relationship of T2 (° C.)> T1-30 (° C.) under the condition of satisfying the relationship of T1 (° C.)> T2 (° C.), and T2 (° C.)> T1 It is more preferable to satisfy the relationship of ⁇ 20 (° C.).
- the ratio (L1 / L2) is in the range of 100 to 200, the resulting resin particles are less coalesced and the nozzle 15 is less likely to be clogged. As a result, high-quality foamable thermoplastic resin particles can be efficiently produced.
- the ratio of L1 / L2 is more preferably in the range of 105 to 180, and the most preferable ratio is in the range of 110 to 170.
- the ratio (L1 / L2) is less than 100, the coalescence of the obtained resin particles increases, and it becomes difficult to obtain spherical and high-quality foamable thermoplastic resin particles.
- the ratio (L1 / L2) exceeds 200, the nozzle 15 is likely to be clogged. As a result, the aperture ratio of the nozzle decreases in a short time, and the production efficiency of the granulating apparatus 100 decreases.
- the pressure of the circulating water when cutting the blowing agent-containing resin discharged from the nozzle 15 in the circulating water with a cutter is preferably 0.5 MPa or more, A range of 0.5 to 3.0 MPa is more preferable, and a range of 0.8 to 2.0 MPa is more preferable. If this pressure is less than 0.5 MPa, the cut resin particles are likely to foam, and it becomes difficult to produce high-quality expandable thermoplastic resin particles.
- the temperature (water temperature) of circulating water when the foaming agent-containing resin 20 discharged from the nozzle 15 is cut in circulating water by a cutter is in the range of 30 to 90 ° C. It is preferably within the range, more preferably in the range of 40 to 80 ° C, and still more preferably in the range of 45 to 70 ° C.
- the temperature is less than 30 ° C.
- the nozzle 15 is easily clogged.
- the aperture ratio of the nozzle 15 decreases in a short time, and the production efficiency of the granulating apparatus 100 is likely to decrease.
- the temperature exceeds 90 ° C. the cut resin particles are easily foamed, and it becomes difficult to produce high-quality expandable thermoplastic resin particles.
- the coalesced particles in the obtained foamable thermoplastic resin particles (however, the coalesced particles are particles in a state where two or more resin particles are fused together). It is preferable to set the temperature T1, T2 and the ratio (L1 / L2) so that the mixing ratio is 1% by mass or less. The smaller the mixing ratio of the coalesced particles, the better. The best is when the mixing ratio is zero. Since these coalesced particles are in a state where two or more resin particles are fused together, they are not separated even if some vibration or impact is applied.
- the coalesced particles have a large number of coalesced resin particles, and if they become large particles, they can be separated from good products (single resin particles) by sieving the resin particles.
- relatively small coalesced particles in which 2 to 3 resin particles are fused may pass through the sieve and be mixed into non-defective products when the resin particles are screened.
- the mixing ratio of the coalesced particles exceeds 1% by mass, when the foamed molded product is produced using the foamable thermoplastic resin particles, poor filling of the pre-foamed particles and deterioration of the appearance of the obtained foamed molded product, Reduction in mechanical strength occurs.
- the foaming agent-containing resin 20 cut into particles in the chamber 4 becomes substantially spherical foaming thermoplastic resin particles.
- the foamable thermoplastic resin particles are transported in the pipeline 5 according to the water flow and reach the dehydration processing unit 8.
- the dehydration processing unit 8 the foamable thermoplastic resin particles are separated from the circulating water, dehydrated and dried, and the separated water is sent to the water tank 7.
- the foamable thermoplastic resin particles separated by the dehydration processing unit 8, dehydrated and dried are sent to the container 9 and accommodated in the container.
- the blowing agent is not limited, but for example, pentane such as normal pentane, isopentane, cyclopentane, neopentane, cyclopentadiene, normal butane, isobutane, propane, CO 2 , N 2 etc. may be used alone or in combination of two or more. Can be used. Further, normal butane, isobutane, propane, CO 2 , N 2 or the like can be mixed and used with the pentane as a main component. In particular, pentanes are preferably used because they tend to suppress foaming of particles when discharged from a nozzle into a water stream.
- the foamable thermoplastic resin particles mean resin particles formed into a granular shape, preferably a small spherical shape, by adding a foaming agent to a thermoplastic resin.
- the foamable thermoplastic resin particles are heated in a free space to be pre-foamed.
- the pre-foamed particles are placed in a cavity of a mold having a cavity having a desired shape, and the pre-foamed particles are melted by steam heating. After being attached, it is released from the mold and used to produce a foamed resin molded product having a desired shape.
- the temperature T1 of the foaming agent-containing resin in the granulation die and the temperature T2 of the granulation die satisfy T1> T2.
- the ratio (L1 / L2) between the flow rate L1 of the cooling medium and the discharge amount L2 of the foaming agent-containing resin discharged from the nozzle is controlled to be in the range of 100 to 200. Meanwhile, expandable thermoplastic resin particles are obtained. For this reason, compared with the conventional manufacturing method in which T1 ⁇ T2, there is less coalescence of the obtained resin particles, and it is possible to efficiently produce spherical and high-quality expandable thermoplastic resin particles with simple manufacturing equipment and processes. it can.
- Example 1 Manufacture of expandable polystyrene resin particles
- a granulating die 1 comprising a die holder 11 and a die body 10 shown in FIGS. 2 and 3 was attached to the extruder 2 shown in FIG. 1 to produce expandable polystyrene resin particles.
- the temperature measuring element 19 shown in FIG. 2 and FIG. 3 all the cartridge heaters 17 and the short heaters 18 were on / off controlled to adjust the temperature of the die body 10 of the granulation die 1.
- the base resin 100 parts by mass of polystyrene resin (trade name “HRM-10N” manufactured by Toyo Styrene Co., Ltd.) and 0.3 parts by mass of fine powder talc are mixed in advance with a tumbler mixer in advance.
- the resin was fed into a 90 mm single screw extruder to heat and melt the resin.
- 6 parts by mass of isopentane as a foaming agent was injected from the middle of the extruder with respect to 100 parts by mass of the resin. And it adjusted so that the temperature of the foaming agent containing resin 20 in the die holder 11 might be set to 195 degreeC, kneading
- the die body 10 was held at 185 ° C. using the cartridge heater 17 and the short heater 18.
- the die body 10 is provided with 200 nozzles having a diameter of 0.6 mm and a land length of 3.0 mm.
- the foaming agent-containing resin 20 of the die holder 11 was conveyed through the die body 10 and extruded into the chamber 4 in which cooling water having a water temperature of 60 ° C., a water pressure of 1.0 MPa, and a water amount (L1) of 20000 kg / hr circulated.
- a high-speed rotary cutter having 10 blades in the circumferential direction is brought into close contact with the resin discharge surface 13 of the die body 10, and the foaming agent-containing resin 20 is cut at 3000 revolutions per minute, dehydrated and dried.
- expandable resin particles spherical expandable polystyrene resin particles (hereinafter referred to as expandable resin particles) were obtained.
- the discharge amount (L2) of the foaming agent-containing resin (expandable resin particles) 1 hour after the start of extrusion is 170 kg / hr, and the mass of 100 expandable resin particles after drying is 0.0726 g.
- the die opening rate was 65%.
- the expandable resin particles obtained from this step had a bulk density of 0.662 g / cm 3 , a proportion of coalesced particles of 0.08%, and a particle sphericity of 0.88.
- L1 / L2 was 118.
- the expandable resin particles produced as described above are placed in a 15 ° C. cool box and allowed to stand for 72 hours, then supplied to a cylindrical batch type pre-foaming machine and heated by steam with a blowing pressure of 0.05 MPa.
- pre-expanded particles were obtained.
- the obtained pre-expanded particles had a bulk density of 0.015 g / cm 3 (bulk expansion ratio: 60 times).
- the pre-expanded particles obtained were allowed to stand for 24 hours in a room temperature atmosphere, and then the pre-expanded particles were filled into a mold having a rectangular cavity of length 400 mm ⁇ width 300 mm ⁇ height 50 mm. did.
- the inside of the mold cavity was heated with water vapor at a gauge pressure of 0.08 MPa for 20 seconds. Then, after cooling until the pressure in the cavity of the mold became 0.01 MPa, the mold was opened, and a rectangular foam molded body having a length of 400 mm ⁇ width of 300 mm ⁇ height of 50 mm was taken out.
- the obtained foamed molded article had a density of 0.015 g / cm 3 (expansion factor: 60 times).
- the bulk density of the expandable resin particles, the bulk density / bulk foaming factor of the pre-foamed particle, the density / foaming factor of the foamed molded product, the porosity were measured and evaluated under the following conditions.
- ⁇ Bulk density / bulk expansion ratio of pre-expanded particles About 5 g of pre-expanded particles are weighed (a) g in the second decimal place. Next, the pre-expanded particles weighed are placed in a 500 cm 3 graduated cylinder having a minimum scale unit of 5 cm 3 , and the pressing tool is applied to the graduated cylinder.
- This pressing tool is a circular resin plate slightly smaller than the diameter of the graduated cylinder, and a rod-shaped resin plate having a width of about 1.5 cm and a length of about 30 cm is fixed upright at the center thereof.
- the pressing tool was applied to a graduated cylinder, the volume (b) cm 3 of the pre-expanded particles was read, and the bulk density and the bulk expansion ratio of the pre-expanded particles were determined by the following equations.
- Opening rate opening rate during extrusion of the discharge nozzle on the die surface
- coalesced particles were evaluated according to the following criteria. Good: Less than 0.5% Somewhat good: 0.5 or more, less than 1.0% Defect: 1.0% or more
- ⁇ Sphericality of expandable particles> Arbitrarily selected expandable resin particles were fixed on an adhesive tape, and the image was taken with a video microscope (manufactured by SCARA: VMS-1000). Measure the shortest diameter (D1) and longest diameter (D2) of the expandable resin particles projected on the video monitor with calipers, determine the ratio of shortest diameter (D1) / longest diameter (D2), and foam this operation. 100 resin particles were measured, and the average value was calculated as the sphericity.
- Example 2 Expandable resin particles, pre-expanded particles and a foamed molded article were produced in the same manner as in Example 1 except that the resin temperature was 200 ° C. (195 ° C. in Example 1).
- Example 3 Expandable resin particles and pre-expanded particles in the same manner as in Example 1 except that the resin temperature was 200 ° C. (195 ° C. in Example 1) and the die temperature was 195 ° C. (185 ° C. in Example 1). And the foaming molding was manufactured.
- Example 4 Expandable resin particles, pre-expanded particles, and expanded molded articles were produced in the same manner as in Example 1 except that the circulating water pressure was 0.4 MPa (1.0 MPa in Example 1).
- Example 5 Expandable resin particles, pre-expanded particles, and expanded molded articles were produced in the same manner as in Example 1 except that the circulating water temperature was 30 ° C. (60 ° C. in Example 1).
- Example 6 Expandable resin particles in the same manner as in Example 1 except that the amount of circulating water L1 was 18000 kg / hr (20000 kg / hr in Example 1) and the ratio (L1 / L2) was 106 (118 in Example 1). Pre-expanded particles and foamed molded articles were produced.
- Example 7 Expandable resin particles in the same manner as in Example 1 except that the amount of circulating water L1 was 30000 kg / hr (20000 kg / hr in Example 1) and the ratio (L1 / L2) was 176 (118 in Example 1). Pre-expanded particles and foamed molded articles were produced.
- Example 8 As a base resin, a mixed resin of 50 parts by mass of polystyrene resin (trade name “HRM-10N” manufactured by Toyo Styrene Co., Ltd.) and 50 parts by mass of low density polyethylene resin (trade name “LC520” manufactured by Nippon Polyethylene Co., Ltd.) is used. Except that, expandable resin particles were produced in the same manner as in Example 1.
- Example 9 100 parts by mass of a styrene / methacrylic acid copolymer resin (manufactured by PSJ, trade name “G9001”) is used as a base resin, the resin temperature is 220 ° C., the die temperature is 210 ° C., and the circulating water temperature is 70 ° C. Except that, expandable resin particles were produced in the same manner as in Example 1.
- Example 1 Example 1 except that the resin temperature was 200 ° C. (195 ° C. in Example 1) and the die temperature was 210 ° C. (185 ° C. in Example 1) (that is, the resin temperature was less than the die temperature). In the same manner as above, expandable resin particles, pre-expanded particles, and a foam-molded article were produced.
- the resin temperature T1 and the die temperature T2 are T1> T2, and the ratio of the circulating water amount L1 and the resin discharge amount L2 (L1 / L2)
- the ratio of coalesced particles in the obtained expandable resin particles is 0.00. Less than 4% and good.
- the circulating water temperature is set to 60 ° C. and the ratio (L1 / L2) of the circulating water amount (L1) to the resin discharge amount (L2) is set to 118 or 106.
- Example 5 in which the circulating water temperature was 30 ° C. and in Example 7 in which the ratio of L1 / L2 was higher than that of the other examples, the open area ratio and the true sphere ratio were both decreased. Furthermore, it was found from Example 8 that even if a mixed resin of a polystyrene resin and a low density polyethylene resin is used, a result almost the same as that of a resin composed only of a polystyrene resin can be obtained.
- Example 9 it was found from Example 9 that even when a styrene-methacrylic acid copolymer resin was used, a result almost the same as that of a resin composed only of a polystyrene resin was obtained except that the porosity was inferior to that of a polystyrene resin. .
- the present invention relates to a method for producing a foamed thermoplastic resin particle used in producing a foamed molded article of a thermoplastic resin such as a polystyrene resin or a polyethylene resin by a hot cut method.
- a foamed thermoplastic resin particle used in producing a foamed molded article of a thermoplastic resin such as a polystyrene resin or a polyethylene resin by a hot cut method.
- Spherical and high-quality foamable thermoplastic resin particles can be efficiently produced with few and simple production equipment and processes.
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Abstract
Description
本発明は、2009年11月30日に、日本に出願された特願2009-271985号に基づき優先権を主張し、その内容をここに援用する。
特許文献1には、分子量Mwが170000g/モルを超える発泡スチレンポリマーを製造する方法であって、少なくとも120℃の温度を有する発泡剤含有スチレンポリマー溶融物を、ダイ出口の孔径が1.5mm以下の孔を有するダイプレートを介して搬送し、次いで押出物を顆粒化する方法が開示されている。この特許文献1では、溶融樹脂温度とダイス温度に関しては、段落[0021]に「ダイプレートは、少なくとも発泡剤含有ポリスチレン溶融物の温度に加熱される。ダイプレートの温度は、発泡剤含有ポリスチレン溶融物の温度より20~100℃高い範囲にあることが好ましい」と記載されている。
この特許文献3において、溶融樹脂温度とダイス温度に関しては、その実施例1中に樹脂温度を約160℃とした旨が記載されているのみであり、ダイス温度は記載されていない。
特許文献1記載の製造方法では、溶融樹脂温度よりもダイス温度が高くなるように設定している。しかしながら、この条件下では、ダイス小孔から水中に押し出され、直後にカットされた樹脂粒子の合着(2つ以上の樹脂粒子同士が融着した状態)が生じ易くなる。そのため、発泡性熱可塑性樹脂粒子の製造歩留まりが悪くなり、また高品質の発泡性熱可塑性樹脂粒子を製造し難いという問題がある。
(1)本発明は、造粒用ダイスを取り付けた樹脂供給装置に熱可塑性樹脂を供給して溶融混練させる工程と、
前記熱可塑性樹脂を前記造粒用ダイスに向けて移動させながら前記熱可塑性樹脂に発泡剤を注入して発泡剤含有樹脂を形成する工程と、
前記造粒用ダイスの樹脂吐出面に開孔したノズルから吐出される前記発泡剤含有樹脂をカッターにより冷却媒体中で切断して発泡性熱可塑性樹脂粒子を得る工程と、を有する発泡性熱可塑性樹脂粒子の製造方法であって、
前記造粒用ダイス内の前記発泡剤含有樹脂の温度T1と、前記造粒用ダイスの温度T2とがT1>T2であり、且つ前記冷却媒体の流量L1と前記ノズルから吐出される前記発泡剤含有樹脂の吐出量L2との比(L1/L2)が100~200の範囲となるように制御しつつ、発泡性熱可塑性樹脂粒子を得る発泡性熱可塑性樹脂粒子の製造方法である。
(8)さらに本発明は、前記(6)または(7)に記載の発泡性熱可塑性樹脂粒子を加熱して予備発泡させ、熱可塑性樹脂発泡粒子を得る熱可塑性樹脂発泡粒子の製造方法を提供する。
(9)さらに本発明は、前記(8)に記載の熱可塑性樹脂発泡粒子の製造方法により得られた熱可塑性樹脂発泡粒子を提供する。
(10)さらに本発明は、前記(9)に記載の熱可塑性樹脂発泡粒子を型内発泡成形して、熱可塑性樹脂発泡成形体を得る熱可塑性樹脂発泡成形体の製造方法を提供する。
(11)さらに本発明は、前記(10)に記載の熱可塑性樹脂発泡成形体の製造方法により得られた熱可塑性樹脂発泡成形体を提供する。
図1及び図2は、本発明の製造方法において使用される造粒装置の一例を示す構成図、図2はその造粒用ダイスの一例を示す側断面図、図3は図2のダイス本体の樹脂吐出面を示す側面図、図4はノズルの配置状態を示す図である。
本造粒装置100は、造粒用ダイス1が先端に取り付けられた押出機2(樹脂供給装置)と、造粒用ダイス1のノズル15から吐出される樹脂(本実施の形態では発泡剤含有樹脂20)を切断するカッター3が収容され、造粒用ダイス1の樹脂吐出面13に水流を接触させるためのチャンバー4とを備えている。チャンバー4には、循環する水などの冷却媒体(以下、水と記す)を流すための管路5が接続され、この管路5の一端(チャンバー4より上流側)が、送水ポンプ6を介して水槽7に接続されている。また、管路5の他端(チャンバー4より下流側)には、循環水から発泡性熱可塑性樹脂粒子を分離し、脱水・乾燥する脱水処理部8が設けられている。この脱水処理部8で分離され、脱水・乾燥した発泡性熱可塑性樹脂粒子は、容器9に送られる。そして、符号21はホッパー、22は発泡剤供給口、23は高圧ポンプである。
なお、造粒装置100および造粒用ダイス1において、樹脂が吐出される側を「先方」、「先端」とし、その反対側を「後方」、「後端」として以下の説明では統一して用いる。
ダイホルダ11は、押出機2のシリンダに連通して設けられ、後端側から先端側に向けて後端側流路11a、先端側流路11bがその順で形成されている。ダイス本体10には、その後端面中央部において、後方側に突出してなる円錐状凸部10aが形成されている。ダイス本体10とダイホルダ11とが接続した状態で、ダイホルダ11の先端側流路11b内に、所定隙間をもって円錐状凸部10aが挿入されている。このため、ダイホルダ11の後端側流路11aを通過した発泡剤含有樹脂20は、先端側流路11aにおいて円錐状凸部10aの周面に沿って流れ、ダイス本体10の後端面に開孔する複数の樹脂流路14(後述する)に連通する。
カートリッジヒーター17および短ヒーター18は、従来周知のカートリッジヒーターの中からダイス本体10の大きさや形状に応じて適宜選択して使用できる。例えば、カートリッジヒーター17および短ヒーター18として、棒状のセラミックに巻き付けた発熱線(ニクロム線)をパイプ(耐熱ステンレス鋼)の中に挿入し、発熱線とパイプの隙間を高熱伝導性と高絶縁性に優れた材料(MgO)で封じ込めた、電力密度の高い棒状ヒーターを用いることができる。カートリッジヒーター17および短ヒーター18は、片側にリード線が2本付いたカートリッジヒーターでも、両側にリード線が1本づつ付いたカートリッジヒーター(シーズヒーター)でもよいが、片側にリード線が2本付いたカートリッジヒーターの方が、電力密度がより高いので好ましい。
また、ダイス本体10を加熱するための手段としては、カートリッジヒーター17および短ヒーター18などの棒状ヒーターに限定されず、ダイス本体10の内部にサーモオイルなどの伝熱媒体を通す流路を形成し、加熱した伝熱媒体によってダイス本体10を加熱してもよい。加熱手段としては、棒状ヒーターのみの加熱、伝熱媒体のみの加熱、または棒状ヒーターと伝熱媒体を併用した加熱であってもよい。
カートリッジヒーター17は、樹脂流路14の前記円周の周方向両側に配置されるとともに、長手方向を円周の径方向に向けてその円周を横切った状態で配置され、樹脂吐出面13の近傍において、樹脂吐出面13、ノズル15、及び樹脂流路14を加熱する機能を有している。本実施形態の複数のカートリッジヒーター17は、それぞれが円周方向に所定の中心角(ここでは、45°の角度)をもって8本設けられている。つまり、個々のノズル15は、2本のカートリッジヒーター17、17によって前記円周の周方向から挟み込まれるようにして配置されている。
そして、カートリッジヒーター17の長さ寸法は、ダイス本体10の半径方向で配置されるノズル15より中心側に延びる位置(すなわち、少なくともカートリッジヒーター17の先端部がノズル15より中心側となる位置)からダイス本体10の略外周までの位置である。
側温体19の位置は、ダイス本体10の厚さt(図2に示す符号t)の後端側(t/10)と先端側(t/10)とを除いた中央部(8t/10)の温度を測定できる位置に設ける。本実施例では、図2に示すように、側温体19をダイス本体10の厚さtの1/2の位置に設けた。測温体19の位置を、後端側(t/10)と先端側(t/10)とを除いた位置とした理由は、後端側と先端側の位置では、ヒーターや伝熱媒体の熱が届きにくく、ダイス本体10の温度を代表していない為である。また、側温体19の先端(センサー部分)は、ダイス本体10の樹脂流路14の近傍に位置している(図3を参照)。本発明では、この測温体19により測定される温度を「造粒用ダイスの温度T2」とする。
なお、ヒートオイルなどの伝熱媒体によって、ダイス本体10の全体温度を均一に調整できる場合は、伝熱媒体の温度を「造粒用ダイスの温度T2」とすることができる。
図1に示す造粒装置100に用いる押出機2(樹脂供給装置)は、従来周知の各種押出機の中から造粒する樹脂の種類等に応じて適宜選択して使用でき、例えばスクリュを用いる押出機またはスクリュを用いない押出機のいずれも用いることができる。スクリュを用いる押出機としては、例えば、単軸式押出機、多軸式押出機、ベント式押出機、タンデム式押出機などが挙げられる。スクリュを用いない押出機としては、例えば、プランジャ式押出機、ギアポンプ式押出機などが挙げられる。また、いずれの押出機もスタティックミキサーを用いることができる。これらの押出機のうち、生産性の観点からスクリュを用いた押出機が好ましい。また、カッター3を収容したチャンバー4も、ホットカット法において用いられている従来周知のチャンバーを用いることができる。
発泡剤含有樹脂20は、押出機2の先端からダイホルダ11を経て、造粒用ダイス1のダイス本体10の樹脂流路14に送られる。樹脂流路14を通って送られた発泡剤含有樹脂20は、ダイス本体10の樹脂吐出面13に開孔した各ノズル15から吐出され、カッター3の回転刃によりチャンバー4の水流中(冷却媒体中)で直ちに切断される。
例えば、熱可塑性樹脂がポリスチレン系樹脂である場合、T1が150~230℃の範囲であることが好ましい。更に好ましいポリスチレン系樹脂のT1の範囲は、160~220℃であり、最も好ましくは170~210℃の範囲である。
また、熱可塑性樹脂がポリエチレン系樹脂である場合、T1が130~210℃の範囲であることが好ましい。更に好ましいポリエチレン系樹脂のT1の範囲は、140~200℃であり、最も好ましくは150~190℃の範囲である。
また、熱可塑性樹脂がポリプロピレン系樹脂である場合、T1が180~270℃の範囲であることが好ましい。更に好ましいポリプロピレン系樹脂のT1の範囲は、190~260℃であり、最も好ましくは200~250℃の範囲である。
また、本発明の製造方法では、様々な熱可塑性樹脂の使用が可能であるが、最も好ましい樹脂は、前記熱可塑性樹脂がポリスチレン系樹脂である。
T1とT2は、T1-5(℃)≧T2(℃)の関係を満たすことが好ましく、T1-10(℃)≧T2(℃)の関係を満たすことがより好ましい。
前記T1とT2とがT1≦T2の関係であると、ノズル15から水中に押し出され、直後にカットされた樹脂粒子の合着(2つ以上の樹脂粒子同士が融着した状態)が生じ易くなるため、発泡性熱可塑性樹脂粒子の製造歩留まりが悪くなり、また高品質の発泡性熱可塑性樹脂粒子を製造することが困難である。
また、ダイスの温度T2(℃)を発泡剤含有樹脂の温度T1(℃)より低くしすぎると、ノズル15の目詰まりを生じ易くなる。このため、ノズルの開孔率が短時間で低下してしまい、開口しているノズル1つ当たりの吐出量が増えるため、得られる発泡性熱可塑性樹脂粒子の粒子径の増大や粒子径ばらつきが大きくなる。そのため、特に限定はしないが、T1(℃)>T2(℃)の関係を満たす条件下において、T2(℃)>T1-30(℃)の関係を満たすことが好ましく、T2(℃)>T1-20(℃)の関係を満たすことがより好ましい。
前記比(L1/L2)が100未満であると、得られる樹脂粒子の合着が増加し、球状で高品質の発泡性熱可塑性樹脂粒子を得ることが困難になる。また、前記比(L1/L2)が200を超えると、ノズル15の目詰まりを生じ易くなりる。その結果、ノズルの開孔率が短時間で低下してしまい、造粒装置100の製造能率が低下する。
この圧力が0.5MPa未満であると、カットされた樹脂粒子が発泡を生じ易くなり、高品質の発泡性熱可塑性樹脂粒子を製造することが難しくなる。
前記温度が30℃未満であると、ノズル15が目詰まりし易くなる。その結果、短時間でノズル15の開孔率が低下してしまい、造粒装置100の製造能率が低下しやすい。一方、前記温度が90℃を超えると、カットされた樹脂粒子が発泡を生じ易くなり、高品質の発泡性熱可塑性樹脂粒子を製造することが難しくなる。
この合着粒子は、2つ以上の樹脂粒子同士が融着した状態であるため、多少の振動や衝撃を加えても分離しない。この合着粒子は、合着した樹脂粒子の数が多く、大粒になれば、樹脂粒子の篩い分けによって良品(単独の樹脂粒子)と区別して分離できる。しかしながら、2~3個の樹脂粒子が融着した比較的小型の合着粒子は、樹脂粒子の篩い分けの際に、篩を通過して良品中に混入してしまう可能性がある。前記合着粒子の混合割合が1質量%を超えると、発泡性熱可塑性樹脂粒子を用いて発泡成形体を製造した場合に、予備発泡粒子の充填不良や得られた発泡成形体の外観悪化、機械強度の低下などが起こる。
(発泡性ポリスチレン系樹脂粒子の製造)
図1に示した押出機2に、図2および図3に示したダイホルダ11とダイス本体10からなる造粒用ダイス1を取り付けて、発泡性ポリスチレン系樹脂粒子を製造した。図2および図3に示した測温体19を用いて、全てのカートリッジヒーター17および短ヒーター18をオンオフ制御して、造粒用ダイス1のダイス本体10の温度調整を行った。
基材樹脂としては、ポリスチレン樹脂(東洋スチレン社製、商品名「HRM-10N」)100質量部に、微粉末タルク0.3質量部を、予めタンブラーミキサーにて均一に混合したものを、口径90mmの単軸押出機内へ供給し、樹脂を加熱溶融させた。その後、発泡剤として樹脂100質量部に対して6質量部のイソペンタンを、押出機途中より圧入した。
そして、押出機内で樹脂と発泡剤を混練しつつ、ダイホルダ11での発泡剤含有樹脂20の温度が195℃となるように調整した。次に、カートリッジヒーター17および短ヒーター18を用いてダイス本体10を185℃に保持した。ダイス本体10には、直径0.6mm、ランド長さ3.0mmのノズルが200個設けられている。ダイホルダ11の発泡剤含有樹脂20を、ダイス本体10を介して搬送し、水温60℃、水圧1.0MPa、水量(L1)20000kg/hrの冷却水が循環するチャンバー4に押し出した。この押し出しと同時に、円周方向に10枚の刃を有する高速回転カッターを、ダイス本体10の樹脂吐出面13に密着させて、毎分3000回転で発泡剤含有樹脂20を切断し、脱水乾燥して球形の発泡性ポリスチレン樹脂粒子(以下、発泡性樹脂粒子と記す)を得た。
この工程での、押出開始1時間後における発泡剤含有樹脂(発泡性樹脂粒子)の吐出量(L2)は170kg/hr、乾燥後の発泡性樹脂粒子100粒の質量は0.0726gであり、ダイスの開孔率は65%であった。
この工程から得られた発泡性樹脂粒子は、嵩密度が0.662g/cm3、合着粒子の割合が0.08%、粒子の真球度が0.88であった。また、L1/L2は118であった。
前記の通り製造した発泡性樹脂粒子を、15℃の保冷庫中に入れ、72時間に亘って放置した後、円筒型バッチ式予備発泡機に供給して、吹き込み圧0.05MPaの水蒸気により加熱し、予備発泡粒子を得た。得られた予備発泡粒子は嵩密度0.015g/cm3(嵩発泡倍数60倍)であった。
続いて、得られた予備発泡粒子を室温雰囲気下で、24時間に亘って放置した後、長さ400mm×幅300mm×高さ50mmの長方形状のキャビティを有する成形型内に予備発泡粒子を充填した。その後、成形型のキャビティ内を水蒸気でゲージ圧0.08MPaの圧力で20秒間に亘って加熱した。その後、成形型のキャビティ内の圧力が0.01MPaになるまで冷却した後、成形型を開き、長さ400mm×幅300mm×高さ50mmの長方形状の発泡成形体を取り出した。得られた発泡成形体は、密度0.015g/cm3(発泡倍数60倍)であった。
乾燥した発泡性樹脂粒子を500cm3メスシリンダー内に容積が一定となるまで、メスシリンダーの底をたたいて発泡性樹脂粒子を充填する。その時の発泡性樹脂粒子の容積と質量を測定し、次式により算出した。なお、容積は1cm3単位で読み取り、質量は最小目盛り0.01gの電子天秤を用いて測定した。
嵩密度(g/cm3)=発泡性樹脂粒子の質量(g)/発泡性樹脂粒子の容積(cm3)
約5gの予備発泡粒子の質量(a)gを小数以下2位で秤量する。次に、最小目盛り単位が5cm3である500cm3メスシリンダーに秤量した予備発泡粒子を入れ、押圧具をメスシリンダーにあてる。この押圧具は、メスシリンダーの口径よりやや小さい円形の樹脂板であって、その中心に幅約1.5cm、長さ約30cmの棒状の樹脂板が直立して固定されている。押圧具をメスシリンダーにあてて、予備発泡粒子の体積(b)cm3を読み取り、次式により予備発泡粒子の嵩密度と嵩発泡倍数を求めた。
嵩密度(g/cm3)=(a)/(b)
嵩発泡倍数(倍)=1/嵩密度(g/cm3)
50cm3以上(半硬質および軟質材料の場合は100cm3以上)の試験片を材料の元のセル構造を変えない様に切断し、その質量を測定し、次式により算出した。
密度(g/cm3)=試験片質量(g)/試験片体積(cm3)
試験片状態調節、測定用試験片は、成形後72時間以上経過した試料から切り取り、23℃±2℃×50%±5%または27℃±2℃×65%±5%の雰囲気条件に16時間以上放置したものである。
また、発泡成形体の発泡倍数は次式により算出される数値である。
発泡倍数(倍)=1/密度(g/cm3)
発泡性樹脂粒子の製造開始から1時間経過後、ダイスを調べ、ノズルの開孔率を次のように算出した。
開孔率(ダイス表面の吐出ノズルの押出時開孔率)=開孔数/ダイス全ノズル数×100(%)
吐出量(kg/hr)=1時間当たり、カッターで切り出される全発泡性樹脂粒子の総質量
=開孔数×切り出し個数×1粒質量
=開孔数×カッター刃数×カッター回転数×1粒質量
よって開孔数は、
開孔数=吐出量(kg/hr)/〔カッター刃数×カッター回転数(rph)×1粒質量(kg/個)
となるため、開孔率は次式で算出できる。
開孔率(E)=開孔数/全ノズル数×100(%)
=〔Q/(N×R×60×(M/100)/1000)〕/H×100(%)
(式中、Qは吐出量(kg/hr)、Nはカッター刃の枚数、Rはカッター回転数(rpm)、Mは100粒質量(g) (発泡性樹脂粒子から任意の100粒を選び、最小目盛0.0001gの電子天秤で計量した100粒質量とした、Hはダイスの全ノズル数をそれぞれ表す。)
任意に選んだ発泡性樹脂粒子約1gを電子天秤にて精秤し質量を求めた(W1)。そのなかから2個以上合着している粒子を選別し、同様に電子天秤にて精秤して質量(W2)を求めて次式により算出した。
合着粒子率=W2/W1×100(%)
合着粒子は以下の基準で評価した。
良好 :0.5%未満
やや良 :0.5以上、1.0%未満
不良 :1.0%以上
任意に選んだ発泡性樹脂粒子を粘着テープ上に固定し、その画像をビデオマイクロスコープ(スカラ社製:VMS-1000)において撮影した。ビデオモニター上に映し出された発泡性樹脂粒子の最短径(D1)と最長径(D2)をノギスにて計測し、最短径(D1)/最長径(D2)の比率を求め、この操作を発泡性樹脂粒子100個について計測し、平均値を算出して真球度とした。
樹脂温度を200℃(実施例1では195℃)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
樹脂温度を200℃(実施例1では195℃)とし、またダイス温度を195℃(実施例1では185℃)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
循環水圧を0.4MPa(実施例1では1.0MPa)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
循環水温を30℃(実施例1では60℃)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
循環水量L1を18000kg/hr(実施例1では20000kg/hr)とし、比(L1/L2)を106(実施例1では118)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
循環水量L1を30000kg/hr(実施例1では20000kg/hr)とし、比(L1/L2)を176(実施例1では118)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
基材樹脂としてポリスチレン樹脂(東洋スチレン社製、商品名「HRM-10N」)50質量部と、低密度ポリエチレン樹脂(日本ポリエチレン社製、商品名「LC520」)50質量部との混合樹脂を使用したこと以外は、実施例1と同様にして発泡性樹脂粒子を製造した。
基材樹脂としてスチレンメタクリル酸共重合樹脂(PSJ社製、商品名「G9001」)100質量部を使用し、樹脂温度を220℃、ダイス温度を210℃とし、また循環水温度を70℃としたこと以外は、実施例1と同様にして発泡性樹脂粒子を製造した。
樹脂温度を200℃(実施例1では195℃)、またダイス温度を210℃(実施例1では185℃)とした(すなわち、樹脂温度<ダイス温度の条件とした)こと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
循環水量L1を16000kg/hr(実施例1では20000kg/hr)とし、比(L1/L2)を94(実施例1では118)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
循環水量L1を35000kg/hr(実施例1では20000kg/hr)とし、比(L1/L2)を206(実施例1では118)としたこと以外は、実施例1と同様にして発泡性樹脂粒子、予備発泡粒子及び発泡成形体を製造した。
また、循環水温60℃、且つ循環水量(L1)と樹脂吐出量(L2)との比(L1/L2)が118又は106となるように設定した実施例1~4、6及び8では、真球度が0.87以上と高く、また開孔率も65%以上となり、安定して高品質の発泡性樹脂粒子を製造できることが分かった。
循環水温が30℃である実施例5、およびL1/L2の比が、他の実施例より高い実施例7では、いずれも開孔率および真球率が低下した。
更に、ポリスチレン樹脂と、低密度ポリエチレン樹脂との混合樹脂を使用しても、ポリスチレン樹脂のみから成る樹脂とほぼ同様な結果が得られることが、実施例8から分かった。また、スチレンメタクリル酸共重合樹脂を使用しても、ポリスチレン樹脂と比べて開孔率が劣る以外は、ポリスチレン樹脂のみから成る樹脂とほぼ同様な結果が得られることが、実施例9から分かった。
また、循環水量(L1)と樹脂吐出量(L2)との比(L1/L2)を94と、本発明の比の範囲の下限(100)未満に設定した比較例2では、得られる発泡性樹脂粒子中の合着粒子の割合が5%と高く、不良であった。
さらに、循環水量(L1)と樹脂吐出量(L2)との比(L1/L2)を206と、本発明の比の範囲の上限(200)を超えるように設定した比較例3では、ダイスのノズル開孔率が28%と低くなり、真球度も低くなり、安定して高品質の発泡性樹脂粒子を製造できなかった。
2 押出機(樹脂供給装置)
3 カッター
4 チャンバー
10 ダイス本体
11 ダイホルダ
13 樹脂吐出面
14 樹脂流路
15 ノズル
16 断熱材
17 カートリッジヒーター
18 短ヒーター
19 測温体
20 発泡剤含有樹脂
100 造粒装置
Claims (11)
- 造粒用ダイスを取り付けた樹脂供給装置に熱可塑性樹脂を供給して溶融混練させる工程と、
前記熱可塑性樹脂を前記造粒用ダイスに向けて移動させながら前記熱可塑性樹脂に発泡剤を注入して発泡剤含有樹脂を形成する工程と、
前記造粒用ダイスの樹脂吐出面に開孔したノズルから吐出される前記発泡剤含有樹脂をカッターにより冷却媒体中で切断して発泡性熱可塑性樹脂粒子を得る工程と、を有する発泡性熱可塑性樹脂粒子の製造方法であって、
前記造粒用ダイス内の前記発泡剤含有樹脂の温度T1と、前記造粒用ダイスの温度T2とがT1>T2であり、且つ前記冷却媒体の流量L1と前記ノズルから吐出される前記発泡剤含有樹脂の吐出量L2との比(L1/L2)が100~200の範囲となるように制御しつつ、発泡性熱可塑性樹脂粒子を得る発泡性熱可塑性樹脂粒子の製造方法。 - 前記ノズルから吐出される前記発泡剤含有樹脂をカッターにより冷却媒体中で切断する際の冷却媒体の圧力が0.5MPa以上である請求項1に記載の発泡性熱可塑性樹脂粒子の製造方法。
- 前記ノズルから吐出される前記発泡剤含有樹脂をカッターにより冷却媒体中で切断する際の冷却媒体の温度が30~90℃の範囲内である請求項1又は2に記載の発泡性熱可塑性樹脂粒子の製造方法。
- 前記熱可塑性樹脂がポリスチレン系樹脂であり、前記造粒用ダイス内の前記発泡剤含有樹脂の温度T1が150~230℃の範囲である請求項1~3のいずれか1項に記載の発泡性熱可塑性樹脂粒子の製造方法。
- 得られる発泡性熱可塑性樹脂粒子中の合着粒子(ただし、合着粒子とは2つ以上の樹脂粒子同士が融着した状態の粒子のことである)の混合割合が1質量%以下となるように前記温度T1,T2及び比(L1/L2)を設定する請求項1~4のいずれか1項に記載の発泡性熱可塑性樹脂粒子の製造方法。
- 請求項1~5のいずれか1項に記載の発泡性熱可塑性樹脂粒子の製造方法により得られた発泡性熱可塑性樹脂粒子。
- ホットカット法により製造され、2つ以上の樹脂粒子同士が融着した粒子の混合割合が1質量%以下である発泡性熱可塑性樹脂粒子。
- 請求項6又は7に記載の発泡性熱可塑性樹脂粒子を加熱して予備発泡させ、熱可塑性樹脂発泡粒子を得る熱可塑性樹脂発泡粒子の製造方法。
- 請求項8に記載の熱可塑性樹脂発泡粒子の製造方法により得られた熱可塑性樹脂発泡粒子。
- 請求項9に記載の熱可塑性樹脂発泡粒子を、型内発泡成形して熱可塑性樹脂発泡成形体を得る熱可塑性樹脂発泡成形体の製造方法。
- 請求項10に記載の熱可塑性樹脂発泡成形体の製造方法により得られた熱可塑性樹脂発泡成形体。
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JP2014065868A (ja) * | 2012-09-27 | 2014-04-17 | Sekisui Plastics Co Ltd | 熱可塑性樹脂粒子とその製造方法、発泡性熱可塑性樹脂粒子とその製造方法、予備発泡粒子及び発泡成形体 |
JP2022009145A (ja) * | 2017-03-03 | 2022-01-14 | 株式会社カネカ | 発泡性熱可塑性樹脂粒子の製造方法 |
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