WO2023282198A1 - 発泡ビーズ、その製造方法、及び成形体 - Google Patents
発泡ビーズ、その製造方法、及び成形体 Download PDFInfo
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- WO2023282198A1 WO2023282198A1 PCT/JP2022/026424 JP2022026424W WO2023282198A1 WO 2023282198 A1 WO2023282198 A1 WO 2023282198A1 JP 2022026424 W JP2022026424 W JP 2022026424W WO 2023282198 A1 WO2023282198 A1 WO 2023282198A1
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- WIPO (PCT)
- Prior art keywords
- foaming
- beads
- resin
- base resin
- foamed
- Prior art date
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- 238000000137 annealing Methods 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- LPRHLAXCXZTKNI-UHFFFAOYSA-N dibutyl methyl phosphate Chemical compound CCCCOP(=O)(OC)OCCCC LPRHLAXCXZTKNI-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- JQVXMIPNQMYRPE-UHFFFAOYSA-N ethyl dimethyl phosphate Chemical compound CCOP(=O)(OC)OC JQVXMIPNQMYRPE-UHFFFAOYSA-N 0.000 description 1
- ANPYQJSSFZGXFE-UHFFFAOYSA-N ethyl dipropyl phosphate Chemical compound CCCOP(=O)(OCC)OCCC ANPYQJSSFZGXFE-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- QZUJCEPTAIXZFA-UHFFFAOYSA-N methyl prop-2-enoate;styrene Chemical compound COC(=O)C=C.C=CC1=CC=CC=C1 QZUJCEPTAIXZFA-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B29C44/36—Feeding the material to be shaped
- B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
- B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
Definitions
- the present invention relates to expanded beads, a method for producing the same, and a molded article containing the expanded beads.
- plastics and metals have been used as materials for internal parts of automobiles and electronic devices. Since plastics are lighter than metals, their applications are expanding to include electronic devices, miscellaneous goods, and automobile parts. materials are sought.
- One of such materials is a resin foam molding.
- foam bead molded articles have recently been attracting attention because of their excellent shapeability and the ability to form complex shapes with good reproducibility.
- a foamed bead molded article can be obtained in a desired shape by filling a molding die with foamed beads and heating and fusing them. When the foam beads are filled into the mold during the molding process, voids are generated between the foam beads, which need to be filled in some way.
- the foam beads are compressed and filled, and the foam beads return to their original size in the mold to fill the voids (compression filling method).
- a method of filling the mold with the mold slightly open to increase the amount of filled beads (cracking method).
- a method of expanding the foamed beads by heating during molding (addition method), or a molding method combining these, for example, a method of performing a small amount of cracking after addition, etc., can be mentioned. Since the compression filling method compresses foamed beads, it is not suitable for resins such as polystyrene that buckle under compression. On the other hand, the cracking method has the disadvantage that the weight of the molded product increases as the amount of filled beads increases.
- the cracking will cause variations in the expansion ratio.
- cracking increases the amount of bead filling, and the force required to compress the beads when closing the mold increases.
- Patent Document 1 Although the foamed beads described in Patent Document 1 are excellent in flame retardancy, molding is only applied to flat plates, and improvements have been made in application to complex shapes, thin-walled moldings, and shapes having parts with different thicknesses. is required, and there are major restrictions on shape design, so its use has been limited. In addition, cracking is essential during molding, and it has been difficult to expand to automobile applications where thickness accuracy is required.
- an object of the present invention is to provide foamed beads that are excellent in expandability during molding, a method for producing the same, and a molded article containing the foamed beads.
- foamed beads having a heat shrinkage rate of 30% or less at a specific temperature have excellent expansion ability during molding processing, and have completed the present invention. rice field.
- the present invention is as follows [1] A foamed bead comprising a base resin containing a thermoplastic resin, and having a heat shrinkage rate of 30% or less when heated at Tsp+10° C. for 5 minutes, where Tsp is the softening point of the base resin. . [2] The expanded bead according to [1], wherein the base resin has a softening point Tsp of 130° C. or higher. [3] The expanded bead according to [1] or [2], wherein the average thickness of the skin layer constituting the surface of the expanded bead is 0.2 to 2.0% of the average particle diameter of the expanded bead.
- the present invention it is possible to provide a foamed bead with excellent expandability during molding, a method for producing the same, and a molded article containing the foamed bead.
- FIG. 1 is an image (magnification: 200 times) of a cross-section of a foamed bead observed with a scanning electron microscope (SEM) for one embodiment of the foamed bead according to the present invention.
- FIG. 4 is a schematic diagram showing molded bodies with different thicknesses molded in Examples and Comparative Examples.
- this embodiment The form for carrying out the present invention (hereinafter referred to as "this embodiment") will be specifically described below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
- the foamed beads of the present embodiment contain a base resin containing a thermoplastic resin, and when the softening point of the base resin is Tsp, the heat shrinkage rate when heated at Tsp + 10 ° C. for 5 minutes is 30% or less. be.
- the foamed beads of the present embodiment have a heat shrinkage rate of 30% or less, preferably 28% or less, more preferably 25% or less when heated at Tsp+10° C. for 5 minutes.
- the heat shrinkage rate is preferably 2% or more, more preferably 3% or more, and still more preferably 5% or more.
- the heat shrinkage rate is defined as (1 ⁇ Xb/Xa) ⁇ 100(%).
- the expansion ratio of the expanded beads is obtained by measuring the mass W (g) of the expanded beads, measuring the volume V (cc) of the expanded beads by the submersion method, and dividing the volume V by the mass W to obtain the value V/W (cc / g).
- the method for making the heat shrinkage rate 30% or less when treated at Tsp + 10°C for 5 minutes there are no particular restrictions on the method for making the heat shrinkage rate 30% or less when treated at Tsp + 10°C for 5 minutes, but for example, it can be achieved by raising the foaming temperature when foaming the resin.
- Hot-air foaming etc. are mentioned as a method of making foaming temperature high. Hot air foaming will be described later.
- heat treatment such as annealing may be performed.
- the expansion ratio of the foamed beads of the present embodiment is not particularly limited, but is preferably 1.5 to 30 cc/g, more preferably 2 to 20 cc/g, and 3 to 18 cc. /g is more preferred.
- the expansion ratio can be controlled by adjusting the content (impregnation) of the foaming agent in the base resin, the heating temperature and time during foaming, and the time the base resin impregnated with the foaming agent is left to stand before foaming. The larger the impregnated amount of the foaming agent, the higher the expansion ratio.
- the primary expansion ratio is preferably 1.4 to 15 cc/g, more preferably 1.7 to 13 cc/g, and even more preferably 2 to 10 cc/g. Within this range, the size of the air bubbles (cells) is likely to be uniform, and the secondary foaming ability is likely to be imparted.
- the expanded beads of the present embodiment preferably have an average particle size of 0.5 to 10 mm, more preferably 0.7 to 7 mm, still more preferably 0.8 to 5 mm.
- the average particle size of the expanded beads can be adjusted by adjusting the expansion ratio and the average particle size of the base resin.
- the average particle diameter of the expanded beads is obtained by measuring the equivalent circle diameters of 500 or more expanded beads using a digital microscope, and taking the average value thereof as the average particle diameter. More specifically, it can be determined by the method described in Examples below.
- the average thickness of the skin layer constituting the surface is preferably 0.2 to 2.0% of the average particle diameter of the expanded beads, more preferably 0.25 to 1.8%. , more preferably 0.3 to 1.5%.
- FIG. 1 is an image (magnification: 200 times) of the cross section of an example of the foamed beads of the present embodiment observed by SEM.
- the skin layer 1 of the expanded bead is the outermost layer constituting the surface of the expanded bead, and is a portion made of unfoamed base resin (that is, does not contain air bubbles 2).
- the skin layer which is the outermost layer constituting the surface, undergoes the greatest amount of deformation and is easily broken.
- the skin layer is broken, the gas existing in the cells of the foamed beads is released to the outside, resulting in a decrease in expandability.
- the skin layer is too thick, the stress required to stretch and deform the skin layer increases when the expanded beads are expanded by heating during molding, and the expansion capacity tends to decrease.
- the thickness of the skin layer is 0.2 to 2.0% of the average particle diameter of the expanded beads, the expansion of the beads during molding is not inhibited, and the breakage of the skin layer is less likely to occur, thereby improving the expandability of the expanded beads. is easier to improve.
- the skin layer is formed by dissipation of the foaming agent from the surface of the base resin, and the thickness of the skin layer increases as the amount of the foaming agent dissipated increases. Therefore, the thickness of the skin layer can be adjusted by controlling the concentration of the foaming agent, the amount of heat applied during foaming, the heating rate, the standing time of the base resin impregnated with the foaming agent before foaming, and the like. Also, the skin layer tends to become thinner as the foaming ratio of the foamed beads increases. This is because the stretch amount of the skin layer increases as the expansion ratio increases.
- the average thickness of the skin layer of the expanded beads is a value obtained by the following method.
- the foamed bead is cut along a plane passing through the center point to divide it into two pieces, and a photograph of the cut surface is taken with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- one bead is photographed at four locations, up, down, left and right, and in each cross-sectional photograph obtained, the thickness of the skin layer is measured for all the cells present on the outermost periphery.
- An arithmetic mean value is obtained for each of the 10 beads with the smallest numerical values, and the arithmetic mean value of the obtained values for each of the top, bottom, left, and right is taken as the thickness of the skin layer of the foamed bead.
- This operation is performed in the same manner for five or more expanded beads, and the arithmetic average value of the thickness of the skin layer of each expanded bead is taken as the average thickness ( ⁇ m) of the skin layer of the expanded beads. More specifically, it can be determined by the method described in Examples below.
- the closed cell ratio of the expanded beads is preferably as high as possible, preferably 50% or more, more preferably 60% or more, and still more preferably 80% or more. When the closed cell content is 50% or more, the foamed beads tend to be more excellent in moldability into molded articles.
- the average cell diameter of the expanded beads is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, still more preferably 15 to 100 ⁇ m.
- the average cell diameter of the expanded beads is a value obtained by the following method. First, the foamed bead is cut along a plane passing through the center point to divide it into two pieces, and a photograph of the cut surface is taken with a scanning electron microscope (SEM). Next, straight lines are drawn at equal intervals in eight directions from the center point of the cut surface of the foamed bead in the obtained cross-sectional photograph, and all the number of bubbles intersecting with the straight lines are counted.
- the value obtained by dividing the total length of the straight lines by the total number of cells counted is taken as the cell diameter of the expanded beads. This operation is similarly performed for 10 or more expanded beads, and the arithmetic average value of the bubble diameters of the expanded beads is taken as the average bubble diameter of the expanded beads.
- the shape of the foamed beads of this embodiment is not particularly limited, and may be various shapes.
- the expanded beads of the present embodiment contain a base resin and can be made of the base resin.
- the base resin contains a thermoplastic resin, and may further contain a flame retardant, a rubber component, and the like.
- the softening point Tsp of the base resin of the expanded beads of the present embodiment is preferably 130°C or higher, more preferably 131 to 270°C, even more preferably 135 to 250°C.
- the softening point Tsp of the base resin is within the above range, the heat resistance of the foamed molded product is further improved.
- the softening point Tsp of the base resin is determined when the ratio (E1/E2) of the storage elastic modulus E1 at a certain temperature T to the storage elastic modulus E2 at a temperature 5° C. lower than T is 0.0 in the dynamic viscoelasticity measurement. The lowest temperature among T that becomes 1 or less. If E1/E2 is not equal to or less than 0.1, the temperature T at which the value of E1/E2 becomes minimum is defined as Tsp. Specifically, it can be measured by the method described in Examples below.
- Thermoplastic resins contained in the base resin include polyolefin resins such as polyethylene, polypropylene, EVA (ethylene-vinyl acetate copolymer), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, ABS (acrylonitrile-butadiene-styrene ) resin, AS (acrylonitrile-styrene) resin, polystyrene resin, methacrylic resin, polyamide resin, polycarbonate resin, polyphenylene ether resin, polyimide resin, polyacetal resin, polyester resin, acrylic resin, cellulose resin
- Thermoplastic engineering for resins, thermoplastic elastomers such as styrene, polyvinyl chloride, polyurethane, polyester, polyamide, 1,2-polybutadiene, fluororubber, polyamide, polyacetal, polyester, and fluorine Examples include plastics and powdered rubber.
- thermoplastic resins containing polyphenylene ether resins and thermoplastic resins containing polyamide resins are preferable from the viewpoint of heat resistance, and thermoplastic resins containing polyphenylene ether resins are more preferable from the viewpoint of workability.
- the polyphenylene ether-based resin refers to a polymer represented by the following general formula (1).
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, or a halogen and general formula (1 ) having at least 2 carbon atoms between it and the benzene ring in ) and not containing the 3rd ⁇ -carbon atom.
- n is an integer representing the degree of polymerization.
- the polyphenylene ether resin preferably has a weight average molecular weight of 20,000 to 60,000.
- the weight average molecular weight is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is a calibration curve obtained from the measurement of a commercially available standard polystyrene (standard polystyrene (prepared using the peak molecular weight of ).
- GPC gel permeation chromatography
- standard polystyrene prepared using the peak molecular weight of .
- Measurements can be made with a solvent flow rate of 1.0 mL/min and a column temperature of 40°C.
- the UV wavelength of the detector is 254 nm for standard polystyrene and 283 nm for polyphenylene ether.
- polyphenylene ether resins include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl -1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6) -propyl-1,4-phenylene) ether, poly(2,6-dibutyl-1,4-phenylene) ether, poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl) -1,4-diphenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether, poly(2,6-diethoxy-1,4-phenylene) ether, poly(2-methoxy-6-ethoxy) -1
- R 1 and R 2 are C 1-4 alkyl groups
- R 3 and R 4 are hydrogen or C 1-4 alkyl groups. These may be used individually by 1 type, or may be used in combination of 2 or more type.
- Polyphenylene ether-based resins in particular, can improve deflection temperature under load (HDT), maintain rigidity even in a high-temperature environment, and can improve dimensional stability.
- Polyphenylene ether resins can be mixed with one or more other resins, examples of which include polystyrene resins, polyolefin resins typified by polypropylene, engineering plastic resins typified by polyamide, and polyphenylene sulfide. Typical examples include super engineering plastic resins. Among these, from the viewpoint of improving workability, it is preferable to mix with a polystyrene resin.
- the content of the polyphenylene ether resin in 100% by mass of the base resin is preferably 30% by mass or more, more preferably 33% by mass or more, still more preferably 35% by mass or more, from the viewpoint of heat resistance. 40 mass % or more, particularly preferably 50 mass % or more. In addition, the foaming temperature and molding temperature are lowered, the processability is excellent, and processing can be easily performed with general-purpose equipment without introducing special equipment. % or less, more preferably 85 mass % or less.
- polystyrene resin refers to a homopolymer of styrene and styrene derivatives, and a copolymer containing styrene and styrene derivatives as main components (components contained in polystyrene resin in an amount of 50% by mass or more).
- styrene derivatives include o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, diphenylethylene, chlorostyrene and bromostyrene. is not limited to
- homopolymer polystyrene resins include polystyrene, poly ⁇ -methylstyrene, and polychlorostyrene.
- Copolymer polystyrene resins include styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene- N-phenylmaleimide copolymer, styrene-N-alkylmaleimide copolymer, styrene-N-alkyl-substituted phenylmaleimide copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methyl acrylate Binary copolymers such as cop
- Graft copolymers such as styrene-grafted polyethylene, styrene-grafted ethylene-vinyl acetate copolymer, (styrene-acrylic acid)-grafted polyethylene, and styrene-grafted polyamide are also included. These may be used individually by 1 type, or may be used in combination of 2 or more type.
- polystyrene resins those having a weight average molecular weight of 180,000 to 500,000 are preferred.
- the weight average molecular weight is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is a calibration curve obtained from the measurement of a commercially available standard polystyrene (standard polystyrene (prepared using the peak molecular weight of ).
- standard polystyrene prepared using the peak molecular weight of .
- Measurements can be made with a solvent flow rate of 1.0 mL/min and a column temperature of 40°C.
- the UV wavelength of the detector is set to 254 nm for both standard polystyrene and polystyrene resin.
- the content of the polystyrene-based resin in the base resin is not particularly limited, and it is used after being appropriately adjusted so that the content of the other components becomes the desired content.
- Polyamide-based resins include, for example, polyamide homopolymers, polyamide copolymers, and mixtures thereof.
- Polyamide homopolymers include, for example, nylon 66, nylon 610, nylon 612, nylon 46, nylon 1212, etc. obtained by polycondensation of diamine and dicarboxylic acid; nylon 6, nylon obtained by ring-opening polymerization of lactam 12 and the like.
- polyamide copolymers include nylon 6/66, nylon 66/6, nylon 66/610, nylon 66/612, and the like. Among them, aliphatic polyamides are preferred, and nylon 6, nylon 66, nylon 6/66, nylon 66/6 and the like are more preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the melting point of the polyamide-based resin is preferably 170°C or higher, more preferably 180°C or higher, from the viewpoint of suppressing coloration of the polyamide-based resin foam beads and ensuring sufficient heat resistance of the foamed molded product.
- the temperature is preferably 270° C. or lower, more preferably 250° C. or lower.
- the degree of crosslinking of the resin can be increased.
- the base resin may contain a flame retardant.
- Flame retardants include organic flame retardants and inorganic flame retardants.
- Organic flame retardants include halogen compounds such as bromine compounds and non-halogen compounds such as phosphorus compounds and silicone compounds. be.
- inorganic flame retardants include metal hydroxides typified by aluminum hydroxide and magnesium hydroxide, and antimony compounds typified by antimony trioxide and antimony pentoxide.
- non-halogen flame retardants are preferable, and phosphorus flame retardants are more preferable, from the viewpoint of the environment, but the present invention is not limited to these.
- Phosphorus-based flame retardants include, for example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cre Dildiphenyl phosphate, dicresylphenyl phosphate, dimethylethyl phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, hydroxyphenyldiphenyl phosphate, resorcinol bisdiphenyl phosphate, etc., and compounds modified with various substituents, and various Condensation type phosphate ester compounds are also included.
- the content of the flame retardant in the base resin is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- the content of the flame retardant is 5 parts by mass or more, desired flame retardancy is likely to be exhibited.
- the amount is 30 parts by mass or less, the plasticizing effect of the base resin by the flame retardant becomes appropriate, and the heat resistance is improved.
- the extensional viscosity of the resin during foaming is improved, the expansion ratio is increased, the closed cell ratio of the foamed beads is improved, and the moldability into a molded product is excellent.
- the base resin contains a rubber component from the viewpoint of improving foamability.
- rubber components include butadiene, isoprene, and 1,3-pentadiene, but are not limited thereto. These are preferably dispersed in the form of particles in a continuous phase made of polystyrene resin.
- the rubber component itself may be added, or a resin such as a styrene-based elastomer or a styrene-butadiene copolymer may be used as a rubber component supply source. In the latter case, the rubber component ratio (R) can be calculated by the following formula.
- R C ⁇ Rs/100 C: rubber concentration in the rubber component supply source (% by mass)
- Rs Content of rubber source in base resin (% by mass)
- the content of the rubber component in the base resin is preferably 0.3 to 10% by mass, more preferably 0.5 to 8% by mass. When it is 0.3% by mass or more, desired flame retardancy is likely to be exhibited. Furthermore, when the content is 0.5% by mass or more, the flexibility and elongation of the resin are excellent, the foamed cell membrane is less likely to break during foaming, the foaming ratio is increased, and the foamed beads are excellent in moldability even after foaming. On the other hand, if the content of the rubber component is 10% by mass or less, the desired flame retardancy is likely to be exhibited. Furthermore, sufficient heat resistance is obtained as it is 8 mass % or less.
- thermoplastic resins stabilizers, impact modifiers, lubricants, pigments, dyes, weather resistance modifiers, antistatic agents, impact modifiers, crystal nucleating agents, glass beads, inorganic fillers
- Additives such as materials, cross-linking agents, and nucleating agents such as talc may be added to the extent that the object of the invention is not impaired.
- the content of the additive in the base resin is not particularly limited as long as it does not impair the object of the invention. It is below.
- the stabilizer examples include organic antioxidants and heat stabilizers such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, phosphite compounds, and thioether compounds; hindered amines, Benzophenone-based, imidazole-based light stabilizers and UV absorbers; metal deactivators, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the shape of the base resin is not particularly limited, but examples thereof include beads, pellets, spheres, pulverized products of irregular shape, and the like.
- the size (length) of the base resin is preferably 0.2 to 5.0 mm, more preferably 0.2 to 3.0 mm. When the size is within this range, the foamed beads obtained by foaming the base resin have a suitable size, are easy to handle, and tend to be more densely packed during molding. As the length and diameter of the base resin become smaller, the surface area per unit volume increases, so the foaming agent tends to dissipate from the surface during the foaming step or when left standing before foaming, and the skin layer tends to become thicker.
- the foaming agent dissipates too much, it becomes difficult to increase the foaming ratio.
- the size of the base resin is within the above range, it becomes easier to obtain foamed beads having a desired expansion ratio while forming a skin layer with an appropriate thickness.
- the foamed beads of the present embodiment can be obtained by containing (impregnating) a foaming agent in a base resin (impregnation step) and foaming the base resin (foaming step).
- the method for incorporating the foaming agent into the base resin is not particularly limited, and commonly used methods can be applied.
- the method of incorporating the foaming agent include a method of using a suspension system such as water in an aqueous medium (suspension impregnation), and a method of using a thermally decomposable foaming agent such as sodium bicarbonate (decomposing the foaming agent). (liquid phase impregnation), gas is brought into contact with the base resin in a gaseous state under a high-pressure atmosphere below the critical pressure. method (vapor phase impregnation) and the like.
- the method of vapor-phase impregnation with a gas under a high-pressure atmosphere below the critical pressure is particularly preferred.
- the vapor phase impregnation method has better solubility of the gas in the resin than the suspension impregnation performed under high temperature conditions, and tends to increase the content of the blowing agent. Therefore, it is easy to achieve a high expansion ratio, and the cell size in the base resin tends to be uniform.
- the blowing agent decomposition method is similarly performed under high temperature conditions, and not all of the added thermally decomposing blowing agent turns into gas, so the amount of gas generated tends to be relatively small. Therefore, vapor phase impregnation has the advantage of making it easier to increase the content of the blowing agent.
- gas phase impregnation tends to make equipment such as a pressure-resistant device and a cooling device more compact, and the cost of equipment can be kept low.
- the gas phase impregnation conditions are not particularly limited, but the atmospheric pressure is preferably 0.5 to 6.0 MPa, more preferably 1.0 to 5.0 MPa. Also, the ambient temperature is preferably 5 to 30°C, more preferably 7 to 15°C. The impregnation time is preferably 0.5 to 48 hours, more preferably 1 to 24 hours. When the atmospheric pressure, atmospheric temperature, and impregnation time are within the above ranges, gas dissolution into the base resin tends to proceed more efficiently. In particular, when the ambient temperature is low, the impregnation amount increases but the impregnation speed slows down, and when the atmosphere temperature is high, the impregnation amount decreases but the impregnation speed tends to increase.
- the ambient temperature is set as described above in order to proceed.
- the base resin impregnated with the foaming agent by vapor phase impregnation is kept at room temperature (23 to 25°C) or preheated before proceeding to the foaming step in order to adjust the foaming ratio of the resulting foamed beads and the thickness of the skin layer. It may be left for a certain period of time without being heated in a foaming machine (40 to 100° C.) that has been warmed by, for example.
- the standing time at room temperature is not particularly limited, and may be appropriately set according to the desired expansion ratio and thickness of the skin layer. It is preferably 0 to 60 seconds.
- the standing time in the foaming machine (40 to 100° C.) is not particularly limited, and may be appropriately set according to the desired foaming ratio and thickness of the skin layer, but is preferably 0 to 30 seconds. More preferably 0 to 20 seconds, still more preferably 0 to 10 seconds.
- the foaming agent is not particularly limited, and commonly used gases can be used. Examples include air, carbon dioxide, nitrogen gas, oxygen gas, ammonia gas, hydrogen gas, argon gas, helium gas, inorganic gases such as neon gas, trichlorofluoromethane (R11), dichlorodifluoromethane (R12), chlorodifluoromethane (R22), tetrachlorodifluoroethane (R112), dichlorofluoroethane (R141b), chlorodifluoroethane (R142b), difluoroethane (R152a), fluorocarbons such as HFC-245fa, HFC-236ea, HFC-245ca, HFC-225ca, propane, n - saturated hydrocarbons such as butane, i-butane, n-pentane, i-pentane, neopentane, dimethyl ether, diethyl ether, methyl
- Inorganic gases are preferred from the viewpoint of gas safety.
- inorganic gases are less soluble in resin than organic gases such as hydrocarbons, and are easily dispersed from the surface of the base resin, so that the formation of the skin layer is facilitated.
- gas is easily released from the resin, so there is also the advantage that the dimensional stability of the molded product over time is more excellent.
- plasticization of the resin due to residual gas is less likely to occur, and there is also the advantage that excellent heat resistance is likely to be exhibited from an early stage after molding.
- carbon dioxide gas is preferable from the viewpoint of solubility in resin and ease of handling, and the impregnation amount thereof is preferably 3 to 13% by mass, more preferably 3.5 to 10% with respect to the resin. % by mass.
- the amount of impregnated carbon dioxide gas is 3% by mass or more, it becomes easier to achieve a higher expansion ratio, and the variation in cell size in the base resin is reduced, suppressing the variation in expansion ratio between base resins. easier. Further, when the amount is 13% by mass or less, the cell size becomes appropriate, and it becomes easy to suppress a decrease in closed cell ratio due to excessive foaming.
- a polyamide-based resin When a polyamide-based resin is used as the thermoplastic resin contained in the base resin, it is preferable to contain a polar solvent before foaming from the viewpoint of foamability.
- the polar solvent include water; alcohols such as methanol, ethanol and isopropanol; and acetone. Above all, it has excellent impregnating properties into polyamide resin, can keep the foaming temperature low, is particularly excellent in the effect of suppressing yellow coloring of polyamide resin foam beads, and can provide polyamide resin foam beads with a particularly high closed cell rate. From the point of view, water, methanol, isopropanol, and acetone are preferred.
- the polar solvents may be used singly or in combination of two or more.
- the method for including a polar solvent in the polyamide resin is not particularly limited, but a polar solvent (eg, a solvent at a temperature of 30 to 80 ° C.) for a predetermined time (eg, 0.5 to 10 hours).
- a polar solvent eg, a solvent at a temperature of 30 to 80 ° C.
- a predetermined time eg, 0.5 to 10 hours.
- Examples include a method of storing for a certain period of time in a humidified environment (eg, temperature of 30 to 50° C., relative humidity of 50 to 95%), and a method of spraying vapor of a polar solvent for a certain period of time.
- the content mass ratio (solvent absorption ratio) of the polar solvent contained in the solvent-containing polyamide resin from the viewpoint of further preventing coloring during foaming, relative to 100% by mass of the polyamide resin in the solvent-containing polyamide resin , preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 6% by mass or more, and particularly preferably 7% by mass or more.
- the content is preferably 35% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and particularly preferably 11% by mass or less.
- the mass ratio of the polar solvent contained in the solvent-containing polyamide resin can be adjusted by, for example, the temperature of the polar solvent to be immersed, the time of immersion in the polar solvent, the storage conditions after the inclusion, and the like.
- the solvent-containing polyamide-based resin preferably contains a polar solvent uniformly from the viewpoint that the foaming temperature can be further lowered and coloration during foaming can be further suppressed.
- a polar solvent uniformly from the viewpoint that the foaming temperature can be further lowered and coloration during foaming can be further suppressed.
- the total length is 100% from one end to 0 to 10% It is preferable that both the mass ratio of the polar solvent in the region and the region from 40 to 50% from the one end are within the above ranges.
- the content mass ratio of the polar solvent in each of the above regions is the mass of the solvent-containing polyamide resin, Wa, and the mass of the polyamide resin before containing the polar solvent (dried for 24 hours in a hot air drying facility at 60 ° C.). , ((Wa ⁇ W)/W) ⁇ 100 (mass %), and can be obtained by measuring the content mass ratio of the polar solvent using each of the above cut regions.
- the solvent-containing polyamide resin may be immediately used in the next step, or may be stored for a certain period of time. Storage includes, for example, a method of storing in an atmosphere containing a polar solvent (for example, under humidification). Above all, from the viewpoint of further suppressing the foaming temperature and further preventing coloration during foaming, it is preferable to use the mixture in the next step continuously after containing the polar solvent.
- the method of foaming the base resin in the foaming step is not particularly limited, but for example, a method in which a high-pressure condition is suddenly released to a low-pressure atmosphere to expand the gas dissolved in the base resin, pressurized steam, hot air, or the like. and a method of expanding the gas dissolved in the base resin (heat foaming).
- the method of heating and foaming is particularly preferred. This is because the cell size inside the base resin tends to be uniform compared to the method in which the high-pressure atmosphere is suddenly released to the low-pressure atmosphere.
- the foaming gas dissipates from the surface layer of the base resin, which facilitates the formation of a skin layer.
- the thickness of the skin layer can be adjusted by adjusting the heating rate and heating temperature, and the faster the heating rate and the higher the heating temperature, the thinner the skin layer tends to be.
- the heat source for heating and foaming is preferably hot air from the viewpoint of ease of high temperature setting and heating rate.
- hot air is used to quickly foam at a higher temperature, the heat shrinkage rate tends to be 30% or less when treated at Tsp+10° C. for 5 minutes.
- pressure steam rises in temperature the degree of temperature rise becomes gradual as the temperature rises, so a high pressure vessel is required to foam at high temperatures.
- the foaming gas dissipates too much, and the cell size in the vicinity of the skin layer tends to increase.
- foaming with pressurized steam water absorption and foaming occur at the same time, so stress is not relieved, and the heat shrinkage rate tends to increase.
- hot air foaming for example, a cylindrical foamer with a jacket on the outside and a stirring blade in the center is equipped with a hot air blower.
- a hot air foaming machine capable of blowing hot air from the bottom of the foaming machine.
- the foaming temperature in the foaming step is preferably Tsp+5° C. or higher, more preferably Tsp+10° C. or higher, of the base resin.
- the foaming temperature is preferably Tsp+40° C. or lower, more preferably Tsp+30° C. or lower, and even more preferably Tsp+25° C. or lower.
- the pellets by exposing the pellets to a high-temperature atmosphere, dissipation of foaming gas from the surface of the pellets can be promoted, so that an appropriate skin layer can be formed. Further, by setting the foaming temperature to Tsp+40° C. or lower, it becomes easier to reduce residual stress during foaming while suppressing blocking.
- the foaming time in the foaming step is preferably 3 to 30 seconds, more preferably 5 to 20 seconds. When the foaming time is within the above range, it becomes easier to reduce the occurrence of blocking while preventing the impregnation gas from dissipating. Further, the wind speed of the hot air in the hot air foaming can be appropriately adjusted according to the size and structure of the foaming machine and the input amount of the base resin.
- the foaming process may be performed in one step to the desired expansion ratio, or may be expanded to the desired expansion ratio in multiple steps such as secondary expansion and tertiary expansion. good.
- the gas used for the pressurization treatment is not particularly limited, but inorganic gas is preferable from the viewpoint of flame retardancy and gas safety.
- inorganic gases include air, carbon dioxide, nitrogen gas, oxygen gas, ammonia gas, hydrogen gas, argon gas, helium gas, and neon gas. Preferred, but not limited to.
- the method of pressurization treatment is not particularly limited, either, but a method of filling a pressurized tank with preliminary beads and supplying an inorganic gas into the tank to pressurize, or the like can be mentioned.
- the foamed beads of the present embodiment can also be molded (molding step) using a general molding method.
- foamed beads are filled in a molding die, foamed by heating, and at the same time, the beads are fused together, and then solidified by cooling to be molded.
- the method of filling the foamed beads is not particularly limited, but examples include a cracking method in which the mold is slightly opened during filling, and a compression method in which beads are compressed by applying pressure while the mold is closed. , a compression cracking method in which cracking is performed after filling compressed beads, and the like.
- a pressurization step in which a pressurization treatment is performed in an inorganic gas atmosphere before filling the expanded beads.
- the pressurization process can apply a constant gas pressure to the cells in the foamed beads, thereby facilitating more uniform foam molding.
- the pressure source for the pressurization treatment is not particularly limited, it is preferable to use an inorganic gas from the viewpoint of flame retardancy, heat resistance, and dimensional stability.
- inorganic gases include air, carbon dioxide, nitrogen gas, oxygen gas, ammonia gas, hydrogen gas, argon gas, helium gas, and neon gas.
- the method of pressurization treatment is not particularly limited, either, but examples include a method of filling a pressurized tank with foamed beads and supplying an inorganic gas into the tank to pressurize.
- the foamed beads of this embodiment it is possible to manufacture compacts with fine or complicated shapes by a known in-mold molding method, and it is also characterized by a wide range of possible uses. Since the foamed beads of the present embodiment have excellent expandability during molding, even if the number of foamed beads packed is small, the gaps between the beads can be filled. Therefore, it is possible to exhibit excellent moldability without creating gaps even in locations where it is difficult to fill with foamed beads, such as thin-walled portions and ribs. Also, even with a simple plate-shaped molded body, when molding a large board with a large molding area, if the filling amount of beads is increased due to cracking, a large amount of force is required to compress the beads when the mold is closed.
- the beads of the present embodiment have excellent expandability, the amount of cracking can be reduced or unnecessary, so that the beads can be molded while the mold is completely closed and the thickness accuracy is excellent. Furthermore, since the amount of cracking is less than usual or unnecessary, there is an advantage that even in a molded article having portions with different thicknesses, a molded article with little variation in expansion ratio can be obtained. This is very useful because it is possible to achieve both weight reduction and flexibility in shape design, which are the advantages of foam.
- a pair of molds for molding conventional foamed beads in the mold are used, and the foamed beads are filled into the mold cavity under pressurized atmospheric pressure or reduced pressure.
- the mold is closed and compressed to reduce the volume of the mold cavity by 0 to 70%, then a heat medium such as steam is supplied into the mold to heat it, and the foam beads are heat-fused.
- Japanese Patent Publication No. 46-38359 discloses that the secondary foaming property of the foamed beads is enhanced and the secondary foaming property is maintained by preliminarily pressurizing the foamed beads with a pressurized gas to increase the pressure inside the foamed beads.
- the foamed beads are filled into the mold cavity under atmospheric pressure or reduced pressure, the mold is closed, and then a heating medium such as steam is supplied into the mold to heat and pressurize to heat and fuse the foamed beads.
- a molding method for example, JP-B-51-22951
- a heating medium such as steam is supplied into the cavity to heat the foamed beads. It can also be molded by a compression filling molding method (Japanese Patent Publication No. 4-46217) in which the are heated and fused together.
- the secondary foaming power of foamed beads is increased under special conditions, and after filling the cavities of a pair of molds under atmospheric pressure or reduced pressure with the foamed beads, a heating medium such as steam is supplied. It is also possible to mold by a normal pressure filling molding method (Japanese Patent Publication No. 6-49795) or a method combining the above methods (Japanese Patent Publication No. 6-22919). can.
- the expansion ratio of the molded product using the foamed beads of the present embodiment is not particularly limited, but is preferably 1.5 to 40 cc/g, more preferably 2 to 25 cc/g.
- the foaming ratio is in the range of 1.5 to 40 cc/g, it tends to be easy to maintain excellent strength while taking advantage of weight reduction.
- Measuring jig SRF10 Measurement mode: Vibration ⁇ , ⁇ Strain: 0.015% Frequency: 1Hz Measurement temperature: 20°C to 250°C Heating rate: 2°C/min Normal force: -0.3N Measurement points: 160 Time unit: s
- Average thickness of skin layer of expanded beads Expanded beads are divided into two by cutting along a plane passing through the center point, and are automatically observed using a scanning electron microscope (trade name: VE-9800, manufactured by Keyence Corporation). A photograph of the cut surface was taken in mode, magnification of 200 times, acceleration voltage of 1.3 kV (image B). For each bead, photographs were taken at four locations on the top, bottom, left, and right, and the thickness of the skin layer was measured for all the cells present on the outermost periphery in each cross-sectional photograph obtained.
- a molded body (Fig. 1) with a width of 150 mm, a depth of 150 mm, and a thickness of 10 to 3 mm is prepared, cut at a point where the thickness changes, and a molded body with a width of 30 mm, a depth of 150 mm, and a thickness of 10 mm.
- Two molded bodies having a thickness of 5 mm and one molded body having a thickness of 3 mm were obtained.
- the expansion ratio of each molded product was measured by the method (2), and the difference between the maximum value and the minimum value was used as the dispersion, and the dispersion of the expansion ratio was evaluated according to the following evaluation criteria.
- Example 1 S201A (manufactured by Asahi Kasei Co., Ltd.) 73% by mass as polyphenylene ether resin (PPE), 12% by mass of impact-resistant polystyrene resin (HIPS) having a rubber concentration of 6% by mass (rubber component content in base resin is 0 .6%), GP685 (manufactured by PS Japan Co., Ltd.) as a general-purpose polystyrene resin (PS), 100 parts by mass of a 15% by mass thermoplastic resin, and bisphenol A-bis (diphenyl phosphate) (BDP) as a non-halogen flame retardant ) was added, and the mixture was heat-melted and kneaded by an extruder, and then extruded to prepare base resin pellets.
- PPE polyphenylene ether resin
- HIPS impact-resistant polystyrene resin
- PS general-purpose polystyrene resin
- BDP bisphenol A-bis (diphenyl phosphat
- the Tsp of the obtained base resin was 140°C.
- the base resin pellets are placed in a pressure-resistant container, the gas in the container is replaced with dry air, and then carbon dioxide gas is injected as a foaming agent,
- the base resin pellets were impregnated with 7% by mass of carbon dioxide over 3 hours under conditions of a pressure of 3.0 MPa and a temperature of 10°C.
- the base resin pellets were placed in a mesh-shaped basket, heated with hot air at 153° C. for 20 seconds while being stirred, and foamed to obtain foamed beads.
- the foamed beads were pressurized to 0.4 MPa over 1 hour and then held at 0.4 MPa for 8 hours for pressure treatment.
- Example 2 Foamed beads and molded articles were produced and evaluated in the same manner as in Example 1, except that the base resin pellets impregnated with the foaming agent were allowed to stand at room temperature for 30 seconds and then foamed. Since the base resin pellets after impregnation were allowed to stand at room temperature, carbon dioxide dissipated from the surface of the base resin pellets. The ratio of the average thickness of the skin layer to the average particle size increased. As in Example 1, the large board molded article exhibited excellent thickness accuracy and appearance, and there was almost no variation in foaming ratio due to the difference in thickness of the molded article with different thicknesses. Table 1 shows the measurement and evaluation results of the obtained foamed beads and moldings.
- Example 3 Foamed beads and molded articles were prepared and evaluated in the same manner as in Example 1 except that the foaming temperature was 165°C. As in Example 1, the large board molded article exhibited excellent thickness accuracy and appearance, and there was almost no variation in foaming ratio due to the difference in thickness of the molded article with different thicknesses. Table 1 shows the measurement and evaluation results of the obtained foamed beads and moldings.
- Example 4 A thermoplastic resin containing 40% by mass of S201A (manufactured by Asahi Kasei Co., Ltd.) as a polyphenylene ether resin (PPE) and 60% by mass of GP685 (manufactured by PS Japan Co., Ltd.) as a general-purpose polystyrene resin (PS) is heated with an extruder. After melt-kneading, extrusion was performed to prepare base resin pellets. The Tsp of the obtained base resin was 150°C. Using this base resin pellet, foamed beads and a molded product were produced and evaluated in the same manner as in Example 1 except that the foaming temperature was set to 157°C.
- S201A manufactured by Asahi Kasei Co., Ltd.
- GP685 manufactured by PS Japan Co., Ltd.
- PS general-purpose polystyrene resin
- Example 1 shows the measurement and evaluation results of the obtained foamed beads and moldings.
- Example 1 Using the same base resin as in Example 1, impregnated with carbon dioxide gas in the same manner as in Example 1, and then heated with pressurized steam while rotating the stirring blade at 77 rpm in a foaming furnace to foam and foam beads. got The foaming temperature at this time was 143°C. Using the foamed beads thus obtained, molding was carried out at a cracking rate of 0 mm in the same manner as in Example 1. As a result, voids were observed in both large board moldings and moldings with different thicknesses, and the appearance was poor. became. In particular, the number of voids increased as the thickness of the molded body with different thickness decreased, and many voids were observed in the 3 mm thick portion.
- the beads are less likely to be filled in the thin-walled portion than in the thick-walled portion, and the amount of beads per unit volume is small, resulting in a high magnification and large variations.
- Table 1 shows the measurement and evaluation results of the obtained foamed beads and moldings.
- thermoplastic resin containing 30% by mass of S201A (manufactured by Asahi Kasei Co., Ltd.) as a polyphenylene ether resin (PPE) and 70% by mass of GP685 (manufactured by PS Japan Co., Ltd.) as a general-purpose polystyrene resin (PS) is heated with an extruder. After melt-kneading, extrusion was performed to prepare base resin pellets. The Tsp of the obtained base resin was 144°C.
- Comparative Example 1 As in Comparative Example 1, voids were observed in both the large board molded body and the molded body with different thicknesses. It was inferior in appearance. In addition, as in Comparative Example 1, the foaming ratios of the molded products with different thicknesses also varied widely. Table 1 shows the measurement and evaluation results of the obtained foamed beads and moldings.
- thermoplastic resin containing 20% by mass of S201A (manufactured by Asahi Kasei Co., Ltd.) as a polyphenylene ether resin (PPE) and 80% by mass of GP685 (manufactured by PS Japan Co., Ltd.) as a general-purpose polystyrene resin (PS) is heated with an extruder. After melt-kneading, extrusion was performed to prepare base resin pellets. The Tsp of the obtained base resin was 136°C.
- Comparative Example 1 As in Comparative Example 1, voids were observed in both the large board molded body and the molded body with different thicknesses. It was inferior in appearance. In addition, as in Comparative Example 1, the foaming ratios of the molded products with different thicknesses also varied widely. Table 1 shows the measurement and evaluation results of the obtained foamed beads and moldings.
- Comparative Example 1 As in Comparative Example 1, voids were observed in both the large board molded body and the molded body with different thicknesses. It was inferior in appearance. In addition, as in Comparative Example 1, the foaming ratios of the molded products with different thicknesses also varied widely. Table 1 shows the measurement and evaluation results of the obtained foamed beads and moldings.
- the molded product obtained by using the foamed beads of the present invention has excellent expansion ability during molding, so it can be used in high-temperature environments such as automobile parts and various tanks, and can also be used for parts that require heat insulation. It is possible. In particular, since thin-wall molding can be performed well, it can be easily applied to automobile members and electronic devices where space is limited. In addition, it is very useful because it satisfies weight reduction while achieving thickness accuracy and foaming ratio accuracy required for automotive parts and the like.
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Abstract
Description
発泡ビーズ成形体は、成形金型に発泡ビーズを充填し、加熱、融着させる事により所望の形状の成形体を得る事ができる。成形加工時に発泡ビーズを金型に充填した際には、発泡ビーズ間に空隙が生じるので、これを何かしらの形で埋める必要がある。一般的には、発泡ビーズを圧縮して充填し、金型内で発泡ビーズが元の大きさに戻る事で空隙を埋める方法(圧縮充填法)、発泡ビーズを金型に充填する際、金型を少し開いた状態で充填し、ビーズの充填量を増やす方法(クラッキング法)、成形前に発泡ビーズに加圧処理を施し、発泡ビーズのセル内に加圧状態の気体を保持し、膨張能を付与する事により、成形時の加熱で発泡ビーズを膨張させる方法(追添法)や、これらを組み合わせた成形法、例えば、追添した上で少量のクラッキングを行う方法等が挙げられる。
圧縮充填法は、発泡ビーズを圧縮する為、ポリスチレン等、圧縮により座屈する樹脂には不向きな方法である。一方、クラッキング法は、ビーズの充填量が増える分、成形品の重量も増す欠点がある。また、厚みが異なる部位を有する場合、クラッキングを行う事により、発泡倍率のばらつきが発生する事にもなる。例えば、厚み10mmと3mmの箇所を有する成形品の場合、クラッキング量(発泡ビーズを充填する時に余剰に金型を開く距離)を1mmとした場合、厚み10mmの箇所は、(10+1)/10=1.1倍に圧縮するのに対し、厚み3mmでは(3+1)/3≒1.3倍以上に圧縮する必要があり、これにより発泡倍率が変わってしまう問題がある。それ以外にも、クラッキングによりビーズ充填量が増える程、金型を閉める際にビーズを圧縮するのに必要な力が大きくなり、結果、金型が閉まりきらない「型開き」が発生し、所望の厚みより成形品が厚くなったり、厚み精度が悪くなる欠点がある。
これらの理由から、樹脂種を問わず適用可能で、より軽量な成形体を得やすい追添法が幅広く用いられており、より薄く、複雑な形状を精度よく成形するには、膨張能に優れた発泡ビーズが必要になる。
一方、耐熱性に優れる発泡ビーズの例として、ポリスチレン系樹脂とポリフェニレンエーテル系樹脂とのブレンド樹脂を発泡させたものが知られている(特許文献1)。
[1]
熱可塑性樹脂を含む基材樹脂を含み、前記基材樹脂の軟化点をTspとしたとき、Tsp+10℃で5分加熱したときの加熱収縮率が30%以下であることを特徴とする、発泡ビーズ。
[2]
前記基材樹脂の軟化点Tspが130℃以上である、[1]に記載の発泡ビーズ。
[3]
前記発泡ビーズの表面を構成するスキン層の平均厚みが、前記発泡ビーズの平均粒子径の0.2~2.0%である、[1]又は[2]に記載の発泡ビーズ。
[4]
前記基材樹脂がポリフェニレンエーテル系樹脂を含む、[1]~[3]のいずれかに記載の発泡ビーズ。
[5]
[1]~[4]のいずれかに記載の発泡ビーズを含むことを特徴とする、成形体。
[6]
Tsp+5℃~Tsp40℃で発泡することを特徴とする、[1]~[5]のいずれかに記載の発泡ビーズの製造方法。
本実施形態の発泡ビーズは、熱可塑性樹脂を含む基材樹脂を含み、前記基材樹脂の軟化点をTspとしたとき、Tsp+10℃で5分加熱したときの加熱収縮率が、30%以下である。
ここで、上記加熱収縮率とは、Tsp+10℃で加熱する前の発泡ビーズの発泡倍率をXa(cc/g)、加熱した後の発泡ビーズの発泡倍率をXb(cc/g)として、(1-Xb/Xa)×100(%)で計算される値である。
発泡ビーズの発泡倍率は、発泡ビーズの質量W(g)を測定した後、水没法で発泡ビーズの体積V(cc)を測定し、その体積Vを質量Wで除した値V/W(cc/g)として求めることができる。
Tsp+10℃で5分処理したときの加熱収縮率を30%以下とする方法としては、特に限定されないが、例えば、樹脂を発泡させる際の発泡温度を高温にすることで達成できる。発泡温度を高温にする方法として、熱風発泡等が挙げられる。熱風発泡については後述する。それ以外にも、アニール等の加熱処理を行ってもよい。
発泡倍率は、基材樹脂における発泡剤の含有(含浸)量や発泡時の加熱温度、加熱時間、発泡剤を含浸した基材樹脂の発泡前の放置時間等を調整する事により制御できる。発泡剤の含浸量が多い程、発泡倍率は高くなりやすい。また、発泡時の加熱量が多い、すなわち、加熱温度が高く、加熱時間が長い程、発泡倍率は高くなりやすいが、加熱量が多すぎると過剰発泡により気泡膜が破膜し、収縮が始まるので適度に調整する必要がある。
多段階で所望の発泡倍率に調整する際には、一次発泡倍率は1.4~15cc/gが好ましく、1.7~13cc/gがより好ましく、2~10cc/gがさらに好ましい。この範囲であると、気泡(セル)サイズが均一になりやすく、二次発泡能も付与しやすくなる。
発泡ビーズの平均粒子径は、発泡倍率と基材樹脂の平均粒子径により調整できる。
なお、発泡ビーズの平均粒子径は、デジタルマイクロスコープを用いて500個以上の発泡ビーズについて円相当径を測定し、その平均値を平均粒子径とする。より具体的には、後述の実施例に記載の方法で求めることができる。
ここで、図1は、本実施形態の発泡ビーズの一例について、その断面をSEMで観察した画像(倍率:200倍)である。図1に示されるように、発泡ビーズのスキン層1は、発泡ビーズの表面を構成する最外層であり、未発泡の基材樹脂からなる(即ち、気泡2を含まない)部分である。
成形加工時に発泡ビーズが加熱により膨張する際、表面を構成する最外層であるスキン層が最も変形量が大きくなる為、破断しやすくなる。スキン層が破断すると、発泡ビーズの気泡(セル)内に存在する気体が外部に散逸してしまう為、膨張能が低下する。一方、スキン層が厚くなりすぎると、成形加工時に発泡ビーズが加熱により膨張する際、スキン層を延伸、変形させるのに必要な応力が高くなり、膨張能が低下しやすくなる。スキン層の厚みが発泡ビーズの平均粒子径の0.2~2.0%であると、成形加工時にビーズの膨張を阻害する事なく、スキン層の破断が起こりにくくなり、発泡ビーズの膨張能がより向上しやすくなる。
スキン層は、基材樹脂の表面から発泡剤が散逸する事により形成され、発泡剤の散逸量が多い程スキン層は厚くなる。よって、スキン層の厚みは、発泡剤の濃度や発泡時に加える熱量、加熱速度、発泡剤を含浸した基材樹脂の発泡前の放置時間等を制御する事により調整できる。また、スキン層は発泡ビーズの発泡倍率が高くなる程薄くなる傾向もある。これは、発泡倍率が高い程スキン層の延伸量も大きくなる為である。
なお、発泡ビーズのスキン層の平均厚みは、以下の方法で求められる値である。まず、発泡ビーズをその中心点を通る面で切断して二分割し、走査型電子顕微鏡(SEM)にて切断面の写真を撮影する。次いで、得られた断面写真において、1つのビーズについて上下左右の4か所撮影を行い、得られた各断面写真において、最外周に存在する全てのセルに対してスキン層の厚みを測定する。数値が小さい方から10個に対してそれぞれ算術平均値を求め、得られた上下左右それぞれの値の算術平均値をその発泡ビーズのスキン層の厚みとする。この操作を5個以上の発泡ビーズについて同様に行い、各発泡ビーズのスキン層の厚みの算術平均値を発泡ビーズのスキン層の平均厚み(μm)とする。より具体的には、後述の実施例に記載の方法で求めることができる。
なお、発泡ビーズの独立気泡率S(%)は、下記式(1)で表される式により算出される値である。
S(%)={(Vx-W/ρ)/(Va-W/ρ)}×100 ・・・(1)
(式中、Vxは、発泡ビーズの真の体積(cm3)であり、Vaは、発泡ビーズの見かけの体積(即ち、発泡倍率×質量)(cm3)であり、Wは、発泡ビーズの質量(g)であり、ρは、発泡ビーズの基材樹脂の密度(g/cm3)である。発泡ビーズの真の体積Vxは、空気比較式比重計を用いて測定することができる。)
なお、発泡ビーズの平均気泡径は、以下の方法で求められる値である。まず、発泡ビーズをその中心点を通る面で切断して二分割し、走査型電子顕微鏡(SEM)にて切断面の写真を撮影する。次いで、得られた断面写真において、発泡ビーズの切断面の中心点から8方向に等間隔に直線を引き、その直線と交わる気泡の数を全てカウントする。該直線の合計長さを、カウントされた合計気泡数で除して得られた値を発泡ビーズの気泡径とする。この操作を10個以上の発泡ビーズについて同様に行い、各発泡ビーズの気泡径の算術平均値を発泡ビーズの平均気泡径とする。
本実施形態の発泡ビーズは、基材樹脂を含み、基材樹脂からなるものとすることができる。
基材樹脂は、熱可塑性樹脂を含み、更に、難燃剤、ゴム成分等を含むことができる。
なお、基材樹脂の軟化点Tspは、動的粘弾性測定において、ある温度Tにおける貯蔵弾性率E1と、Tより5℃低い温度における貯蔵弾性率E2との比(E1/E2)が0.1以下になるTのうちの最低温度とする。E1/E2が0.1以下とならない場合は、E1/E2の値が最小となる温度TをTspとする。具体的には、後述の実施例に記載の方法により測定することができる。
これらは1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。また、本発明の目的を損なわない範囲で変性、架橋された樹脂を用いてもよい。
これらの中でも、耐熱性の観点からポリフェニレンエーテル系樹脂を含む熱可塑性樹脂とポリアミド系樹脂を含む熱可塑性樹脂が好ましく、加工性の観点からポリフェニレンエーテル系樹脂を含む熱可塑性樹脂がより好ましい。
ここで、一般式(1)中、R1、R2、R3及びR4は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、フェニル基、又はハロゲンと一般式(1)中のベンゼン環との間に少なくとも2個の炭素原子を有するハロアルキル基若しくはハロアルコキシ基で第3α-炭素原子を含まないもの、を示す。また、nは、重合度を表す整数である。
なお、本明細書中において、重量平均分子量とは、ゲルパーミュエーションクロマトグラフィー(GPC)による測定を行い、クロマトグラムのピークの分子量を、市販の標準ポリスチレンの測定から求めた検量線(標準ポリスチレンのピーク分子量を使用して作成)を使用して求めた重量平均分子量である。具体的には、昭和電工(株)製ゲルパーミッションクロマトグラフィーSystem21を用い、カラムに昭和電工(株)製K-805Lを2本直列につないだ物を使用し、溶剤にクロロホルムを使用して、溶剤の流量を1.0mL/分、カラムの温度を40℃として測定することができる。検出部のUVの波長は、標準ポリスチレンの場合は254nm、ポリフェニレンエーテルの場合は283nmとする。
これらは1種単独で用いても、2種以上を組み合わせて用いてもよい。
ポリフェニレンエーテル系樹脂は、特に、荷重たわみ温度(HDT)を向上させ、高熱の環境下においても剛性を維持でき、寸法安定性を良好なものにすることができる。
スチレン誘導体としては、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、t-ブチルスチレン、α-メチルスチレン、β-メチルスチレン、ジフェニルエチレン、クロロスチレン、ブロモスチレン等が挙げられるが、これに限定されるものではない。
共重合体のポリスチレン系樹脂としては、スチレン-ブタジエン共重合体、スチレン-アクリロニトリル共重合体、スチレン-マレイン酸共重合体、スチレン-無水マレイン酸共重合体、スチレン-マレイミド共重合体、スチレン-N-フェニルマレイミド共重合体、スチレン-N-アルキルマレイミド共重合体、スチレン-N-アルキル置換フェニルマレイミド共重合体、スチレン-アクリル酸共重合体、スチレン-メタクリル酸共重合体、スチレン-メチルアクリレート共重合体、スチレン-メチルメタクリレート共重合体、スチレン-n-アルキルアクリレート共重合体、スチレン-n-アルキルメタクリレート共重合体、エチルビニルベンゼン-ジビニルベンゼン共重合体等の二元共重合体;ABS、ブタジエン-アクリロニトリル-α-メチルベンゼン共重合体等の三元共重合体等が挙げられるが、これらに限定されるものではない。
また、グラフト共重合体、例えば、スチレングラフトポリエチレン、スチレングラフトエチレン-酢酸ビニル共重合体、(スチレン-アクリル酸)グラフトポリエチレン、スチレングラフトポリアミド等も挙げられる。
これらは、1種単独で用いても、2種以上を組み合わせて用いてもよい。
なお、本明細書中において、重量平均分子量とは、ゲルパーミュエーションクロマトグラフィー(GPC)による測定を行い、クロマトグラムのピークの分子量を、市販の標準ポリスチレンの測定から求めた検量線(標準ポリスチレンのピーク分子量を使用して作成)を使用して求めた重量平均分子量である。具体的には、昭和電工(株)製ゲルパーミッションクロマトグラフィーSystem21を用い、カラムに昭和電工(株)製K-805Lを2本直列につないだ物を使用し、溶剤にクロロホルムを使用して、溶剤の流量を1.0mL/分、カラムの温度を40℃として測定することができる。検出部のUVの波長は、標準ポリスチレンおよびポリスチレン系樹脂ともに254nmとする。
ポリアミド単独重合体としては、例えば、ジアミンとジカルボン酸との重縮合により得られる、ナイロン66、ナイロン610、ナイロン612、ナイロン46、ナイロン1212等;ラクタムの開環重合により得られる、ナイロン6、ナイロン12等が挙げられる。
ポリアミド共重合体としては、例えば、ナイロン6/66、ナイロン66/6、ナイロン66/610、ナイロン66/612等が挙げられる。
中でも、脂肪族ポリアミドが好ましく、ナイロン6、ナイロン66、ナイロン6/66、ナイロン66/6等がより好ましい。
これらは、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
難燃剤としては、有機系難燃剤、無機系難燃剤があり、有機系難燃剤としては、臭素化合物に代表されるハロゲン系化合物や、リン系化合物シリコーン系化合物に代表される非ハロゲン系化合物がある。無機系難燃剤としては、水酸化アルミニウム、水酸化マグネシウムに代表される金属水酸化物、三酸化アンチモン、五酸化アンチモンに代表されるアンチモン系化合物などが挙げられる。
上記難燃剤の中でも、環境の観点から、非ハロゲン系難燃剤が好ましく、リン系の難燃剤がより好ましいが、これに限定されるものではない。
ゴム成分としては、例えば、ブタジエン、イソプレン、1,3-ペンタジエン等が挙げられるが、これに限定されるものではない。これらは、ポリスチレン系樹脂からなる連続相中に粒子状に分散しているものが好ましい。これらゴム成分を添加する方法として、ゴム成分そのものを加えてもよく、スチレン系エラストマーやスチレン-ブタジエン共重合体等の樹脂をゴム成分供給源として用いてもよい。後者の場合、ゴム成分の比率(R)は下記式で計算できる。
R=C×Rs/100
C:ゴム成分供給源中のゴム濃度(質量%)
Rs:基材樹脂中のゴム供給源含有量(質量%)
基材樹脂中のゴム成分の含有量は0.3~10質量%が好ましく、0.5~8質量%がより好ましい。0.3質量%以上であると、所望の難燃性が発現しやすくなる。さらに、0.5質量%以上であると、樹脂の柔軟性、伸びに優れ、発泡時に発泡セル膜が破膜しにくく、発泡倍率が上がり、発泡後も成形加工性に優れる発泡ビーズとなる。一方、ゴム成分の含有量は10質量%以下であれば所望の難燃性が発現しやすくなる。さらに、8質量%以下であると、十分な耐熱性が得られる。
基材樹脂中の上記添加剤の含有量は、発明の目的を損なわない範囲であれば特に限定されないが、熱可塑性樹脂100質量部に対して、30質量部以下としてよく、好ましくは20質量部以下である。
これらは、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
基材樹脂の大きさ(長径)は、好ましくは0.2~5.0mm、さらに好ましくは0.2~3.0mmである。大きさがこの範囲にあると、基材樹脂を発泡して得られる発泡ビーズが適度な大きさになり、取り扱い易く、また、成形時の充填がより密になりやすくなる。基材樹脂の長さや径が小さくなる程、単位体積あたりの表面積が増えるので、発泡工程や発泡前の放置時において発泡剤が表面から散逸しやすくなり、スキン層が厚くなりやすい傾向にある。一方で、発泡剤が散逸しすぎると発泡倍率が高くなりにくくなる。基材樹脂の大きさが上記範囲であると、適度な厚みのスキン層を形成しつつ所望の発泡倍率の発泡ビーズを得やすくなる。
次に、本実施形態の発泡ビーズの製造方法について説明する。
本実施形態の発泡ビーズは、基材樹脂に発泡剤を含有(含浸)させ(含浸工程)、基材樹脂を発泡させること(発泡工程)により得ることができる。
また、気相含浸により発泡剤を含浸させた基材樹脂は、得られる発泡ビーズの発泡倍率、スキン層の厚みの調整のため、発泡工程に移る前に室温(23~25℃)でまたは予熱等で温めておいた発泡機内(40~100℃)で加熱せずに一定時間、放置してもよい。一定時間放置すると、その間に基材樹脂の表面から発泡剤が散逸することにより、放置しない場合と比較して得られる発泡ビーズの発泡倍率は低くなる傾向にあり、スキン層の厚みは厚くなる傾向にある。
上記室温における放置時間は、特に限定されず、所望する発泡倍率やスキン層の厚みに応じて適宜設定されてよいが、0~180秒であることが好ましく、より好ましくは0~120秒、さらに好ましくは0~60秒である。
また、上記発泡機内(40~100℃)における放置時間は、特に限定されず、所望する発泡倍率やスキン層の厚みに応じて適宜設定されてよいが、0~30秒であることが好ましく、より好ましくは0~20秒、さらに好ましくは0~10秒である。
炭酸ガスの含浸量が3質量%以上であると、より高い発泡倍率を達成しやすくなる上、基材樹脂内の気泡サイズのばらつきが少なくなり、基材樹脂間での発泡倍率のばらつきを抑えやすくなる。また、13質量%以下であると、気泡サイズが適度な大きさとなり、過発泡による独立気泡率の低下を抑制しやすくなる。
上記極性溶媒としては、水;メタノール、エタノール、イソプロパノール等のアルコール類;アセトン等が挙げられる。中でも、ポリアミド系樹脂への含浸性に優れ、発泡温度を低く抑えることができ、ポリアミド系樹脂発泡ビーズの黄色の着色抑制効果に特に優れ、独立気泡率が特に高いポリアミド系樹脂発泡ビーズが得られる観点から、水、メタノール、イソプロパノール、アセトンが好ましい。
上記極性溶媒は、1種を単独で用いてもよいし、2種以上を混合して用いてもよい。
含溶媒ポリアミド系樹脂中の極性溶媒の含有質量割合は、例えば、浸す極性溶媒の温度、極性溶媒に浸す時間、含有させた後に保管する条件等により調整することができる。
例えば、含有ポリアミド系樹脂のペレットの任意の方向の断面において、該断面の重心を通る該断面の任意の2端を結ぶ線分の、全長を100%として一方の端から0~10%までの領域と、該一方の端から40~50%までの領域との極性溶媒の含有質量割合が、共に上記範囲であることが好ましい。
上記各領域の極性溶媒の含有質量割合は、含溶媒ポリアミド系樹脂の質量をWa、極性溶媒を含有させる前のポリアミド系樹脂(60℃の熱風乾燥設備にて24時間乾燥)の質量をWとして、((Wa-W)/W)×100(質量%)で求められる値であり、切り取った上記各領域を用いて極性溶媒の含有質量割合を測定することにより、求めることができる。
含溶媒ポリアミド系樹脂は、極性溶媒を含有させた後に、すぐに次の工程に用いてもよいし、一定期間保管してもよい。保管は、例えば、極性溶媒を含む雰囲気下(例えば、加湿下)で保管する方法等が挙げられる。中でも、発泡温度を一層低く抑え、発泡時の着色をより一層防止する観点から、極性溶媒を含有させた後、連続して次の工程に用いることが好ましい。
さらに、高圧条件下から一気に低圧雰囲気下に開放した場合、全箇所から同時に発泡が始まる為、スキン層が形成されにくいという欠点がある。一方、加熱発泡では、基材樹脂が常温から発泡開始温度まで加熱される間に、基材樹脂の表層から発泡ガスが散逸する為、スキン層を形成しやすい。また、加熱速度や加熱温度を調整する事により、スキン層の厚みを調整できる利点があり、加熱速度が速いほど、また、加熱温度が高いほど、スキン層の厚みは薄くなる傾向にある。スキン層を厚くしたい時には、発泡工程に移る前に室温(23~25℃)で一定時間放置したり、あらかじめ予熱等で温めておいた発泡機内(40~100℃)に基材樹脂を投入した後、加熱せずに放置する事により基材樹脂の表層から発泡ガスを散逸させる方法等が挙げられる。
高温の熱風で基材樹脂内に溶解したガスを膨張させる方法、いわゆる熱風発泡については、例えば、外側にジャケットを有し、中心部に撹拌翼を具備した円筒形の発泡器を備え、熱風ブロワーからの熱風を前記発泡器の底面より送風可能な熱風発泡機の中で発泡させる方法等がある。このとき、熱風の風速や温度を最適化することで、Tsp+10℃で5分処理したときの加熱収縮率を30%以下とすることができる。
発泡工程における発泡時間は、3~30秒であることが好ましく、より好ましくは5~20秒である。発泡時間が上記範囲であると、含浸ガスの散逸を防ぎつつブロッキングの発生を低減しやすくなる。
また、熱風発泡における熱風の風速は、発泡機のサイズや構造、基材樹脂の投入量に応じて適宜調整できる。
加圧処理に用いるガスは特には限定されないが、難燃性やガスの安全性の観点から、無機ガスが好ましい。無機ガスの例として、空気、炭酸ガス、窒素ガス、酸素ガス、アンモニアガス、水素ガス、アルゴンガス、ヘリウムガス、ネオンガス等が挙げられ、取り扱いの容易さと経済性の観点から、炭酸ガスや空気が好ましいが、それに限定されるものではない。
加圧処理の方法も特には限定されないが、加圧タンク内に予備ビーズを充填し、該タンク内に無機ガスを供給して加圧する方法等が挙げられる。
本実施形態の発泡ビーズは、一般的な成形加工方法を用いて成形体を得る(成形工程)こともできる。
発泡ビーズの充填方法は特には限定されないが、例として充填時に金型を多少開いた状態で充填するクラッキング法や、金型を閉じたままの状態で加圧して圧縮したビーズを充填する圧縮法、圧縮ビーズを充填後にクラッキングを行う圧縮クラッキング法等が挙げられる。
加圧処理を実施する場合の圧力源は特には限定されないが、前述した難燃性や耐熱性、寸法安定性の観点から無機ガスを用いるのが好ましい。無機ガスの例として、空気、炭酸ガス、窒素ガス、酸素ガス、アンモニアガス、水素ガス、アルゴンガス、ヘリウムガス、ネオンガス等が挙げられ、取り扱いの容易さと経済性の観点から、炭酸ガスや空気が好ましいが、それに限定されるものではない。
加圧処理の方法も特には限定されないが、加圧タンク内に発泡ビーズを充填し、該タンク内に無機ガスを供給して加圧する方法等が挙げられる。
また、圧縮ガスにより大気圧以上に加圧したキャビティー内に、当該圧力以上に加圧した発泡ビーズを充填した後、キャビティー内にスチーム等の熱媒を供給して加熱を行い、発泡ビーズを加熱融着させる圧縮充填成型法(特公平4-46217号公報)により成形することもできる。その他に、特殊な条件にて発泡ビーズの二次発泡力を高め、大気圧下又は減圧下の一対の成形型のキャビティー内に該発泡ビーズを充填した後、スチーム等の熱媒を供給して加熱を行い、発泡ビーズを加熱融着させる常圧充填成型法(特公平6-49795号公報)又は上記の方法を組み合わせた方法(特公平6-22919号公報)などによっても成形することができる。
実施例及び比較例で用いた評価方法について以下に説明する。
基材樹脂に対し、レオメーター(商品名:Physica MCR301、アントンパール社製)を用いて下記条件にて粘弾性測定を行った。測定開始温度から5℃以上高い各測定点に対し、測定温度(T)における貯蔵弾性率(E1)と、Tより5℃低い温度における貯蔵弾性率(E2)との比(E1/E2)を算出し、E1/E2が0.1以下となるTのうちの最低温度(℃)を基材樹脂の軟化点Tspとした。E1/E2が0.1以下とならない場合は、E1/E2の値が最小となる温度TをTspとした。
測定治具 :SRF10
測定モード :振動φ、γ
ひずみ :0.015%
周波数 :1Hz
測定温度 :20℃~250℃
昇温速度 :2℃/分
ノーマルフォース:-0.3N
測定点 :160
時間単位 :s
発泡ビーズ及び大ボード成形体の質量W(g)を測定した後、水没法で体積V(cc)を測定し、その体積を質量で除した値V/W(cc/g)を発泡倍率とした。
発泡ビーズ20ccを、金属トレーの上に重ならない様に入れ、基材樹脂の軟化点Tsp+10℃に設定したオーブンの中に投入し、5分後に取り出した。常温に冷却した後、(2)の方法にて加熱後の発泡倍率Xbを求め、下記式にて加熱収縮率(%)を計算した。
(1-Xb/Xa)×100(%)
Xa:加熱前の発泡倍率(cc/g)
Xb:加熱後の発泡倍率(cc/g)
デジタルマイクロスコープ(商品名:VHX-2000、キーエンス社製)を用いて透明なシャーレ上に設置した発泡ビーズを、レンズから発泡ビーズを挟んで逆方向から光を当て、観察することにより、粒子の正射影像を得た。画像解析ソフト(キーエンス社製デジタルマイクロスコープVHX-2000に搭載)を用いて各発泡ビーズについて円相当径を測定した。この際、撮影画像の端にある、粒子全体が映っていない像に関しては除外した。1回に測定できる発泡ビーズの数は、発泡ビーズの大きさにより異なるが、測定総数が500個になるまで測定を繰り返し実施し、その算術平均値を平均粒子径(mm)とした。
発泡ビーズを、その中心点を通る面で切断して二分割し、走査型電子顕微鏡(商品名:VE-9800、キーエンス社製)を用い、オート観察モード、倍率200倍、加速電圧1.3kV(画像B)にて切断面の写真を撮影した。なお、1つのビーズについて上下左右の4か所撮影を行い、得られた各断面写真において、最外周に存在する全てのセルに対してスキン層の厚みを測定した。数値が小さい方から10個に対してそれぞれ算術平均値を求め、得られた上下左右それぞれの値の算術平均値をその発泡ビーズのスキン層の厚みとした。この操作を5個以上の発泡ビーズについて同様に行い、各発泡ビーズのスキン層の厚みの算術平均値を発泡ビーズのスキン層の平均厚み(μm)とした。
得られたスキン層の平均厚みと、発泡ビーズの平均粒子径とから、発泡ビーズの平均粒子径に対するスキン層の平均厚みの割合(%)を求めた。
大ボード成形体用、厚み違い成形体用それぞれの金型で成形して得られた成形体の外観を、目視で評価した。
〇(良好):空隙部なし
×(不良):空隙部あり
1000mm×1200mm×10mm厚みの成形板(大ボード成形体)を作製し、平面視で四隅と各辺の中心、成形体中心部の計9か所の厚みを測定し、その最大値と最小値の差をばらつきとして、以下の評価基準で厚み精度を評価した。
〇(良好):ばらつきが0.3mm未満
×(不良):ばらつきが0.3mm以上
幅150mm、奥行き150mm、厚み10~3mmの成形体(図1)を作製し、厚みが変わる箇所で切断し、幅30mm、奥行き150mm、厚み10mmの成形体2個、厚み5mmの成形体2個、厚み3mmの成形体1個を得た。(2)の方法にてそれぞれの成形体の発泡倍率を測定し、その最大値と最小値の差をばらつきとして、以下の評価基準で発泡倍率のばらつきを評価した。
〇(良好):ばらつきが1.0cc/g未満
×(不良):ばらつきが1.0cc/g以上
ポリフェニレンエーテル系樹脂(PPE)としてS201A(旭化成(株)製)73質量%、ゴム濃度が6質量%の耐衝撃性ポリスチレン樹脂(HIPS)12質量%(基材樹脂中のゴム成分含有量は0.6%)、汎用ポリスチレン樹脂(PS)としてGP685(PSジャパン(株)製)15質量%の熱可塑性樹脂100質量部に対し、非ハロゲン系難燃剤としてビスフェノールA-ビス(ジフェニルホスフェート)(BDP)を22質量部加え、押出機にて加熱溶融混練の後に押出し、基材樹脂ペレットを作製した。
得られた基材樹脂のTspは140℃であった。
特開平4-372630号公報の実施例1に記載の方法に準じ、基材樹脂ペレットを耐圧容器に収容し、容器内の気体を乾燥空気で置換した後、発泡剤として炭酸ガスを注入し、圧力3.0MPa、温度10℃の条件下で3時間かけて基材樹脂ペレットに対して二酸化炭素を7質量%含浸させた。
基材樹脂ペレットをメッシュ状のかごに投入し、攪拌しながら153℃の熱風で20秒間加熱し、発泡させて発泡ビーズを得た。
この発泡ビーズを0.4MPaまで1時間かけて昇圧し、その後0.4MPaで8時間保持し、加圧処理を施した。これを、大ボード成形体用金型(1000mm×1200mm×10mm厚み)が設置された水蒸気孔を有する型内成形金型内に充填し、クラッキングを0mmに設定し、加圧水蒸気で加熱して発泡ビーズ相互を膨張・融着させた後、冷却し、成形金型より取り出した。得られた成形体の厚み精度は良好であった。
また、金型を図2の形状の厚みの異なる成形体(厚み違い成形体)用の金型に変更し、同様に成形を行った。得られた成形体の外観は3mm厚みの箇所でも空隙はなく、良好であった。また、発泡倍率のばらつきも、厚み違いによる差は殆どなく、良好であった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
発泡剤を含浸した後の基材樹脂ペレットを30秒間室温で放置した後に発泡を行う以外は実施例1と同様にして発泡ビーズ及び各成形体を作製し、評価を行った。
含浸後の基材樹脂ペレットを室温で放置した事により、基材樹脂ペレットの表面から二酸化炭素が散逸した為、得られた発泡ビーズの発泡倍率は実施例1に比べて若干低くなったが、平均粒子径に対するスキン層の平均厚みの割合は大きくなった。
大ボード成形体は実施例1と同様に優れた厚み精度と外観を示し、厚み違い成形体の厚み違いによる発泡倍率のばらつきも殆どなかった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
発泡温度を165℃とする以外は実施例1と同様にして発泡ビーズ及び各成形体を作製し、評価を行った。
大ボード成形体は実施例1と同様に優れた厚み精度と外観を示し、厚み違い成形体の厚み違いによる発泡倍率のばらつきも殆どなかった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
ポリフェニレンエーテル系樹脂(PPE)としてS201A(旭化成(株)製)40質量%、汎用ポリスチレン樹脂(PS)としてGP685(PSジャパン(株)製)60質量%を含む熱可塑性樹脂を押出機にて加熱溶融混練の後に押出し、基材樹脂ペレットを作製した。
得られた基材樹脂のTspは150℃であった。
この基材樹脂ペレットを用い、発泡温度を157℃とする以外は実施例1と同様にして発泡ビーズ及び成形体を作製し、評価を行った。
大ボード成形体は実施例1と同様に優れた厚み精度と外観を示し、厚み違い成形体の厚み違いによる発泡倍率のばらつきも殆どなかった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
実施例1と同じ基材樹脂を用いて、実施例1と同様に炭酸ガスを含浸させた後、発泡炉内で攪拌羽を77rpmにて回転させながら加圧水蒸気により加熱し、発泡させて発泡ビーズを得た。この時の発泡温度は143℃であった。
得られた発泡ビーズを用いて実施例1と同様にクラッキング0mmにて成形を行ったところ、大ボード成形体、厚みの異なる厚み違い成形体、どちらにおいても空隙が見られ、外観に劣る物となった。特に、厚み違い成形体は、厚みが薄くなるにつれて空隙数が増し、3mm厚みの部分に多く空隙が観測された。また、厚み違い成形体においては、厚肉部に比べて薄肉部はビーズが充填されにくく、単位体積当たりのビーズ量が少なくなる為、倍率は高くなり、ばらつきが大きい結果となった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
比較例1と同じ発泡ビーズを用いて、クラッキングを2mmに設定し、比較例1と同様に成形を行った。結果、大ボード成形体の外観は良好になったが、厚み精度は大きく低下し、成形体の発泡倍率も実施例1に比べてかなり低くなる結果となった。また、厚み違い成形体の外観も同様に良好になったが、倍率のばらつきは非常に大きくなった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
ポリフェニレンエーテル系樹脂(PPE)としてS201A(旭化成(株)製)30質量%、汎用ポリスチレン樹脂(PS)としてGP685(PSジャパン(株)製)70質量%を含む熱可塑性樹脂を押出機にて加熱溶融混練の後に押出し、基材樹脂ペレットを作製した。
得られた基材樹脂のTspは144℃であった。
基材樹脂ペレットを耐圧容器に収容し、容器内の気体を乾燥空気で置換した後、発泡剤として炭酸ガスを注入し、圧力2.3MPa、温度20℃の条件下で3時間かけて基材樹脂ペレットに対して二酸化炭素を6質量%含浸させた。
基材樹脂ペレットを発泡炉内で攪拌羽を77rpmにて回転させながら加圧水蒸気により加熱し、発泡させて発泡ビーズを得た。この時の発泡温度は143℃であった。
得られた発泡ビーズを用いて実施例1と同様にクラッキング0mmにて成形を行ったところ、比較例1同様、大ボード成形体、厚みの異なる厚み違い成形体、どちらにおいても空隙が見られ、外観に劣る物となった。また、厚み違い成形体の発泡倍率も比較例1と同様、ばらつきが大きい結果となった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
ポリフェニレンエーテル系樹脂(PPE)としてS201A(旭化成(株)製)20質量%、汎用ポリスチレン樹脂(PS)としてGP685(PSジャパン(株)製)80質量%を含む熱可塑性樹脂を押出機にて加熱溶融混練の後に押出し、基材樹脂ペレットを作製した。
得られた基材樹脂のTspは136℃であった。
基材樹脂ペレットを耐圧容器に収容し、容器内の気体を乾燥空気で置換した後、発泡剤として炭酸ガスを注入し、圧力2.4MPa、温度20℃の条件下で4時間かけて基材樹脂ペレットに対して二酸化炭素を4質量%含浸させた。
基材樹脂ペレットを発泡炉内で攪拌羽を77rpmにて回転させながら加圧水蒸気により加熱し、発泡させて発泡ビーズを得た。この時の発泡温度は138℃であった。
得られた発泡ビーズを用いて実施例1と同様にクラッキング0mmにて成形を行ったところ、比較例1同様、大ボード成形体、厚みの異なる厚み違い成形体、どちらにおいても空隙が見られ、外観に劣る物となった。また、厚み違い成形体の発泡倍率も比較例1と同様、ばらつきが大きい結果となった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
比較例3と同じ基材樹脂100質量部に対し、発泡剤としてn-ペンタン(沸点36.1℃)を10質量部加え、押出機内で加熱混錬し、未発泡の樹脂粒子を得た。
この樹脂粒子を発泡炉内で攪拌羽を77rpmにて回転させながら加圧水蒸気により加熱し、発泡させて発泡ビーズを得た。この時の発泡温度は148℃であった。
得られた発泡ビーズを用いて実施例1と同様にクラッキング0mmにて成形を行ったところ、比較例1同様、大ボード成形体、厚みの異なる厚み違い成形体、どちらにおいても空隙が見られ、外観に劣る物となった。また、厚み違い成形体の発泡倍率も比較例1と同様、ばらつきが大きい結果となった。
得られた発泡ビーズ及び成形体の各測定・評価結果を表1に示す。
2 気泡
Claims (6)
- 熱可塑性樹脂を含む基材樹脂を含み、前記基材樹脂の軟化点をTspとしたとき、Tsp+10℃で5分加熱したときの加熱収縮率が30%以下であることを特徴とする、発泡ビーズ。
- 前記基材樹脂の軟化点Tspが130℃以上である、請求項1に記載の発泡ビーズ。
- 前記発泡ビーズの表面を構成するスキン層の平均厚みが、前記発泡ビーズの平均粒子径の0.2~2.0%である、請求項1又は2に記載の発泡ビーズ。
- 前記基材樹脂がポリフェニレンエーテル系樹脂を含む、請求項1又は2に記載の発泡ビーズ。
- 請求項1又は2に記載の発泡ビーズを含むことを特徴とする、成形体。
- Tsp+5℃~Tsp+40℃で発泡することを特徴とする、請求項1又は2に記載の発泡ビーズの製造方法。
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JP2018175862A (ja) * | 2017-04-05 | 2018-11-15 | アディダス アーゲー | 成形したスポーツ用品、スポーツ用品およびスポーツシューズの少なくとも一部を製造するための複数の個別発泡粒子をポストプロセス処理する方法 |
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- 2022-06-30 EP EP22837614.1A patent/EP4368663A1/en active Pending
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Patent Citations (10)
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JPS4638359B1 (ja) | 1967-02-14 | 1971-11-11 | ||
JPS5122951B2 (ja) | 1972-12-19 | 1976-07-13 | ||
JPH0649795B2 (ja) | 1985-11-29 | 1994-06-29 | 日本スチレンペ−パ−株式会社 | ポリプロピレン系樹脂予備発泡粒子成型体の製造方法 |
JPH0446217B2 (ja) | 1985-12-26 | 1992-07-29 | Mitsubishi Yuka Baadeitsushe Kk | |
JPH0622919B2 (ja) | 1985-12-26 | 1994-03-30 | 三菱油化バ−デイツシエ株式会社 | ポリプロピレン系樹脂発泡粒子の型内成形法 |
JPH03217437A (ja) * | 1989-07-05 | 1991-09-25 | Montedipe Srl | 発泡性ビーズの製造法 |
JPH03192135A (ja) * | 1989-10-26 | 1991-08-22 | General Electric Co <Ge> | 超短波エネルギーによる熱可塑性樹脂ビーズの発泡方法 |
JPH04122741A (ja) * | 1989-12-27 | 1992-04-23 | General Electric Co <Ge> | 低i.v.ポリフェニレンエ―テル発泡性微粒子から得られるポリフェニレンエ―テルフォ―ム |
JPH04372630A (ja) | 1991-06-20 | 1992-12-25 | Asahi Chem Ind Co Ltd | ポリオレフィン系樹脂の低発泡粒子及びその製造方法 |
JP2018175862A (ja) * | 2017-04-05 | 2018-11-15 | アディダス アーゲー | 成形したスポーツ用品、スポーツ用品およびスポーツシューズの少なくとも一部を製造するための複数の個別発泡粒子をポストプロセス処理する方法 |
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