TW424103B - Expanded resin beads - Google Patents
Expanded resin beads Download PDFInfo
- Publication number
- TW424103B TW424103B TW086119979A TW86119979A TW424103B TW 424103 B TW424103 B TW 424103B TW 086119979 A TW086119979 A TW 086119979A TW 86119979 A TW86119979 A TW 86119979A TW 424103 B TW424103 B TW 424103B
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- TW
- Taiwan
- Prior art keywords
- foamed
- beads
- resin
- resin beads
- patent application
- Prior art date
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- 239000012508 resin bead Substances 0.000 title claims abstract description 74
- 238000002844 melting Methods 0.000 claims abstract description 65
- 230000008018 melting Effects 0.000 claims abstract description 58
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005977 Ethylene Substances 0.000 claims abstract description 38
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims description 53
- 239000011248 coating agent Substances 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 239000011324 bead Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 32
- 238000000465 moulding Methods 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 25
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 25
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000000052 comparative effect Effects 0.000 claims description 13
- 238000005187 foaming Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 230000002079 cooperative effect Effects 0.000 claims description 10
- 238000012669 compression test Methods 0.000 claims description 9
- -1 polybutylene Polymers 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229920005673 polypropylene based resin Polymers 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 239000004519 grease Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 229920002647 polyamide Polymers 0.000 claims 2
- 229920001748 polybutylene Polymers 0.000 claims 2
- 229920001225 polyester resin Polymers 0.000 claims 2
- 239000002609 medium Substances 0.000 description 7
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 6
- 239000006260 foam Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001872 inorganic gas Inorganic materials 0.000 description 3
- 229920005679 linear ultra low density polyethylene Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004794 expanded polystyrene Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- LMHUKLLZJMVJQZ-UHFFFAOYSA-N but-1-ene;prop-1-ene Chemical group CC=C.CCC=C LMHUKLLZJMVJQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
經漪部中央標隼局員工消費合作社印^ 424 103 ’ A7 ___B7五、發明説明（1 ) 發明背景 本發明係關於發泡樹脂珠粒。特別地，本發明係關於 發泡樹脂珠粒，其熔解黏合性質極佳，因此能夠降低產製 模製物件之模製溫度且能夠提供機械性質和熱性質極佳的 模製產物。 發泡樹脂珠粒因爲能夠呈現任何所欲的形狀且因爲它 們的密閉蜂窩式構造而使得導熱性低，所以這些珠粒被廣 泛地用來作爲許多模製品（如：絕緣器、襯墊、核心.. 等）的模製材料。至於構成這些發泡樹脂珠粒的熱塑性樹 脂，通常可以使用聚乙烯、聚丙烯、聚苯乙烯之類。 但是，使用熔點高的樹脂（如：以聚丙烯樹脂）作爲 發泡樹脂珠粒時，因爲該類型的樹脂之熔點不低於1 3 5 °C，所以，須要超過2公斤/平方公分G ( Gauge)的高 壓蒸汽來提供使發泡樹脂珠粒在型內（U-mold)操作期間內 彼此熔解黏合所須的壓力。前述模製條件導致一些缺點， 如：模製成本提高及模製循環時間拉長。同樣地，發泡樹 脂珠粒由前述的高熔點樹脂構成時，因爲該類型的樹脂珠 粒無法以此技藝目前常用之用於發泡聚苯乙烯的型內發泡 模製機器模製，因此必須使用配備有高壓蒸汽控制系統之 夾緊壓力高的模製機器。 另一方面，聚乙烯型樹脂的優點在於：因爲聚乙烯類 樹脂的熔點低（低於12 5°C)，所以發泡樹脂珠粒互熔 黏合所須的蒸汽壓低（低於2公斤/平方公分G)，以及 ，可以使用發泡聚苯乙烯所用的模製機器，且實質上不須 ·*^^^1 n nn !eJ {請先聞请背面之注意亨項再4¾本頁) 本紙張尺度適用中國國家樣準（CNS )六4規_格（210X297公釐） 424103 w A7 B7 經濟部中央標準局員工消費合作杜印^ 五、發明説明（2 ) 變動。但是，聚乙烯型樹脂的發泡模製產物之耐熱性低（ 因爲這樣的樹脂之熔點低），特別是高度發泡的模製物件 之能量吸收力小。因此，由聚乙烯型樹脂製得之發泡模製 產物的實際應用被限定在低發泡應用上，此爲其不如由其 他的熱塑性樹脂製得的發泡模製物件之處。 本發明者致力於解決前述問題，結果發現：使用包含 核心（其中包含特定樹脂且處於發泡狀態）和塗層（該塗 層實質上處於未發泡狀態）的發泡樹脂珠粒，可以使發泡 模製物件的機械和熱性質獲得改善。亦基於前述發現而完 成本發明·> 發明槪沭 本發明的目的是要提出一種發泡樹脂珠粒，其所提供 的發泡模製物件之性質與由其他發泡樹脂珠粒所得者相同 ’當此模製物件藉由使用夾緊壓力低的模製機器製得時， 其耐熱性高。 爲達此目的，就本發明之特點，提出一種發泡樹脂珠 粒，包含： 核心，其中包含晶狀熱塑性樹脂且其處於發泡狀態， 和 塗層，其中包含熔點比該熱塑性樹脂來得低或者實質 上並無熔點之以乙烯爲基礎的聚合物，此塗層實質上處於 未發泡狀態。 (請先閲讀背面之注意亨項再4巧大VP' ) ,ιτ 本紙張尺度適用中囤园家標準（CNS ) A4規格（2丨Ο X 297公釐） -5- 424103 ， - 蛵漭部中央標準扃員工消費合作社印裂 五、發明説明（3 ) 發明詳述 下文對本發明作更詳細之說明。 根據本發明的發泡樹脂珠粒具複合構造，包含核心及 其上的塗層。此核心包含晶狀熱塑性樹脂。可用於核心之 晶狀熱塑性樹脂的例子包括以聚丙烯爲基礎的樹脂、以聚 丁烯爲基礎的樹脂、以聚甲基丙烯爲基礎的樹脂、以聚醋 爲基礎的樹脂、以聚醯胺爲基礎的樹脂、以氟爲基礎的樹 脂及以晶狀苯乙烯爲基礎的樹脂。其中，以丙烯均聚物或 丙烯和除了丙烯以外的α —烯烴之無規或團聯共聚物爲佳 〇 此塗層包含熔點比該熱塑性樹脂來得低或者實質上並 無熔點之以乙烯爲基礎的聚合物。此低熔點之以乙烯爲基 礎的聚合物的例子包括高壓加工的低密度聚乙烯、線型低 密度聚乙烯、線型超低密度聚乙烯及乙烯和乙酸乙烯酯* 不飽和羧酸酯、不飽和羧酸、乙烯醇或類似物之共聚物。 該實質上並無熔點之以乙烯爲基礎的聚合物的例子包 括橡膠和彈料，如：乙烯丙烯橡膠、乙烯丙烯二烯橡膠· 乙烯丙烯酸橡膠、氯化聚乙烯橡膠和氯磺化的聚乙烯橡膠 。這些以乙烯爲基礎的聚合物可單獨使用或者以其中的二 或多者之混合物形式使用。 前述以乙烯爲基礎的聚合物中，較佳者是高壓加工的 低密度聚乙烯、線型低密度聚乙烯和線型超低密度聚乙燦 。其中’特別佳者是使用二茂金屬觸媒聚合的線型低密度 聚乙烯和線型超低密度聚乙烯。本發明中，包含以乙烯爲 . , /L-^^^1 *n^i i^i ^^^^1 n -Jyl ^^^^1 (详ilw讀背面之注4亨項再填·ri5本頁) 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公芨） -6- 4241〇3 A7 B7 經漪部中央標準局負工消費合作社印¾ 五、發明説明（4 ) 基礎的聚合物和與用於核心同類型的晶狀熱塑性樹脂之組 成物亦適用以形成塗層。使用這樣之以乙烯爲基礎的聚合 物組成物具有改善核心和其塗層之間之黏合度的優點. 本發明中，以重量計，相對於每1 0 0份以乙烯爲基 礎的聚合物，該晶狀熱塑性樹脂的用量通常是1 〇 〇份。 當此熱塑性樹脂的比例超過以重置計之1 〇 〇份時，塗層 的海一島構造（sea-and-island structure)會改變，使得晶狀 熱塑性樹脂構成連續底相（sea phase)，使得型內蒸汽壓無法 顯著降低。相對於以重量計爲每1 〇 〇份以乙烯爲基礎的 聚合物’熱塑性樹脂的較佳用量是以重量計至1至5 0份 〇 本發明中，希望所選用之以乙烯爲基礎的聚合物之熔 點比構成核心的晶狀熱塑性樹脂低至少1 5 °C »用於塗層 之以乙烯爲基礎的聚合物與用於核心之晶狀熱塑性樹脂之 間的熔點差値以20至60 °C爲佳，20至40 °C更佳。 該熔點的差値不到1 5 °C時，會有包含以乙烯爲基礎的聚 合物的塗層在核心的晶狀熱塑性樹脂發泡的條件下亦發泡 的顧慮》 此外，本發明中，該以乙烯爲基礎的聚合物之熔點通 常不超過125 t，以100至125 °C爲佳。使用熔點 超過1 2 5°C之以乙烯爲基礎的聚合物時，必須要提高模 製此發泡樹脂珠粒所須的蒸汽壓。 根據本發明之發泡樹脂珠粒，塗層厚度通常是1至 1 50微米，以1 0至1 00微米爲佳。此塗層厚度低於 (誚尤閱讀背16之注^事項再填艿本頁) 本紙乐尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消费合作社印裂 424103 A7 _____B7__五、發明説明戸) 1微米時’模製期間所須蒸汽壓的降低效果不明顯。另一 方面’此塗層厚度超過1 5 0微米時，雖然能夠降低模製 操作期間所須的蒸汽壓，但塗層之實質上未發泡的部分提 高’使得模製產物的機械強度低。 根據本發明的發泡樹脂珠粒基本上製自··以揮發性發 @商1浸潤包含核心（包含晶狀熱塑性樹脂）和塗層（包含 以乙烯爲基礎的聚合物，此聚合物的熔點低於該晶狀熱塑 性接f脂之熔點或者實質上並無熔點存在）的複合結構珠粒 ’並藉由加熱而發泡以此方式浸泡的複合結構珠粒《 至於該揮發性發泡劑，可以使用，如：低碳脂族烴（ 如：丙烷、丁烷'戊烷、己烷'環戊烷和環己烷）、鹵化 烴（如：二氯二氟甲烷和三氯一氟甲烷）和無機氣體（如 :氮、空氣和二氧化碳）。這些發泡劑可單獨使用或者以 其中的二或多者之混合物形式使用。 可利用多種方法來產製作爲本發明之發泡樹脂珠粒之 起始材料的複合結構珠粒。舉例言之，可以使用Japanese Patent Publication (KOKOKU) No.41-16125 ' 43-23858 和 44-29522 及 Japanese Patent Application Laid-Open ( KOKAI) No.60- 1 858 1 6所提出的被覆核心型的複合物鑄模 。此處，使用兩組壓出器，其一用於熔解和捏和構成核心 的晶狀熱塑性樹脂，另一壓出器用以熔解和捏和構成塗層 之以乙烯爲基礎的聚合物組成物，自鑲模中將該兩種材料 引至被覆核心型複合體中，以該晶狀熱塑性樹脂形成核心 ，以該以乙烯爲基礎的聚合物組成物形成塗層。 本紙張尺度適用中國團家標準（CNS ) A4規格（2】0X297公釐> · 8· {访^閱讀背而之注意事項再填艿本頁) 訂 4 2 4 103 A7 B7____ 五、發明説明芦) 然後，切割藉此而得的複合體，得到重爲0.1至 1 0毫克的複合珠粒。單個珠粒重量低於0 . 1毫克時* 因爲用以有效降低模製操作所須蒸汽壓之塗層的比例提高 ，所以由這些珠粒得到的發泡模製物件之機械強度較低。 另一方面，珠粒重量超過1 0毫克時，以珠粒充塡鑄模的 情況會變差。 至於加熱及發泡該浸有揮發性發泡劑之被覆核心型複 合珠粒的方法，可以使用，如：Japanese Patent Publication (KOKOKU) No.49-21 83 和 56-1 344 ' German Patent No.l，285，722A 和 2，107·683Α .，等所述的方法。 根據這些方法，此被覆核心型的複合物珠粒和揮發性 發泡劑一起被置於密封容器中，加熱至高於構成核心的晶 狀熱塑性樹脂之軟化溫度的溫度下，使得該複合珠粒被揮 發性發泡劑所浸潤。然後，將密封容器的內容物釋放到壓 力比密封容器的壓力來得小的氣氛中，然後乾燥而得到本 發明的發泡樹脂珠粒。 使此複合珠粒發泡的加熱溫度通常設定不低於核心之 晶狀熱塑性樹脂的軟化溫度，但以高於形成塗層之以乙烯 爲基礎的聚合物（其爲組成物時，以主要組份的熔點爲主 )之熔點的溫度爲佳。本發明中，產製系統中配備攪拌器 ，以免容器中的複合珠粒彼此熔解黏合。 複合珠粒藉加熱而發泡時，以使用水、醇或類似物作 爲其分散介質爲佳。同樣地•爲有利於複合珠粒均勻分散 (诗1閱讀背面之注意事項再^朽表莨) 装· 、1Τ 經"部中央標嗥局負工消费合作社印" 本紙張尺度適用申國國家標孪（^^5)/\4規格（210><297公釐） -9 蛵濟部中央標聿局貝工消费合作社印笨 A7 __B7_ 五、發明説明（7 ) "~~~ 於分散介質中’較佳的方式是使用部分水溶性無機材料（ 如：氧化鋁、磷酸三鈉和氧化鋅）、水溶性保護性膠體（ 如：聚乙烯毗咯啉酮、聚乙烯醇和甲基纖維素）或陰離子 界面活性劑（如：十二碳烷基苯磺酸鈉和α—烯烴苯碟酸 鈉）。這些物質可單獨使用或者以其中的二或多者之混合 物形式使用。 複合珠粒被釋放到低氣壓中時，較佳的情況是由外部 將無機氣體或揮發性發泡劑（如前面所述者）引至密封容 器中，以維持容器內壓的穩定，以利於珠粒的釋出。 可以藉由使用各種類型的鑄模和模製方法，將本發明 的發泡樹脂珠粒模製成產品。舉例言之，模製操作可以根 據壓縮模製法（如 Japanese Patent Publication (KOKOKU )No. 46 — 38359 所述者）進行，此方法中， 複合珠粒於大氣壓或低壓情況下被引至包含母和公模的鑄 模凹槽內，然後壓縮此模使得凹槽的體積減少5至7 0% ，將加熱媒質（如：蒸汽）引至凹槽內，使得發泡樹脂珠 粒彼此熔解黏合。 也可以使用壓力老化法（如Japanese Patent Publicatio n(K〇K0KU)No.51 — 22951 所述者），其中 * 發泡樹脂珠粒先以一或多種類型的揮發性發泡劑或無機氣 體處理以提高樹脂珠粒的二度發泡能力；然後維持其二度 發泡能力，珠粒於大氣壓或低壓情況下被塡入鑄模凹槽內 ，然後將加熱媒質引至凹槽內，使得各個珠粒間熔解黏合 1- I. y I — I ^^^1 - - -I ^^^1 *^r - * 1 I ^^^1 *一eJ (請乇聞讀背而之洼意事項再填艿本頁) 本紙張尺度適用中國國家標準（*^«)八4規格（210乂297公楚） -10- 424 103 A7 B7 Μ 條正Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 424 103 ’A7 ___B7 V. Description of the invention (1) Background of the invention The present invention relates to foamed resin beads. In particular, the present invention relates to foamed resin beads, which have excellent melt-adhesive properties, and therefore can reduce the molding temperature of a molded article to be produced, and can provide molded products with excellent mechanical and thermal properties. Foamed resin beads are widely used as many molded products (such as insulators, gaskets, cores, etc.) because they can assume any desired shape and because of their closed honeycomb structure, they have low thermal conductivity. .. etc.) of molding material. As for the thermoplastic resin constituting these foamed resin beads, polyethylene, polypropylene, polystyrene or the like can be generally used. However, when using a resin with a high melting point (such as polypropylene resin) as the foamed resin beads, the melting point of this type of resin is not lower than 1 35 ° C, so it must exceed 2 kg / cm 2 G ( Gauge) high-pressure steam to provide the pressure necessary to melt and adhere the foamed resin beads to each other during the U-mold operation. The aforementioned molding conditions lead to some disadvantages, such as increased molding cost and lengthened molding cycle time. Similarly, when the foamed resin beads are composed of the aforementioned high-melting resin, because this type of resin beads cannot be molded by the in-mold foam molding machine currently used for expanded polystyrene in this technology, Moulding machines with high clamping pressures equipped with high-pressure steam control systems must be used. On the other hand, the advantages of polyethylene resins are that because of the low melting point of polyethylene resins (less than 125 ° C), the vapor pressure required for the mutual fusion bonding of foamed resin beads is low (less than 2 kg / square). Cm), and the molding machine used for expanded polystyrene can be used without substantial need ** ^^^ 1 n nn! EJ {please listen to the note on the back first, then this page) Paper size applies to China National Standards (CNS) Rule 6_4 (210X297 mm) 424103 w A7 B7 Staff Consumption Cooperation Du Yin of the Central Bureau of Standards of the Ministry of Economic Affairs ^ V. Description of the Invention (2) Changes. However, the foamed molded products of polyethylene resins have low heat resistance (because such resins have a low melting point), and especially the highly foamed molded articles have low energy absorption. Therefore, the practical application of the foamed molded product made of a polyethylene type resin is limited to a low foamed application, which is not as good as a foamed molded article made of other thermoplastic resins. The present inventors have been working to solve the foregoing problems, and have found that using foamed resin beads containing a core (which contains a specific resin and in a foamed state) and a coating (the coating is substantially in an unfoamed state) makes it possible to make The mechanical and thermal properties of the foam molded article are improved. The present invention has also been completed based on the foregoing findings. ≫ Invention 槪 沭 The object of the present invention is to propose a foamed resin bead which provides the same properties as the foamed molded article obtained from other foamed resin beads. 'When this molded article is made by using a molding machine having a low clamping pressure, its heat resistance is high. To achieve this, according to the characteristics of the present invention, a foamed resin bead is provided, comprising: a core, which contains a crystalline thermoplastic resin and is in a foamed state, and a coating, which contains a lower melting point than the thermoplastic resin The ethylene-based polymer has substantially no melting point, and the coating is substantially unfoamed. (Please read the note on the back first and then the 4th big VP '), ιτ This paper size is applicable to the Chinese Gardener's Standard (CNS) A4 specification (2 丨 〇 X 297 mm) -5- 424103,-蛵 漭 部The Central Standard and the Employee Consumer Cooperative Coupling V. Description of the Invention (3) Detailed Description of the Invention The present invention will be described in more detail below. The foamed resin beads according to the present invention have a composite structure including a core and a coating thereon. This core contains a crystalline thermoplastic resin. Examples of crystalline thermoplastic resins that can be used for the core include polypropylene-based resins, polybutene-based resins, polymethacryl-based resins, polyacetate-based resins, and polyamines Based resin, fluorine based resin and crystalline styrene based resin. Among them, a propylene homopolymer or a random or grouped copolymer of propylene and an α-olefin other than propylene is preferred. This coating contains ethylene based on a lower melting point than the thermoplastic resin or substantially no melting point based on ethylene. Polymer. Examples of this low melting point ethylene-based polymer include high-pressure processed low density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, and ethylene and vinyl acetate * unsaturated carboxylic acid esters, unsaturated carboxylic acid Copolymers of acids, vinyl alcohol or the like. Examples of the ethylene-based polymers that have substantially no melting point include rubbers and elastomers such as ethylene propylene rubber, ethylene propylene diene rubber, ethylene acrylic rubber, chlorinated polyethylene rubber, and chlorosulfonated polyethylene. rubber. These ethylene-based polymers may be used alone or as a mixture of two or more of them. Among the aforementioned ethylene-based polymers, preferred are high-pressure-processed low-density polyethylene, linear low-density polyethylene, and linear ultra-low-density polyethylene. Among them, particularly preferred are linear low-density polyethylene and linear ultra-low-density polyethylene polymerized using a metallocene catalyst. In the present invention, ethylene is included. / L-^^^ 1 * n ^ ii ^ i ^^^^ 1 n -Jyl ^^^^ 1 (For details, please read Note 4 on the back and fill in ri5. (This page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 cm) -6- 4241〇3 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Ⅴ. Description of the invention (4) Basic Polymers and compositions of the same type of crystalline thermoplastic resin used for the core are also suitable for forming coatings. The use of such an ethylene-based polymer composition has the advantage of improving the adhesion between the core and its coating. In the present invention, per 100 parts by weight of ethylene-based polymer, The amount of the crystalline thermoplastic resin is usually 100 parts. When the proportion of this thermoplastic resin exceeds 100 parts by replacement, the sea-and-island structure of the coating will change, so that the crystalline thermoplastic resin constitutes a continuous sea phase, This makes it impossible to significantly reduce the internal vapor pressure. The preferred amount of the thermoplastic resin relative to 100 parts by weight of ethylene-based polymer is 1 to 50 parts by weight. In the present invention, it is desirable to use ethylene-based polymerization The melting point is at least 15 ° C lower than the crystalline thermoplastic resin that forms the core »The melting point difference between the ethylene-based polymer used for the coating and the crystalline thermoplastic resin used for the core is between 20 and 60 ° C is better, more preferably 20 to 40 ° C. When the difference in melting point is less than 15 ° C, there is a concern that a coating layer containing an ethylene-based polymer will also foam under conditions where the core crystalline thermoplastic resin foams. In addition, in the present invention, The melting point of this ethylene-based polymer usually does not exceed 125 t, preferably 100 to 125 ° C. When using an ethylene-based polymer having a melting point exceeding 125 ° C, it is necessary to increase the vapor pressure required for molding the expanded resin beads. According to the foamed resin beads of the present invention, the coating thickness is usually 1 to 150 microns, and preferably 10 to 100 microns. The thickness of this coating is less than (read the note of Chiyou 16 below and refill this page) The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The employee's cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed 424103 A7 _____B7__V. Description of the invention 戸) At 1 micron, the effect of reducing the vapor pressure required during molding is not obvious. On the other hand, when the thickness of the coating exceeds 150 micrometers, although the vapor pressure required during the molding operation can be reduced, the substantially non-foamed portion of the coating is increased 'and the mechanical strength of the molded product is low. The foamed resin beads according to the present invention are basically made from a volatile hair @ 商 1 which contains a core (including a crystalline thermoplastic resin) and a coating (containing an ethylene-based polymer, which has a low melting point) The composite structural beads which are immersed in this way by heating at the melting point of the crystalline thermoplastic (or the melting point or substantially no melting point) of the crystalline thermoplastic. "As for the volatile blowing agent, you can Uses such as: lower carbon aliphatic hydrocarbons (such as propane, butane'pentane, hexane 'cyclopentane and cyclohexane), halogenated hydrocarbons (such as dichlorodifluoromethane and trichloromonofluoromethane) and Inorganic gases (e.g. nitrogen, air and carbon dioxide). These foaming agents may be used alone or as a mixture of two or more of them. Various methods can be used to produce composite structural beads that are the starting materials of the foamed resin beads of the present invention. For example, the covering core type proposed by Japanese Patent Publication (KOKOKU) No. 41-16125 '43-23858 and 44-29522 and Japanese Patent Application Laid-Open (KOKAI) No. 60- 1 858 1 6 can be used Compound mold. Here, two sets of extruders are used, one for melting and kneading the crystalline thermoplastic resin constituting the core, and the other extruder for melting and kneading the ethylene-based polymer composition constituting the coating layer, The two materials are introduced into the core-coated composite body from the insert, the core is formed by the crystalline thermoplastic resin, and the coating is formed by the ethylene-based polymer composition. This paper size applies to the Chinese group standard (CNS) A4 specification (2) 0X297 mm > · 8 · {Interview ^ Read the precautions and fill out this page) Order 4 2 4 103 A7 B7____ V. Description of the invention (Lu)) Then, the composite thus obtained is cut to obtain composite beads weighing 0.1 to 10 mg. When the weight of a single bead is less than 0.1 mg *, the mechanical strength of the foamed molded article obtained from these beads is low because the proportion of the coating to effectively reduce the vapor pressure required for the molding operation is increased. On the other hand, when the weight of the beads exceeds 10 mg, filling the mold with the beads becomes worse. As for the method of heating and foaming the coated core-type composite beads impregnated with a volatile blowing agent, for example, Japanese Patent Publication (KOKOKU) Nos. 49-21 83 and 56-1 344 'German Patent No. 1,285,722A and 2,107 · 683A., etc. According to these methods, the coated core-type composite beads and volatile blowing agent are placed together in a sealed container and heated to a temperature higher than the softening temperature of the crystalline thermoplastic resin constituting the core, so that the composite beads are coated with Soaked with volatile foaming agent. Then, the contents of the sealed container were released into an atmosphere having a pressure lower than that of the sealed container, and then dried to obtain the foamed resin beads of the present invention. The heating temperature for foaming this composite bead is usually set not lower than the softening temperature of the core crystalline thermoplastic resin, but it is higher than the ethylene-based polymer forming the coating (when it is a composition, the main group is The melting point is mainly the temperature of the melting point. In the present invention, a stirrer is provided in the production system to prevent the composite beads in the container from melting and sticking to each other. When the composite beads are foamed by heating, it is preferable to use water, alcohol, or the like as the dispersion medium. Similarly, in order to facilitate the uniform dispersion of the composite beads (notes on the back of the poem 1 reading, ^ 朽 表 莨) installed, 1T Ward " Printed by the Ministry of Central Standards Bureau, Offshore Consumer Cooperatives " This paper standard applies to Shen Guo National Standard Twin (^^ 5) / \ 4 Specifications (210 > < 297 mm) -9 Yin Ben A7, Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs __B7_ V. Description of the Invention (7) " ~~~ In a dispersion medium, the preferred method is to use partially water-soluble inorganic materials (such as alumina, trisodium phosphate, and zinc oxide), water-soluble protective colloids (such as polyvinylpyrrolidone, polyvinyl alcohol, and methyl Cellulose) or anionic surfactants (such as: sodium dodecylbenzene sulfonate and α-olefin sodium benzoate). These substances may be used alone or as a mixture of two or more of them. When the composite beads are released into low pressure, it is better to introduce inorganic gas or volatile foaming agent (as described above) into the sealed container from the outside to maintain the stability of the internal pressure of the container to facilitate Release of beads. The foamed resin beads of the present invention can be molded into products by using various types of molds and molding methods. For example, the molding operation can be performed according to a compression molding method (such as described in Japanese Patent Publication (KOKOKU) No. 46-38359), in which the composite beads are introduced under atmospheric pressure or low pressure to The cavity of the male mold is compressed, and then the mold is compressed to reduce the volume of the groove by 5 to 70%, and the heating medium (such as steam) is introduced into the groove, so that the foamed resin beads melt and adhere to each other. It is also possible to use a pressure aging method (as described in Japanese Patent Publicatio n (KOKOKU) No. 51-22951), in which * the foamed resin beads are first treated with one or more types of volatile foaming agents or inorganic gases In order to improve the secondary foaming ability of the resin beads, and then maintain its secondary foaming ability, the beads are pushed into the groove of the mold under atmospheric pressure or low pressure, and then the heating medium is introduced into the groove to make each bead Intergranular melting and adhesion 1- I. y I — I ^^^ 1---I ^^^ 1 * ^ r-* 1 I ^^^ 1 * One eJ (Please read the matter behind the back (Fill in this page) The paper size is applicable to the Chinese national standard (* ^ «) 8 size 4 (210 乂 297 cm) -10- 424 103 A7 B7 Μ
五、發明辨明^附起丨(A):第86119979 ^^^補C 經濟部智慧財產局員工消費合作社印製 中文說明書修正頁 民國89年8月修正 另一個可行的方式是進行壓縮充塡法（如japanese pa tent Publication (KOKOKU)N o . 4-46217 所述者 )，其中，在被壓縮氣體加壓至超過大氣壓的鑄模凹槽中 充塡發泡樹脂珠粒（此發泡樹脂珠粒以先被加壓至高於凹 槽的壓力），然後將加熱媒質引至凹槽內，使得樹脂珠粒 熔解黏合。 也可以進行常壓塡充法（如Japanese Patent Publicaiio n (K〇K〇KU )No.6 — 49795所述者）*其中，於 大氣壓或低壓下，將已於特定條件下處理過之二度發泡能 力高的發泡樹脂珠粒引至鑄模凹槽（由頂部力量和底部塞 子定出其範圍）中，然後將加熱媒質引至凹槽內，使得珠 粒熔解黏合。本發明之模製操作可以前述方法或這些方法 之合倂方式（如 Japanese Patent Pub丨ication (K0K0KU) No·6-22919所述者）進行。 使用前述方法中的任一者時，進行熔解黏合所須的壓 力以低於2公斤/平方公分G爲佳。 根據本發明的發泡樹脂珠粒中，如由其切割截面可見 者，核的晶狀熱塑性樹脂的發泡狀態呈現密閉蜂窩結構1 而形成塗層之以乙烯鳥基礎的聚合物實質上呈現未發泡的 膜狀。 根據本發明，能夠藉前述模製法在低蒸汽壓下製得包 含能夠有效地彼此熔解黏合之該發泡樹脂珠粒的模製產物 根據本發明，相對於凹槽，模製產物之模製尺寸收縮 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） (請先閱讀背面之注意事項再填窝本頁) -11 - 4.24 03 ^ 绍濟部中央標準局負工消費合作社印^ A7 __ B7__五、發明説明（9 ) 率通常不超過2 . 5%。 以前述方式得到的模製產物之機械強度極佳，耐熱性 高，因此，適合用來作爲絕熱器、構成組件、核心之類。 如前所述者，本發明的發泡樹脂珠粒之熔解黏合性質 極佳，即使型內操作中的熱蒸汽壓低時亦然，由這些樹脂 珠粒得到的模製產物之機械強度高、耐熱性高。實例 以下列實例更詳細地說明本發明。但是*應瞭解到， 這些實例僅供說明之用，不欲對本發明之特點造成限制。 下列實例中，珠粒和模製產物的性質以下列方式測定。 <熔點> 此測定係以差示掃描卡計（DSC)進行。首先，3 至5毫克的樹脂樣品加熱至樹脂晶體熔化的溫度，然後以 1 0 °c /分鐘的速率冷卻至室溫。然後樣品再度以1 〇 °c /分鐘的速率加熱，將吸熱曲線所得的峰溫度視爲樹脂樣 品的熔點β <熔解黏合試驗> 由各個模製產物製得2 0 0毫米X 3 0毫米X 1 2 . 5毫米厚的試驗樣品。這些試驗順著直徑5 0毫米 圓筒的圓周彎曲90° ，根據下列標準評估它們的品質。 〇：試樣總數中，8 0%或以上未碎裂。 X:試樣總數中，超過20%碎裂。 請lte讀背面之注意亨邛再41Ϊ:?本頁) 本紙張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） -12- 經潢部中央標準局兵工消費合作社印^ 424103 A7 _B7_ 五、發明説明（10 ) 本發明中，上述評估以〇者爲佳。 <耐熱性試驗> 依照 JIS K 6 7 6 7 測定於110 °c的尺 寸變化百分比，並根據下列標準評估。 〇：尺寸收縮率低於3%。 △:尺寸收縮率爲3至6%。 X :尺寸收縮率大於6%。 本發明中，上述評估以◦或△者爲佳。 實例1 乙烯一丙烯無規共聚物（熔點：1 5 3°C)以內徑 4 0毫米的單螺旋壓出機捏和，線型低密度聚乙烯（熔點 :123°C，密度：0·920)以內徑25毫米的單螺 旋壓出機捏和。經捏和的材料由直徑1.5毫米的鑄模孔 壓成束，所得者的核心部分由乙烯一丙烯無規共聚物形成 ，塗層部分則由線型低密度聚乙烯形成。 此束因通過水槽而冷卻並切成1.2毫克的片段。藉 此而得的複合珠粒延截面切斷，以相對比（phase contrast )顯微鏡觀察切割的截面，其顯示核心乙烯一丙烯無規共 聚物被覆以厚度爲3 0微米的線型低密度聚乙烯》 將100份的此複合珠粒、250份的水、1 . 0份 粒徑爲0.3至0.5微米的磷酸鈣和0.007份 的十二碳烷基苯磺酸鈉引至密閉容器中，繼而在攪拌的同 j---：------' ------訂------f (計尤閱請背面之注意事項再填$本頁) 本紙張尺度適用中困國家標準（CNS ) A4規格（210X297公釐） -13- 經浒部中央標準局負工消費合作社印架V. Identification of the invention ^ Attachment 丨 (A): Article 86119799 ^^^ Supplement C Printed Chinese manual printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Amendment page The Republic of China, August 89. Another feasible way is to perform compression filling method (As described in Japanese patent publication (KOKOKU) No. 4-46217), in which the foamed resin beads (the foamed resin beads) are filled in the mold grooves that are pressurized by the compressed gas to more than atmospheric pressure (Before being pressurized to a pressure higher than the groove), then the heating medium is introduced into the groove, so that the resin beads melt and adhere. Atmospheric pressure filling method (as described in Japanese Patent Publicaiio n (KOKOKU) No. 6-49795) can also be performed * Among them, under atmospheric pressure or low pressure, it will be treated twice under certain conditions The foaming resin beads with high foaming ability are introduced into the mold groove (the range is determined by the top force and the bottom plug), and then the heating medium is introduced into the groove, so that the beads melt and adhere. The molding operation of the present invention can be performed by the aforementioned method or a combination of these methods (such as described in Japanese Patent Pub (K0K0KU) No. 6-22919). When using any of the foregoing methods, the pressure required for melting and bonding is preferably less than 2 kg / cm²G. In the foamed resin beads according to the present invention, as can be seen from its cut cross section, the foamed state of the crystalline thermoplastic resin of the core shows a closed honeycomb structure 1 and the ethylene bird-based polymer forming the coating substantially shows no Foamed film. According to the present invention, a molded product containing the foamed resin beads which can be effectively melt-bonded with each other can be produced under the low vapor pressure by the aforementioned molding method. According to the present invention, the molded product has a molded size relative to the groove. Shrink the paper size to the Chinese National Standard (CNS) A4 size (210X297 mm) (please read the precautions on the back before filling in this page) -11-4.24 03 ^ Printed by the Central Standards Bureau of Shaoji Ministry of Work and Consumer Cooperatives ^ A7 __ B7__ V. Description of the invention (9) The rate usually does not exceed 2.5%. The molded product obtained in the aforementioned manner has excellent mechanical strength and high heat resistance, and is therefore suitable for use as a heat insulator, a component, a core, or the like. As mentioned before, the foamed resin beads of the present invention have excellent melting and adhesion properties, even when the hot steam pressure during in-mold operation is low. The molded products obtained from these resin beads have high mechanical strength and heat resistance. High sex. Examples The following examples illustrate the present invention in more detail. It should be understood, however, that these examples are for illustrative purposes only and are not intended to limit the features of the invention. In the following examples, the properties of the beads and molded products were determined in the following manner. < Melting point > This measurement was performed using a differential scanning card meter (DSC). First, a 3 to 5 mg resin sample was heated to a temperature at which the resin crystals melted, and then cooled to room temperature at a rate of 10 ° c / minute. The sample was then heated again at a rate of 10 ° C / min. The peak temperature obtained from the endothermic curve was taken as the melting point of the resin sample β < melt adhesion test > 200 mm x 300 mm from each molded product X 1 2 .5 mm thick test specimen. These tests were bent 90 ° along the circumference of a 50 mm diameter cylinder, and their quality was evaluated according to the following criteria. 〇: 80% or more of the total number of samples were not broken. X: More than 20% of the total number of samples were broken. Please read the note on the back of the paper. Please read Heng 邛 41Ϊ :? This page) The paper size is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) -12- Printed by the Military Industry Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ 424103 A7_B7_ 5. Description of the invention (10) In the present invention, the above evaluation is preferably 0. < Heat resistance test > The percentage change in size at 110 ° C was measured in accordance with JIS K 6 7 6 7 and evaluated according to the following criteria. 〇: The dimensional shrinkage is less than 3%. Δ: The dimensional shrinkage is 3 to 6%. X: Dimensional shrinkage is greater than 6%. In the present invention, the above evaluation is preferably ◦ or Δ. Example 1 Ethylene-propylene random copolymer (melting point: 153 ° C) was kneaded with a single screw extruder with an inner diameter of 40 mm, and a linear low density polyethylene (melting point: 123 ° C, density: 0 · 920) Knead with a single screw extruder with an inner diameter of 25 mm. The kneaded material was pressed into bundles by a mold hole having a diameter of 1.5 mm. The core portion of the obtained material was formed by an ethylene-propylene random copolymer, and the coating portion was formed by a linear low-density polyethylene. The bundle was cooled by passing through a water tank and cut into 1.2 mg fragments. The composite beads thus obtained were cut along a section, and the cut section was observed with a phase contrast microscope, which showed that the core ethylene-propylene random copolymer was coated with a linear low-density polyethylene having a thickness of 30 microns. " 100 parts of this composite bead, 250 parts of water, 1.0 part of calcium phosphate having a particle size of 0.3 to 0.5 micrometer, and 0.007 part of sodium dodecylbenzenesulfonate were introduced into a closed container, followed by stirring The same j ---: ------ '------ order ------ f (for details, please refer to the note on the back, please fill in this page again) This paper size is suitable for countries with difficulties. Standard (CNS) A4 specification (210X297 mm) -13- Printing stand of the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs
Lit. 'X? ^ A7 ___B7_五、發明説明（11 ) 時添加2 0份丁烷*此材料在容器中的塡充百分比是6 2 %，以長達1小時以上的時間加熱至1 4 5°C，並維持於 此溫度達3 0分鐘。 開啓密閉容器底部的卸氣閥，由外部將氮氣引至容器 的氣相部分中，將容器內容物釋放到大氣中，得到標的發 泡樹脂珠粒。藉此而得的發泡樹脂珠粒之平均整體密度是 1 7公斤/立方米，平均泡沫直徑是1 2 0微米，各珠粒 之間未結塊。 所得的'發泡樹脂珠粒之切截面的相對比顯微觀察結果 顯示形成核心的乙烯一丙烯無規共聚物處於形成密閉蜂窩 結構的發泡狀態，而線型低密度聚乙烯處於實質上未發泡 的膜狀態，並塗覆乙烯一丙烯無規共聚物發泡體。 這些發泡樹脂珠粒在4 0°C、以2 . 0公斤/平方公 分G的壓縮空氣加壓的乾燥容器中良好地乾燥。收縮的珠 粒塡充在包含母和公模並具有蒸汽孔的鋁鑄模的凹槽中> 該凹槽以1.5公斤/平方公分G加壓空氣加壓的處於大 氣壓下。然後，將1.0公斤/平方公分G的蒸汽引至凹 槽中以使得珠粒彼此熔解黏合。 熔解的珠粒進行爲時2 0秒鐘的水冷程序，並以空氣 乾燥35秒鐘，在鑄模表面壓力爲0.3公斤/平方公分 G時，開啓鑄模，取出模製產物。此模製產物密度是 3 0公斤/立方公分，於2 0 0毫米X 3 0毫米x2 5毫 米測定，其相對於鑲模的尺寸收縮率是1 . 9% ° 由前述模製產物製得2 0個測試片（2 0 〇毫米X J 11- I 1· —1 _ I I ^^1 - 1 一 {誚乞閱讀背面之：乂意事項再螭巧本頁) 本紙張尺度適用中國國家標準（CNS〉A4規格（2 ] Ο X 297公釐） • 14- r; v .附件l.¥ 86119979號專利申請案 養广中文說明耆蜂正頁A7民國88年〇9月修正 _ 1 B7__ 五、發明說明彳2 ) 4^1 ^ 7^： 30毫米χ12·5毫米），每個^試片·纏繞㊆直徑„ w 毫米®筒上並彎曲90s 。結果是超過80%的測試片未 破裂。由在前述模製條件下得到的另一模製產物製得5 〇 毫米x50毫米x25毫米厚的測試片，以其進行J I s K 6767 的壓縮試驗。結果顯示50%壓縮應力 是2_9公斤/平方公分。根據 JIS K 6767 另進行1 1 0°C耐熱性試驗時，其尺寸收縮率是3%。這 些試驗結果列於表3。 實例2至1 1及比較例1至· 8 進行與實例1相同的程序，但使用定義於表1至5的 發泡樹脂珠粒，且於表1至5所列的條件加以發泡和模製 。其結果列於表1至5 »發現到：根據本發明之發泡樹脂 珠粒及其模製產物具有極佳的熔解黏合性質、高機械強度 和高耐熱性。 請先閲讀背面之注意事項再A 本頁) 經濟部智慧財產局員工消費合作社印製 -15- 本紙張尺度適用中囤國家標準（CNS)A4規格（210 X 297公釐） Α7 Β7 五、發明説明（13 ) 表1 經溁部中央標準局另工消費合作社印家 實例1 實例2 實例3 實例4 核心樹脂 ET-PR ET-PR ET-PR HT-PR ET含量（％) 1.5 1.5 1.5 3.5 熔點（t ) 153 153 153 142 塗覆樹脂 LLDPE LLDPE ET-VAC(5) LLDPE 密度 0.920 0.920 - 0.920 熔點（°C ) 123 123 102 123 塗層厚度（微 米） 30 100 8 30 複合珠粒重 量（毫克） 1.2 7.0 0.5 1.2 整體平均密 度（公斤/平方 米） 17 20 19 17 核心狀態 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 塗層狀態 實質上未發 實質上未發 實質上未發 實質上未發 泡 泡 泡 泡 模製蒸汽壓（ 公斤/平方公 分G) 1.0 1.0 1.5 1.0 模製產物密 度（公斤/ 立方米） 30 35 30 30 模製尺寸收 縮率（％) 1.9 2.1 1.8 1.9 熔解黏合試 驗 〇 〇 〇 〇 壓縮試驗（公 斤/平方公分） 2.9 3.1 3.1 2.6 耐熱試驗 〇 Δ 〇 Δ . f 一 * Γ ^mt ^^^^1 —J^ii I— I i ^HJ tl^i ^ ^^^^1 i ac^^— TJ J-y*. ，v'e (#先閱讀背面之注意事項再"vi"本頁) 本紙張尺度適用中國國家標準（CNS ) A4规格（2t〇X297公釐） -16- 424 1 〇3 」*ί A7 B7 五、發明説明（M )ET—PR:乙烯一丙烯無規共聚物 LLDPE:線型低密度聚乙烯 物 聚 共 \Jy % 5 /IV 酯 烯 乙 酸} 乙。 I 表 靖附 乙列 : 下 }於 5 用 C適 C 亦 A 寫 V 縮 I 述 T 前 E ( <誚1閱讀背而之注意事項再4¾本頁) 經濟部中央標隼局員工消費合作社印絮 本纸張尺度適用中國國家標率（CNS ) A4規格（210X297公釐） -17- Α7 Β7 經"-部中央標準局負工消費合作社印餐 五、發明説明（15 ) 表2 實例5 實例6 實例7 核心樹脂 PR 1BT-PR 1BT-PR ET含量（％) 0 2.5 2.5 熔點（°C ) 161 156 156 塗覆樹脂 ET-VAC(5) LLDPE LLDPE 密度 - 0.920 0.905 熔點（°C ) 102 123 101 塗層厚度（微 米） 20 30 30 複合珠粒重 量（毫克） 1.2 1.5 1.2 整體平均密 度（公斤/平方 米） 16 15 17 核心狀態 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 塗層狀態 實質上未發 實質上未發 實質上未發 泡 泡 泡 模製蒸汽壓（ 公斤/平方公 分G) 0.8 1.0 1.5 模製產物密 度（公斤/ 立方米） 28 25 30 模製尺寸收 縮率（％) 1.9 1.8 1.9 熔解黏合試 驗 〇. 〇 〇 壓縮試驗（公 斤/平方公分） 3.4 2.9 3.4 耐熱試驗 〇 〇 〇 P R :丙烯均聚物 1BT— PR: 1 — 丁烯一丙烯無規共聚物 (前述縮寫亦適用於下列附表。） . * 八 我 (計1閱谇背面之注意事項再祐巧未頁) 本紙张尺度適用中國國家椋準（CNS ) A4規格（210 X 297公釐） -18- 4 2 4 1 0 3五、發明說明J6 表3 i'Lit. 'X? ^ A7 ___B7_ V. Addition of 20 parts of butane to the description of the invention (11) * The filling percentage of this material in the container is 6 2%, and it is heated to 1 4 for more than 1 hour 5 ° C and maintained at this temperature for 30 minutes. Open the air release valve at the bottom of the closed container, and introduce nitrogen into the gas phase part of the container from the outside to release the contents of the container to the atmosphere to obtain the target foamed resin beads. The average overall density of the foamed resin beads thus obtained was 17 kg / m3, the average foam diameter was 120 micrometers, and no lumps were formed between the beads. The relative ratio microscopic observation results of the cut sections of the obtained 'foamed resin beads show that the core-forming ethylene-propylene random copolymer is in a foamed state forming a closed honeycomb structure, and the linear low-density polyethylene is substantially undeveloped. Foamed film state and coated with ethylene-propylene random copolymer foam. These foamed resin beads were dried well in a drying container pressurized with compressed air at 2.0 kg / cm 2 G at 40 ° C. The contracted beads were filled in a groove of an aluminum mold containing a female mold and a male mold and having steam holes. The groove was pressurized with 1.5 kg / cm2 of G pressurized air at atmospheric pressure. Then, a steam of 1.0 kg / cm2 G was introduced into the recess so that the beads melted and adhered to each other. The melted beads were subjected to a water-cooling procedure for 20 seconds and air-dried for 35 seconds. When the mold surface pressure was 0.3 kg / cm2 G, the mold was opened and the molded product was taken out. The density of this molded product is 30 kg / cm3, measured at 2000 mm x 300 mm x 2 5 mm, and its shrinkage rate relative to the size of the insert is 1.9% ° obtained from the foregoing molded product 2 0 test pieces (200 mm XJ 11- I 1 · —1 _ II ^^ 1-1 诮 {Begging to read the back of the page: Anything to do on this page, and then to this page) The paper size applies to the Chinese National Standard (CNS 〉 A4 specification (2) 〇 X 297 mm) • 14- r; v. Attachment l. Patent application No. 86119979 Yang Guang Chinese description 耆 bee front page A7 Republic of China 88 September 2009 _ 1 B7__ V. Invention Explanation 彳 2) 4 ^ 1 ^ 7 ^: 30 mm x 12 · 5 mm), each ^ test piece · winding ㊆ diameter „w mm ® tube and bent for 90s. As a result, more than 80% of the test piece is not broken. A test piece having a thickness of 50 mm x 50 mm x 25 mm was prepared from another molded product obtained under the foregoing molding conditions, and subjected to a compression test of JI s K 6767. The results showed that the 50% compressive stress was 2-9 kg / cm² When the heat resistance test at 110 ° C was separately performed according to JIS K 6767, the dimensional shrinkage was 3%. The results of these tests are shown in Table 3. Examples 2 to 1 1 and Comparative Examples 1 to · 8 The same procedures as in Example 1 were performed, but using the expanded resin beads defined in Tables 1 to 5 and foamed and molded under the conditions listed in Tables 1 to 5. The results Listed in Tables 1 to 5 »It was found that the foamed resin beads and the molded products thereof according to the present invention have excellent melt-adhesive properties, high mechanical strength and high heat resistance. Please read the precautions on the back first, then A Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -15- This paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) Α7 Β7 V. Description of the invention (13) Table 1 Standards Bureau, Consumer Cooperative, India, Example 1 Example 2 Example 3 Example 4 Core resin ET-PR ET-PR ET-PR HT-PR ET content (%) 1.5 1.5 1.5 3.5 Melting point (t) 153 153 153 142 Coating resin LLDPE LLDPE ET-VAC (5) LLDPE density 0.920 0.920-0.920 melting point (° C) 123 123 102 123 coating thickness (microns) 30 100 8 30 composite bead weight (mg) 1.2 7.0 0.5 1.2 overall average density (kg / Square meters) 17 20 19 17 core state closed honeycomb Shaped closed honeycomb closed honeycomb closed honeycomb coating state is substantially non-issued, substantially non-issued, substantially non-issued, and substantially non-issued. Bubble molding vapor pressure (kg / cm²G) 1.0 1.0 1.5 1.0 Molding Product density (kg / m3) 30 35 30 30 Molded size shrinkage (%) 1.9 2.1 1.8 1.9 Melt adhesion test 0000 Compression test (kg / cm2) 2.9 3.1 3.1 2.6 Heat resistance test 〇Δ 〇Δ. f 一 * Γ ^ mt ^^^^ 1 —J ^ ii I— I i ^ HJ tl ^ i ^ ^^^^ 1 i ac ^^ — TJ Jy *., v'e (#First read the note on the back Matters " vi " this page) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2t〇X297 mm) -16- 424 1 〇3 "* A7 B7 V. Description of the invention (M) ET-PR : Ethylene-propylene random copolymer LLDPE: linear low-density polyethylene copolymer \ Jy% 5 / IV ester ene acetic acid} ethyl. Table I and Table B are attached below: at 5 C is written in C, C is also written in A, V is abbreviated, T is described before E (< 诮 1 read the precautions and then 4¾ page), the Central Bureau of Standards of the Ministry of Economic Affairs, Consumer Cooperatives Printed paper scales are applicable to China National Standards (CNS) A4 specifications (210X297 mm) -17- Α7 Β7 "-Meals printed by the Ministry of Standards and Technology ’s Consumer Cooperatives V. Description of the invention (15) Table 2 Examples 5 Example 6 Example 7 Core resin PR 1BT-PR 1BT-PR ET content (%) 0 2.5 2.5 Melting point (° C) 161 156 156 Coating resin ET-VAC (5) LLDPE LLDPE Density-0.920 0.905 Melting point (° C) 102 123 101 Coating thickness (micron) 20 30 30 Weight of composite beads (mg) 1.2 1.5 1.2 Overall average density (kg / m 2) 16 15 17 Core state Sealed honeycomb closed Honeycomb closed honeycomb coating Status Non-issued and substantially non-foamed bubble molding vapor pressure (kg / cm²G) 0.8 1.0 1.5 Density of molded product (kg / m3) 28 25 30 Molded size shrinkage (%) 1.9 1.8 1.9 Melt adhesion test. 〇〇 Compression test (kg / cm²) 3.4 2.9 3.4 Heat resistance test 〇〇PR: Propylene homopolymer 1BT—PR: 1—Butene-propylene random copolymer (The foregoing abbreviations also apply to the following attached table.). * Eight I (note the note on the back of the book, please read it again) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -18- 4 2 4 1 0 3 Description J6 Table 3 i '
A7 B7 $ m 經濟部智慧財產局員工消費合作社印製 年 比較例1 比較例2 比較例3 比較例4 核心樹脂 ET-PR ET-PR IBT-PR IBT-PR ET含量或1 B T含量（％ ) 1.5 1.5 2.5 2.5 熔點（°C ) 153 153 156 156 塗覆樹脂 二 • 密度 - - - - 熔點（°C ) - • - 塗層厚度（微 米） - - - 複合珠粒重 量（毫克） 1.2 -1.2 1.5 1.5 整體平均密 度（公斤/平方 米） 17 17 15 15 . 核心狀態 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 塗層狀態 - - - 模製蒸汽壓（ 公斤/平方公 分G) 1,0 5.0 1.0 4.5 模製產物密 度（公斤/ 立方米） 30 30 25 25 模製尺寸收 縮率（％) 1.6 2.2 1.6 1.8 熔解黏合試 驗 X 〇 X 〇 壓縮試驗（公 斤/平方公分） 無法測得 3.2 無法測得 3.2 耐熱試驗... 無法測得 〇 無法測得 〇 請 先 閲 讀- 背 之 注 意 事 項 再 Λ 頁 裝 訂 -線 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -19- 4 2 4 10 3 <* A7 B7 五、發明說明（ 經濟部智慧財產局員工消費合作社印製 衣ft 實例10 實例11 [―t~fi ^ ffll S tL較例7 rtrix v'J ° 核心樹脂 ET-PR ET-PR ET-PR LLDPE ET含量（％) 1.5 1.5 1.5 - 熔點（°C ) 153 153 153 123 塗覆樹脂 LLDPE LLDPE ET(3.5)-PR - 密度 0.920 0.920 - 熔點（°c) 123 123 142 - 塗層厚度（微 米） 200 0.8 30 * 複合珠粒重 量（毫克） 7,0 0.5 1.2 3.0 整體平均密 度（公斤/平方 米） 20 19 17 17 核心狀態 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 塗層狀態 實質上未發 泡 實質上未發 泡 開口式蜂窩 狀 - 模製蒸汽壓（ 公斤/平方公 分G) 1.0 1.5 1.3 0.8 模製產物密 度（公斤/ 立方米） 35 30 32 30 模製尺寸收 縮率（％) 2.6 1.6 2.9 1.9 熔解黏合試 驗 〇 X X 〇 壓縮試驗（公 斤/平方公分） 2.2 無法測得 無法測得 1.7 耐熱試驗 X 無法測得 無法測得 X 請 先 閱 背 S} 之 注 項 頁 ΕΤ(3.5) — PR:乙烯（3 聚物（前述縮寫亦適用於下列附表 5%)—丙烯無規共 裝 訂 私紙張尺度適用中國國家標準（CNS)A4規格（210*297公g -20- J 3 ο 4 2 4A7 B7 $ m Printed year of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Core resin ET-PR ET-PR IBT-PR IBT-PR ET content or 1 BT content (%) 1.5 1.5 2.5 2.5 Melting point (° C) 153 153 156 156 Coating resin II • Density----Melting point (° C)-•-Coating thickness (microns)---Weight of composite beads (mg) 1.2 -1.2 1.5 1.5 Overall average density (kg / m 2) 17 17 15 15. Core state closed honeycomb closed honeycomb closed honeycomb closed honeycomb coating state---Moulded vapor pressure (kg / cm2 G) 1,0 5.0 1.0 4.5 Molded product density (kg / m3) 30 30 25 25 Molded size shrinkage (%) 1.6 2.2 1.6 1.8 Melt adhesion test X 〇 X 〇 Compression test (kg / cm²) Unable to measure 3.2 Unable to measure Obtain 3.2 Heat resistance test ... Can't measure 〇 Can't measure 〇 Please read first-Note on the back then Λ Page binding-Thread paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -19- 4 2 4 10 3 < * A7 B7 V. Description of the invention (Printing of clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy ft Example 10 Example 11 [―t ~ fi ^ ffll S tL Comparative Example 7 rtrix v'J ° Core resin ET-PR ET-PR ET-PR LLDPE ET content (%) 1.5 1.5 1.5-Melting point (° C) 153 153 153 123 Coating resin LLDPE LLDPE ET (3.5) -PR-Density 0.920 0.920-Melting point (° c) 123 123 142-Coating thickness (micron) 200 0.8 30 * Weight of composite beads (mg) 7,0 0.5 1.2 3.0 Overall average density (kg / m 2) 20 19 17 17 Core state closed honeycomb closed honeycomb Sealed honeycomb Sealed honeycomb coating state Not substantially foamed, substantially non-foamed open honeycomb-Molded vapor pressure (kg / cm²G) 1.0 1.5 1.3 0.8 Density of molded product (kg / m3) 35 30 32 30 Molded Dimensional Shrinkage (%) 2.6 1.6 2.9 1.9 Melt Adhesion Test XX 〇 Compression Test (kg / cm²) 2.2 Untestable Untestable 1.7 Heat Test X Untestable Untestable X Please read Memorize S} Item Page ET (3.5) — PR: Ethylene (3 polymers (the aforementioned abbreviations also apply to the following Schedule 5%)) — propylene random co-binding private paper size applicable to China National Standard (CNS) A4 specification (210 * 297g) -20- J 3 ο 4 2 4
7 Τ/ A B 五、發明説明（IS ) 表5 _ 經濟部中央標準局負工消費合作社印製 實例8 比較例2 實例9 核心樹脂 ET-PR ET-PR ET-PR ΕΤ含量（％) 1.5 1.5 1.5 熔點（°C ) 153 153 153 塗覆樹脂 組成物A 組成物B M-LLDPE 密度 0.920 0.920 * 熔點（°c) 123 123 102 塗層厚度（微 米） 30 30 30 複合珠粒重 量（毫克） 1.2 1.2 1.2 整體平均密 度（公斤/平方 米） 17 17 17 核心狀態 密閉蜂窩狀 密閉蜂窩狀 密閉蜂窩狀 塗層狀態. 實質上未發 密閉蜂窩狀 實質上未發 泡 泡 模製蒸汽壓（ 公斤/平方公 分G) 1.2 1.2 0.B 模製產物密 度（公斤/ 立方米） 30 30 30 模製尺寸收 縮率（％) 1.7 1.7 1.8 熔解黏合試 驗 〇 X 〇 壓縮試驗（公 斤/平方公分） 3.1 無法測得 2.9 耐熱試驗 〇 無法測得 〇 J--------_\知 —I (讀先閱讀背面之注意事項再填艿本I)7 Τ / AB V. Description of the invention (IS) Table 5 _ Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and printed by the Consumer Cooperative Example 8 Comparative Example 2 Example 9 Core resin ET-PR ET-PR ET-PR ET content (%) 1.5 1.5 1.5 Melting point (° C) 153 153 153 Coating resin composition A Composition B M-LLDPE Density 0.920 0.920 * Melting point (° c) 123 123 102 Coating thickness (microns) 30 30 30 Composite bead weight (mg) 1.2 1.2 1.2 Overall average density (kg / m2) 17 17 17 Core state closed honeycomb closed honeycomb closed honeycomb coating state. Virtually closed airtight honeycomb with substantially no bubble molding vapor pressure (kg / sqm) G) 1.2 1.2 0.B Density of molded product (kg / m3) 30 30 30 Molded size shrinkage (%) 1.7 1.7 1.8 Melt adhesion test 〇X 〇 Compression test (kg / cm2) 3.1 Not available 2.9 Heat resistance test 〇 Can not measure 〇J --------_ \ 知 —I (Read the precautions on the back before filling in this I)
*1T 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） -21 - 4 2 4 ' Ο 3 Λ Α7 _____ 五、發明説明（J9 ) ^ Μ— LLDPE :藉由使用二茂金屬觸媒聚合的線型低密 度聚乙嫌（密度：0，8 9 5 ’熔點：9 1 t )組成物a :100份線型低密度聚乙烯（密度：〇 . 92〇，溶點 :1 2 3 °c ) 2 0份乙烯（1 * 5%) —丙烯無規共聚物（ 熔點：1 5 3 °C ) 組成物B : 1 0 0份線型低密度聚乙烯（密度： 0 . 920，熔點：123°C) 150份乙烯（1 . 5%) —丙烯無規共聚物（焙點 :1 5 3 t )* 1T This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297mm) -21-4 2 4 'Ο 3 Λ Α7 _____ 5. Description of the invention (J9) ^ Μ— LLDPE: By using a metallocene contact Medium polymerized linear low-density polyethylene (density: 0, 8 9 5 'melting point: 9 1 t) composition a: 100 parts of linear low-density polyethylene (density: 0.920, melting point: 1 2 3 ° c) 20 parts of ethylene (1 * 5%)-propylene random copolymer (melting point: 153 ° C) composition B: 100 parts of linear low density polyethylene (density: 0.920, melting point: 123 ° C) 150 parts ethylene (1.5%)-propylene random copolymer (baking point: 1 5 3 t)
(诗先閱讀背面之注意事項再填巧本頁J ,夂卜 -訂 經濟.那中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 22- A7 B7 • V*.(Read the notes on the back of the poem before filling in this page J, 夂 Bu-order economy. Then the paper printed by the Central Standards Bureau Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 22- A7 B7 • V *.
·： V； If I 五、發明説明（）附件二（A):第86119979號 8 中文說明書修正頁 民國89年8月修正 另一個可行的方式是進行壓縮充塡法（如Japanese Pa tent Publication (KOKOKU)N 0.4-46217 所述者 )，其中，在被壓縮氣體加壓至超過大氣壓的鑄模凹槽中 充塡發泡樹脂珠粒（此發泡樹脂珠粒以先被加壓至高於凹 槽的壓力），然後將加熱媒質引至凹槽內，使得樹脂珠粒 熔解黏合。 也可以進行常壓塡充法（如Japanese Patent Publicatio·: V; If I V. Description of the invention () Annex II (A): No. 86119799 No. 8 Chinese manual amendment page August 89, Republic of China Another amendment is possible by compression compression method (such as Japanese Patent Publication ( KOKOKU) N 0.4-46217), in which foamed resin beads are filled in the mold grooves that are pressurized by the compressed gas to more than atmospheric pressure (the foamed resin beads are first pressurized higher than the grooves) Pressure), and then introduce the heating medium into the groove, so that the resin beads melt and stick. Can also be used at normal pressure (such as Japanese Patent Publicatio
(K0K0KU ) N 49795所述者），其中，於 大氣壓或低壓下，將已於特定條件下處理過之二度發泡能 力高的發泡樹脂珠粒引至鑄模凹槽（由頂部力量和底部塞 子定出其範圍）中 > 然後將加熱媒質引至凹槽內，使得珠 粒熔解黏合。本發明之模製操作可以前述方法或這些方法 之合倂方式（如 Japanese Patent Publication (K0K0KU)(K0K0KU) as described in N 49795), wherein, at atmospheric pressure or low pressure, the foamed resin beads that have been treated under specific conditions with a high degree of foaming ability of two degrees are introduced into the mold groove (by the strength of the top and the bottom The stopper defines its range) >> Then the heating medium is introduced into the groove, so that the beads melt and adhere. The molding operation of the present invention can be performed by the foregoing method or a combination of these methods (such as Japanese Patent Publication (K0K0KU)
N (請先閲讀背面之注意事項再填寫本頁) 6-22919所述者）進行 使用前述方法中的任一者時，進行熔解黏合所須的壓 力以低於2公斤/平方公分G爲佳。 經濟部智慧財產局員工消費合作社印製 根據本發明的發泡樹脂珠粒中，如由其切割截面可見 者，核的晶狀熱塑性樹脂的發泡狀態呈現密閉蜂窩結構， 而形成塗層之以乙烯爲基礎的聚合物實質上呈現未發泡的 膜狀。 根據本發明，能夠藉前述模製法在低蒸汽壓下製得包 含能夠有效地彼此熔解黏合之該發泡樹脂珠粒的模製產物 根據本發明，相對於凹槽，模製產物之模製尺寸收縮 本紙張尺度適用中國國家標车（CNS ) A4規格（210X297公釐） -11 -N (Please read the precautions on the back before filling out this page) 6-22919) When using any of the above methods, the pressure required for melting and bonding is preferably less than 2 kg / cm 2 G . In the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the foamed resin beads according to the present invention have a closed honeycomb structure in the foamed state of the crystalline thermoplastic resin as seen from the cut cross section thereof, and the coating is formed thereon. Ethylene-based polymers are essentially unfoamed films. According to the present invention, a molded product containing the foamed resin beads which can be effectively melt-bonded with each other can be produced under the low vapor pressure by the aforementioned molding method. According to the present invention, the molded product has a molded size relative to the groove. Shrink the paper size to the Chinese National Standard Vehicle (CNS) A4 specification (210X297 mm) -11-
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19975996 | 1996-07-10 | ||
| JP01792797A JP3418081B2 (en) | 1996-07-10 | 1997-01-16 | Expanded resin particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW424103B true TW424103B (en) | 2001-03-01 |
Family
ID=26354516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW086119979A TW424103B (en) | 1996-07-10 | 1997-12-30 | Expanded resin beads |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TW424103B (en) |
-
1997
- 1997-12-30 TW TW086119979A patent/TW424103B/en not_active IP Right Cessation
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