1225506 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（1 ) 發明背景 發明範圍 本發明有關一種熱塑性樹脂組成物，其適於製造諸如 熱熔接等，而且擠壓模製條件範圍廣泛，其提供一種良好 外觀與無澤、可撓且膠黏性低表面之模製物件，而且其具 有適當均衡之強度、耐磨蝕性、抗油性等。 相關技藝詳述 通常，無鹵素塑性樹脂是非極性樹脂，因此其存在無 法用以製造諸如與含鹵素樹脂等相當之熱熔接等問題。因 此，使用無氟樹脂大幅受限，而且在某些實例中已指經指 出含鹵素樹脂替代物造成之環境問題等，使其無法再繼續 進行。 尤其是，迄今已使用非剛性氯化乙烯樹脂（P V C ) 作爲冰箱襯墊；不過，因爲該冰箱中貯存食物，所以因爲 荷爾蒙破壞化學物質等而招致異議之氯化乙烯樹脂已造成 環境問題。此外，置棄冰箱時，因爲存在包含在氯化乙嫌 樹脂中之氯所致的戴奧辛等問題，存在無法對其僅進行锻 燒之問題。 已進行使用不包含氯化乙烯樹脂以解決上述問題之硏 究。不過，此等樹脂具有諸如表面膠黏性、耐磨蝕性不足 與頂點部分熱熔接性等困難，所以無法繼續使用由氯化乙 烯樹脂製成之冰箱襯墊的替代物。 發明總結 本發明目的之一係提出一種無鹵素熱塑性樹脂組成物 本纸張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） ---— II---I I I I i l· I I I I I 11111111 I ^ (請先閱讀背面之注意事項再填寫本頁)1225506 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Background of the invention The present invention relates to a thermoplastic resin composition suitable for manufacturing such as heat welding, etc. It provides a molded article with a good appearance and a non-zeable, flexible, and low-adhesive surface, and it has a properly balanced strength, abrasion resistance, oil resistance, and the like. Detailed Description of Related Techniques In general, halogen-free plastic resins are non-polar resins, and therefore, they cannot be used to produce problems such as thermal fusion equivalent to halogen-containing resins. Therefore, the use of non-fluorinated resins has been greatly restricted, and in some instances, environmental problems caused by the replacement of halogen-containing resins have been pointed out, making it impossible to proceed. In particular, non-rigid chlorinated vinyl chloride resin (PVCC) has been used as a refrigerator liner so far; however, because food is stored in the refrigerator, chlorinated vinyl resin which has been criticized due to hormone destruction of chemicals has caused environmental problems. In addition, when the refrigerator is disposed of, there is a problem such as dioxin due to chlorine contained in the chlorinated ethyl chloride resin, and there is a problem that it cannot be calcined only. Studies have been conducted on the use of resins which do not contain vinyl chloride to solve the above problems. However, these resins have difficulties such as surface adhesiveness, insufficient abrasion resistance, and thermal fusion at the apex portion, so it is not possible to continue to use substitutes for refrigerator liners made of chlorinated vinyl resin. Summary of the Invention One of the objectives of the present invention is to propose a halogen-free thermoplastic resin composition. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) ----- II --- IIII il · IIIII 11111111 I ^ (Please read the notes on the back before filling this page)
_ * I Mm MB I * -ϋ 1 I ·1 1 I , -4- 1225506 經濟部智慧財產局員工消費合作社印制取 A7 ______B7_ 五、發明說明（2 ) ，其適於製造諸如熱熔接等，而且擠壓模製條件廣泛，其 提供一種良好外觀與無澤、可撓且膠黏性低表面之模製物 件，而且其具有適當均衡之強度、耐磨蝕性、抗油性等。 本發明其他目的係提出一種由無鹵素樹脂形成之冰箱 襯墊，其具有與習用氯化乙烯樹脂所形成冰箱襯墊相同特 性，但是不會造成諸如戴奧辛、荷爾蒙破壞化學物質等環 境問題。 根據本發明，提出一種熱塑性樹脂組成物，其包括： (a) 15至20重量％之聚丙烯，其熔融流速（下 文稱爲MFR)爲0·5至10克/10分鐘，此係於 2 3 0 °C A S T Μ — D — 1 2 3 8 L條件（相同條件適用 於下文）下測量， (b) 25至41重量％之經氫化嵌段共聚合物，其 數量平均分子量爲100，000至200，000，而 且至少一種聚合物嵌段A主要包括一種乙烯基芳族化合物 ，至少一種聚合物嵌段B主要包括一種共軛二烯化合物， 該乙烯基芳族化合物含量在5至5 0重量％範圍內，而至 少7 0 %之共軛二烯化合物部分經氫化， (c ) 1 2至2 2重量％之熱塑性彈性體，其係一種 聚烯屬烴樹脂與一種乙烯- α -烯屬烴共聚合物橡膠之動 態或靜態硫化摻合物，或是一種聚烯屬烴樹脂與一種乙烯 - α -非共軛二烯共聚合物橡膠之動態或靜態硫化摻合物 ，其具有3 0至5 0重量％不溶解於二甲苯含量〔將該摻 合物浸於1 2 0°C二甲苯2 0小時，然後經由一個1 〇 〇 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------- I l· I I I I I ·11111111 I，一 (請先閱讀背面之注意事項再填寫本頁) -5- 1225506 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（3 ) 網眼過爐器過濾’並且將該1 0 0網眼過濾器上之殘留物 重量除以浸漬前總重以測量該殘留物百分比（下文稱爲凝 膠部分）〕，及 (d ) 2 6至3 8重量％之石蠟型加工油軟化劑，其 黏度（40 °C)爲300至500厘史，且苯胺點爲 1 3 0 至 1 6 0 t。 根據本發明，另外提出一種冰箱襯墊，其中使用上述 熱塑性樹脂組成物。 發明詳述 熱塑性樹脂組成物中之聚丙烯（a )使製得之模製物 件具有良好外觀與耐熱性。聚丙烯之種類並無特殊限制， 其可爲均聚丙烯、無規聚丙烯或嵌段聚丙烯。其中，就耐 熱性觀點而言，以均聚丙烯爲佳。該聚丙烯之M F R爲 0 · 5至10克/10分鐘，當MFR小於〇 · 5克/ 1 0分鐘時，該組成物整體流動性質變低，且其模製性變 差。此外，當MFR超過1 0克/1 0分鐘時，該經氫化 嵌段共聚合物無法良好地分散，並且在最終產物表面造成 凸起，而且物理性質變得不安定。因此，此等MF R不適 用。MFR以1至1 〇克/1 〇分鐘爲佳。 此外，聚丙烯（a )之添加量佔該熱塑性樹脂組成物 1 5至2 1重量％。當該數量少於1 5重量％時，該熱塑 性樹脂組成物之流動性質整體變差，而且模製性變差，當 該數量超過2 1重量％時，可撓性變差。因此，此等數量 _________________ -6- 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) - 訂---------線_ « 經濟部智慧財產局員工消費合作社印製 1225506 A7 ______B7_ 五、發明說明（4 ) 不適用。 視情況需要，只要上述不會受到損害，可使用一種包 含核晶劑、抗靜電劑與耐候化安定劑之聚丙烯。 熱塑性樹脂組成物中之經氫化嵌段共聚合物（b )係 具有至少一種聚合物嵌段A主要包括一種乙烯基芳族化合 物，而且至少一種聚合物嵌段B主要包括一種共軛二烯化 合物之共聚合物，該乙烯基芳族化合物含量在5至5 0重 量％範圍內，而至少7 0%之共軛二烯化合物部分經氫化 〇 此經氫化嵌段共聚合物中之乙烯基芳族化合物包括苯 乙烯、α —甲基苯乙烯、鄰一、間一與對一甲基苯乙烯、 1 ，3 —二甲基苯乙烯、乙烯基萘、乙烯基蒽等。附帶一 提，聚合物嵌段Α係上述化合物之一的均聚物，或是由上 述化合物之混合物組成之聚合物。 該共軛二烯化合物包括1，3 - 丁二烯、異戊間二烯 、2，3 —二甲基一 1，3 —丁二烯、1，3 —戊二烯、 1，3 -己二烯等。聚合物嵌段B係上述化合物之一的均 聚物，或是由上述化合物之混合物組成之聚合物。 該經氫化嵌段共聚合物中之乙烯基芳族化合物含量爲 5至5 0重量％。當該乙烯基芳族化合物含量落在此範圍 外時，整體熱塑性樹脂組成物之剛度變高，可能無法維持 其可撓性。該經氫化嵌段共聚合物之數量平均分子量（ Μη)在100，000至200，000範圍內，在 130，0 0 0至2 00，000範圍內爲佳，其分子量 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------錶！ — 丨訂---------線' (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1225506 A7 B7 五、發明說明（5) 分佈Mw/Mn (Mw :重量平均分子量）不超過1 〇爲 佳，不超過5更佳，不超過2最佳。當該數量平均分子量 小於100，000時，無法提供充分抗油性。此外，當 該數量平均分子量超過200，000時，其流動性質變 得相當低，而且可能無法模製該熱塑性樹脂組成物。 此外，該氫化嵌段共聚合物中至少7 0%共軛二烯化 合物部分經氫化。當該共軛二烯化合物部分之氫化百分比 少於7 0 %時，其耐候化性大幅變差，而且其用途大受限 制，所以此種氫化百分比不適當。附帶一提，該經氫化嵌 段共聚合物之結構可能爲直鏈或分支鏈。 另外，本發明所使用之經氫化嵌段共聚合物可以進一 步模製，即可使該分子末端或該分子鏈中具有一極性基團 ，諸如羥基、羧基、環氧基等。 該經氫化嵌段共聚合物之添加量佔該熱塑性樹脂組成 物2 5至4 1重量％。當該數量超過4 1重量％時，其流 動性質變得相當差，當該數量少於2 5重量％時，其耐油 性變差。該數量係2 7至3 3重量％爲佳。 本發明所使用之熱塑性彈性體（c )係一種聚烯屬烴 樹脂與一種乙烯- α -烯屬烴共聚合物橡膠之動態或靜態 硫化摻合物，或是一種聚烯屬烴樹脂與一種乙烯一 α 一非 共軛二烯共聚合物橡膠之動態或靜態硫化摻合物，其不溶 解於二甲苯含量爲3 0至5 0重量％，其大幅改善熱熔接 特性與模製性，而且即使在外觀與手感與觸感方面亦具有 此等特性，本發明熱塑性樹脂組成物製得之模製物件表面 -----8-_ 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公餐） (請先閱讀背面之注意事項再填寫本頁)_ * I Mm MB I * -ϋ 1 I · 1 1 I, -4- 1225506 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ______B7_ V. Description of the invention (2), which is suitable for manufacturing such as heat welding, etc. Moreover, the extrusion molding conditions are wide, which provides a molded article with good appearance and non-zee, flexible and low adhesiveness, and it has a properly balanced strength, abrasion resistance, oil resistance, etc. Another object of the present invention is to provide a refrigerator gasket formed of a halogen-free resin, which has the same characteristics as a refrigerator gasket formed of a conventional vinyl chloride resin, but does not cause environmental problems such as dioxin, hormone-damaging chemicals, and the like. According to the present invention, a thermoplastic resin composition is provided, which includes: (a) 15 to 20% by weight of polypropylene having a melt flow rate (hereinafter referred to as MFR) of 0.5 to 10 g / 10 minutes, which is about 2 Measured under the conditions of 30 ° CAST M — D — 1 2 3 8 L (the same conditions apply below), (b) 25 to 41% by weight of the hydrogenated block copolymer having a number average molecular weight of 100,000 to 200,000, and at least one polymer block A mainly includes a vinyl aromatic compound, at least one polymer block B mainly includes a conjugated diene compound, and the vinyl aromatic compound content is 5 to 50 weight %, And at least 70% of the conjugated diene compound is partially hydrogenated, (c) 12 to 22% by weight of a thermoplastic elastomer, which is a polyolefinic hydrocarbon resin and an ethylene-α-olefin A dynamic or static vulcanization blend of a hydrocarbon copolymer rubber, or a dynamic or static vulcanization blend of a polyolefinic resin and an ethylene-α-non-conjugated diene copolymer rubber, having 3 0 To 50% by weight insoluble in xylene content The substance was immersed in xylene at 120 ° C for 20 hours, and then passed through a 100-paper scale to apply Chinese National Standard (CNS) A4 (210 X 297 mm) ---------- ---- I l · IIIII · 11111111 I ， One (Please read the precautions on the back before filling this page) -5- 1225506 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) Filter through the oven 'and divide the weight of the residue on the 100 mesh filter by the total weight before immersion to measure the percentage of the residue (hereinafter referred to as the gel portion)], and (d) 2 6 to 38% by weight of a paraffin-type processing oil softener, the viscosity (40 ° C) is 300 to 500 centimeters, and the aniline point is 130 to 160 t. According to the present invention, there is further proposed a refrigerator gasket in which the above-mentioned thermoplastic resin composition is used. DETAILED DESCRIPTION OF THE INVENTION The polypropylene (a) in the thermoplastic resin composition gives a molded article having good appearance and heat resistance. The type of polypropylene is not particularly limited, and it may be homopolypropylene, random polypropylene, or block polypropylene. Among them, homopolypropylene is preferred from the viewpoint of heat resistance. The M F R of the polypropylene is from 0.5 to 10 g / 10 minutes, and when the MFR is less than 0.5 g / 10 minutes, the overall flow properties of the composition become low, and its moldability becomes poor. In addition, when the MFR exceeds 10 g / 10 minutes, the hydrogenated block copolymer does not disperse well, and causes protrusions on the surface of the final product, and the physical properties become unstable. Therefore, these MFRs are not applicable. The MFR is preferably from 1 to 10 g / 10 minutes. The amount of polypropylene (a) added is 15 to 21% by weight of the thermoplastic resin composition. When the amount is less than 15% by weight, the flowability of the thermoplastic resin composition as a whole is deteriorated, and the moldability is deteriorated. When the amount is more than 21% by weight, the flexibility is deteriorated. Therefore, these quantities _________________ -6- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)-Order ----- ---- Line_ «Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 1225506 A7 ______B7_ V. Invention Description (4) Not applicable. If necessary, as long as the above is not damaged, a polypropylene containing a nuclear crystal agent, an antistatic agent, and a weathering stabilizer may be used. The hydrogenated block copolymer (b) in the thermoplastic resin composition has at least one polymer block A mainly including a vinyl aromatic compound, and at least one polymer block B mainly including a conjugated diene compound. Copolymer, the content of the vinyl aromatic compound is in the range of 5 to 50% by weight, and at least 70% of the conjugated diene compound is partially hydrogenated. The vinyl aromatic in the hydrogenated block copolymer Family compounds include styrene, α-methylstyrene, ortho-, meta-, and para-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene, and the like. Incidentally, the polymer block A is a homopolymer of one of the aforementioned compounds, or a polymer composed of a mixture of the aforementioned compounds. The conjugated diene compound includes 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexane Diene, etc. The polymer block B is a homopolymer of one of the aforementioned compounds, or a polymer composed of a mixture of the aforementioned compounds. The content of the vinyl aromatic compound in the hydrogenated block copolymer is 5 to 50% by weight. When the content of the vinyl aromatic compound falls outside this range, the rigidity of the entire thermoplastic resin composition becomes high, and its flexibility may not be maintained. The number average molecular weight (Mn) of the hydrogenated block copolymer is in the range of 100,000 to 200,000, and preferably in the range of 130,000 to 20,000. The molecular weight of this hydrogenated block copolymer is applicable to the country of China. Standard (CNS) A4 specification (210 X 297 mm) ------------- watch! — 丨 Order --------- Line '(Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225506 A7 B7 V. Description of the invention (5) Distribution Mw / Mn (Mw: weight average molecular weight) is preferably not more than 10, more preferably not more than 5, and most preferably not more than 2. When the number average molecular weight is less than 100,000, sufficient oil resistance cannot be provided. In addition, when the number-average molecular weight exceeds 200,000, the flow properties become considerably low, and the thermoplastic resin composition may not be molded. In addition, at least 70% of the conjugated diene compound in the hydrogenated block copolymer is hydrogenated. When the hydrogenation percentage of the conjugated diene compound portion is less than 70%, its weathering resistance is greatly deteriorated, and its use is greatly restricted, so this hydrogenation percentage is not appropriate. Incidentally, the structure of the hydrogenated block copolymer may be linear or branched. In addition, the hydrogenated block copolymer used in the present invention can be further molded, so that the molecular end or the molecular chain has a polar group such as a hydroxyl group, a carboxyl group, an epoxy group, and the like. The hydrogenated block copolymer is added in an amount of 25 to 41% by weight based on the thermoplastic resin composition. When the amount exceeds 41% by weight, its flow properties become rather poor, and when the amount is less than 25% by weight, its oil resistance becomes poor. The amount is preferably from 27 to 33% by weight. The thermoplastic elastomer (c) used in the present invention is a dynamic or static vulcanization blend of a polyolefin resin and an ethylene-α-olefin copolymer copolymer rubber, or a polyolefin resin and a Dynamic or static vulcanization blend of ethylene-α-non-conjugated diene copolymer rubber, which is insoluble in xylene content of 30 to 50% by weight, which greatly improves heat fusion characteristics and moldability, and It has these characteristics even in terms of appearance, feel and touch. The surface of a molded article made of the thermoplastic resin composition of the present invention ----- 8-_ This paper size applies to China National Standard (CNS) A4 (210x297) Meal) (Please read the notes on the back before filling out this page)
· ·1 ϋ ·1 ϋ ϋ 1- ϋ 一·^· 1 ϋ ·1 ϋ ϋ ϋ n · I n ϋ n ϋ ϋ ϋ *1 ϋ I ϋ 1 ϋ I I I ϋ ϋ I ^1 1 I I 『1225506 A7 B7 五、發明說明（6) 狀態與含鹵素樹脂組成物製得之模製物件表面狀態相I胃 近。 具有3至15個碳原子之α—嫌屬烴適於作爲該共聚 合物橡膠中之α -烯屬烴。可以使用二環戊二烯、1 ，4 -己二烯、亞乙基原冰片二烯、伸甲基原冰片二烯等作爲 該非共軛二嫌。本發明中，基於易取得及改善耐熱特性觀 點，以丙烯作爲該α —烯屬烴爲佳。因此，以所謂 E P DM作爲該共聚合物橡膠組份爲佳。上述兩種共聚合 物橡膠中之乙烯/ α —烯屬烴比以5 0 / 5 0至9 0 / 1 0重量比爲佳，以6 0/4 0至8 0/2 0重量比更佳 。該聚烯屬烴樹脂包括聚乙烯、聚丙烯、乙烯-丙嫌共聚 合物、其混合物等。其中，以聚丙烯爲佳。 可使用習用橡膠用硫化劑作爲該硫化劑。特別是，除 了硫之外，適用者爲烷基酚-甲醛樹脂與有機過氧化物， 諸如過氧化枯基。除了該硫化劑之外，可以共同使用一種 硫化夥伴劑、一種抗氧化劑等。基於強度與處理性間平衡 之考量，每1 0 0重量份數共聚合物橡膠中烷基酚-甲醛 樹脂之添加量係0·5至15重量份數。基於強度與處理 性考量，每1 0 0重量份數共聚合物橡膠中有機過氧化物 之添加量在0·05至1重量份數範圍內。相對於1〇〇 重量份數該共聚合物橡膠，保持該處理性不可或缺之聚嫌 屬烴樹脂含量至少5重量份數。藉由添加硫化劑製得熱塑 性彈性體（c )，但是動態熔融捏合摻合該共聚合物橡膠 與聚烯屬烴樹脂或是靜態熔融該摻合物但是不予捏合以硫 ___·9- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） • I ϋ I I I H ϋ ϋ n n n n ϋ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 一•口 T · ^1 ϋ ϋ n ϋ I ϋ Βϋ n ϋ I ·ϋ l_i n an n I ϋ mMMm tmmm I n n n an t— ϋ 1225506 A7 B7 五、發明說明（7 ) 化該摻合物。 上述組份（C )之凝膠部分（將該組份浸於1 2 0 °C 二甲苯2 0小時，然後經由一個1 0 0網眼過濾器過濾， 並且將該1 0 0網眼過濾器上之殘留物重量除以浸漬前總 重以測量該殘留物百分比）爲3 0至5 0重量％。當該凝 膠部分少於3 0重量％時，該頂點熱熔接性變得不足，當 該凝膠部分超過5 0重量時，其耐磨蝕性迅速降低而造成 困難。 組份（c )之摻合量爲1 2至2 2重量％，以1 6至 2 0重量％爲佳，其係以該熱塑性樹脂組成物重量爲基準 。當該數量少於1 2重量％時，該熱熔接性變得不足，無 法抑制表面因使用油作爲軟化劑所致之膠黏性，而且模製 物件外表面之膠黏性變大。其係不良情況。此外，當該數 量超過2 2重量％時，質強度不當地大幅降低，而且耐磨 蝕性變差。 該熱塑性樹脂組成物中之軟化劑（d )具有軟化該組 成物使其具有流動性質之特性。基於相容性考量，石蠟型 加工油適於作爲該軟化劑，而且必須使用黏度（4 0 °C ) 在3 0 0至5 0 0厘史範圍內，而且基於滲漏觀點苯胺點 在1 3 0至1 6 0°C範圍內者。基於流動性質、軟化效果 、滲漏與表面膠黏性考量，軟化劑（c )之添加量必須爲 2 6至3 8重量％。該數量自3 0至3 4重量％爲佳。 視情況需要，可於該熱塑性樹脂組成物中添加一種無 機塡料、一種核晶劑、一種外部潤滑劑、一種內部潤滑劑 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -ϋ iamm emem I mm— 1 ϋ 一so- «^1 IB1 ϋ · I ϋ I ι 經濟部智慧財產局員工消費合作社印製 -10- 經濟部智慧財產局員工消費合作社印製 1225506 A7 B7_ 五、發明說明（8 ) 、一種光安定劑、一種紫外線吸收劑、一種抗氧化劑、一 種著色劑、一種表面改良劑等。 可以採用所有用以製造習用樹脂組成物與橡膠組成物 一般方法作爲製備本發明熱塑性樹脂組成物之方法。基本 上，使用一種機械性熔融摻合法，其使用一種單螺旋擠壓 器、一種雙螺旋擠壓器、一種班伯里混合器、一種捏合器 、一種輥磨機等。此外，可以在1 8 0至3 0 0°C範圍適 當選擇該實例中熔融捏合用之溫度。 該製得之組成物具有熱塑性，因此可以使用常用之熱 塑性樹脂模製機模製。 此外，可以藉由一種常用以模製氯化乙烯樹脂之模製 擠壓器將該製得之組成物模製成冰箱襯墊。將擠壓模製製 得之模製物件裁切成預定長度，將磁鐵夾入接觸該冰箱鐵 板側之袋內，將少量發泡體塞入頂點部分以維持該形狀， 然後使頂點部分彼此熱熔接製得一冰箱襯墊。 根據本發明，製得一種無鹵素熱塑性樹脂組成物，其 適於製造諸如熱熔接等，而且擠壓模製條件廣泛，其提供 一種良好外觀與無澤、可撓且膠黏性低表面之模製物件， 而且其具有適當均衡之強度、耐磨蝕性、抗油性等。特別 是，製得一種冰箱襯墊，其具有與製自氯化乙烯樹脂之冰 箱襯墊特性相同之特性，而且克服環境問題。 較佳具體實例描述 下文所示之實施例與對照實例更詳述本發明；不過， -11 - ___________ 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐) — — — — — — — — — — — I — ·1111111 一"^· — — — — — — — · — · — — — — — — — · — — — — — — — , (請先閱讀背面之注意事項再填寫本頁) 1225506 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（9 ) 本發明不受到該實施例限制。 實施例1至2與對照實例1至1 4 在實施例與對照實例中，摻合組份如下： 組份a (1):聚丙烯（MFR=1克/10分鐘） ，由 Nippon Polyolefin Co.，Ltd.所製。 組份a (2):聚丙烯（MFR=15克/10分鐘 )，由 Nippon Polyolefin Co·，Ltd·所製。 組份b (1):具有經氫化聚苯乙烯聚丁二烯一聚苯 乙烯結構之經氫化嵌段共聚合物（苯乙烯含量：3 0重量 %，氫化百分比：至少7 0%，數量平均分子量： 12 0*0 0 0 )，由 ASAHI CHEMICAL INDUSTRY C〇·， LTD所製。 組份b ( 2 ):具有經氫化聚苯乙烯聚異戊間二烯一 聚苯乙烯結構之經氫化嵌段共聚合物（苯乙烯含量：3 0 重量％，氫化百分比：至少7 0%，數量平均分子量： 6 0 ，0 0 〇 )，由 ASAHI CHEMICAL INDUSTRY C〇·， LTD所製。 組份b ( 3 ):具有經氫化聚苯乙烯聚丁二烯一聚苯 乙烯結構之經氫化嵌段共聚合物（苯乙烯含量：3 0重量 %，氫化百分比：至少7 0 %，數量平均分子量： 1 7 0 ，0 0 〇 )，由 KURARAY C〇·，LTD 所製。 組份b ( 4 ) ••具有經氫化聚苯乙烯聚異戊間二烯一 聚苯乙烯結構之經氫化嵌段共聚合物（苯乙烯含量：3 0 ____-12- _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) — — — 1 — — — — — — — —« — l· — — — !— 一一 e*· « — — — — — — I— — — — — — — — — — — — — — — — — — — — I. (請先閱讀背面之注意事項再填寫本頁) 1225506 經濟部智慧財產局員工消費合作社印制π A7 B7 五、發明說明（10) 重量％，氫化百分比：至少7 0%，數量平均分子量： 8 〇 ，0 〇 〇 )，由 KURARAY C〇·，LTD 所製。 組份c (1):乙烯一丙烯共聚合物（凝膠部分：0 重量 ％ )，由 Japan Syntjeic Rubber Co.，Ltd·所製。 組份c ( 2 ):以一種有機過氧化物動態硫化一種乙 烯-丙烯-非共軛二烯共聚合物橡膠與聚丙烯樹脂之摻合 物所製得的熱塑性彈性體（凝膠部分：4 2重量％ )，由 SUMITOMO CHEMICAL C〇·，LTD.所製。 組份d ( 1 ):石蠟型加工油〔黏度（4 0 °C )： 3 8 2 厘史，苯胺點：1 4 4 °C〕，由 Idemitsu Kosan Κ·Κ· 所製。 組份d ( 2 ):石蠟型加工油〔黏度（4 0 °C ): 9 6 厘史，苯胺點：1 2 8 °C〕，由 Idemitsu Kosan Κ·Κ·所 製。 組份d ( 3 ):石蠟型加工油〔黏度（4 0 °C ): 238 厘史，苯胺點：90 °C〕，由 Idemitsu Kosan Κ·Κ·所 製。 於一班伯界混合器中以2 2 0 °C之捏合溫度捏合上述 組份a至d，並將形成之經捏合產物通過一個輥磨機製成 一薄板。此板於一個粉磨機中粉磨製得熱塑性樹脂組成物 之方形九粒。 使用5 0毫米Φ擠壓器模製該九粒，隨後進行裁切、夾 入磁鐵、塞入發泡體及頂點熱熔接步驟，製得一冰箱襯墊 。將該襯墊裁切成預定試樣，並進行下列評估項目： 本紙張尺度適用中國國家標準（CNS)a4規格（210 X 297公釐） • ϋ I I n .^1 ϋ n ί ϋ- ϋ · ϋ ϋ ϋ ^1 I ί ^1 一φτ · ^1 I ϋ H ^1 ϋ ϋ I ϋ ^1 1 ϋ 1 1 n n Memmw I I ·ϋ ·ϋ ϋ ϋ 1 mmmmm 1 I I ϋ 1.- (請先閱讀背面之注意事項再填寫本頁) -13- 1225506 A7 B7 五、發明說明（11) 一 (1)抗張強度：根據J IS K6 3· 01 (拉伸速度·· (請先閱讀背面之注意事項再填寫本頁) 2 0 0毫米/分鐘） 評估記號與標準1 〇 :至少 lOMpa X :小於 1 0 M p a (2 )模製性與外觀 藉由5 0毫米Φ擠壓器評估模製性，並以肉眼與接觸評 估外觀（表面特性。 評估記號與標準2 〇 :表面不膠黏，而且無大型外來物質等造成之瑕疵 ，可進行相當於軟PVC之模製作用。 X :表面膠黏，而且有大型外來物質等造成之瑕疵， 無法進行相當於軟p v c之模製作用。· · 1 ϋ · 1 ϋ ϋ 1- ϋ 1 ^ · 1 ϋ · 1 ϋ ϋ ϋ n · I n ϋ n ϋ ϋ ϋ * 1 ϋ I ϋ 1 ϋ III ϋ ϋ I ^ 1 1 II 『1225506 A7 B7 5. Description of the invention (6) The state is similar to the surface state of the molded article made of the halogen-containing resin composition. An α-suspected hydrocarbon having 3 to 15 carbon atoms is suitable as the α-olefinic hydrocarbon in the copolymer rubber. As the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, ethylene orthobornadiene, methylendorbornadiene, and the like can be used. In the present invention, propylene is preferably used as the α-olefinic hydrocarbon from the viewpoint of easily obtaining and improving heat resistance characteristics. Therefore, the so-called EPDM is preferably used as the copolymer rubber component. The ethylene / α-olefinic hydrocarbon ratio in the above two copolymer rubbers is preferably a weight ratio of 50/50 to 90/100, and more preferably a weight ratio of 60/40 to 80/20. . The polyolefin resin includes polyethylene, polypropylene, an ethylene-propylene copolymer, a mixture thereof, and the like. Among them, polypropylene is preferred. As the vulcanizing agent, a conventional vulcanizing agent for rubber can be used. In particular, in addition to sulfur, alkylphenol-formaldehyde resins and organic peroxides such as cumyl peroxide are applicable. In addition to the vulcanizing agent, a vulcanizing partner, an antioxidant, and the like may be used together. Based on the balance between strength and handleability, the amount of alkylphenol-formaldehyde resin per 100 parts by weight of copolymer rubber is 0.5 to 15 parts by weight. Based on strength and handling considerations, the amount of organic peroxide added per 100 parts by weight of copolymer rubber is in the range of 0.05 to 1 part by weight. Relative to 100 parts by weight of the copolymer polymer rubber, the content of the poly hydrocarbon hydrocarbon resin which is indispensable for maintaining the handleability is at least 5 parts by weight. The thermoplastic elastomer (c) is prepared by adding a vulcanizing agent, but the melt-kneading blends the copolymer polymer rubber with a polyolefin resin or the melt-static blending does not knead with sulfur ___ · 9- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) • I ϋ IIIH ϋ ϋ nnnn ϋ (Please read the notes on the back before filling out this page) I. T. ^ 1 ϋ ϋ n ϋ I ϋ Βϋ n ϋ I · ϋ l_i n an n I ϋ mMMm tmmm I nnn an t — ϋ 1225506 A7 B7 V. Description of the invention (7) The blend. The gel portion of the above component (C) (immerse the component in xylene at 120 ° C for 20 hours, then filter through a 100 mesh filter, and filter the 100 mesh filter The weight of the residue divided by the total weight before immersion to measure the percentage of the residue) is 30 to 50% by weight. When the gel portion is less than 30% by weight, the thermal fusion property of the vertex becomes insufficient, and when the gel portion exceeds 50% by weight, its abrasion resistance is rapidly reduced to cause difficulty. The blending amount of the component (c) is 12 to 22% by weight, preferably 16 to 20% by weight, which is based on the weight of the thermoplastic resin composition. When the amount is less than 12% by weight, the heat-weldability becomes insufficient, it is impossible to suppress the adhesiveness of the surface due to the use of oil as a softener, and the adhesiveness of the outer surface of the molded article becomes large. It is a bad situation. In addition, when the amount exceeds 22% by weight, the qualitative strength is unduly greatly reduced, and the abrasion resistance is deteriorated. The softening agent (d) in the thermoplastic resin composition has a characteristic of softening the composition so that it has flow properties. Based on compatibility considerations, paraffin-type processing oils are suitable as the softener, and must have a viscosity (40 ° C) in the range of 300 to 500 centimeters, and the aniline point is 1 3 from the perspective of leakage. 0 to 16 0 ° C. Based on considerations of flow properties, softening effect, leakage and surface adhesiveness, the addition amount of the softener (c) must be 26 to 38% by weight. The amount is preferably from 30 to 34% by weight. Depending on the situation, an inorganic filler, a nuclear crystal agent, an external lubricant, and an internal lubricant can be added to the thermoplastic resin composition. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297) (Please read the notes on the back before filling out this page) -ϋ iamm emem I mm— 1 ϋ so- «^ 1 IB1 ϋ · I ϋ I ι Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-10- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1225506 A7 B7_ 5. Description of the Invention (8), a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent, a surface modifier, etc. As the method for preparing the thermoplastic resin composition of the present invention, all the general methods for producing a conventional resin composition and a rubber composition can be adopted. Basically, a mechanical melt blending method is used, which uses a single screw extruder, a double screw extruder, a Banbury mixer, a kneader, a roll mill, and the like. In addition, the temperature for melt-kneading in this example can be appropriately selected in the range of 180 to 300 ° C. The composition obtained is thermoplastic, and thus can be molded using a conventional thermoplastic resin molding machine. Further, the obtained composition can be molded into a refrigerator gasket by a molding extruder commonly used for molding vinyl chloride resin. The molded article obtained by extrusion molding is cut to a predetermined length, the magnet is clamped into a bag contacting the side of the iron plate of the refrigerator, and a small amount of foam is inserted into the vertex portion to maintain the shape, and then the vertex portions are mutually A refrigerator gasket was prepared by heat fusion. According to the present invention, a halogen-free thermoplastic resin composition is prepared, which is suitable for manufacturing such as heat welding, etc., and has a wide range of extrusion molding conditions, which provides a mold with a good appearance and a non-slip, flexible, and low-adhesion surface It can be used to make articles, and it has proper balance of strength, abrasion resistance, oil resistance, etc. In particular, a refrigerator gasket was prepared which has the same characteristics as those of a refrigerator gasket made from a chlorinated vinyl resin and overcomes environmental problems. The preferred specific examples describe the embodiments and comparative examples shown below to describe the present invention in more detail; however, -11-___________ This paper size applies the Chinese National Standard (CNS) A4 specification (210x297 mm) — — — — — — — — — — — I — · 1111111 I " ^ · — — — — — — — — — • — — — — — — — — — — — (Please read the notes on the back before filling in this Page) 1225506 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of Invention (9) The present invention is not limited by this embodiment. Examples 1 to 2 and Comparative Examples 1 to 1 4 In the Examples and Comparative Examples, the blending components were as follows: Component a (1): Polypropylene (MFR = 1 g / 10 minutes), manufactured by Nippon Polyolefin Co. , Ltd .. Component a (2): Polypropylene (MFR = 15 g / 10 minutes), manufactured by Nippon Polyolefin Co., Ltd. Component b (1): hydrogenated block copolymer with hydrogenated polystyrene polybutadiene-polystyrene structure (styrene content: 30% by weight, hydrogenation percentage: at least 70%, quantity average Molecular weight: 12 0 * 0 0 0), manufactured by ASAHI CHEMICAL INDUSTRY Co., LTD. Component b (2): a hydrogenated block copolymer having a hydrogenated polystyrene polyisoprene-polystyrene structure (styrene content: 30% by weight, hydrogenation percentage: at least 70%, Number average molecular weight: 6 0, 0 0 〇), manufactured by ASAHI CHEMICAL INDUSTRY Co., LTD. Component b (3): hydrogenated block copolymer with hydrogenated polystyrene polybutadiene-polystyrene structure (styrene content: 30% by weight, hydrogenation percentage: at least 70%, average number Molecular weight: 17 0, 0 0 0), manufactured by KURARAY CO., LTD. Component b (4) •• Hydrogenated block copolymer with hydrogenated polystyrene polyisoprene-polystyrene structure (styrene content: 3 0 ____- 12- _ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) — — — 1 — — — — — — — — — — — — — — — — e * · «— — — — — — — — — — — — — — — — — — — — — — — — — — — — I. (Please read the notes on the back before filling out this page) 1225506 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Explanation (10) wt%, hydrogenation percentage: at least 70%, number average molecular weight: 80.0, 0.00), manufactured by KURARAY CO., LTD. Component c (1): ethylene-propylene copolymer (gel portion: 0% by weight), manufactured by Japan Syntjeic Rubber Co., Ltd. Component c (2): a thermoplastic elastomer prepared by dynamically vulcanizing an ethylene-propylene-non-conjugated diene copolymer polymer rubber and polypropylene resin with an organic peroxide (gel part: 4 2% by weight), manufactured by SUMITOMO CHEMICAL CO., LTD. Component d (1): paraffin-type processing oil [viscosity (40 ° C): 3 8 2 centimeters, aniline point: 1 4 4 ° C], manufactured by Idemitsu Kosan KK · K ·. Component d (2): paraffin-type processing oil [viscosity (40 ° C): 96 cents history, aniline point: 1 2 8 ° C], manufactured by Idemitsu Kosan KK · K ·. Component d (3): paraffin-type processing oil [viscosity (40 ° C): 238 centimeters, aniline point: 90 ° C], manufactured by Idemitsu Kosan KK · K ·. The above components a to d were kneaded in a Banbury mixer at a kneading temperature of 220 ° C, and the resulting kneaded product was passed through a roll mill to form a thin plate. This plate was pulverized in a pulverizer to obtain nine square pieces of a thermoplastic resin composition. The nine pellets were molded using a 50 mm Φ extruder, followed by cutting, sandwiching magnets, inserting foam, and apex thermal welding steps to obtain a refrigerator gasket. The liner was cut into a predetermined sample, and the following evaluation items were performed: The paper size applies the Chinese National Standard (CNS) a4 specification (210 X 297 mm) • ϋ II n. ^ 1 ϋ n ί ϋ- ϋ · ϋ ϋ ϋ ^ 1 I ί ^ 1 一 φτ · ^ 1 I ϋ H ^ 1 ϋ ϋ I ϋ ^ 1 1 ϋ 1 1 nn Memmw II · ϋ · ϋ ϋ ϋ 1 mmmmm 1 II ϋ 1.- (Please read first Note on the back page, please fill in this page) -13- 1225506 A7 B7 V. Description of the invention (11) One (1) Tensile strength: According to J IS K6 3 · 01 (Tension speed · · (Please read the note on the back first) Please fill in this page again) 200 mm / min) Evaluation marks and standards 1 〇: at least lOMpa X: less than 10 M pa (2) Moldability and appearance Evaluation of moldability by 50 mm Φ extruder And evaluate the appearance (surface characteristics) with the naked eye and contact. Evaluation marks and standards 2 0: The surface is not sticky, and there are no defects caused by large foreign substances, etc., which can be used for molding equivalent to soft PVC. X: Surface sticking In addition, there are defects caused by large foreign materials, which cannot be used for mold making equivalent to soft PVC.
(3 ):可撓性：硬度：j I S K 6 3 0 1 ( J I S 經濟部智慧財產局員工消費合作社印製 A型，於5秒後之値） 評估記號與標準3 〇 :小於8 0 X ··至少8 0 ' (4 )頂點之熱熔接性 將兩個擠壓模製物件放在一起，在一熱熔接機中以 —__· 14·_ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 1225506 A7 B7 五、發明說明（12) 2 0 Ot處理該形成裝配物約1至2分鐘，然後於9 0°C 進行剝離試驗。比較所獲得之熱熔接強度與習用氯化乙烯 樹脂之熱熔接強度以測定其百分比。 評估記號與標準4 〇 :相對於PVC熱熔接強度之百分比至少60%。 X :相對於P V C熱熔接強度之百分比小於6 0 %。 (5 )抗油性：將該試樣浸入大豆油中，並於4 0 °C保持 4 8小時，然後測量其重量改變百分比。 評估記號與標準5 〇 :重量改變百分比小於1 0 %。 X :重量改變百分比至少1 0 %。 (6 )滲漏特性：於加速候化試驗後（晴天氣候，黑板溫 度：6 3 °C，於雨中3 0 0小時），觀察該試樣表面狀態 0 評估記號與標準6 〇 :不會滲漏 X :有些滲漏 (7 )於冰箱中之開關試驗：將一個冰箱裝上襯墊，然後 以1 0，0 0 0次開關試驗/天之速率進行 200，000次開關試驗。 評估記號與標準7 -15- 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^1 ϋ ί I i ϋ ϋ _1 ϋ ϋ ϋ · ϋ ^1 n .^1 ϋ ϋ ϋ 一SOT · «_ϋ ϋ ^1 ϋ ^1 n ·ϋ I ^1 II I ϋ ϋ ϋ ϋ —Bi I n ϋ ϋ I ϋ ϋ ϋ a·— ι ϋ ϋ ϋ , (請先閱讀背面之注意事項再填寫本頁) 1225506 A7 B7_ 五、發明說明（13) 〇 :開關200，000次後無改變。 X :確認有諸如破裂等問題。 -：因爲模製失敗造成無法模製之故，所以無法評估 〇 上述評估結果示於表1至3。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產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（210 X 297公釐） -16- 1225506 A7 B7 4 1 /V 明 說 明 發 經濟部智慧財產局員工消費合作社印製 對照實例4 卜 οι ο X ο ο ο ο I 對照實例3 卜 ON cn ο ο ο ο ο X X 對照實例2 CN CN 卜 ο ο X ο ο ο X 對照實例I wn cn ο X ο ο ο ο I 實施例2 〇〇 cn m C<l m ο ο ο ο ο ο ο 實施例I 〇〇 m m οα cn ο ο ο ο ο ο ο 組份a(l) 組份b(l) 組份b(3) 組份c(2) 組份d(l) 頂點熱熔接性 模製性，外觀 可撓性 抗張強度 滲漏特性 抗油性 冰箱開關試驗 調配物 (重量%) 評估 結果 * — — — — — — — — — — — — — — — — — — I— ^ ·11111111 . (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐) 1225506 A7 B7 五、發明說明（15 ) 經濟部智慧財產局員工消費合作社印製 ΟΟ ΟΟ cn ON ro O X 〇 〇 〇 〇 1 卜 ΟΟ ΟΟ m ON un CvJ o X 〇 〇 〇 〇 1 ΟΟ m m (N as CN o ο 〇 X 〇 〇 X wn ΟΟ v〇 CO i—H wo CO X X 〇 〇 〇 〇 1 對照實例 組份a(l) 組份b(l) 組份b(3) 組份c(2) 組份d(l) 頂點熱熔接性 模製性，外觀 可撓性 抗張強度 滲漏特性 抗油性 冰箱開關試驗 調配物 (重量％) 評估 結果 ----I-------I · I l· I I I I I ^ ·11111111 _ (請先閲讀背面之注意事項再填寫本頁) -ϋ I ϋ ϋ ϋ ·1 ϋ I I ϋ H ·1 ϋ ϋ n ϋ ϋ H ϋ ϋ - 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐) 1225506 A7 B7 五、發明說明（16) 經濟部智慧財產局員工消費合作社印製 寸 〇〇 cn CO CN m O X ο ο X ο 1 oo m cn r- CNJ m o X ο ο X ο 1 CS oo cn cn CN m !X； X ο ο ο ο 1 < i oo CO CO r- Oi cn 〇 ο ο X ο X X Ο oo CO m r- CN cn o ο ο Χί ο XI X ON oo cn m 卜 CN cn o X ο ο ο ο 1 ¢1 m 騸 产·Η C<J 9 11111 < CN CM ·—— X—\ C<l x—s cn m c3 Λ X5 CJ o T3 T3 1WU m |Η <Πί m gi mi 認 amt 鉍 m Μ rid I? 擞 ^ i 囡_ m3» ilni] — — — — — — — — — — — I — — — — — — — I— 11111111 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -19 -(3): Flexibility: Hardness: j ISK 6 3 0 1 (type A printed by JIS Consumers ’Cooperative of Intellectual Property Bureau, Ministry of Economy, 5 seconds later) Evaluation mark and standard 3 0: less than 8 0 X · · The thermal fusion of at least 8 0 '(4) vertices put two extrusion-molded articles together in a thermal fusion machine with —__ · 14 · _ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 1225506 A7 B7 V. Description of the invention (12) 2 0 Ot Process the formed assembly for about 1 to 2 minutes, and then perform a peel test at 90 ° C . The obtained heat-sealing strength was compared with the heat-sealing strength of a conventional vinyl chloride resin to determine its percentage. Evaluation mark and standard 40: at least 60% of the percentage with respect to the strength of PVC heat-welding. X: The percentage with respect to P V C thermal fusion strength is less than 60%. (5) Oil resistance: The sample was immersed in soybean oil and kept at 40 ° C for 48 hours, and then the weight change percentage was measured. Evaluation mark and standard 50: The percentage of weight change is less than 10%. X: The weight change percentage is at least 10%. (6) Leakage characteristics: After accelerated weathering test (sunny weather, blackboard temperature: 63 ° C, 300 hours in rain), observe the surface state of the sample. 0 Evaluation mark and standard 6: No leakage Leak X: Some leaks (7) Switching test in refrigerator: Put a refrigerator on the pad, and then perform 200,000 switching tests at a rate of 10,000 switching tests / day. Evaluation Marks and Standards 7 -15- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ 1 ί Ι I ϋ ϋ _1 ϋ ϋ ϋ · ϋ ^ 1 n. ^ 1 ϋ ϋ S 一 SOT · «_ϋ ϋ ^ 1 ϋ ^ 1 n · ϋ I ^ 1 II I ϋ ϋ ϋ ϋ —Bi I n ϋ ϋ I ϋ ϋ ϋ a · — ϋ ϋ ϋ, (Please read the precautions on the back first (Fill in this page again) 1225506 A7 B7_ V. Description of the invention (13) 〇: No change after switching 200,000 times. X: Confirmation of problems such as cracking. -: Evaluation cannot be performed because molding cannot be performed due to molding failure. ○ The above evaluation results are shown in Tables 1 to 3. (Please read the precautions on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -16- 1225506 A7 B7 4 1 / V Explain that the comparative example 4 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs was used as a comparative example 4 ο ο X ο ο ο ο I Comparative Example 3 was ON cn ο ο ο ο ο XX Comparative Example 2 CN CN 卜 ο ο X ο ο ο X Comparative Example I wn cn ο X ο ο ο ο I Example 2 〇〇cn m C < lm ο ο ο ο ο ο ο Example I 〇〇mm οα cn ο ο ο ο ο ο ο Component a ( l) Component b (l) Component b (3) Component c (2) Component d (l) Vertex heat fusion moldability, Appearance flexibility Tensile strength Leakage characteristics Oil resistance refrigerator switch test deployment (% By weight) Evaluation results * — — — — — — — — — — — — — — — — — — — — 11111111. (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 x 297 mm) 1225506 A7 B 7 V. Description of the invention (15) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇Ο 〇Ο cn ON ro OX 〇〇〇〇1 卜 〇〇 〇〇 m ON un CvJ o X 〇〇〇〇1 〇〇 mm (N as CN o ο 〇X 〇〇X wn ΟΟ v〇CO i—H wo CO XX 〇〇〇〇1 Comparative Example Component a (l) Component b (l) Component b (3) Component c (2) Component d (l) Vertex thermal fusion moldability, appearance flexibility, tensile strength, leakage characteristics, oil resistance refrigerator switch test formulation (% by weight) Evaluation results ---- I ------- I · I l · IIIII ^ · 11111111 _ (Please read the precautions on the back before filling out this page) -ϋ I ϋ ϋ 1 · 1 ϋ II ϋ H · 1 ϋ ϋ n ϋ ϋ H ϋ ϋ-This paper size applies Chinese national standards (CNS) A4 specification (210 x 297 mm) 1225506 A7 B7 V. Description of invention (16) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇〇cn CO CN m OX ο ο X ο 1 oo m cn r- CNJ mo X ο ο X ο 1 CS oo cn cn CN m! X; X ο ο ο ο 1 < i oo CO CO r- Oi cn 〇ο ο X ο XX Ο oo CO m r- CN cn o ο ο Χί ο XI X ON oo cn m bu CN cn o X ο ο ο ο 1 ¢ 1 m 骟 Product · Η C < J 9 11111 < CN CM · —— X— \ C < lx—s cn m c3 Λ X5 CJ o T3 T3 1WU m | Η < Πί m gi mi amt bismuth m Μ rid I? 擞 ^ i 囡 _ m3 »ilni] — — — — — — — — — — — — I — — — — — — — — I— 11111111 (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -19-