1259196 a? ______ B7 五、發明説明（彳） illf領域 (請先閲讀背面之注意事項再填寫本頁) 本發明係關於一種樹脂組成物，其極具耐熱性、耐油 性、耐熱老化性，且拉伸延展特性優異。更詳而言之，係 關於一種適合作爲食品用容器等之樹脂組成物，其係包含 苯乙烯系樹脂或聚伸苯醚系樹脂與烯烴系樹脂、及特定結 構之部分氫化嵌段共聚物。 隻景技術 因本乙矯系樹脂具有良好之加工性、優異之機械特性 ’故廣泛使用以作爲射出成形材料和片狀成形材料。但苯 乙烯系樹脂之耐油性差，若接觸到代奶油和芝麻油等油類 ’則物性會急遽地降低，故有其使用上之界限。是故，一 直嘗試混合烯烴系樹脂，以改良耐油性。然而，因苯乙烯 系樹脂與烯烴系樹脂缺乏相容性，故導致產生剝離現象， 而成爲脆質之組成物。 經濟部智慧財產局員工消費合作社印製 另外，聚伸苯醚系樹脂具優異之機械特性、電氣特性 ’廣泛使用於辦公室機器外罩、各種工業元件等。但其耐 油性和耐衝擊性差，故一直嘗試混合烯烴系樹脂，以改良 此等特性。然而，因兩種樹脂缺乏相容性，故導致產生剝 離現象。 爲解決此等問題點，係提出各種添加嵌段共聚物而成 之組成物。例如日本專利特開昭第56-3 833 8號公報係提出 一種組成物，其包含添加氫化嵌段共聚物而成之聚烯烴系 樹脂與聚苯乙烯系樹脂，該氫化嵌段共聚物係藉由氫化含 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1259196 A7 B7 五、發明説明（2 ) (請先閲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 至少1個乙烯基芳族化合物聚合物嵌段A、與至少1個共軛 二烯系聚合物嵌段B之嵌段共聚物，以使該嵌段共聚物至 少70%之雙鍵飽和所得者，具體而言，係揭示一種氫化嵌 段共聚物，其爲對化合苯乙烯基含量爲50%、氫化前之乙 烯基含量爲13%之A-B型嵌段共聚物，氫化其雙鍵之92% 而得者。另外，日本專利特開平第1 - 174550號公報亦提出 一種組成物，其包含含相同氫化嵌段共聚物之聚烯烴系樹 脂與聚苯乙烯系樹脂，具體而言，係揭示一種氫化嵌段共 聚物，其爲對化合苯乙烯基含量爲35%、氫化前異丁烯中 之乙烯基含量爲8%之A-B型嵌段共聚物，氫化其雙鍵之 93%而得者。但使用此等組成物之氫化嵌段共聚物，因其氫 化率高，故具有生產性低之缺點。例如爲製得特開昭第56-3 833 8號公報所揭示之氫化嵌段共聚物，所需氫化時間爲6 小時，而爲製得特開平第1 - 174550號公報所揭示之氫化嵌 段共聚物，所需氫化時間爲8小時，須耗費相當長的時間 。是故，係期待出現一種聚合物，其爲製造方法容易、生 產性良好之嵌段共聚物，且於添加至含聚烯烴系樹脂與聚 苯乙烯系樹脂之組成物時，其係具優異特性。另外，此處 所揭示之組成物與聚烯烴系樹脂及聚苯乙烯系樹脂雖具改 良之相容性，惟於組成物中之拉伸延展特性並不足，而期 望更進一步的改良。 另外，日本專利特開平第9- 1 2800號公報係提出一種組 成物’其含添加氫化嵌段共聚物而成之聚丙烯系樹脂與聚 伸苯醚，係對含乙烯基芳族化合物聚合物嵌段A、與高乙 ( CNS ) ( 210X297^~ " 經濟部智慧財產局員工消費合作社印製 1259196 A7 __ B7 ____五、發明説明（3 ) 烯鍵量之共軛二烯系聚合物嵌段B之嵌段共聚物，行65至 80%之氫化，而得該氫化嵌段共聚物。具體而言，係揭示一 種氫化嵌段共聚物，其爲對化合苯乙烯基含量爲60%、氫 化前乙烯基含量爲74%之A-B型嵌段共聚物’氫化其雙鍵 之68%而得者。但因此處所使用之氫化嵌段共聚物係含高 乙烯基量之共軛二烯系聚合物，故其缺點爲在高溫下組成 物之耐熱老化性差。 本發明之目的在於提供一種熱塑性樹脂組成物，其極 具耐熱性、耐油性、耐熱老化性，且拉伸延展特性優異， 係藉由於苯乙烯系樹脂及/或聚伸苯醚系樹脂與烯烴系樹脂 中，添加特定結構之部分氫化嵌段共聚物，以製得該熱塑 性樹脂組成物。 發明之揭示 本發明之發明人等於係針對嵌段共聚物進行專心硏究 ，其與苯乙烯系樹脂或聚伸苯醚系樹脂與烯烴系樹脂混合 使用時，係製得極具耐熱性、耐油性、耐熱老化性，且拉 伸延展特性優異之樹脂組成物，且生產性佳，結果發現， 藉由於苯乙烯系樹脂及/或聚伸苯醚系樹脂與烯烴系樹脂中 ，添加特定結構之部分氫化嵌段共聚物，可達成該目的， 而完成本發明。 亦即，本發明係提供一種熱塑性樹脂組成物，其特徵 在於包含：95至5重量％之（人）苯乙烯系樹脂及/或聚伸苯醚 系樹脂；5至95重量％2(B)烯烴系樹脂；以及相對於總計 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) -6 - 1259196 A7 _ B7 五、發明説明（4 ) (請先閱讀背面之注意事項再填寫本頁) 100重量分之成分（A)及（B)爲2至30重量分之（C)部分氫化 嵌段共聚物，其中（C)係藉由氫化一嵌段共聚物，使於該嵌 段共聚物中共軛二烯化合物內之雙鍵之35 %以上70%以下飽 和而得者，該嵌段共聚物係具有至少1個以乙烯基芳族化 合物爲主體之聚合物嵌段X、與至少1個以共軛二烯化合 物爲主體之聚合物嵌段Y，化合乙烯基芳族化合物含量爲 30至80重量％，而氫化前共軛二烯中之乙烯鍵量爲20重量 %以上65重量％以下。 隱式簡單說明 圖1爲本發明實施例1熱塑性樹脂組成物之穿透型電 子顯微鏡照片之一例。大部分之氫化嵌段共聚物（黑色肌紋 狀層），係存在於丙烯樹脂相（未經染色，明相）與苯乙烯樹 脂相（經染色，暗相）之界面上。 用以實施發明之最佳型熊 以下茲詳細說明本發明。 經濟部智慧財產局員工消費合作社印製 使用於本發明（A)成份中之苯乙烯系樹脂可爲苯乙烯、 甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、二甲基苯乙烯 、對甲基苯乙烯、氯基苯乙烯、溴基苯乙烯、乙烯基二甲 苯等單體或共聚物、苯乙烯-馬來酸酐共聚物、苯乙烯一丙 烯酸共聚物、苯乙烯-丙烯酸酯共聚物、苯乙儲—甲基丙烯 酸共聚物、苯乙烯-共聚物、丙烯腈-丁二烯—共聚物等。另 夕^，於上述苯乙烯系樹脂中，可使用混合有丁二烯橡膠、 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ 297公釐） 1259196 A7 B7 五、發明説明（5) 苯乙烯丁二烯橡膠、乙烯-丙烯橡膠等橡膠、抑或經接枝聚 合之耐衝撃性聚本乙烯系樹脂。聚苯乙儀、橡膠改晳耐衝 撃性聚苯乙烯係尤佳者。另外，本發明苯乙烯系樹脂之熔 融流動率（MFR : 200°C、5公斤荷重）較佳爲〇·5至20克/10 分鐘，更佳爲1至10克/10分鐘。 另外，本發明（A)成份之聚伸苯醚系樹脂（以下簡稱爲 PPE)，爲具下示（1)式結構之聚伸苯醚。 其爲單聚物及/或共聚物，所含鍵結單元爲：1259196 a? ______ B7 V. Inventive Note (彳) illf field (please read the back note first and then fill out this page) The present invention relates to a resin composition which is extremely heat-resistant, oil-resistant, and heat-resistant aging, and Excellent tensile and extension properties. More specifically, the present invention relates to a resin composition suitable for use as a food container or the like, which comprises a styrene resin, a poly(phenylene ether) resin, an olefin resin, and a partially hydrogenated block copolymer having a specific structure. The Vision Technology is widely used as an injection molding material and a sheet molding material because of its excellent processability and excellent mechanical properties. However, the styrene-based resin has poor oil resistance, and when it comes into contact with oils such as cream and sesame oil, the physical properties are drastically lowered, so there is a limit in its use. Therefore, attempts have been made to mix olefin-based resins to improve oil resistance. However, since the styrene resin lacks compatibility with the olefin resin, peeling occurs and it becomes a brittle composition. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives. In addition, the polyphenylene ether resin has excellent mechanical properties and electrical properties. It is widely used in office machine covers and various industrial components. However, since it is inferior in oil resistance and impact resistance, attempts have been made to mix olefin-based resins to improve these characteristics. However, due to the lack of compatibility of the two resins, peeling occurs. In order to solve such problems, various compositions in which a block copolymer is added have been proposed. For example, Japanese Laid-Open Patent Publication No. 56-3833-8 proposes a composition comprising a polyolefin-based resin obtained by adding a hydrogenated block copolymer and a polystyrene-based resin. From the standard of hydrogenated paper, the Chinese National Standard (CNS) A4 specification (210X297 mm) 1259196 A7 B7 V. Invention description (2) (Please read the note on the back and fill out this page.) Ministry of Economic Affairs Intellectual Property Office staff consumption The cooperative prints a block copolymer of at least one vinyl aromatic polymer block A and at least one conjugated diene polymer block B such that the block copolymer has at least 70% double bonds. The saturated product, in particular, discloses a hydrogenated block copolymer which is an AB type block copolymer having a compound styrene group content of 50% and a vinyl content of 13% before hydrogenation, hydrogenating the double bond thereof. 92% of the winners. In addition, Japanese Laid-Open Patent Publication No. Hei 1-174550 also proposes a composition comprising a polyolefin-based resin containing the same hydrogenated block copolymer and a polystyrene-based resin, specifically, a hydrogenated block copolymer. The material is an AB type block copolymer having a compound styrene group content of 35% and a vinyl content of 8% in the isobutylene before hydrogenation, and hydrogenation of 93% of the double bonds. However, the hydrogenated block copolymer using these compositions has a disadvantage of low productivity because of its high hydrogenation rate. For example, in order to obtain a hydrogenated block copolymer disclosed in Japanese Laid-Open Patent Publication No. 56-3833-8, the hydrogenation time is required to be 6 hours, and the hydrogenated block disclosed in Japanese Laid-Open Patent Publication No. Hei No. 1-174550 The copolymer, which requires a hydrogenation time of 8 hours, takes a considerable amount of time. Therefore, it is expected that a polymer which is a block copolymer which is easy to produce and has good productivity, and which has excellent properties when added to a composition containing a polyolefin resin and a polystyrene resin, is expected. . Further, although the composition disclosed herein has improved compatibility with the polyolefin resin and the polystyrene resin, the tensile elongation property in the composition is insufficient, and further improvement is desired. In addition, Japanese Laid-Open Patent Publication No. 9-120800 proposes a composition comprising a polypropylene-based resin and a polyphenylene ether which are added with a hydrogenated block copolymer, and a vinyl-containing aromatic polymer. Block A, and Gao B (CNS) (210X297^~ " Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1259196 A7 __ B7 ____ V. Inventions (3) Ethylene bond conjugated diene polymer The block copolymer of block B is hydrogenated at 65 to 80% to obtain the hydrogenated block copolymer. Specifically, a hydrogenated block copolymer is disclosed which has a content of 60% of the compound styryl group. The AB type block copolymer having a vinyl content of 74% before hydrogenation is hydrogenated to 68% of its double bond. However, the hydrogenated block copolymer used in the place is a conjugated diene having a high vinyl content. The polymer has a disadvantage of being inferior in heat aging resistance of the composition at a high temperature. It is an object of the present invention to provide a thermoplastic resin composition which is excellent in heat resistance, oil resistance, heat aging resistance, and excellent in stretch and stretch properties. By styrene resin and / or poly In the phenylene ether-based resin and the olefin-based resin, a partially hydrogenated block copolymer having a specific structure is added to obtain the thermoplastic resin composition. DISCLOSURE OF THE INVENTION The inventors of the present invention are equivalent to focusing on block copolymers. When it is used in combination with a styrene resin or a poly(phenylene ether) resin and an olefin resin, a resin composition which is excellent in heat resistance, oil resistance, heat aging resistance, and excellent in stretchability is produced, and is produced. It is found that the styrene resin and/or the polyphenylene ether resin and the olefin resin are added to the partially hydrogenated block copolymer having a specific structure to achieve the object, and the present invention has been completed. The present invention provides a thermoplastic resin composition comprising: 95 to 5% by weight of (human) styrene resin and/or polyphenylene ether resin; 5 to 95% by weight of 2 (B) olefin system Resin; and applicable to China National Standard (CNS) A4 specification (210X 297 mm) relative to the total paper size (please read the back note before completing this page) -6 - 1259196 A7 _ B7 V. DESCRIPTION OF THE INVENTION (4) (Please read the notes on the back and then fill out this page) 100 parts by weight of components (A) and (B) are 2 to 30 parts by weight of (C) partially hydrogenated block copolymers, (C Is obtained by hydrogenating a block copolymer to saturate 35% or more and 70% or less of the double bonds in the conjugated diene compound in the block copolymer, and the block copolymer has at least one The vinyl aromatic compound is a main polymer block X, and at least one polymer block Y mainly composed of a conjugated diene compound, and the compounded vinyl aromatic compound content is 30 to 80% by weight, and before hydrogenation The amount of the ethylene bond in the conjugated diene is 20% by weight or more and 65% by weight or less. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a transmission electron microscope photograph of a thermoplastic resin composition of Example 1 of the present invention. Most of the hydrogenated block copolymers (black muscle-stranded layers) are present at the interface of the propylene resin phase (unstained, bright phase) and the styrene resin phase (stained, dark phase). BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail. The styrene resin used in the component (A) of the present invention may be styrene, methyl styrene, ethyl styrene, isopropyl styrene or dimethyl styrene. , a monomer or copolymer of p-methylstyrene, chlorostyrene, bromostyrene, vinyl xylene, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-acrylate copolymer Benzene storage-methacrylic acid copolymer, styrene-copolymer, acrylonitrile-butadiene-copolymer, and the like. In addition, in the above styrene resin, a mixture of butadiene rubber can be used, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇χ297 mm) 1259196 A7 B7 5. Invention Description (5 A rubber such as styrene butadiene rubber or ethylene-propylene rubber, or a graft-resistant polyacrylic resin which is graft-polymerized. Polystyrene, rubber, and rubber are more suitable for squeezing polystyrene. Further, the melt flow rate (MFR: 200 ° C, 5 kg load) of the styrene resin of the present invention is preferably from 5 to 20 g/10 min, more preferably from 1 to 10 g/10 min. Further, the polyphenylene ether-based resin (hereinafter abbreviated as PPE) of the component (A) of the present invention is a polyphenylene ether having the structure of the formula (1) shown below. It is a monomer and/or a copolymer, and the bonding unit contained therein is:
(請先閲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 (其中R1、R2、R3及R4係分別選自氫、鹵素、碳數1 至7之一級或二級低碳數烷基、苯基、鹵烷基、胺烷基、 烴氧基、或至少2個碳原子係間隔有鹵原子及氧原子之鹵 化烴氧基所成之群，可互相相同或相異），其還原黏度（0.5 克/厘升、氯仿溶液、30°C)爲0.15至0.70之範圍，更佳爲 0.20至0.60之範圍。 PPE之具體例例如可爲聚（2,6-二甲基-1，4伸苯醚）、聚 (2-甲基-6-乙基-1，4伸苯醚）、聚（2-甲基-6_苯基-1，4伸苯醚） 、聚（2,6-二氯基-1,4伸苯醚）等，另外亦可爲2,6-二甲基酚 與其他酚類（例如2,3,6-三甲基酚和2-甲基-6-丁基酚）之共聚 物般之聚伸苯醚共聚物。於PPE中，聚（2,6-二甲基-M伸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -8- 1259196 A7 B7 五、發明説明（6) (請先閱讀背面之注意事項再填寫本頁) 苯醚）係尤佳者。若爲以眾所公知之方法可得之PPE，則並 無特別之限定，例如美國專利第3306874號說明書所述， 使用藉由Hay之第一氯化銅與胺之錯合物作爲催化劑，例 如藉由2,6-二甲酣氧化聚合，即可簡單地製造ppe。此外， 亦可使用日本專利特開昭第63- 1 52628號公報所述之方法簡 早地加以製造。另外’除上述PPE外，本發明所用之ppe 亦可爲··在自由基產生劑存在或不存在下，於80至350°C 之溫度下，在熔融狀態、溶液狀態、或漿液狀態下，使該 PPE與α、/3不飽和羧酸或其衍生物反應所得之改質ppE， 再者，上述ΡΡΕ與該改質ΡΡΕ之任意比例混合物亦無妨。 本發明之（Α)成份更佳爲苯乙烯系樹脂，其中尤佳爲聚 苯乙烯、耐衝撃性聚苯乙烯。 經濟部智慧財產局員工消費合作社印製 至於使用於本發明（Β)成份中之烯烴系樹脂，凡聚合α 烯烴所得之樹脂均可，並無特別的限定，該α烯烴例如爲 乙烯、丙烯、1-丁儲、異丁燦、4 -甲基-1-戊烯。共聚物可 爲隨機共聚物或嵌段共聚物，亦可包含α烯烴之2種或3 種以上之共聚物橡膠、或α烯烴與其化單體之共聚物等烯 烴系熱塑性彈性體。此等共聚物橡膠可爲乙烯-丙烯共聚物 橡膠（EPR)、乙烯-丁烯共聚物橡膠（EBR)、乙烯-丙烯-二烯 共聚物橡膠（EPDM)等。其中聚丙烯之均聚物或嵌段物係較 佳者，特別言之，若使用間規聚丙烯均聚物、藉由DSC之 結晶熔解尖峰溫度爲155 °C以上之丙烯-乙烯嵌段樹脂，則 所得組成物之耐熱性會提高。另外，本發明烯烴系樹脂之 熔融流動率（MFR : 230°C、2.16公斤荷重）較佳爲〇.5至60 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 1259196 A7 _B7 五、發明説明（7 ) (請先閱讀背面之注意事項再填寫本頁) 克/10分鐘，更佳爲1至20克/10分鐘。若熔融流動率低於 〇·5克/10分鐘，則所得組成物之成形性差，另外，若超過 60克/10分鐘，則會降低耐衝擊性。 至於使用於本發明（C)成份中之部分氫化嵌段共聚物， 其係藉由氫化一嵌段共聚物，使於該嵌段共聚物中共軛二 烯化合物內之雙鍵之35 %以上70 %以下飽和而得者，該嵌段 共聚物係具有至少丨個以乙烯基芳族化合物爲主體之聚合 物嵌段X、與至少1個以共軛二烯化合物爲主體之聚合物 嵌段Y，化合乙烯基芳族化合物含量爲30至80重量％，而 氫化前共軛二烯中之乙烯鍵量爲20重量％以上65重量％以 下。 經濟部智慧財產局員工消費合作社印製 以乙烯基芳族化合物爲主體之聚合物嵌段X，其爲含 乙烯基芳族化合物與共軛二烯化合物之組成範圍重量比爲 100/0至60/40之聚合物嵌段，較佳爲100/0至80/20。於乙 烯基芳族化合物與共軛二烯化合物經共聚合之情況下，於 此嵌段中，共軛二烯化合物之分布可爲隨機、錐度（單體成 分沿著分子鏈增加或減少）、部分嵌段狀、或此等之任意組 合。於此處，乙烯基芳族化合物係自苯乙烯、α甲基苯乙 烯、對甲基苯乙烯、對第三丁基苯乙烯等烷基苯乙烯、對 甲氧基苯乙烯、乙烯基萘、1,1-二苯基乙烯、二乙烯基苯等 中選取1種或2種以上，其中較佳爲苯乙烯。 另外，以共軛二烯化合物爲主體之聚合物嵌段Υ，其 爲含共軛二烯化合物與乙烯基芳族化合物之組成範圍重量 比爲100/0至60/40之聚合物嵌段，較佳爲100/0至80/20。 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇χ297公釐） -10- 1259196 A7 B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 於共軛二烯化合物與乙烯基芳族化合物經共聚合之情況下 ，於此嵌段中，共軛二烯化合物之分布可爲隨機、錐度（單 體成分沿著分子鏈增加或減少）、部分嵌段狀、或此等之任 意組合。於此處，共軛二烯化合物係自丁二烯、異戊二烯 、1，3-戊二烯、甲基戊二烯、苯基丁二烯、3,4-二甲基-Με 二烯、 4,5-二乙基 -1，3-辛 二烯等 中選取 1 種或 2 種 以上， 其中較佳爲丁二烯及/或異戊二烯。 上述嵌段共聚物之分子結構可爲直鏈狀、支鏈狀、放 射狀、或此等之組合等，而較佳爲直鏈狀。其中2個以上 X之結構爲較佳者，χ-γ-χ結構係尤佳者。而且，嵌段X 或嵌段Y分別可爲相同結構，亦可爲單體成分含量、彼等 於分子鏈中之分布、嵌段分子量、微結構等各結構相異之 物。例如亦可爲兩末端X爲分子量不同之X-Y-X’。 經濟部智慧財產局員工消費合作社印製 部分氫化嵌段共聚物（C)之乙烯基芳族化合物含量爲30 至80重量％，較佳爲40至75重量％，更佳爲45至7 0重量 %。若乙烯基芳族化合物含量低於30重量％，嵌段共聚物 與苯乙烯系樹脂及/或PPE(A成分）之親和性不足，使存在於 A成分相與B成分（烯烴系樹脂）相界面之嵌段共聚物量不充 足，而欠缺相容化效果。另一方面，若超過80重量％，其 與A成分之親和性過剩，而導致嵌段共聚物進入A相中， 使得相容化效果仍然不充分。 部分氫化嵌段共聚物（C)之氫化前乙烯鍵量爲20重量％ 以上65重量％以下，較佳爲25至60重量％，更佳爲30至 5 5重量％。於此處，所謂的乙烯鍵量，係於嵌段共聚物中 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇><297公釐) -11- A7 1259196 B7 五、發明説明（9 ) (請先閱讀背面之注意事項再填寫本頁) ’以1，2-鍵結、3,4-鍵結、及1，4-鍵結之鍵結型式組出之共 軛二烯化合物內，以1，2-鍵結及3,4-鍵結組出者之比例。若 氫化前乙烯鍵量低於20重量％，則嵌段共聚物與B成分之 親和性不足，使相容化效果不充分。結果使嵌段共聚物之 界面存在率降低，而變爲拉伸延展性低之組成物。另一方 面，若於65重量％以上，則與B成分之親和性過剩，而導 致嵌段共聚物進入B成分之相中，使相容化效果仍然不充 分。結果使嵌段共聚物之界面存在率降低，而所得組成物 之剛性低，且延展性亦降低。再者，於使用氫化前乙烯鍵 量高之嵌段共聚物時，組成物之耐熱老化性會惡化，而無 法再生使用。 經濟部智慧財產局員工消費合作社印製 使用於本發明之部分氫化嵌段共聚物，其爲藉由氫化 上述嵌段共聚物，使於該嵌段共聚物中共軛二烯化合物內 之雙鍵之35%以上70%以下飽和而得者。若氫化率低於35% ，則嵌段共聚物與B成分之親和性降低，故嵌段共聚物會 進入A成分之相中，使相容化效果不充分。結果變爲拉伸 延展性低之組成物。另外，耐熱老化性會惡化，且無法再 生等。若氫化率超過70%時，除加工性劣化外，生產性係 較氫化率低於70%者低。另外，於使用於本發明之部分氫 化嵌段共聚物中，殘餘乙烯鍵量較佳爲10%以下，更佳爲 5 %以下，再更佳爲5 %以下。於此處，所謂之殘餘乙烯鍵量 ，係相對於起始之共軛二烯1 00，未經氫化而殘餘之乙烯鍵 量。若嵌段共聚物中之乙烯鍵量爲1 0 %以上，則相容化效 果不充分，同時所得組成物之耐熱老化性會劣化。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） "— -12- 1259196 A7 B7 五、發明説明（1〇) (請先閲讀背面之注意事項再填寫本頁) 於部分氫化嵌段共聚物（C)中，以乙烯芳族化合物爲主 體之聚合物嵌段X之重量平均分子量較佳爲5000至50000 ，以共軛二烯化合物爲主體之聚合物嵌段Y較佳爲5000至 70000。若聚合物嵌段X之分子量低於5000，則與A成分之 親和性降低，而若聚合物嵌段Y之分子量低於5000，則與 B成分之親和性降低，使相容化效果變差。另外，若聚合物 嵌段X之分子量尚於50000、或聚合物嵌段Y之分子量高 於70000，嵌段共聚物本身之分子量過大，故其熔融黏度會 上昇，於含A成分與B成分之樹脂組成物中之分散不充分 ，使相容化效果劣化。 部分氫化嵌段共聚物（C)之熔融流動率（MFR : 230°C、 2.16公斤荷重）較佳爲0·1至50克/10分鐘，更佳爲0.5至 20克/10分鐘，再更佳爲1至10克/10分鐘。若熔融流動率 低於0.1克/10分鐘，則熔融黏度過高，無法獲得充分之相 容化效果，另外，若超過5 0克/10分鐘，則會降低Α成分 與B成分之界面增強效果。 經濟部智慧財產局員工消費合作社印製 部分氫化嵌段共聚物（C)之製造方法並無特別的限定， 係採用眾所公知之方法。例如可使用日本專利特公昭第36-1 9286號公報所記述之活陰離子聚合技術，其係使用有機鋰 催化劑，於惰性溶劑中，聚合乙烯基芳族化合物與共軛二 烯化合物，藉此製造嵌段共聚物。使用正丁基鋰、第二丁 基鋰、第三丁基鋰等單鋰化合物作爲有機鋰催化劑，可依 X、Y、X之順序逐次聚合以形成嵌段；可依χ_γ之順序形 成X-Y型活嵌段共聚物後，藉由二官能偶合劑形成χ-γ_χ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- A7 1259196 B7 __ 五、發明説明（彳彳） (請先閱讀背面之注意事項再填寫本頁) 結構之三嵌段共聚物；可使用二鋰化合物’依x' γ之順序 聚合，而形成χ-γ-χ結構之三嵌段共聚物等方法。係藉由 乙烯基芳族化合物與共軛二烯化合物之進料單體組成’以 進行乙烯基芳族化合物含量之調節。另外’係藉由乙烯基 量調整劑之使用，以進行共軛二烯化合物之乙烯鍵量之調 節。乙烯基量調整劑可爲ν，ν，ν’，ν’-四甲基乙二胺、三曱胺 、三乙胺、重氮環[2,2,2]辛烷等胺類、四氫呋喃、二乙二醇 二曱醚、二乙二醇二丁醚等醚類、硫代醚類、膦類、膦醯 胺類、烷基苯磺酸鹽、鉀和鈉之烷氧化物等。 以眾所公知之方法，對上述所得嵌段共聚物進行氫化 反應，藉此製得部分氫化嵌段共聚物。已知氫化反應所使 用之催化劑爲（1)負載型不均勻催化劑、及（2)齊格勒型催化 劑，或使用鈦鐵化合物之均勻催化劑。至於具體方法，例 如藉由日本專利特公昭第43-6636號公報或特公昭第63-5401號公報所載之方法，於惰性溶劑中，氫化催化劑存在 下，添加目標量之氫，可製得部分氫化嵌段共聚物之溶液 〇 經濟部智慧財產局員工消費合作社印製 對以此方式製得之部分氫化嵌段共聚物溶液，可藉由 常用之方法加以去除溶劑，以製得部分氫化嵌段共聚物。 因應需要，可採用使金屬類脫灰之步驟。另外，因應需要 ，亦可使用反應終止劑、抗氧化劑、中和劑、界面活性劑 等。 特別言之，於本發明之組成物中，50%之部分氫化嵌段 共聚物（C )，較佳爲60%以上存在於苯乙烯系樹脂或聚伸 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ~~~'' -14- 1259196 A7 ___ B7 五、發明説明（12) (請先閱讀背面之注意事項再填寫本頁) 本醚系樹脂（A )、與嫌烴系樹脂（b )之界面上，此係較佳 者。存在率高於50%時，苯乙烯系樹脂或聚伸苯醚系樹脂 與烯烴系樹脂之界面接附強度優異，在拉伸延展特性上可 發揮優異性能。 至於本發明各成分之摻合比例，苯乙烯系樹脂及/或聚 伸苯醚系樹脂（A)與烯烴系樹脂（B成分）之摻合比爲95:5至 5 :9 5之重量比。於提高剛性之情況下，係增多a成分之摻 合比，而於著重耐熱性、耐油性之情況下，係增加B成分 之摻合比，可視情況加以調整，惟就剛性與耐熱性、耐油 性之平衡觀之，較佳之A成分與B成分之摻合比爲80:20 至40:60之重量比。 相對於總計100重量分之苯乙烯系樹脂及/或聚伸苯醚 系樹脂（A成分）與烯烴系樹脂（B成分），部分氫化嵌段共聚 物（C)之添加量爲2至30重量分，較佳爲5至15重量分。 低於2重量分時相容化效果不足。另外，超過30重量分時 ，剛性會降低，且不具經濟性。 經濟部智慧財產局員工消費合作社印製 於本發明之熱塑性樹脂組成物中，可因應需要摻合任 意之添加劑。至於添加劑之種類，凡一般使用樹脂摻合中 之物均可，並無特別的限制，惟例如可爲矽氧、碳酸鈣、 碳酸鎂、硫酸鈣、滑石等無機塡料、有機纖維、氧化鈦、 碳黑、氧化鐵等顏料、硬脂酸、二十二烷酸、硬脂酸鋅、 硬脂酸鈣、硬脂酸鎂、伸乙基雙硬脂醯胺等平滑劑、脫型 劑、有機聚矽氧烷、礦油等塑化劑、阻酚系和磷系之抗氧 化劑、阻燃劑、紫外線吸收劑、電荷防止劑、玻璃纖維、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 1259196 A7 B7 五、發明説明（13) 碳纖維、金屬細絲等增強劑、其他添加劑或此等之混合物 等。 (請先閱讀背面之注意事項再填寫本頁) 本發明樹脂組成物之製造方法並無特別的限制，可利 用眾所公知之方法。例如爲使用密閉式混合機、單軸螺旋 擠壓機、雙軸螺旋擠壓機、捏揉機、多軸螺旋擠壓機等一 般混合機之熔融混煉方法；於溶解或分散各成分後，加熱 去除溶劑之方法等。較佳者如下：充分溶解苯乙烯系樹脂 或聚伸苯醚系樹脂（A)、烯烴系樹脂（B)及部分氫化嵌段共聚 物（C)，加以混合，使部分氫化嵌段共聚物（C)向（A)相與（B) 相之界面移動之條件爲：180°C以上，較佳爲200°C以上， 剪切速率爲1 00秒“，於此等條件下混煉，此爲較佳者。另 外，較佳爲使用雙軸螺旋擠壓機之方法。另外，以此等方 法混煉一次，製造主粒，使用其進行成形，因應需要加以 發泡成形，此爲使用本發明樹脂組成物時之較佳成形方法 實施例 經濟部智慧財產局員工消費合作社印製 以下茲例示實施例，以更具體且詳細地說明本發明， 惟本發明並未因此等例示而受任何限定。 (1)使用成分及其製成 (a)苯乙烯系樹脂 市售耐衝擊性苯乙烯系樹脂：475D(A&M苯乙烯（股）製 造） 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ' -16- 1259196 A7 _____________H7 五、發明説明（如 (b) 烯烴系樹脂 (b -1)丙燦系樹脂 (請先閲讀背面之注意事項再填寫本頁) 巾售均聚丙烯系樹脂：PL500A(蒙特耶斯帝計山來茲（ 股）製造） (b-2)乙烯系樹脂 巾售筒密度聚乙烯系樹脂：薩帝克Π01 (旭化成工業（股 )製造） (c) 嵌段共聚物 Φ 洗'淨 '乾燥具備攪拌機及夾套之容量1〇〇升之熱 壓器’並以氮加以取代，投入含3 3重量分之預先純化苯乙 烯之環己院溶液。其次，添加正丁基鋰與四甲基乙二胺， 於70°C下聚合1小時後，加入含34重量分之預先純化丁二 烯之環己院溶液，聚合1小時，再加入含3 3重量分之苯乙 烯之環己烷溶液，聚合1小時。 經濟部智慧財產局員工消費合作社印製 採樣一部分之所得嵌段共聚物溶液，對丨〇〇重量分之 嵌段共聚物，添加0.3重量分之十八基-3-(3,5-二第四丁基-4-羥苯基）丙酸酯，其後加熱去除溶劑（所得共聚物爲聚合物 I)。聚合物I之苯乙烯含量爲66重量％、聚丁二烯部分之 1，2乙烯鍵量爲50重量％、數量平均分子量爲5 6000。 又，係使用紅外線分析法（IR)，以測定苯乙烯含量。另 外，係使用紅外線分析法（IR)，根據漢普敦法計算，以測定 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~ -17- 1259196 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（1)5 乙烯鍵量。另外，係使用膠態穿透層析法（GPC)，以測定數 量平均分子量。 其次，使用殘餘之嵌段共聚物溶液，以二-對三雙（1-環 戊二烯基）鈦與正丁基鋰作爲氫化催化劑，於70t之溫度下 進行氫化，取樣一部分之聚合物溶液，而得聚合物II。聚 合物II之氫化率爲26%。又，係使用核磁共振裝置（NMR)， 以測定氫化率。另外，係以流量計測定供給之氫氣量，於 達成目標氫化率時停止供給氣體，由是控制氫化率。對殘 餘之聚合物溶液再度進行氫化，而得聚合物III、IV之聚合 物溶液。聚合物III之氫化率爲44%，惟自氫化開始之所需 時間爲30分鐘。另外，聚合物IV之氫化率爲65%，惟自 氫化開始之所需時間爲45分鐘。 與聚合物I相同，對各聚合物溶液添加安定劑後，加 熱去除溶劑，以製成各種聚合物（II至IV)。各樣品之聚合 物結構係示於表1。 ② 除改變苯乙烯之投入量、正丁基鋰與四甲基乙二 胺之添加量外，其餘均與①相同，而得嵌段共聚物。所得 聚合物之苯乙烯含量爲60重量％、聚丁二烯部分之1，2乙 烯鍵量爲25重量％、數量平均分子量爲76000(此爲聚合物 V) 〇 再使用嵌段共聚物溶液，與①相同地進行氫化，而製 成聚合物VI。各樣品之聚合物結構係示於表1。 ③ 於②中，除未添加四甲基乙二胺外，其餘均相同 ，而得嵌段共聚物。所得聚合物之苯乙烯含量爲60重量％ (請先閲讀背面之注意事項再填寫本頁) L··, 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 1259196 A7 B7 ——一- ------ 五、發明説明（也 、聚丁二烯部分之1，2乙烯鍵量爲1 2重量％、數量平均分 子量爲74000。 (請先閲讀背面之注意事項再填寫本頁) 再使用嵌段共聚物溶液，與①相同地進行氫化，而製 成聚合物VII、VIII。各樣品之聚合物結構係示於表丄。 ④ 除改變苯乙烯之投入量、正丁基鋰與四甲基乙二 胺之添加量外，其餘均與①相同，而得嵌段共聚物。所得 聚合物之苯乙烯含量爲50重量％、聚丁二烯部分之1，2乙 烯鍵量爲40重量％、數量平均分子量爲62000(此爲聚合物 IX)。 再使用嵌段共聚物溶液，與①相同地進行氫化，而製 成聚合物X、XI。各樣品之聚合物結構係示於表1。 ⑤ 於①中，除改變最初投入之苯乙烯量爲3 7重量分 、丁二烯聚合後所投入之苯乙烯量爲29重量分外，其餘均 相同，而得嵌段共聚物。所得聚合物之苯乙烯含量爲66重 量％、聚丁二烯部分之1，2乙烯鍵量爲48重量％、數量平均 分子量爲54000。 經濟部智慧財產局員工消費合作社印製 再使用嵌段共聚物溶液，與□相同地進行氫化，而製成 聚合物XII。聚合物結構係示於表1。 ⑥ 洗淨、乾燥具備攪拌機及夾套之容量100升之熱 壓器’並以氮加以取代，投入含30重量分之預先純化苯乙 烯之環己烷溶液。其次，添加正丁基鋰與四甲基乙二胺， 於70°C下聚合1小時後，加入含4〇重量分之預先純化異戊 一烯之環己院溶液，聚合1小時，再加入含3 0重量分之苯 乙矯之运己院丨谷液，聚合1小時。 張尺度適用中國國家標準（CNS ) a15^7210'x297公董） 一 -19- 1259196 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（1)7 採樣一部分之所得嵌段共聚物溶液’對100重量分之 嵌段共聚物，添加〇·3重量分之十八基_3-(3，5 -一第四丁基-4-羥苯基）丙酸酯，其後加熱去除溶劑（所得共聚物爲聚合物 XIII)。聚合物ΧΙΠ之苯乙烯含量爲60重量％、聚異戊二烯 部分之乙烯鍵總量爲40重量％、數量平均分子量爲52000。 其次，使用殘餘之嵌段共聚物溶液，以二-對三雙（1-環 戊二烯基）鈦與二丁基鎂作爲氫化催化劑，於70°C之溫度下 進行氫化，而得聚合物XIV。聚合物XIV之氫化率爲52% 。對殘餘之聚合物溶液再度進行氫化，而得聚合物XV之聚 合物溶液。聚合物XV之氫化率爲92%。各樣品之聚合物結 構係示於表1。 ⑦ 於②中，除增加四甲基乙二胺之添加量外，其餘 均相同，而得嵌段共聚物。所得聚合物之苯乙烯含量爲60 重量％、聚丁二烯部分之1，2乙烯鍵量爲74重量％、數量平 均分子量爲78000。 再使用嵌段共聚物溶液，與①相同地進行氫化，而製 成聚合物XVI。聚合物結構係示於表1。 (2)樹脂組成物之調製與物性測定 以表2'表3所示比例摻合各成分、（b)成分、（〇成 分’使用30毫米之雙軸擠壓機，於22(rc之溫度下進行熔 融混煉’以使其粒化。又，實施例及比較例中所示物性之 測定規格、試驗法係如下所述。於22〇〇c下將所得粒狀物射 出成形，測定下述1至少丨個之各種特性。 ^紙張尺度適用中國國家標準公董y -~ - -20- (請先閲讀背面之注意事項再填寫本頁}(Please read the notes on the back and fill out this page.) Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative (where R1, R2, R3 and R4 are respectively selected from hydrogen, halogen, carbon number 1 to 7 or grade 2) a group of a lower alkyl group, a phenyl group, a haloalkyl group, an amine alkyl group, an alkoxy group, or a halogenated alkoxy group having at least two carbon atoms separated by a halogen atom and an oxygen atom, which may be the same or phase The reduction viscosity (0.5 g/cm liter, chloroform solution, 30 ° C) is in the range of 0.15 to 0.70, more preferably in the range of 0.20 to 0.60. Specific examples of the PPE may be, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene oxide), poly(2-methyl) -6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), etc., or 2,6-dimethylphenol and other phenols A poly(phenylene ether) copolymer such as a copolymer of 2,3,6-trimethylphenol and 2-methyl-6-butylphenol. In PPE, poly(2,6-dimethyl-M stretch paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -8- 1259196 A7 B7 V. Invention description (6) (Read first Note on the back side of this page) Phenyl ether) is especially good. There is no particular limitation on the PPE which is available in a manner known per se. For example, as described in the specification of U.S. Patent No. 3,306,874, a complex of copper chloride and an amine by Hay is used as a catalyst, for example. Ppes can be easily produced by oxidative polymerization of 2,6-dimethylhydrazine. Further, it can be manufactured simply by the method described in Japanese Laid-Open Patent Publication No. 63-1526628. In addition, in addition to the above PPE, the ppe used in the present invention may also be in the presence or absence of a radical generating agent at a temperature of 80 to 350 ° C in a molten state, a solution state, or a slurry state. The modified ppE obtained by reacting the PPE with an α,/3 unsaturated carboxylic acid or a derivative thereof may also be a mixture of the above hydrazine and the modified hydrazine in any ratio. The (Α) component of the present invention is more preferably a styrene resin, and particularly preferably polystyrene and impact-resistant polystyrene. The olefin resin used in the composition of the present invention is printed on the olefin-based resin used in the composition of the present invention. The resin obtained by polymerizing the alpha olefin is not particularly limited, and the alpha olefin is, for example, ethylene or propylene. 1-butyl storage, isobutyl can, 4-methyl-1-pentene. The copolymer may be a random copolymer or a block copolymer, or may be an olefin-based thermoplastic elastomer such as a copolymer rubber of two or more kinds of α-olefins or a copolymer of an α-olefin and a monomer thereof. These copolymer rubbers may be ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), ethylene-propylene-diene copolymer rubber (EPDM), and the like. Wherein the homopolymer or block of polypropylene is preferred, in particular, if a syndiotactic polypropylene homopolymer is used, the propylene-ethylene block resin having a peak temperature of 155 ° C or higher is melted by DSC. Then, the heat resistance of the obtained composition is improved. Further, the melt flow rate (MFR: 230 ° C, 2.16 kg load) of the olefin-based resin of the present invention is preferably from 5. 5 to 60. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 1259196 A7 _B7 V. INSTRUCTIONS (7) (Please read the notes on the back and fill out this page) gram/10 minutes, preferably 1 to 20 grams/10 minutes. When the melt flow rate is less than 〇5 g/10 minutes, the formability of the obtained composition is inferior, and when it exceeds 60 g/10 minutes, the impact resistance is lowered. And a partially hydrogenated block copolymer used in the component (C) of the present invention, which is obtained by hydrogenating a block copolymer so that more than 35% of the double bonds in the conjugated diene compound in the block copolymer are 70 % block saturated, the block copolymer has at least one polymer block X mainly composed of a vinyl aromatic compound, and at least one polymer block Y mainly composed of a conjugated diene compound The content of the compounded vinyl aromatic compound is from 30 to 80% by weight, and the amount of the ethylene bond in the conjugated diene before hydrogenation is from 20% by weight to 65% by weight. The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, prints a polymer block X based on a vinyl aromatic compound, which is a composition range of 100/0 to 60 by weight of the vinyl-containing aromatic compound and the conjugated diene compound. The polymer block of /40 is preferably from 100/0 to 80/20. In the case where the vinyl aromatic compound and the conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block may be random, taper (the monomer component increases or decreases along the molecular chain), Partially blocky, or any combination of these. Here, the vinyl aromatic compound is derived from alkylstyrene such as styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-methoxystyrene, vinylnaphthalene, One or two or more selected from the group consisting of 1,1-diphenylethylene and divinylbenzene, among which styrene is preferred. Further, a polymer block ruthenium mainly composed of a conjugated diene compound, which is a polymer block having a composition range weight ratio of a conjugated diene compound and a vinyl aromatic compound of from 100/0 to 60/40, It is preferably from 100/0 to 80/20. This paper scale is applicable to China National Standard (CNS) Α4 specification (21〇χ297 mm) -10- 1259196 A7 B7 V. Invention description (8) (Please read the note on the back and fill in this page) conjugated diene In the case where a compound and a vinyl aromatic compound are copolymerized, in this block, the distribution of the conjugated diene compound may be random, taper (the monomer component increases or decreases along the molecular chain), partially block-like, Or any combination of these. Here, the conjugated diene compound is derived from butadiene, isoprene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-Με One or more selected from the group consisting of alkene, 4,5-diethyl-1,3-octadiene and the like, and preferably butadiene and/or isoprene. The molecular structure of the above block copolymer may be linear, branched, fluoresced, or a combination thereof, and is preferably linear. Among them, two or more X structures are preferred, and a χ-γ-χ structure is preferred. Further, the block X or the block Y may have the same structure, and may have different contents of the monomer component content, the distribution in the molecular chain, the block molecular weight, and the microstructure. For example, X-Y-X' having different molecular weights at both ends X may be used. The content of the vinyl aromatic compound of the partially hydrogenated block copolymer (C) printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is 30 to 80% by weight, preferably 40 to 75% by weight, more preferably 45 to 70% by weight. %. When the content of the vinyl aromatic compound is less than 30% by weight, the affinity between the block copolymer and the styrene resin and/or PPE (component A) is insufficient, and the phase A component and the component B (olefin resin) are present. The amount of block copolymer at the interface is insufficient, and the compatibilization effect is lacking. On the other hand, if it exceeds 80% by weight, the affinity with the component A is excessive, and the block copolymer enters the phase A, so that the compatibilizing effect is still insufficient. The amount of the vinyl bond before hydrogenation of the partially hydrogenated block copolymer (C) is 20% by weight or more and 65% by weight or less, preferably 25 to 60% by weight, more preferably 30 to 5% by weight. Here, the so-called ethylene bond amount is applied to the block copolymer in accordance with the Chinese National Standard (CNS) A4 specification (2丨〇><297 mm) -11- A7 1259196 B7. Description (9) (Please read the note on the back and then fill out this page) 'Conjugated two sets of 1,2-bonded, 3,4-bonded, and 1,4-bonded bond types Within the olefinic compound, the ratio of 1,2-bonded and 3,4-bonded groups is present. When the amount of the ethylene bond before hydrogenation is less than 20% by weight, the affinity between the block copolymer and the component B is insufficient, and the compatibilizing effect is insufficient. As a result, the interface existing ratio of the block copolymer is lowered to become a composition having low tensile ductility. On the other hand, when it is 65% by weight or more, the affinity with the component B is excessive, and the block copolymer is allowed to enter the phase of the component B, so that the compatibilizing effect is still insufficient. As a result, the interface existence ratio of the block copolymer is lowered, and the rigidity of the resulting composition is low, and the ductility is also lowered. Further, when a block copolymer having a high ethylene bond amount before hydrogenation is used, the heat aging resistance of the composition is deteriorated and it is not recyclable. The Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative prints a partially hydrogenated block copolymer used in the present invention, which is a double bond in a conjugated diene compound in the block copolymer by hydrogenating the above block copolymer. 35% or more and 70% or less are saturated. When the hydrogenation rate is less than 35%, the affinity between the block copolymer and the component B is lowered, so that the block copolymer enters the phase of the component A, and the compatibilizing effect is insufficient. As a result, it becomes a composition having low stretchability and ductility. In addition, the heat aging resistance is deteriorated and cannot be reproduced. When the hydrogenation rate exceeds 70%, the productivity is lower than that of the case where the hydrogenation rate is less than 70%, in addition to the deterioration in workability. Further, in the partially hydrogenated block copolymer used in the present invention, the residual ethylene bond amount is preferably 10% or less, more preferably 5% or less, still more preferably 5% or less. Here, the residual ethylene bond amount is the amount of ethylene bonds remaining without hydrogenation relative to the starting conjugated diene 100. When the amount of the ethylene bond in the block copolymer is at least 10%, the compatibilizing effect is insufficient, and the heat aging resistance of the obtained composition is deteriorated. This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) "- -12- 1259196 A7 B7 V. Invention description (1〇) (Please read the note on the back and fill out this page) In the hydrogenated block copolymer (C), the weight average molecular weight of the polymer block X mainly composed of a vinyl aromatic compound is preferably from 5,000 to 50,000, and the polymer block Y mainly composed of a conjugated diene compound is preferred. It is 5,000 to 70,000. When the molecular weight of the polymer block X is less than 5,000, the affinity with the component A is lowered, and when the molecular weight of the polymer block Y is less than 5,000, the affinity with the component B is lowered, and the compatibilizing effect is deteriorated. . In addition, if the molecular weight of the polymer block X is still 50,000 or the molecular weight of the polymer block Y is higher than 70,000, the molecular weight of the block copolymer itself is too large, so the melt viscosity thereof increases, and the component A and the component B are contained. The dispersion in the resin composition is insufficient to deteriorate the compatibilizing effect. The melt flow rate (MFR: 230 ° C, 2.16 kg load) of the partially hydrogenated block copolymer (C) is preferably from 0.1 to 50 g/10 min, more preferably from 0.5 to 20 g/10 min. Good for 1 to 10 g/10 minutes. If the melt flow rate is less than 0.1 g/10 min, the melt viscosity is too high, and a sufficient compatibilizing effect cannot be obtained. Further, if it exceeds 50 g/10 min, the interfacial reinforcing effect of the niobium component and the B component is lowered. . The manufacturing method of the partially hydrogenated block copolymer (C) printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is not particularly limited, and a well-known method is employed. For example, a living anionic polymerization technique described in Japanese Patent Publication No. Sho 36-1 9286, which uses an organolithium catalyst to polymerize a vinyl aromatic compound and a conjugated diene compound in an inert solvent, can be used. Block copolymer. A single lithium compound such as n-butyllithium, a second butyllithium or a third butyllithium can be used as an organolithium catalyst, which can be sequentially polymerized in the order of X, Y and X to form a block; XY can be formed in the order of χγ After the living block copolymer, the χ-γ_χ is formed by the difunctional coupling agent. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -13- A7 1259196 B7 __ V. Invention description (彳彳) ( Please read the precautions on the back and fill out this page.) Structure of the triblock copolymer; can be used to polymerize the dilithium compound 'in the order of x' γ to form a triblock copolymer of χ-γ-χ structure. . The composition of the vinyl aromatic compound is adjusted by the monomer composition of the vinyl aromatic compound and the conjugated diene compound. Further, the use of a vinyl amount adjusting agent is used to adjust the ethylene bond amount of the conjugated diene compound. The vinyl amount adjusting agent may be ν, ν, ν', ν'-tetramethylethylenediamine, tridecylamine, triethylamine, an amine such as diazocyclo[2,2,2]octane, tetrahydrofuran, Ethers such as diethylene glycol dioxime ether and diethylene glycol dibutyl ether; thioethers, phosphines, phosphoniumamines, alkylbenzenesulfonates, alkoxides of potassium and sodium, and the like. The block copolymer obtained above is subjected to a hydrogenation reaction by a known method to thereby obtain a partially hydrogenated block copolymer. The catalyst used in the hydrogenation reaction is known to be (1) a supported heterogeneous catalyst, and (2) a Ziegler-type catalyst, or a homogeneous catalyst using a ferrotitanium compound. As a specific method, a target amount of hydrogen can be obtained by adding a target amount of hydrogen in an inert solvent in the presence of a hydrogenation catalyst, for example, by the method described in Japanese Patent Publication No. Sho 43-6636 or Japanese Patent Publication No. 63-5401. Partially hydrogenated block copolymer solution 〇 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed a partially hydrogenated block copolymer solution prepared in this way, the solvent can be removed by a common method to obtain a partial hydrogenation embedded Segment copolymer. The step of deashing the metal may be employed as needed. Further, a reaction terminator, an antioxidant, a neutralizing agent, a surfactant, or the like may be used as needed. In particular, in the composition of the present invention, 50% of the partially hydrogenated block copolymer (C), preferably more than 60%, is present in the styrene resin or the paper scale for the Chinese National Standard (CNS). Α4 specifications (210X297 mm) ~~~'' -14- 1259196 A7 ___ B7 V. Description of invention (12) (Please read the notes on the back and fill out this page) The ether resin (A), and the suspected hydrocarbon It is preferred at the interface of the resin (b). When the content is more than 50%, the styrene resin or the poly(phenylene ether) resin is excellent in interfacial adhesion strength to the olefin resin, and exhibits excellent properties in tensile elongation properties. The blending ratio of the components of the present invention, the blend ratio of the styrene resin and/or the polyphenylene ether resin (A) to the olefin resin (component B) is a weight ratio of 95:5 to 5:95. . In the case of increasing the rigidity, the blending ratio of the component a is increased, and in the case of focusing on heat resistance and oil resistance, the blending ratio of the component B is increased, and the blending ratio can be adjusted as appropriate, but rigidity and heat resistance and oil resistance are obtained. For the balance of sex, the blend ratio of the A component to the B component is preferably a weight ratio of 80:20 to 40:60. The partially hydrogenated block copolymer (C) is added in an amount of 2 to 30 by weight based on 100 parts by weight total of the styrene resin and/or the polyphenylene ether resin (component A) and the olefin resin (component B). It is preferably 5 to 15 parts by weight. When the amount is less than 2 parts by weight, the compatibilizing effect is insufficient. In addition, when it exceeds 30 parts by weight, the rigidity is lowered and it is not economical. The Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative is printed on the thermoplastic resin composition of the present invention, and any additive may be blended as needed. As for the type of the additive, there is no particular limitation on the general use of the resin blending, but for example, it may be an inorganic cerium such as lanthanum, calcium carbonate, magnesium carbonate, calcium sulfate or talc, organic fiber or titanium oxide. , carbon black, iron oxide and other pigments, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethyl bis-stearylamine and other smoothing agents, release agents, Plasticizers such as organic polyoxane, mineral oil, antioxidants for phenol and phosphorus, flame retardants, UV absorbers, charge inhibitors, glass fibers, this paper scale applies to China National Standard (CNS) A4 specifications (210X297 mm) -15- 1259196 A7 B7 V. INSTRUCTIONS (13) Reinforcing agents such as carbon fibers and metal filaments, other additives or mixtures thereof. (Please read the precautions on the back side and fill out this page.) The method for producing the resin composition of the present invention is not particularly limited, and a publicly known method can be used. For example, a melt mixing method using a general mixer such as an internal mixer, a single-shaft screw extruder, a twin-shaft screw extruder, a kneading machine, or a multi-axis screw extruder; after dissolving or dispersing each component, heating The method of removing the solvent, and the like. Preferably, the styrene resin or the polyphenylene ether resin (A), the olefin resin (B), and the partially hydrogenated block copolymer (C) are sufficiently dissolved and mixed to partially hydrogenate the block copolymer ( C) The conditions for the movement to the interface between the (A) phase and the (B) phase are: 180 ° C or higher, preferably 200 ° C or higher, and the shear rate is 100 seconds ", and kneading under these conditions, Further, it is preferably a method using a biaxial screw extruder. Further, the main particles are kneaded once by the method, and the main particles are used for molding, and foam molding is required as needed. BEST FORMING METHOD FOR INVESTING RESIN COMPOSITIONS EXAMPLES The Ministry of Economic Affairs, Intellectual Property Office, Employees, Consumer Cooperatives, and the following examples are illustrated to illustrate the present invention in more detail and in detail, but the invention is not limited thereto (1) Ingredients and their preparation (a) Styrene resin Commercially available impact-resistant styrene resin: 475D (manufactured by A & M styrene) This paper scale applies to China National Standard (CNS) A4 Specifications (210X297 mm) ' -16- 1259196 A7 _ ____________H7 V. INSTRUCTIONS (eg (b) olefin-based resin (b-1) propylene-based resin (please read the note on the back side and fill out this page). The towel is sold in polypropylene resin: PL500A (Montés Estee (B-2) Ethylene resin towel sold in a cylinder density polyethylene resin: Satik Π 01 (made by Asahi Kasei Industrial Co., Ltd.) (c) Block copolymer Φ Wash 'net' dry A 1 liter autoclave with a stirrer and a jacket is replaced with nitrogen, and a pre-purified styrene ring solution containing 33 parts by weight is added. Secondly, n-butyllithium and tetramethyl are added. Ethylenediamine, after polymerization at 70 ° C for 1 hour, adding 34 parts by weight of pre-purified butadiene ring cyclohexyl solution, polymerization for 1 hour, and then adding a styrene solution containing 33 parts by weight of styrene , Polymerization for 1 hour. The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed and sampled a portion of the resulting block copolymer solution, adding 0.3 weight fraction of octadecyl-3-(3) to the block copolymer of ruthenium weight. , 5-di-tetrabutyl-4-hydroxyphenyl)propionate, followed by heating to remove the solvent ( The copolymer was obtained as polymer I). The styrene content of the polymer I was 66% by weight, the 1,2 ethylene bond amount of the polybutadiene portion was 50% by weight, and the number average molecular weight was 56,000. Analytical method (IR) to determine the styrene content. In addition, the infrared analysis method (IR) is used according to the Hampton method to determine the paper size for the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ -17- 1259196 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (1) 5 ethylene bond amount. In addition, colloidal breakthrough chromatography (GPC) was used to determine the number average molecular weight. Next, using a residual block copolymer solution, di-p-tris(1-cyclopentadienyl)titanium and n-butyllithium are used as hydrogenation catalysts, hydrogenation is carried out at a temperature of 70 t, and a part of the polymer solution is sampled. And get the polymer II. The hydrogenation rate of the polymer II was 26%. Further, a nuclear magnetic resonance apparatus (NMR) was used to measure the hydrogenation rate. Further, the amount of hydrogen supplied was measured by a flow meter, and when the target hydrogenation rate was reached, the supply of the gas was stopped, and the hydrogenation rate was controlled. The residual polymer solution is again subjected to hydrogenation to obtain a polymer solution of the polymers III and IV. The hydrogenation rate of Polymer III was 44%, but the time required for the start of hydrogenation was 30 minutes. Further, the hydrogenation rate of the polymer IV was 65%, but the time required for the start of hydrogenation was 45 minutes. The same as the polymer I, after adding a stabilizer to each polymer solution, the solvent was removed by heating to prepare various polymers (II to IV). The polymer structure of each sample is shown in Table 1. 2 The block copolymer was obtained except that the amount of styrene, the addition amount of n-butyllithium and tetramethylethylenediamine were changed. The obtained polymer has a styrene content of 60% by weight, a polybutadiene portion of 1,2 ethylene bond amount of 25% by weight, a number average molecular weight of 76,000 (this is a polymer V), and a block copolymer solution is used. Hydrogenation was carried out in the same manner as in Example 1 to give a polymer VI. The polymer structure of each sample is shown in Table 1. 3 In 2, except that tetramethylethylenediamine was not added, the others were the same, and a block copolymer was obtained. The styrene content of the obtained polymer is 60% by weight (please read the back note before filling this page) L··, This paper size applies to Chinese National Standard (CNS) A4 size (210X297 mm) -18- 1259196 A7 B7 ——一- ------ V. Inventive Note (Also, the 1,2 ethylene bond amount of the polybutadiene moiety is 12% by weight, and the number average molecular weight is 74000. (Please read the back note first) Further, the block copolymer solution was used, and hydrogenation was carried out in the same manner as in Example 1 to prepare polymers VII and VIII. The polymer structure of each sample is shown in Table 4. The addition amount of n-butyllithium and tetramethylethylenediamine was the same as that of 1, and a block copolymer was obtained. The obtained polymer had a styrene content of 50% by weight and a polybutadiene portion of 1,2. The amount of the ethylene bond was 40% by weight, and the number average molecular weight was 62,000 (this is Polymer IX). Further, the block copolymer solution was used, and hydrogenation was carried out in the same manner as in Example 1 to prepare polymers X and XI. The structure is shown in Table 1. 5 In 1, except for the initial input The amount of styrene was 37 parts by weight, the amount of styrene charged after the polymerization of butadiene was 29 parts by weight, and the others were all the same, and a block copolymer was obtained. The obtained polymer had a styrene content of 66% by weight and agglomerated. The amount of 1,2 ethylene bond in the butadiene portion is 48% by weight, and the number average molecular weight is 54000. The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, prints and uses the block copolymer solution, and hydrogenates it in the same manner as □. Polymer XII. The polymer structure is shown in Table 1. 6 Wash and dry the autoclave with a capacity of 100 liters with a stirrer and a jacket and replace it with nitrogen, and put in a ring containing 30 parts by weight of pre-purified styrene. Hexane solution. Next, n-butyl lithium and tetramethylethylenediamine were added, and after polymerization at 70 ° C for 1 hour, a cycloheximide solution containing 4 〇 parts by weight of pre-purified isoprene was added, and polymerization 1 was carried out. In the hour, add 30% by weight of benzophenone to the sacred sputum, and polymerize for 1 hour. The scale is applicable to the Chinese National Standard (CNS) a15^7210'x297 dongdong) -19- 1259196 A7 B7 economy Ministry of Intellectual Property Bureau employee consumption cooperative printing V. INSTRUCTIONS (1) 7 Sampling a portion of the resulting block copolymer solution 'for a block copolymer of 100 parts by weight, adding 〇·3 parts by weight of 18 bases _3-(3,5 - one fourth The base 4-hydroxyphenyl)propionate is then heated to remove the solvent (the resulting copolymer is polymer XIII). The styrene content of the polymer crucible was 60% by weight, the total amount of the vinyl bond of the polyisoprene portion was 40% by weight, and the number average molecular weight was 52,000. Next, using a residual block copolymer solution, di-p-tris(1-cyclopentadienyl)titanium and dibutylmagnesium are used as hydrogenation catalysts, and hydrogenation is carried out at a temperature of 70 ° C to obtain a polymer. XIV. The hydrogenation rate of the polymer XIV was 52%. The residual polymer solution was again subjected to hydrogenation to obtain a polymer solution of the polymer XV. The hydrogenation rate of the polymer XV was 92%. The polymer structure of each sample is shown in Table 1. 7 In 2, except that the addition amount of tetramethylethylenediamine is increased, the others are the same, and a block copolymer is obtained. The obtained polymer had a styrene content of 60% by weight, a 1,2-vinyl bond of the polybutadiene portion of 74% by weight, and an average molecular weight of 78,000. Further, a block copolymer solution was used, and hydrogenation was carried out in the same manner as in Example 1 to prepare a polymer XVI. The polymer structure is shown in Table 1. (2) Modification of the resin composition and physical property measurement The components (b) were blended in the proportions shown in Table 2' Table 3, (the 〇 component 'using a 30 mm biaxial extruder, at 22 (rc temperature) The melt-kneading was carried out to granulate it. The measurement specifications and test methods of the physical properties shown in the examples and the comparative examples are as follows. The obtained granular material was injection-molded at 22 ° C, and the measurement was carried out. 1. At least one of the characteristics of the paper. ^ Paper scale applies to the Chinese National Standards Director y -~ - -20- (Please read the notes on the back and fill out this page)
1259196 A7 &7 五、發明説明（18) (請先閲讀背面之注意事項再填寫本頁) 1. 拉伸延展特性··依據ASTM D63 8，測定射出成形 試驗片之拉伸破裂伸長率。又，係以5毫米/分鐘之拉張速 度進行。 2. 耐熱性：依據ASTM D 1525，測定射出成形試驗片 於1公斤力荷重下之維卡軟化點，以作爲指標。 3. 剛性：依據ASTM D790，進行射出成形試驗片之 彎曲試驗，以測定彎曲彈性率。 4. 嵌段共聚物之界面存在率：以下述方法測定、計 算相對於嵌段共聚物總摻合量，存在於苯乙烯系樹脂相與 烯烴系樹脂相界面之嵌段共聚物比例。 經濟部智慧財產局員工消費合作社印製 使用超薄切片機，於射出成形時之樹脂流向上，自樹 脂組成物之射出成形體切下平行面之超薄切片，以四氧化 釕染色，以穿透型電子顯微鏡照射10000倍之畫像照片。 藉由此照片之畫像解析，測定存在於苯乙烯系樹脂相或烯 烴系樹脂相之嵌段共聚物面積，而算出其相對於作爲畫像 解析對象之全部面積之比率（a)。再者，由樹脂組成物之摻 合比率所算出之嵌段共聚物重量比率定爲（b)，則存在於苯 乙烯系樹脂相與烯烴系樹脂相界面之嵌段共聚物比例（c)爲 ((b)-(a))/(b)xl00%。以此値作爲指標。 5. 耐油性：使用片狀擠壓機，將樹脂組成物製成厚 1毫米之片狀物，於高2公分X長10公分X寬10公分之容器 內成形，於內面塗布合成椰子油後，求取可使以熱爐加熱1 小時後之容器內容積變化率爲10%之加熱溫度。此溫度愈 高，則判斷其耐油性愈佳。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21 - 1259196 A7 B7 五、發明説明（仏 6· 耐熱老化性··於射出成形熱塑性樹脂組成物時， 於成形機內，在240°C之溫度下留置1〇分鐘，其後射出成 形板狀物’目視判定其表面狀態。藉由光澤的狀況進行3 階段評估。 〇（無）< △(稍有）< X (有） 7. 加工性：測定樹脂組成物粒狀物之MFR(200°C、5 公斤荷重）’以作爲指標。 以下實施例1至7之結果係示於表2。 [實施例1至3] 摻合70重量％之作爲（a)成分之耐衝撃性聚苯乙烯、3〇 重量％之作爲（b)成分之（b-Ι)均聚丙烯、及（c)成分之氫化嵌 1又共:^物’此爲本發明樹脂組成物之例示。可知該樹脂組 成物除具尚拉伸延展特性與剛性外，其耐熱性、耐油性及 耐熱老化性均優異。 [實施例4、5] 摻合45重量％之作爲（a)成分之耐衝擊性聚苯乙烯、55 重里％之作爲（b)成分之（b-Ι)均聚丙烯、及（c)成分之氫化嵌 段共聚物’此爲本發明樹脂組成物之例示。可知該樹脂組 成物除具高拉伸延展特性與剛性外，其耐熱性、耐油性及 耐熱老化性均優異。 [實施例6、7] 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇><297公着） (請先閱讀背面之注意事項再填寫本頁) ----：—訂—----- 經濟部智慧財產局貞工消費合作社印製 -22- 1259196 A7 B7 五、發明説明（20) 與實施例1至3爲相同摻合之例示，惟實施例6爲使 用兩端苯乙烯量相異之部分氫化嵌段共聚物之例示，而實 施例7爲使用異戊二烯作爲共軛二烯化合物之例示。任一 樹脂組成物均與其他實施例相同，除具高拉伸延展特性與 剛性外，其耐熱性、耐油性及耐熱老化性均優異。 另外，測定實施例7之MFR爲5.5克/10分鐘。相對於 此，取代實施例7之聚合物XIV而使用氫化率高之聚合物 XV，所得樹脂組成物之MFR爲4.9克/10分鐘。可知本發 明樹脂組成物之加工性優異。 藉由與以下之比較例比較，可更進一步地淸楚明瞭本 發明樹脂組成物之優異特性。以下比較例1至9之結果係 示於表3。 [比較例1] 此例示爲70重量％之耐衝擊性聚苯乙烯、與30重量％ 之均聚丙烯之樹脂組成物，該組成物並未摻合部分氫化嵌 段共聚物。其相容性差，諸如拉伸延展特性以及耐油性均 顯著地極差。 [比較例2至6、8及9] 此組成物係於70重量％之耐衝擊性聚苯乙烯、30重量 %之均聚丙烯中，摻合苯乙烯系嵌段共聚物而得者，但該嵌 段共聚物並未具有本發明之特定結構，故該樹脂組成物除 拉伸延展特性顯著地極差外，各特性之平衡係低。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 ί 經濟部智慧財產局員工消費合作社印製 -23- A7 經濟部智慧財產局員工消費合作社印製 1259196 B7 五、發明説明（21) [比較例7] 與實施例4、5爲相同摻合之例示，惟嵌段共聚物並未 具有本發明之特定結構，故該樹脂組成物各特性之平衡係 低。 [實施例8] 將實施例1之（b)成分由（b-Ι)變爲（b-2)，相同地製得樹 脂組成物。與實施例1相同’係製得相容性佳之樹脂組成 物。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)1259196 A7 &7 V. INSTRUCTIONS (18) (Please read the precautions on the back and fill out this page) 1. Tensile and ductile properties ·· According to ASTM D63 8, the tensile elongation at break of the injection-molded test piece was measured. Further, it was carried out at a drawing speed of 5 mm/min. 2. Heat resistance: The Vicat softening point of the injection-molded test piece under a load of 1 kg was measured in accordance with ASTM D 1525 as an index. 3. Rigidity: The bending test of the injection-molded test piece was carried out in accordance with ASTM D790 to determine the bending elastic modulus. 4. Interface existence ratio of the block copolymer: The ratio of the block copolymer existing at the interface between the styrene resin phase and the olefin resin phase was measured by the following method and calculated based on the total blending amount of the block copolymer. The Ministry of Economic Affairs, the Intellectual Property Office, and the Employees' Cooperatives Co., Ltd. printed and used the ultra-thin microtome, and the resin flowed upward during the injection molding. The ultra-thin section of the parallel surface was cut out from the injection molded body of the resin composition, and dyed with ruthenium tetroxide to wear A 10,000-fold portrait photograph was irradiated by a transmission electron microscope. By the image analysis of the photograph, the area of the block copolymer existing in the styrene resin phase or the olefin resin phase was measured, and the ratio (a) to the total area of the image analysis target was calculated. In addition, when the weight ratio of the block copolymer calculated from the blending ratio of the resin composition is (b), the ratio of the block copolymer (c) present at the interface between the styrene resin phase and the olefin resin phase is ((b)-(a))/(b)xl00%. Use this as an indicator. 5. Oil resistance: The resin composition was formed into a sheet having a thickness of 1 mm using a sheet-like extruder, and formed in a container having a height of 2 cm, a length of 10 cm, a width of 10 cm, and a synthetic coconut oil coated on the inner surface. Thereafter, a heating temperature at which the volume change ratio of the container after heating in a hot furnace for 1 hour was obtained was 10%. The higher the temperature, the better the oil resistance is judged. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -21 - 1259196 A7 B7 V. Inventive Note (仏6· Heat aging resistance··In the case of injection molding thermoplastic resin composition, in the molding machine, The film was left at a temperature of 240 ° C for 1 minute, and then the formed sheet was ejected to visually judge the surface state thereof. A three-stage evaluation was performed by the condition of gloss. 〇 (none) < △ (slightly) < X (Yes) 7. Processability: MFR (200 ° C, 5 kg load) of the resin composition pellets was measured as an index. The results of the following Examples 1 to 7 are shown in Table 2. [Example 1 to 3] 70% by weight of (3)% of the (a) component of the impact-resistant polystyrene, 3% by weight of the (b) component (b-Ι) homopolypropylene, and (c) component of the hydrogenation embedded 1 Further, this is an example of the resin composition of the present invention. It is understood that the resin composition is excellent in heat resistance, oil resistance, and heat aging resistance in addition to tensile elongation and rigidity. [Example 4 5] Blending 45% by weight of impact-resistant polystyrene as component (a), 55% by weight (b) Component (b-Ι) homopolypropylene, and hydrogenated block copolymer of component (c) 'This is an illustration of the resin composition of the present invention. It is understood that the resin composition has high tensile ductility and rigidity. In addition, it is excellent in heat resistance, oil resistance and heat aging resistance. [Examples 6 and 7] This paper scale applies to the Chinese National Standard (CNS) A4 specification (2丨〇><297 public) (please read first) Note on the back of the page again ----)------- Ministry of Economic Affairs Intellectual Property Bureau Completion Consumer Cooperative Printed -22- 1259196 A7 B7 V. Invention Description (20) and Example 1 To 3 is an illustration of the same blending, except that Example 6 is an example using a partially hydrogenated block copolymer having a different amount of styrene at both ends, and Example 7 is an illustration using isoprene as a conjugated diene compound. Any of the resin compositions was the same as the other examples, and was excellent in heat resistance, oil resistance and heat aging resistance in addition to high tensile ductility and rigidity. Further, the MFR of the measurement example 7 was 5.5 g/10 In contrast, in place of the polymer XIV of Example 7, a hydrogenation rate was used. In the compound XV, the MFR of the obtained resin composition was 4.9 g/10 min. It is understood that the resin composition of the present invention is excellent in workability. The resin composition of the present invention can be further clarified by comparison with the following comparative examples. The results of the following Comparative Examples 1 to 9 are shown in Table 3. [Comparative Example 1] This is a resin composition of 70% by weight of impact-resistant polystyrene and 30% by weight of homopolypropylene. The composition did not blend partially hydrogenated block copolymers, and its poor compatibility, such as tensile ductility and oil resistance, was significantly poor. [Comparative Examples 2 to 6, 8 and 9] This composition was obtained by blending a 70% by weight of impact-resistant polystyrene and 30% by weight of a homopolypropylene with a styrene-based block copolymer. Since the block copolymer does not have the specific structure of the present invention, the resin composition has a very low balance of the properties except that the tensile elongation characteristics are remarkably extremely poor. This paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm) (please read the note on the back and fill out this page). ί Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Print -23- A7 Ministry of Economics Intellectual Property Bureau employee consumption cooperative printing 1259196 B7 V. Invention description (21) [Comparative Example 7] Examples 4 and 5 are the same blending examples, except that the block copolymer does not have the specific structure of the present invention, so the resin The balance of the properties of the composition is low. [Example 8] The component (b) of Example 1 was changed from (b-Ι) to (b-2), and a resin composition was obtained in the same manner. The same procedure as in Example 1 was carried out to obtain a resin composition having good compatibility. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page)
-24 - 1259196 A7 B7 五、發明説明（22) 表 經濟部智慧財產局員工消費合作社印製 樣品 編號 X成分 <注1〉 (重量％) 嵌段 Y成分 〈注2> (重量％) 共聚物之1 氫化前乙 烯鍵量 (重量％) 吉構 Y成分中 氫化率 (%) 氫化後殘 餘乙烯鍵 (重量％) I 66 34 50 0 50 II 66 34 50 26 29 III 66 34 50 44 3 IV 66 34 50 65 0 V 60 40 25 0 25 VI 60 40 25 50 1 VII 60 40 12 60 0 VIII 60 40 12 98 0 IX 50 50 40 0 40 X 50 50 40 40 2 XI 50 50 40 66 0 XII 66 34 今8 60 1 XIII 60 40 _ 40 0 30 XIV 60 40 40 52 1 XV 60 40 40 92 0 XVI 60 40 74 65 14 <注1>聚苯乙烯嵌段 <注2>聚丁二烯嵌段或聚異戊二烯嵌段 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 -25- 1259196 A7 B7 五、發明説明（23) 表2 樹脂組成物 特 性 ⑻成分 (b-Ι)成分 (Q成分 拉伸延 耐熱性 彎曲彈性率 耐油性 界面存在率 耐熱老化性 (重量％) (重量％) 種類 (重量分） 昼 CC) (kg/cm2) CC) (%) (%) 實施例1 70 30 III 10 182 107 17400 100 78 .〇 實施例2 70 30 IV 10 185 107 17400 105 80 〇 實施例3 70 30 VI 10 198 107 17800 110 72 〇 實施例4 45 55 X 8 222 112 15000 115 82 〇 實施例5 45 55 XI 8 240 112 15200 115 85 〇 實施例6 70 30 XII 10 204 106 17800 110 85 〇 實施例7 70 30 XIV 10 180 105 17200 100 70 〇 (請先閱讀背面之注意事項再填寫本頁) 訂 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'乂 297公釐） - 26- 1259196 A7 B7 五、發明説明（24) 表3 樹脂組成物 特 性 ⑻成分 (b-Ι减分 (C减分 拉伸延 耐熱性 彎曲彈性率 耐油性 界面存在率 耐熱老化性 (重量％) (重量％) 種類 (重量分） 星 (%) (°C) (kg/cm2) (°C) (%) 比較例1 70 30 0 6 105 18000 75 比較例2 70 30 I 10 25 105 15500 80 25 X 比較例3 70 30 II 10 64 105 15800 85 35 Δ 比較例4 70 30 V 10 55 107 15500 85 25 X 比較例5 70 30 VII 10 60 108 16400 85 35 〇 比較例6 70 30 VIII 10 50 108 16400 90 45 〇 比較例7 45 55 IX 8 62 110 14200 100 25 X 比較例8 70 30 XIII 10 26 104 15500 80 30 X 比較例9 70 30 XVI 10 112 105 16000 100 40 Δ (請先閱讀背面之注意事項再填寫本頁)-24 - 1259196 A7 B7 V. INSTRUCTIONS (22) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Sample No. X Component <Note 1> (% by weight) Block Y component <Note 2> (% by weight) Copolymerization The amount of the ethylene bond before hydrogenation (% by weight) The hydrogenation rate (%) in the composition of the Y component The residual ethylene bond after hydrogenation (% by weight) I 66 34 50 0 50 II 66 34 50 26 29 III 66 34 50 44 3 IV 66 34 50 65 0 V 60 40 25 0 25 VI 60 40 25 50 1 VII 60 40 12 60 0 VIII 60 40 12 98 0 IX 50 50 40 0 40 X 50 50 40 40 2 XI 50 50 40 66 0 XII 66 34 Today 8 60 1 XIII 60 40 _ 40 0 30 XIV 60 40 40 52 1 XV 60 40 40 92 0 XVI 60 40 74 65 14 <Note 1> Polystyrene block <Note 2> Polybutadiene block Or polyisoprene block paper size applicable to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the note on the back and fill out this page) Order -25- 1259196 A7 B7 V. Invention Description (23) Table 2 Resin composition characteristics (8) Component (b-Ι) component (Q component tensile elongation heat resistance bending elastic modulus oil resistance interface existence rate resistance Heat aging (% by weight) (% by weight) Species (parts by weight) 昼CC) (kg/cm2) CC) (%) (%) Example 1 70 30 III 10 182 107 17400 100 78 . Example 2 70 30 IV 10 185 107 17400 105 80 〇 Example 3 70 30 VI 10 198 107 17800 110 72 〇 Example 4 45 55 X 8 222 112 15000 115 82 〇 Example 5 45 55 XI 8 240 112 15200 115 85 Example 6 70 30 XII 10 204 106 17800 110 85 〇Example 7 70 30 XIV 10 180 105 17200 100 70 〇 (Please read the notes on the back and fill out this page) Order the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Cooperatives, Print this paper The scale applies to the Chinese National Standard (CNS) A4 specification (210'乂297 mm) - 26- 1259196 A7 B7 V. Inventive Note (24) Table 3 Resin Composition Characteristics (8) Composition (b-Ι Subtraction (C Subtraction Extension heat resistance Bending elastic modulus Oil resistance interface existence rate Heat aging resistance (% by weight) (% by weight) Species (parts by weight) Star (%) (°C) (kg/cm2) (°C) (%) Comparative example 1 70 30 0 6 105 18000 75 Comparative Example 2 70 30 I 10 25 105 15500 80 25 X Comparative Example 3 70 30 II 10 64 105 15800 85 35 Δ Comparative Example 4 70 30 V 10 55 107 15500 85 25 X Comparative Example 5 70 30 VII 10 60 108 16400 85 35 〇Comparative Example 6 70 30 VIII 10 50 108 16400 90 45 〇Comparative Example 7 45 55 IX 8 62 110 14200 100 25 X Comparative Example 8 70 30 XIII 10 26 104 15500 80 30 X Comparative Example 9 70 30 XVI 10 112 105 16000 100 40 Δ (Please read the back note first and then fill out this page)
、1T 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 ) Α4規格（210Χ 297公釐） -27- 1259196 A7 B7 五、發明説明（ 25/ 產業上利用性 、/辦脂及/或聚伸苯瞇系樹脂與烯烴系樹 藉由於苯乙烯系樹％、 化嵌段共聚物，可製得一種該熱 脂中’添加特定之部分圉 耐油性、耐熱老化性 塑性樹脂組成物，其極具耐… 且拉伸延展特性優異° (請先閲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 ) Α4規格（210Χ297公釐） -28-1T Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed This paper scale applies Chinese National Standard (CNS) Α4 Specification (210Χ 297 mm) -27- 1259196 A7 B7 V. Invention Description ( 25/ Industrial Utilization, / Office The fat and/or polyphenylene benzoate resin and the olefin system can be obtained by adding a specific part of the thermal grease to the oil resistant and heat aging plastic resin. The composition is extremely resistant to... and has excellent tensile elongation properties. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed on this paper scale, applicable to China National Standard (CNS) Α4 Specifications (210Χ297 mm) -28-