539713 A7 B7 五、發明説明（彳） 1.發明的技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發明有關對瀝青有改質作用的特定構造的芳香族乙 烯化合物及共軛二烯的嵌段共聚物或其組成物，及由此共 聚物（組成物），與直餾瀝青配合而成，具較短的溶解時 間、優異的加工、使用性、高溫儲藏的安定性，且平衡其 伸率、剛性、韌性、軟化點的瀝青組成物。 2 .先行技術 向來直餾瀝青以其價廉且容易入手，廣泛使用於道路 敷設、防水皮、隔音皮，防振材等用途。然而由於直餾瀝 青因其剛性、韌性、軟化點、伸率等不良，很多硏究爲了 改良這些特性爲目的，以添加種種共聚物組成物以改良瀝 青。這些各式各樣的共聚物組成物具體的使用例，如傳統 的苯烯一丁二烯共聚物乳膠（SBR乳膠）、苯乙烯一醋 酸乙烯共聚物（E V A )、乙烯一丙烯酸乙酯共聚物等。 但是添加這些共聚物對剛性、韌性、軟化點及伸率等有一 定程度的改良不充分事實，須再加改良。 經濟部智慧財產局員工消費合作社印製 又近年來，有試以添加芳香族乙烯化合物及共軛二烯 的嵌段共聚物（S B )嵌段共聚物方式對瀝青加以改質。 例如提議作爲瀝青諸物性改良目的，而使用各種醚化合物 或三級胺化合物作爲微構造控制劑，以有機鋰化合物爲聚 合起始劑，添加具特定構造的嵌段共聚物的瀝青組成物。 即日本特公昭4 7 - 1 7 3 1 9號公報、日本特公昭5 9 一 3 6 9 4 9號公報所揭示單獨使用或倂用A - B - A線 -4 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 539713 A7 B7 __ 五、發明説明（2) 型嵌段共聚物、（A-B) nX型徑向共聚物改質瀝青。 但是此揭示例對伸率、剛性、韌性的平衡難以有所替代。 (請先閱讀背面之注意事項再填寫本頁) 對此狀況，近年來，如日本特開平1 一 2 5 4 7 6 8 號公報、日本特公平5 - 4 2 〇號公報揭示，含限定的含 量範圍內的芳香族乙烯化合物的嵌段共聚物，可優異平衡 伸率、剛性、韌性等特性的瀝青組成物。但是，揭示例亦 對瀝青溶解性、高溫儲藏的安定性，伸率、剛性、韌性、 軟化點等的特性的平衡尙未充分’期望開發改善平衡此物 性的瀝青組成物。 現在，一般係將嵌段共聚物分子量化或增加對瀝青的 添加量，以增加剛性、韌性、確保平衡伸率的方法。但此 方法，嵌段共聚物對瀝青的溶解性顯著延長，且所得到的 瀝青的溶解粘度變高，產生損害加工性的問題。 因此，嘗試使用上述S B嵌段共聚物以改善瀝青的性 質，然而不能得到滿意的結果，尙未發見對尙未發見瀝青 的剛性、韌性、軟化點及伸率的平衡的改質用的共聚物， 現狀尙待改善。 經濟部智慧財產局員工消費合作社印製 3 .發明所欲解決之課題 本發明的目的，係以上述技術課題背景產生的共聚物 ，高度控制分子結構，提供對瀝青具優異溶解性、高溫儲 藏的安定性，平衡伸率、剛性、韌性、軟化點等特性，可 使用於道路敷設、防水皮等的瀝青組成物。 一 5 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 539713 A7 B7 五、發明説明（9 4 .用以解決課題之手段 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關（a) —般式（I) ;Ai- B-A2爲 代表的嵌段共聚物及（b) —般式（II) ; (Ai-B-A 2 ) n X爲代表的嵌段共聚物〔一般式（I )〜（I j ) 中，Ai，Α2可相同或相異，重量平均分子量爲 5， 000〜20， 000的芳香族乙烯化合物爲主體的 聚合體塊段，B爲共軛二烯及芳香族乙烯化合物所成，且 芳香族乙烯化合物爲漸增斜度嵌段所成共聚物塊段，（a )〜（b)中的全耦合芳香族乙烯化合物含量爲2 5〜 4 0重量％，B塊段中的共軛二烯乙烯含量爲1 5〜5 0 重量％，且上述芳香族乙烯化合物含1〜5個漸增斜度嵌 段；B塊段共軛二烯的乙烯耦合含量爲9 7 / 3〜8 5 / 1 5，η爲2〜4的整數，X示爲耦合劑殘基，而且以1 〜4個單體單位鍋合的芳香族乙烯化合物的鎖鏈量佔全芳 香族乙烯化合物的5〜50重量％〕 ， （a)/(b)成 經濟部智慧財產局員工消費合作社印製 分以含4 0〜1 0 0 / 6 0〜0比例的重量比組成，且重 量平均分子量爲100，〇〇〇〜300，000的瀝青 改質用嵌段共聚物（組成物），及添加此共聚物的直餾瀝 青的瀝青組成物。 又，本發明係含（A )上述瀝青改質用嵌段共聚物（ 組成物）及（B )直餾瀝青 (A)/(B)(重量比）=2 〜15/98 〜85 比例所組成的瀝青組成物。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 539713 A7 B7 五、發明説明（4) 5 ·發明的實施形態 本發明所使用的（a )〜.（b )成分以芳香族乙烯 化合物爲主的聚合體塊段A i，A 2及以共軛二烯及芳香族 乙烯化合物的共聚物塊段B，以A i - B - A 2或（ A 1 - B - A 2 ) η X排列的嵌段共聚物。 此處爲獲得（a )〜（b )成分，所使用的芳香族乙 烯化合物可爲如苯乙烯、t - 丁基苯乙烯、α -甲基苯乙 烯、對甲基苯乙烯、二乙烯苯、1 ，1 -二苯基苯乙烯、 Ν，Ν二甲基-ρ -胺基乙基苯乙烯、ν，Ν二乙基-Ρ -胺基乙基苯乙烯、乙烯吡啶等，而以苯乙烯、α -甲 基苯乙烯爲佳。 又，爲獲得（a )〜（b )成分，所使用的共軛二烯 可爲如1 ，3 丁二烯、異丁二烯、2，3-二甲基一 1 ， 3 - 丁二烯、1 ，3 -戊二烯、2 - 甲基-1 ，3 -戊二 烯、1 ，3己二烯、4，5 —二乙基—1 ，3-辛二烯、 3，一丁基-1 ，3辛二烯、氯丁二烯等，以1 ，3 丁二 烯、異丁二烯、1 ，3-戊二烯爲佳、最佳爲1 ，3- 丁 二烯。 A i，A 2塊段，可相同或相異，以芳香族乙烯化合物 爲主體聚合體，共軛二烯低於3 0重量％之共聚合者亦可 A 1，A 2塊段爲均等或不均等都沒有關係。 Αι，Α2塊段之重量平均分子量爲5， 000〜 20， 000、最好是8， 000〜17， 〇〇〇。重4 ^— (請先閱讀背面之注意事項再填寫本頁)539713 A7 B7 V. Description of the invention (i) 1. Technical field of the invention (please read the notes on the back before filling this page) The invention relates to the aromatic vinyl compounds with specific structure and modification of asphalt, and the conjugated two A block copolymer of olefin or a composition thereof, and a copolymer (composition) thereof, which is compounded with straight run asphalt, has a short dissolution time, excellent processing, usability, and stability at high temperature storage, and An asphalt composition that balances its elongation, rigidity, toughness, and softening point. 2. Advanced technology The straight-run asphalt has always been cheap and easy to use. It is widely used in road laying, waterproofing, soundproofing, and anti-vibration materials. However, due to the poor rigidity, toughness, softening point, and elongation of straight run asphalt, many studies have been conducted to improve these properties by adding various copolymer compositions to improve the asphalt. Specific usage examples of these various copolymer compositions, such as traditional styrene-butadiene copolymer latex (SBR latex), styrene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer Wait. However, the addition of these copolymers is not sufficient to improve the rigidity, toughness, softening point, and elongation to some extent, and further improvements are required. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In recent years, there have been trials of modifying asphalt by adding block copolymers of aromatic vinyl compounds and conjugated diene (S B) block copolymers. For example, it is proposed to use various ether compounds or tertiary amine compounds as microstructure control agents, use organolithium compounds as polymerization initiators, and add asphalt copolymers with block copolymers having specific structures for the purpose of improving the physical properties of asphalt. That is, Japanese Patent Publication No. 4 7-1 7 3 1 9 and Japanese Patent Publication No. 5 9 1 3 6 9 4 9 are used alone or in use A-B-A line-4-This paper size is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 539713 A7 B7 __ 5. Description of the invention (2) block copolymer, (AB) nX radial copolymer modified asphalt. However, this disclosed example is difficult to replace the balance of elongation, rigidity, and toughness. (Please read the precautions on the back before filling out this page.) In recent years, as disclosed in Japanese Patent Application Laid-Open No. 1-2 5 4 7 6 8 and Japanese Patent Publication No. 5-4 2 0, including limited A block copolymer of an aromatic vinyl compound within a content range, an asphalt composition having excellent properties such as balanced elongation, rigidity, and toughness. However, the disclosed examples also have insufficient balance of characteristics such as the solubility of asphalt, the stability of high-temperature storage, elongation, rigidity, toughness, and softening point, etc., and it is desired to develop an asphalt composition that improves the balance of the physical properties. At present, it is generally a method of increasing the molecular weight of the block copolymer or increasing the addition amount to the asphalt to increase rigidity, toughness, and ensure equilibrium elongation. However, in this method, the solubility of the block copolymer in asphalt is significantly prolonged, and the solubility viscosity of the obtained asphalt becomes high, which causes a problem that the processability is impaired. Therefore, attempts have been made to use the above-mentioned SB block copolymer to improve the properties of asphalt. However, satisfactory results have not been obtained. No improvement has been found on the balance of the stiffness, toughness, softening point, and elongation of asphalt. Copolymer, the status quo needs to be improved. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 3. Problems to be Solved by the Invention The purpose of the present invention is to use copolymers produced in the background of the above technical problems to control the molecular structure to provide excellent solubility in asphalt and high-temperature storage. Stability, balance of elongation, rigidity, toughness, softening point and other characteristics, can be used for asphalt composition of road laying, waterproofing, etc. 5-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 539713 A7 B7 V. Description of the invention (9 4. Means to solve the problem (please read the notes on the back before filling in this (Page) The present invention relates to (a)-general formula (I); block copolymers represented by Ai- B-A2 and (b)-general formula (II); (Ai-BA 2) n X is represented by Block copolymers [General formulae (I) to (I j), Ai, A2 may be the same or different, and the weight average molecular weight is 5,000 to 20,000, and the aromatic vinyl compound is the main polymer block. B is a conjugated diene and an aromatic vinyl compound, and the aromatic vinyl compound is a copolymer block formed by a gradually increasing slope block. The content of the fully-coupled aromatic vinyl compound in (a) to (b) is 25 ~ 40% by weight, the conjugated diene ethylene content in the B segment is 15 ~ 50% by weight, and the above-mentioned aromatic vinyl compound contains 1 to 5 increasing slope blocks; the B segment is a total of The conjugated diene has an ethylene coupling content of 9 7/3 to 8 5/1 5, η is an integer of 2 to 4, X is shown as a coupling agent residue, and 1 to 4 monomer units The amount of chain of the aromatic vinyl compound accounts for 5 to 50% by weight of the wholly aromatic vinyl compound], (a) / (b) is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to include 40 ~ 1 0 0 / A composition with a weight ratio of 60 to 0 and a weight average molecular weight of 100,000 to 300,000 as a block copolymer (composition) for asphalt modification, and an asphalt composition of straight run asphalt to which this copolymer is added In addition, the present invention contains (A) the above-mentioned block copolymer (composition) for asphalt modification and (B) straight run asphalt (A) / (B) (weight ratio) = 2 to 15/98 to 85 Composition of asphalt composition in proportion. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 539713 A7 B7 V. Description of the invention (4) 5 · Implementation mode of the invention (a) ~ (B) Polymer block A i, A 2 mainly composed of aromatic vinyl compounds and copolymer block B composed of conjugated diene and aromatic vinyl compounds, and A i-B-A 2 or ( A 1-B-A 2) η X block copolymer. Here, in order to obtain the components (a) to (b), Group vinyl compounds may be, for example, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, Ν, Νdimethyl- ρ-aminoethylstyrene, ν, N diethyl-P-aminoethylstyrene, vinylpyridine and the like, and styrene and α-methylstyrene are preferred. Further, in order to obtain the components (a) to (b), the conjugated diene used may be, for example, 1,3 butadiene, isobutadiene, 2,3-dimethyl-1,3-butadiene , 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3 hexadiene, 4,5-diethyl-1,3-octadiene, 3, butyl -1,3 octadiene, chloroprene, and the like are preferably 1,3 butadiene, isobutadiene, and 1,3-pentadiene, and most preferably 1,3-butadiene. A i, A 2 blocks can be the same or different. Aromatic ethylene compounds are the main polymer, and those with a conjugated diene content of less than 30% by weight can also be A 1 or A 2 blocks. Inequality doesn't matter. The weight-average molecular weight of the blocks Aι and A2 is 5,000 to 20,000, preferably 8,000 to 17,000. Weight 4 ^ — (Please read the notes on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製Printed by 1T Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs
本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 539713 A7 B7 五、發明説明（5) (請先閱讀背面之注意事項再填寫本頁) 平均分子量低於5，0 0 0時，對瀝青的溶解時間縮短、 加工、操作容易，剛性、韌性則降低成爲不充分。一方面 ’超過2 0，0 0 0時，剛性、韌性充分提昇，對瀝青的 溶解時間則顯著增長，儲藏安定性惡化。 又，B塊段爲共軛二烯及芳香族乙烯化合物的共聚物 塊段，芳香族乙烯化合物則爲漸增斜度嵌段。 (a )〜（b )成分中的全耦合芳香族乙烯化合物含 量爲2 5〜4 0重量％，此全親合芳香族乙烯化合物含量 低於2 5重量％時，剛性、韌性降低，軟化點不充分，且 在高溫時的抗流動變形性成爲不充分。一方面，超過4 0 重量％時，對瀝青的溶解性顯著增長，且瀝青組成物的針 入度變小變硬，低溫可撓性降低。 又，B塊段中的共軛二烯的乙烯耦合含量爲1 5〜 5 0重量％，最好是1 5〜4 0重量％。乙烯耦合含量低 1 5重量％時，結果變成溶解性不足，一方面，超過5 0 重量％時，形成瀝青組成物時，其低溫特性因而變差非所 期望的。 經濟部智慧財產局員工消費合作社印製 此乙烯親合量依後述微構造控制劑的量，可容易的作 調整。 上述B塊段中的斜度嵌段的數量爲1〜5個，最好是 1〜3個。B塊段中的斜度嵌段不存在時，對瀝青的溶解 性惡化，又，成爲瀝青組成物時的物性亦不能得到充分的 物性。一方面，斜度嵌段的數量超過5個時，每一回的芳 香族乙烯化合物的添加量須爲少量，不能得到物性所必須 一 8 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 539713 A7 B7 五、發明説明（e) 的鎖鏈長度的長成分。 (請先閱讀背面之注意事項再填寫本頁) 又’ B塊段中的共軛一烯/方香族乙烯化合物的重量 比爲9 7 / 3〜8 5 / 1 5。B塊段中的共軛二烯的比例 低於8 5重量％時，A 1及A 2的兩末端塊段的分子量變小 ，剛性等的瀝青物性不能充分達到。一方面，超過9 7重 量％時，對瀝青的溶解時間顯著增長。 構成（b )嵌段共聚物的一般式（I I )中的n爲後 述的耦合劑的功能基數，爲2〜4的整數。 又，構成（b )嵌段共聚物的一般式（I I )中的X 爲後述的耦合劑的殘基。 更進一步，嵌段共聚物的芳香族乙烯化合物的鎖鏈分 配爲以1〜4個單體單位耦合的芳香族乙烯化合物的連鎖 量佔全芳香族乙烯化合物的5〜5 0重量％，最好是 1 0〜4 0重量％。 經濟部智慧財產局員工消費合作社印製 在此時，上述鎖鏈分配的單體單位爲0時，即爲B塊 段中不含芳香族乙烯化合物。一方面，超過4個亦爲獲得 瀝青組成物物性的必要成分，含有超過上述範圍時對瀝青 的溶解性顯著增長非所期望。 上述鎖鏈量低於5重量％時，對瀝青的溶解性增長， 一方面，超過5 0重量％時，塊段的分子量變小 ，成爲瀝青組成物時，不能得到充分的強度非所期望。 再之，耦合1〜2個單體單位的芳香族乙烯化合物的 鎖鏈量以1 0〜3 5重量％爲佳，更佳則爲1 5〜3 0重 量％ 〇 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） 一9 一 539713 Α7 Β7 五、發明説明（7) 上述鎖鏈分配，依後述微構造控制劑的量’可容易的 作調整。 (請先閲讀背面之注意事項再填寫本頁) 這樣，B塊段係共軛二烯及芳香族乙烯化合物的共聚 物段塊，芳香族乙烯化合物爲漸進斜度嵌段。此B段塊爲 斜度嵌段，上述B段塊爲以1〜4個單體單位連結的芳香 族乙烯化合物的鎖鏈爲5〜5 0重量％ (此處，連結3〜 4個單體單位的鎖鏈的量相當於5〜15重量％爲主寄與 以下），且由於含溶解性下降影響較小的低聚物成分（ 1 0個單體單位鎖鏈爲限），以增大韌性爲主，使溶解性 及物性的平衡達到高水準。 再者，連結1〜2個單體單位的芳香族乙烯化合物的 鎖鏈量1 0〜3 5重量％爲佳，如此，可提高對直餾瀝青 的溶解性。 經濟部智慧財產局員工消費合作社印製 此斜度嵌段，例如在碳氫溶媒中，以有機鋰爲開始劑 ，因共軛二烯及芳香族乙烯化合物各自均等慢慢的添加， 因聚合活性的不同，首先共軛二烯優先開始聚合，聚合之 後半段芳香族乙烯化合物開始聚合，B段塊中芳香族乙烯 化合物成爲漸增斜度嵌段。例如B段塊聚合時，在聚合中 分m次添加共軛二烯及芳香族乙烯化合物，則B段塊中可 存在m個斜度嵌段。 (a ) / ( b )成分的使用比例，以（a ) / ( b ) (重量比）爲40〜100/60〜Ο，較理想爲60〜 100/40〜0。（3)成分低於40重量％時〔（乜 )成分超過6 0重量％ )對瀝青的溶解時間顯著增長，高 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 539713 A7 ___ B7 五、發明説明（〇) 溫之儲藏安定性顯著惡化，且組成物的溶融粘度顯著上升 ’加工、操作變爲困難。 (a )〜（b)成分全體的重量平均分子量爲 100， 000〜300， 〇〇〇。重量平均分子量低於 10 0，0 0 0時，所得之瀝青組成物的剛性、韌性不充 分’又抗流動性降低很多。一方面，超過3 0 0，000 時’剛性、韌性很充分，對瀝青的溶解時間顯著增長，儲 藏安定性惡化，且組成物的溶融粘度顯著上升，加工、操 作變爲困難。 本發明所使用的（a )〜（b )成分，例如在非活性 氫溶媒中，以有機鋰等爲聚合開始劑，首先芳香族乙烯化 合物開始聚合，其次共軛二烯及芳香族乙烯化合物分1〜 5次同時加入進行聚合，再度使芳香族乙烯化合物聚合， 依反應的需要，與耦合劑反應而製造之。 上述非活性碳氫溶媒爲如戊烷、正已烷、庚烷、辛烷 、甲基環戊烷、環已烷、苯、二甲苯等的碳氫溶媒可供使 用，此中以環已烷爲最理想。 作爲聚合開始劑的有機鹼金屬化合物，以有機鋰化合 物爲最理想。此有機鋰化合物可使用的有機單鋰化合物、 有機二鋰化合物、有機聚鋰化合物。具體例爲乙基鋰、正 丙基鋰、異丙基鋰、正丁基鋰、仲丁基鋰、叔丁基鋰、亞 乙基二鋰。理想的是正丁基鋰、仲丁基鋰，此類聚合開始 劑使用量爲每100重量份單體用0.02〜0.2重量 份。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ϋ.·- ------- (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 539713 A7 B7 _ _ 五、發明説明（9) (請先閱讀背面之注意事項再填寫本頁) 又此時，作爲微結構即共軛二烯部份的乙烯耦合含量 的調整劑，路易斯鹼、如醚、胺等，具體的如二乙醚、四 氫呋喃、丙醚、丁醚、高級醚、又乙二醇二乙醚、乙二醇 丁醇、乙二醇二甲醚、乙二醇二丁醚、三甘醇丁醚、乙二 醇二丁醇、丙二醇二乙醚等的乙二醇類的醚衍生物，胺則 可爲四甲基乙烯二胺、吡啶三丁基胺等的三級胺等。此微 結構調整劑的使用量，每1 0 0重量份單體爲0 . 〇 1〜 0 · 1重量份。又此微結構調整劑可與非活性碳氫溶媒同 時使用。 聚合反應通行在2 0〜1 2 0°C進行，更好爲3 0〜 10CTC。 又聚合可在溫控下實施，或亦可在不去除熱度的昇溫 下實施。 如此所得的嵌段共聚物活性陰離子中、再添加耦合劑 ，延長聚合體分子量鎖鏈以得到（b)段塊共聚物。 (a )〜（b )成分在製造（a )段塊時，加入低於 當量的耦合劑’可得（a )〜（b )成分同時存在的組成 經濟部智慧財產局員工消費合作社印製 物，（a )成分或（b )成分以別的方法製作再混合亦可 〇 此時所用的聯劑爲錫系耦合劑，使用如二丁基二氯錫 、甲基三氯錫、丁基三氯錫、二丁基二溴錫、甲基三溴錫 、丁基三溴錫等鹵化錫，作爲錫系終端處理劑如三苯基錫 、三辛基氯錫，理想的如二丁基二氯錫、四氯錫等。 又酯化合物系耦合劑爲甲酸乙酯、乙酸乙酯、乙酸丁 —12 — 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇'χ 297公羡） 539713 A7 --------B7__ 五、發明説明（化 酯、丙酸甲酯、乙酸苯酯、苯甲酸乙酯、苯甲酸苯酯等， 理想的如乙酸乙酯、苯甲酸乙酯。 (請先閱讀背面之注意事項再填寫本頁) 除錫系、酯系以外的耦合劑爲二溴甲烷、二溴乙烷、 二溴丙烷、氯乙烯、二氯甲烷、二氯丙烷、二氯丁烷、等 的二鹵化鏈烷，二氯化硅烷、三氯化硅烷、化硅烷、甲基 二氯桂烷、二甲基二氯硅烷、乙基二氯硅烷、二乙基二氯 石土院、丁基一氣桂院、二丁基二氯硅院、已基二氯桂院、 二已基二氯硅烷、二溴硅烷、甲基二溴硅烷、二甲基二溴 硅烷等的鹵化硅化合物，二乙烯苯、二乙烯萘等二乙烯芳 香族乙烯化合物，二酚一 A，二酚一 AD、二酚-F、其 他的環氧化合物、丙酸氯化物、已二酸二氯化物等的酸氯 化物’ 1 ’ 4氯曱基苯、曱苯撐異氰酸酯、y -環氧丙氧 基丙基三甲氧基硅烷等。 (b )段塊共聚物製造時的耦合劑的使用量，爲金屬 化合物（理想爲有機鋰化合物）〇〜約〇 · 3 m ο 1比。 經濟部智慧財產局員工消費合作社印製 且，（a )〜（b )成分中的芳香族乙烯化合物的耦 合含量’ g周節聚合時各階段之單體供給量，共轭二烯的乙 烯耦合含量與芳香族乙烯化合物的鎖鏈分配，依上述微結 構控制劑的成分的變量而調節之。 又（a )〜（b)成分的重量平均分子量爲以聚合開 始劑、如仲丁基鋰的添加量及/或親合劑（如二甲基二氯 硅烷）的添加量調節之。 更進一步，有關本發明的共軛二烯及芳香族乙烯物的 嵌段共聚物〔（a )〜（b )成分〕的共軛二烯部份的雙 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 13 539713 A7 B7 五、發明説明（1)1 鍵可添加氫素飽和之。 (請先閱讀背面之注意事項再填寫本頁) 其次，本明所用的（B )直餾瀝青爲瀝青基原油以常 壓蒸餾及水蒸氣或真空蒸餾後所得的殘留物。容易以本發 明的嵌段共聚物的（a )〜（b )成分所溶解，容易加工 、操作。 本發明使用的瀝青以直餾瀝青爲佳，以氧化瀝青代替 直餾瀝青亦無妨礙。 再之，（B)直餾瀝青以針入度爲40〜200者爲 佳，針入度低於4 0時，嵌段共聚物對瀝青的溶解時間力口 長，又伸率有變小的傾向，一方面，超過2 〇 〇時剛性、 韌性有降低的傾向。 經濟部智慧財產局員工消費合作社印製 上述（A )嵌段共聚物（組成物）及（b )直餾瀝青 的重量比爲2〜15/98〜85，以3〜13/97〜 8 7較佳。（A )成分的重量比低於2時對瀝青沒有改質 效果，剛性、韌性不充分，且軟化點、伸率降低，一方面 超過1 5時、有充分的剛性、韌性，對瀝青的溶解時間顯 著加長，且組成物的溶融粘度顯著上升，加工及操作變爲 困難。 本發明的（A )嵌段共聚物（組成物）通常以顆粒狀 、屑狀或粉狀等的形狀使用。 本發明的瀝青組成物，通常以（B )直餾瀝青於 1 4 0〜1 9 0°C溶融攪拌下，投入上述（A)嵌段共聚 物（組成物）加以混合製造的。 再次，本發明的瀝青組成物，可與矽、滑石、碳酸錦 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 539713 A7 B7 五、發明説明（么 等的塡充劑，顏料、老化防止劑、交聯劑、耐燃劑等的添 加劑配合。又作爲道路敷設用時可添加碎石使用。 (請先閲讀背面之注意事項再填寫本頁) 更進一步，本發明的瀝青組成物，可倂用其他熱可塑 性橡膠或熱可塑性樹脂如乙烯-丁二烯乳膠、乙烯-醋酸 乙烯共聚物、乙烯-丙烯酸乙酯共聚物、無規聚丙烯、1 ’ 2聚丁二烯、或乙烯-丙烯橡膠等的聚合體。此時，本 發明的（A )嵌段共聚物（組成物），可事先與上述其他 聚合體以仕意的比例混練後，顆粒化後使用。 6 ·實施例 本發明的實施例具體說明如下，本發明非限定實施例 而已。 實施例例中，份及％如無特別指定時以重量爲準。 又，實施例中各評價，係以下述方法求出者 嵌段共聚物的特忡 (1 )重量平均分子量 經濟部智慧財產局員工消費合作社印製 以GPC裝置〔使用東^一（股）製HLC — 8 0 2 0型，柱體使用杜邦公司製Z0RBAX3支及 3 0 0 S 1支〕測定。以標準聚苯乙烯換算的重量平均分 子量。 (2 )乙烯耦合含量 以紅外線吸光分析裝置（PARKING ELMAER - 15 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 539713 A7 —__B7 五、發明説明（也 1 600型）M〇RER〇法求取9 1 1 cm — 1的吸收強 度。 (請先閱讀背面之注意事項再填寫本頁) (3 )親合苯乙烯含量 以紅外線吸光分析裝置（PARKING ELMAER — 1 6 0 〇型）M〇RER〇法求取6 9 0 cm — 1的吸收強 度。 (4 )段塊中的芳香族乙烯化合物鎖鏈量的測定 以曰本農工大田中教授所開發的方法（高分子學會予 稿集，第2 9卷第7號2 0 5 5頁）使用臭氧之氧化分解 法測定芳香族乙烯化合物鎖鏈量爲基準。 瀝青組成物的特忤 (1 )溶解性時間；A法 經濟部智慧財產局員工消費合作社印製 A法係在調製瀝青組成物時、採取少量混合中的內容 物’敷塗於玻璃載片上，以4 0 0倍光學顯微鏡觀察，至 看不見瀝青與嵌段共聚物分離時的時間。 (2 )溶解性時間；b法 B法係在調製瀝青組成物時、採取少量混合中的內容 物’敷塗於聚對苯二甲酸乙二醇酯（鐵夫龍）膜上，至看 不出嵌段共聚物固體顆粒時的時間。 一 16 — 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 539713 A7 B7 五、發明説明（ώ (3 )剛性、韌性 (請先閲讀背面之注意事項再填寫本頁) 以「舖裝試驗法便覽」（日本昭和6 3年1 1月，社 團法人日本道路協會發行）爲準測定之。 (4 )針入度、伸率、軟化度 以日本J I S Κ 2 2 0 7爲準測定之。 (5 )高溫下的儲藏安定性 於鋁製容器注入已調製好的瀝青組成物，在1 8 0 °C 烤箱中於於氮氣環境下放置二星期，以G P C測定儲藏前 後瀝青組成物中嵌段共聚物的分子量分佈。 依儲藏前後瀝青組成物中嵌段共聚物的分子量分佈， 計算分子量保留率。 嵌段共聚物的調製 將容積1 0 0公升具夾層及攪拌器的不鏽鋼製聚合用 容器充分以氮氣驅換空氣後，投入5 0 k g環已院、 經濟部智慧財產局員工消費合作社印製 1 . 9kg乙二醇二乙醚、1 _ 5kg苯乙烯、夾層通以 溫水使內容物達4 0 °C。 其次，添加9 . 0 g的仲丁基錫開始聚合，苯乙烯聚 合完了後，一邊通冷水使內容物溫度爲爲8 〇 °C，一邊均 分爲三次慢慢的添加8 _ 5 k g 1，3 - 丁二烯及1 k g 苯乙·。B段塊聚合終了後，再另外添加1 . 5 k g苯乙 烯繼續聚合、聚合大約完全後，加入作爲耦合劑的二溴乙 一 17 — 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 539713 A7 B7 ____ 五、發明説明（ 烷4g，反應30分鐘。 (請先閱讀背面之注意事項再填寫本頁) 反應後，添加1 0 m 1甲醇，攪拌1 0分鐘後從聚合 器中取出內容物，加入50g2 ，6二叔丁基一 4 -甲酚 (Β Η T )抗氧化劑。以蒸氣汽提此聚合溶液，得到的含 水聚合體以粉碎機粉碎成屑狀，再以8 0 °C熱風乾燥，得 到苯乙烯-丁二烯嵌段共聚物。 瀝青組成物的調製 以5 7 0 g針入度=7 0的直餾瀝青〔日本共同石油 (股）製6 0/8 0〕及3 0 g上述苯乙烯-丁二烯嵌段 共聚物，以攪拌機〔日本特殊機化工業（股）製T K均質 混合器1 0 . 0 0 0 r p m〕於1 8 0 °C下混合，調製成 瀝青組成物。表1〜2爲各特性的評價結果。 實施例2〜5、比較例1〜1 0 實施例2、比較例2及比較例8爲不使用耦合劑的例 ，此外，除了改變苯乙烯、1 ，3 丁二烯、仲丁基錫、乙 經濟部智慧財產局員工消費合作社印製 二醇二乙醚投入量外，與實施例1同樣製得嵌段共聚物（ 組成物），調製瀝青組成物’評價其性能。 又，實施例5係變更乙二醇二乙醚投入量外，與實施 例1同樣製得嵌段共聚物（組成物），與實施例1同樣調 製瀝青組成物，評價其性能。 上述以外的實施例、比較例依表1、表3、表4所記 載的聚合處方、與實施例1同樣製得嵌段共聚物（組成物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) _ 7〇 — 539713 A7 B7This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 539713 A7 B7 V. Description of the invention (5) (Please read the notes on the back before filling this page) When the average molecular weight is less than 5, 0 0 0 As a result, the dissolution time of asphalt is shortened, processing and operation are easy, and rigidity and toughness are reduced to become insufficient. On the one hand, when it exceeds 20,000, the rigidity and toughness are fully improved, the dissolution time of the asphalt is significantly increased, and the storage stability is deteriorated. The block B is a copolymer block of a conjugated diene and an aromatic vinyl compound, and the aromatic vinyl compound is a gradually-inclined block. (a) ~ (b) The content of the fully-coupled aromatic vinyl compound in the component is 25-50% by weight. When the content of the fully-affiliated aromatic vinyl compound is less than 25% by weight, the rigidity and toughness are reduced, and the softening point is reduced. Insufficient, and insufficient flow deformation resistance at high temperatures. On the other hand, when it exceeds 40% by weight, the solubility in asphalt increases significantly, the penetration of the asphalt composition becomes smaller and harder, and the low-temperature flexibility decreases. The ethylene coupling content of the conjugated diene in the B block is 15 to 50% by weight, and more preferably 15 to 40% by weight. When the ethylene coupling content is as low as 15% by weight, the solubility becomes insufficient. On the other hand, when it exceeds 50% by weight, the low-temperature characteristics of the asphalt composition are deteriorated, which is not desirable. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This amount of ethylene affinity can be easily adjusted according to the amount of the microstructure control agent described later. The number of slope blocks in the B block is 1 to 5, preferably 1 to 3. When the slope block in the B block does not exist, the solubility in asphalt is deteriorated, and the physical properties when the asphalt composition is formed cannot be obtained. On the one hand, when the number of sloped blocks is more than 5, the amount of aromatic vinyl compound added each time must be a small amount, and the physical properties cannot be obtained. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 539713 A7 B7 5. The long component of the chain length of the description of the invention (e). (Please read the notes on the back before filling in this page.) The weight ratio of the conjugated monoene / fangxiang vinyl compound in block B is 9 7/3 to 8 5/15. When the proportion of the conjugated diene in the B block is less than 85% by weight, the molecular weights of the both terminal blocks of A 1 and A 2 become small, and the asphalt physical properties such as rigidity cannot be sufficiently achieved. On the one hand, if it exceeds 97% by weight, the dissolution time to the asphalt increases significantly. N in the general formula (I I) constituting the (b) block copolymer is a functional group number of a coupling agent described later, and is an integer of 2 to 4. In addition, X in the general formula (I I) constituting the (b) block copolymer is a residue of a coupling agent described later. Furthermore, the chain distribution of the aromatic vinyl compound of the block copolymer is such that the chain amount of the aromatic vinyl compound coupled in 1 to 4 monomer units accounts for 5 to 50% by weight of the wholly aromatic vinyl compound, preferably 10 to 40% by weight. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs At this time, when the monomer unit allocated by the above-mentioned chain is 0, it means that the aromatic vinyl compound is not contained in the B block. On the one hand, more than 4 are also necessary components to obtain the physical properties of the asphalt composition, and when the content exceeds the above range, a significant increase in the solubility of the asphalt is not expected. When the amount of the above-mentioned chain is less than 5% by weight, the solubility in asphalt increases. On the other hand, when it exceeds 50% by weight, the molecular weight of the block becomes small, and when the asphalt composition is used, sufficient strength cannot be obtained. In addition, the chain content of the aromatic vinyl compound coupling 1 to 2 monomer units is preferably 10 to 35 wt%, and more preferably 15 to 30 wt%. 〇 This paper size applies Chinese national standards (CNS ) A4 specification (210 X297 mm) 9 9 539 713 A7 B7 V. Description of the invention (7) The above chain distribution can be easily adjusted according to the amount of the microstructure control agent described later. (Please read the notes on the back before filling out this page) In this way, block B is a copolymer block of conjugated diene and aromatic vinyl compound, and the aromatic vinyl compound is a progressive slope block. This B-segment block is a slope block, and the B-segment block is an aromatic vinyl compound linked by 1 to 4 monomer units with a chain content of 5 to 50% by weight (here, 3 to 4 monomer units are connected The amount of chain is equivalent to 5 to 15% by weight, and because it contains oligomer components that have less influence on the decrease in solubility (10 monomer units are limited to chain), it is mainly to increase toughness. To achieve a high level of solubility and physical properties. In addition, the chain amount of the aromatic vinyl compound connecting 1 to 2 monomer units is preferably 10 to 35% by weight. In this way, the solubility to straight run asphalt can be improved. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints this slope block. For example, in a hydrocarbon solvent, organic lithium is used as the starting agent. Because conjugated diene and aromatic vinyl compounds are added slowly and equally, due to polymerization activity. The difference is that first, the conjugated diene starts to polymerize preferentially. After the polymerization, the half-stage aromatic vinyl compound starts to polymerize, and the aromatic vinyl compound in the B-stage block becomes a gradually increasing slope block. For example, when the B-stage block is polymerized, and conjugated diene and aromatic vinyl compound are added m times during the polymerization, m slope blocks may exist in the B-stage block. The use ratio of the (a) / (b) component is (a) / (b) (weight ratio) 40 to 100/60 to 0, and more preferably 60 to 100/40 to 0. (3) When the content is less than 40% by weight [(乜) The content is more than 60% by weight] The dissolution time of asphalt is significantly increased, and the high paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 539713 A7 ___ B7 V. Explanation of the invention (0) The storage stability of temperature is significantly deteriorated, and the melt viscosity of the composition is significantly increased. 'Processing and operation become difficult. The weight-average molecular weights of the entire components (a) to (b) are 100,000 to 300,000. When the weight-average molecular weight is less than 100,000, the rigidity and toughness of the obtained asphalt composition are insufficient, and the fluidity resistance is greatly reduced. On the one hand, when it exceeds 30,000, the rigidity and toughness are very sufficient, the dissolution time of the asphalt is significantly increased, the storage stability is deteriorated, and the melt viscosity of the composition is significantly increased, making processing and handling difficult. The components (a) to (b) used in the present invention, for example, use an organic lithium or the like as a polymerization initiator in an inactive hydrogen solvent. First, the aromatic vinyl compound starts to polymerize, and then the conjugated diene and the aromatic vinyl compound are separated. 1 to 5 simultaneous additions are carried out for polymerization, and the aromatic vinyl compound is polymerized again, and is produced by reacting with a coupling agent according to the needs of the reaction. The above inactive hydrocarbon solvents are hydrocarbon solvents such as pentane, n-hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, xylene and the like, and cyclohexane is used here. For the most ideal. As the organic alkali metal compound as a polymerization initiator, an organic lithium compound is most preferable. Examples of the organic lithium compound include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds. Specific examples are ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, and ethylenedilithium. Ideally, n-butyllithium and sec-butyllithium are used. The amount of such polymerization initiator used is 0.02 to 0.2 parts by weight per 100 parts by weight of the monomer. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ϋ. ·-------- (Please read the notes on the back before filling this page) Order the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 539713 A7 B7 _ _ 5. Description of the invention (9) (Please read the notes on the back before filling this page) At this time, as the regulator of the ethylene coupling content of the conjugated diene part of the microstructure, Lewis Bases, such as ethers, amines, and specifically, diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ethers, and ethylene glycol diethyl ether, ethylene glycol butanol, ethylene glycol dimethyl ether, and ethylene glycol dibutyl ether Ether, triethylene glycol butyl ether, ethylene glycol dibutanol, propylene glycol diethyl ether and other ethylene glycol ether derivatives, and the amine may be tertiary amines such as tetramethylethylenediamine and pyridinetributylamine Wait. The microstructure modifier is used in an amount of 0.01 to 0.1 parts by weight per 100 parts by weight of the monomer. The microstructure modifier can be used simultaneously with an inactive hydrocarbon solvent. The polymerization reaction is generally carried out at 20 to 120 ° C, more preferably 30 to 10CTC. The polymerization may be carried out under temperature control, or may be carried out under elevated temperature without removing heat. A coupling agent is added to the active anion of the block copolymer thus obtained, and the molecular weight chain of the polymer is extended to obtain (b) a block copolymer. (a) ~ (b) When manufacturing (a) block, add less than equivalent couplant 'available (a) ~ (b) co-existing composition of the Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative printed matter The (a) component or (b) component can be prepared by other methods and then mixed. The coupling agent used at this time is a tin-based coupling agent, such as dibutyltin chloride, methyltrichlorotin, butyltrichloride, etc. Tin halides such as chlorotin, dibutyltin bromide, methyltribromotin, butyltribromotin, etc. As tin-based terminal treatment agents such as triphenyltin and trioctylchlorotin, ideally dibutyl dibromide Chlorotin, tetrachlorotin, etc. The ester compound coupling agent is ethyl formate, ethyl acetate, and butyl acetate—12 — This paper is in accordance with China National Standard (CNS) A4 (21〇'χ 297 public envy) 539713 A7 ------- -B7__ 5. Description of the invention (chemical esters, methyl propionate, phenyl acetate, ethyl benzoate, phenyl benzoate, etc., ideally ethyl acetate, ethyl benzoate. (Please read the notes on the back first (Fill in this page again) Coupling agents other than tin and esters are dibromomethane, dibromoethane, dibromopropane, vinyl chloride, dichloromethane, dichloropropane, dichlorobutane, etc. , Dichlorinated silane, trichlorinated silane, silane, methyl dichloromethane, dimethyl dichlorosilane, ethyl dichlorosilane, diethyl dichloride clay institute, Silicon dihalide compounds such as butyl dichlorosilane institute, hexyl chloride dichloride institute, dihexyl dichlorosilane, dibromosilane, methyl dibromosilane, dimethyl dibromosilane, divinylbenzene, divinylnaphthalene Diethylene aromatic vinyl compounds, such as diphenol-A, diphenol-AD, diphenol-F, and other epoxy compounds Acid chlorides, such as propionate chloride, adipic acid dichloride, etc., '1' 4chlorofluorenylbenzene, fluorenyl isocyanate, y-glycidoxypropyltrimethoxysilane, etc. (b) paragraph The amount of coupling agent used in the manufacture of the block copolymer is a metal compound (ideally an organic lithium compound) 〇 ~ about 0.3 m ο 1 ratio. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and (a) ~ ( b) Coupling content of the aromatic vinyl compound in the component 'g The monomer supply amount at each stage during the weekly polymerization, the ethylene coupling content of the conjugated diene and the chain distribution of the aromatic vinyl compound, according to the above-mentioned microstructure control agent. (A) ~ (b) The weight-average molecular weight of the components is based on the addition amount of the polymerization initiator, such as sec-butyllithium, and / or the addition of an affinity agent (such as dimethyldichlorosilane). Furthermore, the paper size of the conjugated diene portion of the conjugated diene and the block copolymer of the conjugated diene and aromatic vinyl of the present invention [(a) ~ (b) component] is applicable to the country of China Standard (CNS) A4 specification (210X297 mm 13 539713 A7 B7 V. Description of the invention (1) The 1 key can be added with hydrogen saturation. (Please read the notes on the back before filling this page.) Secondly, the (B) straight run asphalt used in this application is bitumen-based crude oil. The residue obtained after atmospheric distillation and steam or vacuum distillation. It is easy to dissolve with the components (a) to (b) of the block copolymer of the present invention, and it is easy to process and handle. Asphalt used in the present invention is straight-run asphalt It is better to use oxidized asphalt instead of straight-run asphalt. In addition, (B) straight-run asphalt is better if the penetration is 40 ~ 200. When the penetration is less than 40, the block copolymer will affect the asphalt. The dissolution time is longer, and the elongation tends to decrease. On the one hand, when it exceeds 2000, the rigidity and toughness tend to decrease. The weight ratio of the (A) block copolymer (composition) and (b) straight run asphalt printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is 2 ~ 15/98 ~ 85, and 3 ~ 13/97 ~ 8 7 Better. (A) When the weight ratio of the component is less than 2, the asphalt has no modification effect, the rigidity and toughness are insufficient, and the softening point and elongation are reduced. On the other hand, when it exceeds 15, it has sufficient rigidity and toughness and dissolves the asphalt. The time is significantly longer, and the melt viscosity of the composition is significantly increased, making processing and handling difficult. The (A) block copolymer (composition) of the present invention is usually used in a shape such as a granular shape, a crumb shape, or a powder shape. The bituminous composition of the present invention is generally produced by melting (B) straight-run bitumen at 140 ° to 190 ° C and adding the above-mentioned (A) block copolymer (composition) for mixing. Thirdly, the asphalt composition of the present invention can be used with silicon, talc, and carbonated paper. The Chinese paper standard (CNS) A4 specification (210X297 mm) 539713 A7 B7. 5. Description of the invention , Anti-aging agent, cross-linking agent, flame retardant and other additives. Also used as road laying can be added crushed stone. (Please read the precautions on the back before filling this page) Further, the asphalt composition of the present invention Can use other thermoplastic rubber or thermoplastic resins such as ethylene-butadiene latex, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, random polypropylene, 1 '2 polybutadiene, or ethylene -Polymers of propylene rubber, etc. At this time, the (A) block copolymer (composition) of the present invention can be mixed with other polymers mentioned above at an official ratio in advance, and then granulated and used. 6 · Examples The examples of the present invention are described in detail below, and the present invention is not a limited example. In the examples, parts and% are based on weight unless otherwise specified. In addition, the evaluations in the examples are as follows. Method to find out the characteristics of the block copolymer (1) Weight average molecular weight Printed by GPC device of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [using HLC — 8 0 2 0 type manufactured by Toyoichi (stock), column used (3 branches of Z0RBAX manufactured by DuPont and 3 branches of 300 S)]. Weight average molecular weight in terms of standard polystyrene. (2) Ethylene coupling content is determined by infrared absorption analysis device (PARKING ELMAER-15) CNS) A4 specification (210X297 mm) 539713 A7 —__ B7 5. Description of the invention (also 1 600 type) MORER 0 method to obtain the absorption intensity of 9 1 1 cm — 1. (Please read the precautions on the back before filling in (This page) (3) The content of affinity styrene is determined by the infrared absorption analysis device (PARKING ELMAER — 1 600 type) Moror method. The absorption intensity of 6 900 cm — 1 is obtained. (4) Aromatic vinyl compounds were determined by the method developed by Professor Benaka Akihiro Tanaka (Proceedings of the Polymer Society, Vol. 29, No. 7, page 2 05). The aromatic vinyl compounds were determined by the oxidative decomposition of ozone. Amount of chain (1) Solubility time of asphalt composition; method A printed by the Consumer Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs, Ministry of Economic Affairs, Method A. When preparing the asphalt composition, take a small amount of the contents of the mixture and apply it to the glass. On a piece, observe with a 400x optical microscope until the time when asphalt is separated from the block copolymer is not visible. (2) Solubility time; b method B method uses a small amount of content when preparing the asphalt composition The time until the solid particles of the block copolymer are not visible on the polyethylene terephthalate (Teflon) film. 16 — This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 539713 A7 B7 V. Description of invention (FREE (3) Rigidity and toughness (please read the precautions on the back before filling this page) Pavement test method manual "(shown in Japan in January, 1963, issued by the Japan Road Association). (4) Penetration, elongation, and softness are based on JIS KK 2207. (5) Storage stability at high temperature The prepared asphalt composition was poured into an aluminum container, and it was placed in an oven at 180 ° C under a nitrogen atmosphere for two weeks, and the asphalt composition before and after storage was measured by GPC. The molecular weight distribution of the middle block copolymer. The molecular weight retention rate is calculated based on the molecular weight distribution of the block copolymer in the asphalt composition before and after storage. The block copolymer is prepared by polymerizing 100 liters of stainless steel with a sandwich and a stirrer. After fully replacing the air with nitrogen by using a container, put in 50 kg of printed materials, printed by the Consumers' Cooperative of the Ministry of Economic Affairs and the Intellectual Property Bureau of the Ministry of Economic Affairs, and printed 1.9 kg of ethylene glycol diethyl ether, 1-5 kg of styrene. The content reached 40 ° C. Secondly, 9.0 g of sec-butyltin was added to start polymerization. After the styrene polymerization was completed, the contents were heated to 80 ° C while passing cold water, and the contents were added slowly in three equal portions. 8 _ 5 kg of 1,3-butadiene and 1 kg of styrene. After the polymerization of the B block is completed, an additional 1.5 kg of styrene is added to continue the polymerization. After the polymerization is approximately complete, dibromoethane is added as a coupling agent. 17 — This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 539713 A7 B7 ____ V. Description of the invention (4g alkane, react for 30 minutes. (Please read the notes on the back before filling this page) After the reaction 10 ml methanol was added, and after stirring for 10 minutes, the contents were taken out of the polymerizer, and 50 g of 2,6-di-tert-butyl-4-cresol (BΒT) antioxidant was added. The polymerization solution was stripped with steam, The obtained aqueous polymer was pulverized into crumbs by a pulverizer, and then dried by hot air at 80 ° C to obtain a styrene-butadiene block copolymer. The pitch composition was prepared by a penetration of 5 7 0 g = 7 0 Of straight run asphalt [6 0/8 0 manufactured by Kyodo Petroleum Corporation] and 30 g The styrene-butadiene block copolymer was mixed with a mixer [TK Special Homogeneous Mixer 10.0 0 0 0 rpm, manufactured by Japan Special Machinery & Chemical Industry Co., Ltd.] at 180 ° C to prepare an asphalt composition. Tables 1 to 2 show the results of evaluation of each characteristic. Examples 2 to 5, Comparative Examples 1 to 10 Example 2, Comparative Example 2 and Comparative Example 8 are examples in which a coupling agent is not used. 1, 3 Butadiene, sec-butyltin, B The amount of glycol diethyl ether printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was printed in the same manner as in Example 1 to prepare a block copolymer (composition) to prepare an asphalt composition Evaluate its performance. In addition, Example 5 was prepared in the same manner as in Example 1 except that the amount of ethylene glycol diethyl ether was changed, and the pitch composition was adjusted in the same manner as in Example 1 to evaluate its performance. Except for the above examples and comparative examples, block copolymers were prepared in accordance with the polymerization prescriptions described in Table 1, Table 3, and Table 4 in the same manner as in Example 1. (The composition of this paper applies the Chinese National Standard (CNS) A4 specification.) 210X297 mm) _ 7〇— 539713 A7 B7
五、發明説明（A )’與實施例1同樣調製瀝青組成物，評價其性能。 結果如表1〜6所示。 (請先閱讀背面之注意事項再填寫本頁) 由表2本發明所規定的瀝青組成物（實施例1〜5 ) ’已知對瀝青的溶解性時間較短，儲藏安定性已改善，顯 示良好的剛性、韌性、伸率、軟化點。 與此相比，表5〜表6比較例1其B段塊中共軛二烯 /苯乙烯重量比，及耦合苯乙烯含量明確的在本發明的範 圍外，剛性、韌性、軟化點惡化。 比較例2其聚苯乙烯段塊之M w、B段塊中共軛二烯 /苯乙嫌重量比，及親合苯乙烯含量係在本發明的範圍外 ’溶解性時間顯著延長、儲藏安定性惡化。 比較例3共軛二烯中之耦合乙烯含量及Β段塊中共軛 二烯/苯乙烯重量比，連結1〜4個單體單位的芳香族乙 烯的鎖鏈的比例，係在本發明的範圍以外，韌性、軟化點 惡化。 經濟部智慧財產局員工消費合作杜印製 比較例4共軛二烯中之耦合乙烯含量及Β段塊中共軛 二烯/苯乙烯重量比，係在本發明的範圍外，溶解性時間 延長、剛性、韌性、伸率、軟化點惡化，儲藏安定性亦惡 化。 比較例5共軛二烯中之耦合乙烯含量，係在本發明的 範圍以外，剛性、韌性、軟化點惡化。 比較例6共軛二烯中之耦合乙烯含量，（a ) / ( b )重量比係在本發明的範圍以外，溶解性、儲藏安定性惡 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） —巧一 539713 A7 B7 五、發明説明（☆ 比較例7耦合苯乙烯含量’係在本發明的範圍以外， 剛性、韌性、軟化點惡化。 比較例8耦合苯乙烯含量’係在本發明的範圍以外， 溶解性顯著惡化、韌性、伸率、儲藏安定性亦惡化。 比較例9因B段塊中不含共軛二烯’溶解性顯著惡化 ，儲藏安定性惡化。 比較例1 0因B段塊中斜度段塊數’係超出本發明的 範圍以外，剛性、韌性、軟化點惡化。 (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 -20 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 539713 A7 B7 五、發明説明（4 表1 實施例No. 1 2 3 4 5 聚合處方 (份/單體100份） 仲丁基鋰 0.08 0.07 0.1 0.08 正基鋰 0.06 二乙醚 0.015 丙醚 0.025 乙二醇二乙醚 0.015 0.01 0.01 添加單體重量比 第1階段苯乙烯 13 12 11.5 14 13 第2階段苯乙烯 6 8 4 10 6 第3階段丁二烯 68 68 73 62 68 第4階段苯乙烯 13 12 11.5 14 13 耦合劑種類 二溴 二溴 二甲二 二溴 乙烷 乙烷 氯桂院 乙烷 耦合劑添加量 0.03 0 0.03 0.03 0.03 (份/單體100份） (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（210X297公釐） 539713 A7 7 Β 五、發明説明（作 經濟部智慧財產局員工消費合作社印製 表2 實施例 1 2 3 4 5 嵌段共聚物的特性 聚苯乙烯段塊Mw(萬） 1.06 1.07 1.32 0.92 1.08 (Al，A2 部份） A-Β-As 部份 Mw(萬） 14.2 14.5 16.5 12.2 14.4 B中共軛二烯乙烯耦合含量(％) 28 28 38 19 28 B中共軛二烯/苯乙儒重量比 91.9/8.1 89.5/10.5 94.8/5.2 86.1/13.9 91.9/8.1 斜度段塊數 3 2 3 5 3 B中ST鎖鏈卜4所佔比例 27 37 21 41 26 B中ST鎖鏈卜2所佔比例 19 31 13 34 7 Αι—Β—Α2/(Αι—Β—Α2)ηΧ^Μ;ϋ 72/28 100/0 85/15 65/35 71/29 親合苯乙嫌含量 32 32 27 38 32 瀝青組成物的特性 嵌段共聚物的添加量； 3.5/ 3.5/ 3.5/ 3.5/ 3.5/ [(Α)/(Β)](重量比） 96.5 96.5 96.5 96.5 96.5 溶解時間(分ΧΑ法） 25 20 35 20 40 嵌段共聚物的添加量;[(Α)/(Β)](重量比） 5/95 5/95 5/95 5/95 5/95 溶解時間(分)(Β法） 18 14 16 16 20 IMU性(mPa · S) 32 35 29 28 31 韌性(mPa· S) 24 28 19 21 22 伸率(15°C，cm) 110 110 87 92 82 伸率(4°C，cm) 21 23 20 27 20 針入度(l/10mm) 41 41 40 42 41 軟化點(°C ) 81 76 82 82 82 儲藏安定性 83 75 83 81 60 (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 ) Α4規格（210Χ297公釐） -22 - 539713 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（20 表3 比較例N 〇. 1 2 3 4 5 聚合處方 (份/單體100份） 仲丁基鋰 0.08 0.04 0.09 0.05 0.1 正基鋰 四氫呋喃 一 7 0.01 乙二醇二乙醚 0.015 0.015 0.01 0.04 0.035 丙醚 添加單體重量比 第1階段苯乙烯 9 15.5 15 8.5 12 第2階段苯乙烯 2 12 2 15 8 第3階段丁二烯 80 57 68 68 68 第4階段苯乙烯 9 15.5 15 8.5 12 耦合劑種類 二溴 二溴 二溴 二溴 乙烷 乙烷 乙烷 乙烷 耦合劑添加量 0.04 0 0.04 0.02 0.06 (份/單體100份） (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（210X M7公釐） 23 539713 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（2)| 表4 實施例No. 1 2 3 4 5 聚合處方 (份/單體100份） 仲丁基鋰 0.07 0.04 0.07 0.08 正基鋰 0.07 四氫咲喃 一 7 W 一^乙赃 丙醚 乙二醇二乙醚 0.01 0.015 0.015 0.015 0.015 添加單體重量比 第1階段 12 8 18 16 13 第2階段 8 4 7 0 6 第3階段 68 80 57 68 68 第4階段 12 8 18 16 13 耦合劑種類 二甲二 二溴 二溴 二溴 氯硅院 乙烷 乙烷 乙烷 親合劑添加量 0.04 0.03 0 0.03 0.03 (份/單體100份） (請先閱讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -24 - 539713 A7 B7 五、發明説明（必 經濟部智慧財產局員工消費合作社印製 表5 比較例 1 2 3 4 5 嵌段共聚物的特性 聚苯乙烯段塊Mw(萬） 0.68 2.25 1.02 1.18 0.56 (Ai，A2 部份） Αι-Β- A2部份 Mw(萬） 8.8 22.1 11.3 22.6 7.5 B中共軛二烯乙烯耦合含量(％) 28 28 13 64 58 B中共軛二烯/苯乙烯重量比 97.6/2.4 82.6/17.4 97.1/2.9 81.9/18.1 89.5/10.5 斜度段塊數 3 3 3 3 3 B中ST鎖鏈1〜4所佔比例 12 54 B中ST鎖鏈卜2所佔比例 8 48 Αι-Β-Α2/(Αι-Β-Α2)ηΧ 重量比 65/35 100/. 70/30 70/30 52/48 親合苯乙烯含量 20 43 32 32 32 瀝青組成物的特件 嵌段共聚物的添加量； 3.5/ 3.5/ 3.5/ 3.5/ 3.5/ [(A)/(B)](重量比） 96.5 96.5 96.5 96.5 96.5 溶解時間(分XA法） 18 180 50 150 50 嵌段共聚物的添加量； 5/95 5/95 5/95 5/95 5/95 [(A)/(B)](重量比） 溶解時間(分XB法） 14 62 38 44 48 剛性(mPa· S) 19 29 27 21 18 韌性(mPa · S) 12 21 14 12 11 伸率(15°C，cm) 72 78 75 70 93 伸率(4°C，cm) 13 20 17 10 14 針入度(l/10mm) 44 38 42 40 42 軟化點(°C ) 64 75 76 68 62 儲藏安定性 82 15 35 28 85 (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（210X 297公釐） -25 539713 A7 B7 五、發明説明（壶 經濟部智慧財產局員工消費合作社印製 表6 實施例 6 7 8 9 10 嵌段共聚物的特件 聚苯乙烯段塊Mw(萬） 1.03 0.7 1.96 1.45 0.99 (A!，A2 部份） Αι - B-A2 部份 Mw(禹） 13.8 15.1 16.8 14.2 12.4 B中共軛二烯/苯乙烯重量比 89.5/10.5 95.2/4.6 89.1/10.9 100/0 91.9/8.1 斜度段塊數 3 3 3 0 10 B中ST鎖鏈卜4所佔比例 B中ST鎖鏈卜2所佔比例 Αι-Β-Α2/(Αι-B-A2)nX 重量比 35/65 65/35 100/0 72/28 72/28 親合苯乙烯含量 32 20 43 32 32 瀝青組成物的特性 嵌段共聚體的添加量； 3.5/ 3.5/ 3.5/ 3.5/ 3.5/ [(A)/(B)](重量比） 96.5 96.5 96.5 96.5 96.5 溶解時間(分XA法） 170 30 160 120 20 嵌段共聚的添加量； 5/95 5/95 5/95 5/95 5/95 [(A)/(B)](重量比） 溶解時間(分)(B法） 52 26 58 54 16 剛性(mPa· S) 27 17 25 26 17 韌性(mPa· S) 18 12 15 20 12 伸率(15°C，cm) 82 80 67 78 105 伸率(4°C，cm) 20 24 18 20 31 針入度(l/l〇mm) 41 46 38 42 44 軟化點fc ) 77 64 76 75 64 儲藏安定性 25 80 27 44 78 -“；未測定 (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（210X297公釐） 539713 A7 _ B7 __ 五、發明説明（2)l 7 .發明的效果 本發明的瀝青改質用嵌段共聚物（組成物），係對各 種直觀瀝青具優異溶解性，與傳統製品比較，僅微量即具 良好的溶解性。 又所得的瀝青組成物，在高溫下亦有良好的儲藏安定 性，特別是改質瀝青中聚合體的保留性良好。 更進一步，本發明瀝青改質用嵌段共聚物（組成物） ，將末端芳香族乙烯化合物聚合體予以低分子量化，所得 瀝青組成物的物性亦不降低，物性（剛性、韌性、伸率、 軟化點）與溶解性的平衡很良好。 因此，本發明的瀝青組成物適用於道路的敷設，防水 皮等。 (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 -27 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）5. Description of the invention (A) 'The pitch composition was prepared in the same manner as in Example 1 and its performance was evaluated. The results are shown in Tables 1 to 6. (Please read the precautions on the back before filling this page.) The asphalt composition specified in the present invention (Examples 1 to 5) is shown in Table 2. 'It is known that the solubility time to asphalt is short and the storage stability has been improved. Good rigidity, toughness, elongation and softening point. In contrast, Table 5 to Table 6 Comparative Example 1 shows that the conjugated diene / styrene weight ratio and the content of coupled styrene in the B-stage block are clearly outside the scope of the present invention, and the rigidity, toughness, and softening point are deteriorated. Comparative Example 2 The conjugated diene / styrene ratio in the M w and B blocks of the polystyrene block and the content of the affinity styrene are outside the range of the present invention. The dissolution time is significantly extended and the storage stability deterioration. Comparative Example 3 The content of the coupled ethylene in the conjugated diene and the weight ratio of the conjugated diene / styrene in the B block, and the ratio of the chain chains of the aromatic ethylene connecting 1 to 4 monomer units are outside the scope of the present invention. , Toughness and softening point deteriorate. The consumption cooperation of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs has produced the comparative ethylene content of the conjugated diene in Comparative Example 4 and the weight ratio of the conjugated diene / styrene in the B segment, which are outside the scope of the present invention, the solubility time is extended, Rigidity, toughness, elongation and softening point deteriorate, and storage stability also deteriorates. The coupling ethylene content in the conjugated diene of Comparative Example 5 is outside the range of the present invention, and the rigidity, toughness, and softening point are deteriorated. Comparative Example 6 The content of coupled ethylene in the conjugated diene, the (a) / (b) weight ratio is outside the scope of the present invention, and the solubility and storage stability of this paper are in accordance with the Chinese National Standard (CNS) A4 specification ( 210X297 mm)-Qiaoyi 539713 A7 B7 V. Description of the invention (☆ Comparative Example 7 Coupling styrene content is outside the scope of the present invention, rigidity, toughness, and softening point are deteriorated. Comparative Example 8 Coupling styrene content is at Outside the scope of the present invention, solubility is significantly deteriorated, toughness, elongation, and storage stability are also deteriorated. Comparative Example 9 Because the conjugated diene is not contained in the block B, the solubility is significantly deteriorated, and storage stability is deteriorated. Comparative Example 1 0Because the number of inclination segments in segment B is beyond the scope of the present invention, the rigidity, toughness, and softening point are deteriorated. (Please read the precautions on the back before filling out this page.) -20-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 539713 A7 B7 V. Description of the invention (4 Table 1 Example No. 1 2 3 4 5 Polymerization prescription (parts / 100 monomers) ) Sec-butyl lithium 0.08 0.07 0.1 0.08 N-lithium 0.06 Diethyl ether 0.015 Propyl ether 0.025 Ethylene glycol diethyl ether 0.015 0.01 0.01 Addition of monomer weight ratio of first stage styrene 13 12 11.5 14 13 Second stage styrene 6 8 4 10 6 Butadiene in the third stage 68 68 73 62 68 Styrene in the fourth stage 13 12 11.5 14 13 Type of coupling agent Dibromodibromodimethyldibromoethane ethane Chlorine coupling agent 0.03 0 0.03 0.03 0.03 (parts / 100 parts) (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies Chinese National Standard (CNS) A4 (210X297 mm) 539713 A7 7 Β V. Description of the invention (printed as a table 2 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Example 1 2 3 4 5 Characteristics of block copolymers Polystyrene blocks Mw (10,000) 1.06 1.07 1.32 0.92 1.08 ( Al, part A2) A-B-As part Mw (ten thousand) 14.2 14.5 16.5 12.2 14.4 Content of conjugated diene ethylene coupling in B (%) 28 28 38 19 28 Weight ratio of conjugated diene / styrene ethylbenzene in B 9 1.9 / 8.1 89.5 / 10.5 94.8 / 5.2 86.1 / 13.9 91.9 / 8.1 Number of slope segments 3 2 3 5 3 Proportion of ST chain chain 4 in B 27 37 21 41 26 Proportion of ST chain chain 2 in B 19 31 13 34 7 Αι—Β—Α2 / (Αι—Β—Α2) ηχ ^ Μ; ϋ 72/28 100/0 85/15 65/35 71/29 Asphalt content 32 32 27 38 32 Asphalt composition Characteristics of the addition amount of the block copolymer; 3.5 / 3.5 / 3.5 / 3.5 / 3.5 / [(Α) / (Β)] (weight ratio) 96.5 96.5 96.5 96.5 96.5 Dissolution time (point XA method) 25 20 35 20 40 Adding amount of block copolymer; [(Α) / (Β)] (weight ratio) 5/95 5/95 5/95 5/95 5/95 Dissolution time (minutes) (B method) 18 14 16 16 20 IMU (mPa · S) 32 35 29 28 31 Toughness (mPa · S) 24 28 19 21 22 Elongation (15 ° C, cm) 110 110 87 92 82 Elongation (4 ° C, cm) 21 23 20 27 20 Penetration (l / 10mm) 41 41 40 42 41 Softening point (° C) 81 76 82 82 82 Storage stability 83 75 83 81 60 (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) Α4 Specification (210 × 297 mm) -22-539713 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (20 Table 3 Comparative Example N 〇. 1 2 3 4 5 Polymerization prescription (parts / monomer 100 parts) sec-butyllithium 0.08 0.04 0.09 0.05 0.1 n-lithium tetrahydrofuran 7 0.01 ethylene glycol diethyl ether 0.015 0.015 0.01 0.04 0.035 Weight ratio of propylene ether added monomer 1st stage styrene 9 15.5 15 8.5 12 2nd stage styrene 2 12 2 15 8 3rd stage butadiene 80 57 68 68 68 4th stage styrene 9 15.5 15 8.5 12 Type of coupling agent Dibromodibromodibromodibromoethane Ethane Ethane coupling agent 0.04 0 0.04 0.02 0.06 (parts / 100 monomers) (Please read the precautions on the back before filling in this Page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210X M7 mm) 23 539713 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of Invention (2) | Table 4 Example No. 1 2 3 4 5 Polymerization prescription (parts / monomer 100 parts) sec-butyllithium 0.07 0.04 0.07 0.08 n-lithium 0.07 tetrahydrofuran-1 7 W- ^ ethyl propyl ether glycol diethyl ether 0.01 0.015 0.015 0.015 0.015 Weight ratio of monomer added Phase 1 12 8 18 16 13 Phase 2 8 4 7 0 6 Phase 3 68 80 57 68 68 Phase 4 12 8 18 16 13 Type of coupling agent Dibromochlorosilane institute ethane ethane ethane affinity agent addition amount 0.04 0.03 0 0.03 0.03 (parts / monomer 100 parts) (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards ( CNS) A4 specification (210X 297 mm) -24-539713 A7 B7 V. Description of the invention (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 5 Comparative Example 1 2 3 4 5 Characteristics of block copolymer polystyrene Segment Mw (million) 0.68 2.25 1.02 1.18 0.56 (Ai, A2 part) Ai-B- A2 part Mw (million) 8.8 22.1 11.3 22.6 7.5 Content of conjugated diene ethylene in B (%) 28 28 13 64 58 Conjugated diene / styrene weight ratio in B 97.6 / 2.4 82.6 / 17.4 97.1 / 2.9 81.9 / 18.1 89.5 / 10.5 Number of slope segments 3 3 3 3 3 Proportion of ST chain 1 ~ 4 in B 12 54 B Medium ST Proportion of Chain Chain 2 8 48 Αι-Β-Α2 / (Αι-Β-Α2) ηχ Weight ratio 65/35 100 /. 70/30 70/30 52/48 Affinity styrene content 20 43 32 32 32 Addition amount of special block copolymer of asphalt composition; 3.5 / 3.5 / 3.5 / 3.5 / 3.5 / [(A) / (B)] (weight ratio) 96.5 96.5 96.5 96.5 96.5 Dissolution time (XA method) 18 180 50 150 50 Addition amount of block copolymer; 5/95 5/95 5/95 5/95 5/95 [ (A) / (B)] (weight ratio) Melting time (XB method) 14 62 38 44 48 Rigidity (mPa · S) 19 29 27 21 18 Toughness (mPa · S) 12 21 14 12 11 Elongation (15 ° C, cm) 72 78 75 70 93 Elongation (4 ° C, cm) 13 20 17 10 14 Penetration (l / 10mm) 44 38 42 40 42 Softening point (° C) 64 75 76 68 62 Storage stability Property 82 15 35 28 85 (Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) -25 539713 A7 B7 V. Description of Invention Printed by the Consumer Property Cooperative of Intellectual Property Bureau. Table 6 Example 6 7 8 9 10 Special parts of block copolymer Polystyrene block Mw (10,000) 1.03 0.7 1.96 1.45 0.99 (Part A !, A2) Αι-B- A2 Part Mw (Yu) 13.8 15.1 16.8 14.2 12.4 Conjugated diene / styrene weight ratio in B 89.5 / 10.5 95.2 / 4.6 89.1 / 10.9 100/0 91.9 / 8.1 Block number of slope segment 3 3 3 0 10 Proportion of ST chain chain in B 4 ST chain chain in B 2 Percentage Al-B-A2 / (Al-B-A2) nX Weight ratio 35/65 65/35 100/0 72/28 72/28 Affinity styrene content 32 20 43 32 32 Characteristics of asphalt composition Addition amount of block copolymer; 3.5 / 3.5 / 3.5 / 3.5 / 3.5 / [(A) / (B)] (weight ratio) 96.5 96.5 96.5 96.5 96.5 Dissolution time (XA method) 170 30 160 120 20 Block Addition amount of copolymerization; 5/95 5/95 5/95 5/95 5/95 [(A) / (B)] (weight ratio) Dissolution time (minutes) (B method) 52 26 58 54 16 Rigidity (mPa · S) 27 17 25 26 17 Toughness (mPa · S) 18 12 15 20 12 Elongation (15 ° C, cm) 82 80 67 78 105 Elongation (4 ° C, cm) 20 24 18 20 31 Penetration (l / l〇mm) 41 46 38 42 44 Softening point fc) 77 64 76 75 64 Storage stability 25 80 27 44 78-"; not determined (please read the precautions on the back before filling this page) This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) 539713 A7 _ B7 __ V. Description of the invention (2) l 7. Invention Effect The block copolymer (composition) for asphalt modification of the present invention has excellent solubility in various visual asphalts. Compared with conventional products, it has good solubility in a small amount. The obtained asphalt composition also has good storage stability at high temperatures, and in particular, the retention of the polymer in the modified asphalt is good. Furthermore, the block copolymer (composition) for asphalt modification of the present invention reduces the molecular weight of the terminal aromatic vinyl compound polymer, and the physical properties (rigidity, toughness, elongation, Softening point) is well balanced with solubility. Therefore, the asphalt composition of the present invention is suitable for road laying, waterproofing, and the like. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -27-This paper size applies to China National Standard (CNS) A4 (210X 297 mm)