TWI224125B

TWI224125B - Block copolymer

Info

Publication number: TWI224125B
Application number: TW91100315A
Authority: TW
Inventors: Keiichi Toda; Yukinori Nakamichi
Original assignee: Japan Elastomer Co Ltd
Priority date: 2000-07-14
Filing date: 2002-01-11
Publication date: 2004-11-21
Also published as: JP2002030126A

Abstract

The present invention provides an asphalt composition having a high softening point and excellent extensibility, excellent in the balance between physical properties, such as mechanical strengths, and processability and excellent in storage stability. A composition used for modifying an asphalt is a block copolymer composition consisting of 100-200 wt.% block copolymer (A) which consists of polymer blocks comprising mainly at least two aromatic monoalkenyl compounds and polymer blocks comprising mainly at least one conjugated diene and 0-80 wt.% block copolymer (B) which consists of polymer blocks comprising mainly one aromatic monoalkenyl compound and polymer blocks comprising mainly one conjugated diene and of which the molecular weight is 1/3 to 2/3 of that of the block copolymer (A), wherein (1) the molecular weight distribution of polymer blocks comprising mainly aromatic monoalkenyl compounds, in terms of the ratio of the height (H) of a peak to the half width (W) i.e., (H/W) on the chromatogram obtained by GPC, is 5 to 20, (2) the content (BS) of polymer blocks comprising mainly aromatic monoalkenyl compounds is 10-48 wt.%, (3) the weight-average molecular weight (Mw) is 100,000 to 500,000, and (4) the content of aromatic alkenyl compounds (TS-BS) obtained by subtracting the content (BS) of polymer blocks comprising mainly aromatic monoalkenyl compounds from the total content (TS) of aromatic monoalkenyl compounds is 2-30 wt%.

Description

1224125 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) 本發明係有關單脂嫌基芳香族化合物一共軛二烯嵌段共聚物組成物者。特別是提供一種具有特定結構之嵌段共聚物組成物及以此嵌段共聚物組成物做爲改質劑之具有高軟化點、良好延伸度者，更具有良好的機械性強度等物性以及與加工性均衡性均良好，更具良好貯存安定性之瀝青組成物者，例如：適用於廢水舖裝用之瀝青組成物者。先行技術中，瀝青組成物被廣泛用於道路舖裝、防水薄片、遮音薄片、屋頂等用途者。此時，於瀝青添加各種聚合物，嘗試改良其性質者。做爲其聚合物之具體例者如 :乙烯-醋酸乙烯酯共聚物、乙烯-乙基丙烯酸酯共聚物、橡膠乳膠、丁二烯與乙烯芳香族烴基所成之嵌段共聚物等被使用之。惟，乙烯-醋酸乙烯酯共聚物、乙烯一乙基丙烯酸酯共聚時，其瀝青組成物之低溫特性差，冬天時產生龜裂不理想。且，延伸特性亦差，因此，粘結力（Tenacity )亦不良，特別是舖裝道路時，骨材之掌握性不良。又，橡膠乳膠時，爲使乳膠中水份蒸發，務必進行加熱等經濟面或流程上之問題產生。近來，道路通行車輛的增加、或伴隨高速化，造成多重交通道路、高速道路而被強烈要求良好的強度，維持耐磨性，更以改良排水性、減低躁音爲目的，亦被強烈要求爲進丫丁局空隙率之舖裝道路的局性能歷青組成物（排水舖裝用瀝青粘合劑）、被要求一種更高軟化點、韌性、粘結力等機械性強度。 (請先閱讀背面之注意事項再填寫本頁) I·裝· 、11 國國家標準（CNS ) A4規格（210 X297公釐） -4 - 1224125 A7 ___B7 五、發明説明（2) (請先閱讀背面之注意事項再填寫本頁) 更於石油精製中精製度提昇之同時降低直餾瀝青之品質後降低瀝青組成物之性能，更長期保存瀝青組成物後產生貯存時安定性等新問題點出現。貯存時安定性問題係指其性能，如：軟化點整體下降，且，上層與下層其性能出現差異之相分離等現象出現。該現象至今仍未被解決，呈大問題者。爲解決該問題，嘗試藉由提高上述嵌段共聚物之分子量後進行改良者。惟，單僅提高分子量，雖改善機械性強度，卻提昇熔融粘度，明顯犧牲了道路舖裝等加工性問題。又，針對貯存安定性若提高分子量將大幅降低安定性，安全無改善效果。做爲更具高軟化點，更高性能之瀝青組成物者，被提出添加某特定分子結構之嵌段共聚物之瀝青組成物。（特開平6 - 0 4 1 4 3 9號公報）。此組成物雖爲兼具高軟化點與針入度、延伸度、良好耐寒性、加工性之組成物者，卻仍無法改善貯存安定性，未能用於貯存安定性之需求者。經濟部智慧財產局員工消費合作社印製如此，添加先行各聚合物之瀝青組成物完全無法同時滿足做爲其特性所需之高軟化點、針入度、延伸度、加工性相互之高度均衡性，更不具有良好貯存安定性者，因此被強烈要求此瀝青組成物各需求點。本發明係以提供解決先行瀝青組成物之課題’ 一種先行技術所無法取得之高物性，如：高軟化點與高延伸度、高機械性強度等之發現，且，與加工性呈良好之高度均衡國國家標準（CNS) A4規格（210x297公I) ^" 1224125 A7 _____B7 _ 五、發明説明（3) 及爲提供此性 '更具有良好的貯存安定性之瀝青組成物瀝青組成物之嵌段共聚物組成物爲目的者。 (請先閲讀背面之注意事項再填寫本頁) <發明開示> 本發明者爲開發具有上述性能之瀝青組成物，進行精密硏討後結果發現一種具有某極端受限之特定範圍結構之脂烯基芳香族化合物與共軛二烯相互之嵌段共聚物含於特定範圍中之瀝青組成物顯示具有極良好性能，而達成該目的，進而完成本發明。亦即，本發明係如下者。 1 )以單脂烯基芳香族化合物爲主體之至少2個聚合物嵌段、與以共軛二烯爲主體之至少1個聚合物嵌段所成之1 Ο 0〜2 0重量％嵌段共聚物（A )與，以單脂烯基芳香族化合物爲主體之至少1個聚合物嵌段與以共軛二烯爲主體之至少1個聚合物嵌段所成、其頂點分子量相當於嵌段共聚物（A)之1/3〜2/3之0〜8 0重量％嵌段共聚物（B )所成之嵌段共聚物組成物中：經濟部智慧財產局員工消費合作社印製 (1 )以單脂烯基芳香族化合物做爲主體之聚合物嵌段具有於G P C取得之層析法頂點高度（η )與半値寬度 (W)之比（H/W)爲5〜2 0分子量分佈者； (2 )以單脂烯基芳香族化合物爲主體之聚合物嵌段含量（B S )爲嵌段共聚物（A )及（Β )總重量之1 〇重量％〜4 8重量％者； (3 )嵌段共聚物（A )及（β )總重量平均分子量 -6 - 本^_^^^國國家標準（匚奶）八4規格（210父297公釐） 1224125 A7 B7 五、發明説明（4) (Mw)爲10萬〜50萬者； (請先閱讀背面之注意事項再填寫本頁} (4 )嵌段共聚物（A )及（B )總體中，由總結合脂烯基芳香族化合物之含量（T S )減去以單脂烯基芳香族化合物爲主體之聚合物嵌段含量（B S )之脂烯基芳香族化合物含量（TS - B S)爲2〜3 0重量％之嵌段共聚物組成物。 2 )由9 8〜2 0重量％之嵌段共聚物（A )與2〜 8 0重量％之嵌段共聚物（b )所成之前項（1 )所載之嵌段共聚物組成物。 3 )總結合脂烯基芳香族化合物之含量（τ S )爲 1 〇〜5 0重量％ ;以單脂烯基芳香族化合物爲主體之聚合物嵌段頂點分子量爲5000〜50， 000;嵌段共聚物（A)及（B)之全體中乙烯結合含量爲8重量％〜 7 〇重量％ ;以及以靜態熱機械試驗分析（Τ Μ A )所測定嵌段共聚物組成物之軟化溫度爲8 0 〇C〜1 3 0 °C者，刖項1 )所載之嵌段共聚物組成物。經濟部智慧財產局員工消費合作社印製 4 )單脂烯基芳香族化合物爲苯乙烯者，前項3 )所載之嵌段共聚物組成物。 5 )前項1 )〜4 )中任一項所載之嵌段共聚物組成物2〜3 〇重量份與7 0〜9 8重量份之瀝青所成之瀝青組成物。 <胃明實施之最佳形態> 以下，詳細說明本發明。 §咖家鮮（CNS ) A4規格 (210X297公釐） 1224125 五、發明説明（s) 構成本發明（A )成份者係由以單脂烯基物做爲主體之至少2個聚合物嵌段與以共輕二之至少1個聚合物嵌段所成之嵌段共聚物者。以單脂烯基芳香族化合物做爲主體之聚合含有5 0重量％以上之單脂烯基芳香族化合物單脂烯基芳香族化合物做爲主成份之聚合物嵌以共軛二烯做爲主體之聚合物嵌段係指含有5 上之共軛二烯者，實質上以共軛二烯做爲主成嵌段者。做爲構成本發明嵌段共聚物組成物中之單族化合物者如：苯乙烯、對-曱基苯乙烯、第乙烯甲基苯乙烯苯例者，其中又以苯乙烯爲較佳者。此等單量體，亦可倂用2種以上者。芳香族化合烯做爲主體物嵌段係指，實質上以段者。又， 0重量％以份之聚合物脂烯基芳香 3級丁基苯等單量體之可單獨使用 (請先閱讀背面之注意事項再填寫本頁) C.1224125 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (1) The present invention relates to the composition of a monomeric conjugated diene block copolymer. In particular, to provide a block copolymer composition having a specific structure, and those having a high softening point and good elongation using the block copolymer composition as a modifier, have better physical properties such as mechanical strength, and the like Those who have good processability and well-balanced asphalt composition with better storage stability, such as those who are suitable for asphalt composition for wastewater paving. In the prior art, the asphalt composition is widely used for road paving, waterproof sheet, sound-proof sheet, roof, and the like. At this time, various polymers are added to the asphalt to try to improve its properties. Specific examples of the polymer are: ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, rubber latex, block copolymer of butadiene and ethylene aromatic hydrocarbon group, etc. are used. . However, when ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate are copolymerized, the low-temperature characteristics of the asphalt composition are poor, and cracks are not ideal in winter. In addition, the elongation characteristics are also poor, so the adhesion (Tenacity) is not good, especially when paving the road, the mastery of the aggregate is poor. In addition, in the case of rubber latex, in order to evaporate water in the latex, it is necessary to perform economical or process problems such as heating. Recently, the increase of road traffic or the increase in speed has caused multiple traffic roads and highways to be required to have good strength and maintain abrasion resistance. The purpose of improving drainage and reducing noise is also strongly demanded. The local performance of paved roads with a porosity of Jinyading Bureau is considered as a green composition (asphalt binder for drainage pavement), which requires a higher mechanical strength such as softening point, toughness, and adhesion. (Please read the precautions on the back before filling this page) I · Installation · 11 national standards (CNS) A4 specifications (210 X297 mm) -4-1224125 A7 ___B7 V. Description of invention (2) (Please read first Note on the back, please fill in this page again) It is more important to improve the refinement system of petroleum refining and reduce the quality of straight-run asphalt while reducing the performance of asphalt composition, and new problems such as stability during storage after long-term storage of asphalt composition appear . Stability problems during storage refer to its performance, such as: the overall softening point decreases, and the phase separation of the performance difference between the upper and lower layers appears. This phenomenon has not been resolved so far, and it is a major problem. In order to solve this problem, an attempt has been made to improve the molecular weight of the block copolymer. However, increasing the molecular weight alone, although improving the mechanical strength, increases the melt viscosity, which obviously sacrifices workability problems such as road paving. In addition, if storage molecular stability is increased, increasing the molecular weight will significantly reduce the stability, and there will be no improvement in safety. As an asphalt composition with higher softening point and higher performance, it is proposed to add an asphalt composition with a block copolymer of a specific molecular structure. (Japanese Patent Application Laid-Open No. 6-0 4 1 4 3 9). Although this composition is a combination of high softening point and penetration, elongation, good cold resistance, and processability, it still cannot improve storage stability and cannot be used for those who require storage stability. This is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The addition of the asphalt composition of the leading polymers cannot meet the high softening point, penetration, elongation, and processability required for its characteristics. In addition, those who do not have good storage stability are strongly requested for each demand point of this asphalt composition. The present invention is to provide a solution to the problem of advanced asphalt composition. A kind of advanced physical properties that cannot be obtained by advanced technology, such as the discovery of high softening point, high elongation, high mechanical strength, etc., and it has a high degree of processability. National Standard of the Balanced Country (CNS) A4 specification (210x297 male I) ^ " 1224125 A7 _____B7 _ V. Description of the invention (3) and the asphalt composition embedded in the asphalt composition to provide this property, which has better storage stability The segment copolymer composition is intended. (Please read the precautions on the back before filling in this page) < Invention > In order to develop an asphalt composition with the above properties, the inventor conducted a detailed discussion and found that it has a structure with a specific range that is extremely restricted. The bituminous composition in which the block copolymer of the aliphatic alkenyl aromatic compound and the conjugated diene with each other is contained in a specific range exhibits extremely good properties, and this object is achieved, thereby completing the present invention. That is, the present invention is as follows. 1) 100 to 20% by weight of a block composed of at least two polymer blocks composed mainly of a monoalkenyl aromatic compound and at least one polymer block composed mainly of a conjugated diene. The copolymer (A) is composed of at least one polymer block composed mainly of a monoalkenyl aromatic compound and at least one polymer block composed mainly of a conjugated diene. Segment copolymer (A) from 1/3 to 2/3 of 0 to 80% by weight of block copolymer (B) In a block copolymer composition: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ( 1) The polymer block with a monoalkenyl aromatic compound as the main body has a ratio (H / W) of the apex height (η) of the chromatography obtained from GPC to the half-width (W) of 5 to 20 Distributors; (2) those whose monoblock alkenyl aromatic compound is the main polymer block content (BS) is 10% to 48% by weight of the total block copolymers (A) and (B) ; (3) Block copolymers (A) and (β) total weight average molecular weight -6-this ^ _ ^^^ national national standard (milk milk) 8 4 specifications (210 father 297 mm) 1224 125 A7 B7 5. Description of the invention (4) (Mw) is 100,000 ~ 500,000; (Please read the notes on the back before filling this page} (4) Block copolymers (A) and (B) , The content of the aliphatic alkenyl aromatic compound (TS-BS) from the content of the total bound aliphatic alkenyl aromatic compound (TS) minus the polymer block content (BS) of the monoaliphatic aromatic compound as the main component is 2 to 30% by weight of the block copolymer composition. 2) It is composed of 98 to 20% by weight of the block copolymer (A) and 2 to 80% by weight of the block copolymer (b). The block copolymer composition contained in the foregoing item (1). 3) The content (τ S) of the total bound aliphatic alkenyl aromatic compound is 10 to 50% by weight; the peak molecular weight of the polymer block mainly composed of the monoaliphatic aromatic compound is 5000 to 50,000; The ethylene binding content of the segment copolymers (A) and (B) as a whole is 8 wt% to 70 wt%; and the softening temperature of the block copolymer composition measured by static thermomechanical test analysis (TMA) is 80 ° C to 130 ° C, the block copolymer composition contained in item 1). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 4) The monoalkenyl aromatic compound is styrene, the block copolymer composition contained in the preceding paragraph 3). 5) Asphalt composition composed of 2 to 300 parts by weight and 70 to 98 parts by weight of the asphalt copolymer as described in any one of the items 1) to 4) above. < Best mode for implementing Weiming > The present invention will be described in detail below. § Coffee House Fresh (CNS) A4 specification (210X297 mm) 1224125 V. Description of the invention (s) The components of the invention (A) are composed of at least 2 polymer blocks with monoaliphane as the main component and A block copolymer made of at least one polymer block in total. Polymers with monoalkenyl aromatic compounds as the main polymer Polymers containing more than 50% by weight of monoalkenyl aromatic compounds Monoalkenyl aromatic compounds as the main component Polymers with conjugated diene as the main component The polymer block refers to those containing 5 or more conjugated diene, and the conjugated diene is mainly used as the main block. Examples of the single-group compound constituting the block copolymer composition of the present invention include styrene, p-fluorenylstyrene, and vinylidenemethylstyrene. Among them, styrene is preferred. For these single quantities, two or more kinds can also be used. Aromatic olefins as the main block refers to those that are essentially segmented. In addition, 0% by weight of the polymer such as aliphatic alkenyl aromatic tertiary butylbenzene and the like can be used alone (please read the precautions on the back before filling this page) C.

、1T 又，做爲共烯之例者如 3 — 丁異戊二烯、2 ，3 —二甲基一 1 ，3 — 丁二烯、間一丁基—1 ，3 -辛二烯、苯基—1 ，3 — 丁戊經濟部智慧財產局員工消費合作社印製體例者，其中又以1 ，3 -丁及異烯爲較佳者此等單量體可單獨使用，亦可倂用2種以上者。又，構成本發明（B )成份者係由以單脂化合物爲主體之至少1個聚合物嵌段與以共軛之至少1個聚合物嵌段所成之嵌段共聚物者。以單體脂烯基芳香族化合物爲主體之聚合含有5 0重量％以上之單體脂烯基芳香族化合烯基芳香族二烯爲主體物嵌段係指物者，實質本哪賴萝國家標準（〇奶）六4規格（210乂297公釐） -8- 1224125 A7 _B7 五、發明説明（6) (請先閱讀背面之注意事項再填寫本頁) 上以單脂烯基芳香族化合物爲主成份之聚合物嵌段者。又，以共軛二烯爲主體之聚合物嵌段係指含有5 0重量％以上之共軛二烯者，實質上以共軛二烯爲主成份之聚合物嵌段者。做爲單脂烯基芳香族化合物者如··苯乙烯、對-甲基苯乙烯、第3級丁基苯乙烯、α-甲基苯乙烯、1 ，1一二苯基乙烯等單量體例如，其中又以苯乙烯爲較佳者。此等單量體可單獨使用，亦可倂用2種以上者。另外，做爲共軛二烯者如：1 ，3 -丁二烯、異戊二烯、2，3 -二甲基一 1 ，3 — 丁二烯 '間戊二烯、3 - 丁基一 1 ，3 -辛二烯、苯基一 1 ，3 -丁二烯等單量體之例，其中又以1 ，3 - 丁二烯及異戊二烯爲較佳者。此等單量體可單獨或2種以上倂用之。構成本發明（Β )成份之凝膠滲透層析法（G p c ) •所測定之頂點分子量由其凝聚力、瀝青組成物之軟化點、延伸度、熔融粘度之觀點視之，爲相同測得（A )成份之頂點分子量的1 / 3〜2/ 3範圍者。經濟部智慧財產局員工消費合作社印製構成本發明（A )成份由以單脂烯基芳香族化合物做爲主體之聚合物嵌段凝聚力之觀點視之，單脂儲基芳香族化合物爲主體之2個聚合物嵌段與以共軛二烯爲主體之聚合物嵌段相互3個嵌段所成者宜。4個以上嵌段於未造成性能劣化下結合者尙無妨。本發明（B )成份由其單脂烯基芳香族化合物之凝聚力觀點視之，以單脂烯基芳香族化合物爲主體之聚合物嵌國家標準（〇邵）八4規格（210'乂297公釐） -9 - — 經濟部智慧財產局員工消費合作社印製 1224125 A7 _B7_ 五、發明説明（7) 段與以共軛二烯爲主體之聚合物嵌段之2個嵌段所成者宜。3個以上嵌段於不造成性能劣化下結合者無妨。本發明嵌段共聚物組成物中（A )成份之含量爲 100〜20重量％，（B)成份之含量爲〇〜80重量 %者。由取得瀝青組成物之軟化點、韌性、粘結力等觀點視之，理想範圍之（B )成份含量以6 0重量％以下者宜，更佳者爲4 0重量％以下者。本發明嵌段共聚物組成物中（A )成份之含量以9 8 〜20重量％者宜，（B)成份之含量爲2〜80重量％者。（B)成份之含量又以5〜60重量％爲較佳，更以 1 ◦〜4 0重量％更佳。構成本發明嵌段共聚物組成物中以單脂烯基芳香族化合物爲主體之聚合物嵌段分子量分佈由其G P C取得之層析法頂點高度（Η )與半値寬度（W )之比（H /W )、單脂烯基芳香族化合物聚合物嵌段凝聚力、瀝青組成物之軟化點、韌性、粘結力等性能之觀點視之，務必爲2 〇以下者。較佳者之Η/W爲7〜1 9、更佳者爲9〜1 7者〇構成本發明之嵌段共聚物組成物中以單脂烯基芳香族化合物爲主體之聚合物嵌段之含量（B S )由其單脂;)：希基芳香族化合物聚合物嵌段之凝聚力觀點視之，以1 〇重量 %以上者宜’由取得瀝青組成物之相分離安定性、軟化點之經時變化等貯存安定性之觀點視之，務必爲4 8重量％以下者。較佳者爲1 3〜45重量％，更佳者爲1 5〜本紙爾應國家標準（〇奶）八4規格（210'乂297公釐) 「1〇 - ' (請先閱讀背面之注意事項再填寫本頁) •裝· 、1Τ 1224125 A7 B7 五、發明説明（8) 4 0重量％。 (請先閲讀背面之注意事項再填寫本頁) 本發明中嵌段共聚物（A )及（B )總體之重量平均分子"量由其取得瀝青組成物之軟化點、韌性、粘結力等觀點視之’爲1 0萬以上者宜，由瀝青之溶解性觀之，務必爲5 0萬以下者。較佳者爲1 2萬〜5 0萬，更佳者爲 1 4萬〜3〇萬。本發明嵌段共聚物中由總結合脂烯基芳香族化合物之含旺（T S )減去以單脂烯基芳香族化合物爲主體之聚合物嵌段之含量（B S )後之脂烯基芳香族化合物含量（ T S - B S )由取得瀝青組成物之貯存安定性觀點視之爲 2重量％以上、軟化點、韌性、粘結力等之改質效果視之 ’務必爲3 0重量％以下者。較佳者爲3〜2 0重量％，更佳者爲5〜18重量％。經濟部智慧財產局員工消費合作社印製本發明嵌段共聚物中總結合單脂烯基芳香族化合物之含量（T S )由其以單脂烯基芳香族化合物爲主體之聚合物嵌段之凝聚力，所取得瀝青組成物之韌性、粘結力等機械強度之觀點視之爲1 0 %以上者，由取得瀝青組成物之貯存安定性、低溫特性、瀝青之溶解速度等觀點視之，以 5〇％以下者宜。理想之T S範圍以1 · 5〜4 5重量％，更佳者爲2 0〜4 0重量％。本發明中嵌段共聚物之以單脂烯基芳香族化合物爲主體之聚合物嵌段頂點分子量由其取得瀝青組成物之軟化點、韌性、粘結力等性能之觀點視之爲5 0 0 0以上者，由瀝青之溶解性，取得瀝青組成物之貯存安定性等觀點視之 -11 - 本國國家標準（CNS ) M規格（2丨〇><297公釐） 1224125 A7 B7 五、發明説明（_ 爲5〇〇〇〇以下者宜。理想範圍爲7000〜4000 〇、更佳者爲9000〜30000。 (請先閲讀背面之注意事項再填寫本頁) 又，裝置於本發明嵌段共聚物中之共軛二烯中，1 ， 2結合之比例，即乙烯結合含量由其取得瀝青組成物之軟化點觀點視之以8重量％以上者宜，由嵌段共聚物組成物之熱安定性，取得瀝青組成物之低溫特性，熱安定性之觀點視之以7 0重量％以下者宜。理想範圍之乙烯結合含量爲1 5〜6 0重量％，更佳者爲20〜5 0重量％。更於本發明嵌段共聚物組成物之靜態熱機械試驗機（ Τ Μ A )所計測之軟化溫度、凝聚力、取得之瀝青組成物軟化點、韌性、粘結力等性能之觀點視之，爲8 0 °C以上者宜，由取得瀝青組成物之熔融粘度、與瀝青之互溶性觀點視之，爲1 3 0 °C以下者宜。理想範圍者爲8 5〜 1 2 5 °C，更佳者爲9 0〜1 2 0 t：。經濟部智慧財產局員工消費合作社印製本發明嵌段共聚物中以單體單位連接1〜8個脂烯基芳香族化合物之單體鏈鎖由其取得瀝青組成物之貯存安定性觀點視之爲總脂烯基芳香族化合物之3重量％者宜，由軟化點等性能觀之，以含有4 0重量％以下之比例者宜。理想範圍以5〜3 5 %者，更佳者爲9〜3 0 %。以此單體單位連接1〜8個脂烯基芳香族化合物之單體鏈鎖其實質上形成於以共軛二烯爲主體之嵌段中者。例如：聚合以共I® —^傭爲主體之嵌段時’將共輒一^嫌置入反應容器後，緩緩加入單脂烯基芳香族化合物、或依不同情況下，於任意化劑之存在下，將共軛二烯與脂烯基芳香族本紙㈣ J國家標準（CNS ) A4規格（210X297公釐） 12 1224125 A7 ___B7_ 五、發明説明（和 (請先閱讀背面之注意事項再填寫本頁) 化合物同時置入反應容器後，依情況更同時追加共輥二烯 ’進f了聚合後於以共軛一烯做爲主體之聚合物嵌段中可形成以單體單位連接1〜8個脂燃基芳香族化合物之單體鏈鎖者。本發明所使用之嵌段共聚物組成物之改質瀝青組成物由其瀝青改質效果' 熔融粘度等觀點視之，以2〜3 0重里v份之肷段共聚物組成物與7 0〜9 8重量份歷青所成者宜。較佳者以前者2〜1 5重量份，後者8 5〜9 8重量份者，更佳者爲前者4〜1 2重量份，後者8 8〜9 6重量份者所配合而成。本發明所使用之瀝青並無特別限定，慣用之瀝青如：直餾瀝青、（部份）氧化瀝青、及此等混合物等例。理想者以針入度4 0〜1 2 0之直餾瀝青、針入度1 〇〜3 〇之氧化瀝青及此等混合物例者。經濟部智慧財產局員工消費合作社印製構成本發明（A )成份者如不活性烴基溶媒中，以有機鋰化合物做爲聚合啓發劑聚合苯乙烯後，形成聚合物嵌段後’再聚合丁一烯之同時緩緩加入苯乙儲之聚合方法、或聚合丁 —^細/本乙細之混合物方法，不同情況中，於極性化合物之存在下，進行該方法，依狀況追加共軛二烯之該方法後，形成丁二烯-苯乙烯共聚物嵌段後，再度進行聚合苯乙烯，不同情況下，更重覆進行該操作後被取得。此時，G P C中頂點分子量以標準聚苯乙烯換算爲5〜5 0萬之範圍者，控制有機鋰化合物量後被調整之。形成丁二烯-苯乙烯共聚物嵌段時，藉由上述所載方法以單體單 mfn 中國國家標準（CNS ) A4規格（210X297公釐） 13 __ B7 五、發明説明（1)1 位連接1〜8個脂烯基芳香族化合物之單鏈鎖實質上以共軛二烯爲主體於嵌段中被形成之。又，依情況，構成本發明（B )成份者，如不活性烴基溶媒中，以有機鋰化合物做爲聚合啓發劑聚合苯乙烯後 ’形成苯乙烯聚合物嵌段，再聚合丁二烯之同時緩緩添加苯乙烯進行聚合之方法、或聚合丁二烯/苯乙烯之混合物方法，不同情況，存在極性化合物下進行該方法 > 依情況 ’再追加共軛二烯之聚合方法後，形成丁二烯-苯乙烯共聚物嵌段，不同情況下，重覆上述操作後被取得。此時， G > C中頂點分子量於（A )成份頂點分子量之1 / 3〜 2 / 3倍範圍下，控制有機鋰化合物量後被調製之。形成丁二烯-苯乙烯共聚物嵌段時，藉由該方法後，以單體單位連接1〜8個脂烯基芳香族化合物之單鏈鎖實質上以共軛二烯爲主體於嵌段中被形成之。 (A )成份及（B )成份於反應結束後，添加水、醇 '酸等之後使活性料失活，依情況以所定組成進行摻混各成份溶液後，進行蒸氣脫模後可取得。由構成本發明之（A )成份及（B )成份所成之嵌段共聚物亦可藉由不同於上述方法者取得。亦即，與上述相同方法下，聚合（B )成份後，於聚合系內使適當之偶合劑針對聚合啓發劑，藉由所定量之添加後所取得之共聚物生成物做爲（A )成份後，於同一反應系內取得所期待之組成物。利用此方法後，（A )成份之頂點分子量限定於 -14- (請先閱讀背面之注意事項再填寫本頁) 家標準（CNS ) A4規格（210X297公釐） 1224125 A7 B7 五、發明説明（1)2 (B )成份頂點分子量之整數倍，惟，比較該方法後，於工業上較爲有利者。做爲偶合劑者以2官能性偶合劑之使用爲較佳。做爲此例者如·一氯一甲基砂院、苯基甲基二氯砂院類之鹵化砂化合物、二甲基二甲氯基矽烷類之烷氧基矽化合物、二氯一甲基錫類之錫化合物、苯甲酸甲酯類之酯化合物、二乙燐苯等類之乙烯丙二烯類、2官能性之環氧基化合物等者。構成本發明之嵌段共聚物組成物中，以單脂烯基芳香族化合物做爲主體之聚合物嵌段之分子量分佈可藉由幾個方法進行控制者。如：緩緩加入聚合觸媒後，開始聚合之後使分子量分佈擴散之方法，變更聚合容器之攪拌機旋轉數後進行控制之方法，使聚合觸媒之解離速度變慢後擴散分子量分佈之方法等。一般有機鋰觸媒係於非極性溶媒中進行結合，聚合開始反應其該結合之解離速度呈決定反應之速度。此係，如：以結合強之正丁基鋰於環己烷中做爲聚合觸媒使用者，此時，微量添加極性化合物後藉由控制結合度及解離速度後，可控制嵌段分子量分佈。又，以嵌段共聚物（A )及（B )中之共軛二烯做爲主體聚合嵌段時，添加極性化合物做爲任意化劑後，可調整共軛二烯嵌段中單脂烯基芳香族化合物之不規則性。如 :醚類、第3級胺類等，具體例如：乙二醇二甲基醚、四氫呋喃、α —甲氧基四氫呋喃、Ν，Ν，Ν’ ，Ν’ 一四甲基乙烯二胺等、較佳者可使用四氫呋喃、Ν，Ν，Ν ’ 本紙0^莎§國國家標準（CNS ) Α4規格（210X297公釐） -15 - Λ r (請先閱讀背面之注意事項再填寫本頁) 、1· Γ 經濟部智慧財產局員工消費合作社印製 1224125 Α7 Β7 五、發明説明（1)3 ，N ’ -四甲基乙烯二胺。該極性化合物以有機鋰化合物做爲啓發劑取得聚合物時，可藉由正-己烷、環己烷、苯、甲苯、辛烷等不活化烴基溶媒中之少量添加後，可使用之。又，先置入苯乙烯取代丁二烯/苯乙烯混合物，藉由緩緩添加丁二烯之方法後，亦可調整丁二烯與苯乙烯之不規則性。更且，乙烯結合含量若以有機鋰化合物做爲啓發劑取得聚合時，可於正-己烷、環己烷、苯、甲苯、辛烷等不活性烴基溶媒中，藉由使用醚類、第3級胺類等極性化合物、如：乙二醇二甲醚、四氫咲喃、α —甲氧基四氫咲喃、Ν，Ν，Ν ’ ，Ν ’ —四甲基乙烯二胺等、較佳者以四氫呋喃、Ν，Ν，Ν ’ ，Ν，一四甲基乙烯二胺等後可調整之。本發明組成物中於必要時，亦可添加氧化防止劑、光安定劑等之安定劑。該安定劑之例如：2，6 -二一第3 一丁基一 4 —甲基苯酚、正一辛癸基一 3 -（4，一羥基 —3’ ，5’ 一二一第3 — 丁基苯酚）丙酸酯、2，2，一亞甲基雙（4 一甲基一 6 -第3 -丁基苯酚）、2， 2’ 一亞甲基雙（4 —乙基一 6 -第3 -丁基苯酚）、2 ’ 4 一雙〔（辛基硫代）甲基〕一鄰一曱酚、2 -第3 -丁基—6 -（3 -第3 - 丁基一 2 -羥基一 5 —甲基苄基 )一 4 —甲基苯基丙烯酸酯、2，4 —二-第3-戊基― 6 一〔1— (3，5-二一第3 -戊基—2 —羥基苯基） S基〕苯基丙烯酸酯等之受阻酚系氧化防止劑；二月桂基國國家系準（CNS ) Α4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)1T, as examples of co-olefins such as 3-butisoprene, 2,3-dimethyl-1,3-butadiene, m-butyl-1,3-octadiene, benzene Basic—1, 3—People printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs. Among them, 1,3-butane and isoene are preferred. These single quantities can be used alone or in combination. 2 More than one. The component constituting the component (B) of the present invention is a block copolymer composed of at least one polymer block mainly composed of a monoester compound and at least one polymer block conjugated. Polymerization with monomeric aliphatic alkenyl aromatic compounds as the main polymer containing more than 50% by weight of monomeric aliphatic alkenyl aromatic compound alkenyl aromatic diene as the main substance. The block refers to the substance, which is essentially a national standard (〇奶) 6 specifications (210 乂 297 mm) -8- 1224125 A7 _B7 V. Description of the invention (6) (Please read the notes on the back before filling this page) The monoalkenyl aromatic compound is used as Polymer block of main ingredients. In addition, a polymer block mainly composed of a conjugated diene refers to a polymer block containing 50% by weight or more of a conjugated diene, and a polymer block mainly composed of a conjugated diene. Monomers such as styrene, p-methylstyrene, tertiary butylstyrene, α-methylstyrene, 1,1-diphenylethylene, etc. For example, styrene is preferred. These single bodies can be used alone or in combination of two or more. In addition, as the conjugated diene, such as: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene'-pentadiene, 3-butyl-1 Examples of singular bodies such as 1,3-octadiene, phenyl-1,3-butadiene, etc. Among them, 1,3-butadiene and isoprene are preferred. These single bodies can be used alone or in combination of two or more. Gel permeation chromatography (G pc) constituting the component of the present invention (B pc) • The measured peak molecular weight is determined from the viewpoints of cohesion, softening point, elongation, and melt viscosity of the asphalt composition. A) The range of 1/3 to 2/3 of the peak molecular weight of the component. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs constituting the component (A) of the present invention from the point of view of the cohesion of the polymer block mainly composed of the monoalkenyl aromatic compound, and the monolipid storage aromatic compound is the main component Two polymer blocks and a polymer block mainly composed of a conjugated diene are preferably formed by three blocks each other. It is not a problem to combine four or more blocks without causing performance degradation. The component (B) of the present invention is considered from the viewpoint of the cohesiveness of the monoalkenyl aromatic compound, and the polymer with the monoalkenyl aromatic compound as the main body is embedded in the national standard (0 Shao) standard 8 (210 '乂 297) (%) -9-— Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1224125 A7 _B7_ V. Description of the invention (7) and the two blocks of the polymer block mainly composed of conjugated diene should be used. It does not matter if three or more blocks are combined without causing performance degradation. The content of the component (A) in the block copolymer composition of the present invention is 100 to 20% by weight, and the content of the component (B) is 0 to 80% by weight. From the viewpoint of obtaining the softening point, toughness, and cohesiveness of the asphalt composition, the content of the (B) component in the ideal range is preferably 60% by weight or less, and more preferably 40% by weight or less. The content of the component (A) in the block copolymer composition of the present invention is preferably 98 to 20% by weight, and the content of the component (B) is 2 to 80% by weight. (B) The content of the component is more preferably 5 to 60% by weight, and more preferably 1 to 40% by weight. The ratio of the peak height (Η) to the half-width (W) of the chromatographic method obtained by the GPC of the polymer block containing the monoalkenyl aromatic compound as the main component in the block copolymer composition of the present invention (H / W), mono-alkenyl aromatic polymer polymer block cohesion, softening point, toughness, adhesion and other properties of asphalt composition. Η / W is preferably 7 to 19, and more preferably 9 to 17. The block copolymer composition of the present invention is composed of a polymer block mainly composed of a monoalkenyl aromatic compound. The content (BS) is determined by its single lipid;): from the viewpoint of the cohesiveness of the polymer block of the aryl aromatic compound, it is better to obtain the phase separation stability and softening point of the asphalt composition from 10% by weight or more. From the standpoint of storage stability such as changes over time, it is necessary to be 48% by weight or less. The best is 1 3 to 45% by weight, and the more preferable is 1 5 to 4. This paper is in accordance with the national standard (〇奶) 8 4 specifications (210 '乂 297 mm) "1〇-' (Please read the note on the back first Please fill in this page again for details) • Equipment · 1T 1224125 A7 B7 V. Description of the invention (8) 40% by weight. (Please read the notes on the back before filling this page) The block copolymer (A) and (B) The overall weight-average molecule " It is better to consider it as 'more than 100,000' from the viewpoint of obtaining the softening point, toughness, and adhesion of the asphalt composition, and from the viewpoint of the solubility of the asphalt, it must be 5 Less than 100,000. The better is 120,000 to 500,000, and the more preferable is 140,000 to 300,000. The block copolymer of the present invention is composed of the total bound aliphatic alkenyl aromatic compound (TS). The content of the aliphatic alkenyl aromatic compound (TS-BS) after subtracting the content (BS) of the monoblock alkenyl aromatic compound as the main component is regarded as the storage stability of the asphalt composition from the viewpoint of storage stability If it is 2% by weight or more, the effect of modification such as softening point, toughness, adhesion, etc., must be 30% by weight or less. The best is 3 to 20% by weight, and the more preferable is 5 to 18% by weight. The content of total bound monoalkenyl aromatic compounds in the block copolymer of the present invention (TS ) From the viewpoint of the cohesive force of the polymer block mainly composed of monoalkenyl aromatic compound, the toughness and adhesive strength of the obtained asphalt composition as above 10%, it is composed of the obtained asphalt From the viewpoints of storage stability, low-temperature characteristics, and dissolution rate of asphalt, etc., it is preferably 50% or less. The ideal TS range is 1.5 to 45% by weight, and more preferably 20 to 40% by weight. %. The block copolymer in the present invention is composed of monoalkenyl aromatic compounds as the main polymer block. The peak molecular weight of the polymer is 5 from the viewpoint of obtaining properties such as softening point, toughness, and adhesion of the asphalt composition. Above 0 0 0, depending on the viewpoint of solubility of asphalt and storage stability of asphalt composition, etc.-11-National Standard (CNS) M Specification (2 丨〇 > < 297 mm) 1224125 A7 B7 V. Description of the invention (_ is from 50000 The lower one is preferred. The ideal range is 7000 ~ 4000 〇, more preferably 9000 ~ 30000. (Please read the precautions on the back before filling this page) Also, it is installed in the conjugated diene in the block copolymer of the present invention The ratio of 1, 2 combination, that is, the ethylene binding content is preferably 8% by weight or more from the viewpoint of the softening point of the obtained asphalt composition. The low temperature of the asphalt composition is obtained from the thermal stability of the block copolymer composition. From the viewpoint of characteristics and thermal stability, it is preferable to consider it to be 70% by weight or less. The ethylene content in the ideal range is 15 to 60% by weight, and more preferably 20 to 50% by weight. From the viewpoints of the softening temperature, cohesion, and the softening point, toughness, and adhesion of the obtained asphalt composition measured by the static thermomechanical tester (TMA) of the block copolymer composition of the present invention, it is Above 80 ° C is preferred. From the viewpoint of obtaining the melt viscosity of the asphalt composition and the miscibility with asphalt, it is preferably below 130 ° C. The ideal range is 8 5 ~ 1 2 5 ° C, and the more preferable range is 90 ~ 1 2 0 t :. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the monomer chain linking 1 to 8 aliphatic alkenyl aromatic compounds in the monomer unit of the block copolymer of the present invention is obtained from the viewpoint of storage stability of the asphalt composition It is preferably 3% by weight of the total aliphatic alkenyl aromatic compound, and from the viewpoint of performance such as softening point, it is preferable to include a proportion of 40% by weight or less. The ideal range is 5 to 35%, and the more preferable range is 9 to 30%. The monomer chain linking 1 to 8 aliphatic alkenyl aromatic compounds with this monomer unit is substantially formed in a block mainly composed of a conjugated diene. For example, when polymerizing a block consisting of a co-based polymer, the co-polymer is placed in a reaction vessel, and then the monoalkenyl aromatic compound is slowly added, or in any case, an optional agent is used. In the presence of the conjugated diene and aliphatic alkenyl aromatic paper ㈣ J National Standard (CNS) A4 specification (210X297 mm) 12 1224125 A7 ___B7_ 5. Description of the invention (and (Please read the notes on the back before filling (This page) After the compound is placed in the reaction vessel at the same time, if necessary, a co-roll diene is added at the same time. After polymerization, the polymer block with conjugated monoene as the main body can be connected in monomer units. 1 ~ Monomer chain linker of 8 fat-burning aromatic compounds. The modified asphalt composition of the block copolymer composition used in the present invention is based on its asphalt modification effect, from the viewpoint of melt viscosity, etc., from 2 to 3 0 parts by weight and v parts of the perylene copolymer composition and 70 to 98 parts by weight of Liqing are preferred. The former is preferably 2 to 15 parts by weight, and the latter is 8 to 9 to 8 parts by weight. The former is a combination of 4 to 12 parts by weight of the former and 8 8 to 9 6 parts by weight of the latter. There is no particular limitation on the asphalt used. The commonly used asphalts are: straight run asphalt, (partially) oxidized asphalt, and mixtures of these. Ideally, straight run asphalt with a penetration of 40 to 120, Examples of oxidized bitumen with a penetration of 10 to 30 and examples of such mixtures are printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. If the constituent (A) of the present invention constitutes an inactive hydrocarbon-based solvent, organolithium compounds are used as polymerization. After the heuron polymerizes styrene, after the polymer block is formed, the polymerization method of slowly re-polymerizing butadiene while slowly adding styrene, or the method of polymerizing the mixture of butadiene / benzidine, in different cases, in In the presence of a polar compound, this method is performed. After the method of adding a conjugated diene is added according to the situation, the butadiene-styrene copolymer block is formed, and then the styrene is polymerized again. In different cases, the method is repeated. Obtained after the operation. At this time, the peak molecular weight in GPC is in the range of 50,000 to 500,000 in terms of standard polystyrene. The amount of organolithium compound is controlled and adjusted. The butadiene-styrene copolymer block is formed. By the method described above, the monomer single mfn Chinese National Standard (CNS) A4 specifications (210X297 mm) 13 __ B7 V. Description of the invention (1) A single-positioned 1 to 8 aliphatic alkenyl aromatic compound The chain is essentially formed in the block with the conjugated diene as the main body. In addition, depending on the case, those constituting the component (B) of the present invention, such as an inactive hydrocarbon-based solvent, are polymerized with an organic lithium compound as a polymerization initiator After styrene, a method of forming a styrene polymer block, and slowly polymerizing butadiene while slowly polymerizing styrene, or a method of polymerizing butadiene / styrene mixture, is carried out in the presence of polar compounds in different cases. Method > After the addition of a conjugated diene polymerization method as the case may be, a butadiene-styrene copolymer block is formed. In different cases, it is obtained after repeating the above operation. At this time, the peak molecular weight of G > C is in the range of 1/3 to 2/3 times the peak molecular weight of the (A) component, and the amount of the organolithium compound is controlled after being adjusted. When a butadiene-styrene copolymer block is formed, by this method, a single chain link of 1 to 8 aliphatic alkenyl aromatic compounds in a monomer unit is substantially based on a conjugated diene as a main block. Was formed. The components (A) and (B) are inactivated after adding water, alcohol, acid, etc. after the reaction is completed, and after mixing each component solution with a predetermined composition according to the situation, it can be obtained after steam demolding. The block copolymer formed from the components (A) and (B) constituting the present invention can also be obtained by a method different from the above. That is, in the same method as above, after polymerization of the (B) component, an appropriate coupling agent is aimed at the polymerization heuristic in the polymerization system, and the copolymer product obtained after the quantitative addition is used as the (A) component Then, the desired composition is obtained in the same reaction system. After using this method, the peak molecular weight of (A) component is limited to -14- (Please read the precautions on the back before filling this page) Home Standard (CNS) A4 Specification (210X297 mm) 1224125 A7 B7 V. Description of the Invention ( 1) 2 (B) is an integer multiple of the molecular weight of the apex of the component. However, after comparing this method, it is more industrially advantageous. As the coupling agent, the use of a bifunctional coupling agent is preferred. Examples of such examples include halogenated sand compounds of monochloromonomethyl sand, phenylmethyl dichloro sand, dimethyldimethylsilyl alkoxy silicon compounds, and dichloromonomethyl. Tin compounds such as tin compounds, methyl benzoate ester compounds, diethylbenzene, etc., vinyl allenes, bifunctional epoxy compounds, etc. In the block copolymer composition of the present invention, the molecular weight distribution of the polymer block mainly composed of a monoalkenyl aromatic compound can be controlled by several methods. For example, the method of slowly adding the polymerization catalyst and then starting the polymerization to diffuse the molecular weight distribution, the method of controlling the number of rotations of the stirring vessel of the polymerization container, and the method of controlling the diffusion rate of the polymerization catalyst after slowing the dissociation rate of the polymerization catalyst. Generally, the organolithium catalyst is combined in a non-polar solvent, and the dissociation speed of the combination at the beginning of the polymerization reaction determines the reaction speed. This system, for example, uses strong n-butyllithium as the catalyst user in cyclohexane. At this time, after adding a small amount of polar compounds, the molecular weight distribution can be controlled by controlling the degree of association and dissociation speed. . In addition, when the conjugated diene in the block copolymers (A) and (B) is used as the main polymerization block, a polar compound may be added as an optional agent, and then the monoesterene in the conjugated diene block may be adjusted. Irregularities of Aromatic Compounds. Such as: ethers, tertiary amines, etc., specific examples: ethylene glycol dimethyl ether, tetrahydrofuran, α-methoxytetrahydrofuran, Ν, Ν, Ν ', Ν'-tetramethylethylenediamine, etc., The better one can use tetrahydrofuran, Ν, Ν, Ν 'paper 0 ^ §§ National Standard (CNS) A4 specification (210X297 mm) -15-Λ r (Please read the precautions on the back before filling this page), 1 · Γ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1224125 Α7 Β7 V. Description of the invention (1) 3, N'-tetramethylethylenediamine. When the polar compound uses an organolithium compound as a heuristic to obtain a polymer, it can be used after adding a small amount in an inactive hydrocarbon-based solvent such as n-hexane, cyclohexane, benzene, toluene, and octane. In addition, it is possible to adjust the irregularity of butadiene and styrene by first inserting styrene instead of butadiene / styrene mixture and slowly adding butadiene. In addition, if the ethylene binding content is polymerized using an organolithium compound as a heuristic, it can be used in an inactive hydrocarbon-based solvent such as n-hexane, cyclohexane, benzene, toluene, and octane. Tertiary amines and other polar compounds, such as ethylene glycol dimethyl ether, tetrahydrofuran, α-methoxytetrahydrofuran, N, N, N ', N'-tetramethylethylenediamine, etc., Preferably, it can be adjusted after using tetrahydrofuran, Ν, Ν, Ν ', Ν, tetramethylethylene diamine and the like. To the composition of the present invention, stabilizers such as an oxidation inhibitor and a light stabilizer may be added when necessary. Examples of the stabilizer: 2,6-di-3rd-butyl-4-methylphenol, n-octyldecyl-3- (4,1-hydroxy-3 ', 5'12-three-butylphenol ) Propionate, 2, 2, monomethylenebis (4-methyl-6-three-butylphenol), 2, 2 'monomethylenebis (4-ethyl-6-three- Butylphenol), 2 '4-bis ((octylthio) methyl] -o-monophenol, 2-3-3-butyl-6- (3--3-butyl-1, 2-hydroxy-5 —Methylbenzyl) —4-methylphenylacrylate, 2,4-di-three-pentyl — 6- [1- (3,5-di-three-pentyl-2—hydroxybenzene S)] hindered phenol-based oxidation inhibitors such as phenyl acrylate; national standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling in this page)

經濟部智慧財產局員工消費合作社印製 -16- 1224125 Α7 Β7 五、發明説明（1>1 (請先閱讀背面之注意事項再填寫本頁) 硫代二丙酸酯、月桂基硬脂基硫代二丙酸酯季戊四醇一四 (/5 -月桂基硫代丙酸酯）等之硫系氧化防止劑；三（壬基苯基）磷酸酯、三（2，4 一二一第3 -丁基苯基）磷酸酯等磷系氧化防止劑等例。又，做爲光安定劑之例者如 :2 —（2，一羥基—5，—甲基苯基）苯並三唑、2 --(2，一羥基一 3， ^ 5 一第.3 - 丁基苯基）苯並三唑、2 — (2，一羥基—3，，5，一二一第 3 一丁基苯基 )- 5 -氯苯並三唑等苯並三哩系紫外線吸收劑、2 一羥基- 4 -甲氧基二苯甲酮等二苯甲酮系紫外線吸收劑、或受阻胺系光安定劑等例。經濟部智慧財產局員工消費合作社印製本發明組成物中除該安定劑之外，必要時被慣用先行瀝青組成物之各種添加劑、如：二氧化矽、滑石、碳酸鈣、鑛物質粉末、玻璃纖維等塡充劑、補強劑、鑛物質之骨材顏料或下躐系、環院系及芳香族系之操作油等軟化劑、香豆酮-茚樹脂、萜烯樹脂、等附粘著性樹脂、偶氮二羧醯fe等發泡劑、無規聚丙嫌、乙烯一乙基丙燦酸酯共聚物等聚烯烴系或低分子量乙烯芳香族系熱塑性樹脂；天然橡膠；聚異戊二烯橡膠、聚丁二烯橡膠、苯乙烯一丁二烯橡膠、乙烯-丙烯橡膠、氯丁二烯、丙烯基橡膠、異戊二烯-異丁烯橡膠、聚五烯體橡膠、及本發明以外之苯乙烯 - 丁一烯系嵌段共聚物、苯乙烯一異戊二烯系嵌段共聚物 •等合成橡膠均可添加。特別是做爲道路舖裝用所使用時，通吊s亥瀝青組成物係與鑛物質之石、砂 '礦渣等骨材混合後被使用之。酬家鮮（CNS U4規格（210X297公釐)-~7 ^ --—- 1224125 A7 B7五、發明説明（市混合本發明瀝青組成物之方法並未特別限定，所期待該各種添加劑利用如：滾輥' 捏合器、密閃器、擠壓器等進行熔觸混煉後可進行調製之。藉由本發明組成物所達成之效果可提供具良好瀝青組成物，特別可大幅改善其瀝青組成物之貯存，與溶解性，各特性之均衡度。先行瀝青組成物之各特性，以往要求交通量增提昇耐久性、增大空隙率之排水性、躁音吸收性之均無法滿足。先行亦添加爲提高耐久性、空隙率提良者，惟，此等均造成貯藏安定性惡化之問題點。乙烯-丁提昇苯乙經濟部智慧財產局員工消費合作社印製中苯乙烯含量後，提昇苯乙烯嵌段之凝聚力後，改性、初期物理性能。惟，嵌段共聚物與瀝青之互溶，貯存安定性大幅惡化。又，分子量、苯乙烯含量，貯存安定性雖改善，耐久性、初期物理性能卻不此’嘗試此等均衡性之取得卻無法取得滿意之結果。本發明主要效果係可大幅改善耐久性、初期之能以及貯存安定性之兩者不同要求性能之均衡性，滿足2者之要求者。 <實施例> 以下’藉由實施例進行本發明更詳細之說明，發明並不限於此實施例。又，各種測定依下記方法。本紙1 暫國家標準（CNS ) Μ規格（2ι〇χ297公餐） 18 使藉由式混煉性能之安定性大同時附與等昇之改如：苯烯嵌段善耐久性降低降低後足。因物理性可同時惟，本 (請先閱讀背面之注意事項再填寫本頁) 1224125 A7 B7 五、發明説明（作 )嵌段共聚物組成物之物性測定 1 )總苯乙烯含量：由2 6 2 (請先閱讀背面之注意事項再填寫本頁) 利用紫外線分光光度計（日立U V 2 0 0 之吸收強度進行算取之。 2 )嵌段苯乙烯含量：藉由四氧化餓與第3 - 丁基氫過氧化物之氧化分解法「Journal of polymer science」第 1 卷，第 429 頁（ 1 9 4 6年）〕取得苯乙烯聚合物嵌段（嵌段苯乙烯、 BS )。本乙嫌聚合物之含量測定係利用紫外線分光光度計（日立U V 2 0 0 )、由2 6 2 n m之吸收強度算取之〇 3 ) 丁二烯嵌段部之乙烯含量：利用紫外線分光光度計（Parkinemer製模型 1 7 1 0 )進行測定之，藉由Hampton法（「Analytica chem..21，943Γ43)」進行測定之。 4 )靜態熱機械分析：經濟部智慧財產局員工消費合作社印製使用熱機械分析裝置（島津製作所（股份）製， Τ Μ A - 4 0 使嵌段共聚物呈厚度2 mm壓縮成型之薄片具針徑0 · 5 m m之圓柱狀頂端之石英棒做爲檢出棒使用，藉由針入度法測定溫度變化後，其針入度呈劇烈變化之溫度做爲軟化溫度（載重1 0 g，昇溫速度5 °C /分鐘）。 5 )頂點分子量，及（A )成份與（B )成份之組成張國國家標準（ CNS ) A4規格（210X 297公釐）「19 - 一 1224125 Α7 Β7 五、發明説明（作比二 (請先閱讀背面之注意事項再填寫本頁) 藉由GPC 〔裝置爲waterz製，柱體爲2根Deupon 製之Zorbax PSM 1 000-S與3根PSM 60 — S之計器組合者。溶媒使用四氫呋喃，測定條件爲溫度3 5 °C，流速 0 · 7 2/分鐘，試料濃度〇 . 1重量％，注入量5 0 // 1〕之層析圖求取頂點分子量及組成比。組成比係由層析圖之面積比計算出。各成份可完全分離時以分別之面積比做成組成比。具有連接兩個頂點之谷時，谷底，亦即以色譜曲線之極小値區分之，以面積比做爲組成比。單邊之頂點呈肩時，亦即色譜曲線未具極小値時，色譜曲線之彎曲點下切斷，以面積比做成組成比。 6 )苯乙烯鏈鎖：苯乙烯鏈鎖係以藉由農工大田中教授等所開發之臭氧分解之方法（高分子學會預稿集，第2 9卷7號2 0 5 5 頁）爲基準進行測定之。 7 )苯乙烯聚合物嵌段之頂點分子量、及H/W : 經濟部智慧財產局員工消費合作社印製苯乙烯聚合物嵌段之頂點分子量係使2 )嵌段苯乙烯含莖·取得之樣品利用G PC〔裝置爲Waterz製’柱體爲昭電工製之 shodex K — 80 3，K— 802，K — 8 0 1各1根之組合者。溶媒使用氯仿、測定條件爲溫度 3 5 °C，流速爲1 . 〇 2 /分鐘，試料濃度爲0 _ 0 5重量’％、注入量1 0 0 // 1〕進行測定之。又由取得層析圖、橫軸爲分子量（對數代表），縱軸爲正規化（整體層析圖面積爲1 0 0 )之相對比下進行標繪後，頂點高度爲Η -20- 本紙^^«胂4國國家標準（CNS ) Α4規格（210X297公釐） 1224125 A7 B7_ 五、發明説明（徊、頂點半値寬度爲w，進行計算之。 (請先閱讀背面之注意事項再填寫本頁) (I I )瀝青組成物之物性測定 1 )熔融粘度： 1 8 0 °c下，藉由布魯克磁場型粘度計進行測定之。 2 )韌性、粘結力：依相關舖裝工程之試驗方法（日本道路建設業協會編 )爲基準進行測定之。 3 )延伸度、針入度、軟化點：依J I S — K 2 2 0 7爲基準進行測定之。 4)相分離：將瀝青組成物置入直徑5 . 5 c m，長度1 3 c m之圓筒形容器中後，1 8 0 °C X 3天放置後，進行測定上層部、下層部之軟化點後，以上下層軟化點之溫度差進行評定之。 (實施例1 ) 經濟部智慧財康局員Η消費合作社印製將附外套及攪拌器之1 0 L不銹鋼製反應器充份進行氮取代後，置入7000 c c之環己烷、200g之苯乙烯（第1苯乙烯）、於外套流通溫水後，使內容物設定於 7 〇 °C。隨後，加入正-丁鋰環己烷溶液（純份爲 1 · 1 9 g )後，開始進行第1苯乙烯之聚合。完全聚合第1苯乙烯後，加入1 · 41g四氫呋喃、〇 · 9g之n ，n，N’ ，n’ —四甲基乙烯二胺（tmeda)後，本$||^^^^國國家標準（〇奶）八4規格（210/297公釐） -21^ —" 1224125 A7 B7 五、發明説明（1)9 再加入 700g 之丁二烯（1 ，3 - 丁二烯）、i〇〇g 之苯乙烯（稱第2苯乙烯）後，持續聚合後，使丁二烯、第2苯乙烯幾乎完全聚合後，添加偶合劑，進行偶合。偶合劑添加後，加入〇 . 4 g之水。置入第1苯乙烯後立亥[J 藉由攪拌器連續攪拌系內。之後，抽出嵌段共聚物組成物溶液後，添加1 . 9 g之2，6 -二一第3 — 丁基—4 — 甲基苯酚、1 · 2g之三（壬基苯基）磷酸酯，藉由蒸氣汽提器去除該取得溶液之溶媒，再藉由熱滾輥（1 2 0 °C )進行脫水乾燥後，取得嵌段共聚物。此操作條件示於表 1。以G P C進行測定此取得之嵌段共聚物組成物後，低分子主成份做爲（B )、高分子主成份做爲（A )者。其物性値示於表2。又，將6 g之該聚合物組成物與1 0 0 g之直餾瀝青〔日本石油（股）製，stoas 6 0 / 8 0〕於1 8 0 °C下，進行熔融混煉9 0分鐘後，調製成瀝青組成物。其瀝青組成物之特性如表3所示。 (實施例2〜6，9〜1 ◦及比較例1〜6 ) 實施例2〜6，9〜1 0及比較例1〜6除表1所載條件之外，與實施例1同條件下進行之。其結果所取得之嵌段共聚物組成物之物性値如表2所示。又’瀝青係使用與實施例1相同者，其瀝青配合量，配合方法亦與實施例 1同法進行之。其結果如表3所示。 (實施例7 ) (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -16-1224125 Α7 Β7 V. Description of the invention (1 > 1 (Please read the precautions on the back before filling this page) Thiodipropionate, Lauryl Stearate Dipropionate pentaerythritol-tetrakis (/ 5-laurylthiopropionate) and other sulfur-based oxidation inhibitors; tris (nonylphenyl) phosphate, tris (2,4 one, two, one, three-butane Examples of phosphorus-based oxidation inhibitors such as phosphoryl) phosphate esters. Examples of light stabilizers include 2- (2,1-hydroxy-5, -methylphenyl) benzotriazole, 2- -(2, monohydroxy-3, ^ 5th. 3-butylphenyl) benzotriazole, 2-(2, monohydroxy-3, 5, 5, 12th 3rd butylphenyl) -Examples of benzotrimethyl-based ultraviolet absorbers such as 5 -chlorobenzotriazole, benzophenone-based ultraviolet absorbers such as 2-monohydroxy-4 -methoxybenzophenone, or hindered amine-based light stabilizers, etc. In addition to the stabilizer, the additives of the present invention printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economics are used, if necessary, various additives such as dioxide for the advance asphalt composition. Silicone, talc, calcium carbonate, mineral powder, glass fiber and other fillers, reinforcements, mineral pigments of bone or softeners such as chin, system and aromatic processing oils, coumarone- Polyene-based or low-molecular-weight ethylene aromatics such as indene resins, terpene resins, foaming agents such as adhesive resins, azodicarboxyfluorene, etc., random polypropylene, ethylene-ethyl propionate copolymers, etc. Series thermoplastic resin; natural rubber; polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene, propylene-based rubber, isoprene-isobutylene rubber, Polypentene rubber and synthetic rubbers such as styrene-butadiene-based block copolymers and styrene-isoprene-based block copolymers other than the present invention can be added. Especially for road paving When used, Tonghang shai asphalt composition is mixed with mineral stones, sand and slag and other aggregates. It is used for remuneration (CNS U4 specification (210X297 mm)-7 ^ --- -1224125 A7 B7 V. Description of the invention (the city mixes the asphalt composition of the invention The method is not particularly limited, and it is expected that the various additives can be prepared by melt-contact kneading using, for example, a roll 'kneader, flash condenser, and extruder. The effects achieved by the composition of the present invention can be provided. It has a good asphalt composition, which can greatly improve its asphalt composition's storage, solubility, and the balance of various properties. In advance, the various characteristics of the asphalt composition required the increase of traffic volume to improve the durability and increase the porosity of drainage. Both the performance and the irritability of the noise can not be satisfied. The former also added to improve durability and void ratio. However, these problems caused deterioration in storage stability. After the styrene content is printed in the employee consumer cooperative, the cohesion of the styrene block is improved, and then the physical properties are modified. However, the block copolymer is miscible with asphalt, and storage stability is greatly deteriorated. In addition, although the molecular weight and the styrene content are improved in storage stability, the durability and initial physical properties are not so good. 'Attempts to obtain these balances have failed to achieve satisfactory results. The main effect of the present invention is that it can greatly improve the balance between the different required performances of durability, initial performance and storage stability, and meet the requirements of the two. < Example > Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to this example. In addition, various measurement methods are as follows. This paper 1 Temporary National Standard (CNS) M specification (2ιχχ297 meals) 18 The stability of the performance of the kneading method is large and the same liter is added. For example, the styrene block reduces the durability and reduces the back foot. Due to physical properties, this book (please read the notes on the back before filling this page) 1224125 A7 B7 V. Description of the invention (for) Physical properties of block copolymer composition 1) Total styrene content: from 2 6 2 (Please read the precautions on the back before filling out this page) Use an ultraviolet spectrophotometer (Hitachi UV 2 0 0 to calculate the absorption intensity. 2) Block styrene content: By the starvation and the 3- The oxidative decomposition method of butyl hydroperoxide "Journal of polymer science", Vol. 1, p. 429 (1994)] obtains styrene polymer blocks (block styrene, BS). The content of this polymer is determined by using an ultraviolet spectrophotometer (Hitachi UV 2 0 0) and calculated from the absorption intensity of 26.2 nm. (3) Ethylene content of the butadiene block: Using ultraviolet spectrophotometry The measurement was performed by a meter (Model 1710 manufactured by Parkinemer), and was measured by the Hampton method ("Analytica chem .. 21, 943Γ43"). 4) Static thermomechanical analysis: printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs using a thermomechanical analysis device (manufactured by Shimadzu Corporation, TMM A-40) to make the block copolymer into a 2 mm thickness compression-molded sheet A quartz rod with a cylindrical tip at a needle diameter of 0.5 mm is used as a detection rod. After the temperature change is measured by the penetration method, the temperature at which the penetration degree changes drastically is used as the softening temperature (load 10 g, Heating rate: 5 ° C / min). 5) Apex molecular weight, and composition of (A) component and (B) component. Zhang Guo National Standard (CNS) A4 specification (210X 297 mm) "19-1224125 Α7 Β7 V. Description of the invention (Comparison two (please read the notes on the back before filling this page) By GPC [The device is made of waterz, the column is 2 Deupon Zorbax PSM 1 000-S and 3 PSM 60 — S A combination of chromatograms. Tetrahydrofuran was used as the solvent, and the measurement conditions were 35 ° C, flow rate 0 · 7 2 / min, sample concentration 0.1% by weight, and injection amount 5 0 // 1]. Composition ratio Composition ratio is the area ratio of the chromatogram Calculate. When each component can be completely separated, the composition ratio is made by the respective area ratio. When there is a valley connecting two vertices, the valley bottom is distinguished by the minimum of the chromatographic curve, and the area ratio is used as the composition ratio. Unilateral When the apex is shoulder, that is, when the chromatographic curve is not extremely small, the chromatographic curve is cut off at the bending point, and the composition ratio is made based on the area ratio. 6) Styrene chain: The styrene chain is used by agricultural industry The ozone decomposition method developed by professors (Preliminary Collection of the Polymer Society, Vol. 29, No. 7, page 2, 055) was used as a reference for measurement. 7) The peak molecular weight of the styrene polymer block and H / W: The peak molecular weight of the styrene polymer block printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 2) Block styrene contains stems. Samples obtained are made using G PC [The device is made of Waterz 'and the cylinder is made of Sodenko Shodex K — 80 3, K — 802, K — 8 0 1 each. A combination of chloroform as the solvent, the measurement conditions are at a temperature of 3 5 ° C, the flow rate is 1.0 / minute, and the sample concentration is 0 _ 0 5 weight '%, injection amount 1 0 0 // 1] After obtaining the chromatogram, the horizontal axis is the molecular weight (represented by the logarithm), and the vertical axis is normalized (the overall chromatogram area is 100). After plotting, the peak height is Η -20- This paper ^^ «胂 4 national standards (CNS) A4 specifications (210X297 mm) 1224125 A7 B7_ V. Description of the invention (the width of the vertex and the half height of the vertex is w, and the calculation is performed. (Please read the precautions on the back before filling in this page) (I I) Physical properties of the asphalt composition 1) Melt viscosity: Measured at 180 ° C with a Brook magnetic field viscometer. 2) Toughness and adhesion: Measured in accordance with the test method of the relevant paving project (edited by the Japan Road Construction Industry Association). 3) Elongation, penetration and softening point: Measured according to J I S — K 2 2 0 7. 4) Phase separation: Put the asphalt composition in a cylindrical container with a diameter of 5.5 cm and a length of 13 cm, and then leave it at 180 ° CX for 3 days. Then measure the softening points of the upper and lower layers. The temperature difference between the upper and lower softening points is evaluated. (Example 1) Printed by a member of the Consumer Finance Cooperative of the Ministry of Economic Affairs, the Ministry of Economic Affairs and the Consumer Cooperative. After fully replacing the 10 L stainless steel reactor with a jacket and a stirrer with nitrogen, 7000 cc of cyclohexane and 200 g of styrene were placed. (No. 1 styrene) After circulating warm water through the jacket, the contents were set at 70 ° C. Subsequently, after adding n-butyllithium cyclohexane solution (purity: 1.19 g), the polymerization of the first styrene was started. After completely polymerizing the first styrene, 1.41 g of tetrahydrofuran and 0.9 g of n, n, N ', n'-tetramethylethylenediamine (tmeda) were added. (〇 Milk) 8 specifications (210/297 mm) -21 ^ — " 1224125 A7 B7 V. Description of the invention (1) 9 700g of butadiene (1,3-butadiene), i〇 After 0 g of styrene (referred to as the second styrene), after continuous polymerization, butadiene and second styrene were almost completely polymerized, a coupling agent was added to perform coupling. After the coupling agent was added, 0.4 g of water was added. After placing the first styrene, Li Hai [J was continuously stirred in the system with a stirrer. After that, the block copolymer composition solution was extracted, and then 1.9 g of 2,6-bis-three-butyl-4-methylphenol and 1.2 g of tris (nonylphenyl) phosphate were added. The solvent of the obtained solution was removed by a steam stripper, and then dehydrated and dried by a hot roll (120 ° C) to obtain a block copolymer. This operating condition is shown in Table 1. After the block copolymer composition thus obtained was measured by G PC, the low molecular main component was taken as (B) and the high molecular main component was taken as (A). The physical properties are shown in Table 2. In addition, 6 g of the polymer composition and 100 g of straight run asphalt [manufactured by Japan Petroleum Corporation, stoas 60/80] were melt-kneaded at 180 ° C for 90 minutes. Then, an asphalt composition is prepared. The characteristics of the asphalt composition are shown in Table 3. (Examples 2 to 6, 9 to 1 ◦ and Comparative Examples 1 to 6) Examples 2 to 6, 9 to 10 and Comparative Examples 1 to 6 were the same as those of Example 1 except for the conditions set out in Table 1. Do it. The physical properties of the block copolymer composition obtained as a result are shown in Table 2. The 'asphalt system' is the same as in Example 1, and the amount and method of blending the asphalt are the same as in Example 1. The results are shown in Table 3. (Example 7) (Please read the precautions on the back before filling this page)

丁經濟部智慧財產局員工消費合作社印製㈣麵中國國家標準（CNS ) A4規格（210X297公釐） -22- 1224125 Α7 Β7 五、發明説明（本 (請先閱讀背面之注意事項再填寫本頁) 將附有外套及攪拌器之1 0 L不銹鋼製反應器充份進行氮取代後’置入所定量之環己烷、苯乙烯（稱第1苯乙嫌）’於外套進行流通溫水後，使內容物設定爲約7 〇 t：者。之後，加入所定量之正- 丁鋰環己烷溶液後，開始進行第1苯乙烯之聚合。第1苯乙烯完全聚合後，加入所定量之四氫呋喃，N，N，N，，n，一四甲基乙烯二胺、丁一烯（1 ，3 - 丁二烯）、苯乙烯（稱第2苯乙烯）後，持續聚合之，丁一烯完全聚合後，再度添加所定量之苯乙烯（稱第3苯乙烯）後，持續聚合後，完全聚合第3苯乙;之後’加入水後使活性種完全失活。隨後，再添加2 ，δ -二一第3 - 丁基一 4-甲基苯酚與三（壬基苯酚）磷酸酯（環己烷溶液）。此操作條件如表1所示。所取得嵌段共聚物組成物之物性値如表2所示。又，瀝青係與實施例1使用相同者，瀝青之配合量，配合方法亦與實施例 1同法進行之。其結果如表3所示。 (實施例8 ) 經濟部智慧財產局員工消費合作社印製 (嵌段共聚物（Β)之製造）將附外套與攪拌器之1 〇 L不銹鋼製反應器充份進行氮取代後，置入所定量之環己院、苯乙烯（稱第1苯乙烯 )’於外套流通溫水，使內容物設定爲約7 〇 °c者。之後 ’加入所定量之正-丁鋰環己烷溶液，開始聚合第i苯乙烯。第1苯乙烯完全聚合後，加入所定量之四氫咲喃，N ，Ν，Ν’ ，Ν’—四甲基乙烯二胺、丁二烯（1，3 — 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -23 - 0CB264 1224125 A7 B7D. Printed on the Chinese National Standard (CNS) A4 specification (210X297 mm) of the Consumer Cooperative Society of the Intellectual Property Bureau of the Ministry of Economic Affairs. -22- 1224125 Α7 Β7 5. Description of the invention ) The 10 L stainless steel reactor with a jacket and a stirrer was fully substituted with nitrogen, and the amount of cyclohexane and styrene (referred to as the first styrene) was circulated in the jacket after passing warm water. The content was set to about 70 ℃: After that, the n-butyllithium cyclohexane solution was added in a predetermined amount, and then the polymerization of the first styrene was started. After the first styrene was completely polymerized, the predetermined amount was added. After tetrahydrofuran, N, N, N ,, n, tetramethylethylenediamine, butadiene (1,3-butadiene), and styrene (called second styrene), continue to polymerize it, butadiene After the polymerization is complete, add the specified amount of styrene (referred to as the third styrene), and then continue to polymerize the third styrene ethyl alcohol completely; after that, the active species is completely deactivated after adding water. Then, add 2, δ -Di- 3-Butyl-4-methylphenol and tri (nonyl Phenol) phosphate ester (cyclohexane solution). The operating conditions are shown in Table 1. The physical properties of the obtained block copolymer composition are shown in Table 2. In addition, the same bitumen is used as in Example 1, bitumen The compounding amount and method were also carried out in the same manner as in Example 1. The results are shown in Table 3. (Example 8) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (manufacturing of block copolymer (B)) A 10-liter stainless steel reactor with a jacket and a stirrer was fully substituted with nitrogen, and a predetermined amount of cyclohexane and styrene (called the first styrene) was placed in the jacket to circulate warm water to set the contents. It is about 70 ° C. After that, the quantitative amount of n-butyllithium cyclohexane solution is added to start the polymerization of the i-th styrene. After the first styrene is completely polymerized, the quantitative amount of tetrahydrofuran, N, N is added. , Ν ′, Ν′—Tetramethylethylenediamine, butadiene (1,3 — This paper size applies to China National Standard (CNS) A4 specification (210X297mm) -23-0CB264 1224125 A7 B7

(請先閱讀背面之注意事項再填寫本頁) 丁一條）與苯乙烯（第2苯乙嫌）後，持續聚合之，丁二嫌、弟2本乙細兀全聚合後，加入水使活性種完全失活。再添加2 ，6 -二一第3 - 丁基一 4 一甲基苯酚與三（壬基苯酚）磷酸酯（環己烷溶液）。此操作條件如表丨所示〇 (嵌段共聚物（A )之製造）將附外套與攪拌器之1 〇 L不銹鋼製反應容器充份進行氮取代後，置入所定量之環己烷、苯乙烯（稱第1苯乙烯），外套流通溫水後，內容物設定爲約7 〇 °C者。再加入所定量之正-丁鋰環己烷溶液，開始聚合第1苯乙烯。桌1本乙細元全聚合後’再加入所定量之四氫咲喃，N， N，N ’ ，N，一四甲基乙烯二胺、丁二烯（1 ，3 — 丁一細）、本乙烯（第2苯乙烯）後，持續聚合之，丁二儲完全聚合後，再度加入所定量之苯乙烯（第3苯乙烯），持續聚合後，第3苯乙烯完全聚合後，加水使活性種完全失活。之後，加入2，6 -二一第3 - 丁基一 4 一甲基苯經濟部智慧財產局員工消費合作社印製酚與二（壬基苯酚）磷酸酯（環己院溶液）。此操作條件如表1所示。上述操作取得之嵌段共聚物（B )及嵌段共聚物（A )之聚合物溶液呈所定組成比混合於溶液後，將取得該溶液藉由蒸氣汽提去除溶媒，再藉由熱滾輥（1 2 〇 °C )進行脫水乾燥後’取得嵌段共聚物組成物。此嵌段共聚物組成物之物性示於表2。此取得嵌段共聚物組成物使用與實 -24- 本家標準（CNS ) A4規格（21GX297公釐） 1224125 A7 B7 五、發明説明（衣施例1相同者，相同配合量下做成瀝青組成物。其物性^ 如表3所示。由此等表中證明以某特定範圍結構之嵌段共聚物所^ 質之瀝青組成物具高度軟化點、良好延伸度、及高度之韌性、粘結力，且同時具有良好之貯存安定性。更且，實施例比起比較例其初期軟化點爲相同時，貯存安定性良好，又，貯存安定性相同時，其初期軟化點亦爲良好者。請先閱讀背面之注意事項再填寫本頁) 衣·(Please read the precautions on the back before filling in this page) Dingyi) and styrene (second styrene ethyl benzene), continue to polymerize, after the two dimethyl benzene and diethyl ether are fully polymerized, add water to make the activity This species is completely inactivated. Add 2,6-di- 3rd-butyl-4-methylphenol and tris (nonylphenol) phosphate (cyclohexane solution). The operating conditions are shown in Table 丨 (Production of block copolymer (A)) A 100 L stainless steel reaction vessel with a jacket and a stirrer was fully substituted with nitrogen, and the amount of cyclohexane, For styrene (referred to as the first styrene), after warm water is passed through the jacket, the content is set to about 70 ° C. Then, a predetermined amount of n-butyllithium cyclohexane solution was added to start polymerization of the first styrene. Table 1 After the polymerization of the ethylenic monomers, 'the amount of tetrahydrofuran, N, N, N', N, tetramethylethylenediamine, butadiene (1,3-butadiene), After the ethylene (the second styrene) is continuously polymerized, after the strontium is completely polymerized, the quantitative amount of styrene (the third styrene) is added again. After the continuous polymerization, after the third styrene is completely polymerized, water is added to make it active. This species is completely inactivated. After that, 2,6-bis-three-butyl-1, 4-methylbenzene was added. The phenol and di (nonylphenol) phosphate (cyclohexyl acetate solution) were printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This operating condition is shown in Table 1. After the polymer solution of the block copolymer (B) and the block copolymer (A) obtained in the above operation is mixed with the solution at a predetermined composition ratio, the solution is obtained by steam stripping to remove the solvent, and then by a hot roller (120 ° C.) After dehydration drying, a block copolymer composition was obtained. The physical properties of this block copolymer composition are shown in Table 2. The obtained block copolymer composition is used in accordance with the actual standard of -24- this standard (CNS) A4 (21GX297 mm) 1224125 A7 B7 V. Description of the invention (the same as in Example 1 with the same compounding amount, the asphalt composition is made . Its physical properties are shown in Table 3. From this table, it is proved that the asphalt composition composed of block copolymers with a specific range of structure has a high softening point, good elongation, and high toughness and adhesion. And, at the same time, it has good storage stability. In addition, when the initial softening point of the example is the same as that of the comparative example, the storage stability is good, and when the storage stability is the same, the initial softening point is also good. Please (Please read the notes on the back before filling out this page)

經濟部智慧財產局員工消費合作社印製 -25 國國家標準（CNS ) A4規格（210X297公釐） 1224125 (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -25 National Standard (CNS) A4 Specification (210X297 mm) 1224125 (Please read the precautions on the back before filling this page)

A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（23) 表-1 實施例實施例實施例實施例實施例實施例實施例實施例實施例實施例 No. 1 2 3 4 5 6 7 8 9 10 (B) ㈧丁鋰添加量(g) 1.19 1.19 1.19 1.19 1.3 1.48 0.96 1.19 0.8 1.19 1.17 第1苯乙烯(g) 200 200 210 180 350 200 100 200 100 200 190 丁二烯(g) 700 700 700 700 600 700 700 700 700 700 600 第2苯乙烯(g) 100 100 90 120 50 100 100 100 100 100 210 第3苯乙烯⑻ 0 0 0 0 0 0 100 0 100 0 0 TMEDA(g) 0.9 0.9 0.9 0.8 0.8 0 0.6 0.6 0.55 1.2 0.8 偶合劑種 .(*1) <— <— PMDCS <— DMDCS — — DMDCS <— 比較例比較例比較例比較例比較例比較例 No. 1 2 3 4 5 6 丁鋰添加量(g) 1.19 1.24 1.00 1.58 2.70 1.19 第1苯乙烯(g) 200 210 8 6 20 30 丁二烯(g) 700 690 92 70 70 70 第2苯乙烯(g) 100 100 0 24 10 0 TMEDA(g) 0.70 0.80 0.80 0.80 1.60 0.60 偶合劑種 (*1) <— PMDCS <— <— (*1) *1雙酚類與二縮水甘油醚化合物(nO體98%以上）下記構造式之1與2爲1:1之混合 DMDCS:二甲基二氯矽烷 PMDCS:苯基甲苯二氯矽烷中國國家標準（CNS ) A4規格（210X297公釐）乂心A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (23) Table-1 Example Example Example Example Example Example No. 1 2 3 4 5 6 7 8 9 10 (B) 添加 Lithium butyl lithium (g) 1.19 1.19 1.19 1.19 1.3 1.48 0.96 1.19 0.8 1.19 1.17 1st styrene (g) 200 200 210 180 350 200 100 200 100 200 190 Butadiene (g) 700 700 700 700 600 700 700 700 700 700 600 2nd styrene (g) 100 100 90 120 50 100 100 100 100 100 210 3rd styrene ⑻ 0 0 0 0 0 0 100 0 100 0 0 TMEDA (g) 0.9 0.9 0.9 0.8 0.8 0 0.6 0.6 0.55 1.2 0.8 Coupling agent species. (* 1) < — < — PMDCS < — DMDCS — — DMDCS < — Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example No. 1 2 3 4 5 6 Butyl lithium added (g) 1.19 1.24 1.00 1.58 2.70 1.19 First styrene (g) 200 210 8 6 20 30 Butadiene (g) 700 690 92 70 70 70 Second styrene (g) 100 100 0 24 10 0 TMEDA (g) 0.70 0.80 0.80 0.80 1.60 0.60 Coupling agent species (* 1) < — PMDCS < — < — (* 1) * 1 pair And diglycidyl ether compounds (more than 98% of nO body) The following structural formulas 1 and 2 are 1: 1 mixed DMDCS: dimethyldichlorosilane PMDCS: phenyltoluene dichlorosilane Chinese National Standard (CNS) A4 Specifications (210X297 mm)

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(_iM οο^ϋΗ 比較例 \〇 P 30.0 30.0 〇 19000 ο CN CN wn Η 108.0 Lib較例1 un 1 13.0 I CO I 29.8 I I 20.1 I 4600 CN 1 27.5 I 66.0 比較例 1 12.0 I 〇 L41.〇 1 |__35Ό…| 2400 Ο cn CN I 16.0 I 65.0 比較例 cn | 12.0 I 〇寸 ρ P 〇 4800 g CN S 1 11.0」 73.0 丨比較例| Cvl | 22.4 I 〇 | 30.6 1 | 20.7 1 ON 164⑻ Ο cn οα S τ—Η 107.0 比較例 ^—( P \-1 寸 | 29.6 1 19.9 1 15700 Π 沄 CNl cn Η 101.0 ! BS 分布(H/W) 乙烯結合含有量(重量％) TS(重量％) BS(重量％) TS-BS(重量％) BS分子量 Mw(xl03) (B)成分含有量(重量％) B分子量/A分子量 Ml(g/10mm) TMA軟化溫度fC) (請先閱讀背面之注意事項再填寫本頁)(_iM οο ^ ϋΗ Comparative Example \ 〇P 30.0 30.0 〇19000 ο CN CN wn Η 108.0 Lib Comparative Example 1 un 1 13.0 I CO I 29.8 II 20.1 I 4600 CN 1 27.5 I 66.0 Comparative Example 1 12.0 I 〇L41.〇1 | __35Ό ... | 2400 〇 cn CN I 16.0 I 65.0 Comparative example cn | 12.0 I 〇inchρ P 〇4800 g CN S 1 11.0 ″ 73.0 丨 Comparative example | Cvl | 22.4 I 〇 | 30.6 1 | 20.7 1 ON 164⑻ 〇 cn οα S τ—Η 107.0 Comparative example ^ — (P \ -1 inch | 29.6 1 19.9 1 15700 Π 沄 CNl cn Η 101.0! BS distribution (H / W) Ethylene binding content (wt%) TS (wt%) BS (Wt%) TS-BS (wt%) BS molecular weight Mw (xl03) (B) component content (wt%) B molecular weight / A molecular weight Ml (g / 10mm) TMA softening temperature fC) (Please read the note on the back first (Fill in this page again)

贤辱g用中國國家標準（CNS ) A4規格（210X297公釐 27 1224125 (請先閲讀背面之注意事項再填寫本頁)Chinese National Standard (CNS) A4 specifications (210X297 mm 27 1224125) (Please read the precautions on the back before filling this page)

A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（本表-3 實施例實施例實施例實施例實施例實施例實施例實施例實施例實施例 No. 1 2 3 4 5 6 7 8 9 10 18(TC 粘度(cps) 268 270 269 273 232 223 228 260 266 279 軟化點rc ) 84 82 85 85 87 74 78 85 89 88 針入度(l/l〇mm) 54 53 54 53 55 44 53 55 57 51 15°C 伸度(cm) 132 126 130 126 132 136 131 123 162 131 韋刃性(kg · cm) 269 258 264 276 380 210 226 259 321 323 粘結力(kg · cm) 182 174 177 194 278 125 149 181 218 234 相分離(。C ) 5 8 6 6 11 11 3 6 5 9 比較例比較例比較例比較例比較例比較例 No. 1 2 3 4 5 6 180°C 粘度(cps) 269 270 195 302 170 250 軟化點ΓΟ 59 85 57 61 57 86 針入度(l/l〇mm) 54 54 57 43 48 50 15°C 伸度(cm) 150 135 103 91 98 100 韋刃性(kg · cm) 180 252 119 170 116 270 粘結力(kg · cm) 95 157 77 160 88 180 相分離ΓΟ 2 39 0 5 3 9 本慰伊國家標準（CNS ) A4規格（210X297公釐） -28 - 1224125 A7 B7 五、發明説明（本參考特定實施形態後，詳細說明本發明，惟，本發明在不脫離主旨與範圍下可加以進行各種變更、修正者爲該業者所認知者。 <產業上可利用性> 本發明瀝青組成物具有良好機械強度、軟化點、延伸度等物性，且加工性亦佳之高度均衡性者，另外，貯存安定性亦佳，因此，用於道路舖裝用，亦可利用於防水薄片、遮音薄片、止水材料等、其工業上思義極大者。 (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 - 29- 用中國國家標準（CNS〉A4規格（210X297公釐）A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (this table-3 Example Example Example Example Example Example Example No. 1 2 3 4 5 6 7 8 9 10 18 (TC viscosity (cps) 268 270 269 273 232 223 228 260 266 279 Softening point rc) 84 82 85 85 87 74 78 85 89 88 Penetration (l / l0mm) 54 53 54 53 55 44 53 55 57 51 15 ° C Elongation (cm) 132 126 130 126 132 136 131 123 162 131 Weakness (kg · cm) 269 258 264 276 380 210 226 259 321 323 Adhesion (kg · cm) 182 174 177 194 278 125 149 181 218 234 Phase separation (° C) 5 8 6 6 11 11 3 6 5 9 Comparative example Comparative example Comparative example Comparative example Comparative example No. 1 2 3 4 5 6 180 ° C Viscosity (cps ) 269 270 195 302 170 250 Softening point Γ 59 59 57 61 57 86 Penetration (l / lmm) 54 54 57 43 48 50 15 ° C Elongation (cm) 150 135 103 91 98 100 (kg · cm) 180 252 119 170 116 270 Adhesion (kg · cm) 95 157 77 160 88 180 Phase separation ΓΟ 2 39 0 5 3 9 National Standard (CNS) A4 (210X29) 7mm) -28-1224125 A7 B7 V. Description of the invention (This invention will be described in detail after referring to specific embodiments. However, the invention can be modified and modified without departing from the spirit and scope of the invention. The cognizant. &Lt; Industrial availability > The asphalt composition of the present invention has good mechanical strength, softening point, elongation and other physical properties, and is highly balanced with good processability. In addition, it has good storage stability. Therefore, It is used for road paving, and can also be used in waterproof sheets, sound-shielding sheets, water-proof materials, etc., which have great industrial significance. (Please read the precautions on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative-29- Use Chinese national standard (CNS> A4 specification (210X297 mm)

Claims

1224125 A8 B8 C8 D8 6. Scope of patent application 1 (Please read the notes on the back before filling this page) 1. A block copolymer composition characterized by at least a monoalkenyl aromatic compound as the main body 100 to 20% by weight of a block copolymer (A) formed by two polymer blocks and at least one polymer block mainly composed of a conjugated diene, and a monoalkenyl aromatic A compound having at least one polymer block as a main body and at least one polymer block having a conjugated diene as a main body, and its peak molecular weight is equivalent to 1/3 to 2 / of the block copolymer (A). 3 of 0 to 80% by weight of the block copolymer (B): (1) The polymer block mainly composed of a monoalkenyl aromatic compound has the peak height of the chromatogram obtained by GPC (η) The ratio (H / W) to the half-width (W) is a molecular weight distribution of 5 to 20; (2) the polymer block content (BS) with a monoalkenyl aromatic compound as the main component is a block copolymer ( A) and (B) the total weight of 10% to 48% by weight; (3) the average weight of the total copolymer (A) and (B) The amount (Mw) is 100,000 to 500,000; (4) Block copolymers (A) and (B) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are composed of monoalkenyl aromatic compounds combined The content (TS) minus the polymer block content (BS) of the monoaliphatic aromatic compound as the main component, and the content of the aliphatic alkenyl aromatic compound (TS-BS) is 2 to 30% by weight. 2. The block copolymer composition according to item 1 of the patent scope as claimed in § 靑, wherein the composition is composed of 98 to 20% by weight of the block copolymer (A) and 2 to 80% by weight of the block copolymer. Copolymer (B). 3. If the block copolymer composition of item 1 of the scope of the patent application, the dimensions of this block apply to the Chinese National Standard (CNS) A4 specification (210X297 mm) " "_27l -so- 1224125 A8 B8 C8 D8 The content (τ S) of the total bound aliphatic alkenyl aromatic compound in the scope of the applied patent is 10 to 50% by weight; the molecular weight of the polymer block with the monoaliphatic aromatic compound as the main component is 5000 to 50 10,000; the ethylene copolymer content of the block copolymers (A) and (B) as a whole is 8% to 70% by weight; and the block copolymer composition determined by static thermomechanical analysis (TMA) The softening temperature is 80 ° C ~ 130 t. 4 · The block copolymer composition according to item 3 of the patent application range, wherein the monoalkenyl aromatic compound is styrene. 5.-Asphalt The composition is characterized by being composed of 2 to 30 parts by weight of a block copolymer composition as described in any one of claims 1 to 4 of the patent application scope, and 70 to 98 parts by weight of asphalt. (Please read the notes on the back before filling in this I) Order the Intellectual Property Bureau of the Ministry of Economic Affairs Workers Co-op warehouse i printed sheets scale applicable Chinese National Standard (CNS) A4 size (210X297 mm) 31 -