588054 A7 ________B7_ 五、發明説明（1 ) 【發明之技術領域】 本發明’係有關一種高軟化點共聚物，其製造方法及 其氫化物之發明，詳細言之，係包含有關（二）環戊二稀 與乙烯基取代芳香族化合物之熱共聚物所得之高軟化點共 聚物，及有效率地製造該物之方法，及前記共聚物之氫化 物等’增黏樹脂則例如適合熱熔性黏著劑使用之具有高軟 化點的共聚物氫化物。 【先前技術】 近年、熱熔粘合劑之高速塗佈性、速硬性、省能源性 、經濟性等優異，故擴大利用於各種領域。例如，可使用 於衛生材料用、包裝用、製本用、纖維用、木工用、電氣 材料用、製罐用、建築用、道路用連結劑。 一般的熱熔性粘著劑係使用添加有附有粘著樹酯與可 塑劑等於天然橡膠、乙烯-酢酸乙烯基共聚物、苯乙烯-丁二 烯-苯乙烯嵌段共聚物及其氫化物、苯乙烯-異戊二烯-苯乙 烯嵌段共聚物及其氫化物等之基礎聚合物的組成物。上述 附有粘著樹酯係可使用一般之石油樹酯與香豆酮系樹酯、 酚系樹酯、萜烯系樹酯、松香系樹酯及其氫化物等。而此 熱熔性粘著劑作爲附有粘著樹酯係提昇恒溫蠕變及保持力 ’故往往可使.用軟化點爲125〜160°C左右之高點化點樹酯 。又，此高軟化點之附有粘著樹酯使用一般之聚合方法不 易合成且聚合需要非常長的操作時間，此爲經濟面方面之 困難點。 "r—________________ _ 尽紙張尺度適用中國國家標準（CNS ) A4規格（2】〇X 297公釐） ---------裝-- (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 -4 - 588054 A7 B7 經濟部智慧財產局負工消費合作社印製 五、發明説明（2 ) 發明之開示 本發明於前述情況下提供一種經濟性佳且可適合使用 於熱熔性粘著劑等之共聚物氫化物及作爲其原料可使用之 高軟化點共聚物以作爲具有高軟化點之附有粘著樹酯爲目 本發明者們爲達前記之目的而專心硏究之結果，環戊 二稀及/或二環戊二稀與乙烯基取代芳香族化合物於熱聚合 時，經對單體使用特定的比例之溶媒時，於短時間內所得 之具有高軟化點之共聚物，再將此共聚物氫化而可得到經 濟性佳且可適合使用於熱熔性接著劑等之共聚物氫化物以 作爲具有高軟化點之附有粘著樹酯。本發明係基於此知見 以完成者。 即，本發明係提供 (1) 一種高軟化點共聚物，其特徵爲環戊二稀及/或二環 戊二稀與乙烯基取代芳香族化合物經熱聚合所得之共聚物 中，其熱聚合時之溶媒使用量對全單體重量爲0.1倍以上、 〇·5倍未達且軟化點爲100〜135°C範圍， (2) —種高軟化點共聚物之製造方法，其特徵爲環戊二 稀及/或二環戊二稀與乙烯基取代芳香族化合物於其每100 重量份.、存在10重量份以上、50重量份未達之溶媒存在下 熱聚合，而其軟化點爲1〇〇〜135°C範圍， (3) —種共聚物氫化物，其特徵爲如上記（1)之高軟化點 共聚物經氫化而所得者， (4) 如上記（3)之共聚物氫化物，其軟化點爲125〜160°C 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) —0 項再填· 裝. 訂 -5- 588054 經濟部智慧財產局員工消費合作社印製 A7 _B7 _____五、發明説明（3 ) 範圍及， (5)如上記（4)之共聚物氫化物，其軟化點爲135〜160°C 範圍。 實施發明的最佳形態 本發明之高軟化點共聚物係環戊二稀及/或二環戊二稀 與乙烯基取代芳香族化合物經熱聚合所得之共聚物中，其 熱聚合時之溶媒使用量對全單體重量爲〇·1倍以上、0.5倍 未達且軟化點爲1〇〇〜135°c範圍，而最佳爲100〜135°C範 圍之共聚物。 前述之共聚物中，作爲原料單體成分可使用之乙烯基 取代芳香族化合物，例如苯乙烯、α -甲基苯乙烯、乙烯基 甲苯等，而此可使用單獨一種、可使用兩種以上組合。 當該共聚物於適當之溶媒中，原料單體之環戊二稀及/ 或二環戊二稀與前述乙烯基取代芳香族化合物經熱聚合反 應而製造。因此，溶媒最佳可使用例如苯、甲苯、二甲苯 、環己烷、二甲基環己烷、乙基環己烷等之碳氫化合物等 。此些可使用單獨一種、可使用兩種以上組合。 本發明中溶媒之使用量對於單體1〇〇重量，必須選定 10重量份以上、50重量份未達之範圍。溶媒之使用量超過 上述範圍’ SU短時間內無法得到具有所期望之高軟化點的 共聚物’故無法達到本發明之目的。而最佳溶媒之使用量 爲20〜45重量份。 聚合方法係將前記溶媒使用最佳爲1 〇(rc以上，較佳爲 I紙張尺度適用中國國家標準(―CNS ) A4規格（2]〇χ297公釐)~ " — -6- (請先閲讀背面之注意事 4 項再填‘ 裝— :寫本頁) 訂 588054 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 ) 1 5 0以上加熱，而於此加熱之溶媒中可有效將環戊二稀及/ 或一環戊一稀與乙烯基取代芳香族化合物與之單體混合物 依比例添加、實行共聚合之方法。 运戊一稀及/或一 is戊一稀與乙燒基取代芳香族化合物 與之使用比例並不特定限定，通常重量基準爲7〇:3〇至 20:80，最佳爲60:40至40:60之圍。又，比例添加時間― 般爲0 · 5〜5小時’最佳爲1〜3小時。又，比例最佳爲依據 等份添加。 於此共聚反應中，比例添加環戊二稀及/或二環戊二稀 與乙燒基取代方香族化合物與之單體混合物依比例添加結 束後，持續反應爲佳。此時之反應條件中，並不特定限制 ，一般爲200〜350°C左右，最佳爲220〜300°C，反應壓力 一般爲0〜2MPa · G左右，最佳爲0〜1.5 MPa · G左右，而 反應時間一般爲1〜1 0小時左右，最佳爲2〜8小時。 反應結束後，將反應生成液於例如溫度1〇〇〜30CTC左 右、壓力爲0.1〜10kPa左右、經1〜3小時間左右揮發分且 除去處理而所得本發明之共聚物。 由此所得之共聚物中，軟化點爲100〜135 °C，最佳爲 110〜135 °C之範圍，又，一般乙烯基取代芳香族化合物單 位之含有量爲30〜90重量％、溴價爲30〜90g/100g、數平 均分子量爲5 00〜1，100左右。又，上述數平均分子量係以 浸透色譜法（GPS)法測定之聚苯乙烯換算之數値。（未達相同 ) 又，前述軟化點係依據JAI7-1991，經環球法而測定之 (請先閲讀背面之注意事 4 項再填」 裝— ：寫本頁)588054 A7 ________B7_ V. Description of the Invention (1) [Technical Field of the Invention] The present invention is related to an invention of a high softening point copolymer, a method for producing the same and a hydride thereof. In particular, it includes the related (ii) cyclopentane High softening point copolymers obtained from thermal copolymers of dilute and vinyl-substituted aromatic compounds, and methods for efficiently producing the same, and 'tackifying resins' such as the hydride of the aforementioned copolymer are suitable for hot-melt adhesion, for example Copolymer hydride with high softening point used by the agent. [Prior technology] In recent years, hot-melt adhesives have excellent high-speed coating properties, rapid hardening properties, energy-saving properties, and economical advantages, so they are widely used in various fields. For example, it can be used for sanitary materials, packaging, texturing, fiber, woodworking, electrical materials, can manufacturing, construction, and road linking agents. General hot-melt adhesives use natural rubber, ethylene-acetic acid vinyl copolymers, styrene-butadiene-styrene block copolymers, and their hydrides with adhesive resins and plasticizers added. Composition of basic polymers such as styrene-isoprene-styrene block copolymers and their hydrides. As the adhesive resins mentioned above, general petroleum resins and coumarone-based resins, phenol-based resins, terpene-based resins, rosin-based resins, and hydrogenated products thereof can be used. And this hot-melt adhesive is used as an adhesive resin to improve constant temperature creep and holding force, so it can often be used. A softening point resin with a high point of about 125 ~ 160 ° C can be used. In addition, this high softening point with an adhesive resin attached is difficult to synthesize using a general polymerization method and polymerization requires a very long operation time, which is a difficult point in terms of economy. " r —________________ _ Use the Chinese National Standard (CNS) A4 specification (2) 〇X 297mm as far as possible paper size --------- Install-(Please read the precautions on the back before filling in this Page) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-4-588054 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) Disclosure of the invention The present invention provides an economy in the foregoing circumstances Copolymer hydrides which are suitable and suitable for use in hot-melt adhesives, etc., and high softening point copolymers which can be used as their raw materials, are intended to be adhesive resins having a high softening point, and the inventors have As a result of achieving the purpose of the previous note, cyclopentadiene and / or dicyclopentadiene and vinyl substituted aromatic compounds were thermally polymerized in a short period of time when a specific proportion of the solvent was used for the monomers. A copolymer having a high softening point obtained in-house, and then hydrogenating the copolymer to obtain a copolymer hydride having good economics and suitable for use in hot-melt adhesives, etc., as a cohesive agent with a high softening point. Resin. The present invention has been completed based on this knowledge. That is, the present invention provides (1) a high softening point copolymer characterized by thermal polymerization of a copolymer obtained by thermal polymerization of cyclopentadiene and / or dicyclopentadiene with a vinyl-substituted aromatic compound. The amount of solvent used at the time is 0.1 times or more of the total monomer weight, 0.5 times or less, and the softening point is in the range of 100 to 135 ° C. (2) A method for manufacturing a high softening point copolymer, which is characterized by a ring Glutarene and / or dicyclopentadiene and vinyl-substituted aromatic compounds are thermally polymerized in the presence of a solvent of more than 10 parts by weight and less than 50 parts by weight, with a softening point of 1 〇〇 ~ 135 ° C, (3) a kind of copolymer hydride characterized by hydrogenation of the high softening point copolymer as described in (1) above, (4) hydrogenation of the copolymer as described in (3) above Material, its softening point is 125 ~ 160 ° C. This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) — 0 items and then filling Order-5-588054 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7 _____ Range (3) and (5) referred to above (4) of the hydrogenated copolymer, a softening point of 135~160 ° C range. Best form for carrying out the invention The high softening point copolymer of the present invention is a copolymer obtained by thermal polymerization of cyclopentadiene and / or dicyclopentadiene and a vinyl-substituted aromatic compound, and a solvent used during thermal polymerization A copolymer whose amount is 0.1 times or more to the total monomer weight, 0.5 times or less, and a softening point in the range of 100 to 135 ° C, and most preferably in the range of 100 to 135 ° C. Among the aforementioned copolymers, vinyl-substituted aromatic compounds, such as styrene, α-methylstyrene, vinyltoluene, etc., which can be used as a raw material monomer component, can be used alone or in combination of two or more. . When the copolymer is in an appropriate solvent, cyclopentadiene and / or dicyclopentadiene as a raw material monomer and the aforementioned vinyl-substituted aromatic compound are produced by thermal polymerization reaction. Therefore, as the solvent, hydrocarbons such as benzene, toluene, xylene, cyclohexane, dimethylcyclohexane, ethylcyclohexane, etc. can be preferably used. These may be used alone or in combination of two or more. The amount of the solvent used in the present invention must be in a range of 10 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the monomer. The use amount of the solvent exceeds the above-mentioned range "SU cannot obtain a copolymer having a desired high softening point in a short time", so the object of the present invention cannot be achieved. The optimal amount of solvent is 20 to 45 parts by weight. The polymerization method is to use the previous solvent as the best 1 〇 (more than rc, preferably I paper size applies Chinese National Standard (―CNS) A4 specifications (2) 〇χ297 mm) ~ ——— 6- (please first Read the notes on the back of the 4 items and fill them out. —— — Write this page) Order 588054 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Heating above 150, and the solvent heated here This method can effectively add cyclopentadiene and / or monocyclopentadiene and vinyl substituted aromatic compounds to the monomer mixture in proportion and implement copolymerization. The use ratio of the ethylenically substituted aromatic compound is not particularly limited. Usually, the weight basis is 70:30 to 20:80, and the most preferable range is 60:40 to 40:60. In addition, the ratio addition time-general It is 0 · 5 ~ 5 hours', and the best ratio is 1 ~ 3 hours. In addition, the ratio is best added in equal portions. In this copolymerization reaction, cyclopentadiene and / or dicyclopentadiene and ethyl alcohol are added in proportion. After the radically substituted aromatic compound is added to the monomer mixture in proportion, it is better to continue the reaction. The reaction conditions at this time are not particularly limited, but are generally about 200 to 350 ° C, preferably 220 to 300 ° C, and the reaction pressure is generally about 0 to 2 MPa · G, and most preferably 0 to 1.5 MPa · G The reaction time is generally about 1 to 10 hours, and the best is 2 to 8 hours. After the reaction is completed, the reaction product is, for example, at a temperature of about 100 to 30 CTC, a pressure of about 0.1 to 10 kPa, and a temperature of 1 to 10 kPa. The copolymer of the present invention is obtained by removing the volatile matter in about 3 hours and removing the treatment. In the copolymer thus obtained, the softening point is 100 to 135 ° C, and the optimal range is 110 to 135 ° C. The content of the substituted aromatic compound unit is 30 to 90% by weight, the bromine value is 30 to 90 g / 100 g, and the number average molecular weight is about 500 to 1,100. The number average molecular weight is based on permeation chromatography (GPS). The number of polystyrene conversions measured by the method. (Not the same.) Also, the aforementioned softening point is determined by the global method according to JAI7-1991 (please read the 4 notes on the back before filling). (This page)
、1T 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 588054 經濟部智慧財產局員工消費合作社印製 A7 __^_ B7 __五、發明説明（5 ) 値。關於後述之共聚物氫化物亦相同。 本發明中所得之軟化點爲1 〇〇〜1 3 5 °C之範圍內的共聚 物氫化處理而製造本發明之共聚物氫化物。 此氫化反應中之觸媒，可使用鎳、鈀、鈷、鉑、铑系 等之觸媒。因此，適當的溶媒例如環己烷、乙基環己烷、 二甲基環己烷、甲基環乙烷、四氫呋喃等之溶媒中，於前 述觸媒存在下，將前述之共聚物於溫度120〜300°C左右， 最佳爲150〜25 0°C、反應壓力1〜6 MPa · G左右、反應時 間1〜7小時左右，最佳爲2〜5小時之條件下氫化。 反應結束後，將反應生成液於例如溫度100〜300 °C左 右，壓力0.1〜lOkpa左右下，經1〜3小時左右揮發分除去 處理而所得之本發明的共聚物氫化物。 由此所得之本發明的共聚物氫化物中，軟化點爲125〜 160°C，最佳爲135〜16CTC之範圍內，又，一般乙烯基取代 芳香族化合物單位之含有量爲0〜35重量％，而溴價爲0〜 30g/100g、數平均分子量爲500〜1，1〇〇左右。 前述本發明之共聚物氫化物係作爲具有高軟化點之附 有粘著樹酯，最適合可使用於熱熔性粘著劑等且付與高度 恒溫蠕變及具有保持力之熱熔性粘著劑等。 將本發明之共聚物氫化物作爲附有粘著樹酯使用於熱 熔性粘著劑時，該熱熔性粘著劑一般係添加基礎聚合物及 可塑劑等於該共聚物氫化物而調製。 前述之基礎聚合物並不特定限制，從一般作爲熱熔性 粘著劑中之基礎聚合物所使用者中，可適宜選擇且使用任 本紙張尺度適用中國國家標準（CNS ) A4規格（2】OX29<7公楚） (請先閲讀背面之注意事_ 1· •項再填* 裝-- :寫本頁) Φ -8 - 588054 經濟部智慧財產局員工消費合作社印製 A7 ___B7 _五、發明説明（6 ) 何者。此基礎聚合物之具體例爲天然橡膠、乙烯-酢酸乙烯 基共聚物、非晶性聚α -烯烴或苯乙烯-丁二烯-苯乙烯嵌段 共聚物（SBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物（SIS) 及此些氫化而所得之苯乙烯·乙烯-丁烯-苯乙烯橡膠（SEBS) 、苯乙烯-乙烯-丙烯-苯乙烯（SEPS)等。此些可使用單獨一 種、可使用兩種以上組合。 另一方面，可塑劑並不特別限定，由一般使用於作爲 熱熔性粘著劑中之可塑劑中看來，可適宜選擇且可使用任 意者。此可塑劑之具體例係將原油經常壓蒸留而所得之重 油留分再經減壓蒸留，再使用氫化改質、脫蠟處理經精製 而所得之石蠘系或減壓蒸留後，經溶劑抽出與氫化、白土 處理法而所得之萘系操作油劑，進一步舉例如聚丁烯、液 .狀之聚α -烯烴等。此些可使用單獨一種、可使用兩種以上 組合。 此熱熔性接著劑中之各成分的含有比例係依據所要求 之物性而相異，一般共聚物氫化物爲30〜70重量％、基礎 聚合物爲15〜40重量％、可塑劑爲10〜40重量％之範圍。 又，該熱熔性接著劑，除了前述共聚物氫化物、基礎 聚合物及可塑劑以外，對於所需之物性於無損失之範圍下 ，應其必要可含有氧化防止劑、蠘、塡料等。 該熱熔性接著劑之調製方法並不特定限制，例如可使 用螺旋槳式攪拌機、二軸混練機、湼合機等且可將各成分 使用加熱溶融混合或混練之方法等。而各成分之配合順序 並不特定限制，又，加熱溫度亦不特定限制，一般於120〜 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） — ~ (請先閲讀背面之注意事項再填寫本頁) 4 ▼項再填· 裝· 訂 -9- 588054 A7 B7 五、發明説明（7 ) 190°C之範圍內之溫度，進行加熱溶融混合或混練。 未達係經實施例進一步詳細說明本發明，而本發明係 依據此例且並不特定限定。 實施例1 於氮取代之附有攪拌機的1公升聚合反應器中加入二 甲苯154g(對原料單體100重量份爲48重量份），加熱至 260°C，於攪拌中，以120分鐘將環戊二烯159g與苯乙烯 159g之混合物添加於其中。其後，持續進行140分鐘共聚 合反應。 反應結束後，取出反應生成液而可使用旋轉蒸發器， 於溫度200°C、壓力1.3kp下處理2小時且除去未反應單體 與二甲苯而所得之環戊二烯與苯乙烯之共聚物289g。而此 共聚物之物性所示如第1表。 實施例2 於氮取代之附有攪拌機的1公升聚合反應器中加入二 甲苯120g(對原料單體100重量份爲30重量份），加熱至 230°C，於攪拌中，以120分鐘將環戊二烯200g與苯乙烯 200g之混合物添加於其中。其後，以60分鐘昇溫至260t 而進行160分鐘共聚合反應。 反應結束後，取出反應生成液而可使用旋轉蒸發器’ 於溫度200°C、壓力1.3kp下處理2小時且除去未反應單體 與二甲苯而所得之環戊二烯與苯乙烯之共聚物376g。而此 本紙張尺度適用中國國家標準（CNS ) A4規格（2】0X297公釐） —--------批衣-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局負工消費合作社印製 -10- 588054 經濟部智慧財產局員工消費合作社印製 A7 __ B7__五、發明説明（8) 共聚物之物性所示如第1表。 實施例3 於氮取代之附有攪拌機的1公升聚合反應器中加入二 甲本143g(對原料單體1〇〇重量份爲45重量份），加熱至 240°C，於攪拌中，以120分鐘將環戊二烯159g與苯乙烯 1 59g之混合物添加於其中。其後，以60分鐘昇溫至260°C 而進行80分鐘共聚合反應。 反應結束後，取出反應生成液而可使用旋轉蒸發器， 於溫度200°C、壓力1.3kp下處理2小時且除去未反應單體 與二甲苯而所得之環戊二烯與苯乙烯之共聚物292g。而此 共聚物之物性所示如第1表。 實施例4 於氮取代之附有攪拌機的1公升聚合反應器中加入二 甲苯80g(對原料單體100重量份爲20重量份），加熱至240 t，於攪拌中，以120分鐘將環戊二烯200g與苯乙烯200g 之混合物添加於其中。其後，以60分鐘昇溫至260°C而進 行380分鐘共聚合反應。 反應結束後，取出反應生成液而可使用旋轉蒸發器’ 於溫度200°C、壓力1.3kp下處理2小時且除去未反應單體 與二甲苯而所得之環戊二烯與苯乙烯之共聚物374g。而此 共聚物之物性所示如第1表。 (請先閱讀背面之注意事、 1T This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 588054 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __ ^ _ B7 __ V. Description of the invention (5) 値. The same applies to the copolymer hydride described later. The copolymer obtained in the present invention has a softening point in the range of 100 to 135 ° C and is subjected to hydrogenation treatment to produce the copolymer hydride of the present invention. As the catalyst in the hydrogenation reaction, nickel, palladium, cobalt, platinum, rhodium-based catalysts can be used. Therefore, in a suitable solvent such as a solvent of cyclohexane, ethylcyclohexane, dimethylcyclohexane, methylcycloethane, tetrahydrofuran, etc., in the presence of the aforementioned catalyst, the aforementioned copolymer is heated at a temperature of 120. It is hydrogenated at about ~ 300 ° C, preferably at 150 ~ 25 0 ° C, reaction pressure at about 1 ~ 6 MPa · G, reaction time at about 1 ~ 7 hours, and most preferably at 2 ~ 5 hours. After completion of the reaction, the copolymer hydride of the present invention is obtained by subjecting the reaction product to a temperature of about 100 to 300 ° C, a pressure of about 0.1 to 10 kpa, and a volatile matter removal treatment for about 1 to 3 hours. The thus obtained copolymer hydride of the present invention has a softening point in the range of 125 to 160 ° C, and preferably in the range of 135 to 16CTC. In addition, the content of the general vinyl-substituted aromatic compound unit is 0 to 35 weight. %, And the bromine value is 0 to 30 g / 100 g, and the number average molecular weight is about 500 to 1,100. The copolymer hydride of the present invention described above is an adhesive resin with a high softening point, and is most suitable for use in hot-melt adhesives, etc., and is subject to high-temperature creep and holding hot-melt adhesive.着 剂 etc. When the copolymer hydride of the present invention is used as a hot-melt adhesive with an adhesive resin, the hot-melt adhesive is generally prepared by adding a base polymer and a plasticizer equal to the copolymer hydride. The aforementioned base polymer is not particularly limited. From the users who are generally used as the base polymer in hot-melt adhesives, it can be appropriately selected and used. This paper size is applicable to China National Standard (CNS) A4 specifications (2) OX29 &7; 7) (Please read the notes on the back _ 1 · • Items and fill in * Pack-: Write this page) Φ -8-588054 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7 _Five, Invention Description (6) Which. Specific examples of this base polymer are natural rubber, ethylene-vinylic acid vinyl copolymer, amorphous poly-alpha-olefin or styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene Ethylene-styrene block copolymer (SIS) and styrene · ethylene-butene-styrene rubber (SEBS), styrene-ethylene-propylene-styrene (SEPS), etc. obtained by hydrogenation of these. These can be used alone or in combination of two or more. On the other hand, the plasticizer is not particularly limited. From the viewpoint of plasticizers generally used as hot-melt adhesives, they can be appropriately selected and can be used arbitrarily. The specific example of this plasticizer is that the heavy oil residues obtained from the crude oil under constant pressure distillation are distilled under reduced pressure, and then the shovel system obtained through refining using hydrogenation modification and dewaxing treatment or distilled under reduced pressure is removed by solvent extraction. Examples of the naphthalene-based operation oil obtained by the hydrogenation and white clay treatment methods include polybutene, liquid α-olefin, and the like. These can be used alone or in combination of two or more. The content ratio of each component in this hot-melt adhesive varies depending on the required physical properties. Generally, the copolymer hydride is 30 to 70% by weight, the base polymer is 15 to 40% by weight, and the plasticizer is 10 to 40% by weight. In addition, the hot-melt adhesive, in addition to the copolymer hydride, the base polymer, and the plasticizer, contains a desired physical property in a range where no loss is required, and may contain an oxidation preventive agent, osmium, and concrete as necessary. . The method for preparing the hot-melt adhesive is not particularly limited, and for example, a propeller mixer, a two-shaft kneader, a nibbler, etc. can be used, and the components can be mixed and kneaded by heating and melting. The order of the ingredients is not specifically limited, and the heating temperature is also not limited. Generally, it is 120 ~ This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) — ~ (Please read the back Note: Please fill in this page again) 4 ▼ Fill in, fill, and order-9- 588054 A7 B7 V. Description of the invention (7) 190 ° C temperature range for heating, melting and mixing. The present invention is further explained in detail through examples, and the present invention is based on this example and is not particularly limited. Example 1 In a nitrogen-substituted 1-liter polymerization reactor with a stirrer, 154 g of xylene (48 parts by weight of 100 parts by weight of a raw material monomer) was added, and the mixture was heated to 260 ° C, and the ring was stirred for 120 minutes while stirring. A mixture of 159 g of pentadiene and 159 g of styrene was added thereto. Thereafter, the copolymerization reaction was continued for 140 minutes. After completion of the reaction, a cyclopentadiene and styrene copolymer obtained by removing the reaction generated liquid and using a rotary evaporator at a temperature of 200 ° C and a pressure of 1.3 kp for 2 hours and removing unreacted monomers and xylene is obtained. 289g. The physical properties of this copolymer are shown in Table 1. Example 2 A nitrogen-substituted 1-liter polymerization reactor with a stirrer was charged with 120 g of xylene (30 parts by weight of 100 parts by weight of a raw material monomer), heated to 230 ° C, and the ring was stirred for 120 minutes while stirring. A mixture of 200 g of pentadiene and 200 g of styrene was added thereto. Then, it heated up to 260t in 60 minutes, and performed the copolymerization reaction for 160 minutes. After completion of the reaction, the reaction product can be taken out and a rotary evaporator can be used to treat the copolymer of cyclopentadiene and styrene at a temperature of 200 ° C and a pressure of 1.3 kp for 2 hours and removing unreacted monomers and xylene 376g. And this paper size is applicable to Chinese National Standard (CNS) A4 specification (2) 0X297 mm) ---------- Approval of clothing-(Please read the precautions on the back before filling this page) Order Ministry of Economic Affairs Printed by the Consumer Property Cooperative of the Intellectual Property Bureau -10- 588054 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __ B7__ V. Description of the invention (8) The physical properties of the copolymer are shown in Table 1. Example 3 In a nitrogen-substituted 1-liter polymerization reactor with a stirrer, 143 g of dimethyl formaldehyde (45 parts by weight of 100 parts by weight of raw material monomers) was added, and heated to 240 ° C. To this was added a mixture of 159 g of cyclopentadiene and 159 g of styrene. Thereafter, the temperature was raised to 260 ° C. for 60 minutes, and a copolymerization reaction was performed for 80 minutes. After completion of the reaction, a cyclopentadiene and styrene copolymer obtained by removing the reaction generated liquid and using a rotary evaporator at a temperature of 200 ° C and a pressure of 1.3 kp for 2 hours and removing unreacted monomers and xylene is obtained. 292g. The physical properties of this copolymer are shown in Table 1. Example 4 In a nitrogen-substituted 1-liter polymerization reactor with a stirrer, 80 g of xylene (20 parts by weight of 100 parts by weight of a raw material monomer) was added, and heated to 240 t, and cyclopentane was stirred for 120 minutes under stirring. A mixture of 200 g of diene and 200 g of styrene was added thereto. Thereafter, the temperature was raised to 260 ° C for 60 minutes, and a copolymerization reaction was performed for 380 minutes. After the reaction is completed, the reaction product can be taken out, and a rotary evaporator can be used to treat the copolymer of cyclopentadiene and styrene at a temperature of 200 ° C and a pressure of 1.3 kp for 2 hours and removing unreacted monomers and xylene. 374g. The physical properties of this copolymer are shown in Table 1. (Please read the notes on the back first
Jm •項再填」 裝— 寫本頁) 、11 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 588054 7 Β 五、發明説明（9 ) 比較例1 於氮取代之附有攪拌機的1公升聚合反應器中加入二 甲苯288g(對原料單體100重量份爲90重量份），加熱至 240°C，於攪拌中，以120分鐘將環戊二烯159g與苯乙烯 1 59g之混合物添加於其中。其後，以60分鐘昇溫至2601 而進行500分鐘共聚合反應。 反應結束後，取出反應生成液而可使用旋轉蒸發器， 於溫度20(TC、壓力1.3kp下處理2小時且除去未反應單體 與二甲苯而所得之環戊二烯與苯乙烯之共聚物295g。而此 共聚物之物性所示如第1表。 (請先閱讀背面之注意事項再填寫本頁) 4 項再填· 裝· 經濟部智慧財產局員工消費合作社印製 第1表 實S _ 比較例 1 2 3 4 1 對單體100重量份之溶媒量 (重量份） 48 30 45 20 90 軟化點n (°C) 100 112 102 130 95 苯乙烯單位含有量2) (重量份％) 47 49 54 49 54 溴價 3) (g/l〇〇g) 55 55 55 56 55 數平均分子量 [Mn]4) 730 940 870 980 720 分子量分佈 [Mw/Mn]4) 2.2 2.6 2.5 2.8 2.3 〔注〕 1) 依據MI 7-1991，使用環球法測定 2) 以紅外線分光光度儀（波數700cm·1之吸光度）定量 本紙張尺度適用中國國家標準（CNS ) A4規格（2】OX 公釐）Jm • Refilling of items ”(Writing — write this page), 11 paper sizes are applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -11-588054 7 Β 5. Description of the invention (9) Comparative Example 1 Replacement with nitrogen Into a 1-liter polymerization reactor equipped with a stirrer, 288 g of xylene (90 parts by weight of 100 parts by weight of raw material monomers) was heated to 240 ° C, and 159 g of cyclopentadiene and benzene were mixed in 120 minutes with stirring. A mixture of 59 g of ethylene was added thereto. Then, it heated up to 2601 over 60 minutes, and performed the copolymerization reaction for 500 minutes. After completion of the reaction, the reaction product is taken out, and a rotary evaporator can be used, and the copolymer of cyclopentadiene and styrene obtained by processing at a temperature of 20 ° C. and a pressure of 1.3 kp for 2 hours and removing unreacted monomers and xylenes. 295g. And the physical properties of this copolymer are shown in Table 1. (Please read the precautions on the back before filling out this page.) 4 refills · Packing · Printed on Form 1 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _ Comparative Example 1 2 3 4 1 Solvent amount (parts by weight) to 100 parts by weight of monomer 48 30 45 20 90 Softening point n (° C) 100 112 102 130 95 Unit content of styrene 2) (% by weight) 47 49 54 49 54 Bromine value 3) (g / 100 g) 55 55 55 56 55 Number average molecular weight [Mn] 4) 730 940 870 980 720 Molecular weight distribution [Mw / Mn] 4) 2.2 2.6 2.5 2.8 2.3 [ Note] 1) According to MI 7-1991, measured using the globe method. 2) Quantitative with infrared spectrophotometer (absorbance at wave number 700cm · 1). The paper size applies Chinese National Standard (CNS) A4 (2) OX mm.
、1T -12 - 588054 A7 __ ΒΊ _____ 五、發明説明（10) 3) 以VPO(蒸氣壓浸透壓法）測定 4) 以GPC測定 實施例5 於氮取代之附有攪拌機的1公升聚合反應器中加入二 甲苯70g、實施例1所得之共聚和物7〇g及鎳系觸媒1.5g， 於氫壓力4MPa、溫度230°C下進行4小時氫化反應。 反應結束後，取出反應生成液，添加氧化防止劑〔瑞 士汽巴精密化學公司製造、商品名「Ir2anox 1010」〕 4,000ppm後，可使用旋轉蒸發器，於溫度200 °C、壓力 1.3kp下處理1小時且經除去環己烷而所得之環戊二烯與苯 乙烯之共聚物氫化物70g。而此共聚物之物性所示如第2表 〇 實施例6 於實施例5中’取代實施例1所得之共聚物，可使用 實施例2所得之共聚物以外’與實施例5相同而所得共聚 物氣化物，而其物性表75如第2表。 實施例7 於實施例5中’取代實施例1所得之共聚物’可使用 實施例3所得之共聚物以外’與實施例5相同而所得共聚 物氫化物，而其物性表示如第2表。 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） (請先閱讀背面之注意事 ，項再填· 寫本頁) 經濟部智慧財產局員工消費合作社印製 -13- 588054 A7 ________B7 五、發明説明（11) 實施例8 取代實施例1所得之共聚物，可使用實施例3所得之 共聚物以外，與實施例4相同而所得共聚物氫化物，而其 物性表示如第2表。 比較例2 取代實施例1所得之共聚物，可使用比較例1所得之 共聚物以外，與實施例5相同而所得共聚物氫化物，而其 物性表示如第2表。 第2表 實筑 g例 比較例 5 6 7 8 2 軟化點υ (°〇 127 140 140 158 115 苯乙烯單位含有量2) (重量份％) 17 18 1 20 20 溴價3) (g/100g) 6 4 5 8 8 數平均分子量 〔Μη〕4) 740 950 860 990 730 分子量分佈 [Mw/Mn] 4) 2.2 2.5 2.5 2.8 2.2 〔注〕 5) 依據；IAI 7-1991，使用環球法測定 6) 以紅外線分光光度儀（波數7 0 0 c πΓ1之吸光度）定量 7) 以VPO(蒸氣壓浸透壓法）測定 8) 以GPC測定 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -裝-- (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 -14 - 588054 A7 ——一_B7 ____ 五、發明説明（12) 產業上之利用可能性 本發明之高軟化點共聚物係爲二瓌戊二稀與乙烯基取 代芳香族化合物之熱聚合物所成之共聚物，且熱聚合時溶 媒之使用量經控制，可於短時間內得到經濟性佳之高軟化 點又，前述共聚物之氫化物的本發明之共聚物氫化物係作 爲具有高軟化點之附有粘著樹酯可適合使用於熱熔粘合劑 等且可提供高度恒溫蠕變及具有保持力之熱熔粘合劑等。 I--------φτ 裝----^---訂----- (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 ) Α4規格（2]〇Χ 297公釐） -15-1T -12-588054 A7 __ ΒΊ _____ V. Description of the invention (10) 3) Measurement by VPO (Vapor Pressure Infiltration Pressure Method) 4) Measurement by GPC Example 5 A nitrogen-substituted 1-liter polymerization reactor with a stirrer 70 g of xylene, 70 g of the copolymer obtained in Example 1 and 1.5 g of a nickel-based catalyst were added thereto, and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and a temperature of 230 ° C. for 4 hours. After completion of the reaction, the reaction solution was taken out, and an oxidation inhibitor [Ir2anox 1010 manufactured by Ciba Precision Chemical Co., Ltd.] was added. After 4,000 ppm, a rotary evaporator can be used for treatment at a temperature of 200 ° C and a pressure of 1.3 kp. 70 g of a copolymer of cyclopentadiene and styrene obtained by removing cyclohexane for 1 hour. The physical properties of this copolymer are shown in Table 2. Example 6 In Example 5, the copolymer obtained in the place of Example 1 can be used in place of the copolymer obtained in Example 2 instead of the copolymer obtained in Example 2. The material is gaseous, and its physical property table 75 is as shown in Table 2. Example 7 In Example 5, the copolymer obtained in place of Example 1 may be used in place of the copolymer obtained in Example 3, except that the copolymer obtained in Example 3 is the same as that in Example 5, and its physical properties are shown in Table 2. This paper size is in accordance with Chinese National Standard (CNS) A4 (210x 297 mm) (Please read the notes on the back, and then fill in this page and write this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-13- 588054 A7 ________B7 V. Description of the invention (11) Example 8 Instead of the copolymer obtained in Example 1, the copolymer obtained in Example 3 may be used in addition to the copolymer obtained in Example 4 and the hydride of the copolymer obtained in Example 4 may be used. table. Comparative Example 2 Instead of the copolymer obtained in Example 1, a copolymer hydride obtained in the same manner as in Example 5 except for the copolymer obtained in Comparative Example 1 may be used, and its physical properties are shown in Table 2. Table 2 Example g Example Comparative Example 5 6 7 8 2 Softening point υ (° 〇127 140 140 158 115 Styrene content 2) (% by weight) 17 18 1 20 20 Bromine value 3) (g / 100g ) 6 4 5 8 8 Number average molecular weight [Μη] 4) 740 950 860 990 730 Molecular weight distribution [Mw / Mn] 4) 2.2 2.5 2.5 2.8 2.2 [Note] 5) Basis; IAI 7-1991, measured using the globe method ) Quantitative by infrared spectrophotometer (absorbance at wave number 7 0 0 c πΓ1) 7) Measured by VPO (Vapor Pressure Impregnation Method) 8) Measured by GPC This paper applies Chinese National Standard (CNS) A4 specification (210X 297) (Mm)-Packing-(Please read the notes on the back before filling this page), 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -14-588054 A7 —— 一 _B7 ____ V. Description of Invention (12) Industrial Applicability The high softening point copolymer of the present invention is a copolymer made of dipentadiene and a thermal polymer of a vinyl-substituted aromatic compound, and the amount of solvent used during thermal polymerization is controlled, and High economical high softening point is obtained in a short time. Hydrogenated copolymer-based adhesive resin invention may be adapted for use in hot melt adhesives and provides high creep and having a temperature holding power of hot melt adhesives having a high softening point with. I -------- φτ Packing ---- ^ --- Order ----- (Please read the notes on the back before filling out this page) Printed on paper by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs Standards applicable. National Standards (CNS) Α4 specifications (2) 0 × 297 mm) -15-