經濟部智慧財產局工消費合作社印製 A7 、 _________B7五、發明説明（1 ) 本發明係關於可用於增黏用途之脂族樹脂，其中環 狀、交聯或網路結構含量增高，及控制呈環球軟化點與分子量 間之關係較佳及對芳族溶劑之相容性較佳。此等樹脂用於熱熔 感壓黏著劑組成物具有改良之黏著性能β 熱熔感壓黏著劑通常包含聚合物或共聚物之混合物 (後文之”聚合物”包括均聚物及共聚物），較佳嵌段共聚 物，石油增黏劑樹脂及選擇性其它成份例如增量油（亦名加工 油）’填充劑及其它添加劑例如抗氧化劑或著色劑。 前述聚合物稱為S-I-S(苯乙烯-異戊間二烯-苯乙烯） 嵌段共聚物具有聚苯乙烯及聚異戊間二烯嵌段。此種情況下， 黏著劑組成物又包含聚笨乙烯-聚異戊間二烯二段。 以石油為主的樹脂對黏著劑的物理化學性質有重大 影響’例如熱熔黏性，與芳族溶劑之相容性，剪性及黏性。欲 獲得低熔黏性，對有機溶劑之良好相容性，高黏性及剪性而未 喪失高溫剪性能之最佳平衡，習知使用以石油為主的增黏樹脂 來獲得某些芳族改質。先前技術未含芳族改質之樹脂無法達成 前述性質至滿意的程度。 值得一提下述專利案及/或專利申請案為令人感興 趣之相關文件。 US 4,411，954描述使用如US 3,577,398所述製備的脂 族樹脂約以S-I-S為主之熱熔感壓黏著劑。 ΕΡ 0447855描述使用脂族及芳族改質脂族樹脂於以 S-I-S為主的熱熔熱壓黏著劑《芳族改質之用量為11至15%， 而值得一提使用笨乙烯作為芳族單體。 f請先«讀背面之注意事項再填巧本頁) - -I I —— —裝. 訂 線 本紙張尺度適用中國國家標率（CNS > A4規格（2丨0 X 29"?公釐） A7 B7 五、發明説明（2 ) US 4,623,698描述使用脂族及芳族改質脂族樹脂具 軟化點〇至80°C作為增黏劑用於苯乙烯丁二烯（SB)聚合物。 US 4,078，132描述由熱浸戊間二烯流製備脂族及芳族改質脂族 樹脂。異丁烯及異戊烯作為鏈轉移劑，而α-甲基笨乙烯(AMS) 作為芳族改質劑。某些用途使用軟化點70至85 °C之樹脂。 WO 95/16755描述使用S-I-S聚合物，芳族改質脂族樹脂及增量 劑油之熱熔黏著劑配方β芳族改質使熱熔感壓黏著刺配方具有 低熔點及高黏性。 但芳族改質增黏樹脂有數種缺點。第一芳香化物相當 昂貴。使用非芳香化物可使樹脂較便宜。第二較不適合氫化， 加氫處理及淬熄過程俾改良樹脂色彩用於任何用途。第三芳族 改質脂族樹脂於以熱熔為主的感壓用途中可於較高溫獲得較 低剪性能。故希望提供一種較廉償的以石油為主的樹脂其具有 比較芳族改質樹脂類似或甚至更佳用途。 也希望提供脂族 樹脂其可用於熱炫感壓黏著劑組成物，並組合低炫黏度與絕佳 黏性及剪性；及含有此種樹脂之熱熔感壓黏著劑6 經濟部智慧財產局SK工消骨合作社印製 如此發現含較高量之環狀結構之脂族樹脂具有所需 環球軟化點及分子量，可獲得具有絕佳黏性及剪性而未喪失高 溫剪性此的低黏度熱 '溶感壓黏者劑組成物。本發明之樹脂與業 界現況之脂族樹脂之最大區別為含較高量環狀結構。，，環狀結 構” 一詞定義為任何可提高樹脂内交聯或網路結構含量的結 構特點《此型結構特點係由於但非僅限於下列反應結果：其成 長中的聚合物鏈回咬而沿著主鏈及/或於鏈末端合併環狀結 構’單體二聚合而產生反應性環狀結構其可合併於聚合物鏈， 本紙張尺度糾帽辟^1· ( CNS ) ( 210x297^|t ) * --------**""" 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 ) 旁懸基於聚合物鏈中進行分子内聯結，及短聚合鏈間交聯形成 高度網路結構。可經由測定可指示環狀結構之多種物理化學性 質獲得證實。又發現環狀結構含量可分別控制樹脂環球軟化點 及分子量。 有鑑於此’本發明提供一種以石油為主之脂族樹脂具 有a)環球軟化點於75至110°C之範圍；b)重均分子量（Mw)為 1000至2600道爾呑，z-均分子量（Mz)1900至5000道爾吞及 Mw/Μη低於2.0; c)芳族質子含量藉ih-NMR測得低於總質子之 1.5%及d)混合甲基環己熔苯胺濁點（MMAP)90°C或以下。 又一具體例中本發明提供一種熱熔感壓黏著劑組成 物包括（i)100重量份笨乙烯-異戊間二烯·苯乙烯（S-I-S)橡膠； (ii)70至200重量份以石油為主之脂族樹脂具有環球軟化點於 75至110°C之範圍；重均分子量為1000至2600道爾吞z-均分子 量為1900至5000道爾呑及Mw/Mn低於2.0 ;芳族質子含量低於 藉1H-NMR測得全部質子之1.5% ;及（iii)〇至70重量份增量劑 油，其特徵為組成物具有最高黏度100,000 mpas，較佳80,000 mPas，係根據ASTM方法D3236於175°C使用布魯克菲黏度計測 量。 此外本發明提供一種分別控制脂族樹脂組成物之環 球軟化點及分子量之方法，該方法之特徵為樹脂中環狀結構含 量增加。此種增加較佳經由改變聚合反應中下而參數之一或多 個達成⑴反應溫度’（ii)催化劑舉，（iii)鍵轉移劑量，（ίν)進料 中之環二烯成份量。 本發明之其它目的及特點由下文詳細說明及隨附之 本紙張尺度適用中國國家標率（CNS > A4規格{ 2IOX297公釐> ~ — ：---\----装------1T--------漆. {诗先W讀背*之注意事項再填艿本頁) 4425 53 A7 87 五、發明説明（4 ) 申請專利範圍將顯然易明。 本發明使用之以石油為主的樹脂較佳為裂解石油進 料之弗利列-克拉弗特聚合產物，該進料含有C5稀煙及二稀煙 或C5或C6烯烴混合物及二烯烴與(：4與〇5烯烴或其二元體共聚 合用作鏈轉移劑。更佳石油進料含有若干環狀二烯烴例如環戊 二烯，甲基環戊二烯，二環戊二烯及/或其與活性(^及以成 份之二聚合產物。 所需脂族樹脂内環狀結構含量之增高例如可經由提 高反應溫度及/或催化劑量及使用環戊二烯豐富進料流達 成。樹脂中環狀結構含量增高可經由環球軟化點較高及/或分 子量較低或經由與芳族溶劑之相容性較佳（MMAP較低）獲得證 實。根據本發明之增黏樹脂導致熱熔組成物之熔體黏度下降。 此外可對熱熔組成物提供絕佳黏性及剪性。 於戊間二烯及/或異戊間二烯之弗利列克拉弗特聚 合反應期間，除了 1，2及1,4加成反應外部分單體也被環化二聚 合，隨後聚合或甚至於聚合後環化。 發現環球軟化點較高或分子量類似或甚至更低’或於 類似或甚至更高的環球軟化點分子量較低指示樹脂内之環狀 結構含量較高。發明人發現環狀結構含量可經由改變聚合條 件，例如催化劑含量，反應溫度，鏈轉移劑數量及進料組成物 彩響。 本發明之一個具體例中，脂族石油增黏劑樹脂包括弗 利列克拉弗特聚合石油進料包括C5及C6烯烴及/或二烯 烴，較佳環稀烴及環二烯烴例如環戊二烯，甲基環戊二烯，及 本紙張尺度遥用中國國家標準（CNS > Α4坑格（210X297公* ) ---：---;---—裝-- (請先Μ讀背*之注意事項再填巧本頁) 訂 經濟部智慧財產局員工消黄合作社印製 142 5 53 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（5 ) 其二元體與C4或C5烯烴及/或二元體共聚合作為鏈轉移劑。 此種樹脂之最終黏著性可經由改變反應溫度、催化劑量、鏈轉 移劑量及進料組成控制環狀結構量而獲得最佳。 如此可經由聚合過程中分別獲得具有所需軟化點及分子 量分布之樹脂D較高度環狀結構表示較為剛性結構可經由比較 合較低量環狀結構之樹脂，具有較高環球軟化點連同類似或甚 至更低的分子量，或於類似或甚至更高的環球軟化點具有較低 分子量獲得證實。也觀察到如MMAP濁點較低可知，此種樹脂 於芳族溶劑具有較佳相容性。此並非來自任何有意義的摻混芳 族成份，原因為質子NMR分析未顯示一般脂族樹脂與根據本 發明集備之樹脂間有任何有意義差異。 本發明之最終樹脂具有下列性質：a)環球軟化點為75 至ll〇°C ; b)Mw為1000至2600道爾吞，z•均分子量（Mz)為1900 至5000道爾吞及Mw/Mn低於2.0，Μη表示數均分子量；c)藉 1HNMR測得芳族質子含量相對於總質子低於1.5% ; d)MMAP 濁點為9〇t或以下。 此種聚合樹脂可用於熱熔感壓組成物作為增黏劑，組 成物内又包括聚合物及選擇性增量劑油及其它佐劑。 根據本發明之較佳熱溶感壓組成物包括下列之混合物 (1)100份重量比笨乙烯-異戊間二烯，苯乙烯（S-I_S)嵌段共 聚物例如克莱特（Kraton)D 1107，克萊特d κχ 601 Cs，克萊特 D 1114，凡克特(Vector)4111，合約1〇至3〇重量份笨乙烯：⑼ 每〗⑽份聚合物含有約70至200重董份，以石油為主的脂族樹脂 具有a)環球軟化點於75至100°C之範圍，b)重均分子量（Mw)為 本紙張尺度適用中圉國家標率（CNS M4規格（2丨OX25T7公釐） (請先閱讀背面之注意事磅再填寫本頁) r .1 、τ 丨> 經濟部智法財產局SK工消費合作社印製 A7 B7 五、發明説明（6 ) 1000至2600道爾吞，Z-均分子量（Mz)為1900至5000道_吞及 Mw/Mn低於2.0，及c)藉1HNMR測得芳族質子含量相對於總質 子低於1.5%。 本具體例中所含石油增黏劑樹脂（ii)具有MMAP 90°C 或以下但非必要。 (iii)混合物也含有若干增量劑油含量為〇至70重量份 /100份聚合物例如雪弗列斯（Shellflex)451 FC。 熱熔組成物具有熔體黏度於175°C使用布魯克菲黏度 計根據ASTM-D3236測得低於100,000較佳低於80,000 mPas。 使用根據本具體例之樹脂（ii)於此種熱熔感壓黏著劑組成物， 可獲得比較使用已知脂族樹脂例如匹可德克（Piccoiac)95E及 艾寇瑞斯（Escorez) 1310更低的炫體黏度，滚珠黏性可婉美現有 脂族或芳族改質樹脂例如匹可德克95E或艾寇瑞斯2203或荷寇 德克（Hercotac)U48及具有比較芳族改質樹脂例如艾寇瑞斯 2203 ’荷寇德克1148及荷克莉斯（Hercules)樹脂a更佳的高溫 剪強度。前述商用樹脂之商品名詳述於如下實驗一節（材料與 方法）。 經常本發明之樹脂係經由弗利列克拉弗特聚合反應 製備’其中裂解石油進料與鏈轉移劑於惰性溶劑之混合物以 1.0至8_0wt%催化劑（如氣化鋁’溴化鋁，氟化鋁，三氟化硕 或其溶液漿液或錯合物）處理所用反應溫度為〇至1〇〇。〇。 最終聚合進料通常含約20至60較佳30至50 wt%石油 進料流0至20 wt%鏈轉移劑及4〇至80 wt%惰性溶劑例如曱笨 或工廠回收溶劑。適當聚合進料含有30至50 wt%較佳35至45 本紙張从適用中家縣（CNS ) ( 21Gx297“） '—— ---^----.---ά------ir------線 (锖先M讀背面之注意事項再填寫本頁) 442553 A 7 B7 五、發明説明（7 ) wt%可聚合單體故每次總進料之最終產率為30至50 wt〇/o。 石油進料流通常含未飽和烴係由C5及C6烯烴及/或 二烯烴沸點於20至l〇〇t：較佳30至70°C组成。環戊二烯及甲基 環戊二烯通常係藉於1 〇〇至16〇t熱浸C6/C6烯烴及二烯烴部分 藉蒸餾分離所得二元體去除。但發現含環烯烴及環二烯烴成份 之進料例如環戊二烯及二環戊二烯可促成樹脂更為環狀及剛 性結構’最終導致熱熔感壓配方之更佳黏著性能（參見實例 3 )。其它經由環狀二烯與C5線性共軛二烯或其它反應性烯烴 成份於石油進料流共聚合形成的環狀二烯也可於最終樹脂促 成更高度環狀結構。 所用兩種石油進料流含或未含環二烯烴之平均組成 列舉如下。 未含 含環狀二烯 烴 進料 A B 總烯烴： 13 11 總環烯烴： 17 14 總二烯烴： 65 55 、總環二烯烴： <2 15 稀烴範例有' :異丁烯，1-戊烯 ’ 2-甲基_丨_戊稀及反 及順2-戊烯》 環烯烴範例有環戊烯及環己烯。 二烯烴範例有順及反戊間二烯（1，3-戊二缔）14_戊二 烯，異戊間二烯，1，3-己二烯及1,4-己二烯。 本紙張尺度適用中國國家標率< CNS ) A4規格（210X297公釐） <#先閲谛背面之注意事項再填寫本I) - 、ye 經濟部智慧財產局員工消費合作社印製 •10- 442553 A7 B7 經濟部智慧时產局員工消費合作社印製 五、發明説明（8 ) 環二烯烴範例有環戊二烯，二環戊二烯，二種成份之 甲基及乙基衍生物及環戊二烯烴與二烯烴之共聚二元體。 未含環二烯烴之石油進料商品例有殼牌之（NL)超戊 間二烤泼縮物及含所需環二稀煙之較佳石油進料商品有殼牌 之(NL)普通戊間二烯濃縮物。環二烯烴成分當然也可加至乏環 二烯烴流。 特別適合的石油流含有至少70 wt%可聚合單體及至 少50 wt%戊間二烯》又含有低於2 wt%異戊間二烯。欲獲得熱 熔感壓黏著劑組成物之最低可能的熔體黏度，其含有至少1〇 wt%環戊烯及至少10 wt%，較佳至少15 wt%環二烯烴成分例如 環戊二烯及/或二環戊二烯。 因一般使用異丁烯，2-甲基-1-丁烯，2·甲基-2-丁烯 及其二元體募聚物作為鏈轉移劑來獲得具有較低及較窄分子 量分布之樹脂。各成份可純質施用或稀釋於惰性溶劑例如甲笨 或非反應性C4至C6成份施用。此種流之範例為異丁烯羅芬納 (Raffinate) 1 ex DSM»異戊烯(2-甲基-2-丁烯）作為鏈轉移劑比 較其它鏈轉移劑可於類似的分子量獲得相當高環球軟化點。為 成本價格理由故，較佳使用純質或稀釋型異丁稀。 添加更多鏈轉移劑可降低環球軟化點及/或分子量。 聚合過程中使用的溶劑為純甲苯或工廠回收甲苯。以工廠回收 甲苯為佳*原因為使用工廠回收曱笨含有來自石油進料流未反 應的化合物例如環戊烷、正戍烷、異戊烷及環己烷，可比較使 用純甲苯於類似分子量獲得較高環球軟化點。 聚合催化劑用量占聚合進料中可聚合成份量為1.0至 {許乞閱讀背面之注意事項再4本頁) 丨裝 -訂 線 本紙張尺度適用中國固家揉準（CNS > A4規格（2】OX29?公釐） •11- 442553 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（9 ) 8.0 wt%較佳3.0至6.0 wt%，更佳4.0至5.0 wt%。本發明發現催 化劑含量較高選擇性合併較高溫可降低分子量同時樹脂軟化 點保持常數。所得樹脂於熱熔感壓组成物具有較低熔體黏度。 催化劑含量增高也如MMAP濁點較低，反映呈與芳族溶劑則相 容性增咼（參見實例1) β催化劑可選自任何適圍弗利列克拉 弗特催化劑’例如三氣化鋁、溴化鋁、氟化鋁、三_及四氣化 钬、四氣化錫'三氟化硼及其溶夜、漿液或錯合物。 通常聚合溫度為0至100°c但本發明較為50至120t之 範圍。發現反應溫度更高於樹脂軟化點保持常數值可獲得更多 環狀結構反映為分子量較低《再度所得樹脂造成熱熔感壓組成 物之總體黏度降低並具有絕佳黏性及剪性（參見實例2)。 聚合反應可以連續法或分批模式進行。反應時間典型 為1,0至4.0小時依據反應溫度而定。 聚合反應後殘餘催化劑例如可藉加水或以水萃取去 除。 如此所得聚合物-溶劑混合物可被氣體去除未反應 烴’溶劑及低分子量募聚物。最終樹脂通常具有較高軟化點。 如此所得樹脂最適用於根據本發明作為增黏劑具有：a)環球軟 化點為75至110°C ’較佳90至lOOt； ; b)Mn為600至1300，較佳 700至1000道爾吞’ Mw為1〇〇〇至2600，較佳低於2000道爾吞， z-均分子量（Mz)為1900至5000,較佳低於4000道爾吞及Mw/Mn 低於2.0 ; c)藉NMR測得芳族質子濃度相當於總質子低於 1.5% ;及d)MMAP濁點為9〇t或以下。 通常經由類似石油進料流之未改質脂族樹脂商品之 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS M4規格（2丨0X297公釐） -12 - 442553 A7 ___B7 五、發明説明（10) MMAP濁點為90°C或以上，而較低MMAP值僅能以芳族改 質樹脂獲得。舉例說明如下表： Γ * I | |----1------1 I 丨環球軟化點| Μζ | ΜΜΑΡ丨偖註 丨 丨（°C)丨（道《吞）| fC)丨 | I- I I |----j------1 I艾寇瑞斯2203 I 94 I 3200 | 88 |芳族改質| I-----------1----1------1----1------1 I艾寇瑞斯1310 I 94 I 3000丨96丨脂族樹脂| I f I------1----1------1 i 溫特克（Wingtack)95 I 99 } 2900 | 丨00 | 脂族樹脂 | ^ *裝 {錡先閔讀背面之注意事項再填寫木頁)A7, _________B7 printed by the Industrial and Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy The relationship between ring and ball softening point and molecular weight is better and the compatibility with aromatic solvents is better. These resins are used in hot-melt pressure-sensitive adhesive compositions with improved adhesive properties. Β Hot-melt pressure-sensitive adhesives usually include a mixture of polymers or copolymers (hereinafter, "polymers" include homopolymers and copolymers) Preferred block copolymers, petroleum tackifier resins and optional other ingredients such as extender oils (also known as processing oils) 'fillers and other additives such as antioxidants or colorants. The polymer is referred to as S-I-S (styrene-isoprene-styrene) block copolymer and has polystyrene and polyisoprene blocks. In this case, the adhesive composition further comprises a polyethylene-polyisoprene two-stage. Petroleum-based resins have a significant impact on the physicochemical properties of the adhesives, such as hot-melt viscosity, compatibility with aromatic solvents, shear properties, and viscosity. To obtain the best balance of low melting viscosity, good compatibility with organic solvents, high viscosity and shear without losing high temperature shear performance, it is known to use petroleum-based tackifying resins to obtain certain aromatics Improved. Prior art resins which do not contain aromatic modification cannot achieve the aforementioned properties to a satisfactory level. It is worth mentioning that the following patents and / or patent applications are interesting related documents. US 4,411,954 describes the use of hot melt pressure-sensitive adhesives predominantly S-I-S based on aliphatic resins prepared as described in US 3,577,398. EP 0447855 describes the use of aliphatic and aromatic modified aliphatic resins in SIS-based hot-melt hot-pressing adhesives. The amount of aromatic modification is 11 to 15%, and it is worth mentioning the use of stupid ethylene as the aromatic monomer. body. fPlease «read the precautions on the reverse side and fill in this page first)--II —— — Binding. The paper size of the booklet applies the Chinese national standard (CNS > A4 specification (2 丨 0 X 29 "? mm) A7 B7 V. Description of the invention (2) US 4,623,698 describes the use of aliphatic and aromatic modified aliphatic resins with softening point 0 to 80 ° C as a tackifier for styrene butadiene (SB) polymers. US 4,078 No. 132 describes the preparation of aliphatic and aromatic modified aliphatic resins from hot-dip pentadiene streams. Isobutylene and isoprene are used as chain transfer agents, and α-methylbenzyl ethylene (AMS) is used as aromatic modifier. Some applications use resins with a softening point of 70 to 85 ° C. WO 95/16755 describes the use of SIS polymers, aromatic modified aliphatic resins and extender oils for hot melt adhesive formulations β aromatic modification for hot melt The pressure-sensitive adhesive thorn formula has a low melting point and high viscosity. However, aromatic modified tackifier resins have several disadvantages. The first aromatic compound is quite expensive. The use of non-aromatic compounds can make the resin cheaper. The second is less suitable for hydrogenation and hydrogenation. Treatment and quenching process: Improve resin color for any use. Third aromatic modified aliphatic tree In hot-melt-based pressure-sensitive applications, lower shear performance can be obtained at higher temperatures. Therefore, it is desirable to provide a cheaper petroleum-based resin that has similar or even better uses than aromatic modified resins. It is also desirable to provide aliphatic resins which can be used in heat-sensitive pressure-sensitive adhesive compositions and combine low-gloss viscosity with excellent tack and shear properties; and hot-melt pressure-sensitive adhesives containing such resins 6 Intellectual Property Bureau, Ministry of Economic Affairs SK Engineering Co., Ltd. printed so found that aliphatic resins with a higher amount of ring structure have the required global softening point and molecular weight, and can obtain low viscosity with excellent viscosity and shear properties without losing high temperature shear properties. Hot 'melt-sensitive pressure-sensitive adhesive composition. The biggest difference between the resin of the present invention and the current state of the aliphatic resin is that it contains a higher amount of cyclic structure. The "cyclic structure" is defined as any that can improve the resin internal communication Structural characteristics of the link or network structure content "This type of structural characteristics is due to, but not limited to, the following reaction results: the growing polymer chain bites back and merges cyclic structures along the main chain and / or at the end of the chain ' Body dimerization Produces a reactive ring structure that can be incorporated into polymer chains. This paper scales ^ 1 · (CNS) (210x297 ^ | t) * -------- ** " " " Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperative A7 ____B7 V. Description of the Invention (3) The side suspension is based on the intramolecular connection in the polymer chain and the cross-linking between the short polymer chains to form a highly network structure. The ring can be indicated by measurement. A variety of physicochemical properties of the structure were confirmed. It was also found that the cyclic structure content can control the ring and ball softening point and molecular weight of the resin respectively. In view of this, the present invention provides a petroleum-based aliphatic resin having a) ring and ball softening point of 75 to 110 ° C range; b) weight average molecular weight (Mw) is 1000 to 2600 Daltons, z-average molecular weight (Mz) is 1900 to 5000 Daltons and Mw / Μη is less than 2.0; c) aromatic proton content borrowed ih-NMR measured below 1.5% of the total protons and d) the mixed methylcyclohexylaniline cloud point (MMAP) 90 ° C or below. In yet another embodiment, the present invention provides a hot-melt pressure-sensitive adhesive composition comprising (i) 100 parts by weight of stupid ethylene-isoprene · styrene (SIS) rubber; (ii) 70 to 200 parts by weight of petroleum The main aliphatic resin has a global softening point in the range of 75 to 110 ° C; a weight average molecular weight of 1,000 to 2600 daltons; z-average molecular weight of 1900 to 5000 daltons; and Mw / Mn below 2.0; aromatic Proton content is less than 1.5% of all protons measured by 1H-NMR; and (iii) 0 to 70 parts by weight of extender oil, which is characterized by a composition having a maximum viscosity of 100,000 mpas, preferably 80,000 mPas, according to the ASTM method D3236 was measured at 175 ° C using a Brookfield viscometer. In addition, the present invention provides a method for separately controlling the softening point and molecular weight of a sphere of an aliphatic resin composition. The method is characterized in that the content of the cyclic structure in the resin is increased. This increase is preferably achieved by changing one or more of the parameters of the polymerization reaction to achieve the "reaction temperature" (ii) the catalyst, (iii) the bond transfer dose, and (ίν) the amount of cyclodiene components in the feed. Other objects and features of the present invention are explained in detail below and the accompanying paper standards are applicable to China's national standard (CNS > A4 specification {2IOX297 mm > ~ ~: --- \ ---- 装 --- --- 1T -------- Lacquer. {Notes of Poetry W Read Back * Please fill in this page) 4425 53 A7 87 V. Description of Invention (4) The scope of patent application will be clearly legible. The petroleum-based resin used in the present invention is preferably a Frillet-Crafts polymerization product of a cracked petroleum feed, the feed containing C5 lean smoke and second lean smoke or a C5 or C6 olefin mixture and a diolefin and ( : 4 is copolymerized with 05 olefin or its dimer as a chain transfer agent. A more preferred petroleum feed contains several cyclic diolefins such as cyclopentadiene, methylcyclopentadiene, dicyclopentadiene and / Or it is the polymerization product with the active ingredients and the components. The increase in the content of the cyclic structure in the desired aliphatic resin can be achieved, for example, by increasing the reaction temperature and / or the amount of catalyst and using cyclopentadiene to enrich the feed stream. Resin The increase in the content of the mesocyclic structure can be confirmed by a higher ring and ball softening point and / or a lower molecular weight or better compatibility with aromatic solvents (lower MMAP). The tackifying resin according to the present invention results in a hot-melt composition The melt viscosity of the material decreases. In addition, it can provide excellent tack and shear properties to the hot-melt composition. During the Friecherraft polymerization of pentadiene and / or isoprene, except 1, Some monomers outside the 2 and 1,4 addition reactions are also cyclized and dimerized. , Followed by polymerization or even cyclization after polymerization. It is found that a higher ring and ball softening point or a similar or even lower molecular weight 'or a similar or even higher ring and ball softening point indicates that the cyclic structure content in the resin is higher. The inventors found that the content of the cyclic structure can be changed by changing the polymerization conditions, such as the catalyst content, reaction temperature, amount of chain transfer agent, and the composition of the feed composition. In a specific example of the present invention, the aliphatic petroleum tackifier resin includes Foley Leclaft polymerized petroleum feeds include C5 and C6 olefins and / or diolefins, preferably cyclic dilute hydrocarbons and cyclodiene such as cyclopentadiene, methylcyclopentadiene, and this paper uses Chinese national standards. (CNS > Α4 pit grid (210X297) *) ---: ---; ----- install-(please read the precautions of M * before filling out this page) Order the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Yellow Cooperative Cooperative 142 5 53 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5) The copolymer of its binary with C4 or C5 olefin and / or binary is used as a chain transfer agent. The final adhesion of this resin can be modified by The reaction temperature, the amount of catalyst, the amount of chain transfer, and the feed composition control the amount of cyclic structure to obtain the best. In this way, resins with the required softening point and molecular weight distribution can be obtained through the polymerization process. The structure can be confirmed by comparing lower amounts of resins with a cyclic structure, with higher ring and ball softening points together with similar or even lower molecular weights, or with similar or even higher ring and ball softening points with lower molecular weights. It has also been observed As can be seen from the lower cloud point of MMAP, this resin has better compatibility with aromatic solvents. This does not come from any meaningful blending of aromatic components, because proton NMR analysis does not show that ordinary aliphatic resins and There are any significant differences between the prepared resins. The final resin of the present invention has the following properties: a) the ring and ball softening point is 75 to 110 ° C; b) the Mw is 1000 to 2600 Daltons, and the z · average molecular weight (Mz) is 1900 to 5000 Dalton and Mw / Mn is less than 2.0, Mη means number average molecular weight; c) Aromatic proton content measured by 1HNMR is less than 1.5% relative to total protons; d) MMAP cloud point is 90t Or below. This kind of polymer resin can be used in hot-melt pressure-sensitive composition as a tackifier, and the composition includes polymer and selective extender oil and other adjuvants. A preferred hot-melt pressure-sensitive composition according to the present invention includes the following mixture (1) 100 parts by weight of styrene-isoprene, styrene (S-I_S) block copolymer such as Kraton D 1107, Crete d κχ 601 Cs, Crete D 1114, Van Corte (Vector) 4111, contract 10 to 30 parts by weight of stupid ethylene: ⑼ Each polymer contains about 70 to 200 parts by weight. Petroleum-based aliphatic resins have a) a global softening point in the range of 75 to 100 ° C, and b) a weight average molecular weight (Mw) based on the paper standard applicable to China's national standard (CNS M4 specification (2 丨 OX25T7 mm) ) (Please read the cautions on the back before filling out this page) r .1 、 τ 丨 > Printed by ASK B7 of SK Industrial Consumer Cooperative of Intellectual Property Office of Ministry of Economic Affairs V. Description of Invention (6) 1000 to 2600 Dalton , Z-average molecular weight (Mz) is from 1900 to 5000 channels and Mw / Mn is less than 2.0, and c) the aromatic proton content is less than 1.5% relative to the total protons measured by 1HNMR. The petroleum tackifier resin (ii) contained in this specific example has MMAP 90 ° C or below but is not necessary. (iii) The mixture also contains a number of extender oils with a content of 0 to 70 parts by weight per 100 parts of polymer such as Shellflex 451 FC. The hot-melt composition has a melt viscosity of less than 100,000 and preferably less than 80,000 mPas as measured by a Brookfield viscometer according to ASTM-D3236 at 175 ° C. By using the resin (ii) according to this specific example in such a hot-melt pressure-sensitive adhesive composition, it is possible to obtain a comparison using a known aliphatic resin such as Piccoiac 95E and Escorez 1310. Low dazzling body viscosity, ball viscosity can be beautiful existing aliphatic or aromatic modified resins such as Piccotec 95E or Aike Ruisi 2203 or Hercotac (Hercotac) U48 and have more aromatic modified resins such as Ai Korris 2203 'Hercotec 1148 and Hercules resin a better high temperature shear strength. The trade names of the aforementioned commercial resins are detailed in the experimental section (Materials and Methods) below. Often the resins of the present invention are prepared via a Fleich-Claffert polymerization reaction, in which a mixture of cracked petroleum feed and a chain transfer agent in an inert solvent is used at 1.0 to 8_0 wt% catalyst (such as aluminum vaporized aluminum, aluminum bromide, aluminum fluoride , Trifluoride trifluoride or its solution slurry or complex), the reaction temperature used is 0 to 100. 〇. The final polymerization feed typically contains about 20 to 60, preferably 30 to 50 wt% petroleum feed stream, 0 to 20 wt% chain transfer agent, and 40 to 80 wt% inert solvents such as benzene or plant recovery solvents. Appropriate polymerization feed contains 30 to 50 wt%, preferably 35 to 45 sheets of paper from the applicable Zhongjia County (CNS) (21Gx297 ") '—— --- ^ ----.--- ά ----- -ir ------ line (锖 Please read the precautions on the back of the page before filling in this page) 442553 A 7 B7 V. Description of the invention (7) The final yield of each wt% polymerizable monomer It is 30 to 50 wt./o. The petroleum feed stream usually contains unsaturated hydrocarbons consisting of C5 and C6 olefins and / or diolefins having a boiling point of 20 to 100 t: preferably 30 to 70 ° C. Cyclopentadiene The olefins and methylcyclopentadiene are usually removed by distilling the C6 / C6 olefins and diolefins partially by distillation from 100 to 160 t. However, it is found that Materials such as cyclopentadiene and dicyclopentadiene can contribute to a more cyclic and rigid structure of the resin 'eventually leading to better adhesion properties of the hot melt pressure sensitive formulation (see Example 3). Others are linear with cyclic diene and C5 The cyclic diene formed by the copolymerization of conjugated diene or other reactive olefin components in the petroleum feed stream can also promote a more highly cyclic structure in the final resin. The two petroleum feed streams used contain or not contain cyclic diene. The average composition of hydrocarbons is listed below. Without cyclic diene-containing feed AB Total olefins: 13 11 Total cyclic olefins: 17 14 Total diolefins: 65 55 、 Total cyclic diolefins: < 2 15 Examples of dilute hydrocarbons are:: Isobutylene, 1-pentene '2-methyl_ 丨 _pentene and trans and cis 2-pentene. Examples of cycloolefins are cyclopentene and cyclohexene. Examples of diolefins are cis and transpentadiene (1 , 3-pentadiene) 14_pentadiene, isoprene, 1,3-hexadiene, and 1,4-hexadiene. This paper size applies to China's national standard < CNS) A4 specification ( 210X297 mm) <#Read the notes on the back before filling in this I)-、 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • 10- 442553 A7 B7 Printed by the Consumer Cooperatives of the Smart Industry Bureau of the Ministry of Economic Affairs Explanation of the invention (8) Examples of cyclodiene include cyclopentadiene, dicyclopentadiene, methyl and ethyl derivatives of the two components, and a copolymerized binary body of cyclopentadiene and diene. Examples of petroleum feed products for diolefins include Shell's (NL) Superpentamyl Diastolic Condensate and Preferred Petroleum Feeders with the required ring dilute smoke. Shell (NL) ordinary pentadiene concentrate. Cyclodiene components can of course also be added to the depleted cyclic diene stream. Particularly suitable petroleum streams contain at least 70 wt% polymerizable monomers and at least 50 wt% pentene Diene "contains less than 2 wt% isoprene. To obtain the lowest possible melt viscosity of the hot melt pressure-sensitive adhesive composition, it contains at least 10 wt% cyclopentene and at least 10 wt%. Preferably at least 15 wt% of cyclodiene components such as cyclopentadiene and / or dicyclopentadiene. Isobutylene, 2-methyl-1-butene, 2-methyl-2-butene, and their binary aggregates are generally used as chain transfer agents to obtain resins with lower and narrower molecular weight distributions. The ingredients can be applied pure or diluted in an inert solvent such as methylbenzyl or non-reactive C4 to C6 ingredients. An example of this type of flow is isobutene, roffina 1 ex DSM »isopentene (2-methyl-2-butene) as a chain transfer agent. Compared with other chain transfer agents, it can obtain quite high global softening at a similar molecular weight. point. For reasons of cost and price, it is preferred to use pure or dilute isobutane. Adding more chain transfer agents can reduce the ring and ball softening point and / or molecular weight. The solvent used in the polymerization is pure toluene or factory recovered toluene. It is better to recover toluene in the factory. * The reason is to use the factory to recover toluene. It contains unreacted compounds such as cyclopentane, n-pentane, isopentane and cyclohexane from the petroleum feed stream. It can be compared with pure toluene with similar molecular weight. Higher global softening point. The amount of polymerization catalyst accounts for 1.0 to {the amount of polymerizable components in the polymerization feed. (Xu Qi reads the precautions on the back page, and then 4 pages) 丨 binding-binding. The paper size is applicable to China Gujia standard (CNS > A4 size (2 ] OX29? Mm) • 11- 442553 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) 8.0 wt% is preferably 3.0 to 6.0 wt%, more preferably 4.0 to 5.0 wt%. The present invention It was found that a higher catalyst content combined with higher temperature can reduce the molecular weight while keeping the resin softening point constant. The obtained resin has a lower melt viscosity in the hot-melt pressure-sensitive composition. An increase in the catalyst content also means that the cloud point of MMAP is lower, reflecting the Aromatic solvents are compatible (see Example 1). Beta catalysts can be selected from any suitable Fleclercloft catalysts, such as aluminum tri-gas, aluminum bromide, aluminum fluoride, tri- and tetra-gasification Dysprosium, tetra-gas tin 'boron trifluoride and its solution, slurry or complex. The polymerization temperature is usually 0 to 100 ° C but the present invention is in the range of 50 to 120t. It is found that the reaction temperature is higher than the resin softening point. Keep constant value to get more ring structure inversion Reflected as a lower molecular weight, the resin obtained again caused the overall viscosity of the hot-melt pressure-sensitive composition to decrease and had excellent viscosity and shear properties (see Example 2). The polymerization reaction can be carried out in a continuous or batch mode. The reaction time is typically 1,0 to 4.0 hours depend on the reaction temperature. The residual catalyst after the polymerization can be removed, for example, by adding water or extracting with water. The polymer-solvent mixture thus obtained can be gas-removed of unreacted hydrocarbons' solvents and low molecular weight polymers. The final resin usually has a higher softening point. The resin thus obtained is most suitable for use as a tackifier according to the invention having: a) a global softening point of 75 to 110 ° C 'preferably 90 to 100t;; b) Mn of 600 to 1300 , Preferably 700 to 1000 Dalton 'Mw is 1000 to 2600, preferably lower than 2000 Dalton, z-average molecular weight (Mz) is 1900 to 5000, preferably lower than 4000 Dalton and Mw / Mn is less than 2.0; c) the aromatic proton concentration measured by NMR is equivalent to less than 1.5% of the total protons; and d) the MMAP cloud point is 90 t or less. The unmodified aliphatic resin products that usually pass through a similar oil feed stream (please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS M4 specification (2 丨 0X297 mm) -12- 442553 A7 ___B7 V. Description of the invention (10) The cloud point of MMAP is 90 ° C or above, and the lower MMAP value can only be obtained with aromatic modified resin. An example is shown in the following table: Γ * I | | ---- 1 ------ 1 I 丨 Global Softening Point | Μζ | ΜΜΑΡ 丨 Note 丨 (° C) 丨 (Dow "Swallow) | fC) 丨 | I- II | ---- j ----- -1 I Aikoris 2203 I 94 I 3200 | 88 | Aromatic modification | I ----------- 1 ---- 1 ------ 1 ---- 1 ------ 1 I Acres 1310 I 94 I 3000 丨 96 丨 Aliphatic resin | I f I ------ 1 ---- 1 ------ 1 i Wintec (Wingtack) 95 I 99} 2900 | 丨 00 | Aliphatic Resin | ^ * Packing {Please read the precautions on the back of the book before filling out the wooden pages)
ί匹可德克85E I 95 I 3400 | 95 |脂族樹脂| Η I !! I ΙΓ I j 丨· !荷寇德克1148 I 96 | 4000 | 88 |芳族改質| .J----L. j 線 相對於此，觀察到由於本發明樹脂之相容性改良， ΜΜΑΡ濁點呈環狀結構量之函數下降。 經濟部智楚財產局員工消費合作社印製 本紙張尺度適用中國圉家標準（〇^)六4规格（210><297公着） -13- 經濟部智慧財產局員工消費合作社印製 44255 3 Δ7 Α7 Β7 發明説明（η) 用於熱熔感壓組成物之特佳增黏剞具有下列典型性質（亦 參見實例4): 環球軟化點（t) 96 MMAP(°C ) 86 芳族質子(NMR) 0.7 色度50%於曱笨佳能（Gardner) 6 Μη(道爾吞） 830 Mw(道爾吞） 1460 Mz(道爾吞） 2800 環狀結構量的控制可藉改變催化劑含量及反應溫度 進行。此外預期也與環狀結構有關的所須的環球軟化點可藉鏈 轉移劑數量控制。典型前述樹脂之聚合條件列舉如下。 由於進料f之環狀成份量也會影準樹脂内環狀結構之最 終量，如此影響熱熔感壓組成物之最終熔體黏度，也列舉較佳 組成物。 -------^----装------1Τ------0 (請先閲讀背面之注意事項再填寫本页) 溫度： 55〇C 催化劑含量： 4.0 wt%/可聚合岸 聚合進料： 異丁烯* 8.7 異戊烯* 2.7 反-戊間二烯* 13.4 順·戊間二烯* 8.1 環戊二烯* 1.0 二環戊二烯* 5.5 本紙張尺度適用中國國家揉準（CNS ) Α4規格（2丨0Χ297公釐） •14· A? B7 五、發明説明（12) 環戊烯 8.3 甲苯 32.5 順-2-戊稀 1.0 反-2-戊稀 1.5 環戊烷 7.4 其它C5’S 9,9 總可聚合材料（*) 39.4 442553 本發明樹脂可舆S-I-S聚合物及添加劑攙混，獲得具 有低熔想點度連同絕佳剪性及黏性之熱熔感歷黏著劑組成 物。此種熱炼感壓黏著劑組成物可以多種形式使用。特佳形式 為黏膠帶及標簽。 熱熔感壓黏著劑組成物通常係由S-I-S嵌段共聚物， 本發明所述石油增黏劑樹脂及業界已知其它添加劑例如烴增 量劑油’抗氧化劑，著色劑，填充劑等組成。適當增量劑油選 自芳族油，環烷烴油，鏈烷烴油或其混合物。 與嵌段共聚物合併使用之石油樹脂量係於70至200重 量份/100份嵌段共聚物範圍。更佳範圍為90至150重量份/100 份嵌段共聚物。 使用時增量劑油之添加量至多70重量份/100份嵌段 共聚物，更佳5至50重量份。 S-I-S嵌段共聚物可選自含0至30重量份笨乙烯及0至 40重量份二段之聚合物。此等聚合物範例有克萊特D 1107,克 萊特〇尺又601€3，克萊特〇1114及凡克特4111。 如前述本發明之熱熔配方較佳具有熔體黏度於175°c 本紙張尺度適用中國g家標率（CNS ) /U说格（210X297公釐） ------1----装------IT-------^ i^-t閱讀背面.t/ii意事項再填w-木頁} 經濟部智*財產局員工涓费合作社印製 -15- A7 4 4 2 5 5 3 B7 五、發明説明（13) 測量低於100,000 〇^&3(匚？3)更佳於175°(：低於60,000 111?35。最 佳於175°C之熔體黏度係於35,000至50,000 mPas之範圍。由於 黏度降低非因添加芳族單體至聚合進料所引起，根據本發明之 樹脂具有優於其它眾所周知用於此種用途之樹脂之優點。 1. 由於環狀結構含量較高，樹脂比較相娘美的熱煤感 壓組成物内之匹可德克95E及艾寇瑞斯1310等脂族樹脂具有更 低熔體黏度。 2. 由於環狀結構較多因此樹脂分子量較低，含有本發 明樹脂之熱熔組成物具有滾珠軌跡可媲美現有階段或芳族改 質樹脂例如匹可德克95E或艾寇瑞斯2203及荷宼德克1148或甚 至更佳。 3. 由於含有極少芳香化物，根據本發明製造的樹脂比 較芳族改質樹脂例如艾寇瑞斯2203,荷寇瑞斯1148及荷克莉斯 樹脂A可獲得更佳高溫剪強度。 實例 實例1至4示例說明聚合條件對樹脂性質的影響。於 175°C對最終熔體黏度的優點亦於含克萊特D 1〗07及雪弗利斯 FC 451以聚合物/樹脂/油重量比100/ 120/20之配方獲得 驗證。 用於下列實例之本發明樹脂於後文稱為：本發明脂族 烴樹脂或簡稱為本發明樹脂。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ---------i------1T------^ (請先Κ讀背面之注意事碑再填艿本頁) 經濟部智慈財產局員工消費合作社印製 -16- 4425 53 A7 ________B7五、發明説明（Μ) 所用石油進料流（含及未含環二烯烴）及工廠回收溶劑之 典型組成例舉如下： 流進料 超戊間二烯 A 普通戊間二烯 B 溶 異丁烯* 0,0 0.0 0.0 正戊烷 0,2 0.0 1.5 異戊間二烯* 0.5 0·5 0.0 反-2-戊烯 1，8 0.9 2.5 順-2-戊烯 3.0 1.9 2.2 異戊烯# 78 5.6 0.3 反戊間二烯* 40.8 33.2 (Μ 順戊間二烯* 23.0 18.7 0.0 環戊烯 16.6 13.4 6.7 環戊烷 4.8 3.8 18.3 環戊二烯* 0.6 4.7 0·0 二環戊二烯* 0.0 9.4 0·0 其它 C5+C6_s 1.1 4.4 16.0 甲苯 0.0 0.0 2.4 單體（*) 72.6 72.2 0.5 經濟部智慧財產局員工涓費合作杜印製 實例所述樹脂並非皆使用前述進料流製備但可列舉此等 組成物原因為此等組成物所得結果為典型結果並表示全部其 它使用的石油進料及溶劑。實例使用之催化劑為52wt%氯化鋁 溶夜。 下文使用之縮寫及商品名說明於如以下實驗一節。 實例1 表1顯示對含或未含環二烯烴成分之進料使用較多 催化劑對最終樹脂性質的影響。 表1催化劑含量之影準 進料 A A B B 實例鴆號 la lb lc Id 異戍Μ二烯(Α/Β) 41.3 41.3 36.0 36.0 PR溶劑 58.7 58.7 64.0 64.0 催化劑 3-0 5·0 3.0 5*0 溫度 55 55 45 45 本紙張尺度適用中國國家標準（CNS ) A4规格（2丨0X297公羞） -17· ----------装------1T-------0 f請乇閱埃背面之注意事項再填窍本頁} 442553 A7 B7 五、發明説明（15) 異丁烯 12 12 13 13 環球軟化點 89.2 89,3 90J 93.1 MMAP 94 92 90 88 色度 3.6 4.7 5.2 6‘1 Μη 728 689 920 87ί Mw 1366 1235 1648 1444 Mz 2158 1941 3019 2525 Pd 1.88 1.79 L79 1.66 黏度 52900 1500 52200 44200 滾珠軌跡（cm) 1-2 2.0 1.6 2.4 對鋼撕離（N/25mm) 13.1 1L7 15.2 17.1 環軌跡（N/25mm) 25.4 21.4 28.8 26.4 SAFT(0.5kg,°C ) 97 95 94 93 對紙箱剪力 1130 731 85 56 (40°C ,1kg,min) 對銅剪力 38 52 98 37 (40°C ,2.5kg,min) 對鋼剪力 744 584 960 876 (70°C ,0.5kg,min) 結果明白顯示由於催化劑含量較高，MMAP及分子量 降低同時環球軟化點幾乎保持相等或顯示略增。當使用更多催 化劑時黏度劇降。 ----------装------1T------.&! (請先K讀背*之注意事項再填艿本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4说格（2〗0X297公釐） •18- 442553 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（16) 實例2 表2顯示對含或未含環二烯烴成分之進料使用較高 反應溫度對最終樹脂性質的影響。 表2溫度影響 進料 A A B B 實例編號 2a 2b 2c 2d 異戊間二烯（Α/Β) 41.3 41·3 36.0 36.0 PR溶劑 58.7 58.7 64,0 64.0 催化劑 5.0 5.0 3,0 3.0 溫度 15 55 45 65 異丁烯 12 12 13 T* 13 環球軟化點 83.3 89.3 90.1 92.0 ΜΜΑΡ 93 92 90 89 色度 2,4 4.7 5.2 6.2 Μη 975 689 920 801 Mw 1501 1235 1648 1417 Mz 2402 1941 3019 2636 Pd 1,54 1.79 1.79 1.77 黏度 50700 41500 52200 41200 滚珠軏跡（cm) 1.0 2.0 1.6 1,6 對鋼撕離（N/25mm) 11.9 11.7 15.2 14.1 環轨跡（N/25mm) 26.3 21.4 28.8 28.3 SAFT(0.5kg/C ) 96 95 94 93 對紙箱剪力 856 731 85 32 (40°C ,1kg,min) 對銅剪力 37 52 98 140 (40°C ,2.5kg,min) 對鋼剪力 597 584 960 952 (70°C ,0.5kg,min) 結果明白顯示由於較高溫MMAP及分子量略降而環 球軟化點顯示增高。使用較高溫熔體黏度劇降。 本紙張尺度適用中国國家搮準（CNS ) Α4規格（2丨0Χ297公釐） -------^---d------ΐτ------線 (請先閱讀背面之注意事項再填寫本頁) -19- 4 425 53 A 7 B7 五、發明説明（Π )當溫度由60增至80及100°c時也觀察到樹脂性質相同 的傾向。結果示於下表。表3溫度的影響 經濟部智慧財產局員工消費合作社印製 進料 B Β Β 實例編號 2e 2f 2g 異戊間二烯（A/B) 40.0 40.0 40.0 PR溶劑 60,0 60.0 60,0 催化劑 3.6 3.6 3.6 溫度 60 80 100 異丁烯 8.0 8.0 8.0 環球軟化點 94.1 99.6 101.5 MMAP 85 82 78 色度 5.5 6.9 8.7 Μη 874 82S 765 Mw 1393 1374 1394 Mz 2490 2751 3368 Pd 1.59 1.66 1.82 黏度 42800 37100 29500 滾珠軌跡（cm) 1.4 2,0 2.0 對鋼撕離（N/25mm) 14.δ 17.0 15.6 環執跡（N/25mm) 24.6 27.7 24.9 SAFT(0.5kg,°C ) 94 96 96 對紙箱剪力 27 51 29 (40°C ,lkg,min) 對鋼剪力 158 157 173 (40°C ,2.5kg,min) 對銅贫力 890 1038 1380 (70°C ,〇.5kg,min)實例3表4驗證使用含更多環烯烴及環二烯烴之優點。對本 例而言所用的樹脂具有類似的環球軟化點及分子量。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） <诗先閱讀背面之注意事項再填寫本頁) .裝 訂 線 -20- 442553 A7 B7 五 '發明説明（is ) 表4進料組成物的影举 進料 A B A B 實例編號 3a 3b 3c 3d 異戊間二烯（A/B) 41.3 36.0 41.3 36.0 PR溶剤 58.7 64-0 58.7 64.0 催化劑 3.0 3.0 4.0 3.75 溫度 55 65 35 50 異丁烯 4.0 7.0 8.0 10.0 環球軟化點 104.5 104.9 95.1 96.1 MMAP 95 89 94 87 色度 2.9 5,7 2,7 5,6 Μη 1146 928 1075 837 Mw 2076 1906 1759 1548 Mz 4024 4207 3023 3042 Pd L81 2.05 1.64 1.85 黏度 76000 50000 68200 37900 滾珠軌跡（cm) 1.7 3.S 2.2 3.0 對鋼撕離（N/25mm) 16.1 19.0 15.3 20.7 環軌跡（N/25mm) 27.0 3L4 27.5 32.8 SAFT(0.5kg,°C ) 98 95 101 93 對紙箱剪力 1321 149 511 232 (40°C ,1kg,min) 對銅剪力 303 288 89 120 (40°C ,2.5kg,min) 對鋼剪力 1180 1056 1014 809 ------_----裝------訂------線 <婧先閱讀背面之注意事項再填寫本頁) 經濟部智慧財i局員工消免合作社印製 (70°C ,0.5kg,min) 此等實例明白顯示具有類似環球軟化點及分子量之 樹脂就熱熔感壓組成物之MMAP及熔體黏度而言不同。存在有 環二烯烴例如環戊二烯及二環戊二烯也可促成樹脂之環狀特 性且引起熱熔配方之熔體黏度下降及樹脂MMAP降低。通常可 知於環狀二烯烴存在下，需要更多催化劑或更高溫及更多鏈轉 移劑來獲得類似的環球及分子量。使用含環烯烴及環二烯烴進 本紙張尺度適用中國國家標準（CNS ) A4规格（2〗0X297公釐> •21- 442553 經濟部智慧財產局肖工消«-合作社印製 A7 B7 五、發明説明（l9) 料似乎可略為加寬分子量分布。 實例4 表5樹脂為具有最佳性質可用於熱熔黏著劑組成物 作為增黏劑之樹脂範例。 表5基於兩種進料之最佳樹脂 進料 A B B B 實例編號 4a 4b 4c 4d 異戊間二烯（A/B) 41.3 36.0 40,0 36.0 PR溶劑 58.7 64.0 60.0 64.0 催化劑 4.0 4,0 4.0 3.75 溫度 70 55 55 50 異丁烯 6.0 10,0 9,0 10.0 環球軟化點 98,0 97Λ 96,5 96.1 MMAP 93 87 86 87 色度 4.5 6.1 5.9 5.6 Μη 901 802 827 837 Mw 1470 1436 1459 1548 Mz 2596 2595 2806 3042 Pd 1.63 1,79 1.76 1.85 黏度 49200 43000 -- 37900 滾珠執跡（cm) 2.6 3.2 -- 3.0 對鋼撕離（N/25mm) 14.5 17.3 -- 20.7 滾珠軌跡（N/25mm) 19.1 34.0 -- 32.8 SAFT(0.5kg,°C) 102 95 -- 93 對紙箱剪力 (40°C ,1kg,min) 337 155 -- 232 對鋼剪力 (40°C ,2.5kg,min) 73 168 -- 120 對詞剪力 (70^0 ,0.5kg,min) 1446 1309 - 809 特別4b，4c及4d為根據本發明製備之樹脂之良好實例 。此三種樹脂皆屬於隨附之申請專利範園界定之本發明之 範圍且全部皆基於含環二烯烴成分進料.實例仆及如樹脂 本紙張尺度適用中國國家樣準（CNS ) A4規格（210><297公釐） ---------d------IT------.^ (請先閱讀背面之注意事項再填寫本頁) -22- 經濟部智慧財產局員工消費合作社印製 442553 A7 B7_ 五、發明説明（20) 顯示良好滾珠軌跡及夠高的剪強度。 實例5 欲決定MMAP的降低是否係由於攙混來自製程溶劑之甲 笨或經由環化反應所引起，進行IR及NMR分析來決定樹脂 内之芳族質子存在量》 表6若干樣品之NMR結果 樹脂 6.5-7.5 ppm 4.7-5.4 ppm 0.5-3 ppm 樹腊B 7.84 5.00 87.15 樹脂C 2.58 2.87 94.55 本發明樹脂 0.69 2.76 96.55 荷克莉斯C 0.87 4.15 94.98 匹可德克95E 0.59 3.37 96.04 本表顯示芳族質子百分率（6.5至7.5 ppm)與=匚1類質 子(4.7至5.4 ppm)及脂族質子（0.5至3.0 ppm)百分率之比 較。 明白顯示本發明樹脂之芳族範圍之質子數量可與其它 脂族樹脂例如荷克莉斯C及匹可德克95E相媲美。後二種 樹脂具有MMAP93至95°C而本發明樹脂具有MMAP86°C。樹 脂C為具有MMAP 85°C之5 wt%樹脂芳族改質脂族樹脂，顯 示明顯較高量之芳族質子。較高芳族改質樹脂（樹脂B， 約18 wt%，芳族改質）顯示較高量芳族質子。 實例6 表7顯示數種樹脂於熱熔感壓黏著劑組成物之結果之 本紙張尺度適用中國國家搮準（CNS 规格（2丨OX297公釐） ? 1裝------訂------像 {請乞《請开面之注意事項再填寫衣頁) -23- A7 B7 五、發明説明（21 ) 比較β 表7於克萊特D 1107之HM PSA性能 貧例編號 6a 6b 6c 6d 克萊特D 1107 100 100 100 100 本發明樹脂 120 樹脂B 120 匹可德克95E 120 荷寇德克1148 120 雪弗列斯451 FC 20 20 20 20 伊加诺斯（Irganox)lOlO 2 2 2 2 黏度於 I75°C(mPas) 37900 58800 59500 45500 滚珠軌跡（cm) 3.0 7.0 3,6 5.7 對鋼撕離（N/25mm) 20.7 17.1 16.9 19.9 滾珠軌跡（N/25mm) 32.8 29.0 30,5 30.8 SAFT(0.5kg,*C ) 93 93 96 97 對紙箱剪力 232 391 723 620 (40°C ,1kg,min) 對鋼剪力 120 353 201 121 (40°C ,2.5kg,min) 對銅剪力 809 310 1326 691 {対先閲讀背面之注意事項再填寫本頁) 裝Picotec 85E I 95 I 3400 | 95 | Aliphatic resin | Η I !! I ΙΓ I j 丨 ·! Hokodek 1148 I 96 | 4000 | 88 | Aromatic modification | .J ---- L With respect to the j-line, it was observed that due to the improved compatibility of the resin of the present invention, the cloud point of MMAP decreased as a function of the amount of ring structure. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives. The paper size applies to the Chinese family standard (〇 ^) 6 4 specifications (210 > < 297). Δ7 Α7 Β7 Description of the invention (η) The special viscosity increasing agent for hot melt pressure-sensitive composition has the following typical properties (see also Example 4): Ring and ball softening point (t) 96 MMAP (° C) 86 Aromatic proton ( NMR) 0.7 Chromaticity 50% in Gardner 6 Mn (Dolton) 830 Mw (Dolton) 1460 Mz (Dolton) 2800 The amount of ring structure can be controlled by changing the catalyst content and reaction temperature get on. In addition, it is expected that the required global softening point also related to the ring structure can be controlled by the amount of chain transfer agent. Typical polymerization conditions of the aforementioned resins are listed below. Since the amount of the cyclic component of the feed f will also affect the final amount of the cyclic structure in the resin, this affects the final melt viscosity of the hot-melt pressure-sensitive composition, and the preferred composition is also listed. ------- ^ ---- Packing ------ 1Τ ------ 0 (Please read the notes on the back before filling this page) Temperature: 55 ° C Catalyst content: 4.0 wt % / Polymerizable shore polymerization feed: isobutylene * 8.7 isoprene * 2.7 trans-pentadiene * 13.4 cis · pentadiene * 8.1 cyclopentadiene * 1.0 dicyclopentadiene * 5.5 Applicable to this paper size China National Standard (CNS) A4 specification (2 丨 0 × 297 mm) • 14 · A? B7 V. Description of the invention (12) Cyclopentene 8.3 Toluene 32.5 Cis-2-pentene 1.0 Trans-2-pentene 1.5 ring Pentane 7.4 Other C5'S 9,9 Total polymerizable materials (*) 39.4 442553 The resin of the present invention can be blended with SIS polymers and additives to obtain a hot melt experience with a low melting point and excellent shear and viscosity Adhesive composition. Such a hot-melt pressure-sensitive adhesive composition can be used in various forms. Particularly preferred are adhesive tapes and labels. The hot-melt pressure-sensitive adhesive composition is usually composed of S-I-S block copolymer, petroleum tackifier resin according to the present invention, and other additives known in the industry such as hydrocarbon weight increasing agent oil 'antioxidant, colorant, filler and the like. Suitable extender oils are selected from aromatic oils, naphthenic oils, paraffinic oils or mixtures thereof. The amount of petroleum resin used in combination with the block copolymer ranges from 70 to 200 parts by weight per 100 parts of the block copolymer. A more preferred range is 90 to 150 parts by weight per 100 parts of a block copolymer. When used, the extender oil is added in an amount of up to 70 parts by weight per 100 parts of the block copolymer, more preferably 5 to 50 parts by weight. The S-I-S block copolymer can be selected from polymers containing 0 to 30 parts by weight of stupid ethylene and 0 to 40 parts by weight of two stages. Examples of such polymers are Crete D 1107, Crete 0 ft. And 601 € 3, Crete 0 1114, and Fanect 4111. As mentioned above, the hot-melt formulation of the present invention preferably has a melt viscosity of 175 ° c. The paper size is applicable to China's g standard rate (CNS) / U said grid (210X297 mm) ------ 1 ---- Install ------ IT ------- ^ i ^ -t Read the back. T / ii Note the matter and fill in the w-wood page} Printed by the cooperative staff of the Ministry of Economic Affairs * Property Bureau -15- A7 4 4 2 5 5 3 B7 V. Description of the invention (13) The measurement is less than 100,000, and 3 (&? 3) is better than 175 ° (: less than 60,000 111 ~ 35. The best is 175 ° C The melt viscosity is in the range of 35,000 to 50,000 mPas. Since the reduction in viscosity is not caused by the addition of aromatic monomers to the polymerization feed, the resin according to the invention has advantages over other resins that are well known for this purpose. 1 Due to the higher content of the ring structure, the resin has lower melt viscosity than the aliphatic resins such as Piccolo 95E and Akures 1310 in the comparable thermal coal pressure-sensitive composition. 2. Due to the ring structure More resins have a lower molecular weight. Hot-melt compositions containing the resin of the present invention have ball trajectories comparable to existing stage or aromatic modified resins such as Piccolo 95E or Ecores 2203 and Dutch Dirk 1148 or even better. 3. Because it contains very little aromatics, resins made according to the present invention can achieve better results than aromatic modified resins such as Acrylic 2203, Hercules 1148 and Hercules Resin A. Good high-temperature shear strength. Examples Examples 1 to 4 illustrate the effect of polymerization conditions on the properties of the resin. The advantages of the final melt viscosity at 175 ° C are also included in polymers containing Crete D 1 07 and Chevrolet FC 451. The formula of resin / resin / oil weight ratio of 100 / 120/20 has been verified. The resin of the present invention used in the following examples is hereinafter referred to as: the aliphatic hydrocarbon resin of the present invention or the resin of the present invention for short. This paper size applies to Chinese national standards (CNS) Α4 specification (210X297mm) --------- i ------ 1T ------ ^ (Please read the note on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-16- 4425 53 A7 ________ B7 V. Description of the Invention (M) The typical composition of the petroleum feed stream (with and without cyclic diolefins) and the solvent recovered in the factory are exemplified below: Stream Feed Superpentadiene A Ordinary Pendiene B Dissolved Isobutene * 0,0 0.0 0.0 N-pentyl 0,2 0.0 1.5 Isoprene * 0.5 0.5 0.0 0.0 trans-2-pentene 1, 8 0.9 2.5 cis-2-pentene 3.0 1.9 2.2 isoprene # 78 5.6 0.3 transprene * 40.8 33.2 (M cispentadiene * 23.0 18.7 0.0 cyclopentene 16.6 13.4 6.7 cyclopentane 4.8 3.8 18.3 cyclopentadiene * 0.6 4.7 0 · 0 dicyclopentadiene * 0.0 9.4 0 · 0 Other C5 + C6_s 1.1 4.4 16.0 Toluene 0.0 0.0 2.4 Monomer (*) 72.6 72.2 0.5 Employees of the Intellectual Property Office of the Ministry of Economic Affairs cooperated with each other Du printed examples The resins mentioned are not all prepared using the aforementioned feed stream, but the reasons for these components can be listed The results obtained are typical and represent all other petroleum feeds and solvents used. The catalyst used in the example was 52 wt% aluminum chloride. The abbreviations and trade names used below are described in the experimental section below. Example 1 Table 1 shows the effect of using more catalyst on a feed with or without a cyclodiene component on the properties of the final resin. Table 1 Catalyst content of AABB Example of feed AABB Example No. la lb lc Id Isoisodiene (A / B) 41.3 41.3 36.0 36.0 PR solvent 58.7 58.7 64.0 64.0 Catalyst 3-0 5.0 3.0 5 * 0 temperature 55 55 45 45 This paper size is applicable to Chinese National Standard (CNS) A4 specification (2 丨 0X297 male shame) -17 · ---------- installation ----- 1T ------- 0 f Please read the notes on the back of Egypt and fill in this page again} 442553 A7 B7 V. Description of the invention (15) Isobutylene 12 12 13 13 Global softening point 89.2 89,3 90J 93.1 MMAP 94 92 90 88 Chroma 3.6 4.7 5.2 6'1 Μη 728 689 920 87ί Mw 1366 1235 1648 1444 Mz 2158 1941 3019 2525 Pd 1.88 1.79 L79 1.66 Viscosity 52900 1500 52200 44200 Ball track (cm) 1-2 2.0 1.6 2.4 Tear-off from steel (N / 25mm) 13.1 1L7 15.2 17.1 Loop track (N / 25mm) 25.4 21.4 28.8 26.4 SAFT (0.5kg, ° C) 97 95 94 93 Shear force to carton 1130 731 85 56 (40 ° C, 1kg, min) Shear force to copper 38 52 98 37 (40 ° C, 2.5kg, min) Shear force on steel 744 584 960 876 (70 ° C, 0.5kg, min) The results clearly show that due to the higher catalyst content, MMAP and molecular weight reduction are the same Ball softening point kept almost equal or slightly increased display. Viscosity drops sharply when more catalyst is used. ---------- Equipment ------ 1T ------. &Amp;! (Please read the precautions of K first and then fill out this page) Staff of Intellectual Property Bureau, Ministry of Economic Affairs The paper size printed by the consumer cooperative is applicable to the Chinese National Standard (CNS) A4 (2 0x297 mm) • 18- 442553 Printed by the consumer property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (16) Example 2 Table 2 shows the effect of using higher reaction temperatures on feeds with or without cyclodiene components on the properties of the final resin. Table 2 Temperature Affected Feed AABB Example No. 2a 2b 2c 2d Isoprene (A / B) 41.3 41.3 36.0 36.0 PR Solvent 58.7 58.7 64, 0 64.0 Catalyst 5.0 5.0 3, 0 3.0 Temperature 15 55 45 65 Isobutene 12 12 13 T * 13 Global softening point 83.3 89.3 90.1 92.0 ΜΜΑΡ 93 92 90 89 Color 2,4 4.7 5.2 6.2 Μη 975 689 920 801 Mw 1501 1235 1648 1417 Mz 2402 1941 3019 2636 Pd 1,54 1.79 1.79 1.77 Viscosity 50700 41500 52200 41200 Ball track (cm) 1.0 2.0 1.6 1,6 Pair of steel tear (N / 25mm) 11.9 11.7 15.2 14.1 Ring track (N / 25mm) 26.3 21.4 28.8 28.3 SAFT (0.5kg / C) 96 95 94 93 Shear force to carton 856 731 85 32 (40 ° C, 1kg, min) Shear force to copper 37 52 98 140 (40 ° C, 2.5kg, min) Shear force to steel 597 584 960 952 (70 ° C, 0.5 kg, min) The results clearly show that due to the higher temperature MMAP and a slight decrease in molecular weight, the global softening point shows an increase. With higher temperature melt viscosity drops sharply. This paper size is applicable to China National Standard (CNS) Α4 specification (2 丨 0 × 297 mm) ------- ^ --- d ------ ΐτ ------ line (please read first Note on the back page, please fill in this page) -19- 4 425 53 A 7 B7 V. Description of the invention (Π) When the temperature is increased from 60 to 80 and 100 ° c, the same tendency of resin properties is also observed. The results are shown in the table below. Table 3 Effect of temperature Printed material B of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics Example number 2e 2f 2g Isoprene (A / B) 40.0 40.0 40.0 PR solvent 60,0 60.0 60,0 Catalyst 3.6 3.6 3.6 Temperature 60 80 100 Isobutylene 8.0 8.0 8.0 Ring and ball softening point 94.1 99.6 101.5 MMAP 85 82 78 Chroma 5.5 6.9 8.7 Μη 874 82S 765 Mw 1393 1374 1394 Mz 2490 2751 3368 Pd 1.59 1.66 1.82 Viscosity 42800 37100 29500 Ball track (cm) 1.4 2,0 2.0 Tear off steel (N / 25mm) 14.δ 17.0 15.6 Ring track (N / 25mm) 24.6 27.7 24.9 SAFT (0.5kg, ° C) 94 96 96 Carton shear force 27 51 29 (40 ° C, lkg, min) Shear force on steel 158 157 173 (40 ° C, 2.5kg, min) Poor copper force 890 1038 1380 (70 ° C, 0.5kg, min) Example 3 Table 4 Verification uses more The advantages of cycloolefins and cyclodiene. The resin used for this example has similar ring and ball softening points and molecular weights. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm) < Notes on the back of the poem before filling this page). Gutter -20- 442553 A7 B7 Five 'Invention Description (is) Table 4 Feed composition ABABA Example number 3a 3b 3c 3d Isoprene (A / B) 41.3 36.0 41.3 36.0 PR solvent 58.7 64-0 58.7 64.0 Catalyst 3.0 3.0 4.0 3.75 Temperature 55 65 35 50 Isobutylene 4.0 7.0 8.0 10.0 Global softening point 104.5 104.9 95.1 96.1 MMAP 95 89 94 87 Color 2.9 5,7 2,7 5,6 Μη 1146 928 1075 837 Mw 2076 1906 1759 1548 Mz 4024 4207 3023 3042 Pd L81 2.05 1.64 1.85 Viscosity 76000 50000 68200 37900 Ball track (cm) 1.7 3.S 2.2 3.0 Tear off from steel (N / 25mm) 16.1 19.0 15.3 20.7 Ring track (N / 25mm) 27.0 3L4 27.5 32.8 SAFT (0.5kg, ° C) 98 95 101 93 to carton Shear force 1321 149 511 232 (40 ° C, 1kg, min) Shear force against copper 303 288 89 120 (40 ° C, 2.5kg, min) Shear force against steel 1180 1056 1014 809 ------_-- --Install ------ order ------ line < Jing first read the notes on the back before filling this page) Economy The employees of the Ministry of Intellectual Property and Finance Bureau exempted from printing by cooperatives (70 ° C, 0.5kg, min). These examples clearly show that resins with similar global softening points and molecular weights are in terms of MMAP and melt viscosity of hot-melt pressure-sensitive compositions. different. The presence of cyclodiene such as cyclopentadiene and dicyclopentadiene can also contribute to the cyclic properties of the resin and cause a decrease in the melt viscosity of the hot melt formulation and a decrease in the resin MMAP. It is generally known that in the presence of cyclic diolefins, more catalysts or higher temperatures and more chain transfer agents are needed to achieve similar ring and ball and molecular weights. Use of cyclic olefins and cyclic diolefins in this paper applies Chinese National Standard (CNS) A4 specifications (2〗 0X297 mm > • 21- 442553 Xiao Gongxiao, Bureau of Intellectual Property of the Ministry of Economic Affairs «-Cooperative printed A7 B7 V. Description of the invention (19) The material seems to have a slightly broadened molecular weight distribution. Example 4 Table 5 resins are examples of resins with the best properties for use in hot melt adhesive compositions as tackifiers. Table 5 is based on the best of the two feeds Resin Feed ABBB Example No. 4a 4b 4c 4d Isoprene (A / B) 41.3 36.0 40,0 36.0 PR Solvent 58.7 64.0 60.0 64.0 Catalyst 4.0 4,0 4.0 3.75 Temperature 70 55 55 50 Isobutene 6.0 10,0 9 , 0 10.0 Global softening point 98,0 97Λ 96,5 96.1 MMAP 93 87 86 87 Chroma 4.5 6.1 5.9 5.6 Mn 901 802 827 837 Mw 1470 1436 1459 1548 Mz 2596 2595 2806 3042 Pd 1.63 1,79 1.76 1.85 Viscosity 49200 43000 -37900 Ball track (cm) 2.6 3.2-3.0 Steel tear off (N / 25mm) 14.5 17.3-20.7 Ball track (N / 25mm) 19.1 34.0-32.8 SAFT (0.5kg, ° C) 102 95 -93 pairs of carton shear (40 ° C, 1kg, min) 337 155-232 pairs of steel Shear force (40 ° C, 2.5kg, min) 73 168-120 Word shear force (70 ^ 0, 0.5kg, min) 1446 1309-809 Special 4b, 4c and 4d are good for the resin prepared according to the present invention Example. These three resins belong to the scope of the present invention defined by the attached patent application park and are all based on the cyclic diene-containing component feed. Examples of resins and paper sizes are applicable to China National Sample Standard (CNS) A4 specifications (210 > &297; 297 mm) --------- d ------ IT ------. ^ (Please read the notes on the back before filling this page) -22- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 442553 A7 B7_ V. Description of the Invention (20) Shows good ball trajectory and high enough shear strength. Example 5 To determine whether the decrease in MMAP is due to the mixing of methylbenzene from the process solvent or IR and NMR analysis are performed to determine the amount of aromatic protons in the resin caused by the cyclization reaction. Table 6 NMR results of several samples Resin 6.5-7.5 ppm 4.7-5.4 ppm 0.5-3 ppm Wax B 7.84 5.00 87.15 Resin C 2.58 2.87 94.55 Resin of the present invention 0.69 2.76 96.55 Hercules C 0.87 4.15 94.98 Piccotec 95E 0.59 3.37 96.04 This table shows the ratio of the percentage of aromatic protons (6.5 to 7.5 ppm) to the percentage of type 1 protons (4.7 to 5.4 ppm) and aliphatic protons (0.5 to 3.0 ppm). It is clear that the number of protons in the aromatic range of the resin of the present invention is comparable to other aliphatic resins such as Hercules C and Piccotec 95E. The latter two resins have MMAP93 to 95 ° C and the resin of the present invention has MMAP86 ° C. Resin C is a 5 wt% resin aromatic modified aliphatic resin with MMAP 85 ° C, showing a significantly higher amount of aromatic protons. Higher aromatic modified resins (Resin B, about 18 wt%, aromatic modified) show higher amounts of aromatic protons. Example 6 Table 7 shows the results of several resins in the hot-melt pressure-sensitive adhesive composition. The paper size is applicable to the Chinese national standard (CNS specification (2 丨 OX297 mm)? 1 pack --- order- ---- Like {Please ask "Please pay attention to the note before filling in the clothes page) -23- A7 B7 V. Description of the invention (21) Comparison β Table 7 HM PSA performance in Cleit D 1107 Poor case number 6a 6b 6c 6d Crete D 1107 100 100 100 100 Resin 120 Resin B 120 Piccolo 95E 120 Hocotec 1148 120 Chevrolet 451 FC 20 20 20 20 Irganox 10 2 2 2 2 Viscosity At I75 ° C (mPas) 37900 58800 59500 45500 Ball trajectory (cm) 3.0 7.0 3,6 5.7 Tear off from steel (N / 25mm) 20.7 17.1 16.9 19.9 Ball trajectory (N / 25mm) 32.8 29.0 30,5 30.8 SAFT ( 0.5kg, * C) 93 93 96 97 Shear force to carton 232 391 723 620 (40 ° C, 1kg, min) Shear force to steel 120 353 201 121 (40 ° C, 2.5kg, min) Shear force to copper 809 310 1326 691 (対 Please read the notes on the back before filling this page)
*-ST (70°C ,0.5kg,min) 结果明白顯示使用本發明樹脂之熔體黏度及滾珠軌跡 為所有試驗樹脂中之最佳者。於40°C紙箱之剪力於四種樹 脂並無明顯差異。本發明樹脂於70eC對鋼之剪力優點使用 荷寇德克1148及荷克莉斯樹脂B (約18 wt%芳族改質脂族 樹脂）。使用匹可德克95E (脂族樹脂）可獲得較佳高溫 對鋼剪力但也獲得較高黏度。 本發明樹脂也與若干競爭性樹脂樣品比較。試驗使用 艾寇瑞斯1310 LC，脂族樹脂例如匹可德克95E及艾寇瑞斯 2203 LC為芳香改質樹脂可媿美荷寇德克1H8。 本紙張尺度適用中國S家揲準（CNS ) A4規路（2IOX297公釐） ¾ 經濟部智慧財產局員工涓費合作社印製 -24- 4 A7 _ _B7____五、發明説明（22) 又比較荷克莉斯樹脂A »荷克莉斯樹脂A類似荷克莉 斯B為比較艾寇瑞斯2203及荷寇德克1148更高芳香改質樹 脂。 表8於克萊特D 1107之HM PSA性能 實例编號 6a 6b 6c 6d 克萊特D 1107 100 100 100 100 本發明樹脂 120 艾寇瑞斯1310 LC 120 艾宼瑞斯2203 LC 120 樹脂A 120 S弗列斯451 FC 20 20 20 20 伊加諾斯1010 2 2 2 2 黏度於175°C (mPas) 37900 85400 45000 40000 ί哀珠軌跡（cm) 3.0 2.6 3.8 6.6 對鋼撕離（N/25mm) 20,7 14.5 17.8 18.1 環軌跡（N/25mm) 32.8 19.1 30.7 25J SAFT(0.5kg,t) 93 102 95 85 對紙箱剪力 232 337 242 383 (40°C ,1kg,min) 對鋼剪力 120 73 134 177 (40°C,2.5kg,min) 對鋼剪力 809 1446 781 102 ---τ~丨^---1------.*1------¾ <請先聞讀背面之注意事項再填巧本頁) 經濟部智慧財Ji局員工消費合作社印製 (70°C ,0.5kg,min) 結果再度明白顯示使用本發明樹脂之熔艏黏度及滾珠 軌跡可媲美微芳香改質樹脂例如艾寇瑞斯2203 LC。使用 荷克莉斯樹脂A之滾珠軌跡較高原因為分子量較高之故。 使用艾寇瑞斯1310 LC之熱熔黏度比匹可德克95E特別本發 明之樹脂更高。使用本發明樹脂於7〇°C對銷之剪力優於荷 克莉斯樹脂A。使用艾寇瑞斯1310 LC可得更佳高溫對鋼 剪力類似匹可德克95E但也獲得最高黏度。 本紙張尺度適用中國_家樣率（〇阳>人4规格（210><297公釐> -25- ^4425 5 3 A7 B7 五、發明説明（23 ) 實例7 本發明之脂族烴樹脂也對其它具有相同聚合物/樹脂 /油比之S-I-S聚合物評估β 表9含不同聚合物之組成物之HM PSA性能 實例編號 7a 7b 7c 7d 克萊特D 1107 100 克萊特D KX-601-CS 100 克來特D 1114-X 100 凡克特4111 100 本發明樹脂 120 120 120 120 雪弗列斯451 FC 20 20 20 20 伊加烊斯1010 2 2 2 2 黏度於 175t：(mPas) 37900 48200 37800 47200 滾珠軌跡（cm) 3.0 1,6 l.S 1.6 對銅撕離（N/25mm) 20.7 15.6 14.7 14.3 環执跡<N/25mm) 32,8 27.2 24.6 26.3 SAFT(0.5kg,*C) 93 95 101 100 對紙箱剪力 232 980 1204 924 (4〇r,lkg,min) 對鋼剪力 120 63 325 175 (40"C ,2.5kg,min) 對鋼剪力 809 1647 5210 3604 ----；---;---y 裝-- {閱讀背面之注意事項再填寫本頁}* -ST (70 ° C, 0.5kg, min) The results clearly show that the melt viscosity and ball trajectory of the resin of the present invention are the best of all the test resins. There is no significant difference between the four types of resin in the shear strength of the carton at 40 ° C. The resin of the present invention has the advantage of 70eC shear strength on steel using Hercotec 1148 and Hercules Resin B (about 18 wt% aromatic modified aliphatic resin). Use Piccotec 95E (aliphatic resin) for better high temperature shear on steel but also higher viscosity. The resin of the invention was also compared with several competitive resin samples. The test used Akures 1310 LC, and aliphatic resins such as Piccolo 95E and Akures 2203 LC were aromatic modified resins. This paper size is applicable to China SSC Standard (CNS) A4 (2IOX297 mm) ¾ Printed by the Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economy -24- 4 A7 _ _B7____ V. Description of the Invention (22) Chris Resin A »Hercules Resin A is similar to Hercules B. It is a higher aromatic modified resin comparing Acres 2203 and Hercord 1148. Table 8 Example of HM PSA performance in Crete D 1107 6a 6b 6c 6d Crete D 1107 100 100 100 100 Resin of the present invention 120 Acres 1310 LC 120 Acres 2203 LC 120 Resin A 120 S Fleet 451 FC 20 20 20 20 Iganos 1010 2 2 2 2 Viscosity at 175 ° C (mPas) 37900 85400 45000 40000 ί track of beads (cm) 3.0 2.6 3.8 6.6 Tear to steel (N / 25mm) 20, 7 14.5 17.8 18.1 Loop track (N / 25mm) 32.8 19.1 30.7 25J SAFT (0.5kg, t) 93 102 95 85 Carton shear force 232 337 242 383 (40 ° C, 1kg, min) Shear force against steel 120 73 134 177 (40 ° C, 2.5kg, min) Shear force on steel 809 1446 781 102 --- τ ~ 丨 ^ --- 1 ------. * 1 ------ ¾ < Please Please read the notes on the back of the page and fill in this page again.) Printed by the Consumer Cooperative of Ji Bureau, Ministry of Economic Affairs (70 ° C, 0.5kg, min). The results clearly show that the melt viscosity and ball trajectory of the resin of the present invention are comparable. Micro-aromatic modified resins such as Akures 2203 LC. The higher ball trajectory of Hercules Resin A is due to the higher molecular weight. The heat-melting viscosity using Acoris 1310 LC is higher than that of Picotek 95E resin, particularly the present invention. The shear force of the pin at 70 ° C using the resin of the present invention is superior to that of Hequlis resin A. The use of Akures 1310 LC results in better high temperature to steel shear forces similar to Piccod 95E but also the highest viscosity. This paper scale is applicable to China_Home sample rate (〇 阳> gt; person 4 size (210 > < 297 mm > -25- ^ 4425 5 3 A7 B7 V. Description of the invention (23) Example 7 Aliphatic of the invention Hydrocarbon resins were also evaluated for other SIS polymers with the same polymer / resin / oil ratio β Table 9 HM PSA Performance of Compositions Containing Different Polymers Example No. 7a 7b 7c 7d Crete D 1107 100 Crete D KX-601 -CS 100 Crete D 1114-X 100 Vancate 4111 100 Resin of the present invention 120 120 120 120 Chevres 451 FC 20 20 20 20 Icarus 1010 2 2 2 2 Viscosity at 175t: (mPas) 37900 48200 37800 47200 Ball track (cm) 3.0 1,6 lS 1.6 Copper tear (N / 25mm) 20.7 15.6 14.7 14.3 Ring track < N / 25mm) 32,8 27.2 24.6 26.3 SAFT (0.5kg, * C) 93 95 101 100 Carton shear force 232 980 1204 924 (4〇r, lkg, min) Shear force against steel 120 63 325 175 (40 " C, 2.5kg, min) Shear force against steel 809 1647 5210 3604 --- -; ---; --- y equipment-{Read the notes on the back and fill out this page}
-1T -¾ 經濟部智慧財產局員工消贵合作社印製 (70°C ,0.5kg,min) 結果明白顯示使用本發明之脂族樹脂可於四種聚合物 獲得低熱熔黏度連同軌跡性質及剪力性質的良好平衡。 實例8 表10列舉若干結果但改變黏著劑配方之樹脂及油數量 *使用凡克特4111作為聚合物。 本紙張尺度逍用令國國家揉車（CNS ) Α4Λ格（210X2?7公釐） -26- 553 2 4 4 A7 B7 五、發明説明（24) 表10數種配方之HM PSA性能 實例編號 8a 8b 8c 8d 克萊特4111 100 100 100 100 克萊特4111(wt%) 42 45 45 36 本發明樹脂 120 118,6 98.5 148,6 本發明樹脂（wt%) 50 53 44 53 雪弗列斯451 FC 20 5.2 25.4 37.8 雪弗列斯451 FC(wt%) 8 2 π 11 伊加諾斯1010 2 2 2 2 黏度於 175t：(mPas) 51600 121200 63500 21800 i袞珠軌跡（cm) 2.6 3·0 1·0 1,0 對鋼撕離（N/25mra) 16.7 17,0 13.5 19.3 環軌跡（W25mm) 35.6 31.1 27.7 38.1 SAFT(0.5kg,°C) 103 ill 101 101 對纸箱剪力 409 351 89 60 (40°C ,1kg,min) 對銅剪力 639 1342 298 574 (40°C ,2.5kg,min) 對鋼剪力 2718 14000 835 900 經濟部智慧財產局員工消費合作社印製 (70°C ,0‘5kg，min) 前述配方指示聚合物樹脂及油數量可改變而控制熱熔 黏度同時軌跡及剪力性質仍保持夠高》 實驗一節-材料及方法 縮寫 前文及表中使用下列縮寫： PR溶劑 聚合反應所用溶劑 R&B 環球軟化點（如下述測量） MMAP 混合曱基環己烷苯胺濁點（如下述測量) Mn 數均分子量 本紙張尺度適用中國围家標準<CNS)A4現格（210X297公釐} ^ ^ _裝 訂 線 (請先Μ讀背面之注意事項再填寫本頁) -27- A7 B7 經濟部智慧时產局員工消費合作社印製 五、發明説明（25)-1T -¾ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (70 ° C, 0.5kg, min) The results clearly show that the use of the aliphatic resin of the present invention can obtain low hot melt viscosity along with the trajectory properties and shear properties Good balance of force properties. Example 8 Table 10 lists some results but changed the amount of resin and oil for the adhesive formulation. * Vancate 4111 was used as the polymer. The paper size is easy to use, and the country ’s national kneading car (CNS) Α4Λ grid (210X2? 7 mm) -26- 553 2 4 4 A7 B7 V. Description of the invention (24) Table 10 HM PSA performance examples of several formulas 8a 8b 8c 8d Crete 4111 100 100 100 100 Crete 4111 (wt%) 42 45 45 36 Resin of the present invention 120 118,6 98.5 148,6 Resin of the present invention (wt%) 50 53 44 53 Chevrolet 451 FC 20 5.2 25.4 37.8 Chevrolet 451 FC (wt%) 8 2 π 11 Iganos 1010 2 2 2 2 Viscosity at 175t: (mPas) 51600 121200 63500 21800 i Bead locus (cm) 2.6 3 · 0 1 · 0 1,0 Pairs of steel tear (N / 25mra) 16.7 17,0 13.5 19.3 Loop track (W25mm) 35.6 31.1 27.7 38.1 SAFT (0.5kg, ° C) 103 ill 101 101 Carton shear force 409 351 89 60 (40 ° C, 1kg, min) Shear force against copper 639 1342 298 574 (40 ° C, 2.5kg, min) Shear force against steel 2718 14000 835 900 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (70 ° C, 0 ' 5kg, min) The aforementioned formula indicates that the amount of polymer resin and oil can be changed to control the hot melt viscosity while the trajectory and shear properties are still kept high enough. "Experimental Section-Materials and Methods Before Abbreviation The following abbreviations are used in the table: Solvent used in PR solvent polymerization reaction R & B Global softening point (as measured below) MMAP Mixed fluorenylcyclohexaneaniline cloud point (as measured below) Mn Number average molecular weight Standard < CNS) A4 (210X297mm) ^ ^ _Binder (please read the notes on the back before filling in this page) -27- A7 B7 Printed by the Employees' Cooperatives of Wisdom and Time Bureau of the Ministry of Economic Affairs Invention Description (25)
Mw 重均分子量 Mz ζ·均分子量 Pd 多分散性(=Mw/Mn) AH配方 熱熔黏膠數目 HM PSA 熱熔感壓黏著劑 SAFT 剪黏著性失效溫度 方法 樹脂製法： 本文所述樹脂皆以連續法製備但也可採用分批製法。 樹脂進料與氯化好及分子篩乾燥器脫水，連同鏈轉移劑以 1500 ml/h速率加至容量6升的連續攪拌中的槽式反應器 。同時添加催化劑及混合物由反應器底部循環至催化劑入 口點。混合物以3升層面連續移出故全部實驗之反應時間 為2小時。混•合物以水失活化及於三步驟以水洗滌，隨後 真空以水蒸氣汽提去除溶劑及全部低分子量物質。 環球軟化點之測定方法： 環球軟化點係使用Walter Herzog環球軟化點裝置， 型號MC-735根據ASTMD-36-70測定。 MMAP之測定方法： MMAP(合甲基環己烧苯胺渴點）係使用修改的astm D -611-82程序測定。甲基環己烷替代庚烷用於標準試驗程 序。程序使用樹脂/苯胺/甲基環己烷之比1/2/1(5 g/1〇 ml/5 ml)，濁點係藉冷卻三種成分被加熱的澄清掺合物至 恰完全變混濁測定。 本紙張尺度適用中國困家樣率（CNS > Α4规格（210X297公嫠） :d------訂------i.r (#先Μ讀背面之注意事項#填艿本頁) -28-Mw Weight average molecular weight Mz ζ · Molecular weight Pd Polydispersity (= Mw / Mn) AH formula Number of hot melt adhesives HM PSA Hot melt pressure-sensitive adhesive SAFT Shear adhesion failure temperature method Resin preparation method: It is prepared by a continuous process but a batch process can also be used. Resin feed and chlorination and molecular sieve dryer dehydration, together with the chain transfer agent, were added at a rate of 1500 ml / h to a continuous stirred tank reactor with a capacity of 6 liters. Simultaneously adding the catalyst and the mixture circulated from the bottom of the reactor to the catalyst inlet. The mixture was continuously removed in 3 liter layers so the reaction time for all experiments was 2 hours. The mixture was deactivated with water and washed with water in three steps, followed by vacuum stripping with water vapor to remove the solvent and all low molecular weight substances. Measuring method of ring and ball softening point: Ring and ball softening point is measured using Walter Herzog ring and ball softening point device, model MC-735 according to ASTMD-36-70. MMAP measurement method: MMAP (methylcyclohexylaniline thirst) was measured using a modified astm D -611-82 procedure. Methylcyclohexane was used in place of heptane in the standard test procedure. The program uses a resin / aniline / methylcyclohexane ratio of 1/2/1 (5 g / 10 ml / 5 ml). The cloud point is determined by cooling the clear blend of the three components heated to just complete turbidity. . This paper size is applicable to China ’s home sample rate (CNS > Α4 size (210X297 cm): d ------ order ------ ir (# 先 Ｍread the notes on the back side # fill this page) ) -28-