TW593520B - Adhesive components and process for manufacture - Google Patents

Abstract

Resins and oligomer materials and/or combinations thereof grafted with an unsaturated acid or anhydride, such as maleic anhydride, are disclosed herein. The grafted materials are useful in adhesive formulations, particularly in hot melt adhesive applications.

Description

593520 A7 _B7 五、發明説明（1 ) 背景 本發明係有關接枝烴樹脂和寡聚物組成物，包括（但是 不限制於）合倂接枝組成物之膠黏劑和膠黏性組份，及製造 和使用該等組成物的方法。 較低分子量樹脂（通常具有400到1 5 00圍之Μη分子量 )可使用於許多應用中，包括膠黏劑用增黏劑，油墨添加劑 ，聚合物添加劑，路標樹脂，黏紙膠水和管子包紮。某些 商業等級之高油松酯（TOREs)或萜烯酚樹脂類（TPRs)用以改 良乙烯乙酸乙烯酯（EVA)-基熱熔體膠黏劑（HMAs)的性能。 然而，TOREs在應用溫度下因顏色不穩定和氣味產生性而 受損。烴樹脂，特別是氫化環脂族樹脂，在顏色穩定性和 氣味產生性上極佳，但在極性表面上有顯現高度全方位向 性能，例如聚對苯二甲酸乙二酯（PET)及丙烯酸淸漆，其中 時常使用TOREs。膠黏工業認知這個問題但仍然需要解決 。因此，需要存在一種具有增強之HMA性能而沒有與 T〇RES或TPRS有關之不安定性和氣味產生的膠黏性組份或 烴樹脂。 美國專利第47 19260號揭示一種具有對基材例如聚乙 烯的改良黏著性之熱熔體膠黏組成物，其包括一種包含聚 丙烯之無定形聚合物和多環飽和脂族烴樹脂和順-丁烯二酐 的接枝共聚物。其未揭示一種至少部份氫化之芳族烴樹脂 的使用。進一步地，通常已知芳族樹脂通常與飽和烴聚合 物例如US 47 1 9260中所述者較不相容和沒有呈現黏著至基 材（例如聚乙烯）的相同優點。 本纸張尺度適用中國國家標準（CNS ) Α4規格(_ 2]0X297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣·593520 A7 _B7 V. Description of the invention (1) Background The present invention relates to grafted hydrocarbon resins and oligomer compositions, including (but not limited to) adhesives and tacky components of the grafted graft composition, And methods of making and using those compositions. Lower molecular weight resins (usually having a Mη molecular weight ranging from 400 to 1500) can be used in many applications, including tackifiers for adhesives, ink additives, polymer additives, road marking resins, sticky paper glues, and tube wrapping. Certain commercial grades of tall pine esters (TOREs) or terpene phenol resins (TPRs) are used to improve the performance of ethylene vinyl acetate (EVA) -based hot melt adhesives (HMAs). However, TOREs are impaired at application temperatures due to color instability and odor-generating properties. Hydrocarbon resins, especially hydrogenated cycloaliphatic resins, have excellent color stability and odor-generating properties, but exhibit highly omnidirectional properties on polar surfaces, such as polyethylene terephthalate (PET) and acrylic Lacquer, where TORES are often used. The glue industry recognizes this problem but still needs to address it. Therefore, there is a need for a tacky component or hydrocarbon resin that has enhanced HMA properties without the instability and odor associated with TORES or TPRS. U.S. Patent No. 47 19260 discloses a hot melt adhesive composition having improved adhesion to a substrate such as polyethylene, which includes an amorphous polymer including polypropylene and a polycyclic saturated aliphatic hydrocarbon resin and cis- Graft copolymer of butylene dianhydride. It does not disclose the use of an at least partially hydrogenated aromatic hydrocarbon resin. Further, it is generally known that aromatic resins are generally less compatible with saturated hydrocarbon polymers such as those described in US 47 1 9260 and do not exhibit the same advantages of sticking to a substrate such as polyethylene. This paper size applies to Chinese National Standard (CNS) Α4 specification (_ 2] 0X297 mm) (Please read the precautions on the back before filling this page) Clothing ·

、1T 經濟部智慧財產局員工消費合作社印製 -4 - 593520 五、發明説明（2 ) US 3 16 1 620揭示一種反應順-丁烯二酐與熱製備之烴 樹脂的方法。其未揭示在與順-丁烯二酐反應之前至少部份 氫化樹脂或寡聚物。 EP 0 〇 8 8 5 1 〇揭示極性合成石油樹脂。在其中揭示的具 體實施例中環戊二烯寡聚物混合物與羧酸或酸酐例如鄰苯 二甲酸或順-丁烯二酸反應然後氫化。反應經由與樹脂寡聚 物的不飽和性反應之酸基而進行因此在連接點上形成酯基 。所得樹脂產物通常可被歸類爲降冰片酯。咸信在本文所 揭示的接枝材料經由不同路徑產生，即經由酸或酸酐的不 飽和鍵至如本文所定義之較佳至少部份氫化和更佳實質上 氫化之樹脂上。 烴樹脂，特別是氫化的芳族環脂族樹脂，在極性表面 上的性能可藉由改性該等樹脂以包括極性官能性質而改良 。官能組份接枝至習知烴樹脂及/或樹脂寡聚物和視需要選 擇性合倂接枝樹脂或接枝寡聚物材料與其他增黏樹脂或其 他膠黏性組份改良性能且提供超越TOREs和TPRs之優點 ，當使用於熱熔和其他膠黏調配物時。特別地，申請人已 發現合倂這些接枝組份之膠黏性材料已改良與極性聚合物 例如EVA共聚物的互容性和呈現在困難基材上（例如塗佈的 包裝表面）的之好性能。 槪述 本發明一具體實施例爲一種組成物，其包括至少二種 烴樹脂，其中一種樹脂爲一種以選自酸類，酸酐類，醇類 本纸張尺度適用中國國家標準（CMS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) "tv 「· 經濟部智慧財產局員工消費合作社印製 -5- 593520 A7 ___B7___ 五、發明説明（3 ) ，醯胺類和醯亞胺類，和其衍生物的接枝單體接枝之石油 烴樹脂，其中組成物實質上沒有包括降冰片酯基的環戊二 烯和經取代之環戊二烯的接枝寡聚物和和其中如果接枝單 體爲一種酸，酸酐，醯亞胺或醯胺，至少二種烴樹脂的皂 化値在1和1 〇〇之間和其中如果接枝單體爲一種醇，依照 ASTM E 222 94測量之羥値在1-100之間。另一個烴樹脂可 爲相同樹脂（除了未接枝之外)或任何其他適當的烴樹脂。樹 脂之其中任何一個可包含C5單體的寡聚物，C9單體的寡聚 物，和環戊二烯，經取代之環戊二烯與C9單體的寡聚物。 本文所揭示的樹脂混合物具有各種包括使用於熱熔體膠黏 劑，膠帶，標籤，裝訂和木工的膠黏劑組份之最終用途。 圖式說明 圖1-6說明在聚乙烯和PET基材上包含接枝樹脂的熱 熔體膠黏劑和包含其他樹脂材料的熱熔體膠黏劑之間的比 較性能。 圖7-12說明在聚乙烯和PET基材上包含一種包括接枝 寡聚物的樹脂材料之熱熔體膠黏劑和包含其他樹脂材料的 熱熔體膠黏劑之間的比較性能。 圖13-15說明在塗佈丙烯酸之定向聚丙烯塗佈的厚紙 板基材上包含一種包括接枝寡聚物的樹脂材料之熱熔體膠 黏劑和包含其他樹脂材料的熱熔體膠黏劑之間的比較性能 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣· 經濟部智慧財產局員工消費合作社印製 -6- 593520 A7 ______B7 五、發明説明（4 ) 詳細說明 樹脂之摻合物 本文所揭示之樹脂的摻合物通常包括至少二種烴樹脂 ，其中一種樹脂爲一種以選自酸類，酸酐類，醇類，醯亞 胺類，醯胺類和其衍生物之接枝單體接枝的石油烴樹脂， 其中樹脂摻合物實質上沒有包括降冰片酯基之環戊二烯和 經取代之環戊二烯的接枝寡聚物和其中如果接枝單體爲一 種酸，酸酐，醯亞胺或醯胺，至少二種烴樹脂的皂化値在1 和1 00之間和其中如果接枝單體爲一種醇，依照AsTM E 222 94測量之羥値在κ；! 00之間。如使用在本文中，樹脂 材料係指在本文所述的樹脂，如本文所述的寡聚物或其組 合。 其他烴樹脂之適當例子包括：脂族烴樹脂，至少部份 氫化的脂族烴樹脂，脂族/芳族烴樹脂，至少部份氫化的脂 族芳族烴樹脂，環脂族烴樹脂，至少部份氫化的環脂族樹 脂，環脂族/芳族烴樹脂，至少部份氫化的環脂族/芳族烴樹 脂，芳族烴樹脂，至少部份氫化的芳族烴樹脂，聚萜烯樹 脂，萜烯·酚樹脂，松酯，松脂酸，以接枝單體接枝之樹脂 和其任何二種或以上的混合物。適當的樹脂也包括其他具 有極性官能性質之樹脂，無論是否藉由本文所述之方法或 其他適當方法產生。 一具體實施例一種包括至少二種烴樹脂之組成物，其 中至少一種樹脂爲與接枝單體接枝之接枝樹脂材料和另一 個樹脂爲未接枝石油烴樹脂。“至少二種烴樹脂”也包括烴 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣 訂 經濟部智慧財產局員工消費合作社印製 593520 Α7 Β7 五、發明説明（6 ) 中接枝單體對至少二種烴樹脂的莫耳比在1 : 4和1 : 20之 間。在另一具體實施例中，接枝單體爲一種醇，及在樹脂 混合物中接枝單體對至少二種烴樹脂的莫耳比在5 : 3和1 :20之間，更佳1 : 1到1 : 1 5和更佳2 : 3到1 : 1 〇。在 樹脂混合物中接枝單體之較佳重量範圍爲0.1-10重量％， 更佳0.3-10重量％，更佳0.8-6重量％，和更佳1-5重量％ ，更佳1 _4重量％，基於混合物的總重量。 在一個其中接枝單體爲酸類或醯胺類或其衍生物之具 體實施例中，接枝單體較佳包含0.1和10重量％，更佳 0.3到8重量％，和更佳0.5到5重量％，基於混合物的總 重量。在其中一個接枝單體爲一種酸酐或醯亞胺或其衍生 物之具體實施例中，接枝單體較佳包含0.5和1 0重量％， 更佳〇. 8到6重量％，和更佳1到4重量％，基於混合物的 總重量。在一個其中接枝單體爲一種醇或其衍生物之具體 實施例中，接枝單體較佳包含〇 . 1和1 0重量％，更佳0.3 到8重量％，和更佳〇. 5到5重量％，基於混合物的總重量 〇 樹脂混合物的皂化値的較佳範圍爲1-100，更佳3-100 ，更佳3-80或5-100，更佳5-50或8-60，更佳10-40，更 佳1〇·3〇，更佳15_3〇，和更佳20-3〇。例如，在其中接枝 單體爲一種酸酐或醯亞胺之具體實施例中，樹脂混合物的 皂化値爲5-100，更佳8-60，更佳10-40，更佳15-30,和 更佳20-30。在其中接枝單體爲一種酸或醯胺具體實施例中 ，樹脂混合物的皂化値較佳爲1-100，更佳3-80，更佳5- 本纸張尺度適用中國國家標準（CN’S) Α4規格（2】0X297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣. 訂 經濟部智慈財產局員工消費合作社印製 -9 - 593520 A7 __—_B7 ___ 五、發明説明（7 ) 5〇，更佳5-40，更佳5-30，和更佳5-20。 在接枝單體爲一種醇之情中，樹脂混合物的羥値之較 佳範圍爲1-100，更佳3_100，更隹3_8〇或5-100，更佳5· 50或8-60，更佳10-40，更佳10-30，更佳15-30，和更佳 2〇-3〇。例如，在其中接枝單體爲一種二醇或多-醇（多元醇） 之具體實施例中，樹脂混合物的羥値爲5-100，更佳8-60， 更佳10-4〇，更佳15-30，和更佳20-30。在其中接枝單體 爲一種單-醇之具體實施例中，樹脂混合物的羥値爲較佳1 _ 1〇〇，更佳3-80，更佳5-50，更佳5-40，更佳5-30，和更 佳 5-20 〇 例如，一具體實施例爲一種組成物，其包括0.1-99重 量％之間的接枝樹脂材料和1-99.9重量％之間的其他樹脂 。其他具體實施例包括0.1-50重量％之間接枝樹脂材料， Ο.1-30重量％之間接枝樹脂材料，在0.1-20重量％之間接 枝樹脂材料，在1-25重量％之間接枝樹脂材料，在2-:15重 量％之間接枝樹脂材料，在1 -1 〇重量％之間接枝樹脂材料 ，在5-10%重量之間接枝樹脂材料，和在1〇-3〇重量％之 間接枝材料，基於樹脂摻合物之總重量。 在較佳具體實施例中，樹脂材料包括接枝樹脂及接枝 寡聚物，在0.1和50重量％之間接枝寡聚物，更佳在n 和3 〇重量％之間接枝寡聚物，更佳在〇. i和2 〇重量％之間 寡聚物，更佳0.1和10重量％接枝寡聚物，更佳在1和3〇 重量％之間接枝寡聚物，更佳在1和2〇重量％之間接枝寡 聚物，和更佳在1和1 0重量％之間接枝寡聚物，基於樹脂 本紙張尺度適用中國國家標準（CMS ) A4規格（21 0X 29*7公釐） (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 •10- 593520 A7 B7 五、發明説明（8 ) 摻合物的總重量。較佳範圍也包括在此段所述之任何上限 和任何下限之間。 (請先閱讀背面之注意事項再填寫本頁) 接枝烴樹脂 如使用在本文中，接枝烴樹脂，寡聚物，及/或樹脂材 料，或其組合表示其已與接枝單體合倂，接觸，及/或反應 。接枝爲合倂，接觸，或反應烴樹脂，寡聚物及/或樹脂材 料與接枝單體材料之方法。接枝烴樹脂，寡聚物，及/或樹 脂材料，或其組合以包括至少一些極性官能性產生許多應 用的有用組份例如膠黏調配物，尤其是HMA調配物。這些 調配物時常被設計成與極性聚合物，例如EVAs,乙烯丙烯 酸甲酯（EMAs)，聚丙烯酸酯（PAs)，聚甲基丙烯酸酯（PMAs) ，乙烯丙烯酸烷基酯一起使用和使用於極性基材上，例如 PET，再生紙，厚紙板，和丙烯酸淸漆和在其他基材上例如 木材，玻璃，陶瓷，瀝青，混凝土，和金屬上執行順利。 經濟部智慧財產局員工消費合作社印製 因此，本發明的具體實施例包括接枝和未接枝烴樹脂（ 類）和寡聚物（類）和其組合物及混合物。具體實施例也包括（ 但不限制於）：膠黏劑或膠黏性組份，其包括（i)接枝烴樹脂 ;(Π)接枝寡聚物，（iii)接枝寡聚物+未接枝樹脂（類），（iv) 接枝烴樹脂+未接枝樹脂（類），（v)接枝烴樹脂+未接枝寡 聚物，（vi)接枝烴樹脂+接枝寡聚物，（Vii)接枝寡聚物+未 接枝寡聚物或（viii)接枝烴樹脂+接枝寡聚物+未接枝樹脂（ 類）和其一種或以上之其他適當組合。本文所述的具體實施 例也包括製造及使用前述材料的方法。 本紙張尺度適用中國國家標準（CNS ) A4規格（2】0X297公麓） -11 - 593520 A7 ___B7___ 五、發明説明（9 ) 可被接枝的適當烴樹脂包括：脂族烴樹脂，至少部份 氫化的脂族烴樹脂，脂族/芳族烴樹脂，至少部份氫化的脂 族芳族烴樹脂，環脂族烴樹脂，至少部份氫化的環脂族樹 脂，環脂族/芳族烴樹脂，至少部份氫化的環脂族/芳族烴樹 脂，至少部份氫化的芳族烴樹脂，聚萜烯樹脂，萜烯-酚樹 脂，和其二種或以上之混合物。松酯也可被接枝。較佳， 樹脂爲至少部份氫化，更佳實質上氫化，和更佳包含芳族 単體。 在一具體實施例中，樹脂包含藉由二環戊二烯（DCPD) 或經取代之DCPD的熱聚合作用所產生的烴樹脂，其可進 一步包括如後文所述之脂族或芳族單體。在較佳具體實施 例中，在最後樹脂產物中藉由DCPD或經取代之DCPD和 C9單體的熱聚合所產生的烴樹脂包含少於1〇%芳烴。在另 一具體實施例中樹脂包含藉由C5單體和C9單體的聚合作 用（較佳熱或催化）獲得之C5/C9(脂族/芳族）烴樹脂。 接枝寡聚物 另一具體實施例爲一種包括接枝寡聚物（二聚物，三聚 物，四聚物，五聚物，六聚物類和視需要選擇之七聚物和 八聚物）之材料，較佳得自在30-210°C範圍沸騰的石油餾出 物。寡聚物可得自任何適當方法和時常以樹脂聚合作用的 副產物獲得，無論是熱或催化反應。寡聚物可得自其中寡 聚合及然後接枝適當的DCPD，（：5及/或（：9單體進料（如下 所述）之方法。適當的寡聚物流具有在1 3 0-5 00之間，更佳 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣·Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T -5-593520 V. Description of the Invention (2) US 3 16 1 620 discloses a method for reacting cis-butene dianhydride with thermally prepared hydrocarbon resin. It does not disclose at least partially hydrogenated resins or oligomers before reaction with maleic anhydride. EP 0 8 8 5 1 0 discloses a polar synthetic petroleum resin. In the specific examples disclosed therein, the cyclopentadiene oligomer mixture is reacted with a carboxylic acid or anhydride such as phthalic acid or maleic acid and then hydrogenated. The reaction proceeds via the acid group of the unsaturated reaction with the resin oligomer and thus forms an ester group at the point of attachment. The resulting resin products can generally be classified as norbornyl esters. The graft materials disclosed herein are produced via different pathways, i.e., via unsaturated bonds of acids or anhydrides, onto resins as defined herein which are preferably at least partially hydrogenated and more preferably substantially hydrogenated. The performance of hydrocarbon resins, especially hydrogenated aromatic cycloaliphatic resins, on polar surfaces can be improved by modifying these resins to include polar functional properties. Functional components are grafted to conventional hydrocarbon resins and / or resin oligomers and optionally combined with graft resins or graft oligomer materials and other tackifying resins or other tacky components to improve performance and provide Outperforms the advantages of TOREs and TPRs when used in hot melt and other adhesive formulations. In particular, the applicant has found that adhesive materials incorporating these graft components have improved compatibility with polar polymers such as EVA copolymers and exhibited on difficult substrates such as coated packaging surfaces. Good performance. It is stated that a specific embodiment of the present invention is a composition including at least two hydrocarbon resins, one of which is a resin selected from the group consisting of acids, anhydrides, and alcohols. The size of the paper is applicable to Chinese National Standard (CMS) A4 specifications ( 210X297 mm) (Please read the notes on the back before filling out this page) " tv "· Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- 593520 A7 ___B7___ V. Description of Invention (3), amines and Fluorene imine, a petroleum hydrocarbon resin grafted with a graft monomer of a derivative thereof, wherein the composition is substantially free of graft oligomerization of cyclopentadiene including a norbornyl group and substituted cyclopentadiene And if the grafting monomer is an acid, anhydride, ammonium or amidine, the saponification of at least two hydrocarbon resins is between 1 and 1000 and where if the grafting monomer is an alcohol, according to ASTM E 222 94 measures hydroxyamidine between 1 and 100. The other hydrocarbon resin may be the same resin (except ungrafted) or any other suitable hydrocarbon resin. Any one of the resins may contain a C5 monomer. Oligomer And cyclopentadiene, oligomers of substituted cyclopentadiene and C9 monomers. The resin mixtures disclosed herein have a variety of properties including those used in hot melt adhesives, tapes, labels, binding and woodworking. The end use of the agent component. Illustrated Figures 1-6 illustrate the comparison between hotmelt adhesives containing graft resins on polyethylene and PET substrates and hotmelt adhesives containing other resin materials. Figure 7-12 illustrates the comparison between hot melt adhesives containing a resin material including a graft oligomer on polyethylene and PET substrates and hot melt adhesives containing other resin materials Figures 13-15 illustrate a hot melt adhesive containing a resin material including a graft oligomer and a hot melt adhesive containing other resin materials on an acrylic-oriented oriented polypropylene-coated cardboard substrate Comparative performance between adhesives This paper size applies the Chinese National Standard (CNS) A4 size (210x297 mm) (Please read the precautions on the back before filling out this page) Clothing · Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Cooperatives- 6- 593520 A7 ______B7 4. Description of the invention (4) Detailed description of resin blends The blends of the resins disclosed herein generally include at least two hydrocarbon resins, one of which is a resin selected from the group consisting of acids, anhydrides, alcohols, and imines. Petroleum hydrocarbon resins grafted with graft monomers of amidines and their derivatives, wherein the resin blend is substantially free of grafted oligos including cyclopentadiene and substituted cyclopentadiene based on norbornyl esters. Polymer and if the grafting monomer is an acid, anhydride, amidine or amidine, the saponification of at least two hydrocarbon resins is between 1 and 100 and where if the grafting monomer is an alcohol, according to AsTM E 222 94 measured hydroxyamidine between κ;! 00. As used herein, a resin material refers to a resin described herein, an oligomer, or a combination thereof, as described herein. Suitable examples of other hydrocarbon resins include: aliphatic hydrocarbon resins, at least partially hydrogenated aliphatic hydrocarbon resins, aliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aliphatic aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, at least Partially hydrogenated cycloaliphatic resin, cycloaliphatic / aromatic hydrocarbon resin, at least partially hydrogenated cycloaliphatic / aromatic hydrocarbon resin, aromatic hydrocarbon resin, at least partially hydrogenated aromatic hydrocarbon resin, polyterpene Resin, terpene phenol resin, rosin ester, rosin acid, resin grafted with a graft monomer and a mixture of any two or more thereof. Suitable resins also include other resins having polar functional properties, whether or not produced by the methods described herein or other suitable methods. A specific embodiment is a composition including at least two hydrocarbon resins, wherein at least one resin is a graft resin material grafted with a graft monomer and the other resin is an ungrafted petroleum hydrocarbon resin. "At least two kinds of hydrocarbon resins" also includes hydrocarbon paper size applicable to Chinese National Standard (CNS) A4 specification (2 丨 0X 297 mm) (Please read the precautions on the back before filling this page) Intellectual Property Bureau, Ministry of Economics and Clothing Printed by the employee consumer cooperative 593520 A7 B7 5. In the description of the invention (6), the molar ratio of the graft monomer to at least two hydrocarbon resins is between 1: 4 and 1: 20. In another specific embodiment, the grafting monomer is an alcohol, and the molar ratio of the grafting monomer to the at least two hydrocarbon resins in the resin mixture is between 5: 3 and 1:20, and more preferably 1: 1 to 1: 15 and more preferably 2: 3 to 1: 10. The preferred weight range of the graft monomer in the resin mixture is 0.1-10% by weight, more preferably 0.3-10% by weight, more preferably 0.8-6% by weight, and even more preferably 1-5% by weight, more preferably 1-4% by weight. % Based on the total weight of the mixture. In a specific embodiment in which the grafting monomer is an acid or amidine or a derivative thereof, the grafting monomer preferably contains 0.1 and 10% by weight, more preferably 0.3 to 8% by weight, and more preferably 0.5 to 5 % By weight, based on the total weight of the mixture. In a specific embodiment in which one of the grafting monomers is an acid anhydride or amidine or a derivative thereof, the grafting monomer preferably contains 0.5 and 10% by weight, more preferably 0.8 to 6% by weight, and more 1 to 4% by weight, based on the total weight of the mixture. In a specific embodiment in which the grafting monomer is an alcohol or a derivative thereof, the grafting monomer preferably contains 0.1 and 10% by weight, more preferably 0.3 to 8% by weight, and more preferably 0.5 To 5% by weight, based on the total weight of the mixture, the preferred range of the saponified saponin of the resin mixture is 1-100, more preferably 3-100, more preferably 3-80 or 5-100, more preferably 5-50 or 8-60 , More preferably 10-40, more preferably 10.30, more preferably 15-30, and more preferably 20-30. For example, in a specific embodiment where the grafting monomer is an acid anhydride or amidine, the saponification of the resin mixture is 5-100, more preferably 8-60, more preferably 10-40, more preferably 15-30, and Better 20-30. In a specific embodiment in which the grafting monomer is an acid or amidine, the saponified saponification of the resin mixture is preferably 1-100, more preferably 3-80, and more preferably 5- This paper size is applicable to the Chinese National Standard (CN'S) Α4 specifications (2) 0X297 mm (Please read the notes on the back before filling this page). Order. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -9-593520 A7 __—_ B7 ___ V. Description of the invention ( 7) 50, more preferably 5-40, more preferably 5-30, and more preferably 5-20. In the case where the grafting monomer is an alcohol, the preferred range of the hydroxyamidine of the resin mixture is 1-100, more preferably 3_100, more preferably 3_80 or 5-100, more preferably 5.50 or 8-60, more Better 10-40, better 10-30, better 15-30, and better 20-30. For example, in a specific embodiment in which the grafting monomer is a diol or a poly-alcohol (polyol), the hydroxyamidine of the resin mixture is 5-100, more preferably 8-60, more preferably 10-40, more Better 15-30, and better 20-30. In a specific embodiment in which the grafting monomer is a mono-alcohol, the hydroxyamidine of the resin mixture is preferably 1-100, more preferably 3-80, more preferably 5-50, more preferably 5-40, more 5-30, and more preferably 5-20. For example, a specific embodiment is a composition that includes between 0.1-99% by weight of a graft resin material and between 1-99.9% by weight of other resins. Other specific embodiments include a graft resin material between 0.1-50 wt%, a graft resin material between 0.1-30 wt%, a graft resin material between 0.1-20 wt%, and a graft between 1-25 wt% Resin material, grafted resin material between 2: 15% by weight, grafted resin material between 1-10% by weight, grafted resin material between 5-10% by weight, and 10-30% by weight Grafting material based on total weight of resin blend. In a preferred embodiment, the resin material includes a graft resin and a graft oligomer. The graft oligomer is between 0.1 and 50% by weight, and more preferably between n and 30% by weight. More preferably oligomers between 0.1 and 20% by weight, more preferably 0.1 and 10% by weight grafted oligomers, more preferably between 1 and 30% by weight grafted oligomers, more preferably 1 Graft oligomers between 20% and 20% by weight, and more preferably between 1 and 10% by weight, based on the size of the resin. This paper applies Chinese National Standard (CMS) A4 specifications (21 0X 29 * 7 mm). (%) (Please read the notes on the back before filling out this page) Order printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • 10-593520 A7 B7 5. Description of the invention (8) Total weight of the blend. Preferred ranges are also included between any upper and lower limits described in this paragraph. (Please read the notes on the back before filling this page.) If grafted hydrocarbon resin is used in this article, the grafted hydrocarbon resin, oligomer, and / or resin material, or a combination thereof, indicates that it has been combined with the graft monomer. , Contact, and / or react. Grafting is a method of combining, contacting, or reacting a hydrocarbon resin, an oligomer and / or a resin material with a graft monomer material. Grafting hydrocarbon resins, oligomers, and / or resin materials, or combinations thereof, to include at least some polar functionality produces useful components such as adhesive formulations, especially HMA formulations. These formulations are often designed for use with polar polymers such as EVAs, ethylene methyl acrylates (EMAs), polyacrylates (PAs), polymethacrylates (PMAs), and ethylene alkyl acrylates. Performs well on substrates such as PET, recycled paper, cardboard, and acrylic paint and on other substrates such as wood, glass, ceramics, asphalt, concrete, and metal. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Therefore, specific embodiments of the present invention include grafted and ungrafted hydrocarbon resins (classes) and oligomers (classes), and compositions and mixtures thereof. Specific embodiments also include (but are not limited to): adhesives or tacky components including (i) grafted hydrocarbon resins; (Π) grafted oligomers, (iii) grafted oligomers + Ungrafted resin (class), (iv) grafted hydrocarbon resin + ungrafted resin (class), (v) grafted hydrocarbon resin + ungrafted oligomer, (vi) grafted hydrocarbon resin + grafted oligomer Polymer, (Vii) grafted oligomer + ungrafted oligomer or (viii) grafted hydrocarbon resin + grafted oligomer + ungrafted resin (type) and one or more other suitable combinations thereof. The specific embodiments described herein also include methods of making and using the foregoing materials. This paper size applies to Chinese National Standard (CNS) A4 specifications (2) 0X297 gongs -11-593520 A7 ___B7___ 5. Description of the invention (9) Suitable hydrocarbon resins that can be grafted include: aliphatic hydrocarbon resins, at least partly Hydrogenated aliphatic hydrocarbon resins, aliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aliphatic aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic resins, cycloaliphatic / aromatic hydrocarbons Resins, at least partially hydrogenated cycloaliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene-phenol resins, and mixtures of two or more thereof. Turpentine can also be grafted. Preferably, the resin is at least partially hydrogenated, more preferably substantially hydrogenated, and more preferably contains aromatic carbohydrates. In a specific embodiment, the resin includes a hydrocarbon resin produced by thermal polymerization of dicyclopentadiene (DCPD) or substituted DCPD, which may further include an aliphatic or aromatic monomer as described later. body. In a preferred embodiment, the hydrocarbon resin produced by thermal polymerization of DCPD or substituted DCPD and C9 monomers in the final resin product contains less than 10% aromatics. In another embodiment, the resin comprises a C5 / C9 (aliphatic / aromatic) hydrocarbon resin obtained by the polymerization (preferably thermal or catalytic) of a C5 monomer and a C9 monomer. Another specific embodiment of the graft oligomer is a kind of graft oligomer (dimer, trimer, tetramer, pentamer, hexamer, and heptamer and octamer, as required) Material), preferably from petroleum distillates boiling in the range of 30-210 ° C. The oligomers can be obtained by any suitable method and are often obtained as by-products of resin polymerization, whether by thermal or catalytic reactions. Oligomers can be obtained from methods in which oligomerization and then grafting of appropriate DCPD, (: 5 and / or (: 9 monomer feeds, as described below). Suitable oligomer streams have a range of 1 3 0-5 Between 00, it is better to use the paper size of China National Standard (CNS) A4 (2 丨 0X297 mm) (please read the precautions on the back before filling this page).

、1T 經濟部智慧財產局員工消費合作社印製 -12- 593520 A7 B7 五、發明説明（1〇) 在130-410之間，更佳在1 3 0-3 50之間，更佳在130_27〇之 間，更佳在200-350之間，和更佳在200-320之間的分子量 (Μη) 〇 在一具體實施例中寡聚物包括環戊二烯和經取代之環 戊二烯單體且可進一步包含C9單體。在另一具體實施例中 ，寡聚物包括c5單體和可進一步包括c9單體。其他單體 也可存在，包括c4-c6單-和二-烯烴和萜烯。寡聚物也可單 獨包含c9單體。在各具體實施例中，較佳在與接枝單體接 枝之前至少部份氫化，更佳實質上氫化寡聚物。適當個別 環戊二烯和經取代之環戊二烯單體（包括DCPD)，C9單體和 C5單體的特殊例子描述於下。適當的寡聚物也可包括一種 或以上之如本文所述之較佳寡聚物材料的混合物。 在一較佳具體實施例中，烴樹脂/和或寡聚物具有1-60 %，更佳 1-40%，更佳 1-20%，更佳 1-15%，更佳 10-20 %，更佳15-20%，更佳1-10%，和更佳5-10%的芳族含 量，其中任何芳族含量之上限和任何下限可組合爲芳族含 量的較佳範圍。在一具體實施例中，欲接枝之烴樹脂具有 1 0-200°C的軟化點，更佳10-16(TC，更佳60-1 30°C，更佳 90- 1 3 0°C，更佳 80- 1 20°C，更佳 80-15(TC,和更佳 90-110 °c，其中任何軟化點之上限和任何下限可組合爲軟化點的 較佳範圍。軟化點fc)較佳依照ASTME-28(校訂1 996)測 量爲環球法軟化點。 如使用在本文中芳族含量和烯烴含量係藉由1H-NMR 測量如直接從具有大於3 00MHz(最佳400 MHz(頻率當量）） 尺度適用中國國家標準（CNS ) A4規格（210X297公H ~ -13 - (請先閱讀背面之注意事項再填寫本頁) 衣. 、1Τ 經濟部智慧財產局員工消費合作社印製 593520 A7 B7 五、發明説明（11 ) 的磁場強度的分光計得到之iH-NMR光譜測量。芳族含量 爲芳族質子對質子總數的積分。烯烴質子或烯烴質子含量 爲烯烴質子對質子總數的積分。 樹脂及/或寡聚物較佳被至少部份氫化和更較佳被實質 上氫化。如使用在本文中至少部份氫化表示該材料包含少 於9 0 %烯烴質子，更佳少於7 5 %烯烴質子，更佳少於5 0 % 烯烴質子，更佳少於40%烯烴質子，更佳少於25%烯烴質 子，更佳少於1 5 %烯烴質子，更佳少於1 〇 %烯烴質子，更 佳少於9 %烯烴質子，更佳少於8 %烯烴質子，更佳少於7 %烯烴質子，和更佳少於6%烯烴質子。如使用在本文中， 實質上氫化表示該材料在氫化作用之後（和在與接枝單體反 應之前）材料包含得少於5%烯烴質子，更佳少於4%烯烴 質子，更佳少於3%烯烴質子，更佳少於2%烯烴質子，更 佳少於1 %烯烴質子，更佳少於0.5 %烯烴質子，更佳少於 0.1%烯烴質子，和更佳少於0.05%烯烴質子。典型地進行 氫化程度以使最少化和較佳避免芳族鍵的氫化作用。在其 中樹脂及/或寡聚物實質上氫化的較佳具體實施例中，咸信 與形成（樹脂/寡聚物和接枝單體之）共聚物相反，接枝單體 附接至樹脂/寡聚物主鏈，因爲在實質上氫化的樹脂/寡聚物 上缺乏終端烯烴鍵（如較佳低烯烴質子測量所示）。 如所述，樹脂和寡聚物較佳包括一種或以上的芳族單 體。下式數據諳示芳族材料在包括一種含芳族的接枝材料 之膠黏劑組成物中產生較佳性能。此外，某些接枝單體， 例如順-丁烯二酐，在含芳族之材料中具有良好溶解度，其 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ' "~~~~ -14 - (請先閱讀背面之注意事項再填寫本頁) 衣·Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -12-593520 A7 B7 V. Description of the invention (1〇) is between 130-410, preferably between 1 3 0-3 50, and more preferably 130_27. Molecular weight (Mη) between 200 and 350, and more preferably between 200 and 320. In one embodiment, the oligomer includes cyclopentadiene and substituted cyclopentadiene monomers. And may further include a C9 monomer. In another specific embodiment, the oligomer includes a c5 monomer and may further include a c9 monomer. Other monomers may also be present, including c4-c6 mono- and di-olefins and terpenes. The oligomer may also contain c9 monomer alone. In various embodiments, it is preferred that the oligomer is hydrogenated at least partially before grafting with the grafting monomer, and more preferably substantially hydrogenated. Appropriate individual examples of cyclopentadiene and substituted cyclopentadiene monomers (including DCPD), C9 monomers and C5 monomers are described below. Suitable oligomers may also include a mixture of one or more of the preferred oligomer materials as described herein. In a preferred embodiment, the hydrocarbon resin and / or oligomer has 1-60%, more preferably 1-40%, more preferably 1-20%, more preferably 1-15%, and more preferably 10-20%. , More preferably 15-20%, more preferably 1-10%, and more preferably 5-10% of the aromatic content, wherein the upper limit and any lower limit of any aromatic content can be combined into a better range of aromatic content. In a specific embodiment, the hydrocarbon resin to be grafted has a softening point of 10-200 ° C, more preferably 10-16 (TC, more preferably 60-1 30 ° C, more preferably 90-1 130 ° C , Better 80-1 20 ° C, better 80-15 (TC, and more preferably 90-110 ° c, where the upper limit and any lower limit of any softening point can be combined into a better range of softening point. Softening point fc) It is preferably measured as the ring and ball softening point according to ASTME-28 (Revised 1 996). As used herein, the aromatic content and olefin content are measured by 1H-NMR such as from directly having a frequency greater than 300 MHz (optimally 400 MHz (frequency (Equivalent)) The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 male H ~ -13-(Please read the precautions on the back before filling this page). Clothing, 1T Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Measurement of iH-NMR spectrum obtained by spectrometer with magnetic field strength of the description of the invention (11). The aromatic content is the integral of aromatic protons to the total number of protons. The olefin proton or olefin proton content is the integral of olefin protons to the total number of protons. The resin and / or oligomer is preferably at least partially hydrogenated and more preferably substantially hydrogenated. At least partially hydrogenated in this context means that the material contains less than 90% olefin protons, more preferably less than 75% olefin protons, more preferably less than 50% olefin protons, more preferably less than 40% olefin protons, and more preferably Less than 25% olefin protons, more preferably less than 15% olefin protons, more preferably less than 10% olefin protons, more preferably less than 9% olefin protons, more preferably less than 8% olefin protons, more preferably less than 7 % Olefin protons, and more preferably less than 6% olefin protons. As used herein, substantially hydrogenated means that the material contains less than 5% olefin protons after hydrogenation (and before reaction with the grafting monomer). , Preferably less than 4% olefin proton, more preferably less than 3% olefin proton, more preferably less than 2% olefin proton, more preferably less than 1% olefin proton, more preferably less than 0.5% olefin proton, more preferably less than 0.1% olefin protons, and more preferably less than 0.05% olefin protons. The degree of hydrogenation is typically performed to minimize and preferably avoid the hydrogenation of aromatic bonds. It is preferred that the resins and / or oligomers are substantially hydrogenated. In the specific embodiment, the salt is opposite to the copolymer (resin / oligomer and graft monomer). The grafting monomer is attached to the resin / oligomer backbone because of the lack of terminal olefinic bonds on the substantially hydrogenated resin / oligomer (as shown by the preferred low olefin proton measurement). As stated, resins and oligomers The polymer preferably includes one or more aromatic monomers. The data below show that aromatic materials produce better performance in adhesive compositions that include an aromatic-containing graft material. In addition, certain grafts Monomers, such as cis-butene dianhydride, have good solubility in aromatic-containing materials, and the paper size is applicable to China National Standard (CNS) A4 (210X297 mm) '" ~~~~ -14 -(Please read the notes on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 593520 A7 B7 五、發明説明（12) 可能允許更均勻的反應相和可能避免在接枝反應期間之不 受歡迎的副產物。 接枝單體 較佳接枝單體包括任何包含至少一個烯烴鍵和至少一 個極性基（例如羰基）之不飽和有機化合物，其包括不飽和酸 及酸酐和其衍生物。較佳，有機化合物包含與一種簾基（-C =〇)共軛之乙烯性不飽和度和較佳至少包含一個α，/3烯烴 鍵。較佳接枝單體包括酸類，醇類，酸酐類，醯亞胺類， 醯胺類，和其衍生物。實例包括羧酸類，醯基鹵類或酸酐 ，醇類（酚類，單醇類，二醇類，和多元醇類），和其衍生物 。代表性的酸類和酸類衍生物包括羧酸類，酸酐類，醯基 鹵類，酯類，醯胺類，醯亞胺類和他們的鹽類，金屬及非 金屬二者。例子包括順-丁烯二酸，反-丁烯二酸，丙烯酸， 甲基丙烯酸，依康酸，烏頭酸，檸康酸，雙環庚烯二甲酸 ，四氫苯二甲酸，巴豆酸，α -甲基巴豆酸，和肉桂酸。順_ 丁烯二酐爲特佳的接枝單體。特殊例子包括，依康酐，檸 康酐，丙烯酸甲酯，甲基丙烯酸甲酯，丙烯酸乙酯，甲基 丙烯酸乙酯，丙烯酸縮水甘油酯，順-丁烯二酸單乙酯，順_ 丁烯二酸二乙酯，順-丁烯二酸二丁酯，反-丁烯二酸單甲酯 ，反-丁烯二酸二甲酯，依康酸單甲酯，依康酸二乙酯，丙 烯醯胺，甲基丙烯醯胺，順-丁烯二酸單醯胺，順-丁烯二酸 二醯胺，順-丁烯二酸-Ν-單乙基醯胺，順-丁烯二酸-Ν，Ν-二 乙基醯胺，順·丁烯二酸-Ν-單丁基醯胺，順-丁烯二酸-Ν，Ν· 本纸張尺度適用中國國家標準（CNS ) Α4規格（2丨ΟΧ 297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣· 、1Τ 經濟部智慧財產局員工消費合作社印製 -15- 593520 A7 B7 五、發明説明（13) 二丁基醯胺，反-丁烧二酸單醯胺，反丁燒二酸二醯胺， 反-丁烧二酸-N-單丁基醯胺，反.丁燦二酸_n，n_二丁基釀胺 ’順丁稀Z：醯亞胺，N_ 丁基•順了 t醯胺，&苯基順丁嫌 二醯亞胺，丙龍鈉，甲基_酸鈉，關酸鉀和甲基丙 嶋。較佳接枝單體包括酸類，酸酐類，醇類，醯胺類 和醯亞胺類。 烴樹脂製造 烴樹β曰爲已知且被製造，例如，藉由各種進料（其可爲 純單體進料或包含各種不飽和材料的混合物之煉油流）的呋 里得-夸呋特聚合作用。一般而言，較純進料聚合比較容易 聚合。 例如純苯乙烯，純α -甲基苯乙烯和其混合物比c8/C9 煉油流容易聚合。同樣地，純或濃戊間二烯比C4_c6煉油流 容易聚合。然而，在製造上這些純單體比通常大體積煉油 廠法之副產物的煉油流貴。 脂族烴樹脂可藉由包含裂解石油進料C4，C5，和（：6鏈 院烴，烯烴類，和本文稱爲c5單體之共軛二烯烴類的陽離 子聚合反應製備。如使用在本文中，C5單體較佳排除如下 所述藉由熱浸漬除去之DCPD單體。這些C5單體流包括陽 離子和熱可聚合的單體例如丁二烯，異丁烯，；[，3_戊二烯（ 戊間二烯）與1，4_戊二烯，環戊烯，卜戊烯，^戊烯，2_甲 基-1-戊烯，2-甲基-2-丁烯，2-甲基-2-戊烯，異戊二烯，環 己烯，I-3-己二烯，；1-4-己二烯，環戊二烯和二環 本紙張尺度適用中麵家榡準（CNS ) M規格（21Q>< 297公羡 (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 烯。 -16 593520 A7 ______B7 五、發明説明（Μ) 爲了獲得运些進料，煉油流較佳通常藉由分餾和處理純化 而除去雜質。在一些具體實施例中，C5進料流可包括至少 一些（較佳少於2重量％ )環戊二烯（CPD)和經取代之環戊二 備（例如，甲基環戊一烯）組份。這些組份視需要選擇性地藉 由熱浸漬從C5單體流分離，其中進料流被加熱到〗〇〇。〇和 160°C之間的溫度，較佳在i〇〇°C和150°C之間，經〇.5到 6小時，接著分離DCPD單體以減少在C5單體流中的環戊 一烯及/或一環戊一烯的含量到較佳2重量％以下。低溫熱 浸漬爲較佳以便限制環二烯（環戊二烯和甲基環戊二烯）與 Cs直鏈共軛一烯的共二聚合作用（異戊二烯和戊二烯ι,3順 式-和反式-)。熱浸漬步驟較佳二聚合環戊二烯和經取代之 環戊二烯，以使更容易從C5單體流分離。在分餾和，如果 進行，熱浸漬之後，進料較佳進行蒸餾以除去環共軛二烯 烴類（其爲凝膠先質）（欲除去之環戊二烯和甲基環戊二烯， 如二聚物，三聚物等等）。 c5單體流的實例爲在-1〇它到100°C範圍沸騰之蒸氣裂 解石油流。C5單體進料市售樣品的例子包括得自德州休斯 頓Lyondell石化公司的石腦油石油3戊間二烯類，一般戊 間二烯濃縮液或高級戊間二烯濃縮液二者，皆得荷蘭 Hoogvilet貝殻荷蘭化學B. V·。 樹脂聚合作用進料也可包含C8-C1Q芳族烴單體（本文稱 爲C 9單體）例如苯乙烯，茚，苯乙烯之衍生物，茚之衍生物 ，及其組合物。特佳芳烴烯烴包括苯乙烯，α -甲基苯乙烯 ，/5 -甲基苯乙烯，茚，甲基茚類及丁烯基甲苯類。C9單體 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣. 訂 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 593520 A7 B7 五、發明説明（15) 流的一個實例爲在-lot到210°c (如果C5單體和DCPD組 份不存在，則爲135°C到21(TC)範圍沸騰的蒸氣裂解石油 流。商品C9單體進料的例子包括來自德州休斯頓Lyondell 石化公司的LRO-90，得自荷蘭Geleen的DSM之DSM C9 樹脂進料類，得自Mich. Midland之道化學品公司的RO-60 和RO-80，和得自荷蘭Terneuzen道化學公司之道樹脂油 60-L。 除反應性組份之外，進料中的非可聚合組份可包括可 與不飽和組份共蒸餾的飽和烴類例如戊烷，環戊烷，或2-甲基戊烷。此單體進料可與其他C4或C5烯烴或二聚物共 聚合。然而，較佳純化進料以除去不利影響聚合反應或在 最後樹脂中造成不受歡迎的顏色之不飽和材料（例如，異戊 二烯）。此通常藉由分餾完成。在一具體實施例中，聚合作 用係使用使用呋里得-夸呋特聚合催化劑例如在載體上或不 在載體上之路易斯酸（例如，三氟化硼（BF3)，三氟化硼的錯 合物，三氯化鋁（A1C13)，三氯化鋁的錯合物或烷基鋁鹵化 物，特別是氯化物）進行。呋里得-夸呋特聚合作用之適當反 應條件包括-20°C到100°C的溫度，1 00-2000 kPa的壓力。 在一具體實施例中，C5和C9單體藉由該方法聚合。 典型地，進料流包括20-80重量％單體和20-80重量％ 溶劑。較佳，.進料流包括30-70重量％單體和3 0-70重量％ 溶劑。更佳，進料流包括50-70重量％單體和3 0-5 0重量％ 溶劑。溶劑可包括芳族溶劑，其可爲甲苯，二曱苯，其他 的芳族溶劑，脂族溶劑及/或其一種或以上之混合物。溶劑 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Description of the invention (12) May allow a more uniform reaction phase and may avoid undesired by-products during the grafting reaction. Grafting monomers Preferred grafting monomers include any unsaturated organic compound containing at least one olefinic bond and at least one polar group (e.g., a carbonyl group), including unsaturated acids and anhydrides and derivatives thereof. Preferably, the organic compound contains ethylenic unsaturation conjugated to a curtain base (-C = 0) and preferably contains at least one α, / 3 olefin bond. Preferred grafting monomers include acids, alcohols, anhydrides, amines, amines, and derivatives thereof. Examples include carboxylic acids, fluorenyl halides or anhydrides, alcohols (phenols, monoalcohols, glycols, and polyalcohols), and derivatives thereof. Representative acids and acid derivatives include carboxylic acids, anhydrides, fluorenyl halides, esters, fluorenamines, fluorenimines and their salts, both metal and non-metal. Examples include maleic acid, trans-butylene acid, acrylic acid, methacrylic acid, itaconic acid, aconitic acid, citraconic acid, dicycloheptene dicarboxylic acid, tetrahydrophthalic acid, crotonic acid, α- Methylcrotonic acid, and cinnamic acid. Cis-butene dianhydride is a particularly good grafting monomer. Specific examples include, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, maleic ester of maleic acid, maleic acid Diethyl maleate, Dibutyl maleate, Dimethyl maleate, Dimethyl maleate, Dimethyl maleate, Diethyl maleate , Acrylamide, methacrylamide, maleimide monoamine, maleimide diamine, maleimide-N-monoethylammoniumamine, maleimide Diacid-N, N-diethylamidamine, maleic acid-N-monobutylamidamine, maleic acid-N, N · This paper size applies to Chinese National Standards (CNS) Α4 Specification (2 丨 〇Χ 297mm) (Please read the precautions on the back before filling out this page) Clothing, 1T Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -15- 593520 A7 B7 V. Description of the Invention (13) Dibutylphosphonium amine, trans-butylenedicarboxylic acid monofluorenylamine, transbutylenedicarboxylic acid difluorenylamine, trans-butylenedicarboxylic acid-N-monobutylphosphonium amine, trans.butanedioic acid_n, n _Dibutyl Fermented Amines' Cis Butylene Z: Amines N-butyl-cis-t-amidine, & phenyl-cis-butanimide, diammonium imine, sodium propionate, sodium methyl-sulfate, potassium succinate, and methylpropionamidine. Preferred grafting monomers include acids, anhydrides, alcohols, amidines, and amines. Hydrocarbon resin manufacturing hydrocarbon trees β are known and manufactured, for example, by Furried-Quarfurt with various feeds (which may be pure monomer feeds or refinery streams containing mixtures of various unsaturated materials) Polymerization. Generally speaking, it is easier to polymerize with relatively pure feed polymerization. For example, pure styrene, pure α-methylstyrene, and mixtures thereof are easier to polymerize than the c8 / C9 refinery stream. Similarly, pure or concentrated pentadiene polymerizes more easily than the C4_c6 refinery stream. However, these pure monomers are more expensive to manufacture than refinery streams that are usually by-products of large volume refineries. Aliphatic hydrocarbon resins can be prepared by cationic polymerization of cracked petroleum feeds C4, C5, and (6 chain hydrocarbons, olefins, and conjugated diolefins referred to herein as c5 monomers. As used herein In the C5 monomer, DCPD monomers removed by hot dipping as described below are preferably excluded. These C5 monomer streams include cationic and thermally polymerizable monomers such as butadiene, isobutene, [, 3-pentadiene (Pentadiene) and 1,4-pentadiene, cyclopentene, pentene, pentene, 2-methyl-1-pentene, 2-methyl-2-butene, 2-methyl Iso-2-pentene, isoprene, cyclohexene, I-3-hexadiene, 1-hexadecadiene, cyclopentadiene, and bicyclo This paper is suitable for mid-range furniture standards ( CNS) M specification (21Q > < 297 public envy (please read the notes on the back before filling this page) Order the printed olefins from the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. -16 593520 A7 ______B7 V. Description of the Invention (Μ) In order to obtain these feeds, the refinery stream preferably removes impurities typically by fractional distillation and processing purification. In some embodiments, the C5 feed stream may include at least some (preferably less) 2% by weight) cyclopentadiene (CPD) and substituted cyclopentadiene (eg, methylcyclopentadiene) components. These components are optionally separated from the C5 monomer stream by hot impregnation as needed Where the feed stream is heated to a temperature between 0 ° C and 160 ° C, preferably between 100 ° C and 150 ° C, for 0.5 to 6 hours, followed by separation of the DCPD monomer In order to reduce the content of cyclopentadiene and / or monocyclopentadiene in the C5 monomer stream to preferably less than 2% by weight. Low temperature hot dipping is preferred in order to limit cyclodiene (cyclopentadiene and methyl Copolymerization of cyclopentadiene) with Cs straight-chain conjugated monoene (isoprene and pentadiene, 3 cis- and trans-). The hot impregnation step is preferably dipolymerized cyclopentadiene And substituted cyclopentadiene to make it easier to separate from the C5 monomer stream. After fractionation and, if performed, hot dipping, the feed is preferably distilled to remove cycloconjugated diene (which is a gel Precursor) (Cyclopentadiene and methylcyclopentadiene to be removed, such as dimers, trimers, etc.). Examples of c5 monomer streams are boiling at -10 to 100 ° C. steam Cracked petroleum stream. Examples of commercially available samples of C5 monomer feed include naphtha petroleum 3-pentadienes from Lyondell Petrochemical Company of Houston, Texas, general pentadiene concentrates or advanced pentadiene concentrates. In the case of Hoogvilet, Dutch Chemical B. V. The resin polymerization feed may also contain C8-C1Q aromatic hydrocarbon monomers (referred to herein as C 9 monomers) such as styrene, indene, and derivatives of styrene. , Indene derivatives, and combinations thereof. Particularly preferred aromatic olefins include styrene, α-methylstyrene, / 5-methylstyrene, indene, methylindenes, and butenyltoluene. C9 monomer This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). Printed by the Consumer Cooperative 593520 A7 B7 V. Description of the invention (15) An example of the flow is at -lot to 210 ° c (if C5 monomer and DCPD components are not present, boiling in the range of 135 ° C to 21 (TC) Of steam cracking petroleum stream. Examples of commercial C9 monomer feeds include LRO-90 from Lyondell Petrochemical Company of Houston, Texas, DSM C9 resin feeds from DSM, Geleen, The Netherlands, RO-60 and RO from Mich. Midland Chemical Company -80, and resin resin 60-L from Terneuzen Dow Chemical Company, Netherlands. In addition to the reactive components, the non-polymerizable components in the feed may include saturated hydrocarbons such as pentane, cyclopentane, or 2-methylpentane that can be codistilled with unsaturated components. This monomer feed can be copolymerized with other C4 or C5 olefins or dimers. However, it is preferred to purify the feed to remove unsaturated materials (e.g., isoprene) that adversely affect the polymerization reaction or cause undesirable colors in the final resin. This is usually done by fractionation. In a specific embodiment, the polymerization is performed using a furried-quarfurt polymerization catalyst such as a Lewis acid (for example, boron trifluoride (BF3), boron trifluoride on or not on a carrier). (AlCl3), aluminum trichloride complex or alkylaluminum halides, especially chloride). Suitable reaction conditions for the furried-quarfurt polymerization include a temperature of -20 ° C to 100 ° C, and a pressure of 100-2000 kPa. In a specific embodiment, C5 and C9 monomers are polymerized by this method. Typically, the feed stream includes 20-80% by weight monomer and 20-80% by weight solvent. Preferably, the feed stream comprises 30-70% by weight monomer and 30-70% by weight solvent. More preferably, the feed stream includes 50-70% by weight monomer and 30-50% by weight solvent. The solvent may include an aromatic solvent, which may be toluene, xylene, other aromatic solvents, aliphatic solvents, and / or one or more mixtures thereof. Solvents This paper is sized for Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-18 - 593520 A7 B7 五、發明説明（16) 較佳被回收。溶劑可包含進料的非可聚合組份。溶劑通常 包含少於2 5 0 p p m水，較佳少於1 〇 〇 p p m水，和最佳少於 5 〇 p p m 水。 在另一具體實施例中，進料流包括30_95重量％之c5 卓體，如上所述和5-70重量％包括至少一個選自純單體， C 9單體，和萜烯所組成之成員的共進料。較佳，進料流包 括約5〇-85重量％C5單體和約15_50重量％共進料，包括 至少一個選自純單體，C 9單體，和萜儲所組成之成員。 典型地，所得烴樹脂具有400_3〇00的數目平均分子量 (Mn)，500-6000 的重量平均分子量（Mw)，700- 1 5,000 的 z-平均分子量（Mz)和在I.5和4間之多分散性（PD)，如藉由 Mw/Mn測量。如使用在本文中，分子量（數目平均分子量 (Μη),重量平均分子量（Mw)，和z_平均分子量（Mz))藉由使 用安裝差式折射率檢測器的W a t e r 1 5 0凝膠滲透層析儀和使 用聚苯乙烯標品校準之大小凝膠色層分析測量。樣品在四 氫呋喃（THF)中（4 5 °C)操作。分子量以聚苯乙烯-當量分子量 報告和通常以克/莫耳測量。 單體進料可與作爲鏈轉移劑之（：4或C5烯烴或其烯烴 二聚物共聚合。可加入至高40重量％ (較佳至高20重量 之鏈轉移劑以獲得具有比從單獨使用單體進料製得者爲低 和窄的分子量分佈之樹脂。從某方面而言鏈轉移劑藉由使 終止鏈而停止成長聚合物鏈的增長，其再生聚物起始位置 。組份，其作爲反應中的鏈轉移劑，包括但不限制於2 -甲 基-1-丁儲，2 -甲基-2-丁烯或這些種類的二聚物或寡聚物。 本纸張尺度適用f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) ·裝· 、11 經濟部智慧財產局員工消費合作社印製 -19- 593520 A7 B7 五、發明説明（17) «轉移劑可以純形式或稀釋於溶劑中加至反應。 DCPD樹脂及/或其寡聚物（也稱爲CDP寡聚物）可藉由 從一種包括DCPD及/或經取代之DCPD的不飽和單體之進 料的熱聚合而獲得或衍生。在一具體實施例中，進料也包 括如前所之芳族單體。在該具體實施例中，（a) DCPD流， 較佳爲一種在8〇-2〇〇°C (更佳l4〇°C到200°C)範圍沸騰之蒸 氣裂解石油餾出物，包含環戊二烯和其甲基衍生物的二聚 物和共二聚物，連同（b) C9單體，較佳爲一種在l5〇-2〇〇°C 範圍沸騰之蒸氣裂解石油餾出物，包括甲基苯乙烯，乙烯 基甲苯，茚及甲基茚與其他09及C1Q芳烴類，的混合物， 於重量比（a : b)在90 : 10到5 0 : 50之間，在批次聚合反應 器中於 9.8xl 05-20xl05 巴（更佳 9·8χ105-11·7χ105 巴）的壓力 下加熱到160-3 20°C，經1.2到4個小時（更佳1.5到4個小 時）。在不需要寡聚物內含物的情形中，可汽所得聚合產物 以除去惰性、未反應和低分子量寡聚合組份以產生具有在 8〇-120°C範圍之軟化點的樹脂。 在一具體實施例中，樹脂較佳藉由從一種包含如前所 述之C5單體和C9單體之進料的熱聚合而獲得或衍生。該 在具體實施例中，（a) C5單體，較佳爲一種在80-200 °C範 圍沸騰之蒸氣裂解石油餾出物，連同（b)C9單體，較佳爲一 種在1 50-200°C範圍沸騰之蒸氣裂解石油餾出物，包括α-甲基苯乙烯，乙烯基甲苯，茚及甲基茚與其他C8-C1G芳烴 類的混合物，於重量比（a : b)在90 : 10到5 0 : 50之間，在 批次聚合反應器中於9.8x 1 05-20x 1 05巴（更佳 9.8xl05- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） I-------裝-- (請先閱讀背面之注意事項再填寫本頁)-18-593520 A7 B7 V. Description of the invention (16) It is better to be recovered. The solvent may include non-polymerizable components of the feed. The solvent usually contains less than 250 p p m of water, preferably less than 100 p p m of water, and most preferably less than 50 p p m of water. In another specific embodiment, the feed stream includes 30-95% by weight of c5 zirconium, as described above, and 5-70% by weight, including at least one member selected from the group consisting of pure monomers, C9 monomers, and terpenes. Co-feeding. Preferably, the feed stream comprises about 50-85% by weight C5 monomer and about 15-50% by weight co-feed, including at least one member selected from the group consisting of pure monomer, C9 monomer, and terpene reservoir. Typically, the obtained hydrocarbon resin has a number-average molecular weight (Mn) of 400-30,000, a weight-average molecular weight (Mw) of 500-6000, a z-average molecular weight (Mz) of 700- 1 5,000, and between 1.5 and 4. Polydispersity (PD), as measured by Mw / Mn. As used herein, molecular weight (number-average molecular weight (Mη), weight-average molecular weight (Mw), and z-average molecular weight (Mz)) are penetrated by using a Water 1 50 gel with a differential refractive index detector installed Chromatograph and gel size measurement using polystyrene standards calibrated. The samples were operated in tetrahydrofuran (THF) (45 ° C). Molecular weight is reported as polystyrene-equivalent molecular weight and is usually measured in grams / mole. The monomer feed can be copolymerized with (4 or C5 olefins or olefin dimers thereof) as chain transfer agents. Chain transfer agents can be added up to 40% by weight (preferably up to 20% by weight) to obtain The bulk feedstock is made of resin with low and narrow molecular weight distribution. In a way, the chain transfer agent stops the growth of the polymer chain by terminating the chain, and the starting position of the regenerated polymer. The component, its As a chain transfer agent in the reaction, it includes, but is not limited to, 2-methyl-1-butane, 2-methyl-2-butene, or dimers or oligomers of these kinds. This paper applies to f National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) ··· 11 Printed by the Intellectual Property Bureau of the Ministry of Economy Staff Consumer Cooperatives-19- 593520 A7 B7 V. Description of the invention (17) «The transfer agent can be added to the reaction in pure form or diluted in a solvent. DCPD resin and / or its oligomer (also known as CDP oligomer) can be added by a It is obtained or derived by thermal polymerization of DCPD unsaturated monomer feed. In a specific In the embodiment, the feed also includes the aromatic monomer as previously described. In this specific embodiment, (a) the DCPD stream, preferably one at 80-20 ° C (more preferably 140 ° C) To 200 ° C) boiling steam cracked petroleum distillates, including dimers and co-dimers of cyclopentadiene and its methyl derivatives, together with (b) C9 monomers, preferably one at 15 〇-2200 ° C boiling steam cracking petroleum distillates, including methylstyrene, vinyltoluene, indene and methylindene with other 09 and C1Q aromatic hydrocarbons, in a weight ratio (a: b ) Between 90:10 and 50:50, heated to 160-3 20 ° C in a batch polymerization reactor at a pressure of 9.8xl 05-20xl05 bar (more preferably 9.8x105-11 · 7x105 bar) After 1.2 to 4 hours (more preferably 1.5 to 4 hours). In cases where oligomer inclusions are not required, the resulting polymerization product can be steamed to remove inert, unreacted and low molecular weight oligomeric components to produce Resin having a softening point in the range of 80-120 ° C. In a specific embodiment, the resin is preferably obtained by feeding from a feed comprising a C5 monomer and a C9 monomer as previously described. It is obtained or derivatized by thermal polymerization. In a specific embodiment, (a) the C5 monomer, preferably a steam cracking petroleum distillate boiling in the range of 80-200 ° C, together with (b) the C9 monomer, It is preferably a steam cracking petroleum distillate boiling in the range of 150-200 ° C, including a mixture of α-methylstyrene, vinyltoluene, indene, and methylindene with other C8-C1G aromatic hydrocarbons. The ratio (a: b) is between 90:10 and 50:50, in a batch polymerization reactor at 9.8x 1 05-20x 1 05 bar (better 9.8xl05- this paper size applies to the Chinese national standard (CNS ) A4 size (210X 297mm) I ------- install-(Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 -20- 593520 A7 B7 五、發明説明（18) (請先閱讀背面之注意事項再填寫本頁) 1 1.7xl〇5巴）的壓力下加熱到160_320°C，經1.2到4個小時 (更佳1.5到4個小時）。在不需要寡聚物內含物的情形中， 可汽所得聚合產物以除去惰性、未反應和低分子量寡聚合 組份以產生具有在80- 1 20°C範圍之軟化點的樹脂。 聚合方法的產物包括樹脂和包括進料單體（類）之寡聚物 (二聚物，三聚物，四聚物，五聚物，六聚物類和視需要選 擇之七聚物和八聚物）的寡聚物副產物二者。如使用於後文 中，樹脂材料係指樹脂，寡聚物，或該二者之混合物。在 中寡聚物副產物由DCPD和經取代之DCPD的熱聚合作用 產生的具體實施例中，寡聚物典型地爲一種（較佳如下所述 氫化之）CDP及甲基CDP與低含量之非環C5二烯類例如戊 二烯-1，3和異戊二烯之Diels Alder三聚物及四聚物的複合 混合物。 樹脂材料較佳然後氫化以減少染色及改良顏色穩定性 。可使用任何一個已知用於催化氫化氫化樹脂材料之方法 。特別是該等揭示在US 5 1 7 1 793，US 4629766， 經濟部智慧財產局員工消費合作社印製 US 5 502 1 04 和 US 43 28090 和 WO 95/1 2623 之方法是適合 的。槪括氫化處理條件包括l〇〇-35(TC之溫度範圍和約在五 個大氣壓（5〇6 kPa)和3〇0大氣壓（和至高400大氣壓）之間 的氫壓力，例如，1 0-275大氣壓（10 1 3-27579 kPa)的反應。 在一具體實施例中，溫度在包括1 80-3 3 0°C的範圍及壓力在 包括1 5 1 95-20260 kPa氫的範圍。反應器之氫對進料的體積 比在標準條件下（25°C，1大氣壓（101 kPa)壓力）典型地可從 20 : 1 -200 : 1範圍；對於水-白樹脂，1 00 : 1 -200 : 1爲較 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -21 - 593520 A7 B7 五、發明説明（19 ) 佳。氫化產物可被汽提以除去低分子量副產物和任何溶劑 。此寡聚合副產物爲在250-400°C間沸騰和較佳實質上氫化 之低黏度幾乎無色液體。 樹脂材料的氫化作用可經由熔體或溶液爲主之方法以 批次或更普遍爲連續方法進行。用於烴樹脂的氫化作用之 催化劑典型爲在載體上之以第6,8,9，10或11族元素爲主 的單金屬和二金屬催化劑系統。催化劑例如載體上的鎳（例 如，氧化鋁上的鎳，木炭上的鎳，矽石上的鎳，矽藻土上 的鎳等），在載體之鈀（例如，矽石上的鈀，木炭上的鈀，氧 化鎂上的鈀等）和在載體上之銅及/或鋅（例如在銅及/或氧化 錳上的亞鉻酸銅，在氧化鋁上之銅和鋅等等）爲良好的氫化 催化劑。載體材料典型地由該等多孔性無機耐火氧化物例 如矽石，鎂氧，矽石-鎂氧，氧化銷，矽石-氧化鉻，氧化鈦 ，矽石-氧化鈦，氧化鋁，矽石-氧化鋁，氧化鋁-矽酸鹽等 ，且包含r-氧化鋁之載體爲極佳。較佳，載體基本上沒有 結晶分子篩材料。也預期前述氧化物的混合物，尤其是當 儘可能均勻製備時。可使用的載體材料包括揭示在美國專 利第 4686030，484696 1，4500424，和 4849093 號。適當的 載體包括氧化鋁，矽石，碳，MgO，Ti02，Zr02，Fe2〇3或 其混合物。 氫化樹脂材料的另一適合方法描述在EP 0082726。 EP 0082726描述一種使用在r·氧化鋁載體上的鎳-鎢催化 劑之催化或熱氫化的方法，其中氫壓爲1.47χ1〇7_196χ1〇7 巴及溫度在25 0-3 3 0 °C的範圍。在氫化之後反應器混合物可 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公楚) (請先閱讀背面之注意事項再填寫本頁) C. 、11 經濟部智慧財產局g(工消費合作社印製 -22- 593520 A7 ___B7 五、發明説明（2〇) (請先閱讀背面之注意事項再填寫本頁) 被閃蒸和進一步分離以回收氫化樹脂材料。在一具體實施 例中，蒸汽蒸餾可用以分離寡聚物和較佳在沒有超過3 25 t 樹脂溫度下進行。 在〜具體實施例中，催化劑包含鎳及/或鈷和一種或以 上的鉬，在一種或以上之氧化鋁或矽石載體上的鎢，其中 在載體上的氧化鎳及/或氧化鈷的量在2-10重量％範圍。製 備之後在載體上的氧化鎢或鉬物中的量在5 -2 5重量％範圍 。較佳，催化劑包含4-7重量％氧化鎳和18-22重量％氧化 鎢。此方法和適當催化劑更詳細揭述在美國專利第5 820749 號中。在另一具體實施例中，氫化作用可藉由使用美國專 利第4029 766號所述之方法和催化劑進行。特別地，在r -氧化鋁上的鎳-鎢催化劑爲較佳。 經濟部智慧財產局員工消費合作社印製 在一具體實施例中，在氫化作用之前從樹脂汽提寡聚 物。在該具體實施例中，寡聚物較佳在接枝之前氫化。在 另一具體實施例中，寡聚物與樹脂氫化然後從樹脂汽提， 產生氫化樹脂和氫化寡聚物。在另一具體實施例中，至少 一些寡聚物在氫化作用之前汽提和至少一些氫化寡聚物在 氫化作用之後汽提。然而在另一具體實施例中，氫化樹脂/ 寡聚物產物可如下所述進一步一起加工成單一混合物。然 而在另一具體實施例中，寡聚物可衍生自任何適當來源和 在接枝之前氬化（如果必需的）以使寡聚物在接枝之前典型地 至少部份氫化和較佳實質上氫化。 接枝樹脂材料 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐^ -23 - 593520 A7 ____ B7 五、發明説明（21 ) (請先閱讀背面之注意事項再填寫本頁) 至少一部分的所得樹脂材料，較佳衍生自一種如上述 的方法，然後可與接枝單體合倂及/或接觸，典型地在適當 反應條件下和在適當混合裝置中。在較佳具體實施例中， 反應在沒有顯著剪切下進行。在根據前述的具體實施例中 ，樹脂和寡聚物可分開或同時被接枝，和如果分開地，接 枝寡聚物然後可視需要選擇性與接枝樹脂，非接枝樹脂， 或任何如上所述之其他適當的樹脂，膠黏性組份或組成物 再混合。 經濟部智慧財產局員工消費合作社印製 接枝單體的接枝較佳在選自由有機過氧化物，有機過 酯，和偶氮基化合物所組成之自由基引發劑存在下發生。 該等化合物的例子包括二苯甲醯基過氧化物，二氯苯甲醯 過氧化物，二異丙苯基過氧化物，二-三級-丁基過氧化物， 2,5-二甲基-2,5-二（過氧苯甲酸酯）己炔-3，1，4-雙（三級·丁 基過氧異丙基）苯，月桂醯基過氧化物，過乙酸三級-丁基酯 ，2,5-二甲基-2,5-二（三級-丁基過氧基）己炔-3，2,5-二甲 基-2,5-二（三級-丁基過氧基）己烷，過苯甲酸三級-丁基酯， 乙酸三級-丁基過苯基酯，過異丁酸三級-丁基酯，過-二級-辛酸三級-丁基酯，過特戊酸三級-丁基酯，過特戊酸異丙苯 基酯，三級-丁基氫過氧化物，過二乙基乙酸三級·丁基酯 ，偶氮異丁腈，和偶氮異丁酸二甲基酯。過氧化物較佳在 1 60°C具有約6分鐘的半生期與揮發性非芳族分解產物且該 等將彩色形成減到最少。較佳過氧化物包括二-三級-丁基過 氧化物和2,5-二甲基-2,3-二（三級-丁基過氧基）己烷。合倂 的過氧化物之量典型地視接枝單體的重量而定。在一具體 本紙張I適用中國國家標準（CNS ) A4規格（210X297公釐1 -24- 593520 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（22) 實施例中，在反應混合物中接枝單體：過氧化物的重量比 可在1和20之間，更佳在約1和1 〇之間，更佳在約1和 約5之間，和甚至更較佳約4。 接枝單體可與樹脂材料合倂在於50-200°C之間，更佳 在7 0 - 1 5 0 °C之間，更佳在7 0 -1 2 5 °C之間，更佳在1 4 0 -1 8 0 °C之間，更佳在140-1 80°C之間，更佳在1 55- 1 65 t之間或 在1 65- 1 75 °C之間的溫度和壓力典型爲一個大氣壓但如果需 要可使用更高的壓力。在一具體實施例中反應溫度爲170-1 85 °C。在另一較佳具體實施例中中，接枝反應在大於90 °C ，更佳在9 0 °C和任何上述溫度限制之間，更佳在90 °C和 150°C之間，更佳在90°C和145t之間的溫度發生。一般， 反應溫度的下限由樹脂的軟化點決定，而較佳在欲接枝材 料的軟化點以上之溫度進行接枝反應。 可合倂接枝單體以使在反應混合物中接枝單體：樹脂 材料的重量比小於1，更佳小於.〇. 5，更佳小於3 ·· 1 0和更 佳小於3 : 2〇。在一較佳具體實施例中，反應混合物維持在 均句狀態。較佳攪動或激烈攪拌反應混合物。在反應期間 自由基引發劑一次加入或較佳以連續或半連續的模態與樹 脂材料-接枝單體反應混合物合倂。在反應區的滯留時間較 佳少於75分鐘，更佳少於60分鐘，甚至更佳在30-60分 鐘之間。 在只有寡聚物被接枝之具體實施例中，反應溫度較佳 在50-200°C之間，更佳在70-15(TC之間，更佳在70- 1 25t： 之間，更佳在 1 40- 1 80°C之間，更佳在 1 40- 1 80°C之間，更 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)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-20T-593520 A7 B7 V. Description of the invention (18) (Please read the precautions on the back before filling this page) 1 1.7xl05 bar) 160_320 ° C, after 1.2 to 4 hours (more preferably 1.5 to 4 hours). Where oligomer content is not required, the resulting polymerization product can be steamed to remove inert, unreacted, and low molecular weight oligomeric components to produce a resin having a softening point in the range of 80-1 20 ° C. The products of the polymerization process include resins and oligomers (dimers, trimers, tetramers, pentamers, hexamers) including the monomers (classes) of the feed, and heptamers and octamers selected as required Polymer) oligomer by-products. If used in the following, the resin material means resin, oligomer, or a mixture of the two. In a specific embodiment in which the oligomer by-product is produced by thermal polymerization of DCPD and substituted DCPD, the oligomer is typically a (preferably hydrogenated as described below) CDP and methyl CDP with a low content of Acyclic C5 diene compounds such as Diels Alder trimers and tetramers of pentadiene-1,3 and isoprene. The resin material is then preferably hydrogenated to reduce staining and improve color stability. Any method known for the catalytic hydrogenation of resin materials can be used. In particular, the methods disclosed in US 5 1 7 1 793, US 4629766, and the Intellectual Property Office Employee Consumer Cooperatives of the Ministry of Economy printed US 5 502 1 04 and US 43 28090 and WO 95/1 2623 are suitable. Excluded hydrotreating conditions include 100-35 (temperature range of TC and hydrogen pressure between about five atmospheres (506 kPa) and 300 atmospheres (and up to 400 atmospheres), for example, 10- Reaction at 275 atmospheres (10 1 3-27579 kPa). In a specific embodiment, the temperature is in the range including 1 80-3 3 0 ° C and the pressure is in the range including 1 5 1 95-20260 kPa hydrogen. Reactor The volume ratio of hydrogen to feed under standard conditions (25 ° C, 1 atmosphere (101 kPa) pressure) typically ranges from 20: 1 -200: 1; for water-white resin, 1 00: 1 -200 : 1 is the Chinese National Standard (CNS) A4 specification (210X 297 mm) -21-593520 A7 B7 which is better than the paper size. 5. Description of the invention (19). The hydrogenation product can be stripped to remove low molecular weight by-products and Any solvent. This oligomerization by-product is a low-viscosity, almost colorless liquid that boils at 250-400 ° C and is preferably substantially hydrogenated. The hydrogenation of the resin material can be done in batches or via a melt or solution-based method It is generally carried out continuously. The catalyst for the hydrogenation of hydrocarbon resins is typically on a support. Mono- and di-metal catalyst systems based on Group 6, 8, 9, 10 or 11 elements. Catalysts such as nickel on a carrier (for example, nickel on alumina, nickel on charcoal, nickel on silica, Nickel on diatomaceous earth), palladium on the carrier (for example, palladium on silica, palladium on charcoal, palladium on magnesium oxide, etc.) and copper and / or zinc (for example on copper and / or Copper chromite on manganese oxide, copper and zinc on alumina, etc.) are good hydrogenation catalysts. The support materials are typically made of such porous inorganic refractory oxides such as silica, magnesia, silica-magnesium Oxygen, oxidation pins, silica-chromium oxide, titanium oxide, silica-titanium oxide, alumina, silica-alumina, alumina-silicate, etc., and a carrier containing r-alumina is excellent. The support is essentially free of crystalline molecular sieve materials. It is also expected that mixtures of the foregoing oxides, especially when prepared as homogeneously as possible. Support materials that may be used include those disclosed in U.S. Patents 4,860,030, 484696 1, 4500424, and 4,849,093. Appropriate Carriers include alumina, silica, carbon, M gO, Ti02, Zr02, Fe203 or mixtures thereof. Another suitable method for hydrogenating resin materials is described in EP 0082726. EP 0082726 describes a method for catalytic or thermal hydrogenation using a nickel-tungsten catalyst on an r · alumina support. , Where the hydrogen pressure is 1.47 × 107—196 × 107 bar and the temperature is in the range of 25 0-3 30 ° C. After hydrogenation, the reactor mixture can be used in accordance with Chinese National Standard (CNS) A4 specifications (210X29? Gongchu) ) (Please read the precautions on the back before filling out this page) C., 11 Intellectual Property Bureau of the Ministry of Economic Affairs (printed by Industrial and Consumer Cooperatives-22- 593520 A7 ___B7 V. Invention Description (2〇) (Please read the back Note for refilling this page) is flashed and further separated to recover the hydrogenated resin material. In a specific embodiment, steam distillation can be used to separate oligomers and is preferably performed at a resin temperature not exceeding 3 25 t. In ~ specific embodiments, the catalyst comprises nickel and / or cobalt and one or more molybdenum, tungsten on one or more alumina or silica supports, wherein the amount of nickel oxide and / or cobalt oxide on the support In the range of 2-10% by weight. The amount of tungsten oxide or molybdenum on the support after preparation ranges from 5 to 25% by weight. Preferably, the catalyst comprises 4-7 wt% nickel oxide and 18-22 wt% tungsten oxide. This method and suitable catalysts are disclosed in more detail in U.S. Patent No. 5,820,749. In another embodiment, the hydrogenation can be performed by using the method and catalyst described in U.S. Patent No. 4,029,766. In particular, a nickel-tungsten catalyst on r-alumina is preferred. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In a specific embodiment, the oligomer is stripped from the resin before hydrogenation. In this embodiment, the oligomer is preferably hydrogenated before grafting. In another embodiment, the oligomer is hydrogenated with the resin and then stripped from the resin to produce a hydrogenated resin and a hydrogenated oligomer. In another specific embodiment, at least some of the oligomers are stripped before hydrogenation and at least some of the hydrogenated oligomers are stripped after hydrogenation. In yet another specific embodiment, the hydrogenated resin / oligomer product can be further processed together into a single mixture as described below. However in another specific embodiment, the oligomer may be derived from any suitable source and argonized (if necessary) prior to grafting such that the oligomer is typically at least partially hydrogenated and preferably substantially prior to grafting hydrogenation. Grafted resin material This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm ^ -23-593520 A7 ____ B7 V. Description of invention (21) (Please read the precautions on the back before filling this page) At least A portion of the resulting resin material is preferably derived from a method as described above, and may then be combined and / or contacted with the graft monomer, typically under appropriate reaction conditions and in a suitable mixing device. In the preferred embodiment In the specific reaction according to the foregoing, the resin and the oligomer can be grafted separately or simultaneously, and if separately, the grafted oligomer can then be selectively combined with the graft as needed. Resin, non-grafted resin, or any other suitable resin, tacky component or composition as described above, and then remixed. Graft monomers printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the grafting monomers are preferred in It is selected from the group consisting of an organic peroxide, an organic perester, and an azo compound to occur in the presence of a radical initiator. Examples of such compounds include benzhydryl peroxide, dichloride Formamyl peroxide, dicumyl peroxide, di-tertiary-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne- 3,1,4-bis (tertiary · butylperoxyisopropyl) benzene, lauryl peroxide, tertiary-butyl peracetate, 2,5-dimethyl-2,5-di (Tertiary-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane, tertiary-butyl perbenzoate , Tertiary-butyl perphenyl acetate, tertiary-butyl perisobutyrate, tertiary-butyl per-secondary-octanoate, tertiary-butyl pervalerate, perpentyl Acid cumyl ester, tertiary-butyl hydroperoxide, tert-butyl perethyl acetate, azoisobutyronitrile, and dimethyl isobutyrate. Peroxide It has a half-life of about 6 minutes and volatile non-aromatic decomposition products at 160 ° C and these minimize color formation. Preferred peroxides include di-tertiary-butyl peroxide and 2, 5-Dimethyl-2,3-di (tertiary-butylperoxy) hexane. The amount of conjugated peroxide typically depends on the weight of the graft monomer. In a specific paper I, the Chinese National Standard (CNS) A4 specification (210X297 mm 1 -24-593520 is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by A7 B7. V. Description of the invention (22) In the embodiment, the reaction mixture The weight ratio of medium grafting monomer: peroxide may be between 1 and 20, more preferably between about 1 and 10, more preferably between about 1 and about 5, and even more preferably about 4. The grafting monomer can be combined with the resin material at 50-200 ° C, more preferably between 70-150 ° C, more preferably between 7 0-1 2 5 ° C, and even more preferably Temperature and pressure between 1 4 0 -1 8 0 ° C, more preferably 140-1 80 ° C, more preferably 1 55- 1 65 t or 1 65- 1 75 ° C It is typically one atmosphere but higher pressures can be used if desired. In a specific embodiment, the reaction temperature is 170-1 85 ° C. In another preferred embodiment, the grafting reaction is greater than 90 ° C, more preferably between 90 ° C and any of the above temperature limits, more preferably between 90 ° C and 150 ° C, and more preferably Occurs at temperatures between 90 ° C and 145t. Generally, the lower limit of the reaction temperature is determined by the softening point of the resin, and the grafting reaction is preferably performed at a temperature above the softening point of the material to be grafted. The graft monomer may be combined so that the weight ratio of the graft monomer: resin material in the reaction mixture is less than 1, more preferably less than 0.5, more preferably less than 3 ·· 10, and more preferably less than 3: 2. . In a preferred embodiment, the reaction mixture is maintained in a homogeneous state. The reaction mixture is preferably agitated or vigorously stirred. During the reaction, the free radical initiator is added all at once or preferably in a continuous or semi-continuous mode with the resin material-graft monomer reaction mixture. The residence time in the reaction zone is preferably less than 75 minutes, more preferably less than 60 minutes, and even more preferably between 30 and 60 minutes. In specific embodiments where only the oligomer is grafted, the reaction temperature is preferably between 50-200 ° C, more preferably between 70-15 ° C, and more preferably between 70-1 25t: Preferably between 1 40- 1 80 ° C, more preferably between 1 40- 1 80 ° C, and the paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the back (Please fill in this page again)

-25- 593520 A7 B7__ 五、發明説明（23) 佳在1 5 5- 1 65 °C之間，和更佳約160 °C。在一具體實施例中 反應溫度爲1 70- 1 85 °C。在另一較佳具體實施例中，接枝反 應在大於90°C的溫度發生，更佳在90°C和任何上述的溫度 制之間，更佳在90t和15(TC之間，更佳在9(TC和145°C 之間。 加入接枝單體的量典型地視寡聚物的量而定。較佳， 寡聚物：接枝單體莫耳比在5和0.2之間，更佳在2和0.5 之間，更佳在約1.5和0.67之間和更佳約1。其後，未接 枝寡聚物從產物汽提和選擇性循環到反應區。所得之接枝 寡聚物通常具有在〇-120°C之間，更佳在25-120°C之間，更 佳在50- 1 20°C之間和甚至更佳在80-1 10°C之間的軟化點和 4-1 〇加登的顏色。加登顏色，如使用在本文中，係使用 ASTMD-6166測量。接枝寡聚物產物然後可與樹脂（接枝或 未接枝）再組合，從其與其他樹脂，聚合物，及/或其他的材 料衍生或組合和調配成膠黏劑材料。 在只有樹脂被接枝之具體實施例中，反應溫度較佳在 50-200°C之間，更佳在70- 1 50°C之間，更佳在70- 1 25 °C之 間，更佳在140-l8〇°C之間，更佳在140- 1 80°C之間，更佳 在1 65 - 1 75 °C之間，和更佳約170°C。在另一較佳具體實施 例中，接枝反應在大於90°C,更佳在90°C和任何上述的上 限溫度之間的溫度發生。加入接枝單體的量典型視樹脂的 量而定。在反應混合物中接枝單體：樹脂重量比較佳少於1 :5，更佳少於1 : 1 0，更佳少於1 : 2 0，和甚至更較佳約1 :4 0。通常，接枝造成樹脂的軟化點少於1 〇 °C，更佳少於 本紙張尺度適用中國國家標準（CNS ) A4規格（]10X297公釐） (請先閱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 -26- 593520 Α7 Β7 五、發明説明（24) 5 C和產生一種具有在〗_6加登之間的顏色之接枝樹脂。 (請先閱讀背面之注意事項再填寫本頁) 在另一具體實施例中，不從樹脂產物汽提寡聚物，且 樹脂和寡聚物同時接枝。反應條件與前述接枝樹脂相似， 但接枝單體··樹脂材料的重量比通常保持在〇 . 5以下，更佳 在0.25以下和更佳在3 : 2〇以下。在接枝完成時，如果需 要材料可進一步汽提，以產生所要軟化點的樹脂及/或除去 未反應寡聚物。如果需要也可進行從接枝樹脂分離接枝寡 聚物，但是產物可沒有該進一步處理而被使用。在許多包 括接枝樹脂及接枝寡聚物之具體實施例中，在樹脂材料中 接枝寡聚物：接枝樹脂的重量比將大於〇 . 〇〇 5，更佳大於 〇.〇1，更佳大於0.02，更佳大於〇.〇5，和更佳大於0.1。 經濟部智慧財產局員工消費合作社印製 樹脂材料的接枝也可經由溶液路徑進行，其中樹脂材 料分散在溶劑中且與接枝單體合倂，接觸及/或反應。額外 «3 ^ 擇地，接枝單體可在加到樹脂材料之前分散於溶劑 中。這些路徑允許較低反應溫度（低如10(TC)且允許在低反 應、溫度具有6分鐘半生期之不同過氧化物的選擇。適當溶 齊U @括（但是不限制於）脂族溶劑，環脂族溶劑，芳族溶劑， 和芳族-脂族溶劑。典型的例子包括苯，甲苯，二甲苯，氯 苯，正戊烷，正己烷，正庚烷，正辛烷，正癸烷，異庚烷 ，異癸烷，異辛烷，環己烷，烷基環己烷，和其二種或以 上之組合物。 咸信接枝單體經由接枝單體的烯烴鍵例如α，Θ烯烴 鍵接枝到樹脂材料。咸信經由這條路徑接枝寡聚物，在接 枝樹脂材料中降冰片酯基的形成被減到最少及較佳被避免 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 593520 A7 B7 五、發明説明（25) 。因此，所得接枝樹脂材料實質上沒有降冰片酯基，也就 是，其較佳包含少於0.5重量％，更佳少於0.1重量％，更 佳少於〇.〇5重量％，更佳少於〇 〇1重量％之降冰片酯基。 所得接枝寡聚物及/或接枝樹脂較佳爲至少一個之（i)單烷基 順-丁烯二酸，酸酐或其衍生物，或（ii)/5-烷基取代的丙酸 或其衍生物。樹脂材料和接枝單體的反應產物或樹脂材料 和接枝單體之組合物的產物也可包括一些接枝單體的寡聚 物，其可在或不在調配最終組成物之前除去。 所得之接枝樹脂材料較佳具有在15-2 1 0°C之間，更佳 15-170°C，更佳 65- 1 40°C，更佳 65- 1 3 0°C，更佳 80- 120°C ，更佳90-110°C，和更佳在約85-110°C的軟化點。接枝樹 脂材料較佳具有少於120°C，更佳少於110°C，更佳在25-l〇〇°C之間，更佳在60-100°C之間，更佳60-80°C之間，和 更佳在3 5-70°C之間的玻璃轉化溫度（Tg)。差式掃描量熱法 (DSC，ASTMD 3 4 1 - 8 8)用來測量Tg。所得接枝樹脂材料較 佳具有大於10，更佳大於12，更佳大於15，更佳大於16 ，更佳大於17，更佳大於18，更佳大於19，更佳大於20 ，更佳大於25之皂化値（毫克KOH/克樹脂材料）。所得接枝 材料較佳具有大於10，更佳大於15，更佳大於20之酸値 〇 在一具體實施例中，接枝寡聚物材料具有在50和0.5 之間，更佳在1 〇和2之間，更佳在5和2之間，更佳在 1.5和0.67之間，和更佳約1的寡聚物：接枝單體莫耳比 。在一些具體實施例中，在接枝樹脂產物中接枝單體：樹 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) -裝·-25- 593520 A7 B7__ 5. Description of the invention (23) The temperature is preferably between 1 5 5- 1 65 ° C, and more preferably about 160 ° C. In a specific embodiment, the reaction temperature is from 1 70 to 1 85 ° C. In another preferred embodiment, the grafting reaction occurs at a temperature greater than 90 ° C, more preferably between 90 ° C and any of the above temperature systems, more preferably between 90t and 15 ° C, and more preferably Between 9 ° C and 145 ° C. The amount of grafting monomer added typically depends on the amount of oligomer. Better, oligomer: Mole ratio of grafting monomer is between 5 and 0.2, More preferably between 2 and 0.5, more preferably between about 1.5 and 0.67 and more preferably about 1. Thereafter, the ungrafted oligomer is stripped from the product and selectively recycled to the reaction zone. The resulting grafted oligomer is Polymers usually have a softening between 0-120 ° C, more preferably between 25-120 ° C, more preferably between 50-1 120 ° C and even more preferably between 80-1 10 ° C Dot and 4-1 〇 Garden's color. Garden's color, as used herein, is measured using ASTMD-6166. The grafted oligomer product can then be combined with the resin (grafted or ungrafted), from which it can be combined with Other resins, polymers, and / or other materials are derived or combined and formulated into adhesive materials. In specific embodiments where only the resin is grafted, the reaction temperature is preferably between 50-200 ° C, and more preferably At 70- 1 50 ° C, more preferably 70-1 25 ° C, more preferably 140-180 ° C, more preferably 140-1 80 ° C, more preferably 1 65-1 75 ° C, and more preferably about 170 ° C. In another preferred embodiment, the grafting reaction occurs at a temperature greater than 90 ° C, more preferably between 90 ° C and any of the above mentioned upper limits The amount of grafting monomer added typically depends on the amount of resin. The weight of grafting monomer: resin in the reaction mixture is preferably less than 1: 5, more preferably less than 1: 1, more preferably less than 1: 2 0, and even more preferably about 1: 4 0. Generally, the softening point of the resin caused by grafting is less than 10 ° C, preferably less than this paper size. Applicable to China National Standard (CNS) A4 specification () 10X297 mm (Please read the notes on the back before filling this page) £-， 11 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -26- 593520 Α7 Β7 V. Description of the invention (24) 5 C and a kind of _6 Graft resin between colors (Please read the notes on the back before filling this page) In another embodiment, the oligomer is not stripped from the resin product, and the resin and The oligomers are grafted at the same time. The reaction conditions are similar to the aforementioned graft resins, but the weight ratio of the grafting monomers · resin materials is usually kept below 0.5, more preferably below 0.25 and more preferably below 3: 2 When the grafting is completed, the material can be further stripped if necessary to produce the resin at the desired softening point and / or remove unreacted oligomers. If necessary, separation of the grafted oligomers from the graft resin can also be performed, but It can be used without this further processing. In many specific embodiments including a graft resin and a graft oligomer, the weight ratio of the graft oligomer to graft resin in the resin material will be greater than 0.005, more preferably greater than 0.001, It is more preferably greater than 0.02, more preferably greater than 0.05, and more preferably greater than 0.1. Grafting of resin materials printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics can also be performed via a solution path, in which the resin materials are dispersed in a solvent and combined with the graft monomer, contact and / or react. In addition «3 ^ Alternatively, the grafting monomer may be dispersed in a solvent before being added to the resin material. These pathways allow lower reaction temperatures (as low as 10 (TC) and allow the selection of different peroxides at low reactions and temperatures with a half-life of 6 minutes. Appropriately dissolve U @ bracket (but not limited to) aliphatic solvents, Cycloaliphatic solvents, aromatic solvents, and aromatic-aliphatic solvents. Typical examples include benzene, toluene, xylene, chlorobenzene, n-pentane, n-hexane, n-heptane, n-octane, n-decane, Isoheptane, isodecane, isooctane, cyclohexane, alkylcyclohexane, and combinations of two or more thereof. Salty grafting monomers via olefinic bonds of the grafting monomers such as α, Θ The olefin bond is grafted to the resin material. By using this path, the oligomer is grafted, and the formation of norbornyl ester groups in the grafted resin material is minimized and preferably avoided. This paper applies the Chinese national standard (CNS) ) A4 specification (210X297 mm) 593520 A7 B7 5. Invention description (25). Therefore, the obtained graft resin material does not substantially have a norbornyl ester group, that is, it preferably contains less than 0.5% by weight, more preferably less Less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less 001% by weight of norbornyl ester groups. The obtained graft oligomers and / or graft resins are preferably at least one of (i) a monoalkylmaleic acid, an anhydride or a derivative thereof, or ( ii) / 5-alkyl substituted propionic acid or derivative thereof. The reaction product of the resin material and the graft monomer or the product of the combination of the resin material and the graft monomer may also include oligomerization of some graft monomers. It can be removed before or after the final composition is prepared. The obtained graft resin material preferably has a temperature between 15-2 1 0 ° C, more preferably 15-170 ° C, more preferably 65-1 40 ° C. , More preferably 65-130 ° C, more preferably 80-120 ° C, more preferably 90-110 ° C, and more preferably a softening point of about 85-110 ° C. The graft resin material preferably has less than 120 ° C, preferably less than 110 ° C, more preferably between 25-100 ° C, more preferably between 60-100 ° C, more preferably between 60-80 ° C, and more preferably 3 Glass transition temperature (Tg) between 5 and 70 ° C. Differential scanning calorimetry (DSC, ASTMD 3 4 1-8 8) is used to measure Tg. The obtained graft resin material preferably has a temperature greater than 10, more Preferably greater than 12, more preferably greater than 15, more preferably greater than 16, more preferably greater than 17, It is preferably greater than 18, more preferably greater than 19, more preferably greater than 20, and more preferably greater than 25. Saponified saponin (mg KOH / g resin material). The obtained graft material preferably has greater than 10, more preferably greater than 15, and more preferably greater than 20 In a specific embodiment, the graft oligomer material has a value between 50 and 0.5, more preferably between 10 and 2, more preferably between 5 and 2, and even more preferably between 1.5 and 0.67. And the oligomer of about 1: the molar ratio of the grafting monomer. In some specific embodiments, the grafting monomer in the grafted resin product: the paper size of the tree applies the Chinese National Standard (CNS) A4 Specifications (210X297 mm) (Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 -28 - 593520 A7 ___B7 五、發明説明（26 ) 脂的重量比更佳少於1，在其他具體實施例中在0.0 0 1和1 之間，在其他具體實施例中在0.01和1之間，在其他具體 實施例中在0.01和0.3之間，在其他具體實施例中在0.02 和1之間，在其他具體實施例中在0.1和1之間，在其他具 體實施例中在0.3 3和1之間，和在其他具體實施例中在 〇·1和0.2之間，其中較佳範圍可包括在任何描述在此段之 上限和下限之間。 混合於膠黏性組份和組成物中 任何前述具體實施例可與其他膠黏性組份合倂和調配 成用於例如膠帶，標籤，紙浸漬應用之壓敏膠黏劑，HMAs ，或觸壓膠黏劑。HM A應用包括木工，包裝，裝訂或尿布 。本文所述的具體實施例也可調配成密封劑，橡膠化合物 ，管子包紮，地毯襯裡，觸壓膠黏劑，路標及/或輪胎之組 成物。當在HMAs的情況，這些組成物可直接使用而沒有 進一步稀釋時或他們可稀釋成適當溶劑以形成以溶劑主的 膠黏劑（SB As)或分散在水中以形成以水爲主的膠黏劑 (WBAs)的樹脂乳液。 任何前述具體實施例可合倂或調配成包括極性聚合物 之膠黏劑。當使用在本文中，極性聚合物包括該等包含極 性基例如酯類，醚類，酮類，醯胺類，醯亞胺類，醇類， 酚類，鹵化物類，酸類，酸酐類，硫化物類，腈類，異氰 酸酯類，芳族和雜芳族基團之均聚物，共聚物，和三元共 聚物。這些極性取代可發現於聚合物主鏈，聚合物主鏈的 本紙丧尺度適用中國國家標準（CNS ) A4規格（210X 297公釐) ' -29- (請先閱讀背面之注意事項再填寫本頁) !·裝· 、11 經濟部智慧財產局員工消費合作社印製 593520 A7 _________ B7 _ 五、發明説明（27 ) (請先閱讀背面之注意事項再填寫本頁) 側鏈或連接至可合倂在聚合物主鏈或聚合物主鏈之側鏈的 芳基。適當例子包括c2到C2〇烯烴（例如乙烯及/或丙烯及/ 或丁烯）與一種或以上之極性單體例如乙烯基酯類或醇類， 酸類，酸酐類，丙烯或甲基丙烯酸或酯類的共聚物。極性 聚合物也包括任何包含一種能夠與存在於樹脂材料中之不 飽和酸或酸酐互相作用的官能基之熱塑性共聚物。例子包 ί舌（但不限制於）例如聚酯類，聚醯胺類，聚脲類，聚碳酸酯 類，聚丙烯腈類，聚丙烯酸酯類，聚甲基丙烯酸酯類，乙 烯乙酸乙烯基酯類，鹵化聚合物類，聚氯乙烯類，聚對苯 甲二酸乙二酯，聚苯二甲酸丁二酯（ΡΒΤ)，聚縮醛，丙烯酸 或甲基丙烯酸，丙烯酸烷基酯，或甲基丙烯酸酯和相似物 的聚合物（或共聚物）。因此，在一具體實施例中，接枝樹脂 材料可與極性聚合物（例如EVA)調配。其視需要選擇地包 括其他組份例如一種或以上的鱲或油類。 經濟部智慧財產局員工消費合作社印製 任何前述具體實施例可倂或與聚烯烴（基礎聚合物） 合倂以形成膠黏劑。典型的基礎聚合物包括聚乙烯，與一 種或以上C3到C2G直鏈、支鏈或環α -烯烴類共聚合的乙烯 ，聚丙烯，與一種或以上之乙烯及/或C4到C2G直鏈、支鏈 或環α-烯烴類共聚合的丙烯，聚丁烯，與一種或以上之C5 到Cw直鏈、支鏈或環α-烯烴類共聚合的丁烯，低密度聚 乙烯（LPDE)(密度0.915到小於〇.93 5克/公分3)，線性低密 度聚乙烯（LLPDE)，超低密度聚乙烯（密度0.86到於0.908 克/公分3)，非常低密度聚乙烯（密度〇·9〇到於0·915克/公 分3)，中低密度聚乙烯（密度0·93 5到少於〇·945克/公分3) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -30- 593520 A7 B7 五、發明説明（28) ，高低密度聚乙烯（HDPE)(密度0.945到0.98克/公分3)。 其他的烴類聚合物（或共聚物）包括：聚丁烯-1，聚異丁 烯，聚丁烯，聚異戊二烯，聚丁二烯，丁基橡膠，無定形 聚丙烯，乙烯丙烯二烯單體橡膠，天然橡膠，苯乙烯丁二 烯橡膠，異丁烯和對-烷基苯乙烯的共聚物和鹵化共聚物， 彈性體例如乙烯·丙烯橡膠（EPR)，硫化EPR，EPDM，耐綸 ，聚碳酸酯，PET樹脂，芳族單體例如聚苯乙烯的聚合物 ，異丁烯和對-烷基苯乙烯的共聚物，高分子量HDPE,低 分子量HDPE，接枝共聚物通常，聚丙烯腈均聚物或共聚物 ，熱塑性聚醯胺，聚縮醛，聚偏氟乙烯（polyvinylidine)和 其他氟化彈性體，聚乙二醇類，聚異丁烯，或其摻合物。 較佳α-烯烴包括丙烯，丁烯，戊烯，己烯，庚烯，辛烯， 壬烯，十二碳烯，環戊烯，3,5,5-三甲基己烯-1，3-甲基戊 烯-1，4-甲基戊烯-1和上述單體的三元共聚物。在另一具 體實施例中，共聚物包括一種⑴乙烯及/或（ii)C3到C2〇共 聚單體，和（iii)二烯的三元共聚物。較佳二烯包括丁二烯， 戊二烯，己二烯，降冰片烯，亞乙基降冰片烯，亞乙烯基 降冰片烯，二環戊二烯，和其經取代者。該等聚合物之結 構可爲直鏈，實質上直鏈，短鏈支鏈，長鏈支鏈，星形支 鏈或其任何的其他組合。該等支鏈或支臂可與主鏈相同或 不同例如支鏈-嵌段共聚物或多支臂星形聚合物。 適當的聚合物也包括苯乙烯及一種或以上共軛二烯的 嵌段共聚物例如SI(苯乙烯-異戊二烯），SBs(苯乙烯-丁二 烯-苯乙烯），SB(苯乙烯-丁二烯），SIS(苯乙烯-異戊二烯-苯 本紙财晒家標準（CNS ) A4規格（210X 297公釐) ~ -31 - (請先閱讀背面之注意事項再填寫本頁) •裝· 、11 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 593520 A7 _B7 五、發明説明（29 ) 乙烯）。包括選自 SISI，SISB，SBSB，SBSI，ISISI，ISISB ，BSISB，ISBSI，BSBSB，和BSBSI的四嵌段或五嵌段共 聚物之苯乙烯嵌段共聚物也是適當的。該等嵌段共聚物可 完全或部份氫化以產生一種所得SEBS(苯乙烯-乙烯-丁烯-苯乙烯）聚合物。嵌段共聚物的結構包括直鏈，輻射形或多 支臂星形，或多支鏈且可包括各種的苯乙烯，異戊二烯， 或丁二烯的組合，其可被氫化或不被氫化。 任何前述具體實施例可與接枝聚合物或接枝聚合物及/ 或非接枝聚合物之摻合物混合。聚合物及該等摻合物之實 例包括（但不限制於）該等描述於US 5,936,058中者。 任何前述具體實施例可與彈性體混合以形成膠黏密封 劑。較佳彈性體包括天然橡膠，聚異戊二烯，聚丁二烯， 丁二烯與苯乙烯的共聚物，丁二烯與丙烯腈的共聚物，丁 基橡膠，聚戊二烯，乙烯/丙烯橡膠和乙烯，丙烯和非共軛 二烯的彈性體共聚物，苯乙烯嵌段共聚物例如苯乙烯及/或 甲基苯乙烯與烷二烯（例如異戊二烯或丁二烯）之直鏈、輻射 ，及/或錐形嵌段共聚物。 在一具體實施例中，基礎聚合物可爲一種使用金屬茂 催化劑系統所產生的聚合物。典型地，該等金屬茂均聚物 或共聚物係使用單-或雙-環戊二烯基過渡金屬催化劑與鋁氧 烷（alumoxane)及/或非配位陰離子的活化劑組合之溶液、漿 料、局壓或氣體相。催化劑系統可具有載體，或沒有載體 和該等環戊二烯基環可經取代或未經取代。鈦，锆和鈴爲 較佳過渡金屬。數種使用該等催化劑/活化劑組合物所製備 本纸張尺度適用中國國家標準（CMS ) A4規格（210X 297公釐） ""~~"~' -32- (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -28-593520 A7 ___B7 V. Description of the invention (26) The weight ratio of fat is better than 1, and in other specific embodiments is between 0.0 0 1 and 1, In other specific embodiments, between 0.01 and 1, in other specific embodiments, between 0.01 and 0.3, in other specific embodiments, between 0.02 and 1, and in other specific embodiments, between 0.1 and 1 Time, between 0.3 3 and 1 in other specific embodiments, and between 0.1 and 0.2 in other specific embodiments, wherein the preferred range may be included between any upper and lower limits described in this paragraph . Any of the foregoing embodiments mixed with adhesive components and compositions can be combined with other adhesive components and formulated into pressure-sensitive adhesives, HMAs, or adhesives for use in, for example, tapes, labels, and paper impregnation applications. Press the adhesive. HM A applications include woodworking, packaging, bookbinding or diapers. The specific embodiments described herein can also be formulated as a combination of sealant, rubber compound, tube wrap, carpet lining, pressure-sensitive adhesive, road signs and / or tires. When in the case of HMAs, these compositions can be used directly without further dilution or they can be diluted to a suitable solvent to form a solvent-based adhesive (SB As) or dispersed in water to form a water-based adhesive (WBAs) resin emulsion. Any of the foregoing embodiments may be combined or formulated into an adhesive including a polar polymer. As used herein, polar polymers include those containing polar groups such as esters, ethers, ketones, amidines, amines, alcohols, phenols, halides, acids, anhydrides, sulfurized Homopolymers, copolymers, and terpolymers of species, nitriles, isocyanates, aromatic and heteroaromatic groups. These polar substitutions can be found in the polymer main chain. The paper size of the polymer main chain applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) '-29- (Please read the precautions on the back before filling this page )! ·· 11, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _________ B7 _ V. Description of the invention (27) (Please read the precautions on the back before filling this page) Side chain or connect to the combinable An aryl group on the polymer backbone or a side chain of the polymer backbone. Suitable examples include c2 to C20 olefins (such as ethylene and / or propylene and / or butene) and one or more polar monomers such as vinyl esters or alcohols, acids, anhydrides, propylene or methacrylic acid or esters Copolymers. The polar polymer also includes any thermoplastic copolymer containing a functional group capable of interacting with an unsaturated acid or an acid anhydride present in the resin material. Examples include, but are not limited to, polyesters, polyamides, polyureas, polycarbonates, polyacrylonitrile, polyacrylates, polymethacrylates, ethylene vinyl acetate Esters, halogenated polymers, polyvinyl chlorides, polyethylene terephthalate, polybutylene terephthalate (PBT), polyacetals, acrylic or methacrylic acid, alkyl acrylates, or Polymers (or copolymers) of methacrylates and analogs. Therefore, in a specific embodiment, the graft resin material can be formulated with a polar polymer such as EVA. It optionally includes other components such as one or more tinctures or oils. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Any of the foregoing embodiments may be combined with polyolefin (base polymer) to form an adhesive. Typical base polymers include polyethylene, ethylene copolymerized with one or more C3 to C2G linear, branched or cyclic alpha-olefins, polypropylene, and one or more ethylene and / or C4 to C2G linear, Propylene, polybutene copolymerized with branched or cyclic α-olefins, butene copolymerized with one or more C5 to Cw linear, branched or cyclic α-olefins, low density polyethylene (LPDE) ( Density 0.915 to less than 0.93 5 g / cm3), linear low density polyethylene (LLPDE), ultra-low density polyethylene (density 0.86 to 0.908 g / cm3), very low density polyethylene (density 0.9 〇As of 0.915 g / cm 3), medium and low density polyethylene (density 0.993 5 to less than 0.945 g / cm 3) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -30- 593520 A7 B7 5. Description of the invention (28), high and low density polyethylene (HDPE) (density 0.945 to 0.98 g / cm3). Other hydrocarbon polymers (or copolymers) include: polybutene-1, polyisobutylene, polybutene, polyisoprene, polybutadiene, butyl rubber, amorphous polypropylene, ethylene propylene diene Monomer rubber, natural rubber, styrene butadiene rubber, copolymers and halogenated copolymers of isobutylene and p-alkylstyrene, elastomers such as ethylene · propylene rubber (EPR), vulcanized EPR, EPDM, nylon, poly Carbonates, PET resins, polymers of aromatic monomers such as polystyrene, copolymers of isobutylene and p-alkylstyrene, high molecular weight HDPE, low molecular weight HDPE, graft copolymers, usually polyacrylonitrile homopolymers Or copolymers, thermoplastic polyamides, polyacetals, polyvinylidine and other fluorinated elastomers, polyethylene glycols, polyisobutylene, or blends thereof. Preferred alpha-olefins include propylene, butene, pentene, hexene, heptene, octene, nonene, dodecene, cyclopentene, 3,5,5-trimethylhexene-1,3 A terpolymer of methylpentene-1,4-methylpentene-1 and the above monomers. In another specific embodiment, the copolymer includes a terpolymer of ethylene and / or (ii) a C3 to C20 comonomer, and (iii) a diene. Preferred dienes include butadiene, pentadiene, hexadiene, norbornene, ethylidene norbornene, vinylidene norbornene, dicyclopentadiene, and substituted ones. The structure of these polymers may be linear, substantially linear, short-chain branched, long-chain branched, star-branched, or any other combination thereof. The branches or arms may be the same as or different from the main chain such as a branched-block copolymer or a multi-armed star polymer. Suitable polymers also include block copolymers of styrene and one or more conjugated diene such as SI (styrene-isoprene), SBs (styrene-butadiene-styrene), SB (styrene -Butadiene), SIS (styrene-isoprene-benzene paper standard (CNS) A4 specification (210X 297 mm) ~ -31-(Please read the precautions on the back before filling this page) • Installation · 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _B7 V. Description of the Invention (29) Ethylene) Also suitable are styrene block copolymers comprising tetra- or penta-block copolymers selected from SISI, SISB, SBSB, SBSI, ISISI, ISISB, BSISB, ISBSI, BBSSB, and BSBSI. These block copolymers can be completely or partially hydrogenated to produce a resulting SEBS (styrene-ethylene-butene-styrene) polymer. The structure of the block copolymer includes linear, radial or multi-armed star, or multi-branched and may include various styrene, isoprene, or a combination of butadiene, which may be hydrogenated or not hydrogenation. Any of the foregoing specific embodiments may be mixed with graft polymers or blends of graft polymers and / or non-grafted polymers. Examples of polymers and such blends include, but are not limited to, those described in US 5,936,058. Any of the foregoing embodiments may be mixed with the elastomer to form an adhesive sealant. Preferred elastomers include natural rubber, polyisoprene, polybutadiene, copolymers of butadiene and styrene, copolymers of butadiene and acrylonitrile, butyl rubber, polyprene, ethylene / Elastomer copolymers of propylene rubber and ethylene, propylene and non-conjugated diene, styrene block copolymers such as styrene and / or methylstyrene and alkadiene (such as isoprene or butadiene) Linear, radiant, and / or tapered block copolymers. In a specific embodiment, the base polymer may be a polymer produced using a metallocene catalyst system. Typically, these metallocene homopolymers or copolymers are solutions or slurries using a combination of a mono- or bis-cyclopentadienyl transition metal catalyst and an alumoxane and / or non-coordinating anion activator. Material, partial pressure or gas phase. The catalyst system may or may not be supported and the cyclopentadienyl rings may be substituted or unsubstituted. Titanium, zirconium and bell are the preferred transition metals. Several papers prepared using these catalyst / activator compositions are sized to the Chinese National Standard (CMS) A4 (210X 297 mm) " " ~~ " ~ '-32- (Please read the back first (Notes to fill out this page)

593520 B7 五、發明説明（3〇) 之商業產物爲得自德克薩斯州Baytown之ExxonMobil化學 公司的商標名EXCEED®和EXACT®的或得自道化學公司之 商標名ENGAGE®和AFFINITY®的市售商品。 上述金屬茂製備之共聚物較佳具有少於4之多分散性 和5 0%或以上，較佳60%以上，甚至更佳70%以上的組成 分佈寬度指數（€〇31)。在一具體實施例中，€〇81爲80%以 上，甚至更佳90%上，甚至更佳95%以上。在一具體實施 例中，聚乙烯共聚物具有在60-85 %之間，甚至更佳在65-85%之間的CDBI。 組成分佈寬度指數（CDBI)爲一種單體在聚合物鏈內的 組成分佈的衡量且藉由公開於1 993年2月18日之PCT公 告WO 93/03 093所述的步驟測量，當測定CDBI時包括忽 略具有重量平均分子量（Mw)在1 5000以下的部份。 任何前述具體實施例可存在於樹脂和基礎聚合物的摻 合物中。樹脂：基礎聚合物之適當比包括1 : 1 〇〇〇到2 : 1 ，更佳1 : 2到2 : 1和甚至更佳在3 : 1和1 : 3之間。 任何前述具體實施例可與該技藝已知的添加劑例如加 工油類，性能油類，抗阻塞劑，抗靜電劑，抗氧化劑，交 鏈劑，矽石，碳黑，滑石，顏料，塡充劑，加工助劑，XJV 安定劑，中和劑，潤滑劑，防滑劑，滑爽劑，界面活性劑 及/或成核劑混合。通常添加劑的例子包括：例如Irgan〇x® 1010，一氧化砂，一氧化欽，聚一甲基砂氧院，滑石，染 料，鱲，硬脂酸鈣，碳黑和玻璃小珠。在HMA應用中，適 當的合成鱲包括具有在約5 5 °C到約1 3 0 °C範圍之熔點的石 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 丁 經濟部智慧財產局員工消費合作社印製 -33- 593520 Μ ____Β7_ 五、發明説明（31) (請先閲讀背面之注意事項再填寫本頁) 蠟和微晶蠟和低分子量聚乙烯及費雪-闕布希蠘。蠟含量較 佳爲從約1到約3 5重量％之總摻合組成物。在PS A應用中 ，適當的油類包括得自ExxonMobil化學公司之FLEXON® 876或PRIMOL® 3 52，於少於50%的濃度。 任何前述具體實施例可調配成可應用至任何習知襯裡 層例如紙，箔，聚合膜，離型襯，織物或非織物襯裡材料 的壓敏膠黏劑以製造例如包裝膠帶，蒙版黏帶和標籤。 熱熔壓敏的一具體實施例包括1〇〇重量份之基礎聚合 物，較佳苯乙烯嵌段共聚物，50- 1 50phr(份每100重量份基 礎聚合物）之本文所述之樹脂，0-50 p hr，更佳10-50 p hr， 更佳 15- 50 phr，更佳 20-50 phr，更佳 25-50 phr,更佳 30-50 phr，更佳 35-50 phr，更佳 40-50 phr，更佳 45-50 phr的增量油，和〇-5phr抗氧化劑。 經濟部智慧財產局員工消費合作社印製 咸信本文之樹脂材料調配物提供熱熔壓敏膠黏劑的優 點，即增加使用在調配物中之油量1 〇份以上每一百份聚合 物（phr)，更佳10-50 phr,更佳15 phi*以上，更佳15-50 phr，更佳20 phr以上，更佳20-50 phr,更佳25 phr以上 ，更佳25-5 0 phr,更佳30 phr以上，更佳30-50 phr,更 佳3 5 - 5 0 phi*，更佳40-50 phr,而維持膠黏調配物的內聚強 度的能力（如在熱剪切和SAFT測量中所示）。 在HMA具體實施例中之視需要選擇的組份爲塑化劑或 其他添加劑例如油類，增黏劑，界面活性劑，塡充劑，色 母料，和相似物。較佳塑化劑包括礦物油類，聚丁烯，對 苯二甲酸酯類，和相似物。特佳塑化劑包括鄰苯二甲酸酯 本紙恢尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 ' -34- 593520 A7 B7 五、發明説明（32 ) 類例如鄰苯二甲酸二異癸酯（DI〇p)，二異壬基鄰苯二甲酸 酯（DINP)，二辛基鄰苯二甲酸酯（D0P)。特佳油類包括脂族 環烷油類。 HMA組成物之另一視需要選擇的組份爲低分子量產物 例如蠟，油，或低Μη聚合物，（低表示5000以下的Μη， 較佳4000以下，更佳3000以下，甚至更較佳25 00以下） 。較佳油類包括脂族環烷油類，白油類，或相似物。較佳 低Μη聚合物包括低級α烯例如丙烯，丁烯，戊烯，和己烯 的聚合物。特佳的聚合物包括具有Μη小於1〇〇〇之聚異丁 烯。該等聚合物的例子可得自ExxonMobil化學公司商標名 PARAPOL™ 950 〇 PARAPOLtm 950 爲一種具有 950 之 Μη 和於l〇〇°C爲220cSt之動態黏度（如以ASTMD 445測量）的 液態聚丁烯聚合物。HMAs之適當具體實施例通常包含20-70重量％本文上述樹脂材料或摻合物，3 0-80重量％基礎 聚合物，和0-35重量％蠘。 HMAs具體實施例可用於用完即可丟棄的尿布和衛生棉 底部結構，用完即可丟棄的貨物，印染加工（converting)， 包裝，標記，裝訂，木工，和其他的裝配應用中的彈性附 件。特別的例子包括：嬰孩尿布腿部鬆緊帶，尿布前膠帶 ，尿布固定腿部袖口，尿布底部結構，尿布核心穩定作用 ，尿布液態轉移層，尿布外覆蓋層壓結構，尿布彈性袖口 層壓結構，女性衛生棉核心穩定作用，女性衛生棉膠黏條 ，工業過濾結合，工業濾料的層壓結構，濾器罩層壓結構 ，外科長袍層壓結構，外科布簾層壓結構，和易腐壞產品 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) 、1· 經濟部智慧財產局R工消費合作社印製 593520 A7 B7 五、發明説明（33 ) 包裝。木工應用之適當具體實施例包括30-50重量％基礎 聚合物，較佳EVA, 1S-35重量％本文所述之樹脂，2〇-5〇 重量％塡充劑，例如碳酸鈣，硫酸鋇，矽石或二氧化欽。 裝訂應用適當的具體實施例包括3 5-45重量％基礎聚合物 ，較佳EVA，3 545重量％本文所述之樹脂，和10_25重量 %蠟。 本發明樹脂材料可用於改良形成部件之膠黏劑的伸長 性質。與一些習知樹脂比較，當膠黏劑合倂一種如本文所 述之樹脂材料或摻合物時，可看見伸長性質的改良。 咸信本發明的樹脂材料可用於減少形成部件之熱溶膠 黏劑的凝固時間。習知HMAs具有約2秒之凝固時間。咸 fg合倂本文所述的樹脂材料可減少到1 . 5秒或更少，1.4秒 或更少，1. 3秒或更少，1.2秒或更少，1. 1秒或更少，或甚 至1秒或更少的凝固時間。 聚合物的添加劑 本發明的具體實施例在許多應用中具有作爲聚合物添 加劑之新穎利用性。可視應用而存在其他材料。許多種類 之聚合物先前已描述在本文中。他們可使用於聚合物加工 ，例如在需要良好螺旋流動和需要保留物理性質的各種模 製應用。廣泛範圍的聚合物，從聚丙烯到工程熱塑性塑膠 ，在此範疇中。本發明的樹脂也幫助黏著，黏結，和粘性 。廣泛範圍的聚合物，例如聚烯烴膜，輪胎橡膠組份或橡 膠過模製物件，在此範疇中。他們也可加至油墨調配物以 本紙張尺度適用中國國家標準（CNS ) a4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -36- 593520 A7 B7 五、發明説明（34) 幫助組份以及對基材之膠黏。其他的應用爲塗料乾燥和混 凝土硬化。 路標的添加劑 在本文所揭示的具體實施例可調配成熱塑性路標（TRM) 組成物。该等gj|配物包含樹脂，增塑劑或油，顏料，塡充 劑，玻璃小珠。本發明的接枝材料可作爲路標組成物之主 女樹S曰或作爲加到路標組成物之添加劑使用。包含本發明 的接枝材料之路標組成物可額外包括EVA，聚異丁烯，包 括苯乙烯及共軛二烯例如異戊二烯或丁二烯之嵌段共聚物（ 包括但不限制於SI, SIS, SB,及/或SBS)，聚乙烯蠟，松 酯，松脂衍生物，順-丁烯二酸/酸酐改質之烴樹脂。本發明 的接枝材料幫助塡充劑和顏料的分散而產生流動性和顏色 的改良性質。TRM應用的一具體實施例包含丨〇-4〇重量％ 如本文所述之樹脂材料或摻合物，2 - 2 0重量％顏料，例如 Ti〇2，1-1〇重量％油，〇-7重量％基礎聚合物，及餘量之包 含塡充劑例如玻璃小珠，砂，碳酸鈣，矽石或其他如本文 所述者。 交聯和反應性加工 本發明的具體實施例具有作爲油墨和建築和路標應用 中的聚合物添加劑的進一步優點。他們能夠藉由與膠黏調 配物的另一組份交聯而在組成物介質中產生和參與交聯。 樹脂上的酸酐或酸基之較佳例子可與他們本身或與其他存 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ----燊-- (請先閱讀背面之注意事項再填寫本頁) 、r 經濟部智慧財產局員工消費合作社印製 -37- 593520 A 7 _B7___ 五、發明説明（35 ) 在於組成物介質中之聚合物交聯。一些包含胺或醇官能性 質之聚合物將直接與接枝樹脂材料反應，例如，該等包含 一些乙烯醇基之聚合物。當加入交鏈劑時，其他聚合物將 會交聯。在這些具體實施例中，所加的交鏈劑之量典型地 視接枝單體的存在量而定。典型的數量包括在1 0 0 : 1和1 :1 〇〇之間，更佳1 : 1在份交聯劑每份存在於調配物中的 接枝單體（莫耳比）。這些包括該等包含一些丙烯酸之聚合物 例如乙烯烷基-丙烯酸酯丙烯酸三元共聚物或包含順-丁烯二 酐或酸基的聚合物例如順-丁烯二酐接枝之乙烯丙烯二烯橡 膠。該等交聯可以許多方式達成，包括加入具有與酸或酸 酐基反應之二官能劑。該等材料的例子爲該等包含醇和胺 官能性質者例如二醇，二胺，尤其一級胺。具有這些官能 基之材料可被混合或具有不同的取代基，例如二胺，其中 一個基爲一級和另一個基爲三級。較弱交聯可經由不形成 共價鍵例如離子和氫鍵之交互作用達成。能夠以該方式交 聯之材料的例子爲二價金屬離子例如Ca + +或包含四級胺之 二胺類。 薄膜 具有一層或以上之包含本文所揭之成分的薄膜可以單-或多層薄膜或層板使用且可能藉由任何習知方法製造，包 括簡單吹塑擠壓，雙軸定向法（例如棚架，夾泡，或雙氣泡 法），簡單流延/板擠壓-層壓，共擠壓，層壓，擠壓貼合， 和共擠貼合，吹塑和流延等。如需要多層薄膜，可經由傳 本紙張尺度適用中國國家標準（CMS ) Α4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) C·593520 B7 V. The commercial product of invention description (30) is a trademark of EXCEED® and EXACT® from ExxonMobil Chemical Company of Baytown, Texas or a trademark of ENGAGE® and AFFINITY® of Dow Chemical Company Commercial goods. The copolymer prepared by the above metallocene preferably has a polydispersity of less than 4 and a composition distribution width index (€ 0) of 50% or more, preferably 60% or more, and even more preferably 70% or more. In a specific embodiment, € 81 is 80% or more, even more preferably 90%, or even more preferably 95% or more. In a specific embodiment, the polyethylene copolymer has a CDBI between 60-85% and even more preferably between 65-85%. The Composition Distribution Width Index (CDBI) is a measure of the composition distribution of a monomer within a polymer chain and is measured by the procedure described in PCT Publication WO 93/03 093, published February 18, 1993. When CDBI is determined This includes ignoring portions with a weight average molecular weight (Mw) of less than 15,000. Any of the foregoing specific embodiments may be present in a blend of a resin and a base polymer. Suitable ratios of resin: base polymer include 1: 1 to 2: 1, more preferably 1: 2 to 2: 1 and even more preferably between 3: 1 and 1: 3. Any of the foregoing embodiments may be combined with additives known in the art such as processing oils, performance oils, anti-blocking agents, antistatic agents, antioxidants, cross-linking agents, silica, carbon black, talc, pigments, fillers , Processing aids, XJV stabilizers, neutralizers, lubricants, anti-slip agents, slip agents, surfactants and / or nucleating agents. Examples of common additives include, for example, Irganox® 1010, sand oxide, nitric oxide, polymethyl methoxide, talc, dyes, gadolinium, calcium stearate, carbon black, and glass beads. In HMA applications, suitable synthetic materials include stone paper with a melting point in the range of about 55 ° C to about 130 ° C. Applicable Chinese National Standard (CNS) A4 size (2! 0X 297 mm) (Please Please read the notes on the back before filling this page) D-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -33- 593520 Μ ____ Β7_ V. Description of the invention (31) (Please read the notes on the back before filling this page) Wax and Microcrystalline wax and low molecular weight polyethylene and Fisher- 聚乙烯 busch. The wax content is preferably from about 1 to about 35 weight percent of the total blended composition. In PS A applications, suitable oils include FLEXON® 876 or PRIMOL® 3 52 from ExxonMobil Chemical Company at concentrations of less than 50%. Any of the foregoing embodiments can be formulated as a pressure sensitive adhesive that can be applied to any conventional backing layer such as paper, foil, polymeric film, release liner, woven or non-woven backing material to make, for example, packaging tape, masking tape And tags. A specific example of hot melt pressure sensitivity includes 100 parts by weight of a base polymer, preferably a styrene block copolymer, 50 to 150 phr (parts per 100 parts by weight of the base polymer) of the resin described herein, 0-50 p hr, better 10-50 p hr, better 15-50 phr, better 20-50 phr, better 25-50 phr, better 30-50 phr, better 35-50 phr, more 40-50 phr, 45-50 phr extender oil, and 0-5 phr antioxidant. The resin material formulation of this article printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs provides the advantage of hot-melt pressure-sensitive adhesives, which is to increase the amount of oil used in the formulation by more than 10 parts per 100 parts of polymer ( phr), better 10-50 phr, better 15 phi * or more, better 15-50 phr, better 20 phr or more, better 20-50 phr, more than 25 phr, better 25-5 0 phr More than 30 phr, more preferably 30-50 phr, more preferably 3 5-50 0 phi *, more preferably 40-50 phr, and the ability to maintain the cohesive strength of the adhesive formulation (such as in hot shear and As shown in SAFT measurements). The components selected as needed in the specific embodiment of HMA are plasticizers or other additives such as oils, tackifiers, surfactants, extenders, masterbatches, and the like. Preferred plasticizers include mineral oils, polybutenes, terephthalates, and the like. Very good plasticizers include phthalate esters. This paper is restored to the standard applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm)-'34-593520 A7 B7 5. Description of the invention (32) such as phthalic acid Diisodecyl ester (DIop), diisononyl phthalate (DINP), dioctyl phthalate (DOP). Particularly preferred oils include aliphatic naphthenic oils. Another optional component of the HMA composition is a low molecular weight product such as a wax, an oil, or a low Mn polymer. Below 00). Preferred oils include aliphatic naphthenic oils, white oils, or the like. Preferred low Mn polymers include polymers of lower alpha olefins such as propylene, butene, pentene, and hexene. Particularly preferred polymers include polyisobutylene having an η of less than 1,000. Examples of such polymers are available from ExxonMobil Chemical Company under the trade name PARAPOL ™ 950. PARAPOLtm 950 is a liquid polybutene having a Mn of 950 and a dynamic viscosity of 220 cSt at 100 ° C (as measured by ASTMD 445). polymer. Suitable specific examples of HMAs typically include 20-70% by weight of the resin materials or blends described herein, 30-80% by weight of the base polymer, and 0-35% by weight of rhenium. Specific embodiments of HMAs can be used for disposable diapers and sanitary napkin bottom structures, disposable goods, printing, converting, packaging, marking, binding, woodworking, and other flexible attachments in assembly applications . Specific examples include: baby diaper leg elastics, diaper front tape, diaper fixed leg cuffs, diaper bottom structure, diaper core stabilization, diaper liquid transfer layer, diaper outer cover laminated structure, diaper elastic cuff laminated structure, women Core stabilizing effect of sanitary napkins, adhesive strips for feminine sanitary napkins, industrial filtration combined, laminated structure of industrial filter material, laminated structure of filter cover, laminated structure of surgical gown, laminated structure of surgical curtain, and perishable products Paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page), 1. Printed by the R Industrial Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Invention Instructions (33) Packaging. Suitable specific examples of woodworking applications include 30-50% by weight of the base polymer, preferably EVA, 1S-35% by weight of the resin described herein, and 20-50% by weight of fillers such as calcium carbonate, barium sulfate, Silica or Chin dioxide. Suitable specific examples of binding applications include 3 to 45% by weight of the base polymer, preferably EVA, 3,545% by weight of the resin described herein, and 10 to 25% by weight of wax. The resin material of the present invention can be used to improve the elongation properties of the adhesive forming the part. Compared to some conventional resins, when the adhesive is combined with a resin material or blend as described herein, an improvement in elongation properties is seen. It is believed that the resin material of the present invention can be used to reduce the setting time of the thermosol adhesive forming the part. Conventional HMAs have a setting time of about 2 seconds. The resin material described herein can be reduced to 1.5 seconds or less, 1.4 seconds or less, 1.3 seconds or less, 1.2 seconds or less, 1.1 seconds or less, or Even a setting time of 1 second or less. Polymer Additives Specific embodiments of the present invention have novel utility as polymer additives in many applications. Other materials exist depending on the application. Many kinds of polymers have been previously described herein. They can be used in polymer processing, for example in various molding applications where good spiral flow is required and where physical properties need to be retained. A wide range of polymers, from polypropylene to engineering thermoplastics, is in this category. The resin of the present invention also aids adhesion, stickiness, and tackiness. A wide range of polymers, such as polyolefin films, tire rubber components or rubber overmolded articles, fall into this category. They can also be added to the ink formulation to apply the Chinese National Standard (CNS) a4 specification (210X297 mm) at this paper size (please read the precautions on the back before filling this page). Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives. -36- 593520 A7 B7 V. Description of the invention (34) Helps the components and the adhesion to the substrate. Other applications are coating drying and concrete hardening. Road Sign Additives The specific embodiments disclosed herein can be formulated into thermoplastic road sign (TRM) compositions. These gj | formulations include resins, plasticizers or oils, pigments, fillers, glass beads. The graft material of the present invention can be used as a host tree of a road marking composition or as an additive to a road marking composition. The signpost composition containing the graft material of the present invention may additionally include EVA, polyisobutylene, block copolymers including styrene and conjugated diene such as isoprene or butadiene (including but not limited to SI, SIS , SB, and / or SBS), polyethylene wax, turpentine, turpentine derivatives, maleic acid / anhydride modified hydrocarbon resin. The graft materials of the present invention help disperse fillers and pigments to produce improved flow and color properties. A specific example of a TRM application includes a resin material or blend as described herein, 2-20 weight% pigment, such as Ti02, 1-10 weight% oil, 0- 7% by weight of the base polymer, and the balance contains a filler such as glass beads, sand, calcium carbonate, silica or others as described herein. Crosslinking and Reactive Processing Embodiments of the present invention have further advantages as polymer additives in inks and architectural and road marking applications. They are able to generate and participate in cross-linking in the composition medium by cross-linking with another component of the adhesive formulation. The best examples of acid anhydrides or acid groups on the resin can be used with them or with other paper sizes. Chinese National Standard (CNS) A4 specification (210X 297 mm) ---- 燊-(Please read the back Please fill in this page again for attention) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -37- 593520 A 7 _B7___ V. Description of the invention (35) lies in the crosslinking of the polymer in the composition medium. Some polymers containing amine or alcohol functionality will react directly with the graft resin material, for example, these polymers containing some vinyl alcohol groups. When a crosslinker is added, other polymers will crosslink. In these specific examples, the amount of crosslinker added typically depends on the amount of graft monomer present. Typical amounts include between 100: 1 and 1: 1, more preferably 1: 1 in parts of crosslinking agent, each part of the grafting monomer (molar ratio) present in the formulation. These include such polymers containing some acrylic acids such as ethylene alkyl-acrylate acrylic terpolymers or polymers containing cis-butene dianhydride or acid groups such as ethylene-propylene diene grafted with cis-butene dianhydride rubber. Such cross-linking can be achieved in a number of ways, including the addition of a bifunctional agent having a reaction with an acid or anhydride group. Examples of such materials are those containing alcohol and amine functional properties such as glycols, diamines, and especially primary amines. Materials with these functional groups can be mixed or have different substituents, such as diamines, where one group is primary and the other is tertiary. Weaker cross-linking can be achieved via interactions that do not form covalent bonds such as ions and hydrogen bonds. Examples of materials that can be crosslinked in this manner are divalent metal ions such as Ca + + or diamines containing quaternary amines. Films One or more films containing the ingredients disclosed herein can be used as single- or multilayer films or laminates and may be made by any conventional method, including simple blow extrusion, biaxially oriented methods (such as scaffolding, Encapsulation, or double-bubble method), simple cast / board extrusion-lamination, coextrusion, lamination, extrusion lamination, and coextrusion lamination, blow molding and casting, etc. If multi-layer film is required, the paper size can be adapted to Chinese National Standard (CMS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling this page).

、1T 經濟部智慧財產局員工消費合作社印製 -38- 593520 A7 ____B7_ 五、發明説明（36 ) (請先閲讀背面之注意事項再填寫本頁) 統技術例如膠黏層壓或擠壓層壓從可與另一個層組合之單 層吹塑或流延薄膜獲得。單層和共擠壓薄膜也可藉由雙軸 定向法產生。擠壓貼合爲另一適當方法。包含如本文所述 之密封層的熱密封膜可以單層或多層共擠壓基材的形式擠 壓貼合在基材上。多擠壓物可經由多站串聯線上的多擠壓 機製備。該等層可與多層薄膜的其他層（等）共擠壓，或密封 層可層壓在其他層（等）或基材上，包括紙，箱，定向聚丙儲 ，聚醯胺，聚酯，聚乙烯，聚對苯二甲酸乙二酯，金屬和 金屬化基材和其他在本文中所討論之基材。 經濟部智慧財產局員工消費合作社印製 薄膜可藉由平薄膜或管狀方法獲得，其可接著在薄膜 平面單軸方向或二個互相垂直方向定向。一層或以上的薄 膜層可在橫向及/或縱向定向至相同或不同程度。此定向可 在個別層進行之前或之後發生。例如聚乙烯層可擠壓貼合 或層壓在定向聚丙烯或定向聚酯層或聚乙烯和聚丙烯可一 起共擠壓成薄膜然後定向。同樣地，定向聚丙儲可層合至 定向聚乙烯或定向聚乙烯可佈塗至聚丙烯上然後組合物視 要需要選擇性甚至可進一步定向。典型地薄膜定向於高至 15，較佳在5和7之間的比例之機器方向（MD)，和在至高 15較佳7到9之比例的橫向（TD)定向。然而在另一具體實 施例中薄膜在MD和TD方向兩者皆定向於相同程度。 該等薄膜層可包含任何的聚烯烴，如本文所述之極性 聚合物，包括成對二取代烯烴，雜原子烯烴及/或苯乙烯 單體的聚合物或共聚物的陽離子聚合物。較佳成對二取代 烯烴包括異丁烯，異戊烯，異庚烯，異己烷，異辛烯，異 本紙張尺度適用中國國家標準（CN7S ) Α4規格（210X297公釐） -39- 經濟部智慧財產局員工消費合作社印製 593520 Μ Β7 _ 五、發明説明（37 ) 癸烯，和異十二烯。較佳α-雜原子烯烴包括乙烯醚和乙烯 基咔唑，較佳苯乙烯單體包括苯乙烯，烷基苯乙烯，對-烷 基苯乙烯，α-甲基苯乙烯，氯基-苯乙烯，和溴基-對-甲基 苯乙烯。較佳陽灕子聚合物的例子包括丁基橡膠，與對曱 基苯乙烯共聚合的異丁烯，聚苯乙烯，和聚曱基苯乙烯 〇 其他較佳層可爲紙，木材，厚紙板，金屬，金屬箔（例 如鋁箱和錫范），金屬化表面，玻璃（包括以蒸發砂氧化物在 薄膜表面上塗覆的矽氧化物（SiOx)塗層），織物，紡黏纖維 ，和非織物（特別是聚丙烯紡黏纖維或非織物），和以油墨， 染料，顏料，PVC和相似物塗佈的基材。 該等薄膜可視所欲之應用改變厚度，然而厚度在1到 25〇微米的薄膜通常是適當的。 意欲用於包裝的薄膜通常在10到60微米厚度。在許 多情況下，密封層應具有在5和60微米之間，更佳在1 0 和5 0微米之之間，和最佳在1 5和3 0微米之之間的厚度。 密封層可在薄膜內和外表面上或密封層可僅存於內或外表 面上。 薄膜添加劑例如黏結劑，防黏連劑，抗氧化劑，滑爽 添加劑，顏料，塡充劑，加工助劑，UV安定劑，中和劑， 潤滑劑，界面活性劑及/或成核劑也可存在於一層或以上之 薄膜中。較佳添加劑包括二氧化矽，二氧化鈦，聚二甲基 甲砂氧烷，滑石，染料，鱲，硬脂酸鈣，碳黑，低分子量 樹脂和玻璃小珠。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁)， 1T Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-38- 593520 A7 ____B7_ V. Invention Description (36) (Please read the notes on the back before filling this page) System technology such as adhesive lamination or extrusion lamination Obtained from a single layer blown or cast film that can be combined with another layer. Monolayer and coextruded films can also be produced by biaxial orientation. Extrusion fit is another suitable method. A heat-sealing film comprising a sealing layer as described herein may be extruded and bonded to a substrate in the form of a single layer or a multilayer co-extruded substrate. Multiple extrudates can be prepared via multiple extruders on multiple stations in series. These layers can be coextruded with other layers (etc.) of the multilayer film, or the sealing layer can be laminated on other layers (etc.) or substrates, including paper, boxes, oriented polypropylene storage, polyamide, polyester, Polyethylene, polyethylene terephthalate, metal and metallized substrates and other substrates discussed herein. The film printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be obtained by a flat film or a tubular method, which can then be oriented uniaxially in the film plane or in two mutually perpendicular directions. One or more thin film layers may be oriented to the same or different degrees in the transverse and / or longitudinal direction. This orientation can occur before or after the individual layers. For example, a polyethylene layer can be extruded and laminated or laminated on an oriented polypropylene or oriented polyester layer or polyethylene and polypropylene can be co-extruded into a film and then oriented. Likewise, oriented polypropylene reservoirs can be laminated to oriented polyethylene or oriented polyethylene can be cloth coated onto polypropylene and the composition can be optionally oriented even further, as desired. The film is typically oriented in a machine direction (MD) of up to 15, preferably between 5 and 7, and a transverse (TD) orientation in a ratio of up to 15, preferably 7 to 9. However, in another embodiment, the film is oriented to the same degree in both the MD and TD directions. The film layers may comprise any polyolefin, such as the polar polymers described herein, including cationic polymers of polymers or copolymers of paired disubstituted olefins, heteroatomic olefins, and / or styrene monomers. Preferred paired di-substituted olefins include isobutene, isopentene, isoheptene, isohexane, isooctene, and iso-paper. Applicable to China National Standard (CN7S) A4 (210X297 mm) -39- Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Consumption Cooperative 593520 Μ B7 _ 5. Description of the invention (37) decene, and isododecene. Preferred alpha-heteroatom olefins include vinyl ether and vinyl carbazole, and preferred styrene monomers include styrene, alkylstyrene, p-alkylstyrene, alpha-methylstyrene, and chloro-styrene. , And bromo-p-methylstyrene. Examples of preferred cationic polymers include butyl rubber, isobutylene copolymerized with p-styrene, polystyrene, and polystyrene. Other preferred layers may be paper, wood, cardboard, metal , Metal foils (such as aluminum boxes and tin fans), metallized surfaces, glass (including silicon oxide (SiOx) coatings on the film surface with evaporated sand oxide), fabrics, spunbond fibers, and non-wovens ( Especially polypropylene spunbond fibers or non-woven fabrics), and substrates coated with inks, dyes, pigments, PVC and the like. These films can vary in thickness depending on the desired application, however films with a thickness of 1 to 25 microns are usually suitable. Films intended for packaging are typically between 10 and 60 microns thick. In many cases, the sealing layer should have a thickness between 5 and 60 microns, more preferably between 10 and 50 microns, and most preferably between 15 and 30 microns. The sealing layer may be on the inner and outer surfaces of the film or the sealing layer may be present only on the inner or outer surface. Film additives such as adhesives, anti-blocking agents, antioxidants, slip additives, pigments, fillers, processing aids, UV stabilizers, neutralizers, lubricants, surfactants and / or nucleating agents may also be used Exist in one or more films. Preferred additives include silicon dioxide, titanium dioxide, polydimethylmethoxide, talc, dyes, osmium, calcium stearate, carbon black, low molecular weight resins, and glass beads. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

-40- 593520 A7 B7 五、發明説明（38 ) (請先閱讀背面之注意事項再填寫本頁) 在一具體實施例中，層（等）可包含交聯劑。較佳交聯劑 包括醇類，多元醇類，胺類，二胺類及/或三胺類。可使用 於本發明的交聯劑之例子包括多元胺例如乙二胺，二乙撐 三胺，己二胺，二乙胺基丙胺，及/或甲烷二胺。 較佳抗氧化劑包括酣系抗氧化劑，例如Irganox 1010， Irganox，1076二者皆得自汽巴嘉基和3,5三級-丁基4-羥 基甲苯。較佳油類包括石臘或環院（n a p t h e n i c )油類例如，可 得自法國巴黎ExxonMobil化學法國S.A.之Primol 352，或 Primol 876。更佳的油類包括脂族環烷油類，白油類或相似 物。 較佳塑化劑及/或佐劑包括礦物油類，聚丁烯類，鄰苯 二甲酸酯類和相似物。特佳塑化劑包括鄰苯二曱酸酯類例 如鄰苯二甲酸二異十一基酯（DIUP)，鄰苯二甲酸二異壬基 酯（DINP)，鄰苯二甲酸二辛基酯（DOP)和聚丁烯，例如得自 德克薩斯州休斯頓的ExxonMobil化學公司之Parapol 950 和 Parapol 1300。 經濟部智慧財產局員工消費合作社印製 較佳薄膜加工助劑，潤滑劑，蠟，及/或油類包括低分 子量產物例如鱲，油或低Μη聚合物，（低表示在5000以下 ，較佳在4000以下，更佳在3000以下，甚至更佳在2500 以下之Μη)。較佳蠟包括極性或非極性蠟，官能化蠟，聚 丙烯鱲，聚乙烯蠟，和蠘改質劑。較佳蠟包括ESC OMER 1 〇 1 °較佳低Μη聚合物包括低級α -烯例如丙烯，丁烯，戊 烯，已烯和相似的聚合物。特佳的聚合物包括具有小於 1 00 0之Μη的聚丁烯。該類聚合物的例子爲得自Exxon化 i紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 一 -41 - 經濟部智慧財產局員工消費合作社印製 593520 A7 _____B7__ 五、發明説明（39 ) 學公司的商標名PARAPOL95 0。PARAPOL 95 0爲一種具有 950之Μη和100 C之220cSt動態黏度（如以ASTMD 44 5測 量）的液態聚丁烯聚合物。 在另一具體實施例中，一或以上的層可以電暈處理， 電子束輻射，r輻射，火焰處理或微波改性，在較佳具體 實施例中一或兩個表層都以電暈處理改性。 上述薄膜可作爲拉伸及/或黏結薄膜使用。拉伸/黏結薄 膜可使用在各種綑綁，包裝和堆積操作。爲了賦予特殊薄 膜之黏結性質，或改良黏結性質，許多已知的增黏添加劑 已被利用。通用增黏添加劑包括聚異丁烯，萜烯樹脂，和 氫化松脂和松酯。薄膜的黏結性質也可被稱爲電暈放電之 已知物理方法改性。一些聚合物（例如乙烯丙烯酸甲酯共聚 物）不需要黏結添加劑且可作爲沒有增黏劑的黏結層使用。 拉伸/黏結薄膜可包括滑爽層，其包括任何適當的聚烯烴或 聚烯烴（例如聚乙烯，聚丙烯乙烯和丙烯的共聚物）和得自與 小量其他烯烴（特別是C4到C12烯烴）共聚合的乙烯及/或丙 烯之聚合物的組合物。特佳爲聚丙烯和直鏈低密度聚乙烯 (LLDPE)。適當的聚丙烯正常爲固體和等規的，也就是，大 於90%熱庚烷不溶解，具有約0.1到約3〇〇克/1〇分鐘之廣 泛熔融流動率。此外，滑爽層可包括一種或以上的抗黏結（ 滑爽及抗防黏連）添加劑，其可在聚;1¾烴製造期間或後來混 合加入以改良此層的滑爽性質。該等添加劑在該技藝爲已 知且包括，例如，矽石，矽酸鹽，矽藻土，滑石和各種的 潤滑劑。這些添加劑較佳以從約1 0 0 p p m到約2 0，0 0 0 p p m 本紙張尺度適用中國國家標準（CNS ) A4規格（210>( 297公釐） " ~ -42- (請先閱讀背面之注意事項再填寫本頁)-40- 593520 A7 B7 V. Description of the Invention (38) (Please read the notes on the back before filling this page) In a specific embodiment, the layer (etc.) may contain a cross-linking agent. Preferred crosslinking agents include alcohols, polyols, amines, diamines and / or triamines. Examples of the crosslinking agent which can be used in the present invention include polyamines such as ethylenediamine, diethylenetriamine, hexamethylenediamine, diethylaminopropylamine, and / or methanediamine. Preferred antioxidants include actinide-based antioxidants, such as Irganox 1010, Irganox, 1076, both of which are available from Cibaggaki and 3,5 tertiary-butyl 4-hydroxytoluene. Preferred oils include paraffin or naphtha oils. For example, Primol 352, or Primol 876, available from ExxonMobil Chemical France S.A., Paris, France. More preferred oils include aliphatic naphthenic oils, white oils or the like. Preferred plasticizers and / or adjuvants include mineral oils, polybutenes, phthalates and the like. Particularly good plasticizers include phthalates such as diisoundecyl phthalate (DIUP), diisononyl phthalate (DINP), and dioctyl phthalate ( DOP) and polybutenes, such as Parapol 950 and Parapol 1300 available from ExxonMobil Chemical Company of Houston, Texas. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs print better film processing aids, lubricants, waxes, and / or oils including low-molecular-weight products such as rhenium, oil, or low-Mη polymers, (low means less than 5000, better (Mη below 4000, more preferably below 3000, even more preferably below 2500). Preferred waxes include polar or non-polar waxes, functionalized waxes, polypropylene tinctures, polyethylene waxes, and tincture modifiers. Preferred waxes include ESC OMER 101. Preferred low Mn polymers include lower alpha-olefins such as propylene, butene, pentene, hexene, and similar polymers. Particularly preferred polymers include polybutenes having a Mn of less than 1,000. An example of this type of polymer is obtained from Exxon Chemical Paper Standard Applicable Chinese National Standard (CNS) A4 Specification (210X 297 mm) I-41-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _____B7__ V. Description of the Invention (39) Trademark of the company PARAPOL95 0. PARAPOL 95 0 is a liquid polybutene polymer with a dynamic viscosity of ηη of 950 and 220 cSt of 100 C (as measured by ASTM D 44 5). In another embodiment, one or more layers may be modified by corona treatment, electron beam radiation, r radiation, flame treatment or microwave modification. In a preferred embodiment, one or both surface layers are modified by corona treatment. Sex. The film can be used as a stretched and / or adhesive film. Stretch / bond films can be used in a variety of bundling, packaging, and stacking operations. To impart or improve the adhesion properties of special films, many known tackifying additives have been used. Common tackifier additives include polyisobutylene, terpene resins, and hydrogenated turpentine and turpentine. The adhesive properties of the film can also be modified by known physical methods known as corona discharge. Some polymers (such as ethylene methyl acrylate copolymers) do not require a tackifier additive and can be used as a tackifier without a tackifier. The stretch / bond film may include a slip layer that includes any suitable polyolefin or polyolefin (eg, polyethylene, polypropylene, ethylene, and propylene copolymers) and is obtained from small amounts of other olefins (especially C4 to C12 olefins). ) A composition of copolymerized polymers of ethylene and / or propylene. Particularly preferred are polypropylene and linear low density polyethylene (LLDPE). Suitable polypropylenes are normally solid and isotactic, i.e., greater than 90% hot heptane is insoluble and has a wide melt flow rate of about 0.1 to about 300 g / 10 minutes. In addition, the slip layer may include one or more anti-blocking (slip and anti-blocking) additives, which may be added during the manufacture of the hydrocarbons or later to improve the slip properties of this layer. These additives are known in the art and include, for example, silica, silicate, diatomaceous earth, talc and various lubricants. These additives are preferably from about 100 ppm to about 20,000 ppm. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 > (297 mm) " ~ -42- (Please read first (Notes on the back then fill out this page)

經濟部智慧財產局員工消費合作社印製 593520 A7 B7 五、發明説明（4〇) ，更佳在約500 ppm到約10,000 ppm之間，以滑爽層重量 爲基礎，的數量利用。如果需要，滑爽層也可包括一種或 以上如上所述之其他添加劑。 實例 在下列實例中，HMAs係如下製備。HMA調配物之組 份引入至先前在氮氣層下加熱於180它之Z_葉片式混合器 中。在10分鐘之後引入蠟及混合繼續另60分鐘。停止混 合器，停止氮氣層及摻合物倒入盤子內。摻合物在氮氣層 下進一步冷卻和以離型紙覆蓋。 如下製備試驗用HMA樣品。膠黏劑引入accumeter的 漏斗中且在氮氣下於1 5〇t熔化。切割和以熔化膠黏劑塗佈 所要基材載體條（2 00//厚度的聚乙烯薄膜，100//厚度的 PET薄膜，90//厚度的鋁及/或丙烯酸塗佈之定向聚丙烯 (OPP)薄膜厚紙板）。 爲了 T-剝離試驗，藉由將塗佈及未塗佈的基材切割成 約25公分長度和1〇公分寬度片製備試驗用HMA樣品。未 塗佈的基材放置在塗佈之基材的上端。樣品包裹在離型紙 中，其以熱壓機在視基材而給定之溫度下（1 1 0 °C用於聚乙 烯丙烯酸塗佈的OPP厚紙板，1 5 〇°C用於氫氧化鋁，聚丙烯 和聚對苯二甲酸乙二酯（PET))在壓力 4400磅 (114psi/783 kPa)下進一步層壓30秒。使用切紙機在塗佈向 從層壓樣品（等）切割2公分寬度的長條。T-剝離強度以拉伸 試驗機（Zwick)測量。測量F-平均剝離力（克/公分）（每個層 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ' " -43- (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Description of the invention (40), more preferably between about 500 ppm and about 10,000 ppm, based on the weight of the slip layer, the quantity is used. If desired, the slip layer may also include one or more other additives as described above. Examples In the following examples, HMAs were prepared as follows. The components of the HMA formulation were introduced into a Z-blade mixer previously heated at 180 ° under a nitrogen blanket. The wax was introduced after 10 minutes and mixing continued for another 60 minutes. Stop the mixer, stop the nitrogen blanket and pour the blend into a plate. The blend was further cooled under a nitrogen blanket and covered with release paper. HMA samples for testing were prepared as follows. The adhesive was introduced into the accumeter's funnel and melted at 150 t under nitrogen. Cutting and coating the desired substrate carrier strip with melt adhesive (200 // thick polyethylene film, 100 // thick PET film, 90 // thick aluminum and / or acrylic coated oriented polypropylene ( OPP) film cardboard). For the T-peel test, HMA samples for testing were prepared by cutting coated and uncoated substrates into pieces of about 25 cm in length and 10 cm in width. The uncoated substrate is placed on top of the coated substrate. The samples were wrapped in release paper, which was heat-pressed at a given temperature depending on the substrate (1 10 ° C for polyethylene acrylic coated OPP cardboard, 1 500 ° C for aluminum hydroxide, Polypropylene and polyethylene terephthalate (PET)) were further laminated for 30 seconds under a pressure of 4,400 pounds (114 psi / 783 kPa). Using a paper cutter, cut a 2 cm wide strip from the laminated sample (etc.) in the coating direction. The T-peel strength was measured with a tensile tester (Zwick). Measure F-average peel force (g / cm) (paper size of each layer applies Chinese National Standard (CNS) A4 specification (210X297 mm) '" -43- (Please read the precautions on the back before filling in this page)

593520 A7 B7 五、發明説明（41 ) (請先閱讀背面之注意事項再填寫本頁) 壓板平均至少3個試驗樣品）。當指示急跳時，記錄最大峰 的2/3。破壞類型也記錄在表1-5中：膠黏破壞（AF)，內聚 破壞（CF)，急跳或不急跳，和撕裂。 剪切膠黏破壞溫度（SAFT)和熱剪切試驗樣品相同於T-剝離樣品製備，除了使用25x70毫米的長條且放置在先淸 理之不銹鋼板以外。 SAFT係藉由將經選擇基材之塗佈條黏著至具有 12.5x25毫米的接觸面積之不銹鋼，將樣品懸掛於固定在25 °C的烤箱中和自長條底部懸掛500克重量。溫度以0.41 / 分鐘升高及測量結合破壞溫度。剪切膠黏破壞溫度爲三個 試驗的平均。 經濟部智慧財產局員工消費合作社印製 熱剪切係藉由將以膠黏調配物塗佈之經選擇的基材之 25毫米寬長條（其黏著至具有12.5x25毫米的接觸面積之不 銹鋼板上）懸掛1〇〇〇克重量來測量。樣品放置在40 °C通風 烤箱30分鐘。溫度於30分鐘期間升高l〇°C直到應力破壞 發生，至高1 1 〇°C。典型地，這些試驗個別進行及記錄以測 定黏固力之可信度。結果在60°C測量之分鐘相等物表示， 也就是當破壞發生時，各10°C增加60°C以上，30分鐘加至 該時間。 皂化値，如使用在本文中，依照下列步驟測量。2克欲 評估之粉末樹脂材料溶解在25毫升甲苯/異丙醇（1 : 1重量 比）中和以吸量管加入50毫升0. 1N的KOH醇溶液。在回流 30分鐘和冷卻到室溫之後使用酚酞（phenolphthaleine：^·* 劑滴定溶液對〇. 1 NHC1。以沒有樹脂材料進行空白實驗。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -44 - 593520 A7 B7 五、發明説明（42 ) 然後藉由56.1(ΚΟΗ的大約分子量）x標準HC1的體積xHCl 的當量濃度除以樹脂材料的重量計算皂化値（毫克1<：011/克 樹脂）。 酸値，如使用在本文中，依照下列步驟測量。2克欲評 估之粉末樹脂材料溶解在3 0毫升甲苯/異丙醇（2 : 1重量比 )中。樣品完全溶解之後，其在烈攪拌下以〇·1Ν四丁基氫 氧化銨（ΤΒΑΟΗ)電位滴定，使用具有外LiCl電解質在飽和 乙醇中之Pt titrode和Ag/AgCl電極。以沒有樹脂材料進行 空白實驗。然後藉由56.1 (KOH的大約分子量）乘以用來滴 定樣品的TBAOH體積減去滴定空白的TBAOH體積乘以 TBAOH的當量濃度除以樹月旨材料的重量計算酸値。酸値以 每克樹脂的氫氧化鉀的毫克數表示，（毫克KOH/克樹脂）。 在下列實例中，除非另有指示否則所有的份，比例， 和百分比以重量計。使用下列材料： (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本纸張纽適财麵㉟iicNS—) Α4^Τ7Γ〇χ 297公釐) -45 - 593520 A7 B7 五、發明説明（43) i fi?<4^^lo— !i?«[s> 10— fi?<4s> Ιο— (％)餵S栽ho氍κ]593520 A7 B7 V. Description of the invention (41) (Please read the notes on the back before filling this page) The average pressure plate is at least 3 test samples). When a sharp jump is indicated, 2/3 of the maximum peak is recorded. The types of failure are also recorded in Tables 1-5: Adhesive Failure (AF), Cohesive Failure (CF), Jump or not jump, and Tear. The shear adhesive failure temperature (SAFT) and thermal shear test samples were prepared the same as the T-peel samples, except that a 25x70 mm strip was used and placed on a pre-treated stainless steel plate. SAFT consists of attaching a coated substrate of a selected substrate to stainless steel with a contact area of 12.5x25 mm, suspending the sample in an oven fixed at 25 ° C and hanging a weight of 500 grams from the bottom of the strip. The temperature was increased at 0.41 / min and the combined destruction temperature was measured. Shear adhesive failure temperature is the average of three experiments. The Ministry of Economic Affairs, Intellectual Property Bureau, Employee Consumer Cooperative printed thermal shearing by 25 mm wide strips of a selected substrate coated with an adhesive formulation (which adheres to a stainless steel plate with a contact area of 12.5x25 mm (Top) Hanging weight of 1,000 grams to measure. The samples were placed in a ventilated oven at 40 ° C for 30 minutes. The temperature increased by 10 ° C during 30 minutes until stress failure occurred, up to 110 ° C. These tests are typically performed individually and recorded to determine the confidence of the adhesion. The result is expressed as the equivalent of a minute measured at 60 ° C, that is, when damage occurs, each 10 ° C increases by more than 60 ° C, and 30 minutes is added to the time. Saponified samarium, as used herein, is measured according to the following steps. 1N of KOH alcohol solution was dissolved in 25 ml of toluene / isopropanol (1: 1 weight ratio) in a powder resin material to be evaluated. After refluxing for 30 minutes and cooling to room temperature, a phenolphthaleine: ^ · * agent titration solution was used to 0.1 NHC1. Blank experiments were performed with no resin material. This paper size applies Chinese National Standard (CNS) A4 specifications (210X297) Centrifuge) -44-593520 A7 B7 V. Description of the invention (42) Then calculate saponified tritium (mg 1 <: 011 /) by dividing 56.1 (approximate molecular weight of ΟΟΗ) x volume of standard HC1 x equivalent concentration of HCl by the weight of the resin material Grams of resin). Acid osmium, as used herein, is measured according to the following steps. 2 grams of powdered resin material to be evaluated are dissolved in 30 ml of toluene / isopropanol (2: 1 weight ratio). After the sample is completely dissolved, It was titrated at a potential of 0.1N tetrabutylammonium hydroxide (TBA〇 烈) under vigorous stirring, using a Pt titrode and an Ag / AgCl electrode with saturated LiCl electrolyte in saturated ethanol. A blank experiment was performed with no resin material. 56.1 (approximate molecular weight of KOH) multiplied by the volume of TBAOH used to titrate the sample minus the volume of TBAOH of the titration blank multiplied by the equivalent concentration of TBAOH divided by the weight of the material値. Acid 値 is expressed in milligrams of potassium hydroxide per gram of resin, (mg KOH per gram of resin). In the following examples, all parts, ratios, and percentages are by weight unless otherwise indicated. Use the following materials : (Please read the precautions on the back before filling out this page) Printed on the paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper is suitable for commercial use (iicNS—) Α4 ^ Τ7Γ〇χ 297 mm) -45-593520 A7 B7 5 Description of the invention (43) i fi? ≪ 4 ^^ lo—! I? «[S > 10— fi? ≪ 4s > Ιο— (%) Feeding S 栽 ho 氍 κ]

OOCN 61 6rn (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 (1)i 寸 ε6.0 S6.0 經濟部智慧財產局員工消費合作社印製 (賴φοι/职) s 00寸 οείη 09 8S0 寸 τη 6Ι0εςτη _3MS8S3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -46- 593520OOCN 61 6rn (Please read the notes on the back before filling out this page) Binding · Ordering (1) i inch ε6.0 S6.0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (Lai φοι / position) s 00 inch οείη 09 8S0 inch τη 6Ι0εςτη _3MS8S3 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -46- 593520

7 7 A B 五、發明説明（44 ) i7 7 A B V. Description of the invention (44) i

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0。9寸§10011|《pcn6ds)s5Mi:iu/u ε§ %28S3 ExxonMobil化學公司 汽巴-嘉基 增量油 酚系抗氧化劑 Flexon⑧ 876 Irganox⑧ 1010,1076 SEOSISH -00¾ P009 _μ? SQHN oss-umulunqos i^i.smHNmvwd 1ΪΡΗ —-------裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 CN 準 標 一家 國 國 中 用 適 I度 尺 張 紙 I本 s0.9 inch §10011 | 《pcn6ds) s5Mi: iu / u ε§% 28S3 ExxonMobil Chemical Company Ciba-Geigy Extender Oil Phenolic Antioxidant Flexon⑧ 876 Irganox⑧ 1010,1076 SEOSISH -00¾ P009 _μ? SQHN oss-umulunqos i ^ i.smHNmvwd 1ΪΡΗ --------- install-(Please read the precautions on the back before filling out this page) Order the standard of the standard for a country in China with a suitable I ruler paper I s

釐 公 7 9 2 X -47- 593520 kl _B7_ 五、發明説明（45 ) 實例1(比較） (請先閱讀背面之注意事項再填寫本頁) 將包含DCPD樹脂的熱聚合之氫化芳烴（可得自 ExxonMobil化學公司的Escorez⑧5600，具有103°C的軟化 點，Μη 270，和Tg 5 5°C )混合於根據表1之HMA調配物中 〇 實例2(比較） 將得自亞利桑那化學公司的Sylvalite® RE100(軟化點 96 °C，Μη 95 0，Mw 1110，皂化値26，和酸値5· 5)的高油 松酯混合於根據表1之HMA調配物中。 實例3(比較） 得自亞利桑那化學公司的Sylvalite® RE1 00(軟化點 10CTC，Μη 810，Mw 1060，皂化値 28，和酸値 13,7)的高 油松酯混合於根據表1之HMA調配物中。 實例4(比較） 經濟部智慧財產局員工消費合作社印製 得自 Resiniques Terpeniques 的 Dertophene T(軟化點 95°C，Μη 4 90，Mw 700，和最初顏色4.5加登）之萜烯酚醛 樹脂混合於根據表1之HMA調配物中。然後使用聚乙烯對 聚乙烯和PET對PET之T-剝離，和在聚乙烯對不銹鋼和 PET對不銹鋼的熱剪切和SAFT檢查實例1-4。得自實例1-4的結果顯示在表中且作爲以後實例的比較之參考使用。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -48- 593520 A7 __B7 五、發明説明（46 ) 實例5 100克之包含DCPD樹脂的熱聚合氫化之芳烴，與試驗 於實例1中之Es corez® 5 6〇0樹脂相同，但沒有抗氧化劑， 包含7.5%芳族質子和0.01%烯烴質子，具有1〇3它的軟化 點，在氮氣下以配備有擾泮器的2 5 0毫升燒瓶中加熱到且 維持在170°C。加入5.5克順-丁烯二酸二丁酯。在15分鐘 間隔加入四等分的0.75毫升2,5-二甲基-2,5-二（三級-丁基 過氧基）己烷（Luperox® 101)。在過氧化物加入完成之後， 混合物在氮流下進一步攪拌7 5分鐘以除去揮發性材料。從 反應器倒出所得反應產物，冷卻及分析。接枝樹脂產物具 有3.5之加登顏色（5 0重量％在甲苯中），84°C之軟化點， 和1 7之皂化値。 實例6 1〇〇克之包含DCPD樹脂的熱聚合部分氫化之芳烴，與 試驗於實例1中之Escorez® 5600樹脂相同，但沒有抗氧化 劑，具有l〇3°C的軟化點，7.5%芳族質子和0.01%烯烴質 子（以1H-NMR光譜指示），在氮氣下以配備有攪拌器的 5 00毫升燒瓶中加熱到且維持在1 70 °C。當液體時，加入 1.23克順-丁烯二酐粉末且混合。五個0.1毫升等分的2,5-二甲基-2,5-二（三級-丁基過氧基）己烷（Luperox 101)在15分 鐘間隔加至攪拌之液體中及反應在氮流下繼續另60分鐘以 除去揮發性過氧化物分解產物和任何殘餘的未反應順-丁烯 二酐。熔體從反應燒瓶倒出且使冷卻及凝固。所得接枝樹 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智慧財產局員工消費合作社印製 -49 - 593520 A7 ____ B7 五、發明説明（47 ) 脂產物具有1 〇 5 °c之軟化點，3 . 5之加登顏色和1 〇之皂化値 〇 實例7 250克之包含DCPD樹脂的熱聚合部分氫化之芳烴，與 試驗於實例1中之Escorez® 5600樹脂相同，但沒有抗氧化 劑，具有103°C的軟化點，7.5%芳族質子和0.01%烯烴質 子（以1H-NMR光譜指示），在氮氣下以配備有攪拌器的 5 〇〇毫升燒瓶中加熱到且維持在1 7〇 °C。當液體時，加入 6.1 3克順-丁烯二酐粉末且混合。在1 〇分鐘間隔加入五個 〇.25毫升等分的2,5-二甲基-2,5-二（三級-丁基過氧基）己烷 及反應在氮流下繼續另20分鐘以除去揮發性過氧化物分解 產物和任何殘餘的未反應順-丁烯二酐。熔體從反應燒瓶倒 出且使冷卻及凝固。所得接枝樹脂產物具有i 〇 5 °C之軟化點 ，3.6之加登顏色和20之皂化値。 實例8 100克之包含DCPD樹脂的熱聚合部分氫化之芳烴，與 試驗於實例1中之Escorez® 5600樹脂相同，但沒有抗氧化 劑，具有l〇3°C的軟化點，7.5%芳族質子和0.01%烯烴質 子（以1H-NMR光譜指示），在氮氣下以配備有攪拌器的 5 00毫升燒瓶中加熱到且維持在170 °C。當液體時，加入 4.9克順-丁烯二酐粉末且混合。在1 5分鐘間隔加入四個 0.5毫升等分的2,5-二甲基-2,5-二（三級-丁基過氧基）己烷及 本紙張尺度適用中國國家標準（CNS ) A4規格（210/ 297公釐） (請先閲讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局員工消費合作社印製 -50- 593520 A7 ___B7 五、發明説明（48 ) (請先閱讀背面之注意事項再填寫本頁) 反應在氮流下繼續另7 5分鐘以除去揮發性過氧化物分解產 物和任何殘餘的未反應順-丁烯二酐。熔體從反應燒瓶倒出 且使冷卻及凝固。所得接枝樹脂產物具有1 1 2 °C之軟化點， 8之加登顏色和40之皂化値。 實例9-12 將得自實例5 -8之接枝樹脂混合於根據表1之HM A調 配物中。然後使用聚乙烯對聚乙烯和PET對PET之T-剝離 ，和在聚乙烯對不銹鋼和PET對不銹鋼的熱剪切和SAFT 檢查實例9- 1 2。得自實例9-1 2的結果顯示在表1和圖1 -6 中。注意T-剝離：只有表示剝離力（F-平均）。當樣品只有 急跳時，其相當於零膠黏力。 經濟部智慈財產局員工消費合作社印製 這些結果顯示在聚乙烯基材上，大部份接技樹脂實施 與參考例1 -4相似之膠黏。另一方面，接枝樹脂的熱剪切 和SAFT優於參考例1-4，尤其是其中接枝單體爲順-丁烯二 酐實之例6/10，7/11和8/12。這些結果也說明在極性基材 上例如PET，與實例1未拉接枝樹脂和實例2及3的高油 松酯比較，該等接枝樹脂具有較佳膠黏，其顯僅示急跳。 如圖1-6所說明，熱剪切和SAFT結果顯示實例6/10，7/1 1 和8 /1 2之接枝樹脂等於或優於參考實例1 - 4。 實例13 從 '種法國 Notre Dame de Gravenchon 的 ExxonMobil 製造工廠的包含DCPD烴樹脂之熱聚合芳烴之商業製造方 一··----- - _______ - — - - _________ ______ — - - _ _ ________-_______ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -51 - 經濟部智慧財產局員工消費合作社印製 593520 A7 B7 ______ 五、發明説明（49 ) 法中的產物汽提塔的塔頂餾出物流移出700克之環戊二烯 ，甲基環戊二烯和C9-C1()芳族烯烴之寡聚物的氫化三聚物 和四聚物混合物。所得的寡聚物沒有包含抗氧化劑且包含 7.4%芳烴質子和0%烯烴質子。寡聚物在2升量瓶中於氮 氣下l6〇°C與70克順-丁烯二酐粉末一起攪拌。在0，10， 20，30，45和75分鐘時間加入六個3毫升等分之2,5-二甲 基-2,5_二（三級-丁基過氧基）己烷。反應在氮氣流經燒瓶下 繼續另45分鐘以除去任何揮發性組份。反應器冷卻到140 °C且產物倒進以ASTM D-1078測定沸點在160-192°C範圍 之冷石臘烴溶劑中（可得自ExxonMobil化學公司的Exxsol D)。過濾不溶解的產物和以庚烷洗滌以除去殘餘痕量的未 反應寡聚物和任何的過氧化物分解產物。產量爲120克之 具有軟化點107°C，加登顏色12(丙酮：甲苯1 : 1重量）， 和3 3 6之皂化値的接枝寡聚物。 實例14-17 得自實例13的接枝寡聚物與包含DCPD樹脂（Escorez® 5 60 0)之熱聚合氫化芳烴混合於各種的寡聚物對樹脂比例以 形成樹脂材料。接枝寡聚物在樹脂材料中的量在5和30重 量之間％改變。樹脂材料然後混合於根據表1之HMA調配 物中。已測量聚乙烯對聚乙烯和PET寺PET的T-剝離，和 聚乙烯對不銹鋼和PET對不銹鋼的熱剪切及SAFT。得自實 例14-1 7的結果在顯示表2和4及圖7-1 2中。實例1 5和 17之T_剝離試驗也在丙烯酸塗佈的0PP厚紙板（以AC表 本紙張尺度適用中國( CNS ) Α4規格（210Χ 297公釐） ~ " -52 - (請先閲讀背面之注意事項再填寫本頁) £· -、1Τ 593520 A7 _ _B7 ____ 五、發明説明（5〇 ) 示）上進行和與由實例2製得的HMA調配物產生的相似結 果比較。該等結果顯示在表2和圖1 3 -1 5中。 表2和圖7-1 2說明當與參考例1 -4比較時，包含接枝 寡聚物之樹脂材料顯示在聚乙烯基材上的全部可比較的行 爲。這些結果也說明在極性基材例如PET上，包含接枝寡 聚物之樹脂材料達成顯著的優點，尤其是黏著。這些結果 也說明當與參考例1 -4比較時，包含接枝寡聚物之樹脂材 料的剪切和SAFT顯著較高。從表5和圖13-15的結果也說 明包含接枝寡聚物之樹脂材料具有超越在實例2中丙烯酸 塗佈之OPP厚紙板上試驗的高油松酯之性能，尤其是黏著 (請先閱讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局员工消費合作社印製 實例18-23 具有表3所示組份之包裝膠帶調配物在WinkwcKth AZ 混合器中於1 4 5 °C以5 9 RPM後葉片速度混合。在1 4 5 t的 設定溫度達成後十分鐘，開始塡充氮氣和加入及混合嵌段 共聚物，總樹脂的1/5，和Irganox抗氧化劑。當加入嵌段 共聚物之時間，認爲是開始時間。在混合1 0分鐘之後，加 入總樹脂的額外2/5。當觀察到剪切時，加入樹脂其餘的 1/5。在開始時間後30分鐘，加入所有的油，及混合組份直 到從開始時間70分鐘。混合物然後倒進盤子內和以離型紙 覆蓋。藉由以accumeter塗覆機於175°C塗怖Mylar基材至 約1 9克/公尺2之總塗佈重量製備樣品。在試測之前所有的 樣品於23°C和50%相對濕氣調節至少16個小時。樣品然 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 一 -53- 593520 A7 __B7_ 五、發明説明（51 ) 後視進行試驗之要求切割成條。下列試驗步驟使用於實例 18-23° 球黏著性藉由根據PSTC試驗方法的試驗方法6之步驟 試驗。切割樣品2.5公分寬和25公分長和移去離型襯墊。 樣品以膠黏側固定在實驗台上。球黏著性試驗器以樣品縱 軸線放置在樣品上。以鑷子從溶劑取出鋼球（5.6克，7/16 吋（1 . 1 1公分）直徑）且以紙擦乾。以鑷子將擦乾的球放置在 離型位置之球粘著性試驗器的木缽，釋離和在膠黏層上滾 動。測量從球的中心到球粘著性試驗器的傾斜端之距離（公 分）。在二個取自相同壓敏材料的額外樣品上重複測量及將 平均測量記錄在表中。 以於界定之速度膠黏劑環從標準試驗片分開所需之力 評估環粘著性。不銹鋼片儲存在Nappar 6溶劑中。試驗以 前他們以吸收紙吸乾和以丙酮淸潔。試驗在樣品塗佈方向 實施。膠黏劑以離型紙覆蓋和切割試驗樣品（2.5公分寬和 22公分長）。然後從試驗樣品移去離型襯墊。在外側上以膠 黏層形成環。膠黏劑在環二端的以紙保護致使在膠黏劑和 剝離試驗器之空氣夾之間的沒有直接接觸。二個被保護的 環端在離垂直向下懸掛之環1 5毫米的距離夾住。乾淨的試 驗片放置在環粘著固定物，具垂直放置於環平面的片之長 度方向。拉伸試驗器以3 00毫米/分鐘的設定速度開始使膠 黏薄膜之環與試驗片接觸。樣品沒有任何樣品重量本身以 外的其他力量下施用至試驗片上。一旦環已與試驗完全接 觸停止機器及開始記錄。以300毫米/分鐘的速度從試驗片 本紙張又度適用中國國家標準（CNS ) A4規格（210X 297公釐） — -54 - (請先閱讀背面之注意事項再填寫本頁) •裝. -訂 經濟部智慧財產局員工消費合作社印製 593520 A7 _B7_^_ 五、發明説明（52) (請先閱讀背面之注意事項再填寫本頁) 樣品分開樣品。測量至少3個相同調配物之試驗樣品和記 錄試驗片完全分開環所需之最大力。在表中給予的値爲三 個試驗的平均値。 經濟部智慧財產局g(工消費合作社印製 1 80°剝離黏著評估樣品的剝離黏著。剝離黏著評估從 標準試驗片在所界定的角（在這情形爲lSCT )和速度剝離壓 敏膠黏劑所需要的力量。不銹鋼片儲存在溶劑（Nappar 6)中 。在試驗之前，該等試片以吸收紙乾燥及以丙酮淸潔。試 驗在樣品的塗佈方向進行。欲試驗之樣品的膠黏表面覆蓋 離型紙和切割成25毫米寬和22公分長的樣品。從長條除 去部份離型襯墊，後文鬆端。樣品的沒有離型紙的部分在 長度方向黏在乾淨和調整過的試驗片上，沒有任何的力量 。樣品放置在自動下捲機中和設定於60公分/分鐘的速度。 樣品（等）上下滾兩次。樣品在製備一分鐘內試驗。剝掉三公 分在鬆端之樣品上的離型紙。試驗樣品的金屬片在下夾子 中垂直夾住。樣品之鬆端向後摺（180° )和固定在上夾子上 。記錄從金屬片剝離樣品所需的力量。每個膠黏樣品測量 三件樣品和取得各曲線的平均，忽略作圖之極端的峰和開 始/結束部份。在急跳之情形，記錄最高峰的2/3之平均。 厚紙板上的剪切藉由以膠黏調配物塗佈之樣品（其黏著 至具12.5x25毫米的接觸面積的厚紙板）的25毫米寬長條懸 掛1 000克重量而測量。樣品放置在4〇°C通風烤箱中。記錄 時間直到應力破壞發生。典型地，這些試驗個別進行及記 錄以測定黏固力之可信度。 S AFT(剪切膠黏破壞溫度）方法用以測量當溫度以0.4t 本纸張尺度適用中國國家標準（CNS ) A4規格（2丨0>< 297公f ) -55 - 593520 A7 ___________B7_ 五、發明説明（53) /分鐘升高時，其受到一界定之應力時的黏合破壞溫度。 SAFT試驗如下進行。儲存在溶劑（Nappar 6)中之不銹鋼片 以吸收紙乾燥及以丙酮淸潔。試驗在樣品的塗佈方向進行 。製造2.5公分寬和最小6公分長的離型紙覆蓋之樣品，和 除去離型襯墊。藉由獲得離型襯墊之2.5公分寬和3公分長 之片和將1. 5公分離型襯墊黏著至樣品一端上來強化樣品的 一端。其餘的1 · 5公分向後摺覆蓋在離型襯墊的黏著端上且 以釘書針水平釘兩次。樣品然後在沒有壓力下放置在不銹 鋼試驗片上。在樣品和厚紙板之間的接觸面積爲25毫米寬 x25毫米高度。對於SAFT，樣品和不銹鋼碟之間的接觸積 爲25毫米寬xl2.5毫米高度。接觸面積使用0.9公斤（2磅） 橡膠滾筒以適度速度沒有滾筒本身重量之其他應力在各寬 度方向滾動兩次。剪切三角的一個臂然後放置在離型襯墊 的皺摺中以使沒有接觸膠黏劑之剪切三角的部份。所製備 的樣品然後安裝在樣品支撐上，0.5公斤的重量固定在剪切 三角上然後放置在烤箱中。實驗於24°C開始。溫度以每分 鐘0.4 °C升高。SAFT記錄黏合敗的溫度。每個膠黏調配物 進行五個試驗及五個試驗的平均列在表中。 表3中的數據顯示於40°C在厚紙板上之剪切在包含習 知烴樹脂和本文所述之接枝烴樹脂二者的壓敏膠黏調配物 顯著增加，同時產生3.9公分的球粘著性，其遠小於3 · 0公 分的工業較佳選擇。在實例22和23中，球黏著性降至3.0 或以下，但最令人驚訝地在厚紙板上的熱剪切，値甚至升 到較高水平。因此當膠黏調配物包含習知烴樹脂和本文所 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公麓） (請先閱讀背面之注意事項再填寫本頁) •裝· 、-ιτ 經濟部智慧財產局S工消費合作社印製 -56- 593520 A7 ---—B7__ 五、發明説明（54) ' '一 ^ -— 述接枝樹脂一者時具有料想不到的熱剪切的性能增強。 從前述說明顯然可知，所製備之材料和依照方法係有 關廣泛發明的特佳具體實施例。從前述一般說明和特殊具 體實施例顯然可知，同時本發明的形式已說明且描述，各 種不同的修正可在沒有離開本發明精神和範圍下進行。因 此，不意欲本發明因此被限制。在下列表示本發明之特定 具體實施例的申請範圍中，下列各獨立具體實施例的每個 附屬具體實施例可以一種或以上的其他附屬體實施例之限 制實施以使表示在所請本發明之範圍內的其他可操作的具 體實施例。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -57- 593520Centimeter 7 9 2 X -47- 593520 kl _B7_ V. Description of the Invention (45) Example 1 (Comparison) (Please read the precautions on the back before filling out this page) Thermal polymerization of hydrogenated aromatic hydrocarbons containing DCPD resin (available Escorez (R) 5600 from ExxonMobil Chemical Company, with a softening point of 103 ° C, Mn 270, and Tg 5 5 ° C) was mixed in the HMA formulation according to Table 1 Example 2 (Comparative) Sylvalite® from Arizona Chemical Company RE100 (softening point 96 ° C, Mn 95 0, Mw 1110, saponified hydrazone 26, and acid hydrazone 5.5) were mixed with the homopine esters in the HMA formulation according to Table 1. Example 3 (comparative) Sylvalite® RE100 (softening point 10CTC, Mn 810, Mw 1060, saponified rhenium 28, and acid hydration 13, 7) from Arizona Chemical Company was blended in a HMA formulation according to Table 1 In. Example 4 (comparative) Terpene phenolic resin printed by Dertophene T (softening point 95 ° C, Mn 4 90, Mw 700, and initial color 4.5 Garden) from Resiniques Terpeniques' Consumer Consumption Cooperative printed on the basis of In the HMA formulation of Table 1. Examples 1-4 were then examined using polyethylene-to-polyethylene and PET-to-PET T-peel, and thermal shear and SAFT on polyethylene to stainless steel and PET to stainless steel. The results obtained from Examples 1-4 are shown in the table and used as a reference for comparison of later examples. This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) -48- 593520 A7 __B7 V. Description of the invention (46) Example 5 100 grams of thermally polymerized hydrogenated aromatic hydrocarbons containing DCPD resin, and tested in Example 1 The Es corez® 5 6000 resin is the same, but without antioxidants. It contains 7.5% aromatic protons and 0.01% olefin protons, has a softening point of 103, and is equipped with a perturbator 2 5 under nitrogen. The 0 ml flask was heated to and maintained at 170 ° C. 5.5 grams of dibutyl maleate are added. At 15 minute intervals, aliquots of 0.75 ml of 2,5-dimethyl-2,5-bis (tertiary-butylperoxy) hexane (Luperox® 101) were added. After the peroxide addition was complete, the mixture was further stirred under a nitrogen stream for 75 minutes to remove volatile materials. The resulting reaction product was decanted from the reactor, cooled and analyzed. The graft resin product had a Gardner color of 3.5 (50% by weight in toluene), a softening point of 84 ° C, and a saponified samarium of 17. Example 6 100 grams of a thermally polymerized partially hydrogenated aromatic hydrocarbon containing DCPD resin, the same as the Escorez® 5600 resin tested in Example 1, but without antioxidants, with a softening point of 103 ° C, 7.5% aromatic protons And 0.01% olefin protons (indicated by 1H-NMR spectrum), heated to and maintained at 1 70 ° C in a 500 ml flask equipped with a stirrer under nitrogen. When liquid, 1.23 grams of cis-butene dianhydride powder was added and mixed. Five 0.1 ml aliquots of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane (Luperox 101) were added to the stirred liquid at 15 minute intervals and reacted under nitrogen. Flowing is continued for another 60 minutes to remove volatile peroxide decomposition products and any residual unreacted maleic anhydride. The melt was poured from the reaction flask and allowed to cool and solidify. The paper size of the obtained grafted tree is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back before filling this page). 49-593520 A7 ____ B7 V. Description of the invention (47) The fat product has a softening point of 105 ° C, a Gardner color of 3.5, and a saponification of 1.0. Example 7 250 grams of thermally polymerized DCPD resin partially hydrogenated Aromatic hydrocarbons, the same as the Escorez® 5600 resin tested in Example 1, but without antioxidants, with a softening point of 103 ° C, 7.5% aromatic protons and 0.01% olefin protons (indicated by 1H-NMR spectrum), under nitrogen Next, a 500 ml flask equipped with a stirrer was heated to and maintained at 170 ° C. When liquid, add 6.1 g of cis-butene dianhydride powder and mix. Five 0.25 ml aliquots of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane were added at 10 minute intervals and the reaction was continued under nitrogen flow for another 20 minutes to The volatile peroxide decomposition products and any residual unreacted maleic anhydride were removed. The melt was poured from the reaction flask and allowed to cool and solidify. The obtained graft resin product had a softening point of 105 ° C, a Gardner color of 3.6, and a saponified hydrazone of 20. Example 8 100 grams of a thermally polymerized partially hydrogenated aromatic hydrocarbon containing a DCPD resin, the same as the Escorez® 5600 resin tested in Example 1, but without antioxidants, with a softening point of 103 ° C, 7.5% aromatic protons, and 0.01 % Olefin protons (indicated by 1H-NMR spectrum), heated to and maintained at 170 ° C in a 500 ml flask equipped with a stirrer under nitrogen. When liquid, add 4.9 grams of cis-butene dianhydride powder and mix. Add four 0.5 ml aliquots of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane at a 15-minute interval, and the Chinese paper standard (CNS) A4 applies Specifications (210/297 mm) (Please read the precautions on the back before filling out this page) • Binding and printing printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs -50- 593520 A7 ___B7 V. Description of the invention (48) (Please Read the notes on the back before filling this page) The reaction is continued under nitrogen flow for another 7 5 minutes to remove the volatile peroxide decomposition products and any remaining unreacted cis-butadiene dianhydride. The melt was poured from the reaction flask and allowed to cool and solidify. The obtained graft resin product had a softening point of 112 ° C, a Gardner color of 8 and a saponified tincture of 40. Examples 9-12 The graft resins obtained from Examples 5-8 were mixed in the HMA formulation according to Table 1. Then use T-peel for polyethylene-to-polyethylene and PET-to-PET, and heat shear and SAFT inspection for polyethylene-to-stainless steel and PET-to-stainless steel. Example 9-12. Results from Example 9-1 2 are shown in Table 1 and Figures 1-6. Note the T-peel: only the peel force (F-average) is shown. When the sample has only a sharp jump, it is equivalent to zero adhesive force. Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs. These results show that most of the resins used on the polyethylene substrate are similar to those in Reference Examples 1-4. On the other hand, the thermal shear and SAFT of the graft resin were superior to those of Reference Examples 1-4, especially Examples 6/10, 7/11, and 8/12 in which the graft monomer was cis-butene dianhydride. These results also show that compared to the unstretched graft resins of Example 1 and the tall oleoresin of Examples 2 and 3 on polar substrates, these graft resins have better adhesion, which shows only a sharp jump. As shown in Figure 1-6, the results of hot shear and SAFT show that the graft resins of Examples 6/10, 7/1 1 and 8/1 2 are equal to or better than Reference Examples 1-4. Example 13 Commercial manufacturer of thermally polymerized aromatic hydrocarbons containing DCPD hydrocarbon resins from ExxonMobil manufacturing plant in Notre Dame de Gravenchon, France _______ This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -51-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 ______ V. Product Stripper in the Method of Invention (49) Over 700 grams of cyclopentadiene, methylcyclopentadiene, and oligomers of C9-C1 () aromatic olefins were hydrogenated trimer and tetramer mixtures from the overhead distillate stream. The resulting oligomers contained no antioxidants and contained 7.4% aromatic protons and 0% olefin protons. The oligomers were stirred in a 2 liter flask under nitrogen at 160 ° C with 70 g of cis-butene dianhydride powder. Six 0 ml portions of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane were added at 0, 10, 20, 30, 45 and 75 minutes. The reaction was continued for another 45 minutes under nitrogen flow through the flask to remove any volatile components. The reactor was cooled to 140 ° C and the product was poured into a cold paraffin solvent (exxsol D available from ExxonMobil Chemical Company) having a boiling point in the range of 160-192 ° C as determined by ASTM D-1078. The insoluble product was filtered and washed with heptane to remove residual traces of unreacted oligomers and any peroxide decomposition products. The yield was 120 g of a grafted oligomer with a softening point of 107 ° C, Garden Color 12 (acetone: toluene 1: 1 by weight), and 3,36 saponified samarium. Examples 14-17 The graft oligomers obtained from Example 13 were mixed with a thermally polymerized hydrogenated aromatic hydrocarbon containing a DCPD resin (Escorez® 5 60 0) in various oligomer to resin ratios to form a resin material. The amount of grafted oligomer in the resin material varies between 5 and 30% by weight. The resin material was then mixed in the HMA formulation according to Table 1. T-peeling of polyethylene to polyethylene and PET to PET, and thermal shear and SAFT of polyethylene to stainless steel and PET to stainless steel have been measured. The results obtained from Examples 14-1 7 are shown in Tables 2 and 4 and Figures 7-12. Example 1 The T_Peel test of 5 and 17 is also acrylic coated 0PP thick paperboard (applicable to China (CNS) A4 size (210 × 297 mm) with AC paper size) ~ " -52-(Please read the back first Please note this page and fill in this page) £ ·-, 1T 593520 A7 _ _B7 ____ V. Description of the invention (5) and comparison with the similar results produced by the HMA formulation prepared in Example 2. These results are shown in Table 2 and Figs. Table 2 and Figures 7-1 2 illustrate all comparable behaviors of a resin material containing a graft oligomer on a polyethylene substrate when compared with Reference Examples 1-4. These results also indicate that on polar substrates such as PET, resin materials containing grafted oligomers achieve significant advantages, especially adhesion. These results also indicate that when compared with Reference Examples 1-4, the shear and SAFT of the resin material containing the grafted oligomer were significantly higher. The results from Table 5 and Figures 13-15 also show that the resin material containing the grafted oligomers has a performance that exceeds that of the high turpentyl esters tested on the acrylic-coated OPP cardboard in Example 2, especially the adhesion (please first (Please read the notes on the back and fill in this page again) • Binding and ordering Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 18-23 Packaging tape formulations with the composition shown in Table 3 in the WinkwcKth AZ mixer on 1 4 5 ° C was mixed at a leaf speed of 5 9 RPM. Ten minutes after the set temperature of 145 t was reached, nitrogen gas charging was started and block copolymers were added and mixed, 1/5 of the total resin, and Irganox antioxidant. The time when the block copolymer is added is considered the start time. After 10 minutes of mixing, add an additional 2/5 of the total resin. When shear was observed, the remaining 1/5 of the resin was added. 30 minutes after the start time, add all the oil and mix the ingredients until 70 minutes from the start time. The mixture is then poured into a plate and covered with release paper. Samples were prepared by coating a Mylar substrate at 175 ° C with a accumeter coater to a total coating weight of about 19 g / m2. Prior to testing, all samples were conditioned for at least 16 hours at 23 ° C and 50% relative humidity. Samples The size of this paper is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm). -53- 593520 A7 __B7_ V. Description of the invention (51) The requirements of the test for rear view are cut into strips. The following test procedure was used in Example 18-23 °. Ball adhesion was tested by the procedure of Test Method 6 according to the PSTC test method. Cut the sample 2.5 cm wide and 25 cm long and remove the release liner. The sample was fixed on the experimental table with the adhesive side. The ball adhesion tester is placed on the sample with its longitudinal axis. Remove the steel ball (5.6 g, 7/16 inch (1.11 cm) diameter) from the solvent with tweezers and wipe dry with paper. The tweezers were used to place the dried ball in the wooden bowl of the ball adhesion tester in the release position, released and rolled on the adhesive layer. Measure the distance (cm) from the center of the ball to the inclined end of the ball adhesion tester. Repeat the measurement on two additional samples taken from the same pressure-sensitive material and record the average measurement in the table. The force required to separate the adhesive ring from the standard test strip at the defined rate was evaluated for ring adhesion. Stainless steel sheets were stored in Nappar 6 solvent. Prior to the test they were blotted dry with absorbent paper and cleaned with acetone. The test was carried out in the sample application direction. The adhesive covered and cut the test samples (2.5 cm wide and 22 cm long) with release paper. The release liner was then removed from the test sample. A ring is formed on the outside with an adhesive layer. The adhesive was paper protected at both ends of the ring so that there was no direct contact between the adhesive and the air clip of the peel tester. The two protected ring ends are clamped at a distance of 15 mm from the vertically hanging ring. The clean test piece is placed on the ring adhesive fixture with the length direction of the piece placed vertically on the ring plane. The tensile tester started contacting the ring of the adhesive film with the test piece at a set speed of 300 mm / min. The sample is applied to the test piece without any force other than the weight of the sample itself. Once the ring has made full contact with the test stop the machine and start recording. At the speed of 300 mm / min, the test paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) — -54-(Please read the precautions on the back before filling this page) • Loading.- Order printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _B7 _ ^ _ V. Description of Invention (52) (Please read the precautions on the back before filling this page) Samples are separated from samples. Measure at least 3 test specimens of the same formulation and record the maximum force required to completely separate the rings. The tritium given in the table is the average tritium for the three trials. Intellectual Property Bureau of the Ministry of Economic Affairs (industrial and consumer cooperative printing 1 80 ° peel adhesion evaluation sample peel adhesion. Peel adhesion evaluation peels pressure-sensitive adhesive from a standard test piece at a defined angle (in this case, lSCT) and speed Required strength. Stainless steel sheets are stored in a solvent (Nappar 6). Prior to testing, the test pieces are dried with absorbent paper and cleaned with acetone. The test is performed in the direction of sample application. Adhesion of the sample to be tested The surface is covered with release paper and cut into 25 mm wide and 22 cm long samples. Remove the part of the release liner from the strip, the end is loose. The part of the sample without the release paper sticks clean and adjusted in the length direction. There is no force on the test piece. The sample is placed in an automatic unwinder and set at a speed of 60 cm / min. The sample (etc.) is rolled up and down twice. The sample is tested within one minute of preparation. Peel off three centimeters at the loose end The release paper on the sample. The metal piece of the test sample is clamped vertically in the lower clip. The loose end of the sample is folded back (180 °) and fixed on the upper clip. Record the need to peel the sample from the metal piece. Strength. Measure three samples per glue sample and obtain the average of each curve, ignoring the extreme peaks and the start / end portions of the plot. In the case of a sharp jump, record the average of 2/3 of the highest peak. Thick cardboard Shear was measured by hanging a 25-mm wide strip of a sample coated with an adhesive formulation that adhered to a cardboard with a contact area of 12.5 x 25 mm to a weight of 1,000 grams. The sample was placed at 40 ° C. Ventilate the oven. Record the time until stress failure occurs. Typically, these tests are individually performed and recorded to determine the credibility of the adhesion. S AFT (shear adhesive failure temperature) method is used to measure when the temperature is 0.4t This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0 > < 297 male f) -55-593520 A7 ___________B7_ V. Description of the invention (53) / minute when it is subjected to a defined stress The SAFT test was performed as follows. The stainless steel sheet stored in the solvent (Nappar 6) was dried with absorbent paper and cleaned with acetone. The test was performed in the coating direction of the sample. A 2.5 cm wide and a minimum 6 cm long Release paper Cover the sample and remove the release liner. Strengthen one end of the sample by obtaining a 2.5 cm wide and 3 cm long piece of release liner and adhering a 1.5 cm release liner to one end of the sample. 1 · 5 cm is folded back to cover the adhesive end of the release liner and stapled horizontally twice with a staple. The sample is then placed on a stainless steel test piece without pressure. The contact area between the sample and the cardboard is 25 Mm width x 25 mm height. For SAFT, the contact product between the sample and the stainless steel dish is 25 mm width x l2.5 mm height. The contact area uses a 0.9 kg (2 lb) rubber roller at a moderate speed without other stress on the weight of the roller itself Scroll twice in each width direction. One arm of the shear triangle is then placed in the crease of the release liner so that the portion of the shear triangle that is not in contact with the adhesive. The prepared sample was then mounted on the sample support, a weight of 0.5 kg was fixed on the shear triangle and placed in the oven. The experiment started at 24 ° C. The temperature rises at 0.4 ° C per minute. SAFT records the temperature of adhesion failure. Five tests were performed for each adhesive formulation and the average of the five tests is listed in the table. The data in Table 3 show that shearing on cardboard at 40 ° C significantly increased pressure-sensitive adhesive formulations containing both conventional hydrocarbon resins and the grafted hydrocarbon resins described herein, while producing 3.9 cm balls Adhesiveness, which is far less than 3.0 cm industrially preferred. In Examples 22 and 23, the ball adhesion dropped to 3.0 or below, but most surprisingly, the thermal shear on thick paperboards, 値 even rose to higher levels. Therefore, when the adhesive formulation contains the conventional hydrocarbon resin and the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 feet) (please read the precautions on the back before filling this page). ιτ Printed by S Industrial Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs -56- 593520 A7 ----- B7__ V. Description of the Invention (54) '' 一 ^ -— The graft resin has unexpected thermal shear Enhanced performance. It is apparent from the foregoing description that the materials prepared and the methods according to them are particularly preferred embodiments of a wide range of inventions. It is obvious from the foregoing general description and specific specific embodiments that, while the form of the present invention has been illustrated and described, various modifications may be made without departing from the spirit and scope of the present invention. Therefore, it is not intended that the present invention be limited thereby. In the scope of the following applications representing specific embodiments of the present invention, each subsidiary embodiment of each of the following independent specific embodiments may be implemented with one or more other subsidiary embodiment restrictions so that Other operable embodiments within the scope. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -57- 593520

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本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -60-This paper size applies to China National Standard (CNS) A4 (210X 297mm) -60-

Claims (1)

593520 % A8 B8 C8 D8 六、申請專利範圍i 附件4 : 第91121888號專利申請案修正後無劃線之 中文申請專利範圍替換本 民國92年9月19日修正 L 一種組成物，其包括至少二種烴樹脂，其中之一種 樹脂的存在量基於組成物重量計爲0.1-99重量％及其爲經 由以組成物總重計〇 · 1 -1 〇重量％接枝單體接枝之石油烴樹 脂，其中接枝單體係選自：酸類，酸酐類，醯亞胺類，醯 胺類，醇類和其衍生物，其中該組成物實質上沒有包括降 冰片酯基的環戊二烯和經.取代之環戊二烯的接枝寡聚物， 其中： 如果接枝單體爲一種酸，酸酐，醯亞胺，醯胺或其衍 生物，至少二種烴樹脂的皂化値爲1 -1 〇〇，或者 如果接枝單體爲一種醇或其衍生物，依照ASTM E 222 94測量之羥基値爲1-100。 2. 如申請專利範圍第1項之組成物，其中其他烴樹脂 的存在量基於組成物的重量計爲1-99.9重量％及其係選自 由下列所組成之群：脂族烴樹脂，至少部份氫化的脂族烴. 樹脂，脂族/芳族烴樹脂，至少部份氫化的脂族/芳族烴樹脂 ，環脂族烴樹脂，至少部份氫化的環脂族樹脂，環脂族/芳 族烴樹脂，至少部份氫化的環脂族/芳族烴樹脂，芳族烴樹 脂，至少部份氫化的芳族烴樹脂，聚萜烯樹脂，萜烯-酚樹 脂，.松酯，松脂酸和其任何二種或以上的混合物。 3. 如申請專利範圍第1或2項之組成物，其中接枝石 油烴樹脂在接枝之前包含0-5%烯烴質子。 本紙張尺度適用中國國家標準（CNS )六4既格（210X297公釐） ~ ~ (請先閱·«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 593520 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 々、申請專利範圍2 4. 如申請專利範圍第1或2項之組成物，其中接枝樹 脂包含卜20%芳族。 5. 如申請專利範圍第1或2項之組成物，其中接枝烴 樹脂選自C5單體的寡聚物，C9單體的寡聚物，和環戊二燒 ，經取代之環戊二烯及C9單體的寡聚物。 6. 如申請專利範圍第1或2項之組成物，其中接枝石 油烴樹脂爲一種至少部分氫化的熱聚合芳族環脂族烴樹脂 〇 7. 如申請專利範圍第1或2項之組成物，其中接枝石 油烴樹脂係藉由C5單體及C9單體之聚合作用獲得。 8. 如申請專利範崮第1或2項之組成物，其中接枝烴 樹脂選自由下列所組成之群：環戊二烯和經取代之環戊二 烯的寡聚物，其中寡聚物實質上沒有降冰片酯基及其中寡 聚物包括至少一個之單烷基順-丁烯二酸，酸酐或其衍生物 ，或/3-烷基取代的丙酸或其衍生物。 9. 如申請專利範圍第1或2項之組成物，包括1-75 重量％接枝石油烴樹脂。 1 0.如申請專利範圍第1或2項之組成物，尙包括至 少一種聚烯烴。 1 1 .如申請專利範圍第10項之組成物，其中聚烯烴選 自由下列所組成之群：聚乙烯，乙烯α -烯烴（C3-C2())共聚 物，聚丙烯，丙烯α-烯烴（C4-C2G)共聚物，聚丁烯，丁烯 烯烴（C5-C2〇)共聚物，聚異丁烯聚合物，α-烯烴二烯共 聚物，包括笨乙烯和共軛二烯之嵌段共聚物，及其二種或 本紙张尺度適用中國國家標準（CNS ) 格（2Ι0Χ297公釐） (請先閲令背面之注意事項再填寫本頁)593520% A8 B8 C8 D8 6. Scope of patent application i Annex 4: Chinese application for patent application without amendment underlined after the amendment of Patent Application No. 91121888 Replaces the amendment of the Republic of China on September 19, 1992 L A composition that includes at least two Hydrocarbon resin, wherein one of the resins is present in an amount of 0.1 to 99% by weight based on the weight of the composition and is a petroleum hydrocarbon resin grafted via a graft monomer of 0.1 to 10% by weight based on the total weight of the composition Wherein the grafted monosystem is selected from the group consisting of: acids, anhydrides, amidines, amidines, alcohols, and derivatives thereof, wherein the composition does not substantially include cyclopentadiene and Grafted oligomers of substituted cyclopentadiene, wherein: if the grafting monomer is an acid, anhydride, amidine, amidine or a derivative thereof, the saponification ratio of at least two hydrocarbon resins is 1 -1 〇〇, or if the grafting monomer is an alcohol or a derivative thereof, the hydroxyamidine measured according to ASTM E 222 94 is 1-100. 2. As for the composition in the scope of the patent application, the other hydrocarbon resin is present in an amount of 1-99.9% by weight based on the weight of the composition and is selected from the group consisting of: aliphatic hydrocarbon resin, at least part of which Parts of hydrogenated aliphatic hydrocarbons. Resins, aliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aliphatic / aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic resins, cycloaliphatic / Aromatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, at least partially hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene-phenol resins, turpentine esters, turpentine resins Acids and mixtures of any two or more thereof. 3. The composition according to item 1 or 2 of the patent application scope, wherein the grafted petroleum oil resin contains 0-5% olefin protons before grafting. This paper size applies to the Chinese National Standard (CNS) 6 4 grid (210X297 mm) ~ ~ (Please read · «Notes on the back before filling out this page) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 593520 Ministry of Economic Affairs Printed by A8, B8, C8, D8, Consumer Cooperative of Intellectual Property Bureau 々, patent application scope 2 4. For the composition of patent application scope item 1 or 2, the graft resin contains 20% aromatic. 5. If the composition of claim 1 or 2, the grafted hydrocarbon resin is selected from the group consisting of C5 monomer oligomer, C9 monomer oligomer, and cyclopentadiene, substituted cyclopentadiene Olefin and C9 monomer oligomers. 6. The composition according to item 1 or 2 of the patent application, wherein the grafted petroleum hydrocarbon resin is an at least partially hydrogenated thermally polymerized aromatic cycloaliphatic hydrocarbon resin. 7. The composition according to item 1 or 2 of the patent application scope The grafted petroleum hydrocarbon resin is obtained by the polymerization of C5 monomer and C9 monomer. 8. The composition according to item 1 or 2 of the patent application, wherein the grafted hydrocarbon resin is selected from the group consisting of cyclopentadiene and substituted oligomers of cyclopentadiene, of which the oligomers Substantially no norbornyl groups and oligomers therein include at least one monoalkylmaleic acid, anhydride or derivative thereof, or / 3-alkyl substituted propionic acid or derivative thereof. 9. The composition according to item 1 or 2 of the patent application scope, including 1 to 75% by weight of a grafted petroleum hydrocarbon resin. 10. If the composition of the scope of claims 1 or 2 of the patent application, 尙 includes at least one polyolefin. 1 1. The composition according to item 10 of the scope of patent application, wherein the polyolefin is selected from the group consisting of polyethylene, ethylene α-olefin (C3-C2 ()) copolymer, polypropylene, propylene α-olefin ( C4-C2G) copolymers, polybutenes, butene olefins (C5-C20) copolymers, polyisobutylene polymers, α-olefin diene copolymers, including block copolymers of styrene and conjugated diene, And its two or this paper size is applicable to the Chinese National Standard (CNS) grid (2Ι0 × 297 mm) (please read the precautions on the back of the order before filling out this page) -2 593520 A8 B8 C8 D8 六、申請專利範圍3 以上之混合物。 (請先閲部背面之注意事項再填寫本頁) 12. 如申請專利範圍第1或2項之組成物，尙包括至 少一種極性聚合物。 13. 如申請專利範圍第12項之組成物，其中極性聚合 物選自由下列所組成之群：聚酯類，聚醯胺類，聚脲類， 聚碳酸酯類，聚丙烯腈類，·聚丙烯酸酯類，聚甲基丙烯酸 酯類，乙烯乙酸乙烯酯共聚物，聚氯乙烯，聚對苯甲二酸 乙二酯，聚苯二甲酸丁二酯，聚縮醛類，乙烯丙烯酸甲酯 ，乙烯丙烯酸丁酯及其二種或以上之混合物。 14. 如申請專利範圍第1或2項之組成物，尙包括一 種包括乙烯或丙烯且具有CDBI爲50- 1 00%和多分散性少於 4的聚合物。 1 5 .如申請專利範圍第1或2項之組成物，尙包括至 少一種蠘或油。 16.如申請專利範圍第1或2項之組成物，尙包括至 少一種交聯劑。 經濟部智慧財產局員工消費合作社印製 1 7 . —種膠黏性組成物，其包含如申請專利範圍第1或 2項之樹脂組成物。 1 8 . —種熱熔體壓敏劑，包括： (a) 100重量份的苯乙烯嵌段共聚物； (b) 5 0- 1 5 0 phr之如申請專利範圍第1或2項之樹脂組 成物；及 (c) 0-5 0 phr之增量油，其選自環烷油、脂族油及白油 本紙張尺度適用中國國家禚準（CNS ) A4規格（210 X 297公釐） -3--2 593520 A8 B8 C8 D8 6. Mixtures with a patent scope of 3 or more. (Please read the notes on the back of the section before filling out this page.) 12. If the composition in the scope of patent application 1 or 2 includes at least one polar polymer. 13. The composition of claim 12 in which the polar polymer is selected from the group consisting of polyesters, polyamides, polyureas, polycarbonates, polyacrylonitrile, and poly Acrylates, polymethacrylates, ethylene vinyl acetate copolymers, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyacetals, ethylene methyl acrylate, Ethylene butyl acrylate and mixtures of two or more thereof. 14. As for the composition in the scope of claims 1 or 2, the polymer includes a polymer including ethylene or propylene, having a CDBI of 50 to 100% and a polydispersity of less than 4. 1 5. If the composition of the scope of claims 1 or 2 of the patent application, rhenium includes at least one rhenium or oil. 16. If the composition of the scope of claims 1 or 2 of the patent application, 尙 includes at least one crosslinking agent. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 17. — A kind of adhesive composition, which contains the resin composition as described in the first or second scope of the patent application. 18. A hot-melt pressure-sensitive agent, including: (a) 100 parts by weight of a styrene block copolymer; (b) 50 to 150 phr of a resin as described in claims 1 or 2 Composition; and (c) 0-5 0 phr extender oil selected from naphthenic oil, aliphatic oil and white oil. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -3-