TWI248964B - Adhesives and sealants from controlled distribution block copolymers - Google Patents

Adhesives and sealants from controlled distribution block copolymers Download PDF

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TWI248964B
TWI248964B TW092102542A TW92102542A TWI248964B TW I248964 B TWI248964 B TW I248964B TW 092102542 A TW092102542 A TW 092102542A TW 92102542 A TW92102542 A TW 92102542A TW I248964 B TWI248964 B TW I248964B
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block
polymer
resin
styrene
weight
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TW200303344A (en
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Dale Lee Handlin Jr
Carl L Willis
David John St Clair
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Kraton Polymers Res Bv
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
    • C09D153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

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(2) 1248964 發明說明績頁 聚合物製造商能夠改變橡膠鏈段相容性特徵之新種類 SBC’s。 —在文獻上亦知不飽和s B S和SIS聚合物在熱熔性黏著劑和 密封劑處理期間易於氫化降解，且經氫化類似物在熱熔處 理期間具有優良得多的抗降解性。經氫化SEBS和SEPS SBC’s中的橡膠鏈段比不飽和SBS和SIS聚合物中的橡膠更 加高度纏結。因此，在恒定聚合物含量的調配物中，以經 風化SBC’s爲基礎的pSA一般比以未經氫化sbc，4基礎的 PSA具有較差黏性。所以，理想用經氫化和不飽和me、 之摻合物得到年體穩定性和黏性的最佳平衡。然而，由於 相今1±差異，以SEBS和SIS聚合物之摻合物爲基礎的黏著 dJ不相谷。以此等摻合物爲基礎的黏著劑通常最初混濁， 且在持續保持時相分離。以此等摻合物爲基礎的黏著劑薄 膜缺乏以相容性黏著劑爲基礎黏著劑的高光澤，且此等黏 著劑之性能通常差。 現已發現一種以單烯基芳烴末端嵌段和單烯基芳烴與共 軛二烯之經控制分佈中間嵌段爲基礎之新穎陰離子性嵌段 共聚物，該共聚物描述於同在申請中的普通轉讓美國專利 申請案第6G/355,21G號，其標題爲“新穎嵌段共聚物及其製 造方法’，（NOVEL BLOCK COP〇LYM£HS AND Methqd FOR MAKING SAME)。冑造此等共聚物之方法詳細描述 於上述專利申請案。專利所有人已發現此等新聚合物的樹 脂相容性實際不同於習知經氫化SBC，s，這允許樹脂製造 商有機會開發與此等新穎SBC’s相容的新樹脂。專利所有 1248964 發明說明續頁 (4) 、以溶劑爲主之黏著劑及類似物。 本發明另一方面顯示，澄清、相穩定黏著劑組合物可用 >、某些SIS類型SBC’s摻合的經控制分佈嵌段共聚物製備。 該黏著劑組合物包括100重量份之經控制分佈嵌段共聚物 25至3 00重罝份之苯乙烯/異戊二烯未經氫化嵌段共聚物 50至400重量份之增黏性樹脂以及〇至重量份之聚合 物、里油。可將该新穎聚合物加入一種以sis聚合物爲基 礎之黏著劑’錢良穩定性，或可在以該新穎聚合物爲基 礎之黏著劑中包括一種SIS聚合物，以改良黏性。 f施方式 么明的關鍵成分爲包含單稀基芳煙末端㈣和單烯邊 2與共輛二烯之獨特中間喪段之新穎嵌段共聚物。令/ ::::⑴早體加入之獨特控制和(2)用乙醚或其他这 組分(該組分將被稱爲“分佈劑。之㈣ f兩；早體的一定特徵分佈(在此稱爲“控制分佈，，聚洽 中存在某此富含單烯、、、。構)’亦導致聚合物嵌我 、牡呆一田3早烯基方烴之區域及某些富含共 區域。按照本發明意圖，“經控制分佈，，定義爲具有以下 性之分子結構：（1)與單烯美 " 下屬 h、早飾基方垣同聚物 末端區域富含(即，具有大於 )：:又相相 ”人1又不相郴的一或多個區域富含， > 量）單烯基芳烴單位；及（3)且 〃、有大於平均之 。按照本發明意圖，“富含，，：：對低嵌段度之總體結構 於平均量之5%〇用差-p j …大於平均之量，較佳大 用差以描量熱法（“DSC”)熱方法或機械 (5) 1248964 發明說明績頁 方法分析，或由質子核磁共振（“H_NMR”）方法顯示，相對 低肷段^可由只存在任一單獨單體Tg，S間控制分佈嵌段中 間體的早一玻璃轉移溫度（Tg)顯示。嵌段度的可能性亦可 自測篁適用於檢測B嵌段聚合期間聚苯乙烯基鋰端基波長 ，圍的UV·可見吸收度推斷。此值的尖銳及實質增加顯示 聚苯乙烯基鐘鏈末端的實f增加。在此製程中，這僅在共 軛二烯濃度下降到低於保持經控制分佈聚合的臨界水平發 生。在此點存在的任何苯乙烯單體將以嵌段體方式加入。 由熟諳此藝者用質子NMR檢測，“苯乙烯嵌段度，，定義爲在 聚合物鏈上具有兩個S最接近相鄰體的聚合物中8單位之比 例。苯乙烯嵌段度在如下用NMR測量兩個試驗量後決 定： 百先測定苯乙烯單位的總數（即，測定時消除的任意儀 器單位），爲此，將Η-1 NMR波譜中的全部苯乙烯芳系信 號自7.5至6.2 ppm積分，並將該量除以5，以說明各苯乙烯 方壤上5個芳系氫。 其次測定嵌段體苯乙烯單位，爲此，將Η— 1 NMR波譜中 的那部分芳系信號自6.88和6.80間之信號最小值至6.2 ppm 積分，並將該量除以2，以說明各嵌段體笨乙烯芳環上的2 们部位氣。將此彳§被賦予具有兩個苯乙浠最接近相鄰體的 那些苯乙烯單位環上的兩個鄰位氫報告於F A·鮑維 ，高分子高分辨 NMR (High Resolution NMR of Macromolecules) (Academic Press，New York and London，1972)，第 6章。 苯乙烯嵌段度簡單爲嵌段體苯乙烯對全部苯乙烯單位之 1248964 _ ^6) 發明說明縝頁 百分比： 嵌段體％ = 100χ(嵌段體苯乙烯單位/全部苯乙烯單位） 士將η大於〇時如此表示的聚合物_Bd_s_(s)n-S-Bd聚合物 疋義爲欺段體本乙稀。例如，如果以上實例中η等於8，則 其嵌段度指數應爲80%。嵌段度指數較佳小於4〇。對於具 有10重量％至40重量％苯乙烯含量的一些聚合物，嵌段度 指數較佳小於1 〇。
該經控制分佈結構對控制所得共聚物之強度及Tg很重要 ，因爲该經控制分佈結構保證兩種單體實質上沒有相分離 即與其中早-體貫際作爲具有不同T g，s的分離微相對照 仁同時又確貫化學結合在一起。該控制分佈結構保證只 存在一個Tg，因此，所得共聚物之熱性能可以預言，並可 實際測定。此外，在隨後將具有此控制分佈結構之共聚物 作爲個肷段用於二嵌段、三嵌段或多嵌段共聚物時，則 由存在適宜組成經控制分佈共聚物區域可能産生的相對較 间Tg傾向於改良流動性及處理性。亦可取得某些其他性能 改進。 八 山在本么明車乂佳具體貫施例中，主題經控制分佈共聚物 肷^具有三個不同區域_兩個在嵌段末端上富含共軛二烯 之區域及一在接近嵌段中間或中心的富含單烯基芳烴單位 只區域所的要者爲單烯基芳烴/共軛二烯經控制分佈共 聚物肷^又’其中單烯基芳烴單位之比例在接近嵌段中間或 :心逐漸增加到最大，隨後逐漸降低，直至聚合物嵌段完 全聚合化。此結構有別且不同於先前技藝中討論的錐形及 -11 - 1248964 _ 發明說明縝頁 /或無規結構。 用於製備本發明新穎經控制分佈共聚物之原料爲初始單 體。稀基芳烴可選自苯乙烯、α-甲基苯乙烯、對甲基笨乙 烯、乙烯基甲笨、乙烯基萘和對丁基苯乙烯或其混合物。 在此等物質中，苯乙烯最佳並可自各製造商購得而且相對 廉價。在此所用的共軛二烯爲二烯及經取代丁二烯 ，如異戊二烯、戊間二烯、2,3_二甲基。，、丁二烯及卜苯 基-1,3 -丁二稀或其混合物。在此等物質中，i，3_丁二稀最 佳。在本文及申請專利範圍中，丁二烯明確指“丨，3_丁二烯”。 如上所討論經控制分佈聚合物嵌段具有一（多）個與A 嵌段相鄰的富含二烯之區域及一與A嵌段不相鄰且一般接 近B嵌段中心的富含芳烴之區域。與八嵌段相鄰的區域— 般包括第一 15至25%嵌段，且包括一（多）個富含二烯之區 域，餘者被認爲富含芳烴。“富含二烯，，指該區域比富含芳 烴區域具有可測較高二烯對芳烴之比。另一種表示方式爲 ，單稀基芳烴單位之比與聚合物鏈一道在接近嵌段中間或 中心逐漸增加到最大限度（如果描述ΑΒΑ結構），然後逐漸 降低直到聚合物嵌段完全聚合化。對於經控制分佈嵌段 B，單烯基芳烴之重量百分比在約1〇和約75%之間。 在本文中，‘‘熱塑性嵌段共聚物”定義爲具有至少一單烯 基方蛵之第一嵌段（如苯乙烯）和二烯與單烯基芳烴之經控 制分佈共聚物之第二♦段之嵌段共聚物。製備此熱塑性嵌 段共聚物之方法係由一|已知用於喪段聚合的方法進行。 本毛月已括種熱塑性共聚物組合物作爲一具體實施例， -12- 1248964 ⑻ 發明說明繽頁 該組合物可爲二嵌段、三嵌段共聚物或多嵌段組合物。如 果爲二嵌段共聚物組合物，則一個嵌段爲以烯基芳烴爲基 礎的同聚物嵌段，而與之聚合的則爲一種二烯和烯基芳烴 之經控制分佈共聚物之第二嵌段。如果爲三嵌段組合物， 則其包括玻璃態以烯基芳烴爲基礎的同聚物作爲端嵌段， 並包括一種二烯和烯基芳烴之經控制分佈共聚物作爲中間 嵌段。在製備三嵌段共聚物組合物時，在本文中將經控制 分佈二烯/烯基芳烴共聚物指定爲“B”，而將以烯基芳烴爲 基礎的同聚物指定爲“A”。可由順序聚合或偶合製造冬B_ A，三嵌段組合物。在順序溶液聚合技術中，首先引入單 烯基芳烴，以産生相對較硬芳系嵌段，隨後引入經控制分 佈二烯/烯基芳烴混合物，以生成中間嵌段，再隨後引入 單烯基芳烴’以生成末端嵌段。除線性a_b_a構型外，可 使嵌段構成輻射狀（分支）聚合物（Α_Β)ηΧ，或使兩種類型結 構在混合物中組合。爲給予強度，可存在一些Α_Β二嵌段 聚合物’但較佳至少約3〇重量。之嵌段共聚物爲八_3_八或 輻射狀（或另外分支，以每分子具有2或更多個末端樹脂性 嵌段）。 控制不同嵌段的分子量亦很重要。對ΑΒ二嵌段，所需 肷ί又重ϊ對單烯基芳烴Α嵌段爲3,〇〇〇至6〇,〇〇〇，而對經控 制为佈共#厄二烯/單烯基芳烴B嵌段爲3〇,〇〇〇至3〇〇,〇〇〇。a 敗段的較佳範圍爲5〇〇〇至45,〇〇〇，而B嵌段的較佳範圍爲 5〇,0〇0至25〇,〇〇〇。對於可爲順序人3八或經偶合（八^2：^嵌段 共物的二喪段而言，A嵌段應爲3,000至60,000，較佳 1248964 發明說明績頁 (9) 5000至45,000，而順序嵌段的B嵌段應爲約30,000至 300,000，而經偶合聚合物的B嵌段（兩個）則爲那量的一半 。三嵌段共聚物的總平均分子量應爲40,000至400,000，而 輻射狀共聚物應爲60,000至600，000。此等分子量由光散射 檢測精確測定，並作爲數量平均分子量表示。 本發明的另一重要方面爲控制經控制分佈共聚物嵌段中 共扼二烯的微結構或乙烯基含量。“乙烯基含量，，乙詞指由 1，2-加成聚合的共軛二烯（在丁二烯情況下-如果爲異戊二 烯’則應爲3,4-加成）。雖然在i，3-丁二烯的ι，2-加成聚合 下只生成純“乙-稀”基，但異戊二烯的3,4_加成聚合（及其它 共輛二婦的類似加成）對嵌段共聚物的最終性能影響將相 似。“乙烯基”指在聚合物鏈上存在懸垂乙烯基。當提及用 丁二烯作爲共輛二烯時，由質子Nmr分析測定，較佳共聚 物嵌段中的20至80莫耳％經縮合丁二烯單位具有丨，孓乙烯 基構型，較佳3 0至70莫耳％經縮合丁二浠單位應具有^ 乙烯基構型。這由改變分佈劑的相對量有效控制。如吾等 所瞭解，分佈劑服務於兩個目的，其産生單烯基芳烴和共 軛二烯的經控制分佈，且亦控制共軛二烯的微結構。分^ 劑對鋰的適合比例揭示且教示於美國專利第Re 27，1C號 ，其揭示係以引用之方式併入本文中。 b 本發曰讀塑性彈性體二谈段及三欲段聚合&包括一或多 個經控制分佈二烯/烯基芳烴共聚物嵌段及一或多個單烯 基芳烴嵌段，言亥聚合物的—個重要特徵爲它們具有至少兩 個Tg’s，較低者係作爲其組成單體Tg，s中間體的經控制分 -14- 1248964 _ 發明說明績頁 佈共聚物嵌段之組合Tg。此Tg較佳至少爲_6(rc，更佳自 -40°C至+30°C，最佳自-扣至+^艺。單烯基芳烴“玻璃態，， 嵌段之第二Tg較佳大於8(rc，更佳自8〇至11〇。〇。存在兩 個Tg’s說明嵌段的微相分離，這將有助於寬範圍應用中材 料的顯著彈性和強度及其容易處理和理想熔體流動特性。 肷段共？κ物係選擇性氫化。氫化可由先前技藝上已知的 系種氫化或選擇性氫化方法進行。例如，此氫化已用一些 方法完成，如美國專利第3,494,942號、第3,634,594號、 第3,670,054號、第3,700,633號及第Re· 27，145號所教示者 。氫化可在此已減少至少90%共軛二烯雙鍵且已減少〇 和1〇重量％間之芳烴雙鍵之條件下進行。較佳範圍爲減少 至少95%共辆二烯雙鍵，更佳減少共輛二晞雙鍵。或 者，可將聚合物氫化，使芳系不飽和度亦減少到低於上述 10%水平以上。在那種情況下，共軛二烯和芳烴二者的雙 鍵可減少90%或更多。 在另一選擇性方面，可以數種方式使本發明之嵌段共聚 物g能化。一種方式爲用具有一或多個官能基或其衍生物 之不飽和單體處理，如羧酸基團及其鹽、酐、酯、醯亞胺 基、醯胺基團及醯氣。欲接枝到嵌段共聚物的較佳單體爲 馬來酸酐、馬來酸、富馬酸及其衍生物。官能化此等嵌段 共聚物的進一步說明可發現於格真（Gergen)等人的美國專 利第4,578,429號及美國專利第5,506,299號。在另一種方 式中，可藉由將含矽或硼之化合物接枝到聚合物使本發明 之選擇性氮化後段共聚物官能化，如美國專利第4，8 8 2，3 8 4 !248964 (11) - 發明說明績頁 儿：教不在另外一種方式中，可使本發明之嵌段共聚物 ’、、兀氧基石夕燒化合物接觸，以生成經石夕烧改質的後段共聚 物在另—種方式巾，爲使本發明之礙段共聚物官能化，·· 可使至v J衣氧乙烷分子與聚合物反應，如美國專利第 _ ，98,9 145虎所教不，或使該聚合物與二氧化碳反應，如$ . =專利第4,970,265號所教示。此外，可使本發明之散段共 、 κ物金屬 匕女口美國專利第5,2〇6,3〇〇號及第⑽號 所教不，其中使聚合物與一種烧基驗金屬接觸，如烧基《里 。更進-步’可藉由㈣基接枝到聚合物使本發明之錢 · 共聚物官能化如美國專利第5,516,831號所教示。 本U黏著劑和密封劑所用的—種組分爲一種增黏性樹 脂。增黏性樹脂包括聚苯乙烯嵌段相容性樹脂和中間嵌段 相今性树脂。聚苯乙烯嵌段相容性樹脂可選自苯并呋喃_ 茚樹脂、聚茚樹脂、聚(甲基茚)樹脂、聚苯乙烯樹脂、乙 烯基甲苯_α_甲基苯乙婦樹脂、α_甲基苯乙烯樹脂及聚伸苯 基縫，特別爲聚（2,6-二甲基-；1，4_伸苯基驗）。此等樹脂（例 如）在商‘ HERCURES”、“ENDEX”、“KRISTALEX”、 ^ “NEVCHEM，，及“ PICC0TEX”下售出。與經氫化（中間）嵌段-相容的樹脂可選自由相容性q烴樹脂'經氫化匕烴樹脂、 、 經苯乙烯化的C5樹脂、Cs/C9樹脂、經苯乙烯化的萜烯樹 ▲ 脂、經完全氫化或部分氫化的q烴樹脂、松香酯、松香衍 · 生物及其混合物所組成之群組。此等樹脂在商標 · “REGALITE”、“REGALREZ”、“ESCOREZ”、“WINGTACK” - 及“ARKON”下售出。 -16- 1248964、 (12) Γ---— 發明說明績頁 本發明黏著劑和密封劑所用的另一種組分爲聚合物增量 油或增塑劑。尤佳爲與援段共聚物之彈性體鍵段相容的類 型，。雖然較高芳系含量的油令人滿意，但較佳使用以石 油爲基礎的具有低揮發性及小於5〇%芳系含量之白油。此 等油包括石蠟油或環烷油。油應額外具有低揮發性，較佳 具有高於260°C (50〇°F )之初始沸點。 #可用於本發明的選擇性增塑劑之實例爲無規或順序聚合 苯乙烯及共軛二烯（如丁二烯或異戊二烯）之寡聚物、共軛 二烯之寡聚物、液態聚丁烯-丨及乙烯-丙烯_二烯橡膠，且 均具有在300至_35,000之重量平均分子量，較佳小於25 〇〇〇 莫耳重量。 所用油或增塑劑之量以每1〇〇重量份橡膠或嵌段共聚物 計自〇至300重量份，較佳20至150重量份。
感壓黏著劑經調配，以得到黏性、剝落、剪切和黏度的 滿意平衡。通常最廣泛使用具有1〇〇,〇〇〇至35〇,〇〇〇之分子 量及12重量％至20重量％之SIS聚合物，因爲它們給予極佳 黏性及優良剪切。然而，如果它們正被混合且作爲熱熔體 在最終PSA帶或標簽塗覆，則必須受到抗降解保護，不應 。十劃在尚溫或暴露於陽光延期使用，因爲SIS聚合物將會 降解。與之對照，SEBS在暴露於高溫或陽光時具有極佳 抗降解性，它們會給予在調配物中具有有限黏性的具優良 剪切之黏著劑。已發現，如果爲改良抗降解性將SEBS聚 合物摻入以SIS聚合物爲基礎的PSA，則黏著劑通常變混 且^生相分離。如果爲改良黏性將Sis聚合物摻入以sebS -17· 1248964 聚合物爲基礎的PSA，黏著劑通常同樣變混且發生相分離 。頃發現，可將新穎聚合物與較佳SIS聚合物摻合，=著 β且在保持時不會相分離。與較佳SIS聚合物作用最 佳的新穎聚合物爲具有25,〇〇〇和15〇,〇〇〇間之分子量且在末 端嵌段相中具有15重量％至25重4%之苯乙烯含量以及具 有共聚入橡膠鏈段的約25重量％苯乙烯者。 +可在黏著劑調配物中包括各種填料和顏料，以對黏著劑 著色並降低成本。適用填料包括碳酸鈣、黏土、滑石、^夕 石、氧化鋅、二氧化鈦及類似者。填料之量以調配物之無 洛劑部分計通—常_在〇至3〇重量％之範圍内，該量依所用填 料類型及黏著劑預期的應用而定。尤佳填料爲二氧化鈦。 如果欲將自溶劑溶液塗覆黏著劑，則調配物的有機部分 將溶於溶劑或溶劑之摻合物。芳烴溶劑即可適用，如甲苯 、一甲苯或Shell Cyclo Sol 53。亦可使用脂系烴溶劑，如 =烧、石腦油或礙物油。如需要，可使用由烴溶劑與極性 溶劑組成的溶劑摻合物。適合極性溶劑包括酯（如乙酸異 丙酯）、酮（如曱基異丁基酮）及醇（如異丙醇）。所用極性溶 劑之量依賴所選擇特定極性溶劑及調配物中所用的特定聚 合物之結構。所用極性溶劑之量通常在溶劑摻合物的〇和 50%之間。 了進^用加入其他聚合物、油、填料、增強劑、抗氧 化劑、穩定劑、阻燃劑、防黏劑、爛滑劑及其它不脫離本 發明範圍的橡膠和塑性混合成分將本發明之組合物改質。 此等成分揭示於各專利中’包括美國專利第3,239,478號及 1248964 _ (14) 發明說明縝頁 第5,777,043號，其揭示係以引用之方式併入本文中。
可將本發明之組合物設計用於多種用途和應用。可將它 們塗覆到紙、紙板、木、金屬箔、聚烯烴薄膜、聚氯乙烯 薄膜、賽璐紛（cellophane)、毛範、織造織物、非織造織 物、玻璃等，並用於將二或多種此等材料黏著在一起。該 黏著劑用於感壓帶（如，覆蓋膠帶）、黏著片、用於其他黏 著劑的底膠、黏著帶、修補帶、電絕緣帶、層合物、熱熔 性黏著劑、瑪帝脂（mastics)、水泥、腻子膠、黏合劑、密 封劑、延遲黏性黏著劑、黏著網（lattice)、數毯襯材、水 泥等。 關於各種成分的相對量，此量部分依賴特定最終用途及 用於特定最終用途選擇的特定嵌段共聚物。以下表A顯示 一些冬發明中包括的概念性組合物。“CD聚合物”指本發 明之經控制分佈聚合物： 表A:應用、組合物及範圍
應用 成分 組合物，重量份 黏著劑 CD聚合物 增黏性樹脂 增量油 100 25 至 300 0 至 200 熱溶性黏著劑 (較佳範圍） CD聚合物 增黏性樹脂 末端嵌段樹脂 增量油 100 75 至 200 0至50 0 至 150 以溶劑爲基礎之黏著劑 (不包括溶劑） CD聚合物 增黏性樹脂 增量油 100 25 至 300 0 至 100 感壓黏著劑 CD聚合物 苯乙烯/異戊二烯嵌段共聚物 增黏性樹脂 100 25 至 300 50 至 500 -19- 1248964 _ (15) 發明說明績頁 增量油 0 至 200 構造黏著劑或密封劑 CD聚合物 增黏性樹脂 末端嵌段樹脂 碳酸鈣 100 0 至 200 0 至 200 100至800 防水塗料 CD聚合物 瀝青 100 200至1000 實例 提供以下實例用於說明本發明。此等實例不用於限制本 發明之範圍，且不應如此解釋。除非另外指明，各量係以 重量份或重量百分比計。實例中所用試驗方法爲美國材料 試驗學會方法（ASTM)，並使用以下特定方法： 滾球黏性 ASTM D-3121 波利坎探針黏性（Polyken Probe Tack) ASTM D-2979 環黏性 ASTM D-6195 180°剝落 ASTM D-903 固定能力（holding power) ASTM D-6463 SAFT ASTM D-4498 熔體黏度 ASTM D-3236 加熱老化黏度穩定性 ASTM D-4499 實例1 根據以上引用的同在申請中專利申請案第60/355,2 10號 (包括同時申請的其接續申請案）中揭示方法製備本發明的 各種經控制分佈嵌段共聚物。所有聚合物均爲選擇氫化的 AB或ΑΒΑ嵌段共聚物，其中A嵌段爲聚苯乙烯嵌段，而氫 化前的B嵌段爲具有富含丁二烯單位之末端區域及富含苯 乙烯單位之中心區域之苯乙烯丁二烯經控制分佈嵌段。各 -20- 1248964 (16) 發明說明績頁 種聚合物顯示於以下表1中。然後將此等聚合物用於其他 實例中所述的各種用途。步驟I MW爲第一 A嵌段之分子量 ，步驟II MW爲AB嵌段之分子量，步驟111 MW爲ABA嵌段 之分子量。將聚合物氫化，以使減少大於約95%之二烯雙 鍵0 表1·經控制分佈聚合物 聚合物 編號 步驟I MWfk) 步驟II MW(k) 步驟III MW(k) 步驟II中 苯乙烯°/〇 苯乙烯 嵌段度 1,2-BD PSC (%) (%) 25 9.1 89 97 25 0 36 39 27 7.5 70 77 25 3 36.1 40 28 7.8 * -39 25 16 36 39 26 7.3 43 50 37 0 36.7 47 在此，“MW(k)” =以千計的分子量，“PSC(%)” =最終聚 合物中的苯乙烯重量％。“苯乙烯嵌段度”只用於B嵌段。 因此，聚合物#25爲具有9,500 - 80,000 - 9,500之數量平 均嵌段莫耳重量之線性ΑΒΑ三嵌段共聚物；聚合物#27爲 具有7,5 00 - 62,600 - 7,3 00之嵌段莫耳重量之線性ΑΒΑ三 嵌段共聚物；聚合物#28爲具有7,800_31，500之嵌段莫耳重 量之ΑΒ二嵌段共聚物；且聚合物#26爲具有7,300 -之 嵌段莫 耳重量之線性 ΑΒΑ三 嵌段共 聚物。 實例2 實例2顯示增黏性樹脂組合物對與CD聚合物#25之橡膠 中間嵌段鏈段之相容性之影響。核磁共振（NMR)分析顯示 ，自古葉（Goodyar)購得的Wingtack樹脂基本爲脂系C5類型 樹脂，但它們用C5流和芳系C9流聚合。它們主要在芳系含 量上不同。NMR顯示，Wingtack 95、Plus、Extra、ET和 -21 - 1248964 _ (17) 發明說明績頁 86中的芳系質子之分數分別爲0、1.7、2.5、4.2和9.4。結 果顯示，所有樹脂均爲該CD聚合物#25的有效增黏劑。具 有最低芳系含量的樹脂得到最佳波利坎探針黏性，而具有 最高芳系含量的樹脂得到最佳滾球黏性。ShellHex 371爲 一種具有-64°C之Tg之環烷系增量油。 表2 組合物，Dhr #2-1 #2-2 #2-3 #2-4 #2-5 CD聚合物#25 100 100 100 100 100 WINGTACK 95 140 WINGTACKPLUS 140 WINGTACK EXTRA 140 WINGTACK ET 140 WINGTACK 86 140 SHELLFLEX 371 40 40 40 40 40 性能a) 滾球黏性，釐米 >30 >30 >30 >30 25 波利坎探針黏性，千克 0.91 0.68 0.43 0.30 0.57 環黏性，盘司/英寸 50 44 41 50 46 180°剝落，每線性英寸磅數 4.3 4.0 4.2 3.8 3.6 HP對鋼(1x1，2千克），分鐘 >7000 >7000 >7000 >7000 >7000 8^丁對“71&1*(1><1，.5千克），°〇 104 98 98 95 90 a)將PS A溶於甲苯，並以1.8密耳（mil)乾燥厚度澆鑄於1密 耳Mylar上。 實例3 實例3顯示CD聚合物#25與經氫化水-白增黏性樹脂之相 容性。咸信Regalite R91 (自Eastman購得）由〇9流聚合且隨 後由氫化消除接近100%芳香度製造。Regalrez樹脂系列由 純芳系單體（如，苯乙烯或乙烯基甲苯）聚合且隨後氫化製 造。Regalrez 1 094、6 1 08和3 1 02分別經氫化消除1 00%、 -22- 1248964 - (18) I發明說明績頁 60%和3 0%芳香度。結果顯示，雖然具有70%芳香度的 Regalrez 3 1 02爲最低效增黏劑，但所有四種樹脂均爲CD 聚合物#25的有效增黏劑。DRAKEOL 34自盤瑞克（Penreco) 購得，其係一種具有-64°C之Tg之石蠟系處理油。 表3 組合物，重量％ #3-1 #3-2 #3-3 #3-4 CD聚合物#25 35.0 35.0 35.0 35.0 REGALITE R91 44.0 REGALREZ 1094 41.5 REGALREZ 6108 41.5 REGALREZ 3102 41.5 DRAKEOL 34 21.0 23.5 23.5 23.5 性能a) 滾球黏性，釐米 6 4 9 26 波利坎探針黏性，千克 0.62 0.74 0.73 0.21 環黏性，盘司/英寸 32 63 69 47 1800剝落，每線性英寸磅數 1.9 2.6 1.9 1.7 8^丁對1^^1&1*(1><1，.5千克），°〇 90 92 82 84 a)將PS A在甲苯中混合，並以1.9密耳乾燥厚度澆鑄於1密 耳Mylar上。 實例4 實例4顯示使用CD聚合物#27與經氫化樹脂和水-白油時 黏著劑組合物對性能之影響。調配物4-1、4-2和4-3顯示聚 合物含量將用弗克斯（Fox)公式計算的玻璃轉移溫度（Tg)恒 定保持在-14°C之作用。結果顯示增加聚合物含量使SAFT 和熔體黏度增加而對黏性和剝落無大影響的預期傾向。調 配物4 - 3、4 - 4和4 - 5顯示增加黏著劑T g使聚合物含量恒定 保持40重量％之作用。結果顯示增加Tg減小黏性且增加剝 -23- 1248964 _ (19) 發明說明縝頁 落而對SAFT或熔體黏度無大影響之預期傾向。 表4 組合物，重量％ #4-1 #4-2 #4-3 #4-4 #4-5 CD聚合物#27 30.0 35.0 40.0 40.0 40.0 REGALITE R-91 46.0 44.0 42.1 45.2 48.1 DRAKEOL 34 24.0 21.0 17.9 14.8 11.9 計算Tg，°C 14 14 -14 -10 7 性能a) 滾球黏性，釐米 8 10 13 14 >30 波利坎探針黏性，千克 0.70 0.58 0.54 0.59 0.40 環黏性，盘司/英寸 55 64 65 79 69 1800剝落，每線性英寸磅數 1.8 1.7 1.7 2.1 2.5 SAFT對Mylaf(rxl，.5千克），1 77 80 88 83 84 熔體黏度@177°C，帕·秒(Pa.s) 8 15 29 35 39
a)將PSA作爲熱熔體混合，溶於甲苯，並以2密耳乾燥厚 度洗鑄於1密耳Mylar上。 實例5
實例5顯示聚合物結構對黏著劑性能之影響。樣品5-1和 5-2顯示聚合物分子量之影響。結果顯示，較高分子量聚 合物得到較高SAFT及較高熔體黏度。樣品#5-2至#5-6顯示 聚合物中三嵌段/二嵌段比之影響。CD聚合物#28爲一種 AB二嵌段共聚物。結果顯示熔體黏度隨聚合物中三嵌段 的分數降低而降低。如樣品#5-6中那樣，接著劑性能到聚 合物二嵌段含量接近1 00重量％才發生戲劇性變化。此樣 品的内聚強度低得使固定能力樣品内聚失敗。 -24- 1248964 (20) 發明說明縝頁 表5 組合物，重量％ #5-1 #5-2 #5-3 #5-4 #5-5 #5-6 CD聚合物#25 40 CD聚合物#27 40 30 20 10 CD聚合物#28 10 20 30 40 REGALITE R-91 45 45 45 45 45 45 DRAKEOL 34 15 15 15 15 15 15 性能a) 滾球黏性，釐米 7 15 7 7 6 3 波利坎探針黏性，千克 0.47 0.30 0.39 0.35 0.38 0.97 環黏性，盎司/英寸 34 75 77 76 72 110 180〇剝落，每線性英寸磅數 2.4 1.9 2.3 2.1 2.2 2.1 HP對鋼(1x1，2千克），小時 >100 >100 >100 >100 >100 13c SAFT對Mylar (Id _，.5千克），°C 94 82 85 82 76 70 熔體黏度@177°C，帕.秒 80 36 24 13 8 3 a)將PS A作爲熱熔體混合，溶於曱苯，並以2密耳乾燥厚 度洗鑄於1密耳Mylar上。 實例6 實例6顯示，以溶劑爲基礎的含一般SIS聚合物SIS #1與 習知經氫化SBC，SEBS #1或與新穎CD聚合物#25之摻合物 之黏著劑之相穩定性。SIS #1具有約245,000之GPC峰分子 量、約13,000之聚苯乙烯末端嵌段及約44%之偶合效率。 SEBS #1爲一種具有約10,000之聚苯乙烯末端嵌段及約 50,000之經氫化聚丁二烯中間嵌段之選擇氫化SBS嵌段共 聚物。將表6中顯示的所有七種黏著劑以40重量％溶於曱 苯，然後使含黏著劑溶液的瓶不受干擾保持，以檢驗其是 否相分離。結果顯示，以單獨聚合物爲基礎的全部三種樣 品#6_1、6-4和#6-7均開始澄清，且在不受干擾保持時保 持不變。以SIS #1和SEBS #1之摻合物爲基礎的樣品#6-2 -25- 1248964 - (21) I發明說明績頁 和#6-3開始混濁，且在持續成兩個澄清層時相分離。凝膠 滲透色譜（GPC)分析顯示，上澄清層含SEBS #1，下澄清層 含SIS #1。與之對照，以SIS #1和CD聚合物#25之摻合物 爲基礎的樣品#6-4和#6-5開始澄清，甚至在不受干擾保持 後仍保持澄清。接近溶液#6-4上部所取樣品和接近溶液 #6-4底部所取樣品之GPC分析顯示，兩種樣品均具有該量 兩種聚合物，表明摻合物實際相穩定。Piccotac 1095主要 爲由混合單體組成且具有95°C軟化點之脂系樹脂。 表6 調配物，重量％ #6-1 #6-2 #6-3 #6-4 #6-5 #6-6 #6-7 SIS#1 35.0 23.4 11.7 23.4 11.7 SEBS#1 11.7 23.4 35.0 CD聚合物#25 11.7 23.4 35.0 PICCOTAC 1095 50.0 50.0 50.0 50.0 50.0 50.0 50.0 SHELLFLEX 371 15.0 15.0 15.0 15.0 15.0 15.0 15.0 黏著劑溶液 開始 澄清 混濁 混濁 澄清 澄清 澄清 澄清 3天後 澄清 分離 分離 澄清 澄清 澄清 澄清 實例7 實例7顯示以SIS #1與CD聚合物#25之摻合物爲基礎的黏 著劑之性能。將以單獨聚合物爲基礎的黏著劑#7-1和#7-4 作爲熱熔性黏著劑在西格馬（sigma)葉片式混合機中混合， 然後以40重量％溶於甲苯。將溶液#7-1和#7-4以2/1或1/2比 摻合，得到溶液#7-2和#7-3。所有四種溶液澄清且相穩定 。將它們以2密耳乾燥厚度澆鑄於1密耳聚酯襯材上。並檢 測其黏著性能。對樣品#7-1和7-2檢測的結果顯示，至少 1/3 SIS #1可用CD聚合物#25代替，且黏性降低很小。可 -26- 發明說明績頁 1248964 ㈤ 期望在樣品#7-2中存在經氫化聚合物給予該黏著劑比#7-1 更佳的穩定性。對樣品#7-3和7-4檢測的結果顯示，由SIS #1代替1/3 CD聚合物#25給予有意義黏性改良，同時保持 南固定能力。 表7 調配物，重量％ #7-1 #7-2 #7-3 #7-4 SIS#1 35.0 CD聚合物#25 35.0 PICCOTAC 1095 45.0 45.0 SHELLFLEX 371 20.0 20.0 摻合物#7-1 67 33 摻合物#7-4 33 67 黏著劑性能 滾球黏性，釐米 2 4 15 >30 環黏性，盎司/英寸 89 83 60 49 180°剝落，每線性英寸磅數 6.1 3.5 2.2 2.0 HP對鋼，1x1，2千克，小時 19 30 >80 >80 SAFT，1x1，.5千克，°C 75 80 88 97 實例8 聚合物SIS #1具有44%之效率，意味其包含44% SIS三嵌 段聚合物及56%未經偶合的SI二嵌段共聚物。可由以44/56 比摻合爲100%三嵌段聚合物的CD聚合物#27和爲100%二嵌段 聚合物的CD聚合物#28模擬具有44%偶合效率的CD聚合物 。表8顯示以SIS #1之摻合物爲基礎之黏著劑之性能，且該 黏著劑具有44/56比的CD聚合物#27和CD聚合物#28之摻合 物。黏著劑#8-1以SIS #1爲基礎，黏著劑#8-4以CD聚合物 #27和#28之摻合物爲基礎。在黏著劑#8-2中，1/3的SIS聚合 物已由CD聚合物取代，而在黏著劑#8-3中，1/3的CD聚合 -27- 1248964 發明說明績頁 (23) 物已由SIS聚合物取代。結果顯示，用CD聚合物代替黏著劑 #8_1中1/3的SIS聚合物只導致黏性很小降低，而用SIS聚合 物代替1/3 CD聚合物卻得到有意義黏性改良。 爲檢測此四種黏著劑的加熱老化特性，將50克各熱熔性 黏著劑樣品放入一個100毫升燒杯中，用鋁箱蓋上燒杯，並 在177 c烘相中使接著劑老化。所有四種黏著劑在加熱老化 期間均澄清且無相分離，說明SIS #1和。〇聚合物#27和 具有優良相容性。在供箱中於未經老化、8小時、24小時和 48小日守後測定黏著劑炼體黏度。對黏著劑料」的結果顯示 ’ SIS聚合物由加_熱老化不良降解，在烘箱老化⑽時後只 保持6/。其初始黏度。對黏著劑#8_4的結果顯示，聚合物 具有優Ml定性，錢箱老化48小時後保持83%其初始黏度 。對黏著劑#8-2的、结果顯*，用⑶聚合物代替1/3的sis聚 口物減小黏度損失率’由此改良黏著劑的加熱老化穩定性。 表8 調配物，重量％ SIS#1 CD聚合物#27 CD聚合物#28 REGALITE R91 DRAKEOL 34 黏荖劑性能a) 滾球黏性，釐米 環黏性，盘司/英寸 180°剝落，每線性英寸傍數 HP對鋼，1x1，2千克，小時 SAFT，1x1，.5千克，。c 、 手指黏性 #8-1 35.0 45.0 20.0 #8-2 23.3 5.2 6.4 45.0 20.0 #8-3 11.7 10.5 12.8 45.0 20.0 #8-4 15.8 19.3 45.0 20.0 1.5 95 1.8 >100 85 極佳 1.8 81 1.5 >100 77 極佳 2.7 53 2.0 >100 76 很佳 5.5 47 2.1 >100 77 佳 -28- 1248964 _ (24) 發明說明縝頁 搲艚黏唐@177°C，帕•秒 初始 8460 6540 5200 6140 @177°C 8小時後 5020 4620 4740 5360 @177°C 24小時後 2700 2040 4320 5460 @177°C 48小時後 520 1540 3020 5080 遂體黏度保持，_% 初始 100 100 100 100 @177°C 8小時後 59 71 91 87 @177〇C 24小時後 32 31 83 89 @177°C 48小時後 6 24 58 83 a)將黏著劑作爲熱熔體混合，溶於甲苯，以1.8密耳乾燥 厚度澆鑄於2密耳Mylar上。 實例义 - 實例9比較習知經氫化SBC、SEBS #2和CD聚合物#26在 一種烴溶劑甲苯與VOC免除溶劑對-氯三氟甲基苯（PCBTF) [作爲KESSCHEM 100自凱斯勒化學公司購得（Kessler Chemical)]或與乙酸第三丁酯（tBAc)(預期不久成爲v〇C免 除的溶劑）之混合物中的溶解性。SEBS #2爲一種具有約 7,〇〇〇之聚苯乙烯末端嵌段及約65,000之經氫化聚丁二烯中 間嵌段之經選擇性氫化SBS嵌段共聚物。結果顯示，如預 期那樣，兩種聚合物均易溶於甲苯，因爲甲苯爲兩種聚合 物的聚苯乙烯末端嵌段和橡膠中間嵌段二者的優良溶劑。 然而，由於政府對VOC的限制，使用烴溶劑受嚴格限制。 表9中結果顯示，在用PCBTF代替曱苯時，黏度增加，但 聚合物仍溶於含多達80% PCBTF之摻合物。儘管如此， SEBS #2不溶於100% PCBTF，因爲PCBTF不爲橡膠鏈段的 優良溶劑。與之對照，PCBTF爲CD聚合物#26之橡膠嵌段 -29- 1248964 _ (25) 發明說明績頁 的優良溶劑，所以溶於完全V 0 C免除溶劑。 表9中結果顯示，SEBS #2溶於甲苯與含多達60重量°/〇 tBAc之tBAc之摻合物。具有80% tBAc之掺合物爲一種澄 清膠凝，而具有100% tBAC之溶劑極性太過，以致不能溶 解SEBS #2之橡膠嵌段。與之對照，如果有必要滿足VOC 限制，CD聚合物#26將溶於100% tBAc。然而，含20重量°/〇 甲苯和80重量％ tBAc之溶劑摻合物爲一種較佳溶劑，因爲 其給予CD聚合物#26之溶液低得多的黏度。 表9 溶劑摻合物，重量％ 黏度a) ，厘泊 甲苯 PCBTF SEBS #2 CD聚合物#26 100 0 500 160 80 20 750 - 60 40 1110 - 40 60 2070 530 20 80 5120 960 0 100 澄清凝膠 1980 溶劑摻合物，重量％ 黏度a) ，厘泊 甲苯 t-BAc SEBS #2 CD聚合物#26 100 0 500 160 80 20 600 - 60 40 1210 _ 40 60 12900 280 20 80 澄清 450 0 100 不溶 9300 a)布魯克·費爾德（Brookfield)黏度@25 °C@ 20%聚合物 ，溶於溶劑摻合物。 -30-

Claims (1)

124勒純2542號專利申請案 中文申請專利範圍替換本(94年8月） 拾、申請專利範圍 i•-種黏著劑組合物，丨包括1〇〇重量份至少一種具有單 烯基芳烴和共軛二稀之經控制分佈嵌段之經氫化欲段共 聚物25至300重量份之至少一種增黏性樹脂，以及〇至 200重里伤之增里油，其中該經氫化嵌段共聚物具有至 少一聚合物嵌段A和至少一聚合物嵌段B，且其中在 氫化之前，各A嵌段獨立爲單烯基芳烴同聚物嵌段，且 各B嵌奴獨立爲至少一共軛二烯和至少一單烯基芳烴之 經控制分佈共聚物嵌段；（b·)在氯化後，已減少〇至㈣ 之芳烴雙鍵及至少90%之共軛二烯雙鍵；（c)各a嵌段具 有3,〇〇〇和60,000間之數量平均分子量，各6嵌段具有 3〇,〇〇〇和300，_間之數量平均分子量；（d)各⑽段包括 與A嵌段相鄰的富含共輛二稀單位<末端區域及一或多 個與A不相鄰的虽含單稀基芳烴單位之區域；…）經氮化 嵌段共聚物中的單烯基芳烴之總量係自2〇至8〇重量〇/〇 ; 且（f·)各B嵌段中的單烯基芳烴之重量百分比係介於…和 75〇/❶之間，嵌段共聚物的一般構型較佳爲A-B、A-B-A、 (Α-Β)η、（Α-Β)η·Α、（A-B-A)nX 或（A-B)nX ;其中 11爲 2 至 30之整數，且X爲一偶合劑殘基，本發明之黏著劑組合 物包括熱熔性黏著劑、感壓黏著劑、以溶劑爲主之黏著 劑及類似物。 2·根據申請專利範圍第i項之黏著劑組合物，其中該單烯 基芳烴爲苯乙烯，且該共軛二烯係選自異戊二烯及丁二 烯。 83487-940802.doc 申請專利範圍續頁 1248964 3.根據中請專利範圍第1或2項之黏著劑組合物，其中該共 軛一烯爲丁二烯，且其中該嵌段]5中2〇至8〇莫耳％之經縮 合丁二烯單位具有12-構型。 4·根據申請專利範圍第丨項之黏著劑組合物，其中該嵌段b 之苯乙烯嵌段度係小於4〇莫耳％，該苯乙烯喪段度指數 係定義爲在聚合物鏈上具有兩個苯乙烯相鄰體之嵌段B 中的苯乙烯單位之比例。 5 ·根據申請專利範圍第丨項之黏著劑組合物，其中該各b嵌 段中的苯乙烯之重量百分比係介於1〇%和3〇%之間，而 各嵌段B之苯乙烯嵌段度指數係小於丨〇。 6 ·根據申請專利範圍第1項之黏著劑組合物，其中該經氫 化嵌段共聚物爲一 ΑΒΑ、（A-B)n、（A-B)nA或 段共聚物，其中該n爲2至3〇之整數，χ爲偶合劑殘基， 該嵌段共聚物具有40,000至140,000之總分子量，且其中 各Β嵌段具有1 〇和3 0重量％間之苯乙烯。 7.根據申請專利範圍第1項之黏著劑組合物，其中該增黏 劑树脂係選自由C5烴樹脂、經氫化c5煙樹脂、經苯乙稀 化的C5樹脂、Cs/C9樹脂、經苯乙烯化的萜烯樹脂、經完 全氫化或部分氫化的C9烴樹脂、松香酯、松香衍生物及 其混合物所組成之群組及/或選自由苯并吱喃·印樹脂、 聚茚樹脂、聚（曱基茚）樹脂、聚苯乙烯樹脂、乙烯基甲 苯-α-甲基苯乙烯樹脂、α-甲基苯乙烯樹脂和聚伸苯基醚 及其混合物所組成之群組。 8·根據申請專利範圍第1項之黏著劑組合物，其包括1〇〇重 83487-940802.doc -2- 申請專利範圍續頁 1248964 量份之至少一種該經氫化嵌段共聚物、25至3 00重量份 之相容性苯乙烯/異戊二烯未經氫化嵌段共聚物、50至 500重量份之增黏性樹脂以及0至200重量份之聚合物增 量油。 83487-940802.doc
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