TW200838965A

TW200838965A - Adhesive composition, preparation method thereof and laminate using the adhesive composition

Info

Publication number: TW200838965A
Application number: TW096146688A
Authority: TW
Inventors: Masashi Koide; Hiroyuki Kobayashi
Original assignee: Toyo Ink Mfg Co
Priority date: 2006-12-08
Filing date: 2007-12-07
Publication date: 2008-10-01
Also published as: JP5267129B2; TWI410470B; WO2008069298A1; JPWO2008069298A1

Abstract

The present invention provides an adhesive composition, the preparation method thereof and a laminate using the adhesive composition, the composition being possible to form an adhesive layer which is excellent in initial tack, adherence with adherend (substrate), thermal resistance, humid-thermal resistance and transparency, and possible to be used suitably as a pressure sensitive adhesive. The adhesive composition contains a polyester resin (D) having a polyester main chain (I) and plural side chains branched from the polyester main chain (I), and a cross-linking agent (E) being able to cross-link with the polyester resin (D). The plural side chains have a first side chain (II) having a function group selected from the group consisting of a hydroxyl group and a carboxyl group, and a second side chain (II') without hydroxyl group. The occupation rate of said plural side chins in the molecule of polyester resin (D), in average value and by weight, is 5 to 80%. When said cross-linking agent (E) is reactable with the hydroxyl group, the hydroxyl group value of the polyester resin (D) is under 50 mg KOH/g; while the cross-linking agent (E) is reactable with the carboxyl group, the hydroxyl group value of the polyester resin (D) is under 100 mg KOH/g, the acid value is under 50 mg KOH/g. The adhesive composition is produced by using the polyester resin (D) which is obtained by way of the preparation process in which the following steps are carried out: forming reaction of polyester main chain which has plural hydroxyl groups coming out through ring-opening polyaddition of divalent acid (a-l) and compound (a-2) having, two cyclic ether groups; forming reaction of side chain by way of ring-opening addition of cyclic ester compound (b) to the hydroxyl group of polyester main chain; and sealing reaction of hydroxyl group by way of the sealing compound (c).

Description

200838965 九、發明說明：【發明所屬之技術領域】本發明係關於以聚酯樹脂作為主體之接著劑組成物、其衣造方法、及使用該接著劑纽成物所製造之積層體；尤其係關於與各種被著體之接著性、耐熱性、耐濕熱性及透月〖生&優兴且在光學構件之積層方面可適合作為感壓接著劑使用的接著劑組成物、其製造方法、以及使用於各種光學裝置等之製造方面利用接著劑組成物的積層體。 •【先前技術】近年來，由於電子學的飛躍進步，液晶顯示器（LCD)、電漿顯示器（PDF)、背投影顯示器（Rpj)、EL顯示器、發光 -極體頒不器等各種平面顯示器（FpD)係以作為顯示裝置 :八用於廣泛範圍之領域。此等卿，不僅是如同個人電月自之,、、、頁不裔或液晶電視般固定於屋内來使用，亦可如汽車導航用顯=等搭載於料肋移動狀態來使用。 _ ;匕等’、、員示衣置，一般係使用因應用途之各種薄膜，用 ^ 外界光源而來之反射的抗反射薄膜、或是 (防止頭不裝置之表面受損冑的保護薄膜（protect film) η 、只為有偏光薄膜或相位差薄膜（卩1^86也£;^1^11(^ 設置觸不僅是利用作為顯示裝置，亦可在其表面又’寻胰、抗反射薄膜或ITO蒸鍍樹脂薄膜等。 319793 6 200838965 如此之薄膜，係經由感壓接著劑黏貼於被著體上而使用於頒不I置。顯示裝置所使用之感壓接著劑，由於首先要求其透明性優異，故—般係使用以丙烯酸系樹腊作為主劑的感壓接著劑。然而，在上述之各種薄膜中，偏光薄膜係呈現以三乙酸纖維素系或環稀㈣之保護薄膜將聚乙烯之兩面失住而成的3層結構。因此，於偏光薄膜，因為各層之材枓之特性，而產生由伴隨著溫度或濕度的變化之馨伸縮所造成的顯著的尺寸變化。另外，近年來，從有效利用光的觀點來看，尋求藉由光學構件與被著體之折射率差所致之界面反射的抑制。9已 =於2層之界面之折射率差為大，則產生全反射之入射 :小，且光之有效湘度降低，故在光學構件之接著處 © ’使用.具有光學構件之折射率與被著體之折射率的間折射率的感M接著劑來形成接著劑層係為有利。拳 ^而’使用以往之丙烯酸系樹腊的接著劑層的折射率例如由if/相對於此，形成光學構件之材料之折射率，七…〜為1,52左右、甲基丙埽酸系樹脂時為1.51左 154左右、聚對酞酸乙二醋（PET)系樹 "為1.60左右，故兩者之折射率差為大。此外，例如，山將由玻璃所成之光學構件、與由甲基丙埽酸系亦益法成之光學構件進行接著時，丌…、法&传兩者之中間之折射率。所以，為了將偏光薄膜使用丙烯酸系感壓接著劑黏貼 319793 7 200838965 於液晶單元用的玻璃構件i，必須抑制偏光薄膜本身之尺寸變化、或更加提高接著劑層之折射率。、可藉由使感㈣著劑層本身變硬、或是使接著強度辦大，而使尺寸變化比較小、或是使尺寸變化抑制為較^ 間。此外，可藉由使用含有芳香環之單體、或 — 族化合物或含有硫原子之化合物或無機化合物，：：率提高某種程度。n 曰曰曰曰 ’隨著近年來液晶面板之大晝面化，偏光薄膜之馨尺寸亦大型化’且偏光薄膜之熱變形量亦變得增大。因此，當使用以社之感壓接著劑時，殘留於接著劑層之黏貼時之應力未被充分緩和，接著劑層無法充分追隨偏光薄膜之术曲。因此，以大型液晶面板暴露於高溫或高濕度之結果ς 引起偏光薄膜之變色或透明性降低、偏光薄膜從液。單兀之玻璃基板剝離，造成應力集中於偏光薄膜而使液面板產生漏光、或是產生揮發性氣體等問題。鲁 3外’液晶面板歷經長期使用之㈣，偏光薄膜亦產生尺寸變化，而其應力蓄積於接著劑層。應力持續蓄積於接著劑層，則偏光薄膜與液晶單元用玻璃構件之間的力分布變得不均勻。然後，在長期間之使用中，應力特別集中於偏光薄膜之周緣部，結果，液晶元件之周緣部變得比中央更亮或更暗，或是在液晶元件表面產生顏色不均、白點。此外，經將偏光薄膜等貼附於液晶單元用之玻璃面而成的積層體的檢查成品步驟中，對於有捲入積層時之空氣 319793 8 200838965 〆粉塵者，將偏光薄膜等剝離而重新貼上新的偏光薄膜等。，而’黏貼後的積層體，—般而言，為了提高接著性而在高温下保管時間後再檢查，因此，在那段期間中，不僅疋剝離強度變高而難以剝取偏光薄膜等，再剥離性降低而使得在剝離後產生殘留黏糊。如上所述，對於用以使偏光薄膜積層於液晶單元用玻璃構件的感麼接著劑，係要求具有良好之光學特性（透明性）、耐熱性及耐濕熱性、良好之應力緩和性、折射率之斤籲制性、再剝離性等。對於用以將相位差薄膜或各_矛: 之覆蓋膜予以積層的感壓接著劑，亦要求同樣之性能。騎此㈣種要求，從以前到現在，已提案有: 樣之感壓接著劑。例如，關於含有丙稀酸系樹脂與交聯: 之感壓接著劑的發明，係揭示於下述文獻1至4。 / 具體而言，依據下述文獻i，已知一種感壓接著气，其係由以烧基碳數為(甲基）丙稀酸之燒基酉旨ς 暑主成分的丙烯酸系樹脂所成者’並且，該感壓接著劑含有15重量％以下之重量平均分子量1〇萬以下之樹分、且含有10重量。以上之重量平均分子量1〇〇萬以^之聚合物成分的丙烯酸系樹脂所成者。另外’在下述文獻2.中，記載_種偏光板用感壓接著劑，其係由重量平均分子量為100萬以上之高分子量、丙烯酸系共聚物100重量份、重量平均分子量為3萬以ζ 之低分子量（曱基）丙烯酸系共聚物20至200重量份、以多官能性化合物0.005至5重量份所成者。刀 319793 9 200838965 ^再者，在下述文獻3中，提案一種偏光薄膜用感壓接著劑，其係由具有反應性官能基之重量平均分子量1〇〇萬至200萬之高分子量丙烯酸系樹脂、玻璃轉移溫度幻為 01至一8(TC之重量平均分子量3萬至1〇萬之低分子量丙烯酸系樹脂、以及具有可與該等形成交聯結構之官能基的多官能性化合物所成者。此外，依據下述文獻4, 6知一種以丙稀酸系共聚物作為成分且折射率經調控的感壓接著劑，其中，該丙烯酸系共聚物係以含有芳香環之單體作為共聚合成分，且該含有芳香環之單體成分的共聚合比率為全單體成分的^至 90重量％〇 r料，在下述文獻5中，記载—種折射率經調控的感壓接者劑，其係於丙烯酸系感壓接著齊]4〇至％重量％中含有增黏劑樹脂（tackifier resin) 1O i 6G重量％並可射率的感塵接著劑。藉由將上述之丙烯㈣樹脂作為錢船可抑制接著層之發泡或偏光板從液晶單元的浮㈣離。】 I由於热法吸收、緩和因偏光板之尺寸變化而造成之應力，且應力集中於偏光板之周緣部，班μ 緣部與中央部之明亮度不同，：二:^ 表面產生顏色不均、白點之門題決在液晶顯剛 s ，問碭。再者，為了調整接著南丨 ::二::、:：该=5系樹脂中必須大量地與芳香族成刀/、來口或此合，故接者性之透明，、著(tack)之咖產生少量的浮起_容 319793 10 200838965 在高溫下或高濕度下保管一定時間，則亦有著色、或是接著物性與折射率之平衡受損而使液晶顯示裝置中之圖像對比度及可視性降低等問題。在感壓接著劑中，除了含有丙烯酸系樹脂與交聯劑的丙烯酸系感壓接著劑以外，亦有併用丙烯酸系樹脂與聚酯樹脂或聚胺酯樹脂（polyurethane resin)者。例如’依據下述文獻6 ’已知一種感壓接著劑，其係將玻璃轉移溫度（T g)為一 6 0至一 5 °C之黏彈性樹脂與玻璃 _轉移溫度（Tg)為一 51：以下之聚胺酯系樹脂等彈性樹脂混合而成。另外，在下述文獻7中，記載一種感壓接著劑，其含有：丙烯酸系樹脂100重量份、含胺基之聚胺酯系樹脂1〇至5 0重量份。再者，在下述文獻8中·，揭示一種感壓接著劑，其含有·丙烯酸系樹脂、以及含羥基之聚胺酯系樹脂。藝此外’在下述文獻9中，提案一種感壓接著劑，其含有：丙烯酸系樹脂、以及聚己内酯等聚酯系樹脂。如此混合複數種樹脂而得到的感壓接著劑，一般係認為能栢互彌補各樹脂之缺點而提高與被著體之接著性、或提升折射率等，改善各種性能。但是，實際上，丙烯酸系樹脂與聚酯樹脂或聚胺酯樹脂的相溶性差，若對於丙烯酸系樹脂只混合少量之聚酯樹脂或聚胺酯樹脂，並不損害到透明性，但若混合大量之聚酯樹脂或聚胺酯樹脂，則造成感壓接著劑本身之白化或分離。用以將偏光薄膜等黏貼於 π 319793 200838965 液晶單元用之玻璃上的感壓接著劑，由於要求極古之透性，故若使用如前述之相溶性差之感壓接著劑來將偏光^ 膜等黏貼於液晶單元用之玻璃上，則有在接著劑層產生= 分離或搖動等問題。目另方面，在下述文獻1 0中，揭示一種感壓接著劑，其係由二聚酸（dimer acid)與30莫耳％以上之在侧鏈^有烷基之二醇成分的共聚合聚酯樹脂所構成，且其玻璃轉移溫度（Tg)係在一 60至0°C之範圍。 τ夕 _ 又’在下述文獻11中，記載一種感壓接著劑，其含有 =下列者所合成之重量平均分子量丨萬以上之聚酯以聚石厌酸酯二醇作為必須的二元醇成分、以碳數2至之脂肪族或脂環族之烴基當作分子骨架之二羧酸作為必須的酸成分。、在下述文獻12中’.揚示一種感壓接著劑，其含有：在主鏈具有聚内酯（polylact〇ne)結構且重分、量 •萬以上之生物分解性聚醋。刀千里為】依據下述文獻13，已知一種感屢接著劑，其係由下述成者·在側鏈具有甲基之二醇與叛酸之g旨以聚異氰酸醋予以連結之單元係經重覆、且Tg為—狀以下的脂肪族聚酯。口沈使用此等聚醋系樹脂的感壓接著劑而言，―般認為 :丙烯I系樹脂的缺點，尤其是可提升耐熱性或耐濕 2士笠然而，實際上，其初期黏著性（tack)太低、或沒有凝 ’：缺乏作為感壓接著劑所需要之機能。另外，由於 12 319793 200838965 相ί性係不充^，故當使用於偏光薄膜或相位差薄艇等先學薄膜時，在黏著層會產生相分離或摇動、突出: ，况。同時，因為此等狀況，而不僅引起發泡或偏斜等現象、’亦會造成黏貼後之剝離強度過度上升、使偏光薄膜等難以剝離，並且在剝離後會殘留黏糊。又，由於再剥離性久不充足故不適於作為用以黏貼偏光薄膜或相位差薄膜等光學薄膜的感壓接著劑。 ^ ' 方面關於^^酯糸樹脂組成物，例如有下述文獻 14至16，在文獻14中記載一種改質聚酯樹脂組成物，其具有於線狀聚酯樹脂之侧鏈將内酯類予以開環加成結構。 "口在文獻15中，揭示一種含有羥基之聚酯掛脂的製造方法，其特徵為將内酯開環加成於藉由使二環氧丙基化合物與二羧酸化合物之聚加成反應所生成之化合物之2級羥基。 _ 在文獻16中，揭示一種内酯接枝共聚物的製造方法，其特徵為將内酯系單體開環加成於藉由使羧酸化合物反應於聚合物中之環氧丙基所產生的羥基。再者’依據下述文獻17，已知一後含有多羧酸樹脂之樹月旨組成物，其係籍由使分子中至少具有2個以上環氡丙基之環氧丙基化合物與多元羧酸的反應物，與多元性羧酸或其酸酐進行反應而獲得。在下述文獻18中，記載一種含有不飽和基之樹脂，其係、藉由使環氧樹脂與含有不飽和基之羧酸或其酸酐的反應 13 319793 200838965 物’與多元羧酸或其酸酐進行反應而獲得。另外，下述文獻19中，揭示一種接著劑樹脂組成物，其含有··玻璃轉移溫度（Tg)為45至80°C之聚酯樹脂、環氧丙基樹脂、以及未封端（bl〇ck free)之異氰酸酯。此外，依據下述文獻20，已知一種接著劑用樹脂組成物，其係以下述者作為主成分··藉由使分子末端具有羥基及/或羧基之聚酯樹脂、環氧丙基樹脂、以及二異氰酸酯化合物進行反應而獲得的樹脂。此等聚酯系樹脂，由於對廣泛範圍之被著體具有優異之接著性，且具有耐藥品性等之耐久性，故作為塗料用之黏結劑（binder)樹脂或熱熔型接著劑而使用於各種領域中然而，一般而言，此等由於樹脂之熔融溫度或熔融黏度為高，或是難以溶解於低沸點溶劑中，或是在調配交聯之適用期（pot Hfe)短，故在塗裝時或接著時之作業性不良；另外，由於樹脂之玻璃轉移溫度（Tg)高，且缺‘初，4著f生（tack)等，故若將熔融或溶解於溶劑之聚醋系樹脂予以塗佈在㈣體並冷卻，則有缺乏對於被著體之沾濕 ^传7"，且再剝離性為不充足，故不適合作為感壓接者劑。文獻1 文獻2 文獻3 文獻4 曰本特開平01-066283號公報曰本特開平10_279907號公報曰本特開2002-121521號公報曰本特開2003-013029號公報 319793 14 200838965 文獻5 :日本特開2002-014225號公報文獻6:日本特開2003-073646號公報文獻7:日本特開2004-002827號公報文獻8 :日本特開2004-083648號公報文獻9 :日本特開2002-053835號公報文獻10:日本特開平04-328186號公報文獻11:日本特開平09-263749號公報文獻12 :日本特開平11-158452號公報 _ 文獻13 :日本特開平11-021340號公報文獻14:日本特開平06-025395號公報文獻15:日本特開平08-165337號公報文獻16 :日本特開平09-077855號公報文獻17 :日本特開2003-107694號公報文獻18:日本特開2005-352472號公報文獻19:日本特開平08_199147號公報文獻20:曰本特開平09-208654號公報 # 【發明内容】本發明之課題係提供一種接著劑組成物、其製造方法及使用接著劑組成物之積層體，該接著劑組成物可形成初期黏著性（tack)、與被著體（亦即基材）之密著性、耐熱性、耐濕熱性及透明性皆優異的接著劑層，且該接著劑組成物可適合使用作為感壓接著劑。依據本發明之一態樣，可提供一種接著劑組成物，其含有：聚酯樹脂（D)，其為具有聚酯主鏈⑴與從聚酯主鏈（I) 15 319793 200838965 分支之複數侧鏈者，前述複數侧鏈含有具選自羥基及羧基所成組群之官能基的第i侧鏈（11)、以及不具有經基的第^ 侧鏈（π’），且前述複數側鏈在前述聚酯樹脂（D)之分子中所占有的比率，依據重量比之平均值為5至8〇% ;以及可與聚酯樹脂（D)交聯的交聯劑（E);其中，當前述交聯劑（e)對於經基為可反應時，前述聚酯樹脂（D)之羥基價為 5+OmgKOH/g以下；當前述交聯劑（E)對於羧基為可反應 %，丽述聚酯樹脂（D)之羥基價為1〇〇mgK〇H/g以下，酸籲價為50mgKOH/g以下。、依據本發明之一態樣，提供一種積層體，其具有：光學構件、以及積層於前述光學構件之前述接著劑組成物之層。再者，液晶單元用構件，係可為光學構件、前述接著劑組成物之層、以及液晶單元用玻璃構件所積層的積層體。依據本發明之一怨樣，提供一種接著劑組成物之製造 _方法’其具有調製聚酯樹脂（D)之調製步驟，其中，該聚酯树脂①）具有聚酯主鏈⑴、與從聚酯主鏈⑴分支之第工側鏈（II)及第2側鏈（ΙΓ)，前述第！側鏈（11)具有選自羥基及鲮基所成組群之官能基，且前述第2侧鏈（11，)具有藉由前述封閉化合物（c)而封閉羥基之結構；其中，前述調製步驟係進行下列反應·藉由二元酸（^丨）與具有2個環狀醚基之化合物(a-2)的開環加成聚合之具有複數羥基的聚酯主鏈的形成反應；藉由環狀酯化合物（1))對於前述聚酯主鏈之羥基的開環加成的側鏈形成反應；以及藉由封閉化合物（0的 319793 16 200838965 羥基封閉反應。在上述製造方法中，可在上述封閉反應前先進行上求側鏈形成反應，亦可在上述側鏈形成反應前先進行上述= 閉反應。、【實施方式】 I要將硬化性㈣旨使麟為錢接著劑，則必須使經硬化之樹脂形成有具備不因加壓而崩解之程度的形狀保持力(亦即適田之堅固度)之層，同時必須對被著體具有親和 # ^以使树月曰層表面可表現黏著性（tack)。_於此點，與丙烯酸系聚合物之主鏈相比’聚酯之主鏈係因酯基(尤其是羰基鍵結）之極性，所以對於玻璃基板等被著體具有親和性: f潤性或黏著性，同_羰基鍵結之剛性，所形成之樹脂 i之耐久性及形狀保持性變高，故基本上聚g旨可說是有用於作為接著劑素材。另外，亦認為藉由將原料之酸成分及/ 或酵成分因應需要而變更，則可更加將分極性、親水性或 φ親油性、柔軟性或堅硬性、硬度、耐久性等賦予於聚醋分 :。當為了構成如光學組件等精密機器製品而使用感屡接者，，必須使因熱或濕度而對製品造成之影響盡可能地更加減J ’因此’期望具有例如使接著後之樹脂層因熱或 f度所產生之變化能適度地抑制住被著體之變化，同時並 2追隨該被著體之變化等的適應性優良的樹脂特性。為了 =成此等要求，將具有從㈣旨主鏈分支之錄側鏈之分子、、·。構的聚_㈣作為錢接著劑之硬化性樹脂主成分，係為有效。雖然硬化性樹腊分子之侧鏈係經由與調配於樹 319793 17 200838965 月旨中之交聯劑進行反應並形成交聯而使樹脂硬化，但為了使經硬化之樹脂以作為感愿接著劑而表現黏著性⑽叫，則必須使經硬化之樹脂既不失去柔軟性、又具有適當之堅固度„，故交聯係限制於側鏈之一部分。未經交聯之側鍵會因與鄰近之聚酯分子之主鏈或側鏈的親和性，而使分子彼此適度地互相束缚，限制分子間的相對移動，同時並以某種程度地將歪斜予以吸收、缓和。亦即，未交聯之側鍵係且有使經硬化之樹脂層對於從外界來之壓力等能具彈性地作鲁用而提高形狀保持性的機能。因此，以備較多的有某種程度以上長度的柔軟性侧鏈為:：= 此等侧鏈可為鄰接且規律性地並列的狀態中，由於可能因侧鏈之配向而產生結晶化，故以在側鍵間具有適度間隔的分子結構為較佳。如上述般具有在分子間產生適度束缚之側鏈的聚酯，係可藉由對於在聚酯主鏈上結合有官能基之聚醋分子進行 _加成反應並將分支側鏈導入官能基而生成。具體而言，例如藉由一羧酸（a_ 1)與二環狀醚化合物（心2)之開環加成聚合而調製出具有2級羥基作為分支用官能基的聚酯（c)，並於該聚酯（C)使酸酐、内酯等環狀酯等進行開環加成，藉此而在聚酯主鏈上經由酯鍵（ester b〇nd)而形成結合有開環結構的分支侧鏈。藉由如此之開環加成反應所生成的加成型聚酯的侧鏈，係在末端具有羧基或經基，經由此官能基而可與父聯劑反應。具有酯鍵的侧鏈，不僅是聚酯分子間的束‘，即使因魏基鍵結而增強與被著體之親和性，亦可 18 319793 200838965 ==1::::持性:且表現醋主鏈分支的側鏈為較佳，=般以適當間隔從聚狀_之開環加成而形成側鏈時:形成羊環並且，若使開環加成多工^ τ.成“人“之側鏈，開環結構單元之㈣料i (mUltlplexing)，财環狀醋之鏈。此係從接古2 介著醋基之聚醋鍵而構成側對於被著體之親和性及鄰接分子間之親和性的觀點來看，係為較佳，又，葬从子門之使對鄰接分子之袁盥9 ，鏈之伸長，亦較佳係以具有相：；;= 易。為了使侧鏈有效地作用，形成手法係以環狀· 此，在本發明…二感遂接著以基本雜之形㈣躲及㈣性， 2 :醋Γ分支之側鏈的加成型聚醋樹綱。前述從聚鏈分支之側鏈’係具有環狀⑽)之開環結利用封閉劑（C)的側鏈。. 』％利側鏈在前述之聚醋樹月旨（D)之分子中所占有的比率鍵占有率>，係從使用之原料（二缓酸、二環狀㈣合物、環狀酉旨及封閉化合物）之重量以平均值大致估算出的比去 [=ι〇〇%χ(環狀酯（b)之重量+封閉化合物⑷之^量原^ 總重量1。藉由使此側鏈占有率依據重量比之平均值為5 δ〇%，較佳為7至7〇%，更佳為10至0〇%，則可以較佳之 319793 19 200838965 、、有側鏈，並且經硬化之樹脂對於外部來之屡力且 =生地仙、形㈣持性為高，料為錢發揮良好之機能。 X诨父聯之側鏈與未交聯之侧鏈的比率（或是交聯度）係可 i豕调配於聚自旨樹脂中之交聯劑之比率而調於樹脂中之官能基與作為感嶋劑冰心 ^關和性’而發現藉由聚g旨樹紅側鏈的改良而可改接著劑之特性。具體而言，#側鏈具有祕作為官錘T未交聯而殘留之經基、或未形成側鏈而殘存在 H基的量為多’則經硬化之樹脂之耐濕熱性 έ士人纟在本發明中’係以在侧鏈及/或聚醋主鏈上所經基經封閉化合物⑷所封閉並使經基價成為預定里m_B(D)作為硬化性樹脂之主成分，並將交聯雜）调配於此硬化.性樹脂中而構成接著劑組成物。將聚醋 &物（C)結構之輕基的側鍵。封閉化合物⑷不僅是藉羥基之封閉而結合著非官r 的化合物’亦可為藉封閉而結合著具有經基以外： ::::基的化合物，在此情況下’若生成之官能基可使則亦可與能和該官能基反應之交聯劑組合而構成接者劑組成物。亦即，交聯劑⑻之種類，係可依酯樹脂⑼所含有之官能基而適當地變更。就封閉化勿 Μ ’可列舉如我化劑⑽獅。nagent)、酸酐及口異氛(酸）酉曰化合物，而酸酐及異氰酸醋化合物係不具有羥基之化合 319793 20 200838965 、田使用&酐作為封閉化合物⑷時，係以生成敌基代替封閉羥基，此係可利用於交聯。關於經硬化之樹脂之耐濕熱性的改善，所容許之聚酉旨樹脂⑼之㈣價係依據接著劑組成物所調配之交聯劑⑻ =致分為2種情形。當所調配之交聯劑係與㈣進行反 ,'才來i曰树知（D)之羥基價若為5〇mgK〇H/g以下，則可濕熱性之降低。當㈣與絲以作為聚酯樹脂⑼ =此基而共存’亚且所調配之交聯劑（£)係與羧基進行反 ^ ’聚醋樹脂（D)之經基價為l〇〇mgKOH/g町。此理案’但可推測是縣用之交聯劑具有將經基配位 =〜之性質’並因交聯劑之影響而抑雜基與外部之作用’藉此而可容許直至1〇〇mgK〇H/g左右。上述之封閉，而在聚酯樹脂（D)之聚酯主鏈所分且古之側鏈上存在有經交聯之側鍵、以及未經交聯且不使$基（崎閉）之側鏈。亦即，本發明之聚醋樹脂⑼為〇封nΓ又^之g旎基的側鏈（第一側鏈）與不具羥基 (:封閉）的侧鏈（第二侧鏈）之複數㈣子，全顧之數目之1观上含有伴隨著2 ^基鍵，）之環狀s旨的_結構，又以规以上為更佳。有閉之型態’針對第1側鏈及第2侧鏈，可分別有含結構者與不含有者。又，若聚醋主鏈上所子凝隹經基係殘留，則因經基之結合而容易使聚醋分不。▲狀接著劑組成物之塗佈加工會變得困難，故、口此，在本發明中，採用適當之調製方法，以使 319793 21 200838965 原料之聚酯主鏈上所直接結合之羥基實質上全都與環狀酯 (b)或封閉化合物（c)進行反應而令殘留經基成為極少量。基於此見解，全側鏈數係設為相當於主鏈聚酯之2級羥基數者，主鏈聚酯之2級羥基數係相當於原料之環狀醚基數及具有環狀醚之2級羥基數的合計。所以，含有環狀酯之開環結構的側鏈數的比率，係可以主鏈聚酯之2級羥基數作為基準而估算求得。以下，針對聚酯樹脂（D)之封閉型態加以說明。 _ 依據經基之封閉型態，而可將聚酯樹脂（D)之分子結構大致區別為以下之型態。第1型態係一種聚酯樹脂（D1)，其中，對聚S旨主鏈實質上全部所結合之羥基藉由開環加成而形成側鏈（第1側鏈），並對所形成之侧鏈之至少一部分施行藉由封閉化合物（c)而進行之羥基封閉，以轉換成第2 側鏈。第·2型態係一種聚酯樹脂（D2)，其中，將聚酯主鏈所結合之羥基之一部分經封閉化合物（c)所封閉並形成第2 側鏈，對於殘餘部分之羥基則藉由開環加成而形成侧鏈（第 1侧鏈）。第2型態之聚酯樹脂（D2)係更進一步藉由將第1 侧鏈之一部分之羥基予以封閉，而成為具有2種類的第2 側鏈的第3型態之聚酯樹脂（D3)。從可補整第2型態之聚酯樹脂（D2)之羥基量的觀點來看，第3型態係為有用。另外，當使用酸酐作為封閉化合物（c)時，藉由環狀酯之開環加成而將所形成之侧鏈之全部末端羥基加以封閉，且可將羧基利用於交聯。但是，若可與交聯劑反應之官能基為多，則因交聯反應之昂進而使接著劑組成物之適用期變短、且 22 319793 200838965 塗佈加工性降低，故當以酸酐封閉時，係以在經基價為 5〇mgKOH/g以下之範圍使經基殘存之方式進行封閉，並租合與經基反應之交聯劑，或者是再使封閉缓基之化合物進行作用，使酸價降低，並使用幾基用之交聯劑。為了使接著劑組成物之適用期及塗饰加工性良好、並使交聯劑可有效地作用，當交聯劑是與羥基進行反應時，聚酯樹脂⑴) 之經基價係以0· i至5〇mgK〇H/g左右為佳，並且當交聯劑是與羧基進行反應時，酸價係以〇1至5〇mgK〇H/g左右為鲁佳，更佳之範圍係各為0.5至3〇mgK〇H/g左右，故無論是在上述任一種封閉狀態，皆能因應所調配之交聯劑之類型’而調整反應條件或原料之調配比率等，以使聚酯樹脂之酸價及羥基價成為適當值。亦即，當交聯劑（£)對於羥基具反應性時，以使聚酯樹脂（D)之羥基價成為5〇mgK〇H/g 以下之方式適宜調整封閉化合物〇)及_其使用量；當交聯劑 (E)對於羧基具反應性時，以使聚酯樹脂⑴)之羥基價成為鲁100mgKOH/g以下且酸價成為5〇mgK〇H/g以下之方式適宜調整封閉化合物（C)及其使用量。聚酯樹脂(D)之調整方法係因應封閉狀態而經適當選擇。在第1至第3型態中之任一型態，聚酯樹脂（D)皆係藉由聚酯主鏈之形成反應、侧鏈形成反應、以及羥基之封閉反應的3個反應而生成。具體而言，聚酯主鏈之形成反應係為二羧酸與二環狀it化合物（a-2)之聚加成反應。二叛酸（a-1)係具有2個羧基之二元酸化合物（以下，有時亦稱為二元酸（a-1))，而 23 319793 200838965 =她合物(a-2邮二官能化合物。雖“可使用三官能以上官物，但二官能化合物在分子設計二 =張’同時生成直接結合於聚酯主鏈⑴之經基:因 θ= ::使經基增加’而形成具有複數經基之聚酯主鏈：開产力反應係為環狀轉)對於聚醋主鏈之經基的 /加成，由於生成側鏈從聚g旨主鏈（1)分支之加成型聚曰亚且側鏈具有在聚g|主鏈（1)經由酯鍵而結至少一個=醋⑻之開環結構單元與末端之經基，故可作為料 :乂如之官能基的第1側鏈(11)而進行作用。此開環加心若環狀醋⑻相對於經基之比率 :，故藉由精研該調製步驟’即可提供側鏈之形成= 隹的製造方法。文卞更之Flifi封閉反應，係為封閉化合物⑷對於藉環狀醋⑻ =開壤加歧形成顯之㈣或㈣域絲形成具有使經基經封閉化合物⑷所封閉之結構側鍵’亦即’形成不具有誠之第2側鏈(11，）。當封閉化合物⑷為酸酐時，形成於末端具有缓基之側鍵，此側鍵亦可使用作為第1側鏈（Π)。由於比起聚酯主鏈之經基，侧鏈之經基具更高之反應性，故在包含聚酉旨主鏈所直^士人之輕基^封閉的第2及第3實施型態中，係以在側鏈^ f反應則施行羥基之封閉反應為較佳。又，在第丨實施型悲中’以令聚醋主鏈所直接結合之經基殘留之方式使少量 319793 24 200838965 之％狀醋⑻反應，若使過量之封閉化合物⑷對於 (b)之開環加成而形成之側鏈之經基進行反應，可―§曰 =化合物⑷而將聚醋主鏈所直接結合之殘存經::: 以下’分別針對第！至第3封閉型態中之聚酯之調製方法的詳細内容加以說明。 —曰 ^第1封閉型態中’較佳為使聚®旨主鏈所直接結合之搜基實質上全部藉由環狀醋（b)而形成側鏈，且側鍵之: ♦分係經封閉化合物(c)所封閉。嶋成型聚醋樹脂。，可依據如下所述之三階段型、擬似二階段型、以及型的三種製造方法而獲得。白又三階段型的製造方法，係為藉由下述步驟⑴至⑺的三步驟而階段性地獲得加成型聚酯樹脂（D1)的方法。步驟⑴：藉由二元酸㈤）與二環㈣化合物（亦即且有2個環狀_基之化合物）㈣的開環加成聚合，而獲得具陕有使源自二元酸（a_l)與二環㈣化合物卜2)之各结構單元經賴㈣互地錢連結的聚酯主鏈（1)、以及直接連結於該聚酯主鏈（I)的複數羥基之聚酯（3)的步驟。㈣⑺：對於上述聚醋之聚醋主鏈(1)所直接結合的經基使環錢⑻進行_加歧應，並藉由形成以環狀醋⑻ 之開環結構單元所構成之側鏈（11)而獲得加錢聚醋前驅物（C1)的步驟。步驟（3):使加成型聚醋前驅物（C1)之侧鍵（ιι)之末端經基之-部分與封閉化合物(c)進行反應，藉由形成不具有 319793 25 200838965 羥基（經封閉）之侧鏈（Π’）而減少聚酯樹脂（di)之經基價的步驟。此三階段製造方法，由於可藉由步驟（2)、（3)前後之測定而確認聚合度或羥基價的變化，故在反應條件之調節上為有利。然而，在步驟（2)中，因為使環狀酯（b)加成之羥基，會在步驟（1)最終生成之聚酯中以密集之狀態存在於聚酯中，故生成氫鍵，步驟（1)最終生成之聚酯即變成極高黏度並塊狀化，妨礙步驟（2)之加成反應之效率。就此點而言二以後述之擬似二階段型以及二階段型的製造方法為較有一擬似二階段型的製造方法，係為藉由下述步驟（4)至（6) 的三步驟而階段性地獲得加成型聚酯樹脂（d丨）的方法。步驟（4):藉由例如相當於5〇至7〇%(重量換算）左右之量的二元酸㈤)及二環狀，匕合物(a-2)的開環加成聚合而形成聚酯主鏈（I)之一部分，以獲得酸價為5gK〇H/g左右之聚酯的步驟；其中，此聚酯具有使源自二元酸0_丨）與二環狀趟化合物㈣之各結構單元經由醋鍵而交互地重複連、D之來知主鏈（I )、以及直接連結於該聚酯主鏈（f)之複數羥基，就此點而言，係與步驟（1)之聚酯相同。 y驟（5).於上述聚酯主鏈（Γ)添加環狀酯（b)，使環狀酉旨(b)於聚醋主鏈（1，）之經基進行開環加成而形成側鏈 Π)，R時藉由絲之：元酸㈣舆：環狀㈣合物（a_2) :加成聚合而使聚酉旨主鏈(Γ)伸張並完成主鏈之形成，而獲件加成型聚g旨前驅物（C1)的步驟。 319793 26 200838965 ,步驟（6).使加成型聚酯前驅物（ci)之側鏈（II)之末端經基之-部分與封閉化合物⑷進行反應，獲得具備不且_ 基（經封閉）之側鏈(11，）的聚醋樹脂（D1)的步驟。八亦可使上述步驟（4)、（5)成為連續作業步驟。此擬似二 iw又型的製造方法’由於步驟⑷中之聚§旨主鏈形成係於進 t中，且步驟（5)中的環狀醋⑻相對於聚醋主鍵（1，）之經基量的比率變高，故能提升環狀酉旨（b)之開環加成之反應^ 而:易开少成侧鏈。因此，比起前述之三階段型方法，此擬 •似一階段型的方法較易於減少殘留在加成型聚酯前驅物 (C1)之水80主鏈上之未反應經基。然而，相反地，由於在乂驟（5)中所生成之聚g旨主鏈（1，）之經基係亦有助於形成氣鍵，故即使與上述三階段型方法相比為不易變成高黏度: 但仍以後述之二階段型方法為更佳。 - 段型的製造方法’係為藉由下述步驟⑺至⑻的二步驟而階段性地獲得加成型聚醋樹脂（m)的方法。一 • 步驟（7).將二元酸（a·1)與二環狀醚化合物（a-2)與環狀酯（b)同時反應，使聚加成及開環加成並行，並且使源自二 το，〇1)與二環狀醚化合物（a_2)之各结構單元經由醋鍵而交互地重複連結的聚醋主鏈⑴、與以經由醋鍵結合於聚酉旨主鍵(1)之環狀酉旨⑻之開環結構單元所構成的側鏈（11)並订形成，以獲得加成型聚酯前驅物（C1)的步驟。步驟（8):使加成型聚酯前驅物（C1)之側鏈（π)之末端羥基之-部分與封閉化合物（c)進行反應，獲得具備不具經基(經封閉）之側鏈（11，)的聚酯樹脂①丨）的步驟。 319793 27 200838965 、此二階段型的製造方法，由於步驟⑺中之聚醋主鍵形成，側鏈加成係同時進行，環狀醋（b)相對☆聚醋主鍵之經基量的比率會變得極高，故能更加提升環狀醋⑻之開環加成之反應效率。因此，比起前述之擬似二階段型方法，此二階段型方法更易於減少殘留在加成型聚酯前驅物(c”之聚酯主鏈上之未反應羥基。另外，由於實質上不發生因聚醋主鏈所直接結合之經基所導致的聚醋分子之結合及塊狀化，故反應系係易於均一化，且反應效率極佳。亦即上述二種製造方法之差異，係為當獲得具有聚酯主鏈（I)與侧鏈（11)的前驅物加成型聚酯之形成開始時之聚酷主鍵(1)之形成度係形成完中、未形成中的任-者，且環狀醋⑻之開環加成之反應效率為不同。 . ,、其次，針對第2封閉型態中之加成型聚醋谢脂（D2)的製造方法加以說明。 f.第2封閉型態之加成型聚酯樹脂（D2)中，聚醋主鍵⑴ 所直接結合之經基之一部分係經封閉化合物⑷所封閉，而形成不具有經基（經封閉）之第2側鏈（11，），並且在殘餘部分之經基加成含有環狀醋（b)之開環結構單元的第i侧鏈 (Π)。第2侧鏈(11 ’）不含有環狀醋（b)之開環結構單元。於加 ί型^旨樹脂_之製造中，在進行環狀醋⑻之開環加成别，先使聚酉旨主鏈⑴所直接結合之經基與封閉化合物⑷ 進，反應。之所以先施行封閉反應，係由於藉環狀酉旨⑻ 形成側鏈後的殘餘經基易因侧鏈而阻礙反應，且可在封閉 319793 28 200838965 反應後殘留之故。第2封閉型態之加成型聚酯樹脂(D2)之製造方法亦盥第^閉型態同樣地，可使用依據藉封閉化合物⑷開始形成第2側鏈(II )B$之聚醋主鏈形成度而不同的三種製造方法來獲得。一-P6 4又型的製造方法’係為藉由下述步驟⑼至⑴）的三步驟而階段性地獲得加成型聚酯樹脂（D2)的方法。、步驟（9)·藉由二元酸⑹）與二環狀喊化合物㈤）的聚成而獲得具有使源自二元酸（a巧）與二環狀謎化合物 (a-2)之各結構單元經由酯鍵而交互地重複連結的聚醋主鏈（）以及直接連結於該聚醋主鍵⑴的複數經基之聚& 的步驟。 ^ 步驟（10):對於聚酯主鏈（1)所直接結合之羥基之一邛錢封閉化合物⑷進行反應，形成不具有.經基(經封閉): 弟2側鏈（11，），並減少經基數，而獲得加成 (C2)的步驟。 J柳 …卿1):對於形成有第2側鏈(ΙΓ)之加成型聚醋前驅物（C2)之殘留經基使環肤詩)仃應’藉由形成含有環 ^曰(）心衣結構單元及末端經基的第1侧鏈(11)，而獲侍加成型聚酯樹脂（D2)的步驟。 y尤第2封閉型怨之情形而言，在步主=)上直接W基之—部分與_^‘^ 而減少羥基，a牛·μ 汉應句)第1側鍵之形成比率係依據 y驟（10)之封閉程度而受到控制。. 319793 29 200838965 擬,二階段型的製造方法，係為藉由下述步驟⑼至 ()的一步，驟而階段性地獲得加成型聚酯樹脂⑽)的方法。旦步驟Π2):藉由例如相當於50至70%(重量換算)左右之里的—兀酉夂㈤）及二環狀騎化合物⑹）的開環加成聚。而开ν成水知主鏈⑴之_部分，以獲得酸價為左右^聚醋的步驟；其中，此聚酯具有使源自二元酸（a-l) /、+衣狀醚化合物（a_2)之各結構單元經由酯鍵而交互地 ♦重複連結的聚酯主鏈（1，）、以及直接結合於該㈣主鍵⑻ 之稷數羥基，就此點而言，係與步驟（9)之聚酯相同。取匕步驟（13):於上述聚酯主鏈（1，）添加封閉化合物，使 xkS日主鏈（I )之經基與封閉化合物反應而形成第2侧鏈 (π )同％藉由殘餘之二元酸（a-1)與二環狀醚化合物（心2) 之聚加成而使聚醋主鏈（Γ)伸張並完成主鏈之形成，而獲得加成型聚酯前驅物（C2)的步驟。 _ 步驟（14):對於加成型聚酯前驅物（C2)之殘留羥基使環狀酯（b)進行開環加成，形成含有環狀酯（b)之開環結構單 70及末端羥基的第1侧鏈（II)，而獲得加成型聚酯樹脂（D2) 的步驟。亦可使上述步驟（12)、（13)成為連續作業步驟。此擬似二/階段型的製造方法，由於步驟（12)中之聚酯主鏈形成係進^中者，而步驟（13)中之聚酯主鏈（1，）之羥基量係比前述之二階段型製造方法為較少，故能使因聚酯主鏈所直接結合之羥基之結合所導致的聚酯塊狀化所造成的阻礙與封閉 319793 30 200838965 化合物（C)之反應的情形變少，環狀酯（b)對於加成型聚酯前驅物（C2)之開環加成之反應效率亦相對性地較佳。一 ^段型的製造方法，係為藉由下述步驟（15)至（16) 的一步驟而階段性地獲得加成型聚酯樹脂（D2)的方法。步驟（15) ·將二元酸（a-1)與二環狀醚化合物（a-2)與封閉化合物（c，）同時進行反應，使聚加成及封閉反應並^，，且使源自二元酸（&_υ與二環狀醚化合物（a_2)之各結構單元、:二由gg鍵而父互地重衩連結的聚酯主鏈⑴、與由將聚 •酉曰主鏈2)所直接結合之經基以封閉化合物(。，)封閉而成的結構的乐2侧鏈（11)並行形成，以獲得加成型聚酯前驅物 (C2)的步驟。步驟（16):對於加成型聚酯前驅物（C2)之殘留羥基使環狀醋⑻進行開環加成，而獲得具備含有環狀醋⑻之開環詰構单元及末端經基的第1側鏈(II)、以及不具有經基（經封閉)的第2側鏈(Π，）之加成型聚醋樹脂（D2)的步驟。 • Λ—階段型的製造方法，由，步驟（15)中之聚醋主鍵的形成與經基的封閉係同時進行，實質上不發生因聚醋主鍵所直接結合之經基所導致的聚酉旨分子之結合及塊狀化，故絲系係易於均-化，且非常容易進行反應。因此，比起料之擬似二階段型方法，此二階段型方法之係更佳。 (上述二種製造方法之差異，係為當獲得具有聚酯主鏈 I)與侧鏈(ΙΓ)的前驅物加成型聚酯（C2)時，在側鏈⑴，）的形成開始時之聚酯主_之形成度係形成完畢、形成中、 319793 200838965 未形成中的任—者。此時’為了防止封閉化合物（c，)所致之側鍵（II )之伸張比聚醋主鍵⑴之伸張變得更優先，封閉化合物（c，）必須為單官能化合物。反應中間體之塊狀化而導致的反應系均一性降低，由於大幅影響到反應效率，故關於此點是以擬似二階段型及二階段型的製造方法為較佳。另—方面，$ 了詳查生成之聚酯樹脂（D)之材料特性及各反應狀況，則以三階段型的製造方法為較適宜。因此，聚酯樹脂⑼的製造方法可因應需 _要而從上述製造方法中適當選擇。其-人，針對第3封閉型態之加成型聚酯樹脂（D3)的製造方法加以說明。 & 第3封閉型態之加成型聚醋樹脂（D 3 )，係經由下述步驟（17)所獲件.使第2封閉型態之加成型聚酯樹脂⑽）再二、封閉化σ物扣）進行反應，.而將加成型聚酯樹脂（D2)中的含有環錢（b)之開環結構單元的第.〗側鏈（π)之末端經基 _之-部份予以封閉的步驟（17)。亦即，第3封閉型態的製造方法’係具有第2封閉型態製造方法之三階段型、擬似一階段型或二階段型的任一步驟以及上述步驟（Η)。如此之加成型聚醋樹脂（D3〇，具有：使源自二元酸與—狀化合物fa-2)之久έ士接结-/一，么十 ^ ) σ、、、σ構早兀經由酯鍵而交互地重複連結的聚醋主鏈⑴、具有環狀醋（b)之開環結構單元及末端經基的第1側鏈（11)、聚醋主鏈（1)所直接結合之經基經封閉化合物⑷所封閉之側鏈及前述帛i側鏈⑻之末端經基經封閉化合物（c)所封閉之侧鏈的2種的第2侧鍵⑽。 319793 32 200838965 在上述第2及第3封閉狀態中，以使從之側鏈，亦即使聚酯*雜叮曰一曰王鍵刀支便水s日主鏈可具有之羥基數的约15% 含有環狀酯（b)之開璟έ士搂--A 上為樹職佳，更上:早7°的方式來調製加成型㈣更佺為側鏈之羥基總數之3〇%以環結構單元，此點孫丨、/叮士馬3有開為更佳。 ^係以可有效發揮源自環狀醋（b)之性質而合物(t)= = 3封閉狀態中，使用酸軒作為封閉化合對縣進行交聯反應之化合物作為交耳外劑（E) ’即可借妙封々々美之第1魏α、（ΙΓ)亦具有作為具官能土之罘1側鏈⑴的作用，就_美僧之_黜&‘十封閉。但是，此時，為了戒而S亦可完全地期或涂你士為了防止因交聯速度之昂進而使適用以;了口工性降低1必須將樹脂之酸價限制至預定值之封pi::之使用置受到限制。因此，藉由併用酸酐以外之封閉化合物（C)而應對。用之成型聚酿樹月旨（D1)、（D2)、（D3)的製造方法所用之各原料，於下述加以說明。來i日主鏈（I)之形成所使用的二元酸較低分子量（例接使用介人你r , 里90至500左右）之公知之二羧酸類生二，其包括如下述之各種二叛酸、其酸酐及衍中之任I:月曰肪無化合物、芳香族化合物及脂環式化合物就月曰肪族二叛酸而言’可列舉如乙二酸、丙二酸、丁一酉夂、己二酸、癸_辦氯順丁缔二酸、Git二酸、辛二酸、順丁婦二酸、汉丁烯一酸、十二烷二酸、庚二酸、檸康 319793 33 200838965 酸（citraconic acid)、片-缺，酸酐、順丁婦二酸了 =酸（itaconic acid)、丁二酐。又，亦可利用丁々，用此寻脂肪族二羧酸及其酸二，基丁二酸酐、丁其丁…特基丁二酸酐、2,2- 丁二酸酐、辛基丁二美=一酉文酐、己基酸酐等）、戊二酸醉夕…丄知基丁一酸酐、苯基丁二酐、24_-甲美成物（戍二酸酐、3_婦丙基戊二酸町Α4 一甲基戊二酸酐、2,4·二乙紅酸酐、己基戊二酸酐等） -夂_、丁基戊二針寺）順丁烯二酸酐之衍峰物〇田f 順丁烯二酸酐、2,3_ 町之何生物（2-甲基 _ f基順丁蝉二酸酐、丁其順丁降酸酐、戊基順丁稀二酸酐、己^丁/ 了基順丁沐二細二酸野、癸基順丁婦二 ^辛基順丁〇 ^ ^ 丁一知基順丁烯二酸軒、 ;ΓΛ稀二酸軒、苯基順丁埽二酸酐、2,3-二丁稀一 ^酐等）等酸酐衍生物。、酞：2芳5香族二賴而言’可列舉如鄰酞酸、異酞·酸、對酞酉^，5-:甲基魏酸、4,4_聯苯二㈣㈣1 奈二竣酸、降冰片烯二幾酸、二苯基甲烧_4,仏二羧二Ϊ基節滿二羧酸、酞酸酐、4_甲基酞酸酐等，可利用羧酸及其酸酐等。χ，亦可利用六氫駄酸軒 ’丁务（-甲基·六氫酞酸酐、4_甲基_六氫酞酸酐）、四氫敝酸酐之衍生物（1，2,3,6•四氫敌酸酐、3_甲基]，^ 酞，酐4-甲基_1，2,3,6-四氫酞酸酐、甲基丁烯基^ 四虱駄k哥等）等S太酸酐衍生物。丄γ，脂環族二羧酸而言，可列舉如二聚酸、六氳對酞酸、六氫異酞酸、六氳酞酸、四氫酞酸等，可利用此等脂環族 319793 34 200838965 二羧酸及其酸酐等。再者，可列舉如氯橋酸酐(chl〇rendic anhyddde)、海特酸酐（Het anhydride)、聯苯二羧酸酐、海米克酸酐阳如。 anhydnde)、内亞甲基·四氫酞酸酐、甲基_3,6_内亞 f基·1，2,3,6-四氫酞酸酐、1>2•環己燒二羧酸酐、卜環戍稀 ·?二羧酸酐、甲基環己烯二羧酸軒、认萘二鲮酸酐、八氫-1，3-二酮基_4,5-異苯并呋喃二羧酸酐等。此等低分子量二幾酸類化合物㈤」）可各自單獨或組合2種以上而作為二元酸（a·”使用。、另外，在本發明卜就二元酸⑹）而言，可使用比前述低分子量二羧酸類化合物（add)為更高分子量的二羧酸類化合物，該等例可列舉如下述者。、、例使前述之低分子量二缓酸類化合物小υ與後述之夕70私成/刀〇小α )在缓酸過量之條件下反應而獲得的每一分子平均具有約2個竣基的高分子量二緩酸 (a 12)’/吏後述之3官能以上之多致酸類化合物（&小点）二夕το醇成刀（a-1-α )在羧酸過量之條件下反應*獲得的母^刀：平均具有約2個羧基的高分子量二羧酸(a-1-3); 以及使前述之低分子量二致酸類化合物㈤巧）與後述之多兀胺成分（a小7)在緩酸過量之條件下反應而獲得可使用作為二元酸（a-Ι)的聚醯胺二羧酸（a_〗_4)等。上述高分子量二竣酸⑹士 &小3)之調製所使用的多讀，分（a_l·。），有數平均分子量：約5Q至獅之較低分子量之二元醇類（a-1· ry η 々各/ τ #八i α-i)、或數平均分子量：約5〇〇至 319793 35 200838965 50,0⑽之較高分子量之多元醇類(a-1-α-2)。以較低分子量之二元醇類（a-1 - α · 1)而言，可列舉例如乙二醇、丙二醇（propylene glycol)、二丙二醇、二乙二醇、三乙二醇、丁二醇、3_甲基义^戊二醇、2,4_二乙基q，％戊二醇、2-曱基l，8-辛二醇、3,3，-二經曱基庚烧、2-丁基 2-乙基-1，3-丙二醇、聚氧基乙二醇（加成莫耳數為1〇以下）、聚氧基丙二醇（加成莫耳數為1〇以下）、丙二醇 (propanediol)、i，3-丁二醇、1，4·丁二醇、1，5-戊二醇、工卜200838965 IX. The present invention relates to an adhesive composition mainly composed of a polyester resin, a method for producing the same, and a laminate produced by using the adhesive; An adhesive composition which can be suitably used as a pressure-sensitive adhesive as a pressure-sensitive adhesive for adhesion to various substrates, heat resistance, heat and humidity resistance, and vapor permeability, and a method for producing the same, and a method for producing the same, And a laminate using an adhesive composition for use in the manufacture of various optical devices and the like. • [Prior Art] In recent years, due to the rapid advancement of electronics, various flat panel displays such as liquid crystal display (LCD), plasma display (PDF), rear projection display (Rpj), EL display, and illuminator-polar amplifier ( FpD) is used as a display device: eight is used in a wide range of fields. This kind of clerk is not only used as a personal electric moon, but also a page or a LCD TV, and can be used in a moving state such as a car navigation display. _ ; 匕匕、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、 Protect film) η, only for polarized film or retardation film (卩1^86 also £;^1^11(^ The contact is not only used as a display device, but also on the surface of the 'pancreas, anti-reflection film Or ITO vapor-deposited resin film, etc. 319793 6 200838965 Such a film is applied to a subject via a pressure-sensitive adhesive, and is used for a pressure-sensitive adhesive. The pressure-sensitive adhesive used in the display device is first required to be transparent. It is excellent in the properties, so a pressure-sensitive adhesive using acrylic wax as a main agent is generally used. However, among the above various films, the polarizing film is formed by a protective film of cellulose triacetate or ring thin (iv). A three-layer structure in which both sides of ethylene are lost. Therefore, in the polarizing film, significant dimensional changes caused by the elastic expansion and contraction accompanying changes in temperature or humidity are caused by the characteristics of the material of each layer. From the viewpoint of efficient use of light, the suppression of interfacial reflection caused by the difference in refractive index between the optical member and the object is sought. 9 = The refractive index difference at the interface between the two layers is large, and the whole is generated. The incidence of reflection: small, and the effective degree of light is reduced, so at the end of the optical component © 'use. It is advantageous to form an adhesive layer system with an adhesive M having an intermediate refractive index between the refractive index of the optical member and the refractive index of the object. The refractive index of the adhesive layer using the conventional acrylic wax is, for example, from if/relative to the refractive index of the material of the optical member, and is about 1,52, and the methylpropionic acid system When the resin is 1. 51 left 154 or so, polyparaphenyl acid vinegar (PET) tree " is 1. Around 60, the difference in refractive index between the two is large. Further, for example, when the mountain is made of an optical member made of glass and an optical member made of a methacrylic acid-based method, the refractive index in the middle between the two is transmitted. Therefore, in order to bond the polarizing film with an acrylic pressure-sensitive adhesive 319793 7 200838965 to the glass member i for the liquid crystal cell, it is necessary to suppress the dimensional change of the polarizing film itself or to further increase the refractive index of the adhesive layer. The dimensional change can be made smaller or the dimensional change can be suppressed by making the sensing layer (4) the coating layer itself hard or the bonding strength being increased. Further, the ratio can be increased to some extent by using a monomer containing an aromatic ring, or a compound or a compound containing a sulfur atom or an inorganic compound. n 曰曰曰曰 ' With the recent increase in the thickness of the liquid crystal panel, the size of the polarizing film is also increased, and the amount of thermal deformation of the polarizing film is also increased. Therefore, when a pressure sensitive adhesive is used, the stress remaining in the adhesion of the adhesive layer is not sufficiently alleviated, and the adhesive layer cannot sufficiently follow the curvature of the polarizing film. Therefore, as a result of exposure of a large liquid crystal panel to high temperature or high humidity, discoloration or transparency of the polarizing film is lowered, and the polarizing film is liquid. The glass substrate of the single crucible is peeled off, causing problems such as stress concentration on the polarizing film and light leakage of the liquid panel or generation of volatile gas. The long-term use of the liquid crystal panel (4), the polarizing film also produces dimensional changes, and its stress accumulates in the adhesive layer. When the stress continues to accumulate in the subsequent layer, the force distribution between the polarizing film and the glass member for a liquid crystal cell becomes uneven. Then, during the long period of use, the stress is particularly concentrated on the peripheral portion of the polarizing film, and as a result, the peripheral portion of the liquid crystal element becomes brighter or darker than the center, or color unevenness and white spots are generated on the surface of the liquid crystal element. In addition, in the step of inspecting the laminated body in which the polarizing film or the like is attached to the glass surface of the liquid crystal cell, the polarizing film or the like is peeled off and re-applied to the air 319793 8 200838965 when the laminated film is entangled. A new polarizing film and the like. In addition, in the case of the adhesive layer, the laminate is inspected at a high temperature for the purpose of improving the adhesion, and therefore, the peeling strength is increased and the polarizing film is difficult to be peeled off during the period. The removability is lowered to cause residual stickiness after peeling. As described above, the adhesive for laminating the polarizing film on the glass member for a liquid crystal cell is required to have good optical properties (transparency), heat resistance and moist heat resistance, good stress relaxation, and refractive index. The jins are appealing, re-peeling, etc. The same performance is also required for the pressure-sensitive adhesive for laminating the retardation film or the cover film of each of the lenses. Riding this (four) requirements, from the past to the present, has been proposed: the kind of pressure-sensitive adhesive. For example, the invention of a pressure-sensitive adhesive containing an acrylic resin and crosslinking: is disclosed in the following documents 1 to 4. / Specifically, according to the following document i, a pressure-sensitive gas is known which is formed of an acrylic resin having a base of a carbon atom of (meth)acrylic acid Further, the pressure-sensitive adhesive contains 15% by weight or less of a tree having a weight average molecular weight of 10,000 or less and contains 10% by weight. The above acrylic resin having a weight average molecular weight of 10,000 to 10,000 is a polymer component. In addition, in the following document 2. In the above, a pressure-sensitive adhesive for a polarizing plate is used, which is a high molecular weight having a weight average molecular weight of 1,000,000 or more, 100 parts by weight of an acrylic copolymer, and a low molecular weight (fluorenyl group) having a weight average molecular weight of 30,000 or less. 20 to 200 parts by weight of the acrylic copolymer, with a polyfunctional compound. 005 to 5 parts by weight. Knife 319793 9 200838965 Further, in the following document 3, a pressure-sensitive adhesive for a polarizing film is proposed, which is a high molecular weight acrylic resin having a weight average molecular weight of from 1,000,000 to 2,000,000 having a reactive functional group. The glass transition temperature is imaginary from 01 to 8 (a low molecular weight acrylic resin having a weight average molecular weight of 30,000 to 10,000, and a polyfunctional compound having a functional group capable of forming a crosslinked structure. Further, according to the following documents 4 and 6, a pressure-sensitive adhesive having a refractive index controlled by an acrylic acid copolymer having a monomer containing an aromatic ring as a copolymerization component is known. And the copolymerization ratio of the monomer component containing the aromatic ring is from 2 to 90% by weight of the total monomer component, and in the following Document 5, a pressure-sensitive adhesive agent whose refractive index is regulated is described. It is a dust-sensitive adhesive containing a tackifier resin 1O i 6G wt% and a transmittance in an acrylic pressure-sensitive adhesive layer of 4% to % by weight. By using the above-mentioned propylene (tetra) resin as Money boat The foaming of the adhesive layer or the floating (four) separation of the polarizing plate from the liquid crystal cell can be suppressed.] I absorbs and relaxes the stress caused by the dimensional change of the polarizing plate due to thermal absorption, and the stress concentrates on the peripheral portion of the polarizing plate. The brightness of the ministry is different from that of the central part: 2:^ The surface is unevenly colored, and the white point is determined by the liquid crystal display. Ask again. In addition, in order to adjust, then Nanzhao::2::,:: In the =5 series resin, a large amount of aromatic knives must be formed into a knife, a mouth, or the like, so that the contact is transparent, and the (tack) coffee produces a small amount of floating _ 319793 10 200838965 at high temperatures or When stored under high humidity for a certain period of time, there is also a problem of coloring or a decrease in the balance between physical properties and refractive index, which causes image contrast and visibility in a liquid crystal display device. In the pressure-sensitive adhesive, in addition to acrylic acid In addition to the acrylic pressure-sensitive adhesive for the resin and the crosslinking agent, an acrylic resin, a polyester resin or a polyurethane resin may be used in combination. For example, a pressure-sensitive adhesive is known according to the following document 6 ' Its glass The viscoelastic resin having a transfer temperature (T g) of 60 to 5 ° C is mixed with an elastic resin such as a polyurethane resin having a glass transition temperature (Tg) of 51 or less. Further, in the following Document 7 A pressure-sensitive adhesive comprising 100 parts by weight of an acrylic resin and 1 to 50 parts by weight of an amine group-containing polyurethane resin. Further, in the following document 8, a pressure-sensitive adhesive is disclosed. It contains an acrylic resin and a hydroxyl group-containing polyurethane resin. In addition, in the following document 9, a pressure-sensitive adhesive is proposed which contains an acrylic resin and a polyester resin such as polycaprolactone. The pressure-sensitive adhesive obtained by mixing a plurality of kinds of resins is generally considered to be capable of compensating for the defects of the respective resins, improving the adhesion to the object, or increasing the refractive index, and improving various properties. However, in fact, the acrylic resin is inferior in compatibility with the polyester resin or the polyurethane resin, and if only a small amount of the polyester resin or the polyurethane resin is mixed with the acrylic resin, transparency is not impaired, but if a large amount of polyester is mixed The resin or polyurethane resin causes whitening or separation of the pressure-sensitive adhesive itself. A pressure-sensitive adhesive for adhering a polarizing film or the like to a glass for a liquid crystal cell of π 319793 200838965, since an extremely ancient permeability is required, if a pressure-sensitive adhesive having poor compatibility as described above is used, the polarizing film is used. When it is adhered to the glass for the liquid crystal cell, there is a problem that the adhesive layer is separated or shaken. On the other hand, in the following document 10, a pressure-sensitive adhesive is disclosed which is obtained by copolymerization of dimer acid with 30 mol% or more of a diol component having an alkyl group in a side chain. It is composed of an ester resin and its glass transition temperature (Tg) is in the range of 60 to 0 °C. In the following document 11, a pressure-sensitive adhesive containing a weight average molecular weight of 10,000 or more synthesized by the following is used as a necessary glycol component. A dicarboxylic acid having a carbon number of 2 to an aliphatic or alicyclic hydrocarbon group as a molecular skeleton is an essential acid component. , in the following document 12'. A pressure-sensitive adhesive comprising: a biodegradable polyester having a polylact〇ne structure in a main chain and having a weight fraction of 10,000 or more. According to the following document 13, a sensitizing adhesive is known which is composed of a diol having a methyl group in a side chain and a tickling acid which is linked by polyisocyanuric acid. The unit is an aliphatic polyester which is repeated and has a Tg of -. In the case of a pressure-sensitive adhesive using such a vinegar-based resin, it is generally considered that the propylene-based resin has a disadvantage, in particular, it can improve heat resistance or moisture resistance. However, in fact, its initial adhesion ( Tack) Too low, or no condensation': lacks the function required as a pressure-sensitive adhesive. In addition, since 12 319793 200838965 is not compatible, when used in a polarizing film or a phase difference thin boat, the film will be phase-separated or shaken and protruded in the adhesive layer. At the same time, due to such a situation, not only foaming or deflection, but also the peeling strength after the adhesion is excessively increased, the polarizing film or the like is hardly peeled off, and the adhesive remains after the peeling. Further, since the removability is insufficient, it is not suitable as a pressure-sensitive adhesive for adhering an optical film such as a polarizing film or a retardation film. In the aspect of the invention, there are, for example, the following documents 14 to 16, in which a modified polyester resin composition having a side chain of a linear polyester resin and a lactone is described. Open loop addition structure. " In the literature 15, a method for producing a polyester-containing grease containing a hydroxyl group is disclosed, which is characterized in that a lactone ring-opening addition is carried out by polyaddition of a diepoxypropyl compound and a dicarboxylic acid compound. The second-order hydroxyl group of the compound formed by the reaction. _ In Document 16, a method for producing a lactone graft copolymer is disclosed, which is characterized in that a lactone monomer is subjected to ring-opening addition to a glycidyl group obtained by reacting a carboxylic acid compound in a polymer. Hydroxyl group. Further, according to the following document 17, a composition of a polycarboxylic acid resin containing a polyvalent carboxylic acid resin and a polyvalent carboxy group having at least two cyclopropyl propyl groups in the molecule are known. The acid reactant is obtained by reacting with a polyvalent carboxylic acid or an anhydride thereof. In the following document 18, a resin containing an unsaturated group is described, which is carried out by reacting an epoxy resin with a carboxylic acid having an unsaturated group or an anhydride thereof 13 319 793 200838965 ' with a polycarboxylic acid or an anhydride thereof Obtained by reaction. Further, in the following document 19, an adhesive resin composition containing a polyester resin having a glass transition temperature (Tg) of 45 to 80 ° C, a epoxy propyl resin, and an uncapped (bl〇) is disclosed. Ck free) isocyanate. Further, according to the following document 20, a resin composition for an adhesive is known, which is characterized in that a polyester resin having a hydroxyl group and/or a carboxyl group at a molecular terminal, a epoxy propyl resin, or the like is used as a main component. And a resin obtained by reacting a diisocyanate compound. These polyester-based resins are excellent in adhesion to a wide range of substrates and have durability such as chemical resistance. Therefore, they are used as a binder resin or a hot-melt adhesive for coatings. However, in general, these are generally due to the fact that the melting temperature or melt viscosity of the resin is high, or it is difficult to dissolve in a low boiling point solvent, or the pot life of the blending crosslink is short. The workability at the time of coating or the next time is poor. In addition, since the glass transition temperature (Tg) of the resin is high, and there is a lack of 'initial, 4', etc., if it is melted or dissolved in a solvent, the vinegar is melted or dissolved in a solvent. When the resin is applied to the (four) body and cooled, there is a lack of wetness and adhesion to the object, and the re-peelability is insufficient, so it is not suitable as a pressure-sensitive adhesive. Document 1 Document 2 Document 3 Document 4 曰本特开平01-066283号曰本特开平10_279907号曰本本开开开开开开开开开开开开开开开开开开开开开开开开开开开开开开开开开开Japanese Laid-Open Patent Publication No. JP-A-2004-053826, No. JP-A-2004-053826 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem of the Invention] The object of the present invention is to provide an adhesive composition, a method for producing the same, and a laminate using an adhesive composition. The adhesive composition can form an initial adhesive layer (tack), an adhesive layer excellent in adhesion to the object (that is, a substrate), heat resistance, moist heat resistance, and transparency, and the adhesive agent The composition can be suitably used as a pressure-sensitive adhesive. According to an aspect of the present invention, there is provided an adhesive composition comprising: a polyester resin (D) having a polyester backbone (1) and a plurality of sides branched from a polyester backbone (I) 15 319793 200838965 In the chain, the plural side chain includes an i-side chain (11) having a functional group selected from a group consisting of a hydroxyl group and a carboxyl group, and a side chain (π') having no warp group, and the plurality of side chains The ratio of the ratio of the weight ratio of the polyester resin (D) to the average of 5 to 8 % by weight; and the crosslinking agent (E) crosslinkable with the polyester resin (D); When the aforementioned crosslinking agent (e) is reactive with a trans group, the hydroxyl value of the polyester resin (D) is 5+OmgKOH/g or less; when the crosslinking agent (E) is reactive with respect to a carboxyl group, Li The polyester resin (D) has a hydroxyl value of 1 〇〇 mg K 〇 H / g or less and an acid value of 50 mg KOH / g or less. According to an aspect of the invention, there is provided a laminated body comprising: an optical member; and a layer laminated on the adhesive composition of the optical member. Further, the member for a liquid crystal cell may be a laminate in which an optical member, a layer of the above-described adhesive composition, and a glass member for a liquid crystal cell are laminated. According to one of the complaints of the present invention, there is provided a method for producing an adhesive composition which has a preparation step of preparing a polyester resin (D), wherein the polyester resin 1) has a polyester backbone (1), and a polycondensation The first side chain (II) and the second side chain (ΙΓ) of the ester main chain (1) branch, the aforementioned! The side chain (11) has a functional group selected from the group consisting of a hydroxyl group and a thiol group, and the second side chain (11) has a structure in which a hydroxyl group is blocked by the blocking compound (c); wherein the aforementioned modulation step The following reaction is carried out by forming a polyester backbone having a plurality of hydroxyl groups by ring-opening addition polymerization of a dibasic acid (^) with a compound (a-2) having two cyclic ether groups; a cyclic ester compound (1)) for the side chain formation reaction of the ring-opening addition of the hydroxyl group of the aforementioned polyester main chain; and a hydroxyl group blocking reaction by blocking the compound (0937936 16 200838965. In the above manufacturing method, Before the blocking reaction, the side chain formation reaction may be performed first, or the above-mentioned = blocking reaction may be performed before the side chain formation reaction. [Embodiment] I must use the hardenability (4) to make the linum a money adhesive. The hardened resin is formed with a layer having a shape retaining force (that is, a firmness of the field) which does not disintegrate due to pressurization, and must have an affinity for the object to make the surface of the tree layer Can show tack (tack). _ at this point, Compared with the main chain of the acrylic polymer, the main chain of the polyester has an affinity for the substrate such as a glass substrate because of the polarity of the ester group (especially carbonyl bond): f-run or adhesion, the same as _ The rigidity of the carbonyl bond is high, and the durability and shape retention of the formed resin i are high. Therefore, it is basically used as an adhesive material. It is also considered that the acid component of the raw material and/or When the yeast ingredient is changed as needed, the polarity, hydrophilicity, φ lipophilicity, flexibility or hardness, hardness, durability, and the like can be further imparted to the polyester: when it is used to form a precision machine product such as an optical component. In the case of a sense of use, it is necessary to make the influence on the product by heat or humidity as much as possible. Therefore, it is desirable to have, for example, make the subsequent change of the resin layer due to heat or f degree moderately a resin property that is excellent in adaptability, such as a change in the shape of the object, and a change in the shape of the object, etc., in order to meet such requirements, a molecule having a side chain branched from the main chain of (4) ·.The formation of poly_ (four) It is effective as a main component of the curable resin for the money adhesive. Although the side chain of the curable wax molecule is hardened by reacting with a crosslinking agent formulated in the tree 319793 17 200838965, and forming a crosslink. However, in order for the hardened resin to exhibit adhesiveness as a resisting adhesive, it is necessary to make the hardened resin neither lose softness nor have appropriate firmness, so the connection is limited to one part of the side chain. The uncrosslinked side bonds will bind the molecules to each other moderately due to the affinity with the main chain or side chain of the adjacent polyester molecules, limiting the relative movement between molecules, and to some extent The skew is absorbed and moderated, that is, the unbonded side key has a function of making the hardened resin layer elastically repel the pressure from the outside to improve shape retention. Therefore, a plurality of flexible side chains having a certain length or more are prepared as follows::= These side chains may be adjacent and regularly juxtaposed, and may be crystallized due to the alignment of the side chains. Therefore, a molecular structure having a moderate interval between the side bonds is preferred. A polyester having a side chain which forms a moderate bond between molecules as described above can be obtained by performing an _addition reaction on a polyester molecule having a functional group bonded to a polyester main chain and introducing a branched side chain into a functional group. generate. Specifically, for example, a ring-opening addition polymerization of a monocarboxylic acid (a-1) and a dicyclic ether compound (heart 2) produces a polyester (c) having a secondary hydroxyl group as a branching functional group, and In the polyester (C), a cyclic ester such as an acid anhydride or a lactone is subjected to ring-opening addition, whereby a branch having an open-loop structure bonded thereto is formed on the polyester main chain via an ester bond. Side chain. The side chain of the addition type polyester produced by such a ring-opening addition reaction has a carboxyl group or a merido group at the terminal, through which the parent group can be reacted. The side chain having an ester bond is not only a bundle between the polyester molecules, but even if it is enhanced by affinity with the host due to the Wei group bonding, it can also be 18 319793 200838965 ==1::::holding: and the vinegar main The side chain of the chain branch is preferably, when the side chain is formed by the ring-opening addition of the poly-forms at appropriate intervals: the sheep ring is formed and the open-loop addition is multiplexed. The side chain of "human", the open-loop structural unit (4) material i (mUltlplexing), the chain of vinegar. This is based on the fact that the vinegar bond of the vinegar is formed by the vinegar-based vinegar bond, and the affinity between the affinities and the affinity between the adjacent molecules is preferred. The elongation of the chain adjacent to the molecule, 9 is also preferably with a phase:;; = easy. In order to make the side chain function effectively, the method is formed into a ring shape. In the present invention, the second feeling is followed by the basic shape (four) and the (four) sex, 2: the addition of the side chain of the vinegar branch to the shaped vinegar tree Outline. The above-mentioned side chain which has a ring (10) from the side chain of the branch of the polymer has a side chain of the blocking agent (C). . 』%% of the side chain in the above-mentioned vinegar tree (D) occupies the ratio of the ratio of key occupancy>, from the raw materials used (di-acid, bicyclic (tetra), cyclic And the weight of the blocking compound) is roughly estimated by the average value of [= 〇〇〇〇 χ χ (the weight of the cyclic ester (b) + the amount of the blocking compound (4) ^ total weight 1 by making this side chain The occupancy rate is 5 δ 〇 % based on the weight ratio, preferably 7 to 7 〇 %, more preferably 10 to 0 〇 %, and 319793 19 200838965, which has a side chain and a hardened resin. For the external comes from the force and = the birth of the immortal, the shape (four) is high, it is expected to play a good function of money. X 诨 father's side chain and uncrosslinked side chain ratio (or degree of cross-linking) It can be found that the functional group adjusted to the ratio of the crosslinking agent in the poly-resin resin and the functional group in the resin can be improved by the improvement of the side chain of the polyglycoside red. Specifically, the # side chain has a secret group which is left as a residue of the official hammer T, or a side chain which does not form a side chain, and the amount of the H group remains. 'The heat-resistant heat of the hardened resin is in the present invention' is blocked by the blocking compound (4) on the side chain and/or the polyester backbone, and the base price becomes a predetermined m_B. (D) as a main component of the curable resin, and blending the crosslinked impurities). The adhesive composition constitutes an adhesive composition. The side chain of the light base of the polyacetate & (C) structure. The blocking compound (4) is not only a compound which binds to the non-an official group by a hydroxyl group, but also a compound having a radical other than the radical: -:: group, in which case the functional group may be formed. Alternatively, a binder composition can be formed by combining with a crosslinking agent capable of reacting with the functional group. In other words, the type of the crosslinking agent (8) can be appropriately changed depending on the functional group contained in the ester resin (9). As for the closure of the 勿 Μ ‘ can be listed as a chemical (10) lion. Nagent), an acid anhydride and an alicyclic (acid) ruthenium compound, and the anhydride and isocyanate compound do not have a hydroxyl group 319793 20 200838965, when using & anhydride as a blocking compound (4), the formation of an enemy group The hydroxyl group is blocked, which can be utilized for crosslinking. Regarding the improvement of the heat and humidity resistance of the cured resin, the (four) price of the resin (9) which is tolerated is based on the crosslinking agent (8) formulated in the adhesive composition. When the cross-linking agent is reacted with (4), the hydrophilicity of the hydroxy group of (i) is less than 5 〇 mg K 〇 H / g. When (4) and silk are coexisted as a polyester resin (9) = this base, and the prepared cross-linking agent (£) is reacted with a carboxyl group. The base price of the polyester resin (D) is l〇〇mgKOH/ g town. This case is 'but it can be assumed that the cross-linking agent for the county has the property of the base-based coordination = ~ and the action of the anti-hybrid and the external due to the influence of the crosslinking agent' can be tolerated up to 1〇〇 mgK〇H/g or so. The above is closed, and there are cross-linked side bonds on the side chain of the polyester main chain of the polyester resin (D), and the side which is not crosslinked and does not make the base (salt) chain. That is, the polyester resin (9) of the present invention is a complex (fourth) of a side chain (first side chain) of a fluorene group and a side chain (second side chain) having no hydroxyl group (:blocking), The number of the whole number of views contains the _ structure of the ring s with the 2 ^ base bond, and the above is better. There is a closed type. For the first side chain and the second side chain, there may be a structure with or without a structure. Further, if the condensed condensate on the main chain of the vinegar remains through the base, the vinegar is easily separated by the combination of the bases. It is difficult to apply the composition of the ▲-like adhesive composition. Therefore, in the present invention, an appropriate preparation method is employed so that the hydroxyl group directly bonded to the polyester main chain of the raw material of 319793 21 200838965 is substantially All of them react with the cyclic ester (b) or the blocking compound (c) to make the residual radical into a very small amount. Based on this finding, the total number of side chains is set to be equivalent to the number of hydroxyl groups of the main chain polyester, and the number of hydroxyl groups of the main chain polyester is equivalent to the number of cyclic ether groups of the starting material and the level of the cyclic ether. The total number of hydroxyl groups. Therefore, the ratio of the number of side chains of the ring-opening structure containing a cyclic ester can be estimated by using the number of hydroxyl groups of the main chain polyester as a reference. Hereinafter, the closed form of the polyester resin (D) will be described. _ The molecular structure of the polyester resin (D) can be roughly distinguished into the following types depending on the closed form of the base group. The first type is a polyester resin (D1) in which a side chain (first side chain) is formed by ring-opening addition of a hydroxyl group substantially bonded to a main chain of a poly-S chain, and is formed. At least a portion of the side chain is subjected to a hydroxyl group blocking by blocking the compound (c) to be converted into a second side chain. The second type is a polyester resin (D2) in which a part of the hydroxyl group to which the polyester main chain is bonded is blocked by the blocking compound (c) and forms a second side chain, and the hydroxyl group of the residual portion is used. Open-loop addition forms a side chain (first side chain). The polyester resin (D2) of the second type is further encapsulated by a hydroxyl group of one of the first side chains to form a third type of polyester resin (D3) having two types of second side chains. . The third type is useful from the viewpoint of the amount of hydroxyl groups of the polyester resin (D2) of the second type. Further, when an acid anhydride is used as the blocking compound (c), all terminal hydroxyl groups of the formed side chain are blocked by ring-opening addition of a cyclic ester, and a carboxyl group can be used for crosslinking. However, if the number of functional groups which can be reacted with the crosslinking agent is large, the application period of the adhesive composition is shortened due to the crosslinking reaction, and the coating processability of 22 319793 200838965 is lowered, so when it is blocked with an acid anhydride And blocking the base residue in a range of a base price of 5 〇 mgKOH/g or less, and renting a crosslinking agent which reacts with the radical, or further blocking the compound of the slow base The acid value is lowered and a crosslinking agent for several bases is used. In order to make the pot life of the adhesive composition and the coating processability good, and to make the crosslinking agent work effectively, when the crosslinking agent reacts with the hydroxyl group, the base price of the polyester resin (1) is 0. Preferably, i to 5 〇 mg K 〇 H / g, and when the crosslinking agent is reacted with a carboxyl group, the acid value is about 1 to 5 〇 mg K 〇 H / g, and more preferably each is 0. 5 to 3 〇 mgK 〇 H / g, so whether in any of the above closed state, the reaction conditions or the ratio of the raw materials can be adjusted according to the type of the cross-linking agent to be adjusted, so that the polyester resin The acid value and the hydroxyl value are appropriate values. That is, when the crosslinking agent (£) is reactive with a hydroxyl group, the blocking compound 适宜) and the amount thereof are suitably adjusted so that the hydroxyl value of the polyester resin (D) becomes 5 〇 mg K 〇 H / g or less. When the crosslinking agent (E) is reactive with a carboxyl group, the blocking compound is appropriately adjusted so that the hydroxyl value of the polyester resin (1)) becomes less than 100 mgKOH/g and the acid value becomes 5 〇 mg K 〇 H / g or less. C) and its usage. The adjustment method of the polyester resin (D) is appropriately selected in accordance with the closed state. In any of the first to third types, the polyester resin (D) is produced by three reactions of a formation reaction of a polyester main chain, a side chain formation reaction, and a blocking reaction of a hydroxyl group. Specifically, the formation reaction of the polyester main chain is a polyaddition reaction of a dicarboxylic acid with a dicyclicit compound (a-2). Di-reactive acid (a-1) is a dibasic acid compound having two carboxyl groups (hereinafter, sometimes referred to as dibasic acid (a-1)), and 23 319793 200838965 = her compound (a-2 post two) a functional compound. Although "three or more functionalities can be used, the difunctional compound in the molecular design of two = Zhang" simultaneously forms a radical directly bonded to the polyester backbone (1): due to the addition of θ = :: to increase the radical Polyester backbone with complex warp groups: The reaction force is cyclically transferred.) For the base/addition of the polyester backbone, the addition of the side chain from the polyg-chain (1) Polypyrene and a side chain having a ring-opening structural unit and a terminal group at least one = vinegar (8) via an ester bond in the polyg| backbone (1), so that it can be used as a material: The side chain (11) acts. If the ring-opening is centered on the ratio of the cyclic vinegar (8) to the warp group, the method of producing the side chain = 隹 can be provided by lapping the preparation step. The Flifi blocking reaction of hydrazine is a blocking compound (4) for the formation of (4) or (4) domain filaments by cyclic vinegar (8) = open soil disintegration The structural side bond ''blocked by the compound (4)' is formed without the second side chain (11,). When the blocking compound (4) is an acid anhydride, a side bond having a slow group at the end is formed, and the side bond can also be used. As the first side chain (Π), since the side chain has a higher reactivity than the base of the polyester main chain, the light base is closed in the main chain containing the polyether In the second and third embodiments, it is preferred to carry out a blocking reaction of a hydroxyl group in the side chain reaction. Further, in the third embodiment, the type of the vinegar main chain is directly bonded. The basis of residual reaction is a small amount of 319793 24 200838965% vinegar (8) reaction, if the excess blocking compound (4) reacts with the side chain of the side chain formed by the ring-opening addition of (b), "§ 曰 = compound (4) The residuals directly combined with the main chain of the vinegar are::: The following details of the preparation method of the polyester in the third to the closed form are respectively described. - 曰^ in the first closed type' Preferably, the direct combination of the poly® main chain is substantially formed by the cyclic vinegar (b) to form a side chain. And the side key: ♦ The part is closed by the blocking compound (c). The 嶋-formed polyester resin can be obtained according to the three-stage type, the pseudo-two-stage type, and the three manufacturing methods described below. The three-stage type production method is a method of obtaining the addition-molded polyester resin (D1) stepwise by the three steps of the following steps (1) to (7). Step (1): by dibasic acid (5)) and bicyclic (four) a ring-opening addition polymerization of a compound (that is, a compound having two cyclic groups) (IV), and obtaining each structural unit derived from a dibasic acid (a-1) and a bicyclic (tetra) compound 2) A step of a polyester backbone (1) linked to each other by a money, and a polyester (3) of a plurality of hydroxyl groups directly bonded to the polyester backbone (I). (4) (7): The base group directly bonded to the above-mentioned polyester vinegar main chain (1) is subjected to _addition of the ring money (8), and by forming a side chain composed of an open-loop structural unit of the cyclic vinegar (8) ( 11) The step of obtaining a rich vinegar precursor (C1). Step (3): reacting the terminal of the side bond (1) of the addition-formed polyacetic acid precursor (C1) with the blocking compound (c) through the base portion, by forming a hydroxyl group (closed) having no 319793 25 200838965 The side chain (Π') reduces the base price of the polyester resin (di). In the three-stage production method, since the degree of polymerization or the change in the hydroxyl value can be confirmed by the measurement before and after the steps (2) and (3), it is advantageous in the adjustment of the reaction conditions. However, in the step (2), since the hydroxyl group added to the cyclic ester (b) is present in the polyester in a dense state in the polyester finally produced in the step (1), hydrogen bonding is carried out. (1) The finally produced polyester becomes extremely high viscosity and lumps, which hinders the efficiency of the addition reaction of the step (2). In this regard, the manufacturing method of the two-stage type and the two-stage type, which will be described later, is a manufacturing method having a pseudo-two-stage type, which is staged by the three steps of the following steps (4) to (6). A method of adding a polyester resin (d丨) is obtained. Step (4): formed by, for example, a dibasic acid (5) corresponding to an amount of from about 5 Å to about 7 % by weight (by weight) and a ring-opening addition polymerization of the conjugate (a-2) a step of obtaining a polyester having an acid value of about 5 gK 〇H/g in a part of the polyester main chain (I); wherein the polyester has a compound derived from a dibasic acid and a bicyclic quinone compound (IV) Each of the structural units is alternately connected via a vinegar bond, D is known to be the main chain (I), and a plurality of hydroxyl groups directly bonded to the polyester backbone (f), in this regard, the step (1) The polyester is the same. y (5). The cyclic ester (b) is added to the polyester main chain (Γ), and the cyclic ring (b) is subjected to ring-opening addition to the base of the polyacetic acid main chain (1,) to form a side chain Π), R By the silk: the acid (four) 舆: the cyclic (tetra) compound (a_2): addition polymerization to make the main chain (Γ) stretch and complete the formation of the main chain, and the acquisition of the formation of the pre-existing The step of the object (C1). 319793 26 200838965, step (6). The end of the side chain (II) of the addition polyester precursor (ci) is reacted with the blocking compound (4) via the base portion to obtain a polyacetic acid having a side chain (11,) which is not (blocked). The step of the resin (D1). 8. The above steps (4) and (5) can also be made into a continuous operation step. This pseudo-iw-type manufacturing method is based on the formation of the main chain in step (4), and the cyclic vinegar (8) in step (5) is relative to the base of the polyacetic primary bond (1). The ratio of the amount becomes high, so that the reaction of the ring-opening addition of the ring-shaped object (b) can be improved. Therefore, this one-stage type method is easier to reduce the unreacted meridine remaining on the water 80 main chain of the addition polyester precursor (C1) than the above-described three-stage type method. However, conversely, since the base system of the main chain (1,) generated in the step (5) also contributes to the formation of a gas bond, it is not easily changed even compared with the above three-stage type method. High viscosity: It is still better to use the two-stage method described later. The method of producing a segment type is a method of obtaining the addition-molded polyester resin (m) stepwise by the two steps of the following steps (7) to (8). One • Step (7). The dibasic acid (a·1) and the bicyclic ether compound (a-2) are simultaneously reacted with the cyclic ester (b) to form a polyaddition and a ring-opening addition in parallel, and are derived from the two το, 〇1 a polylactic acid main chain (1) in which the structural units of the dicyclic ether compound (a_2) are alternately and repeatedly linked via an vinegar bond, and a cyclic ring (8) which is bonded to the poly-primary primary bond (1) via a vinegar bond. The side chain (11) of the open-loop structural unit is formed and formed to obtain a step of adding the polyester precursor (C1). Step (8): reacting a terminal hydroxyl group-portion of the side chain (π) of the addition polyester precursor (C1) with the blocking compound (c) to obtain a side chain having no warp group (closed) (11) ,) the step of polyester resin 1 丨). 319793 27 200838965 The manufacturing method of the two-stage type, since the primary bond of the polyacetate in the step (7) is formed, the side chain addition system is simultaneously performed, and the ratio of the base amount of the annular vinegar (b) to the ☆ primary key of the vinegar becomes It is extremely high, so it can improve the reaction efficiency of the ring-opening addition of the ring vinegar (8). Therefore, this two-stage type method is more likely to reduce the unreacted hydroxyl groups remaining on the polyester backbone of the addition polyester precursor (c" than the aforementioned two-stage type method. In addition, since substantially no cause occurs. The combination and lumps of the polyacetate molecules caused by the direct combination of the vinegar main chain, the reaction system is easy to homogenize, and the reaction efficiency is excellent. That is, the difference between the above two manufacturing methods is Obtaining the degree of formation of the poly primary bond (1) at the beginning of the formation of the precursor addition molding polyester having the polyester main chain (I) and the side chain (11), and forming the middle or the unformed one, and The reaction efficiency of the ring-opening addition of the cyclic vinegar (8) is different. Next, a method for producing the shaped polyglycol (D2) in the second closed form will be described. f. In the second closed form of the addition-molded polyester resin (D2), one of the bases directly bonded to the polyacetic primary bond (1) is blocked by the blocking compound (4) to form a second side having no transbasal (closed) The chain (11,), and the base of the residue, is added to the ith side chain (Π) containing the ring-opening structural unit of the cyclic vinegar (b). The second side chain (11') does not contain an open-loop structural unit of the cyclic vinegar (b). In the production of the resin, the ring-opening vinegar (8) is subjected to ring-opening addition, and the permeation group directly bonded to the main chain (1) of the polyfluorene is first introduced and reacted with the blocking compound (4). The reason for the blocking reaction is that the residual reaction via the side chain after the formation of the side chain (8) hinders the reaction, and can remain after the reaction of blocking 319793 28 200838965. The second closed type of the addition-molded polyester resin (D2) can also be used in the same manner as in the first closed form. The same can be used to form the second side chain (II) B$ based on the blocking compound (4). Three manufacturing methods with different degrees of formation are obtained. The one-P6 4-type manufacturing method is a method of obtaining the addition-molded polyester resin (D2) stepwise by the three steps of the following steps (9) to (1)). Step (9): obtaining a compound derived from a dibasic acid (a complex) and a bicyclic compound (a-2) by polymerization of a dibasic acid (6)) and a bicyclic compound (5)) The structural unit repeats the step of repeatedly linking the linked ruthenium backbone () and the poly-base group of the poly-acetic acid primary bond (1) via an ester bond. ^ Step (10): For the polyester backbone (1), one of the hydroxyl groups directly bonded to the valency blocking compound (4) is reacted to form no. The basis of the addition (C2) is obtained by the base (closed): the 2 side chain (11,) and the reduction of the base number. J Liu... Qing 1): For the formation of the second side chain (ΙΓ) of the addition of the shaped vinegar precursor (C2), the residue of the base is made by the 肤 ' ' ' 藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉The structural unit and the terminal 1 chain (11) of the terminal are subjected to a step of adding a polyester resin (D2). In the case of y, especially the second closed type of grievance, the ratio of the formation of the first side bond is based on the direct basis of the W-based part and the _^'^ and the hydroxy group, a cattle·μ Han should be sentenced. The degree of closure of y (10) is controlled. . 319793 29 200838965 A two-stage production method is a method in which the addition-molded polyester resin (10) is obtained stepwise by a step (9) to (). Step Π2): Addition polymerization by, for example, ring-opening compound (6) corresponding to 50 to 70% (by weight) and ring-and-loop riding compound (6). And the step of obtaining the _ part of the main chain (1) to obtain the acid value is about the step of polyacetal; wherein the polyester has a compound derived from the dibasic acid (al) /, + ketone ether (a_2) Each of the structural units alternately ♦ repeats the linked polyester backbone (1,) via an ester bond, and the number of hydroxyl groups directly bonded to the (four) primary bond (8), in this regard, the polyester of step (9) the same. Step (13): adding a blocking compound to the polyester backbone (1,) to react a radical of the xkS day main chain (I) with a blocking compound to form a second side chain (π) with % by residue Addition of the dibasic acid (a-1) and the dicyclic ether compound (heart 2) to stretch the polyester backbone (Γ) and complete the formation of the main chain to obtain an additive polyester precursor (C2) )A step of. _ Step (14): for the residual hydroxyl group of the addition polyester precursor (C2), the cyclic ester (b) is subjected to ring-opening addition to form a ring-opening structure mono 70 and terminal hydroxyl group containing the cyclic ester (b). The first side chain (II) is obtained by the step of adding the polyester resin (D2). The above steps (12) and (13) can also be made into a continuous operation step. In the pseudo-second/stage type manufacturing method, since the polyester main chain in the step (12) is formed into a system, the amount of the hydroxyl group of the polyester main chain (1) in the step (13) is higher than that described above. The two-stage type production method is small, so that the hindrance caused by the blocking of the polyester due to the combination of the hydroxyl groups directly bonded to the polyester main chain and the reaction of blocking the compound (C) of 319793 30 200838965 become Less, the reaction efficiency of the cyclic ester (b) for the ring-opening addition of the addition polyester precursor (C2) is also relatively preferred. The manufacturing method of the one-stage type is a method of obtaining the addition-molded polyester resin (D2) stepwise by one step of the following steps (15) to (16). Step (15): The dibasic acid (a-1) and the dicyclic ether compound (a-2) are simultaneously reacted with the blocking compound (c,) to form a polyaddition and blocking reaction, and the source is From the structural units of the dibasic acid (&_υ and the dicyclic ether compound (a_2), the polyester backbone (1) which is double-joined by the gg bond, and the poly-ruthenium main chain 2) The linear 2 side chain (11) of the structure in which the directly bonded group is blocked by the blocking compound (.,) is formed in parallel to obtain a step of adding the polyester precursor (C2). Step (16): ring-opening addition of the cyclic vinegar (8) to the residual hydroxyl group of the addition-form polyester precursor (C2), and obtaining the first ring-opening oxime unit and the terminal group containing the cyclic vinegar (8) The step of adding the side chain (II) and the addition of the second side chain (Π) of the base (closed) to the polyester resin (D2). • Λ-stage type manufacturing method, in which the formation of the primary urethane bond in step (15) is carried out simultaneously with the hydration of the thiol group, and substantially no aggregation occurs due to the base directly bonded by the primary urethane bond. Since the molecules are combined and lumped, the silk system is easy to homogenize and is very easy to react. Therefore, this two-stage method is better than the pseudo-like two-stage method. (The difference between the above two manufacturing methods is that when the precursor-added polyester (C2) having the polyester main chain I) and the side chain (ΙΓ) is obtained, the aggregation at the beginning of the formation of the side chain (1), The degree of formation of the ester main _ is formed, formed, and 319793 200838965 is not formed. At this time, in order to prevent the stretching of the side bond (II) due to the blocking compound (c,) from being more preferential than the stretching of the polyhydric primary bond (1), the blocking compound (c,) must be a monofunctional compound. The homogeneity of the reaction system caused by the block formation of the reaction intermediate is greatly affected, and since the reaction efficiency is greatly affected, it is preferable to use a two-stage type and a two-stage type. On the other hand, it is preferable to use a three-stage type manufacturing method in order to examine the material properties and reaction conditions of the polyester resin (D) which are produced in detail. Therefore, the method for producing the polyester resin (9) can be appropriately selected from the above production methods as needed. The method for producing the third-formed addition-molded polyester resin (D3) will be described. & The third closed form of the addition of the polyacetate resin (D 3 ) obtained by the following step (17). The second closed type of addition-molded polyester resin (10) is further subjected to a reaction by blocking the sigma-like material. And the addition of the ring-opening structural unit containing the ring (b) in the polyester resin (D2). The step (17) of closing the end of the side chain (π) via the portion of the base. That is, the third closed type manufacturing method's has any one of the three-stage type, the pseudo-one-stage type or the two-stage type of the second closed type manufacturing method, and the above step (Η). Such a shaped polyacetate resin (D3〇, having: a long-term gentleman derived from a dibasic acid and a compound fa-2) is bonded to a gentleman--one, 十10^) σ, , σ a polyester backbone (1) in which an ester bond is alternately and repeatedly linked, a ring-opening structural unit having a cyclic vinegar (b), a first side chain (11) having a terminal via group, and a polyester backbone (1) directly bonded thereto. The second side bond (10) of the side chain blocked by the blocking compound (4) and the side chain of the 帛i side chain (8) via the side chain blocked by the blocking compound (c). 319793 32 200838965 In the above second and third closed states, so that the side chain, even if the polyester * 叮曰曰曰键键便便便主主主主主主主主主主主主主主主主主主主The opener of the cyclic ester (b) is a good grade for the tree, and the upper layer is 7° earlier to prepare the addition (4) and the total number of hydroxyl groups of the side chain is 3〇% to the ring structure. Unit, this point Sun Hao, / gentleman horse 3 has opened for better. ^A compound which can effectively exert the nature of the cyclic vinegar (b) and the compound (t) = = 3 in the closed state, and the compound which is cross-linked by the acid hydrazine as a closed compound is used as an extra-earing agent (E) ) 'You can borrow the wonderful 1st Wei α, (ΙΓ) also has the role of a side chain (1) with a functional soil, which is _ 僧僧 amp amp amp 十十。。。。。。。。。。。。。。。。。。。。 However, at this time, in order to quit, S can also be completely applied or coated to prevent it from being applied due to the speed of cross-linking; the decrease in the mouth-to-mouth property is required to limit the acid value of the resin to a predetermined value. The use of :: is limited. Therefore, it is dealt with by blocking the compound (C) other than the acid anhydride. The respective raw materials used in the production method for forming the shaped trees (D1), (D2), and (D3) for use in the molding are described below. The dibasic acid used in the formation of the main chain (I) of the i-day is a lower molecular weight (usually used in the vicinity of 90 to 500) of the known dicarboxylic acid, which includes the following two Resin, its anhydride, and the scent of it I: **** 无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无无, adipic acid, hydrazine _ chlorine cis-butanedioic acid, Git diacid, suberic acid, cis-butane diacid, butyl butyric acid, dodecanedioic acid, pimelic acid, citrine 319793 33 200838965 Acid (citraconic acid), tablet-deficient, acid anhydride, cis-butanic acid = acid (itaconic acid), succinic anhydride. Alternatively, it is also possible to use dibutyl hydrazine to find aliphatic dicarboxylic acid and its acid di, succinic anhydride, butyl succinate, succinic anhydride, 2,2-succinic anhydride, octyl butyl succinide = one Anthraquinone anhydride, hexyl anhydride, etc.), glutaric acid drunkenness 丄丄基一一酸酐酸酐苯基苯基苯基 24 24 24 24 24 24 24 24 24 24 24 一一一一一一一一一一一Methyl glutaric anhydride, 2,4·diethylene erythric anhydride, hexyl glutaric anhydride, etc.) - 夂 _, butyl pentane bismuth) derivatives of maleic anhydride, 〇田 f maleic anhydride, 2,3_ 町之何生物(2-methyl_f-based cis-butane phthalic anhydride, butyl cis-butane anhydride, pentyl cis-butyl succinic anhydride, hexidine / bis-butane bis-dicarboxylic acid field, 癸基顺丁妇二^辛基顺丁〇^ ^ Ding Yizhiji succinyl sulphate, ΓΛ diacid sulphate, phenyl cis succinic anhydride, 2,3-dibutyl sulphate, etc.) Anhydride derivative.酞: 2 芳5香族二赖's can be cited as o-nonanoic acid, isoindole acid, p-quinone^, 5--methyl-fietic acid, 4,4-dibiphenyl (tetra) (tetra) 1 naphthoic acid And a carboxylic acid, an acid anhydride, etc., a norbornene bis-acid, a diphenyl ketone _4, a quinone dicarboxy fluorenyl sulphate dicarboxylic acid, phthalic anhydride, 4-methyl phthalic anhydride, etc. χ, you can also use hexahydrophthalic acid ''s (-methyl hexahydrophthalic anhydride, 4-methyl hexahydrophthalic anhydride), derivatives of tetrahydrophthalic anhydride (1, 2, 3, 6 • S-hydrogen anhydride, 3-methyl], hydrazine, anhydride 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl^tetrakis, etc. derivative. Examples of the 丄γ and the alicyclic dicarboxylic acid include dimer acid, hexamethylene phthalic acid, hexahydroisophthalic acid, hexamethylene acid, and tetrahydrofurfuric acid, and these alicyclic 319793 can be used. 34 200838965 Dicarboxylic acid and its anhydride. Further, there may be mentioned, for example, chloro-branched anhydride (hept anhydride), heptanic anhydride (Het anhydride), biphenyldicarboxylic anhydride, and hemiic anhydride. Anhydnde), endomethylene tetrahydrophthalic anhydride, methyl_3,6-enda f-group, 1,2,3,6-tetrahydrophthalic anhydride, 1>2•cyclohexene dicarboxylic anhydride, Cyclohexane, dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid, naphthalene diacetic anhydride, octahydro-1,3-diketo-4,5-isobenzofuran dicarboxylic anhydride, and the like. These low molecular weight diacid acids (5)") may be used alone or in combination of two or more kinds as a dibasic acid (a·). Further, in the present invention, the dibasic acid (6) may be used in comparison with the above. The low molecular weight dicarboxylic acid compound (add) is a higher molecular weight dicarboxylic acid compound, and examples thereof include the following: and the above-described low molecular weight dibasic acid compound small sputum and the later-described 70 sec. A high molecular weight dibasic acid (a 12)' per molecule having an average of about 2 mercapto groups per mole of a large amount of an acid compound (hereinafter referred to as a sulfonate) &small point. The reaction of the Erxi το alcohol knives (a-1-α) under the condition of excess carboxylic acid*. The obtained master knife: a high molecular weight dicarboxylic acid having an average of about 2 carboxyl groups (a-1- 3); and the above-mentioned low molecular weight diacid compound (5) and the polyamine component (a small 7) described later are reacted under conditions of an excessive acid retardation to obtain a dibasic acid (a-fluorene). Polyamine dicarboxylic acid (a_〗_4), etc. The above high molecular weight diterpenic acid (6) & small 3) The multi-read used, sub-(a_l·.), has a number average molecular weight: about 5Q to the lower molecular weight of the lion (a-1·ry η 々 / τ #八 i α-i), or Number average molecular weight: about 5 〇〇 to 319793 35 200838965 50, 0 (10) of higher molecular weight polyols (a-1-α-2). Lower molecular weight diols (a-1 - α · 1 For example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-i-pentanediol, 2,4_2-B Base q,% pentanediol, 2-mercapto l,8-octanediol, 3,3,-di-purinyl heptyl, 2-butyl 2-ethyl-1,3-propanediol, polyoxyl Ethylene glycol (additional molar number is 1 〇 or less), polyoxypropylene glycol (additional molar number is 1 〇 or less), propanediol, i,3-butanediol, 1,4·butyl Alcohol, 1,5-pentanediol, workbench

己二醇、1，9_壬二醇、新戊二醇、辛二醇、丁基乙基戊二醇、2-乙基-1，3_己二醇、環己二醇、環己烧二甲醇、三環癸烷二甲醇、環戊二烯二曱醇、二聚二醇(dimer 等脂肪族或脂環式二元醇類；15弘雙（2-羥基乙氧基）苯、^^曰雙d經基乙氧基）苯、丨，扣雙（2-羥基乙氧基）苯、、亞甲基二酚、4,4入(2-亞降冰片基）二酚 ’ (M’-(2-norbornylidene)diphen〇1)、4,4，'二經 =及對-二經基苯、4,4，_異亞丙基驗、在雙紛:成二原：：？成型雙驗等芳香族二元醇類等。加成型雙盼如環i乙：列=雙酶A、雙.F等，原料環氧烷可列衣虱乙烷、％氧丙烷等。上述較低分子量之二元醇類組合2種以上而使用。可各自單獨使用亦可，可列舉如高、高分子量聚面分子量聚碳八^交高分子量之多元醇類（a-1-α-2)而言刀山子！聚S旨义元醇、高分子量㈣胺多元滅酉曰多兀醇、及高分子量聚胺酯多元醇： 319793 36 200838965 酸酯多元醇係藉由使上述較低分子量之二元醇與碳酸酯或光氣進行反應而獲得。酸價<0.5 酸價<0.5 酸價<0.5 酸價<0.5 酸價<0.5 酸價<0.5 酸價<0.5 羥基價=28，羥基價=22，羥基價=19，羥基價=28，羥基價=19，上述高分子量聚酯多元醇的市售品，可列舉例如東洋紡績公司製之Vylon GK640[數平均分子量（以下，亦記載為「]^11」）=18,000，玻璃轉移溫度（以下，亦記載為「丁&」）=79 °C，羥基價=5，酸價<4，線形類型]、Vylon GK880 (Mn=18,000，Tg=84t：，羥基價=5，酸價<4，線形類型）、 Vylon 300(Mn=23,000，Tg=7°C，羥基價=5，酸價 <2，線形類型）、Vylon 500(Mn=23,000，Tg=4〇C，羥基價=5，酸價 <2，線形類型）、Vylon 560(Mn=19,000，Tg=7°C，羥基價，酸價 <2，分支類型）、以及 Vylon 630(1^11=20,000，Tg=75 °C，羥基價=5，酸價=1，線形類型）；KURARAY公司製之 UE-3600(Mn=20,000，Tg=75°C，經基價=4，酸價=1)、 UE_3690(Mn=H，000，Tg=91〇C，經基價=8，酸價=1)[以上為 UNI1TIKA 公司製造]、P1010(Mn=l，000，羥基價=112，酸價<0.5，線形液狀類型）、P2010(Mn=2,000，羥基價=56，線形液狀類型）、P4010(Mn=4,000 線形液狀類型）、P5010(Mn=5,000 線形液狀類型）、P6010(Mn=6,000 線形液狀類型）、P4050(Mn=4,000 線形液狀類型）、P6010(Mn=6,000 線形液狀類型）、N4010(Mn=4,000，羥基價=28，線形液狀類型）、PNOA4014(Mn=4,000，經基價 :28，酸價<0.5，線形液狀類型）、P2011(Mn=2,000，羥基 37 319793 200838965 價=56,酸價<0.5，線形液狀類型）、以及P4011(Mn=4,000，羥基價=28，酸價<0.5，線形液狀類型）；協和發酵化學公司製之 Kyowapol 2000BA(Mn=2,000，經基價=58，酸價 <0·5，線形液狀類型）、以及 Kyowapol 5000PA(Mn=5,000，羥基價=22，酸價<0.5，線形液狀類型）等。上述高分子量聚醯胺多元醇的市售品，可列舉例如富士化成工業公司製之TPAE617(Mn=15,000，Tg=90°C，羥基價=16，酸價=1，線形類型）等。馨上述高分子量聚碳酸酯多元醇的市售品，可列舉例如 PERSTORP 公司製之 Oxymer N112(Mn=l，000，Tg=60〇C，羥基價=112，酸價<0·5，線形類型）；旭化成化學公司製之 PCDL-T5651(Mn=l,000，羥基價=110，酸價 <0.05，線形液狀類型）、PCDL-T5652(Mn=25000,羥基價=56,酸價 <0·05， -線形液狀類型）、PCDL-T4671(Mn=l，000，羥基價=110，酸價 <0.05，線形液狀類型）、以及 PCDL_T4672(Mn=2,000，羥基價=52，酸價<0.05，線形液狀類型）；KURARAY公司修製之 PMHCM050(Mn=l，000，羥基價=112，酸價<0.5，線形液狀類型）、PMHC-2050(Mn=2,000，羥基價=56，酸價 <0.5，線形液狀類型）、C-1090(Mn=l，000，經基價=112，酸價<0.5，線形液狀類型）、C-2090(Mn=2,000,羥基價=56，酸價<0.5,線形液狀類型）、C-3090(Mn=3,000,羥基價=37，酸價<0.5，線形液狀類型）、〇-4090(1^11=4,000，羥基價=28, 酸價<0.5,線形液狀類型）、C-5090(Mn=5,000,羥基價=22，酸價<〇·5，線形液狀類型）、C-1065N(Mn=l,000，羥基價 38 319793 200838965 = 112，酸價 <0·5，線形液狀類型）、C-2065N(Mn=2,000，羥基價=56，酸價<0.5，線形液狀類型）、C-1015N(Mn=l，000，羥基價=112，酸價<0.5，線形液狀類型）、以及C-2015N (Mn=2,000，羥基價=56，酸價<0.5，線形液狀類型）等。上述高分子量聚胺酯多元醇的市售品，可列舉例如東洋紡績公司製之 Vylon 1^1350(1^11==30,000，Tg=3°C，經基價=46，酸價 <1，線形類型）、Vylon UR1400(Mn=40,000， Tg=83°C，羥基價=2，酸價<1，線形類型）、Vylon UR3210 參（Mn=40,000，Tg=—，羥基價=3，酸價<1，線形類型）、 Vylon UR5537(Mn=20,000，Tg=34°C，經基價=17，酸價 <1，線形類型）、以及 Vylon UR9500(Mn=25,000，Tg=15t：，羥基價=5，酸價<1，線形類型）；三井化學聚胺酯公司製之 Takelac E15 8(羥基價=20，酸價 <3)、Takelac E551T(羥基價 =30，酸價 <3)、以及 Takelac A2789(經基價=10，酸價 <2) 等。 $ 其他例如聚己内酯二醇、聚（β _甲基-7-戊内酯）二醇、聚戊内酯二醇等將内酯類開環聚合而獲得的聚酯多元醇等，亦包括於可作為上述高分子量多元醇（a-1-α -2)使用的高分子量二元醇。在本發明中，上述高分子量多元醇（a-1-α-2)可各自單獨或組合2種以上而使用。另外，亦可與上述低分子量多元醇併用。由於若在此等多元醇類中使用2官能之二元醇，則可獲得接著性、耐熱性、耐濕熱性及透明性優異的感壓式接著劑，故以2官能之二元醇為最佳。 39 319793 200838965 上述高分子量多元醇（a小α·2)之分子量，只要是可溶解於所使用之溶媒即無特別限定，以數平均 500至50,〇〇〇之範圍之高分早旦夕_以（；马〇㈣之回刀子里多轉㈤-3b)為較佳。若使用如此之兩分子量多元醇㈤,，即可獲得密著性、渴潤性，異的感壓式接著劑。更佳為使用Μ〇〇至3〇，_ 者，最佳為使用1，〇〇〇至！〇，_者。高分子量多元醇㈤_ α -2)之數平均分子量（Μη)若小於綱，則生成之加成型聚醋樹脂（D1)至（D3)會變得太硬，當調製接著劑組成物並形成感壓式接著薄片時會變得難以顯現初期接著性（黏著性）。此外，若使用含有太硬之加成型聚酯樹脂（D1)至（D3) 的感麼式接著劑來將塑膠彼此或玻璃板與塑膠薄膜予以積層’則接著強度會變弱，且如此之積層體在高溫高濕下放置長時間後會變得容易剝離。另一方面，若高分子量多元醇（a-1 · α -2)之Mn超過..50,000，則加成型聚酯樹脂(里= (D3)對於溶媒之溶解性降低，且感壓式接著劑之黏度會上升’故塗佈加工時之處理變得困難，因而不佳。兩分子量多元醇（a_l_ α _2)之玻璃轉移溫度（Tg)雖然並無特別限制，但以—7〇至8〇它為佳，更佳為—5〇至20 C。右玻璃轉移溫度未達— 7〇〇c，則接著劑組成物之揍著性或凝集力有變得不充分之情形’亦有積層後引起凝集破壞並產生剝離。另一方面，若超過8(rc，則塗膜會變得太硬，而热法顯現初期接著性（黏性），或是會對塗佈加工性 k成〜专。兩分子量多元醇（a_ 1 _ α _2)之玻璃轉移溫度，係可藉由適當選擇其原料之多羧酸、多元胺及低分子量多元 319793 40 200838965 =之種類而調節二此外，亦可使用2種以上不同破璃轉移溫度之多元醇來調整成適當之玻璃轉移溫度。高分子量多元醇（a-lU)之經基價較佳為在$至 200mgKOH/g之範圍，更佳為在1〇至1〇〇mgK〇H/g之範圍。若羥基價超過2〇〇mgKOH/g，則加成型聚醋樹脂(d: 至（D3)會變得太硬，而變得難以顯現初期接著性（黏著性）。若經基價未達5mgKOH/g ’則加成型聚醋樹脂⑼）至 (D3)對於溶媒之溶解性降低，且所難之接著劑組成物的黏度上升’故塗佈加工時之處理變得困難，對加工枓成障礙。寺& 其次，針對為了使上述高分子量多元醇類“ _ 反應並獲得高分子量二羧酸類（a·^)而使用的3官能以上之多鲮酸類（a-1-冷）加以說明。土 3官能以上之多羧酸類⑻^沒）係以具有酐環者為 =，具有一個酐環之3官能以上之多羧酸類沒）係可列，如偏苯三甲酸酐（trimellitic anhydride)。具有二個以上酐裱之3官能以上之多羧酸類係可列舉如丁烷四羧酸二酐、^,3,4•環丁烷四羧酸二 ’ •1 2 λ d TM U 一一 f 基 2，44-¾ 丁烷四羧酸二酐、U，3,4_環戊烷四羧酸二酐、 — 竣基環戊基乙酸一酐、2,3,5,6 -四竣基環己院二 =、2^3,5,6-四叛基降冰片烧二酐、3,5,6_三緩基降冰二= _ _乙酸二酐、2,3,4,5•四氫呋喃四羧酸二酐、$ _二飞夫南基）_3_曱基環己烯二羧酸二酐、雙環 2.2.2]·辛-7-埽_2,3,5,6-四羧酸二酐、均苯四甲酸=: 319793 41 200838965 1，2,4,5-苯四叛酸二酐、乙一醇二（偏苯三曱酸酐）|旨、丙二酉事二（偏本二甲酸Sf)酉曰、丁一醇二（偏苯三曱酸針）酉旨、 3,3’，4,4’-二苯曱酮四缓酸二酐、2,2，，3,3，-二苯甲酮四缓酸二酐、3,3’，4,4’-聯苯颯四叛酸二酐、2,2，，3,3，-聯苯石風四叛酸二酐、1，4,5,8-萘四羧酸二酐、2,3,6,7-萘四缓酸二酐、萘 •1，8 : 4,5-四羧酸二酐、4,4’-(六氟亞丙基）二酞酸酐、 3,3’，4,4’-聯苯醚四叛酸二酐、3,3’，4,4’_二曱基二苯基石夕完四羧酸二酐、3,3’，4,4’-四苯基矽烷四羧酸二酐、i，2,3,4-籲呋喃四羧酸二酐、4,4’-雙（3,4-二羧基苯氧基）二苯基硫化物二酐、4,4’-雙（3,4-二羧基苯氧基）二苯基颯二酐、4,4,·雙 (3,4-二叛基苯氧基）二苯基丙烧二野、3,3’，4,4，-全氟異亞丙基二酜酸二酐、3,3’，4,4’-聯苯四羧酸二酐、雙（酜酸）苯基膦氧化物二酐、對-伸苯基-雙（三苯基酞酸）二酐、間-伸苯基"雙（二本基敝酸）《—Sf 雙（二本基欧酸）-4,4’^二苯基喊二酐、雙（三苯基酜酸）-4,4’-二苯基甲烧二酐、9,9-雙[4-(3,4_ 馨二羧基苯氧基）苯基]第酐、乙二醇雙(偏苯三甲酸酐）、3,4_ 一緩基-1，2,3，4_ 四氬 _ 1 -萘丁二酸二肝、3，4-二缓基-1，2,3 4-* 四氫-6-甲基·1_萘丁二酸二酐、9,9-雙（3,4_二羧基苯基）第二酐、雙環[2·2·1]庚-5-烯_2,3_二叛酸酐、甲基納迪克酸哥 (Methyl nadic anhydride)、烯丙基雙環[2·2·1]庚-5_烯-2,3_ 二羧酸酐、甲基烯丙基雙環[2·2·1]庚-5_烯-2,3-二羧酸酐、烯丙基甲基雙環[2.2.1]庚_5_烯-2,3-二羧酸酐、甲基烯丙基甲基雙環[2·2·1]庚-5-稀-2,3-二叛酸酐等。前述低分子量二羧酸類（a-1-l)及前述多羧酸類（^-沒> 319793 42 200838965 可各自單獨或組合2锸，、,L I + 反應中。作為在〜=7 與多元醇（心)之環之環狀酐，即可心=( ;:)，若使用保有-個酐柯俱田』紋侍接者性、耐熱性、耐濕熱性及透明卜4兴的感壓接著劑，故為較佳。古，在本發明中，就聚醋主鏈（1)形成用之二元酸㈤）而 :比起直接使用低分子量二叛酸㈤…，係以將低分子里—竣酸類⑹.1)或3宫能以上之多叛酸類㈤…先盘士述多元醇成分(…)反應而獲得的較高分子量二羧酸類（a-1-2、a-i-3)為較適用。若將經高分子量化之二羧酸(a]_2、“·”作為二元酸 (a 1)使用並形成聚酯主鏈⑴，則比起直接使用低分子量二致酸（a’之情形，可使因聚加成所產生之聚酯主鍵⑴中 ^酯鍵間的距離變長，並使二級羥基間亦產生適當之間史可抑制因羥基之結合而造成的聚酯塊狀化，同時使馨加成型聚酯樹脂（D1)、（D2)之羥基的減少變得容易。若使用如此之加成型聚酯樹脂（D1)、（D2)來調製感壓接著劑組成=，則可維持接著特性之平衡（尤其是黏著性與凝集力的同守成立）。因此，較佳為使用咼分子量之二缓酸（a_ U、 a 1 3)作為二元酸（a_i)來形成聚酯主鏈⑴。可作為二元酸（a-1)使用之聚醯胺二羧酸（心2_4)，係為將前述低分子量二羧酸類（a-1-l)與多元胺類（心〗-^ )在羧酉文過1之條件下縮合而成者，故為在末端具有2個叛基且以醯胺鍵連結而成者。 319793 43 200838965 聚醯胺二羧酸之調製所用之多元胺（a-l-r )，只要是具有2個以上1級胺基之多元胺，即可無特別限制地使用。例如，就脂肪族系多元胺而言，可列舉如2,5-二甲基 -2,5_六亞甲二胺、盖烧二胺（menthane diamine)l，4-雙（2-胺基-2-曱基丙基）旅哄、在分子兩末端之丙烯分支壤結合有胺基的聚丙二醇、丙烯骨架之二胺、Suntechno化學公司製之製品「Jeffamine D230」及「Jeffamine D400」等、丙烯骨架之三胺、Suntechno化學公司製之製品「Jeffamine T403」 _等、伸乙二胺、伸丙二胺、伸丁二胺、二伸乙三胺、三伸乙四胺、四伸乙五胺、五伸乙六胺、六亞曱二胺、三曱基六亞甲二胺、N-胺基乙基哌畊、1，2-二胺基丙烷、亞胺基雙丙基胺、曱基亞胺基雙丙基胺、H2N(CH2CH20)2(CH2)2NH2 [Suntechno化學公司製之乙二醇骨架之二胺「Jeffamine EDR148」]等在胺氮上結合有亞甲基啲聚醚骨架之二胺、 1，5-二胺基-2-甲基戊烷（DuPont日本公司製「MPMD」）、間伸茗二胺（Metaxylylene diamine)(DuPont 曰本公司製馨「MXDA」）、聚醯胺基胺（三和化學公司製之「X2000」）、異佛爾酮二胺、1，3-雙胺基曱基環己烷（三菱瓦斯化學公司製「1，3BAC」）、1-環己基胺基-3·胺基丙烷、3-胺基甲基 -3,3,5-三甲基-環己基胺、降冰片烷骨架之二亞甲基胺（三井化學公司製「NBDA」）等。另外，上述多元胺與酮之反應生成物的酮亞胺 (ketimine)係亦可作為多元胺（a-1-r )而使用於聚醯胺二羧酸之調製中，且就聚合安定性或反應性之調整的觀點來 44 319793 200838965 看，較佳例可列舉如：苯乙酮或苯丙酮、與丨，3-雙胺基曱基環己烧的反應物；苯乙酮或苯丙酮、與降冰片烷骨架之二亞甲基胺（NBDA)的反應物；苯乙酮或苯丙酮、與間伸茬一月女的反應物，苯乙酮或苯丙酮、與為乙二醇骨架或丙烯骨架之二胺之 jeffamine EDR148、jeffamine 〇230、 Jeffamine D400等或是為丙烯骨架之三胺之Jeffamine T403等的反應物等。上述之多元胺可各自單獨使用，亦可組合2種以上使 •用。在本發明中，為了形成於側鏈位具有羥基之聚酯主鏈 (I)而使用的二元酸（a_l)，係可適當從上述低分子量二羧酸類（a小1)、高分子量二羧酸㈤^、^3)、以及聚醯胺二羧酸（a-1-4)中選擇丨種或2種以上而使用。其次，針對用以形成聚酯主鏈（I)的二環狀醚化合物 (a-2)，亦即在分子内具有2個環狀醚基的化合物加以說 _明。-核狀趟化合物(a_2)係與上述二元酸㈤）進行聚加成反應，而生成酯鍵與二級羥基。源自上述二元酸及二環㈣化合物㈣之結構單元，係經由醋鍵而交互地重複連結，形成聚醋主鏈(1)。二級經基係直接結合於聚酉旨主鍵 (I)上，參與分支側鏈之形成。本^明所使用之二環狀鱗化合物㈣，係可適用含有 :知之環氧丙基及/或氧雜環丁基(。xeta_之化合物。且 ::氧化合物(亦即環氧丙基化合物)可為脂肪族：方“'化合物、脂環式化合物中之任一者，亦可為 319793 45 200838965 高分子量之樹脂。就脂肪族二環氧丙基化合物而言，可列舉如乙二醇二環氧丙基鍵、二乙二醇二環氧丙基鱗、三乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、二丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、丁二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1，6-己二醇二環氧丙基醚、甘油二環氧丙基醚、二環氧丙基胺、丁二稀二氧化物、二聚酸之二環氧丙基醚等。就芳香族二環氧丙基醚化合物而言，可列舉如2,6-二環氧丙基苯基醚、酞酸二環氧丙酯、偏苯三曱酸二環氧丙基醚、雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、雙酚 S二環氧丙基醚、2,2-雙（4-羥基苯基）丙烷二環氧丙基醚、雙（4-羥基苯基）曱烷二環氧丙基醚、1，1-雙（4-羥基苯基）乙烷二環氧丙基醚、3,3’，5,5’-四曱基-4,4’-二羥基聯苯二環氧丙基鍵、2,2_雙（4-(/5 -經基丙乳基）苯基）丙烧二架乳丙基醚、間苯二盼二環氧丙基醚（resorcinol diglycidyl ether)、聯苯*"4，4’-二架氧丙基謎、1，5 -二輕基奈二银乳丙基鍵、1，6_ 二輕基奈二壞氧丙基鍵、2,7 -二輕基秦二壤氣丙基鍵、雙酚苐二環氧丙基醚、雙苯氧基乙醇苐二環氧丙基醚等。就脂環族二環氧丙基醚化合物而言，可列舉如環己烷二曱醇二環氧丙基醚、二環戊二烯二氧化物、3,4-環氧丙基環己基曱基-3,4-環氧丙基環己烷羧酸酯、3,4-環氧丙基 -6 -曱基壤己基曱基-3，4- 5辰氧丙基-6 -曱基壤己烧竣酸醋、乙烯基環己稀二氧化物、二環二烯醇環氧化物環氧丙基醚、 46 319793 200838965 四氳酞酸二環氧丙基醚、氫化雙酚A二環氧丙基醚、氫化雙酚F二環氧丙基喊、2,2_雙（4_經基環己基）丙烧二環氧丙基醚、雙-(3,4-環氧基環己基）己二酸酯等。就尚分子$二環氧丙基樹脂而言，可列舉如雙酚A型高分子量環氧丙基樹脂、雙酚F型高分子量環氧丙基樹脂、或使上述二環氧丙基化合物進行反應而獲得的丙氧基樹脂等。雙紛樹脂系（AS、F型等）之二環氧丙基化合物係具有二級經基，此二級經基係與使二元酸⑷）之叛基聚加 _成於裱狀醚基（環氧丙基）而產生的二級羥基同樣地，作為用以形成側鏈之起點。就具有氧雜環丁基（oxetanyl)之化合物而言，可列舉如礙酸醋雙氧雜環丁烧、己二酸雙氧雜環丁燒、伸茗基雙氧，環丁烧、對駄酸酉旨雙氧雜環丁燒、環己燒二羧酸雙氧雜環丁烷、雙（3_乙基_3·氧雜環丁基甲基）醚、Μ·雙川3·乙基-3-氧雜環丁基）甲氧基]甲基}苯、二{1乙基_(3_氧雜環丁參基）}甲基醚等。上述二環狀醚化合物（a_2)，可單獨或組合2種以上而使用。 1次，針對本發明所使用之環狀酯（b)加以說明。環狀酯(b)係對於上述聚酯主鏈（1)之側鏈所直接結合之二級羥基進行開環加成反應，而形成加成型聚酯樹脂 CD1 D2 D3)之側鏈。此側鏈係經由酯鍵而結合於聚酯主鍵（I) ’亚含有環狀醋⑻之開環結構單元、以及末端之羥基側鏈之末端經基係與後述之交聯劑⑹進行反應，藉此 319793 47 200838965 而使聚酯樹脂（D)硬化，而形成感壓接著劑層。藉由將對於水酉曰主鏈⑴之一級經基反應的環狀酯⑻之量加以調節，即可控制開環酯結構之側鏈之導入量，依據側鏈之導入量，而可確保含有加成型聚酯樹脂（D1)至（D3)之接著劑組成物作為感壓接著劑的接著特性的平衡（尤其是黏著性與凝集力之同時成立）。如上所述加成型聚酯樹脂（D1至D3)係可依據三階段型、擬似二階段型、或二階段型的製造方法而獲得，環 •狀醋⑻之開環加成或封閉化合物⑻之加成開始時的聚醋，鏈（I)之形成反應（聚加成反應）之進行程度係不同。由於 :力成反應已①畢之聚_係具有多數之經基，故黏度為呵有羥基彼此的結合或副反應的可能性，並且因盥環狀 _>或與封閉化合物⑷之均一混合受到阻礙，故反應效率 =易降低，且環狀8旨（b)或封閉化合物之加成反應受到抑制2此，與環狀醋⑻或與封閉化合物⑷之反應開始時的 φ =基量若為較少，則反應效率較佳、反應的進行安定性提高、不均程度會減少。所以，使聚醋主鏈上之形成、與侧鏈(ΙΙ、ΙΓ)之形成實質上為同時並行的二 ==製造方法’係由於聚加錢應所生成讀基會逐: 狀醋（b)或封閉化合物（e)之加成反 ‘為少量，故比三階段型製造方法為更佳。吊、准美=發明：Γ側鍵之形成所使用的環狀醋（b)，係為由_ 缓酸在分子内或分子間進行脫水縮合而开: 成衣、、、。構的酉曰，且為包含經基幾酸之環狀單體、二聚物、 319793 48 200838965 或二聚物以上之多聚物者。口 f卷明所用之環狀酯（b)，由於沒有限制環的大小，故二要疋作為％狀酯（b)前驅物之羥基羧酸卬，)可藉由脫水縮。而幵/成％ ’即無特別限制，以脂肪族、脂環式、芳香族及4 %、式之經基竣酸之一種或一種以上作為前驅物的分子内j分子間縮合物係可作為環狀酯（b)使用。以下，例示作為環狀酯（b)前驅物之經基叛酸（y)。就脂肪族羥基羧酸而言，可列舉如乙醇酸（glycolic ♦ acid)、乳酸、3_經丙酸（Hydracrylic扣⑷、心經丁酸、』_ 爹二/、丁酉欠、每基戊酸、α _經基己酸、ά _經基己酸、甘油酸、羥丙二酸（tartronic acid)、蘋果酸、檸檬酸、辛酸、月桂酸、t麻油酸（ricinoleic acid)、α _羥基三十二酸（α •hydroxy dotriacontanoic acid)、經基三十四酸、α-經基—十’、酉夂、α -輕基二十八酸、α -經基四十酸乂 a -hydroxy tetracontanoic acid)、羥基三曱基乙酸、羥基丙酸、6_羥基籲戊酸、α -經基庚酸、1〇·經基硬脂酸、12-經基硬脂酸、1〇_ 經基癸酸、12-經基癸酸、3-經基十四酸、16-經基十六酸、 15-羥基十五酸、α -羥基二十酸、α -羥基二十二酸、α _ 經基二十四酸、α-羥基二十六酸、羥基二十八酸、羥基三十酸、β ·羥基十四酸、二羥曱基丙酸、3,5-二-三級丁基水楊酸等。就脂環式、芳香族及雜環式羥基羧酸而言，可列舉如水楊酸、2_羥基苯曱酸、3-羥基苯甲酸、3,4-二經基苯曱酸、 4-羥基-3-苯基笨曱酸、4-羥基-3-曱氧基苯曱酸、4-羥基 49 319793 200838965 _3,5·二甲氧基苯甲酸、4’_羥基_4_羧基聯苯、&羥基_2_茧 Τ酸、3-羥基-2-萘甲酸、5-羥基萘τ酸等。丁羥基窺酸只要是在-分子内具有幾酸與經基之有機化合物即可，不受上述例示者所限制。於本發明巾，能作為環狀_)使用之絲羧酸之環狀早肢係可使用内醋，並無特別限制，可列舉例如々·丁内酯、/?-丙内醋、r·丁内酉旨、r_戊内酉旨、戊内酉旨、£ 赢;内酉旨、卜己内酉曰匕、卜庚内醋（r-hePtanolactone) •辛内醋…辛内醋、ε_辛内醋、ε己内醋乙交醋 ΓΡΓ〇1⑽。ne glycolide)、三甲基乙内酯（咖__叫、7_ 酉l(7_heptan〇lide)、8-辛内酉旨、11十-炫内酉旨、12卄 -汉内酷、15_十五烷内§旨、16_十六烷内丙内醋、心甲基π-丙内酿、α β $^基沒· 曰α，α — T基-石·丙内酯等。 =本發明中，可作為環狀醋⑻使用之經基缓酸 ^物，可列舉如乳酸之交g旨㈣ide)、乙醇酸之乙交酉旨單獨：開：加成，係可對於聚㈣聚合物的加;=重複減分子之開環加成所形成狀醋⑻，則多:v分=聚醋之經基供給張。、刀展狀酉曰（^0加成聚合並使側鏈可伸從藉開環所形成酯（b)之單獨加成中，環狀S曰（b)為佳。另外之侧鏈的有效性的觀點來看，在環狀係以構成酯環結構之碳數為4以上的為了使其與聚酯主鍵⑴之經基效率 319793 50 200838965 良好地進行開環加成反應，係以構成酯環結構之碳數為6 至18的環狀單體的内酯類為較佳，又以£_己内酯為更佳。其次，針對用以封閉羥基的封閉北合物（c)加以說明。封閉化合物（c)係為與羥基反應並藉由加成而可封閉羥基的化合物，其係與加成型聚酯前驅物（C1、C2)之側鏈 (II)之末端羥基、或聚酯主鏈（1)所直接結合之羥基之一部分進行反應並封閉羥基，同時形成至少構成側鏈之一部分且不具有輕基的弟2側鏈（ΙΓ)。因此，藉由使用封閉化合擧物（c) ’即可提供羥基量比加成型聚酯前驅物更少的加成型聚酯樹脂（D1至D3)。亦即，藉由使用封閉化合物（c)，即可控制作為能與交聯劑（E)反應的官能基之羥基量。然後’藉由減少加成型聚酯樹脂（D1至D3)中的羥基，可使調製接著劑組成物並作為感壓接著劑利用時的耐熱性及耐濕熱性提升。 ^ ^另外，在第2封閉型態中，可與羥基反應之化合物（c) 麟係用於與藉由二元酸（a_i)與具有2個環狀醚基之化合物 (a-2)的聚加成反應所生成之聚酯主鏈部⑴中之二級羥基之一部分進行反應，並形成加成型聚酯樹脂（D2)中之側鏈部（Π，）。側鏈部（11，)不具有經基。然後，對於殘留於聚醋主鏈部σ)之二級經基M吏上述環狀酯化合物（b)進行開環加成反應’而开> 成於末端具有羥基的側鏈部（η)。亦即，藉由封閉化合物⑷，即可調節作為與環狀師)之反應點的聚醋主鏈（I)中之經基之量，亦即，可調節聚醋主鍵部⑴所結合之側鏈中所占有的具有環狀g|⑻之開環結構單元的侧鏈 319793 51 200838965 的^率。因此，可利用於將加成型聚醋樹脂（D2)作為感壓接者劑使用時的接著特性平衡（尤其是黏性與凝集力之同日守成立）的調整。更進:步’封閉化合物⑷亦可用於使加成型聚醋樹脂 ()中之第1側鏈(II)之末端經基減少、並獲得第3封閉型態之加成型聚酯樹脂_，該封閉化合物⑷亦具有能將聚酯樹脂之羥基進行最終性地調整的作用。本發明所使用的封閉化合物⑷，係較佳為例如石夕烷化攀劑（Cl)、酸軒（C2)或異氰酸酯化合物（c3)中之任一者，更佳為保有單g能或不具交聯作用之複數官能基的化合物 ⑹。封閉化合物⑷可單獨使用，亦可組合2種以上使用。本發明所使用之㈣化劑⑹，可列舉如氫石夕院類 (hydrosilane)、燒氧基石夕燒類、氯石夕燒類、石夕燒醇類、烷基胺類、或此等之環狀化合物..。、以氫矽烷類而言，可列舉如三甲基矽烷、三乙基矽烷、基料、三丁基我、三己基我、二乙基甲基錢、 U基石夕烧、二甲基苯基石夕烧、三苯基錢、甲基苯基乙細基石夕燒、五甲基二石夕氧燒、烯丙基二甲基錢、參（三甲基石夕燒氧基）發燒、七甲基三梦氧院、 =1，3,5,7,7,7_八甲基时氧烧八苯基環四石夕氧烷專保有單官能之Si-H基的氫矽烷類。以烷氧基矽烷類而言，可列舉如甲氧基三甲基矽烷、甲氧基三乙基矽烷、甲氧基二甲基乙婦基矽烷、：二氧基乙块基石夕烧、乙氧基三甲基石夕燒、乙氧基三乙初;、 319793 52 200838965 烯丙氧基三曱基矽烷、乙氧基二曱基乙烯基矽烷、三曱基丙氧基矽烷、三甲基異丙氧基矽烷、ι_曱基丙氧基三曱基矽烷、丁氧基三曱基矽烷、異丁氧基三甲基矽烷、三級丁氧基三甲基梦烧、己氧基三曱基發烧、3 -胺基丙基二甲基乙氧基梦烧、四氮咬喃甲氧基二甲基碎烧 (tetrahydrofurfuryloxy trimethyl silane)、苯氧基三曱基石夕烷、環己氧基三甲基矽烷、1-環己烯氧基三曱基矽烷、二曱基乙氧基苯基矽烷、苄氧基三甲基矽烷、甲氧基三丙基 _矽烷、苄基二曱基乙氧基矽烷、2-乙基己氧基三曱基矽烷、辛氧基三曱基矽烷、十二烷氧基三曱基矽烷等保有單官能之烧氧基的烧氧基石夕烧類。以氯矽烷類而言，可列舉如三曱基氯矽烷、二曱基乙稀基氯梦烧、稀丙基二曱基氯碎烧、二甲基丙基氯梦烧、二曱基異丙基氯矽烷、三&基氯矽烷、三級丁基二曱基氯砍烧、二曱基苯基氯梦烧、甲基苯基乙稀基氯發烧、节基二曱基氯矽烷、三丙基氯矽烷、二甲基辛基氯矽烷、三丁 # 基氯矽烷、二苯基甲基氯石夕烷、二苯基乙烯基氯矽烷、三苯基氯矽烷、三己基氯矽烷、二甲基十八烷基氯矽烷、三苄基氯矽烷等保有單官能之氯矽烷基的氯矽烷類。以矽烷醇類而言，可列舉如三甲基矽烷醇、三乙基矽烷醇、三苯基矽烷醇等保有單官能之矽烷醇基的矽烷醇化合物。以矽烷基胺類而言，可列舉如三甲基矽烷基二曱基胺、三甲基矽烧基二乙基胺、二甲基胺基三曱基矽烷、烯 53 319793 200838965 丙基胺基三甲基矽烷、曱基-N-三甲基矽烷基乙醯胺、苯胺基三甲基矽烧、1-三甲基矽烷基吡咯、L三甲基矽烷基吼嘻啶酮、1-三甲基矽烷基咪唑、三曱基矽烷基4,2,4-一哇專保有單官能之石夕烧基胺基的石夕烧基胺類；如1，1，3，3_ 四甲基一石夕氮文元、六曱基二石夕氮焼（HexamethylHexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexane Dimethanol, tricyclodecane dimethanol, cyclopentadienyl dimercaptan, dimer diol (dimer or other aliphatic or alicyclic diols; 15 bis (2-hydroxyethoxy) benzene, ^ ^曰 double d-based ethoxy)benzene, anthracene, bis(2-hydroxyethoxy)benzene, methylene diphenol, 4,4 (2-norbornyl) diphenol (M '-(2-norbornylidene)diphen〇1), 4,4, 'dimension= and p-di-diphenyl, 4,4,_isopropylidene test, in double: two original::? Forming double-checking and other aromatic diols. Addition molding double hope, such as ring i B: column = double enzyme A, double. F, etc., the raw material alkylene oxide can be listed as hexane, % oxypropane and the like. Two or more kinds of the above lower molecular weight glycols are used in combination. They may be used singly or in combination, and may be exemplified by high-molecular-weight, high-molecular-weight molecular weight polycarbons, high-molecular-weight polyols (a-1-α-2). Poly S-type alcohol, high molecular weight (tetra) amine multi-polynonanol, and high molecular weight polyurethane polyol: 319793 36 200838965 The acid ester polyol is obtained by making the above lower molecular weight glycol and carbonate or light Gas is obtained by carrying out a reaction. Acid value <0.5 acid value <0.5 acid value <0.5 acid value <0.5 acid value <0.5 acid value <0.5 acid value <0.5 hydroxy valence = 28, hydroxy valence = 22, hydroxy valence = 19, The valence of the hydroxy group is 28, and the valence of the hydroxy group is 19, and the commercially available product of the high molecular weight polyester polyol is, for example, Vylon GK640 manufactured by Toyobo Co., Ltd. [number average molecular weight (hereinafter also referred to as "]^11") = 18,000. , glass transition temperature (hereinafter, also referred to as "Ding &") = 79 ° C, hydroxyl value = 5, acid value < 4, linear type], Vylon GK880 (Mn = 18,000, Tg = 84t:, hydroxyl value =5, acid value < 4, linear type), Vylon 300 (Mn = 23,000, Tg = 7 ° C, hydroxyl value = 5, acid value < 2, linear type), Vylon 500 (Mn = 23,000, Tg = 4〇C, hydroxyl value = 5, acid value < 2, linear type), Vylon 560 (Mn = 19,000, Tg = 7 ° C, hydroxyl value, acid value < 2, branch type), and Vylon 630 (1) ^11=20,000, Tg=75 °C, hydroxyl value=5, acid value=1, linear type); UE-3600 manufactured by KURARAY Co., Ltd. (Mn=20,000, Tg=75°C, base price = 4, acid Price = 1), UE_3690 (Mn = H, 000, Tg = 91 〇 C, base price = 8, acid value = 1) [ The above is manufactured by UNI1TIKA Company], P1010 (Mn=l,000, hydroxyl value=112, acid value <0.5, linear liquid type), P2010 (Mn=2,000, hydroxyl value = 56, linear liquid type), P4010 (Mn = 4,000 linear liquid type), P5010 (Mn = 5,000 linear liquid type), P6010 (Mn = 6,000 linear liquid type), P4050 (Mn = 4,000 linear liquid type), P6010 (Mn = 6,000 linear liquid) Type), N4010 (Mn = 4,000, hydroxyl value = 28, linear liquid type), PNOA 4014 (Mn = 4,000, base price: 28, acid value < 0.5, linear liquid type), P2011 (Mn = 2,000) , hydroxy 37 319793 200838965 valence = 56, acid value < 0.5, linear liquid type), and P4011 (Mn = 4,000, hydroxyl value = 28, acid value < 0.5, linear liquid type); manufactured by Kyowa Fermentation Chemical Co., Ltd. Kyowapol 2000BA (Mn = 2,000, base price = 58, acid value < 0.5, linear liquid type), and Kyowapol 5000PA (Mn = 5,000, hydroxyl value = 22, acid value < 0.5, linear liquid Type) and so on. For example, TPAE617 (Mn = 15,000, Tg = 90 ° C, hydroxyl group = 16, acid value = 1, linear type) manufactured by Fujisei Kogyo Co., Ltd., and the like can be used as a commercial product of the high molecular weight polyamine polyol. For the commercial product of the above-mentioned high molecular weight polycarbonate polyol, for example, Oxymer N112 manufactured by PERSTORP Co., Ltd. (Mn=l,000, Tg=60〇C, hydroxyl value=112, acid value <0·5, linear shape) Type); PCDL-T5651 (Mn=l,000, hydroxyl number=110, acid value <0.05, linear liquid type), PCDL-T5652 (Mn=25000, hydroxyl value=56, acid value) manufactured by Asahi Kasei Chemical Co., Ltd. <0·05, - linear liquid type), PCDL-T4671 (Mn = 1,000, hydroxyl number = 110, acid value < 0.05, linear liquid type), and PCDL_T4672 (Mn = 2,000, hydroxyl value = 52, acid value < 0.05, linear liquid type); PMHCM050 (Mn = 1,000, hydroxyl number = 12, acid value < 0.5, linear liquid type), PMHC-2050 (Mn =) 2,000, hydroxyl value = 56, acid value < 0.5, linear liquid type), C-1090 (Mn = 1,000, base price = 12, acid value < 0.5, linear liquid type), C-2090 (Mn = 2,000, hydroxyl value = 56, acid value < 0.5, linear liquid type), C-3090 (Mn = 3,000, hydroxyl value = 37, acid value < 0.5, linear liquid type), 〇-4090 (1^11=4,000, hydroxyl value = 28, acid value < 0.5, linear liquid Type), C-5090 (Mn = 5,000, hydroxyl number = 22, acid value < 〇 · 5, linear liquid type), C-1065N (Mn = 1,000, hydroxyl price 38 319793 200838965 = 112, acid value <0·5, linear liquid type), C-2065N (Mn=2,000, hydroxyl value=56, acid value <0.5, linear liquid type), C-1015N (Mn=l,000, hydroxyl value = 112, acid value < 0.5, linear liquid type), and C-2015N (Mn = 2,000, hydroxyl value = 56, acid value < 0.5, linear liquid type) and the like. For the commercially available product of the above-mentioned high-molecular-weight polyurethane polyol, for example, Vylon 1^1350 manufactured by Toyobo Co., Ltd. (1^11 == 30,000, Tg = 3 ° C, base price = 46, acid value < 1, linear shape Type), Vylon UR1400 (Mn=40,000, Tg=83°C, hydroxyl value=2, acid value <1, linear type), Vylon UR3210 gin (Mn=40,000, Tg=-, hydroxyl value=3, acid value <1, linear type), Vylon UR5537 (Mn = 20,000, Tg = 34 ° C, base price = 17, acid value < 1, linear type), and Vylon UR9500 (Mn = 25,000, Tg = 15t:, Hydroxyl valence = 5, acid value <1, linear type); Takelac E15 8 (hydroxyl price = 20, acid value < 3), Takelac E551T (hydroxyl price = 30, acid value < 3) manufactured by Mitsui Chemicals Polyurethane Co., Ltd. ), and Takelac A2789 (base price = 10, acid price < 2) and the like. Other polyester polyols obtained by ring-opening polymerization of lactones, such as polycaprolactone diol, poly(β-methyl-7-valerolactone) diol, and polyvalerolactone diol, etc. It is included in a high molecular weight diol which can be used as the above high molecular weight polyol (a-1-α-2). In the present invention, the above-mentioned high molecular weight polyol (a-1-α-2) may be used singly or in combination of two or more. Further, it may be used in combination with the above low molecular weight polyol. When a bifunctional diol is used for such a polyol, a pressure-sensitive adhesive having excellent adhesion, heat resistance, moist heat resistance, and transparency can be obtained, so that a bifunctional diol is the most good. 39 319793 200838965 The molecular weight of the above-mentioned high molecular weight polyol (a small α·2) is not particularly limited as long as it is soluble in the solvent to be used, and the number average is 500 to 50, and the high score of the range of 〇〇〇 is early _ It is better to turn (5)-3b in the knife back to Ma Rong (4). When such a two-molecular weight polyol (V) is used, a pressure-sensitive adhesive having a different adhesion and stagnation property can be obtained. It is better to use Μ〇〇 to 3〇, _, the best is to use 1, 〇〇〇 to! Hey, _. If the number average molecular weight (Μη) of the high molecular weight polyol (5)_α -2) is smaller than the order, the resulting addition-formed polyester resins (D1) to (D3) become too hard, and when the adhesive composition is prepared and formed into a feeling When the sheet is pressed, it becomes difficult to develop initial adhesion (adhesion). In addition, if a plastic adhesive film containing too hard addition molding polyester resins (D1) to (D3) is used to laminate plastics or glass sheets with a plastic film, the strength is weakened, and the laminate is so thick. The body becomes easy to peel off after being left for a long time under high temperature and high humidity. On the other hand, if the Mn of the high molecular weight polyol (a-1 · α -2) exceeds .. 50,000, the addition of the polyester resin (L = (D3) to the solvent is reduced, and the pressure-sensitive adhesive The viscosity of the coating increases, so the processing during coating processing becomes difficult and thus poor. The glass transition temperature (Tg) of the two molecular weight polyol (a_l_α _2) is not particularly limited, but is -7 to 8 inches. It is better, more preferably -5〇 to 20 C. If the right glass transfer temperature is less than -7〇〇c, the adhesion or cohesive force of the adhesive composition may become insufficient. Causes agglomeration damage and peeling. On the other hand, if it exceeds 8 (rc, the coating film will become too hard, and the thermal method will show initial adhesion (viscosity), or the coating processability will become The glass transition temperature of the two-molecular weight polyol (a_ 1 _ α _2) can be adjusted by appropriately selecting the polycarboxylic acid, polyamine and low molecular weight 319793 40 200838965 of the raw materials, and can also be used. 2 or more different glass transition temperature polyols to adjust to the appropriate glass transition temperature The base price of the high molecular weight polyol (a-lU) is preferably in the range of from $ to 200 mgKOH/g, more preferably in the range of from 1 to 1 mgK〇H/g. If the hydroxyl value exceeds 2〇〇 When the mgKOH/g is added, the addition of the polyacetal resin (d: to (D3) becomes too hard, and it becomes difficult to express the initial adhesion (adhesiveness). If the base price is less than 5 mgKOH/g', the addition polymerization is performed. The solubility of the vinegar resins (9)) to (D3) for the solvent is lowered, and the viscosity of the adhesive composition is difficult to increase. Therefore, the handling during coating processing becomes difficult, and the processing becomes a barrier. Temple & Second, A trifunctional or higher polydecanoic acid (a-1-cold) used for the above-mentioned high molecular weight polyols to react with a high molecular weight dicarboxylic acid (a·^) will be described. The acid (8) is not a compound having an anhydride ring =, and a polycarboxylic acid having a tricyclic or higher functional group of one anhydride ring is not listed, such as trimellitic anhydride. The polycarboxylic acid of a functional group or more may, for example, be butane tetracarboxylic dianhydride, ^, 3, 4 • cyclobutane tetracarboxylic acid II' 1 2 λ d TM U-f-group 2,44-3⁄4 butane tetracarboxylic dianhydride, U,3,4-cyclopentane tetracarboxylic dianhydride, —nonylcyclopentyl acetic acid monohydride, 2, 3,5,6 -tetradecylcyclohexanin 2=, 2^3,5,6-four rebel base norbornene dianhydride, 3,5,6_three slow-base ice-cold two = _ _ acetic anhydride dianhydride , 2,3,4,5•tetrahydrofuran tetracarboxylic dianhydride, $ _ DFMF NAN) _3_ fluorenylcyclohexene dicarboxylic dianhydride, double ring 2.2.2]· xin-7-埽_2 ,3,5,6-tetracarboxylic dianhydride, pyromellitic acid =: 319793 41 200838965 1,2,4,5-benzenetetrahydro acid dianhydride, ethylene glycol di(trimellitic anhydride) |丙二酉事二(Sf), butyl hexanolate (trimellitic acid needle), 3,3',4,4'-diphenyl ketone four acid dianhydride, 2,2,,3,3,-benzophenone tetrazoic acid dianhydride, 3,3',4,4'-biphenyl fluorene tetrahydro acid dianhydride, 2,2,,3,3,-linked Benzoite four tetrahydro acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene tetrasulphonic acid dianhydride, naphthalene·1,8: 4,5-four Carboxylic dianhydride, 4,4'-(hexafluoropropylene) diacetic anhydride, 3,3',4,4'-diphenyl ether tetra-retensive dianhydride, 3,3',4,4'_ Dimercaptobiphenyl Shi Xiwan tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic dianhydride, i,2,3,4-furfuran tetracarboxylic dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4,·double (3,4-di-respective phenoxy)diphenylpropane dim, 3,3',4,4,-perfluoroisopropylidene dicarboxylic acid dianhydride, 3,3',4,4 '-Biphenyltetracarboxylic dianhydride, bis(decanoic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphosphonic acid) dianhydride, m-phenylene bis(bis) Benzoic acid)--Sf bis(di-based acid)-4,4'^diphenyl phthalic anhydride, bis(triphenylphosphonic acid)-4,4'-diphenyl succinic anhydride 9,9-bis[4-(3,4-disindenylcarboxyphenoxy)phenyl] anhydride, ethylene glycol bis(pellisine), 3,4_a buffer-1,2,3, 4_ tetraar _ 1 -naphthic acid dihepatic, 3,4-disulfo-1,2,3 4-* tetrahydro-6-methyl·1_naphthalene succinic anhydride, 9,9- Bis(3,4-dicarboxyphenyl)second anhydride, bicyclo[2·2·1]hept-5-ene_2,3_dioxalic anhydride, Methyl nadic anhydr Ide), allyl bicyclo [2·2·1]hept-5-ene-2,3-dicarboxylic anhydride, methallyl bicyclo[2·2·1]hept-5-ene-2,3- Dicarboxylic anhydride, allylmethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methallylmethylbicyclo[2·2·1]hept-5-rare- 2,3-dioxalic anhydride, etc. The above-mentioned low molecular weight dicarboxylic acid (a-1-l) and the above polycarboxylic acid (^-not > 319793 42 200838965 may be used alone or in combination, in the LI + reaction. As in the case of ~=7 and polyol (Heart) ring of cyclic anhydride, can be heart = (;:), if you use the possession - an anhydride Kejitian pattern, the contact resistance, heat resistance, heat and humidity resistance and transparency In the present invention, in the present invention, the dibasic acid (5) for the formation of the vinegar main chain (1) is used: in comparison with the direct use of the low molecular weight two oxonic acid (5), - the higher molecular weight dicarboxylic acids (a-1-2, ai-3) obtained by the reaction of the tannins (6).1) or the three or more palaces (5) More suitable. When the high molecular weight dicarboxylic acid (a)_2, "·" is used as the dibasic acid (a 1) and the polyester backbone (1) is formed, it is compared with the case where the low molecular weight diacid (a' is directly used. The distance between the ester bonds in the polyester primary bond (1) due to the polyaddition can be lengthened, and the relationship between the secondary hydroxyl groups can be appropriately prevented, and the polyester block formation due to the combination of the hydroxyl groups can be suppressed. At the same time, it is easy to reduce the hydroxyl groups of the singly-molded polyester resins (D1) and (D2). If such a molded polyester resin (D1) or (D2) is used to modulate the pressure-sensitive adhesive composition = It is possible to maintain the balance of the subsequent properties (especially the adhesion of the adhesion and the cohesive force). Therefore, it is preferred to use the bismuth molecular weight of the bismuth acid (a_U, a1 3) as the dibasic acid (a_i) to form a poly Ester main chain (1). Polydecyl dicarboxylic acid (heart 2_4) which can be used as the dibasic acid (a-1), which is a low molecular weight dicarboxylic acid (a-1-l) and a polyamine (heart) 〗〖-^ ) Condensation under the conditions of carboxy hydrazine over 1 , so it is composed of two rebel groups at the end and linked by a guanamine bond. 319793 43 200838965 The polyamine (alr) used for the preparation of the guanamine dicarboxylic acid is not particularly limited as long as it is a polyamine having two or more amine groups. For example, as the aliphatic polyamine, Such as 2,5-dimethyl-2,5-hexamethylenediamine, menthane diamine, l-4-bis(2-amino-2-mercaptopropyl), in the molecule "Propylene-based polypropylene glycol, propylene skeleton diamine, Suntechno Chemical Co., Ltd. products "Jeffamine D230" and "Jeffamine D400", propylene skeleton triamine, and Suntechno Chemical Co., Ltd." Jeffamine T403" _, etc., ethylenediamine, propylene diamine, butyl diamine, diethylenetriamine, triethylenetetramine, tetraethyleneamine, pentaethyleneamine, hexamethylenediamine , tridecyl hexamethylenediamine, N-aminoethylpiped, 1,2-diaminopropane, iminodipropylamine, mercaptoimidodipropylamine, H2N(CH2CH20) 2(CH2)2NH2 [Diamine of ethylene glycol skeleton manufactured by Suntechno Chemical Co., Ltd. "Jeffamine EDR148"], etc., in which a diamine of a methylene oxime polyether skeleton is bonded to an amine nitrogen, 1,5-Diamino-2-methylpentane ("MPMD" manufactured by DuPont Japan Co., Ltd.), Metaxylylene diamine ("DuPont", "XMX"), polyamidoamine ("X2000" manufactured by Sanwa Chemical Co., Ltd.), isophorone diamine, 1,3-diaminodecylcyclohexane ("1,3BAC" manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1-cyclohexylamino group -3. Aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, dimethyleneamine of norbornane skeleton ("NBDA" manufactured by Mitsui Chemicals Co., Ltd.), and the like. Further, the ketimine of the reaction product of the above polyamine and a ketone can also be used as a polyamine (a-1-r) in the preparation of polyamine dicarboxylic acid, and is in terms of polymerization stability or From the viewpoint of the adjustment of reactivity, see, for example, 44 319793 200838965, preferred examples include acetophenone or propiophenone, a reaction product with hydrazine, 3-diaminomercaptocyclohexene; acetophenone or propiophenone, a reaction with a dimethyleneamine (NBDA) of a norbornane skeleton; a acetophenone or a propiophenone, a reaction with a female in January, a acetophenone or a propiophenone, and an ethylene glycol backbone or The copolymer of the propylene skeleton diamine, jeffamine EDR 148, jeffamine 〇 230, Jeffamine D400, or the like, or a reaction product such as Jeffamine T403 which is a triamine of a propylene skeleton. The above polyamines may be used singly or in combination of two or more. In the present invention, the dibasic acid (a-1) used for forming the polyester main chain (I) having a hydroxyl group at the side chain position can be suitably selected from the above-mentioned low molecular weight dicarboxylic acids (a small 1) and high molecular weight two. Among the carboxylic acid (f), (3), and polyamine carboxylic acid (a-1-4), one or two or more kinds are used. Next, the dicyclic ether compound (a-2) for forming the polyester main chain (I), that is, a compound having two cyclic ether groups in the molecule will be described. The nuclear ruthenium compound (a_2) is subjected to a polyaddition reaction with the above-mentioned dibasic acid (5)) to form an ester bond and a secondary hydroxyl group. The structural unit derived from the above dibasic acid and the bicyclo (tetra) compound (IV) is alternately reciprocally linked via an vinegar bond to form a polyacetamide backbone (1). The secondary via system is directly bonded to the poly-primary primary bond (I) and participates in the formation of the branched side chain. The two cyclic squaring compound (IV) used in the present invention may be a compound containing: a known epoxy propyl group and/or an oxetanyl group (xeta_): and an oxygen compound (ie, a propylene group) The compound) may be an aliphatic: "any of the compound or the alicyclic compound may be 319793 45 200838965 high molecular weight resin. For the aliphatic diepoxypropyl compound, it may be exemplified as ethylene Alcohol diepoxypropyl bond, diethylene glycol diepoxypropyl scale, triethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, two Propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, butanediol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6 - hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, diepoxypropylamine, butyl dioxide, diethylene oxide diepoxypropyl ether, etc. Examples of the oxypropyl ether compound include 2,6-diepoxypropylphenyl ether, diglycidyl phthalate, diepoxypropyl ether of trimellitic acid, and bisphenol A. Oxypropyl propyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, 2,2-bis(4-hydroxyphenyl)propane diepoxypropyl ether, bis(4-hydroxyl Phenyl)decane diepoxypropyl ether, 1,1-bis(4-hydroxyphenyl)ethane diepoxypropyl ether, 3,3',5,5'-tetradecyl-4,4 '-Dihydroxybiphenyl diglycidyl bond, 2,2_bis(4-(/5- mercaptopropyl)phenyl)propene-fired two-breast propyl ether, m-phenylene di-epoxy Resorcinol diglycidyl ether, biphenyl*"4,4'-dioxypropyl mystery, 1,5-di-light ketone, silver propyl bond, 1,6-di-light ketone An oxypropyl bond, a 2,7-di-light dimethyl sulphate propyl bond, a bisphenol quinone diepoxypropyl ether, a bisphenoxyethanol hydrazine diepoxypropyl ether, etc. Examples of the oxypropyl ether compound include cyclohexanedimethanol diepoxypropyl ether, dicyclopentadiene dioxide, and 3,4-epoxypropylcyclohexyldecyl-3,4-. Epoxypropylcyclohexanecarboxylate, 3,4-epoxypropyl-6-mercapto-based hexyldecyl- 3,4- 5 oxopropyl-6-indenyl hexanoic acid citrate, Vinyl cyclohexane dioxygen , dicyclodienol epoxide epoxy propyl ether, 46 319793 200838965 tetradecanoic acid diepoxypropyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diepoxypropyl Shout, 2,2_bis (4_ylcyclohexyl)propane-fired diepoxypropyl ether, bis-(3,4-epoxycyclohexyl) adipate, etc. Examples of the propyl resin include a bisphenol A type high molecular weight epoxy propyl resin, a bisphenol F type high molecular weight epoxy propyl resin, or a propoxy group obtained by reacting the above-mentioned diepoxy propyl compound. Resin, etc. The di-epoxy propyl compound of the double resin system (AS, F type, etc.) has a secondary mercapto group, and the secondary base system and the dibasic acid of the dibasic acid (4)) are added to the ruthenium. The secondary hydroxyl group produced by the ether group (epoxypropyl group) is similarly used as a starting point for forming a side chain. Examples of the compound having an oxetanyl group include acetoacetic acid, dioxetane, adipic acid, dioxetane, dioxane, cyclobutane, and oxime.酉双双双双、、环环环环环环环环环环环环环环环环环双双双双双双双双双双双双双双双双双双双-oxetanyl)methoxy]methyl}benzene, bis{1ethyl-(3-oxetanyl)methyl ether, and the like. The above-mentioned dicyclic ether compound (a_2) may be used alone or in combination of two or more. The cyclic ester (b) used in the present invention will be described once. The cyclic ester (b) is subjected to a ring-opening addition reaction to the secondary hydroxyl group directly bonded to the side chain of the above polyester main chain (1) to form a side chain of the addition-molded polyester resin CD1 D2 D3). The side chain is bonded to the polyester primary bond (I) via an ester bond, and the ring-opening structural unit containing the cyclic vinegar (8) and the terminal end of the hydroxyl side chain of the terminal are reacted with a crosslinking agent (6) described later via a substrate. By this, 319793 47 200838965 is used to harden the polyester resin (D) to form a pressure-sensitive adhesive layer. By adjusting the amount of the cyclic ester (8) which is subjected to the reaction of one of the hydroquinone main chain (1), the amount of the side chain of the ring-opening ester structure can be controlled, and the amount of introduction of the side chain can be ensured. The adhesive composition of the addition-molding polyester resins (D1) to (D3) serves as a balance of the subsequent characteristics of the pressure-sensitive adhesive (especially at the same time as adhesion and cohesive force). The addition of the polyester resin (D1 to D3) as described above can be obtained according to a three-stage type, a pseudo-two-stage type, or a two-stage type, and the ring-opening addition or blocking compound (8) of the ring-shaped vinegar (8) The degree of progress of the formation reaction (polyaddition reaction) of the chain (I) is different in the polyester at the start of the addition. Since the force reaction has been completed, the viscosity is such that the hydroxyl groups are combined or side-reacted with each other, and the ring is _> or uniformly mixed with the blocking compound (4). If it is hindered, the reaction efficiency = easy to decrease, and the addition reaction of the ring 8 (b) or the blocking compound is inhibited, and the φ = base amount at the start of the reaction with the cyclic vinegar (8) or the blocking compound (4) is If it is less, the reaction efficiency is better, the stability of the reaction is improved, and the degree of unevenness is reduced. Therefore, the formation of the main chain of the vinegar and the formation of the side chains (ΙΙ, ΙΓ) are substantially parallel and the two == manufacturing method is based on the accumulation of money to generate the reading base will be: vinegar (b Or the addition of the blocking compound (e) is a small amount, so it is more preferable than the three-stage production method. Hanging, quasi-beauty = invention: the ring-shaped vinegar (b) used for the formation of the Γ-side bond is opened by dehydration condensation in the molecule or in the molecule by the _ tempering acid: ready-to-wear, and. The structure is a ruthenium and is a heteropolymer comprising a cyclic monomer, a dimer, a 319793 48 200838965 or a dimer. The cyclic ester (b) used for the f-recognition is not limited by the size of the ring, so the hydroxy carboxylic acid hydrazine which is the precursor of the % ester (b) can be reduced by dehydration. And 幵/%%' is not particularly limited, and an intramolecular j intermolecular condensate of aliphatic, alicyclic, aromatic, and 8%, or one or more of the sulfonic acids may be used as a precursor. The cyclic ester (b) is used. Hereinafter, the transbasic acid (y) which is a precursor of the cyclic ester (b) is exemplified. Examples of the aliphatic hydroxycarboxylic acid include, for example, glycolic acid, lactic acid, 3-propionic acid (Hydricic acid (4), peroxybutyric acid, _ 爹 /, butyl hydrazine, per valeric acid, _ hexylhexanoic acid, ά _ hexyl hexanoic acid, glyceric acid, tartronic acid, malic acid, citric acid, octanoic acid, lauric acid, ricinoleic acid, α _ hydroxy Alpha acid (α • hydroxy dotriacontanoic acid), trans-methane tetradecanoic acid, α-pyruyl-de-s-, fluorene, α-light octadecanoic acid, α-hydroxytetradecanoic acid ), hydroxytrimercaptoacetic acid, hydroxypropionic acid, 6-hydroxy valeric acid, α-pyridylheptanoic acid, 1 hydrazine, stearic acid, 12-hydroxystearic acid, 1 〇癸癸癸, 12-by-furoic acid, 3-peryltetradecanoic acid, 16-alkylhexadecanoic acid, 15-hydroxypentadecanoic acid, α-hydroxyicosuccinic acid, α-hydroxytetracosic acid, α _ Twenty four acid, α-hydroxyglutamic acid, hydroxy octadecanoic acid, hydroxy thirty acid, β-hydroxytetradecanoic acid, dihydroxymethyl propionic acid, 3,5-di-tertiary butyl salicyl Acid, etc. Examples of the alicyclic, aromatic, and heterocyclic hydroxycarboxylic acids include salicylic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 3,4-diphenylbenzoic acid, and 4-hydroxyl group. -3-phenyl alum acid, 4-hydroxy-3-indolyl benzoic acid, 4-hydroxy 49 319793 200838965 _3,5·dimethoxybenzoic acid, 4′-hydroxy-4_carboxybiphenyl, & hydroxy_2_decanoic acid, 3-hydroxy-2-naphthoic acid, 5-hydroxynaphthyl tauric acid, and the like. The butylated hydroxy spectabilizing acid is not limited to the above-exemplified ones as long as it has an organic compound having several acids and a trans group in the molecule. In the present invention, the inner vinegar can be used as the ring-shaped early limbs of the carboxylic acid to be used in the form of a ring, and is not particularly limited, and examples thereof include yttrium butyrolactone, /?-propene vinegar, and r· Ding Neizhi, r_ 戊内酉, 戊内酉, £ win; 酉酉, 卜酉曰匕内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内内_ Xin vinegar, ε 内 vinegar vinegar vinegar ΓΡΓ〇 1 (10). Ne glycolide), trimethyl ethyl lactone (coffee __call, 7_ 酉l (7_heptan〇lide), 8-inner 酉、, 11 - 炫酉、, 12 卄汉汉、、卄Pentane, hexadecane, 16-hexadecane vinegar, heart methyl π-propane, α β $ 基 · , α, α — T-based-stone · propiolactone, etc. In the case of the cyclic vinegar (8), the base acid can be used, for example, the lactic acid can be used as the (four) ide, and the glycolic acid can be used alone: open: addition, which can be used for the poly(tetra) polymer. Add; = repeat vinegar (8) formed by the ring-opening addition of the molecule, then more: v = the base of the vinegar is supplied. , knife-like 酉曰 ((0) addition polymerization and the side chain can be extended from the individual addition of the ester (b) formed by the ring opening, the ring S 曰 (b) is better. In addition, the side chain is effective From the viewpoint of the ring, the number of carbon atoms constituting the ester ring structure is 4 or more in order to form a good ring-opening addition reaction with the base efficiency of the polyester primary bond (1) 319793 50 200838965 The lactone of the cyclic monomer having a ring number of 6 to 18 is preferred, and more preferably, the caprolactone is used. Next, the blocked north compound (c) for blocking the hydroxyl group is explained. The blocking compound (c) is a compound which reacts with a hydroxyl group and can block a hydroxyl group by addition, which is a terminal hydroxyl group of the side chain (II) of the addition polyester precursor (C1, C2), or a polyester. A portion of the hydroxyl group directly bonded to the main chain (1) reacts and blocks the hydroxyl group, while forming a side chain (ΙΓ) of at least one part of the side chain and having no light group. Therefore, by using a closed combination ( c) 'Additional polyester resins (D1 to D3) with less hydroxyl groups than the addition of polyester precursors. That is, by using the blocking compound (c), the amount of the hydroxyl group which is a functional group reactive with the crosslinking agent (E) can be controlled. Then, by reducing the hydroxyl group in the addition-molded polyester resin (D1 to D3) It is possible to improve the heat resistance and the moist heat resistance when the adhesive composition is used as a pressure-sensitive adhesive. ^ ^ In addition, in the second closed form, the compound (c) which can react with a hydroxyl group is used for Reacting with a part of the secondary hydroxyl group in the polyester main chain portion (1) formed by the polyaddition reaction of the dibasic acid (a_i) with the compound (a-2) having two cyclic ether groups, and forming Adding a side chain portion (Π) in the polyester resin (D2). The side chain portion (11,) does not have a warp group. Then, for the secondary mercapto group M remaining in the polyester main chain portion σ) The cyclic ester compound (b) undergoes a ring-opening addition reaction and is opened to form a side chain portion (η) having a hydroxyl group at its terminal. That is, by blocking the compound (4), the amount of the base group in the polyester backbone (I) which is a reaction point with the ring-shaped engineer) can be adjusted, that is, the side where the polylactic acid main bond portion (1) is bonded can be adjusted. The rate of the side chain 319793 51 200838965 of the open-loop structural unit having the ring g|(8) occupied by the chain. Therefore, it can be used for the adjustment of the subsequent characteristic balance (especially the same as the viscosity and the cohesive force) when the addition of the polyacetal resin (D2) is used as the pressure-sensitive adhesive. Further, the step of blocking the compound (4) can also be used to reduce the terminal group of the first side chain (II) in the addition-formed polyester resin (), and obtain the third closed form of the addition-formed polyester resin _, which The blocking compound (4) also has a function of finally adjusting the hydroxyl group of the polyester resin. The blocking compound (4) used in the present invention is preferably any one of, for example, a linsinizing agent (Cl), an acid (C2) or an isocyanate compound (c3), more preferably a single g or not Compound (6) having a plurality of functional groups cross-linked. The blocking compound (4) may be used singly or in combination of two or more. The (4) chemical agent (6) used in the present invention may, for example, be hydrosilane, burnt alkaloids, chlorite, orthraquinone alcohol, alkylamines, or the like. Cyclic compound... In the case of hydrohaloxanes, for example, trimethyl decane, triethyl decane, base, tributyl I, trihexyl I, diethyl methyl ketone, U keshi kiln, dimethyl phenyl stone Xishao, triphenylene, methyl phenyl thiocarbazide, pentamethyl oxalate, allyl dimethyl ketone, ginseng (trimethyl sulphate), heptamethyl three Oxygen, =1,3,5,7,7,7-octamethyl oxyoctane octacycline tetrahydroxane is monotonous with a monofunctional Si-H based hydrooxane. Examples of the alkoxy decane include methoxytrimethyl decane, methoxytriethyl decane, methoxy dimethyl ethoxylated decane, dioxyethyl bromide, and B. Oxyl trimethyl sulphate, ethoxy triethyl sulphate; 319793 52 200838965 allyloxy tridecyl decane, ethoxy dinonyl vinyl decane, tridecyl propoxy decane, trimethyl isopropyl Oxydecane, iota-propenylpropoxytridecyldecane, butoxytridecyldecane, isobutoxytrimethyldecane, tert-butoxytrimethylmethane, hexyloxytrimethyl Fever, 3-aminopropyl dimethyl ethoxylate, tetrahydrofurfuryloxy trimethyl silane, phenoxy sulphate, cyclohexyloxy Methyl decane, 1-cyclohexenyloxytridecyl decane, dimercaptoethoxy phenyl decane, benzyloxy trimethyl decane, methoxytripropyl decane, benzyl dimercapto ethoxylate Monofunctional alkoxylated alkoxylates such as decane, 2-ethylhexyloxytridecyldecane, octyloxytridecyldecane, dodecyloxytridecyldecane Xia burning class. In the case of chlorinated alkane, for example, tridecylchlorodecane, dimercaptoethyl chloromethane, dipropyl dimethyl chlorohydrazine, dimethyl propyl chlorinated, dimercapto isopropyl Chlorodecane, tris/amp; chlorodecane, tert-butyl dimethyl decyl chloride chopping, dimercaptophenyl chlorination, methyl phenyl vinyl fluorocarbon, benzyl didecyl chlorodecane, Tripropyl chlorodecane, dimethyloctylchlorodecane, tributyl chloroform, diphenylmethyl chlorin, diphenyl vinyl chlorodecane, triphenyl chlorodecane, trihexyl chlorodecane, A chlorodecane having a monofunctional chlorodecane group such as dimethyloctadecylchlorodecane or tribenzyl chlorodecane. The stanol may, for example, be a stanol compound having a monofunctional stanol group such as trimethylstanol, triethylstanol or triphenylstanol. Examples of the mercaptoalkylamines include trimethyldecyldidecylamine, trimethylsulfonyldiethylamine, dimethylaminotridecyldecane, and alkene 53 319793 200838965 propylamino group Trimethyl decane, decyl-N-trimethyldecyl decylamine, anilinotrimethyl oxime, 1-trimethyldecylpyrrole, L-trimethyldecyl acridone, 1-three Methyl decyl imidazole, tridecyl decyl 4, 2, 4- y y y y y y y y y y y y y y y y y y y y y y Hexazepine, Hexamethyl

Disilazane)、1，3-二乙烯基-l，i，3,3-四甲基二石夕氮烧、n，N，- 雙（二曱基矽烷基）苯基脲等保有2官能之矽烧基胺基的矽烷基胺類；如1，1，3,3,5,5-六曱基環三矽氮烷、着1，1，3,3,5,5,7,7-八甲基環四矽氮烷等保有3官能以上之環狀矽烷基胺基的矽烧基胺類等。子量二羧酸類（a-1-l)的酸酐為較佳。本發明所用之酸酐（C2)，可列舉例如作為形成前述聚酉曰主鏈（I)所使甩之二元酸（a-1)所例示的低分子量二致酸犬員（a-1-l)中的酸針、《是形成高分子量二動曼類（&小3)所使用的3官能以上的多羧酸類沒）中的酸酐，又以低分 #、另外，當以^段型製造方法獲得第2封閉型態之加Disilazane), 1,3-divinyl-l,i,3,3-tetramethyldiazepine, n,N,-bis(dimercaptoalkyl)phenylurea, etc. a mercaptoamine-based mercaptoalkylamine; such as 1,1,3,3,5,5-hexamethylenecyclotriazane, 1,1,3,3,5,5,7,7-eight A mercaptoamine or the like which retains a trifunctional or higher cyclic mercaptoalkylamine group, such as methylcyclotetraazane. The acid anhydride of the sub-dicarboxylic acid (a-1-l) is preferred. The acid anhydride (C2) used in the present invention may, for example, be a low molecular weight diacid acid dog (a-1-) exemplified as the dibasic acid (a-1) which forms the ruthenium main chain (I). The acid needle in l), "is an acid anhydride in the formation of a trifunctional or higher polycarboxylic acid used in the high molecular weight second-acting type (& small 3), and has a low score of #, in addition, when Type manufacturing method to obtain the second closed type

卞歿評造成障礙。The review caused obstacles.

吳氰酸丙酯、異氰酸丁酯、異氰酸辛g旨、 W中，就單官能異 §旨、異氰酸乙，酯、、異氰酸癸酯、異 319793 54 200838965 氰魷十八:ki曰、異氰酸硬脂酯、異氰酸環己酯、異氰酸苯酉曰兴氰齔苄酗、異氰酸對氯苯酯、異氰酸對硝基苯酯、異㈣^氯乙81、異氰酸2,4-二氯苯酯、異氰酸氣| 曱基苯酯、二氯乙醯基異氰酸酯、氯磺醯基異氰酸酯、曱基苄基異氰酸酯、S-(—)-a-甲基苄基異氰酸知、R-(一萘基）乙基異氰酸酯、苯基乙基異氰酉欠知s ( )_ 1 -本基乙基異氰酸酯、對-曱苯石黃蕴基異氰酸醋等。馨h —70酉夂（a-1)與二環狀鱗化合物〇2)之聚加成反應，只要疋使用A知f貝用的方法即可。例如，可為下述任一種型 =· 1)使二元酸（aq)與二環狀醚化合物（a_2) 一起調配並進 /亍反應，2) ϋ—元酸（a_l)缓緩地添加至二環狀醚化合，（a 2)中邊使其反應，或是—邊將二環狀_化合物（以) 緩緩地添加至二元.酸（ael)中一邊使其反應。 &在本發明之加成型聚酯樹脂（D1)、（D2)中，藉由二元馨酸（心1)與二環狀醚化合物（a_2)之聚加成反應所生成的直鏈狀聚酯主鏈(I)，於其末端具㈣基或環狀醚基。四相對於一το酸（a_i)之羧基！莫耳，二環狀醚化合物（心2) 之壞狀鱗基之莫耳數係在〇·5至2〇莫耳之範圍内，又以在〇·8至1·2之範圍内為較佳。若相對於羧基1莫耳，環 =基之莫耳數少於q.5莫耳或多於』莫耳，則難以提高聚酯主鏈（I)之分子量，而不易獲得具有作為目標感壓接著劑之特性的加成型聚酯樹脂。田形成聚酯主鏈（I)時，若使用如雙酚型之二環氧丙基 319793 55 200838965 醚化合物等具有2級經基之二環狀_化合物（a-2)，則在直鍵狀聚酉旨主鏈⑴所直接結合之二級羥基中，存在有因環狀 ^基之開環加成而產生之經基、以及二環狀醚化合物（a.2) $本即具有之给基等2種類。2種類之二級經基，任一者皆f為與環狀酯（b)或封閉化合物⑷的反應基點，而形成具有衣狀酉曰之開環結構單元與末端美里基的帛工4則鏈（π)、或經 f閉化合物（c)而使羥基被封閉的第2侧鏈。此外，經考察传知，比起原本即具有的2級經基，該藉環狀醚基之開環成斤產生之每基係更富有與環狀醋（b)或封閉化合物⑷ 的反應性。當聚酯主鏈（1)含有多量芳香族基時，雖然所得之加成型聚酯樹脂OM至D3)之耐熱性會變高，但其硬度亦會增而使黏著性難以顯現。另外，若含有多量脂肪族基，，樹脂之生物分解性變高，但耐熱性降低。因此，顧 f到此等問題’作為原料使用的二元_·1)及二環狀鱗化鲁5物（a_2)，係因應接著劑組成物之用途，並以使聚醋主鏈 (二)之芳香族基及脂肪族基之比率成為較佳的方式而適當 :擇一為了，力口成型聚酯樹脂(D)良好地顯5見耐熱性及黏著彡A基在聚s旨樹脂（D)分子中所佔有&比率(芳香環 3有卞曰)係以、、、勺〇.〇1至6〇%左右為佳，更佳為」至左 (重里比）树月日分子中之芳香環之比率，係可使用由所用口原料之刀子I、分子量中芳香環所占之質量比率及調配比致計算出的質量（或重量）平均值。田藉第1封閉型態調製加成型聚醋樹脂（間時，相對 319793 56 200838965 於直鏈狀聚酯主鏈⑴所直接結合之二級羥基i莫酯係以成為0.2莫耳以上之比率來反應為佳，、又以:為 0.5莫耳以上之比率來反應為較佳，再以成為0.8至莫耳之範圍内之比率來反應為更佳，尤以_ 15至*耳之範圍内之比率來反應為最佳。、士另外’當藉第2封閉型態調製加成型聚酯樹脂 ¥ ’ _於直鏈狀㈣旨域_直接結合之二級絲 XΓΓΓα?^^ °*15 ^^^^^^^^^ ^ 至6。莫耳之:以上之比率來反應為較I， 0旲耳之乾圍内之比率來反應為更佳，尤以成為〇二,力耳：範圍内之比率來反應為最佳。當藉第2封閉型離 _加成型聚㈣脂㈣時，由於封閉化合 = 醋相對於直鏈狀聚酯主 —、、及經基i莫耳，環狀醋⑻之量的較佳下限係第封閉型態調製加成型聚酯樹腊(D1)時變得更小。'、曰、及上述範圍，則難以獲得能調製出可成為黏著性 _脂⑼。因此，為了成為如上述部形成用的二環她合耳^ 成用的環卿)之重量。環狀酯（b)，係盥铖門浐力忐n土3過該莫耳的份量的日（bH糸贴開加成之側鍵的末端經基反應以被數之環狀酯分子經開環聚人 μ / ⑼。藉由環狀醋（b)之開環所^成口之^合物所構成的侧鏈有_美，而且古乂側鏈(11)係於其末端具 “ 有來酉曰主鍵部⑴與經基末端之側鏈部（Π)的 319793 57 200838965 加成型聚醋前驅物（C1)係以其羥基價為在5〇至 mr/g之範圍為佳，又以在5G至8GmgK_之範若將上述加成型聚醋前驅物（C1)之側鏈末端的羥基之一部分與上述封閉化合物⑷反應而轉換成第2側鍵(π，），則可獲得加成型聚醋樹月旨（D1)，#具有聚醋主鍵m、㈣末端之第、侧綱、以及於末端不具經基之第2 ‘ σ I ’）°加成型聚酯樹脂（D i)之經基價係可調節封閉化合物修⑷之使用量而調整成所期望之值，較佳為調整成〇1至編gK〇H/g之範圍’更佳為調整成0.5 S 30mgKOH/g之範圍。惟，當侧鏈具有羧基、且交聯劑⑻與絲反應時，加成型聚酯樹脂之羥基價係容許至100mgKOH/g左右，又以80mgKOH/g以下為更佳。 .依據使用之封閉化合物（c)，，亦有加力型聚酯樹脂（di) 之羧基比起加成型聚酯前驅物（C1)變得更多之情形，若封籲閉化合物（C)為酸酐，則形成具有末端羧基之側鏈。當交聯釗（E)與羥基反應時’酸價可容許至某種程度高之值，但當交聯劑（E)與羧基反應時，則加成型聚酯樹脂（D1)之酸價^ 以0.1至5〇mgKOH/g之範圍為佳，更佳為〇 5至3〇mg KOH/g之範圍。羥基價或酸價若低於〇」mgK〇H/g，則交聯劑（E)對於. 羥基或羧基之反應性差，經硬化之樹脂之凝集力不足，故不僅是經接著之偏光薄膜等之剝離變得困難，剝離後亦產生殘餘黏糊、或是再剝離性變得不充足。另外，羥基價或 319793 58 200838965 酸價若高於50mgKOH/g，則調配有交聯劑（E)之接著劑組成物的適用期變短，塗佈加工時或接著時之作業性明 P牛。此知點係共通於加成型聚酯樹脂⑴1至)，依^交聯劑（E)之類型（反應於羥基及羧基中之任一者），關於反= 對象之值較佳為調節成G·!至5QmgK〇H/g，更佳為調節^ 0.5 至 30nigICOH/g。、〜在加成型聚輯樹脂（D2)之製造中，為了調節上述酸價或羥基價，較佳為相對於直鏈狀聚酯主鏈⑴之二級羥基工莫耳，以使可與封閉化合物（c)之羥基反應的宫能為 0:01至0.85莫耳（更佳為〇1至〇 7莫耳）的比率與原料進行反應。然後，相對於未反應錄〗莫耳，較佳為以使環狀醋⑻成為0.8至40莫耳（更佳為2 〇 i 2〇〇莫耳）的比率進行反應，而獲得加成有源自環狀_)之第】側加成型聚酯樹脂(D2)。 ·· 封閉化合物（C)之官能基相對於聚醋主鍵⑴之声美合，㈣若未達（UH料，則環錢削無論其加成^多二’加成型聚酯獅(D2)之經基價皆變高。推測此係由於 ^主鏈直接結合之㈣殘餘多量時，即使大量添加環狀醋乂比起城酯⑻對於主鏈直接結合之經基的開環加成，衣狀酯⑻更為進行其自身之開環加成，而主直接处經基減少得並不多之故。因A + 士、別¥ 丧、、、口口之 “小户之故因為加成型聚醋樹脂_之羥基面，故經硬化之樹脂㈣熱性及耐濕熱性變低。另一 =玄面，封閉化合物⑷之宫能基相對於聚酯主鏈⑴之經基的 ¥若多於〇.85莫耳，則幾乎無法藉由環狀醋⑻形成側 319793 59 200838965 鏈（π)，而難以獲得可調製出成為使黏著性及凝集力皆滿足之感壓接著劑的接著劑組成物的加成型聚酯樹脂（D2)。加成型聚酯前驅物（ci、C2)係如前述，可依據三階段型、擬似二階段型、以及二階段型之任一種製法而獲得，原料之調配比率係與前述相同。當談製法為二階段型時，例如，只要是使二元酸（aq)、與二環狀醚化合物（a_2卜與 %狀酯（b)或與封閉化合物（c) 一起調配並反應即可；當該製法為擬似二階段型時，可藉由在使二元酸（a_1}與二環狀= 馨化合物（a-2)之反應的進行中，一邊滴下環狀酯（|?)或封閉化合物（c)，一邊使三者反應而獲得。二元酸（a_l)與二環狀醚化合物卜2)的聚加成反應係即使無觸媒亦可進行反應，但為了使反應順利進行，亦可適當使用觸媒。就可使用之觸媒而言，可列舉如氨、胺類、四級銨鹽類、四級鱗鹽類，金屬氫氧化物類、驗土類金屬氫氧化物類、路易斯酸類；含有錫、鉛、鈦、鐵、鋅、鲁鍅、鈷等之有機金屬化合物類；金屬鹵化物類等。若使用四級銨鹽類作為反應觸媒，則可獲得無色至淡黃色之加成型聚酯樹脂（Dl)、（D2)，故為較佳。可作為聚加成反應用觸媒使用的胺類，可列舉例如三乙基胺、吡啶、苯胺、嗎啉、N-甲基嗎啉、吡洛啶、哌啶、 N甲基哌啶、環己基胺、正丁基胺、二甲基噚唑啉、咪唑、 I甲基咪唑、Ν，Ν·二甲基乙醇胺、N，N_二乙基乙醇胺、N，N_ —甲基異丙醇胺、N-曱基二乙醇胺等。就四級銨鹽類而言，可列舉例如溴化四曱基銨、氯化 319793 60 200838965 四甲基銨、三水合氟化四曱基銨、六氟磷酸四甲基銨、氳酞酸四甲基銨、五水合氫氧化四甲基銨、氫氧化四甲基銨、蛾化四曱基銨、硝酸四曱基銨、過氯酸四曱基銨、四氟硼酸四曱基銨、三溴化四甲基銨、溴化苯基三曱基銨、溴化四乙基銨、氯化四乙基銨、三水合氟化四乙基銨、氳氧化四乙基按、蛾化四乙基錢、過氣酸四乙基錢、四氣侧酸四乙基銨、對甲苯磺酸四乙基銨、溴化四丙基銨、氯化四丙基銨、碘化四丙基銨、氫氧化四丙基銨、過氯酸四丙基銨、 _氫硫酸四正丙基銨、過釕酸（VII)四正丙基錢、漠化四丁基銨、三溴化四丁基銨、氯化四丁基銨、碘化四丁基銨、氫氧化四丁基銨、六氟磷酸四丁基銨、氫硫酸四丁基銨、硝酸四丁基銨、四氫硼酸四丁基銨、四氟硼酸四丁基銨、氰基三氫硼酸四丁基銨、二氟三苯基錫酸四丁基銨、三水合氟化四丁基銨、·四丁基銨四硫代酚鹽（IV) (tetrabutylammonium tetrathiophenate(IV))、水合氟化四丁基銨、二氫三氟化四正丁基銨、三氟甲磺酸四正丁基銨、雙（2,3-二巯基-2- 丁烯二腈合-S，S’）鎳酸三丁基銨 (tributylammonium bis(2,3-dimercapto-2-butenedinitrilato- S，S’）nickelate)、溴化四正庚基銨、氯化四正庚基銨、填化 . . 1 * 四正庚基銨、苯曱酸四正己基銨、溴化四正己基銨、氯化四正己基銨、碘化四正己基銨、過氯酸四正己基銨、溴化四辛基銨、漠化四（十八基）銨等。就四級鱗鹽類而言，可列舉如氯化苄基三苯基鱗、溴化四苯基鐫、漠化乙基三苯基鱗、蛾化乙基三苯基鎸、氯 j . 61 319793 200838965 化四丁基鱗、溴化四丁基鱗、四氟硼酸四丁基鐫、六氟磷酸四丁基鱗、四苯基硼酸四丁基鱗、苯并三唑酸四丁基鱗、 (Tetrabutylphosphonium benzotriazolate)、雙（1，2·苯二硫合) 鎳酸（III)四丁基鱗（Tetrabutylphosphonium bis(l,2-benzenedithiolato)nickelate(III))、雙（4·甲基-1，2-苯二硫合）鎳酸(III)四丁基鱗、雙(4,5-二Μ基-1，3-二硫醇_2-硫代硫酸 -S4，S5)鎳酸（III)四丁基鱗（丁61^1)1^)^卩11〇3卩11〇11丨111111^5(4,5-dimercapto-1，3-dithiol-2-thionato-S4，S5)nickelate(III))等。驗金屬或驗土類金屬之氳氧化物，可列舉如：氫氧化鋰、氫氧化納、氫氧化卸等驗金屬氫氧化物類；如氫氧化鎂、氫氧化鈣、氳氧化锶、氳氧化鋇等鹼土類金屬氳氧化物類。Propyl propyl cyanate, butyl isocyanate, isocyanate, W, in the monofunctional, ethyl isocyanate, ester, isocyanate, 319793 54 200838965 : ki曰, stearyl isocyanate, cyclohexyl isocyanate, benzoquinone isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, iso(tetra)^ Chloroethyl 81, 2,4-dichlorophenyl isocyanate, isocyanate gas | mercaptophenyl ester, dichloroacetyl isocyanate, chlorosulfonyl isocyanate, mercaptobenzyl isocyanate, S-(-) -a-methylbenzyl isocyanate, R-(mononaphthyl)ethyl isocyanate, phenylethyl isocyanide, s ( ) _ 1 - benzyl ethyl isocyanate, p- benzophene Isocyanic acid, etc. The addition reaction of xin h - 70 酉夂 (a-1) with the two cyclic squama compound 〇 2) can be carried out by using the method of A. For example, any of the following types can be used: 1) the dibasic acid (aq) is mixed with the dicyclic ether compound (a_2) and the reaction is carried out, 2) the quinone-acid (a-1) is slowly added to The two cyclic ethers are combined, and (a 2) is allowed to react in the middle, or the two cyclic compound (s) is gradually added to the binary acid (ael) to cause a reaction. & In the addition-molded polyester resins (D1) and (D2) of the present invention, a linear form formed by a polyaddition reaction of a dibasic acid (heart 1) and a dicyclic ether compound (a_2) The polyester backbone (I) has a (tetra) or cyclic ether group at its end. Four relative to a τ o acid (a_i) carboxyl! Moer, the molar number of the squaring of the dicyclic ether compound (heart 2) is in the range of 〇·5 to 2 〇 Mo, and is in the range of 〇·8 to 1-2. good. If the number of moles of the ring = group is less than q.5 moles or more than the moles of the carboxyl group, it is difficult to increase the molecular weight of the polyester backbone (I), and it is not easy to obtain the target pressure. A modified polyester resin characterized by the nature of the agent. When the polyester backbone (I) is formed in the field, if a bisphenol-type diglycol propyl 319793 55 200838965 ether compound or the like has a 2-stage thiol-cyclic compound (a-2), the direct bond is used. In the secondary hydroxyl group directly bonded to the main chain (1), there is a radical formed by ring-opening addition of a cyclic group, and a dicyclic ether compound (a.2) Give 2 types such as base. 2 kinds of secondary meridians, either of which is a reactive base point with the cyclic ester (b) or the blocking compound (4), and forms an open-loop structural unit having a smear-like enthalpy and a terminal Miri 4 A chain (π) or a second side chain in which a hydroxyl group is blocked by a compound (c). In addition, it has been found that, compared with the original 2-stage meridine, the ring-opening ether group is more reactive than the cyclic vinegar (b) or the blocking compound (4). . When the polyester main chain (1) contains a large amount of aromatic groups, although the heat resistance of the obtained addition type polyester resins OM to D3) becomes high, the hardness thereof is also increased to make the adhesion difficult to be exhibited. Further, when a large amount of the aliphatic group is contained, the biodegradability of the resin is increased, but the heat resistance is lowered. Therefore, Gu f to these problems 'binary _·1 used as a raw material) and two ring-shaped squaring 5 (a_2), in response to the use of the composition of the adhesive, and to make the vinegar main chain (two The ratio of the aromatic group to the aliphatic group is preferably a suitable mode: alternatively, the lip-forming polyester resin (D) is excellent in heat resistance and adhesion to the A-based resin. D) The ratio of the & ratio in the molecule (the aromatic ring 3 has a 卞曰) is preferably about 1 to 6〇%, more preferably to the left (heavy ratio). The ratio of the aromatic ring can be calculated from the mass I (or weight) calculated from the knives I of the raw materials used, the mass ratio of the aromatic rings in the molecular weight, and the blending ratio. The first closed-type preparation and addition of a polyacetate resin (in the case of a second-order hydroxyl i-ester directly bonded to the linear polyester backbone (1) in a ratio of 319,793, 56,389,395 to a ratio of 0.2 m or more. The reaction is preferably carried out, and the reaction is preferably carried out at a ratio of 0.5 mol or more, and further preferably reacted at a ratio of 0.8 to a molar range, particularly in the range of _15 to * ears. The ratio is the best response. 士,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ^^^^^^^ ^ to 6. Moer: The above ratio is more than the ratio of the inner circumference of the I, 0 旲 ear to better reflect, especially to become the second, the ear: within the range The ratio is best to react. When the second closed type is used to form poly(tetra) (4), because of the closed combination = vinegar relative to the linear polyester main, and the base i mole, the ring vinegar The preferred lower limit of the amount of (8) is smaller when the first closed type modulation and molding of polyester wax (D1) is formed. ', 曰, and the above range, it is difficult to obtain an adjustable The fat may be tack _ ⑼. Thus, in order to be used as the bicyclic her engagement portion is formed into the ear ring with ^ State) of the weight. The cyclic ester (b) is the day when the mass of the molybdenum is passed through the end of the side bond of the bH 糸加加加加加加经经Cyclosporin μ / (9). The side chain formed by the ring-opening of the ring-shaped vinegar (b) has a beautiful side chain, and the ancient side chain (11) is attached at its end. 319793 57 200838965 Addition of a polyester precursor (C1) to the main bond portion (1) and the side chain portion (Π) at the base end is preferably in the range of 5 〇 to mr/g, and If a part of the hydroxyl group at the end of the side chain of the above-mentioned addition-formed polyester precursor (C1) is reacted with the above-mentioned blocking compound (4) to be converted into the second side bond (π,) at 5G to 8GmgK_, an addition molding can be obtained. Poly vine tree month (D1), # has the main urethane bond m, (four) the end of the end, the side class, and the second ' σ I ' at the end without the basis of the base of the polyester resin (D i) The valence is adjusted to a desired value by adjusting the amount of the blocking compound (4), and is preferably adjusted to a range of 〇1 to 克g〇H/g', more preferably to a range of 0.5 S 30 mgKOH/g. When the side chain has a carboxyl group and the crosslinking agent (8) reacts with the silk, the hydroxyl value of the addition-molded polyester resin is allowed to be about 100 mgKOH/g, and more preferably 80 mgKOH/g or less. c), also, the carboxyl group of the afterburning polyester resin (di) is more than the additive polyester precursor (C1), and if the compound (C) is an acid anhydride, it has an end. a side chain of a carboxyl group. When the crosslinked ruthenium (E) reacts with a hydroxyl group, the acid value can be tolerated to a certain high value, but when the crosslinking agent (E) reacts with a carboxyl group, a polyester resin (D1) is added. The acid value ^ is preferably in the range of 0.1 to 5 〇 mgKOH/g, more preferably in the range of 〇5 to 3 〇 mg KOH/g. If the valence or acid value is less than 〇"mgK〇H/g, then The cross-linking agent (E) has poor reactivity with respect to a hydroxyl group or a carboxyl group, and the cohesive force of the hardened resin is insufficient, so that it is difficult not only to peel off the polarizing film or the like, but also to cause residual stickiness after peeling, or to peel off again. Sex becomes insufficient. In addition, if the hydroxyl value or 319793 58 200838965 acid value is higher than 50 mgKOH/g, the pot life of the adhesive composition prepared with the crosslinking agent (E) becomes short, and the workability at the time of coating processing or the subsequent operation is clear. . This knowledge is common to the addition of the polyester resin (1) 1 to), depending on the type of the crosslinking agent (E) (reacting in either of the hydroxyl group and the carboxyl group), and the value of the inverse object is preferably adjusted to G. ·! Up to 5QmgK〇H/g, more preferably adjusted from 0.5 to 30nigICOH/g. In the manufacture of the addition polymer resin (D2), in order to adjust the above acid value or hydroxyl value, it is preferred to be a secondary hydroxyl group with respect to the linear polyester backbone (1) so as to be The hydroxy group reacting with the compound (c) has a ratio of 0:01 to 0.85 moles (more preferably 〇1 to 〇7 moles) to react with the starting material. Then, it is preferred to carry out the reaction by reacting the cyclic vinegar (8) at a ratio of 0.8 to 40 mTorr (more preferably 2 〇i 2 〇〇 mol) with respect to the unreacted moromole. The polyester resin (D2) is formed from the side of the ring_). ·· The functional group of the blocking compound (C) is comparable to the polyester primary bond (1), and (4) If it is not (UH material, the ring is cut regardless of its addition ^ more than two 'added polyester lion (D2) The base price is high. It is speculated that this is due to the fact that the main chain is directly bonded to the (4) residual amount, even if a large amount of cyclic vinegar is added, the ring-shaped addition of the base directly bonded to the main chain is compared with the ester (8). (8) It is more to carry out its own open-loop addition, and the main direct basis is not reduced much. Because of A + 士,别¥ 丧,,,,,,,,,,,,,,,, Resin _ the hydroxyl surface, so the hardened resin (4) heat and heat resistance is low. Another = mysterious surface, the compound (4) of the palace energy base relative to the polyester backbone (1) of the base more than 〇. 85 mol, it is almost impossible to form the side 319793 59 200838965 chain (π) by the annular vinegar (8), and it is difficult to obtain an adhesive composition which can be prepared as a pressure-sensitive adhesive which satisfies the adhesion and cohesive force. Molded polyester resin (D2). The shaped polyester precursor (ci, C2) is as described above and can be based on a three-stage type. It is obtained by any one of the two-stage type and the two-stage type, and the ratio of the raw materials is the same as described above. When the method is a two-stage type, for example, as long as the dibasic acid (aq) and the two-ring are The ether compound (a_2 is mixed with the % ester (b) or with the blocking compound (c) and reacted; when the preparation is a pseudo-two-stage type, the dibasic acid (a_1} and the bicyclic ring can be made In the course of the reaction of the fragrant compound (a-2), the cyclic ester (|?) or the blocking compound (c) is added while the reaction is carried out. The dibasic acid (a-1) and the dicyclic ether are obtained. The polyaddition reaction of the compound 2) can be carried out without a catalyst, but a catalyst can be suitably used in order to allow the reaction to proceed smoothly. Examples of the catalyst that can be used include ammonia and amines. Quaternary ammonium salts, quaternary scale salts, metal hydroxides, soil-based metal hydroxides, Lewis acids; organometallic compounds containing tin, lead, titanium, iron, zinc, reckless, cobalt, etc. Class; metal halides, etc. If a quaternary ammonium salt is used as the reaction catalyst, The colorless to pale yellow addition-molding polyester resins (D1) and (D2) are preferred. The amines which can be used as a catalyst for the polyaddition reaction include, for example, triethylamine, pyridine, and aniline. Morpholine, N-methylmorpholine, pyrididine, piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, Imethylimidazole, hydrazine, hydrazine Dimethylethanolamine, N,N-diethylethanolamine, N,N-methylisopropanolamine, N-decyldiethanolamine, etc. Examples of the quaternary ammonium salt include, for example, tetradecyl bromide Ammonium, chlorination 319793 60 200838965 tetramethylammonium, tetramethylammonium fluoride trihydrate, tetramethylammonium hexafluorophosphate, tetramethylammonium citrate, tetramethylammonium hydroxide pentahydrate, tetramethylammonium hydroxide Ammonium, mothyl tetradecyl ammonium, tetradecyl ammonium nitrate, tetradecyl ammonium perchlorate, tetradecyl ammonium tetrafluoroborate, tetramethylammonium tribromide, phenyltriammonium bromide, bromine Tetraethylammonium, tetraethylammonium chloride, tetraethylammonium fluoride trihydrate, tetraethylammonium oxide, tetraethylmethane, tetraethylcoholic acid, tetrakisole tetraacetate Base ammonium, Tetraethylammonium tosylate, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium perchlorate, tetrahydrogen sulfate Base ammonium, perrhenic acid (VII) tetra-n-propylammonium, desertified tetrabutylammonium, tetrabutylammonium tribromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium hydroxide , tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium nitrate, tetrabutylammonium tetrahydroborate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium cyanotrihydroborate, difluoro Tetrabutylammonium triphenyltinate, tetrabutylammonium fluoride trihydrate, tetrabutylammonium tetrathiophenate (IV), tetrabutylammonium hydride hydrate, dihydrogen fluoride Tetrabutylammonium trifluoride, tetra-n-butylammonium triflate, bis(2,3-dimercapto-2-butenedionitrile-S,S') tributylammonium nickelate (tributylammonium) Bis(2,3-dimercapto-2-butenedinitrilato-S,S')nickelate), tetra-n-heptyl ammonium bromide, tetra-n-heptyl ammonium chloride, filled. 1 * tetra-n-heptyl ammonium, phenylhydrazine Tetra-n-hexylammonium bromide, tetra-n-hexyl bromide Tetrachloride-n-hexyl ammonium iodide, tetra-n-hexyl ammonium perchlorate, tetra-n-hexyl ammonium bromide, tetraoctylammonium, desertification tetra (octadecyl) ammonium. Examples of the quaternary scale salts include benzyltriphenyl sulphate chloride, tetraphenylphosphonium bromide, desertified ethyltriphenyl sulphate, mothyl ethyltriphenyl sulfonium, and chlorine j. 61. 319793 200838965 tetrabutyl sulphate, tetrabutyl sulphate, tetrabutyl sulfonium tetrafluoroborate, tetrabutyl squarate hexafluorophosphate, tetrabutyl sulphate tetraphenylborate, tetrabutyl sulphate benzotriazole (Tetrabutylphosphonium benzotriazolate), bis(1,2·benzenedisulfide), tetrabutylphosphonium bis(l,2-benzenedithiolato)nickelate(III), bis(4·methyl-1, 2-phenyl disulfide) nickel acid (III) tetrabutyl scale, bis(4,5-dimercapto-1,3-dithiol-2-thiosulfate-S4,S5)nickic acid (III) Tetrabutyl scale (Ding 61^1) 1^)^卩11〇3卩11〇11丨111111^5(4,5-dimercapto-1,3-dithiol-2-thionato-S4,S5)nickelate(III ))Wait. For the detection of metal or soil-based metal cerium oxide, for example, lithium hydroxide, sodium hydroxide, water hydroxide and other metal hydroxides; such as magnesium hydroxide, calcium hydroxide, barium oxide, strontium oxide Alkaline earth metal lanthanum oxides such as lanthanum.

有機錫化合物類，可列舉如二氯化二丁基錫、氫氧化二丁基錫、二溴化二丁基錫、二（順丁稀二酸）二丁基錫、二月桂酸二丁基錫（DBTDL，Dibuty Itin dilaurate)、二乙酸二丁基錫、硫化二丁基錫、硫化三丁基錫、氫氧化三丁基錫、乙酸三丁基錫、乙氧基化三乙基錫、乙氧基化三丁基錫、氳氧化二辛基錫、氯化三丁基錫、三氯乙酸三丁基錫、 2-乙基己酸錫等。有機鍅化合物類，可列舉如乙酸錘、苯曱酸鍅、環烷酸錯（zirconium naphthenate)等。有機鈦化合物類，可列舉如二氯化二丁基鈦、四丁基鈦酸酯、四丁氧基鈦酸酯、四乙基鈦酸酯、三氯化丁氧基鈦等。 62 319793 200838965 有機鉛化合物類，可列舉如乙酸鉛、油酸鉛、2_乙基己酸鉛、苯甲酸鉛、環烷酸鉛等。有機鐵化合物類，可列舉如2_乙基己酸鐵、乙醯丙酮Examples of the organotin compound include dibutyltin dichloride, dibutyltin hydroxide, dibutyltin dibromide, dibutyltin bis(succinic acid), dibutyltin dilaurate (DBTDL, Dibuty Itin dilaurate), and Dibutyltin acetate, dibutyltin sulfide, tributyltin sulfide, tributyltin hydroxide, tributyltin acetate, triethyltin ethoxylate, tributyltin ethoxylate, dioctyltin ruthenium oxide, tributyltin chloride, three Tributyltin chloroacetate, tin 2-ethylhexanoate, and the like. Examples of the organic ruthenium compound include acetic acid hammer, bismuth benzoate, and zirconium naphthenate. Examples of the organic titanium compound include dibutyl titanium dichloride, tetrabutyl titanate, tetrabutoxy titanate, tetraethyl titanate, and titanium butoxide. 62 319793 200838965 Organic lead compounds, such as lead acetate, lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, and the like. Examples of the organic iron compound include iron 2-ethylhexanoate and acetone

AM 鐵导0 有機鈷化合物類，可列舉如乙酸鈷、苯甲酸鈷、2-乙基己酸始等。有機鋅化合物類，可列舉如乙駿鋅、乙二酸鋅、環烷酸鋅、2_乙基己酸鋅等。 ^ 就金屬齒化物而言，可列舉如氯化錫（II)、漠化錫（Π)、碘化錫（II)等。除了上述者以外，三氟化硼、三氯化鋁、氯化鋅、氯化鈦等路易斯酸類亦可使用作為聚加成反應用觸媒。、來加成反應用觸媒並不受上述舉例者所限定，另外，了僅使用一種’亦可併用二種以上。、上述觸媒之使用量，相對於反應成分100重量份較佳 _為1〇重里份以下左右。若使用超過10重量份之量，則有生成物著色、或在環狀酯（b)之開環加成反應時作為負觸媒而進行作用等不良狀況。聚加成反應係在.20至220°C之範圍之溫度中進行，較 t為50至200 C。反應時間通常可為1至6〇小時左右。可使用溶劑，亦可不使用溶劑。就可使用之溶劑而言，可列舉如甲苯、二甲苯、己烷、庚烷等烴系溶劑；乙酸乙酯、乙酸丁酯等酯系溶劑；丙酮、甲基乙基酮等酮系溶劑；二氯甲烧、氯仿等鹵化烴系溶劑；二乙基醚、甲氧基甲苯、 319793 63 200838965 二曙烧等醚系溶劑等，此等可單獨使用，亦可組合2種以上使用。惟，含有經基之溶劑係由於使後續之與環狀酉旨⑻ 之反應中的反應率大幅下降，故不可使用該種溶劑。聚醋主鏈(I)之經基與環狀醋⑻的開環加成反應，係可使用公知之反應條件而進行。具體而言，反應溫度為加至220 C ’又以6G至18〇°c：為佳。反應時間通常可設為工至30小時左右。另夕卜，雖然可使用冑媒亦可不使用觸媒，但以使用為較佳。就開環加成用之觸媒而言，同樣地可使用二元酸（a-1)與二環狀鍵化合物（a_2)之反應中所用的上 f聚加成反應用的觸媒。尤其是從加成型聚酉旨樹脂（D)不易者色之特點來看，以四級銨鹽類較適用於作為觸媒。使封閉化合物⑷反應於具有末端經基之第i側鏈（11) 而獲得加成型聚酯樹脂（D卜D3)時的觸媒，從反應性及加成型聚酯樹脂⑼不易著色之特點來看，係以四級銨鹽類為較適用。，丨而在獲得加成型聚i旨樹脂(D2)時，因同樣之理由，在各步驟中，亦以四級錢鹽類較適用於作為觸媒。為:使接著劑組成物能發揮作為感屢接著劑之平衡的 1好接者特性（尤其是黏著性與凝集力之同時加摩至_以其玻璃轉移卿一^ 未^土价若加成型聚醋樹脂（D1至D3)之玻璃轉移溫度 ^ ，貝1H吏用聚醋樹脂(D1至D3)所調製之接著劑組成物热法發揮適於感屋接著劑之凝集力，變得易於產生洋起剝離。另-方面，若玻璃轉移溫度超過阶則= 319793 64 200838965 :感，接著劑接觸於被著體，接著劑層亦無法充足地將被者體濕潤，而有無法獲得充足接著办的可能性。因此，為了可生成Tg較佳為一80至10〇c、更佳為_6〇至—1〇它的加成型聚酯樹脂（D1至D3)，在作為二元酸㈣、二環狀 _化合物（’、環狀酯⑻及封閉化合物⑷使用之各成分之選擇方面係適當考慮。從接著性之觀點來看，加成型聚酯樹脂至之重量平均分子量（Mw)係以在），GGG至1，_，_之範圍為 •較佳，又以在8，_至5〇〇，_之範圍為更佳。若MW未達2,0〇〇，則热法發揮本發明之加成型聚酯樹脂（Di至特有之凝集力，耐熱性及耐濕熱性降低。另一方面，若 Mw超過1，000,000，則含有加成型聚酯樹脂⑴}至之接著劑組成物之流動性變不良，而變得難以製作感壓接薄片。 - 本發明之接著劑組成物係含有能與上述加成型聚酯樹 _脂（〇1至D3)之官能基反應的交聯劑（£)，藉由與官能基之交聯反應而使加成型聚酯樹脂硬化並形成接著劑層。本發明所·使用之交聯劑（E)，係為於分子内具有能與加成型聚酯樹脂（D1至D3)中之羥基或羧基反應之官能基的化合物，而為了使其作為交聯劑進行作用，係以於分子内具有2個以上能與羥基或羧基反應之官能基的化合物為較適用。就如此之化合物而言，可列舉如多異氰酸酯化合物、多官能石夕烧化合物、含有N-經曱基之化合物、環氧化人物、胺化合物、氮丙淀（aziridine)化合物、石户二四〜 319793 65 200838965 (carbodiimide)化合物、曙嗤琳化合物、三聚氰胺化合物及金屬螯合化合物等。此等係在交聯反應後之接著劑組成物之接著性、或是對於被著體或基材之密著性方面為優異。可與經基反應之交聯劑（E)，係如多異氰酸醋化合物、多官能矽烷化合物、含有N-羥曱基之化合物、胺化合物以及三聚氰胺化合物；可與羧基反應之交聯劑（E)，係如氮丙唆化合物、環氧化合物、_嗤淋化合物、碳二亞胺化合物及金屬螯合化合物。如上所述，由於依交聯劑（E)之類型，加成鲁型聚酯樹脂（D)之酸價或羥基價係存在有適當範圍，故當加成型聚酯樹脂（D1至D3)之羥基價為0.1至50mgKOH/g 時，所組合之交聯劑（E)可為能與羥基及羧基中之任一者反應的類型；若當加成型聚酯樹脂（D1至D3)之羥基價超過 50mgKOH/g且為100mgKOH/g以下時，所組合之交聯劑（E) /為能與羧基反應的類型；更進一步，從適用期之觀點來看，以加成型聚酯樹脂（D1至D3)之酸價係0.1至50mgKOH/g I為較佳。作為交聯劑（E)使用的多異氰酸酷化合物，係如芳香族多異氰酸醋、脂肪族多異氰酸醋、芳香脂肪族多異氰酸酯、脂環族多異氰酸酯等，可為任一化合物。芳香族多異氰酸酯係可列舉如1，3-伸苯基二異氰酸酯、4,4’-二苯基二異氰酸酯、1，4-伸苯基二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、2,4-伸曱苯基二異氰酸酯、2,6-伸曱苯基二異氰酸酯、4,4’-曱苯胺二異氰酸酯(4,4’-toluidine diisocyanate)、2，4,6-三異氰酸酯甲苯、1，3,5-三異 66 319793 200838965 氰酸S旨苯、聯大茴香胺二異氰酸醋（dianisidine diisocyanate)、4，4’-二苯基醚二異氰酸酯、4,4’，4’’-三苯基曱烷三異氰酸酯等。脂肪族多異氰酸酯係可列舉如三亞曱基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯 (Hexamethylene diisocyanate，亦即 HMDI)、五亞甲基二異氰酸酯、1，2-伸丙基二異氰酸酯、2,3-伸丁基二異氰酸酯、 1，3-伸丁基二異氰酸酯、伸十二烷基二異氰酸酯、2,4,4-三 _甲基六亞甲基二異氰酸酯等。芳香脂肪族多異氰酸酯係可列舉如ω，ω 二異氰酸酉旨-1，3_二曱基苯、6ι)，6ϋ 二異亂酸醋-1，4-二曱基苯、〇， ω 二異氰酸g旨-1，4-二乙基苯、1，4_四甲基伸茬基二異氰酸酯、1，3-四甲基伸茬基二異氰酸酯等。脂環族多異氰酸酯係可列舉如3-異氰酸基甲基-3,5,5-三曱基環己基異氰酸酯（3-Isocyanatomethyl-3,5,5· trimethylcyclohexyl isocyanate，亦即 IPDI)、1,3-環戊烧二異氰酸酯、1，3-環己烷二異氰酸酯、1，4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、曱基-2,6_環己烷二異氰酸酯、4,4’-亞曱基雙（環己基異氰酸酯）、1，4-雙（異氰酸甲酯）環己烷等。 • ' . -亦可使用上述多異氰酸酯化合物的三經甲基丙烧加成物、或具有三聚異氰酸環之三聚物等。另外，亦可使用聚苯基曱烷聚異氰酸酯 (polyphenylmethane polyisocyanate ? ^ PAPI) - # # ^ ^ 67 319793 200838965 異亂酸s旨、以及該等之多異氰酸g旨改質物等。又，就少里氛酸酉旨改質物而言，係可使用具有選自破二亞胺美，、= 嗣（Uretedi〇ne)基、脲亞胺基、已與水反應之縮二卵^ 基、異氰酸基中之任1種或2種以上的改質物。此外’多元醇與二異滅㈣反應生成物係亦可作為多異氰酸酯使用。於上述多異氰酸酯化合物中，若使用4,4、二苯基曱烷二異氰酸酯、六亞甲基二異氰酸酯、3_異氰酸基甲基_3,5,^_ ♦三甲基環己基異氰酸醋(別名：異佛_二異氰酸醋)、伸 f基二異氰酸酯、4,4，_亞甲基雙（環己基異氰酸酯X別名：虱化MDI)等無黃變型或難黃變型的多異氰酸醋化合物，則從耐侯性、耐熱性及耐濕熱性之觀點來看，係為特佳。當使用多異氰酸酯化合物作為交聯劑（幻時，可因應需要而使用公知之觸媒以促進反應。就可使用之觸媒而言而可列舉如三級胺系化合物、有機金屬系化合物等，可單獨 _使用’亦可組合複數種而使甩。就作為交聯劑（E)使用之環氧化合物而言，可列舉如雙酚冬表氯醇型之環氧系樹脂、乙二醇二環氧丙基醚、聚乙一醇二環氧丙基醚、甘油二環氧丙基醚、甘油三環氧丙基喊、丄6-己二醇二環氧丙基醚、三羥甲基丙烷三環氧丙基醚、二環氧丙基苯胺、N，N，N，，N、四環氧丙基/間伸茬基二胺、雙（N，N，-二環氧丙基胺基甲基）環己烷等。就作為交聯劑（E)使用之氮丙唆化合物而言，可列舉如 -二苯基甲烧-4,4’-雙（1-氮丙咬羰基化物）（亦即 319793 68 200838965 N，N’-diphenyl propane -4,4’_bis(l-aziridine carboxide))、 N，N’-甲苯-2,4-雙（1-氮丙啶羰基化物;）、雙異酞醯基-1-(2-甲基氮丙啶）、氧化三-1·氮丙啶基膦、N，N，-六亞甲基-1，6-雙（1-氮丙啶羰基化物）、三羥甲基丙烷-三-β -氮丙啶基丙酸酯、四羥甲基曱烷-三-/3-氮丙啶基丙酸酯、參-2,4,6_(1-氮丙啶基）-1，3,5_三畊、三羥甲基丙烷參卩-(1-氮丙啶基）丙酸酯]、三羥曱基丙烷參[3-(1-氮丙啶基）丁酸酯]、三羥甲基丙烷參[3-(1_(2-甲基）氮丙啶基）丙酸酯]、三羥甲基丙烷鲁參[3-(1-氮丙啶基）-2-甲基丙酸酯]、2,2，-雙羥基甲基丁醇參 [3-(1-氮丙啶基）丙酸酯]、季戊四醇四[^(^氮丙啶基）丙酸酯]、二苯基甲烷-4,4-雙-N，N’-伸乙基脲、1，6_六亞曱基雙 -N，N’-伸乙基脲、2,4,6_(三伸乙基亞胺基）_對稱三哄、雙 [1-(2_乙基）氮丙咬基]苯-i，3-叛酸酸胺等。作為父兩卩劑（xi)使用之碳二亞胺化合物，係在分子内呈有2個以上碳一亞胺基（_n=C=N_)的化合物，可適用公知 _之聚碳二亞胺、或是於碳二亞胺化觸媒存在下藉由使二異氰酸酯進行脫碳酸縮合反應而生成之高分子量聚碳一亞胺' , * * . · · 生成高分子量聚碳二亞胺之原料異氰酸酯，係可列舉如4,4 -一本基甲烧二異氰酸酯、3,3，_二甲氧基_4 4，一 # 基甲烷二異氰酸酯、3,3，_二甲基·4,4’_二苯基甲烷‘異氰：酯、4,4 -二苯基醚二異氰酸酯、3,3，_二曱基·4 4，一#* _ ^ ，_ —本基醚二兴氰酸酯、2,4-伸甲苯二異氰酸醋、2 6_伸一田〆，丨τ τ本一異氰酸酯、1·甲氧基苯基-2,4-二異氰酸酯、異佛爾酮二異氰酸酯、 319793 69 200838965 4,4’-二環己基曱烷二異氰酸酯、四甲基伸茬基二異氰酸酯專’可使用此等中之1種或2種以上之混合物。以碳二亞胺化觸媒而言，可列舉如^苯基_2_環磷烯氧化物（l-Phenyl-2-Ph〇Spli〇lene-l-oxide)、夂曱基 _2-環磷烯 -1-氧化物、1-乙基-3-甲基-2-環磷烯氧化物、·乙基-2_ 環磷烯-1-氧化物、以及此等之3_環磷烯異構物等環磷烯氧化物。以可獲得之高分子量聚碳二亞胺之市售品而言，可列 ❿舉如曰清纺積股份公司製之Carb〇dilite系列。其中，由於 CarbodiHte V-01、03、05、〇7、_ 〇9在與有機溶劑之相溶性方面為優異，故為較佳。一作為交聯劑（E)使用之噚唑琳化合物，係以在分子内具有2個以上曙嗤琳基之化合物為適用，具體而言，可列舉如2，_亞甲基雙（2·曙唑琳）、2,2，_伸乙基雙(2_曙唑琳）、2,2，_ 伸乙基雙（4-曱基-2-嚶唑啉）、2,2，_伸丙基雙(2_噚唑啉卜 _ 2,2’·四亞甲基雙(2导坐琳）、2,2，_六亞甲基雙(2_嗜唾琳）、 2,2，’·八亞甲基雙（2_曙唾啉）、2,2，_對伸苯基雙（2_曙唾啉）、 2,2對伸苯基雙（4,4’_二甲基_2-曙唑琳）、2,2，_對伸苯基雙 (4曱基-2-[^唑啉）、2,2’-對伸苯基雙（4_苯基_2_噚唑啉）、㈣）、2,2，-間伸苯基雙（4,4，_二甲基_2_嗜唾琳）、仏本基雙（4-伸苯基雙_2哥坐淋）、2,2:鄰伸苯基雙（2_卩等唑淋）2,2 -鄰伸苯基雙（4_甲基_2_噚唑啉）、2,2，_雙（2_噚唑啉）2,2 -雙(4-曱基-2-卩等唾琳）、2,2，_雙（4-乙基_2_嗜。坐 319793 70 200838965 啉）、2,2，-雙（4_苯基-2-噚唑啉）等。另外，亦可使用如2_ 異丙烯基-2_噚唑啉或2-異丙烯基_4,4-二甲基_2_噚唑啉等與乙烯系單體、與能和乙烯系單體共聚合之其他單體的共聚物。、 ^ 作為父聯劑（E)使用之金屬螯合化合物，可列舉如使乙 .醯丙銅或乙醯乙酸乙酯配位於鋁、鐵、銅、辞、錫、欽、鎳、銻、鎂、釩、鉻、鍅等多價金屬的化合物。上述交聯劑（E)可單獨使用，亦可組合複數種而使用。鲁本發明之接著劑組成物係含有作為硬化性樹脂成分之聚酯樹脂（D)與交聯劑（E) ’就聚酯樹脂（D)而言，可使用上述加成型聚醋樹脂(D1至D3)。其組成比率係以相對於聚酯樹脂（D)l〇〇重量份的交聯劑（E)之量為〇〇〇1至2〇重量知為佺，又以〇.〇1至10重量份為更佳。若交聯劑（E)之使 1量超過2G重量份，則將所得之接著劑組成物作為感壓接者劑使用時的接著性（濕潤性、附著性）有降低之傾向，樹 _脂層之凝集力低，反覆使用時之形狀保持性或耐久性差。，，可因樹脂之硬化而作為接著固定之接著劑使用。另外， ^未達G.GG1重量份，則無法獲得充足之交聯結構，故凝集力降低，且耐熱性及耐濕熱性有降低之傾向。當其作為感壓接著劑組成物以外之接著劑組成物或塗料組成物時，主财之官能基I乎全與交聯卿)反應，而了製成硬化接著層或硬化塗膜。然而，當其作為感壓接著 y組成物¥，為了使黏貼時已硬化之感壓接著層能濕潤被著體表面，則必須使已硬化之感壓接著層為一種具有表面 319793 71 200838965 :著:(黏著性)之半固體狀態。因此，當其作為綱著為使上述加成型聚酯樹脂（D1至D3)令 ^交聯性官能基⑽基❹基）之一部分與交聯劑⑻反應’亚形成硬化感壓接著層。力口成型聚醋樹月旨⑼至叫中之經基或幾基與交聯劑主之S能基的反應，係可使樹脂三次元交聯並提高形狀保、」，因未交聯之侧鏈而使樹脂與各種基材或被著體的密 f性提升。更進—步，因以封閉化合物⑷封閉歸而降低树脂之經基價，即使在比以往更嚴厲之條件下亦可使财敎 ^耐濕熱性提升，故可適用於作^學構件用之感壓接者劑。、於不損及本發明之效果之範_，在本發明之接著劑 :組成亦可調配各種樹脂、偶合劑、軟化劑、染料、顏料、抗氧化劑、紫外線吸收劑、耐候安定劑、增黏劑 (taCkifier)、可塑劑、填充劑、抗老化劑等。者劑層與薄、土材所成之積層體’其係可利用於作為接著薄片。 ^著薄片係例如藉由將本發明之接著劑組成物塗佈於各種薄片狀基材並進行乾燥、硬化而獲得。、當塗佈接著额成物時，為了提升健性，亦可添加醇、其他烴系溶媒等有機溶媒或水以調整接著劑組成物之黏度，另外，亦可加熱接著劑組成物以使黏度降低。惟，若水或醇類大量添加，則有引起加成型聚酯樹脂（D1至D3) 319793 72 200838965 與交聯劑（E)之反應抑制 tl -¾ Μ 々了月"性，故必須留意添加量。就/專月狀基材而言，丨、塑膠、橡膠、發泡體、梢=以破璃紙（Cen〇phane)、木材等素材，成形為具有柔軟性之平坦形狀専片狀基材可為以單獨素材所構成者，亦可為以複數種素材所積層之多㈣f万了為基材之表面_離處理者。者又’亦可使用將薄片狀塑膠製之基材係有久插湖挪—/ 墙"、一…有各種塑膠溥膜，可列舉如聚乙稀醇 X 芦京潯胰，聚丙烯、聚乙烯、聚環烯烴、乙細-乙酸乙烯酯共聚物等聚嬌 — 予♦緙焱糸树月曰之溥膜；聚對酞酸 =*對駄& 丁 _ g旨、聚萘二甲酸乙二醋等聚醋系樹薄膜，聚芳酸醋系樹脂之_赠· 亍树細之潯膜，丙烯酸系樹脂之薄膜；聚苯硫SI樹脂之薄膜·學絮 — — 寻、來本乙烯树月曰之溥膜；乙烯基系樹脂之薄膜.；聚ϋ胺系樹脂之薄膜；聚酸亞胺系樹脂之薄膜；環氧系樹脂之薄膜等。將接著劑組成物塗佈於上述薄片狀基材的塗佈方法，亚無特別限制，可依據常法並選擇適當之塗佈手段進行。塗佈手段係可列舉如纏線棒、散佈器（applicator)、刷毛、喷霧、輥輪、凹版塗佈器、模具塗佈器、唇狀塗佈器、逗號塗佈器（comma coater)、刀式塗佈器、逆式塗佈器(reverse coater)、疑轉塗佈益等。當接著劑組成物含有有機溶媒或水等液狀媒體時，可藉由於塗佈後乾燥去除液狀媒體而在薄片狀基材上形成接著劑層；當接著劑組成物不含有應去 319793 73 200838965 除之液狀媒體、且因加埶㈣態之接著劑層冷;=使:度 W方法並無特別限制，可列舉喊鮮外線或減壓的方法。乾焊欠』用.、、、風軏紅、紅㈣、膜戶切田依據接著劑組成物之硬化一心膜与*、或使用之溶杳丨j笨而τ m 左右之熱風加熱為適用^而不同，但通常請至⑽ 又基材，之接著劑層之厚度係以0.1 m至1〇〇Am為更佳。若未達〇._， ♦則有無法獲得充足之接著力接著力等特性亦無法更加提升使超過200_， :用本發明之接著劑組成物，可提供一種將以接著劑體成成之接著劑層積層於光學構件上而成的積層 ^可利用於光學機㈣零件之組裝、製造方面。例如， 2杨定光學特性m或薄膜狀之光學構件上積層有接者劑層的積層體，係藉由將接著劑層黏貼於液晶單元拳Ιί璃構件上’ Γ可獲得由光學構件/感壓接著劑層/玻璃所成之液晶單元用構件。此等可利用於光學機.器之夢造=面的積層體的光學構件，係可列舉如偏光薄膜、相位' 差薄膜私圓偏光薄膜、抗反射薄.膜、提高亮度之薄膜等各種光學薄膜。積層體亦可具有用以保護使用前接著劑層之另一面的經剝離處理之薄片狀基材。'θ 積層體可藉由下述製程而獲得：將接著劑組成物塗佈 =剝離處理之薄片狀基材之剝離處理面並乾燥而形成接者薄片，然後在此接著劑層之表面積層薄片狀之光學構 319793 74 200838965 〇或疋在薄片狀之光學構件直接塗佈接著劑組成物並乾、矿：、、、:後在接著劑層之表面積層經剝離處理之薄片狀美姑之剝離處理面。土仗如此操作而獲得之積層體將覆蓋接著劑層表面之經相處理之薄片狀基材予以剝離，藉由黏貼於光學構件，而可湘於各種光學機器或零件之組裝、製造方面。本i明之接著劑組成物係由於以聚酯樹脂所構成，故、/、可塑舰或m著性優異。因此，亦可適用 ;茜求對於如發泡體等基材之密著性的用途。材料另Lr構件用薄膜或玻撕材枓，其折射率為约！ 5〇 ^ 7 之製造方面所使用的接菩〜·右’若在光學零件等 …，則與光學薄硬化後之折射率未達著劍層設構;^料差變大，當接射，而降低光之有效利用率。二引起全反或硬化後之折射率^5敕盔片。且成物之乾爍及/ Κ㈣羊㈣為較佳值係 + 量而使樹脂之折射率维持於含有節芳香環導入至主鏈骨牟中、，上尤其疋可容易地調及/或硬化後之折射率調整成口㈣供折射率為1.50至！ 55 .之乾圍，而可提 • 之乾圍的接著劑層。 • > . 319793 75 200838965 (實施例）以下，將本發明之具體實施例與比較例一併說明，但本發明不受限於下述實施例。另外，於下述實施例及比較例中’「份」及Γ %」係分別表示「重量份」及「重量。」《第1封閉型態：使用矽烷化劑（Cl)作為封閉化合物（c)》在下述合成例1至20中，使用矽烷化劑（ci)作為封閉化合物（c)以調製聚酯樹脂。合成例丨至6係依據三階段型製造方法、合成例7係依據擬似二階段型製造方法、合成 _例8至18係依據二階段型製造方法而調製，而合成例19 及20係在二階段型製造方法中省略環狀酯（b)或封閉化合物⑷。 [以三階段型製造方法製造加成型聚酯樹脂（D1)] (合成例1) <步驟（1):聚酯主·鏈之形成;> ，將攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入 _管設於聚合槽而構成聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入二元酸（a-丨）、具有2個環狀醚基之化合物（a-2)、觸媒、以及有機溶劑。 [聚合槽] 己二酸(a-1) 438份 .異酜酸（a-1) 332份乙酸乙酯 135份甲苯 135份 [滴下裝置] 319793 76 200838965 1995 份 5.5份 135份 135份雙酚A二環氧丙基醚（心2) 四氫硼酸四丁基銨（觸媒) 乙酸乙酯甲苯將聚合槽内之空氣以氮氣置換後，一邊攪拌槽内之二元酸溶液一邊升溫至100它。其次，於攪拌中之二元酸混合物’藉由滴下裝置而將二環狀醚化合物之混合物耗費】小時以等速滴下。滴下完畢後，再一邊攪拌一邊每隔s小籲％加入觸媒5:5份，共加入2次後，再使其熟成24小時，然後添加1307份乙酸乙酯並冷卻至室溫，結束反應。此反應溶液係獲得淡黃色透明、且其不揮發成分6〇.5 重量0/〇、黏度20,〇〇〇mpa · s、酸價ojmgKOH/g、經基價 155mgKOH/g、玻璃轉移溫度60°c、重量平均分子量5〇,〇〇〇之聚酯樹脂（B)溶液。 . <步驟（2):環狀酯（b)之開環加成反應> 馨準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及濟下裝置中分別以下述比率加入步驟（1)所得之主鏈用聚酯樹脂 (B)溶液、環狀酯（b)、觸媒、以及有機溶劑。 [聚合槽] 聚酯樹脂（B)溶液 219份乙酸乙酯 3 3份 [滴下裝置] … ε 己内酯（b) 114份 319793 77 200838965 四氫硼酸四丁基銨（觸媒） 13份乙酸乙酯 66份將聚合槽内之空氣以氮氣置換後，一邊授掉樹月旨一邊升溫至100C。其次’於攪拌中之樹脂溶液中，萨滴下裝置而將環狀酯（b)混合物耗費1小時以等速滴下、下完畢後’再-邊攪拌一邊使其熟成12小時，然後添: 66份乙酸乙酯並冷卻至室溫，結束反應，而獲得加成有環狀酯（b)之加成型聚酯前驅物(C1)之溶液。衣此反應溶液係淡黃色透明、且其不揮發成分6〇·2重量 %、黏度 15,000mPa · s、酸價〇〇5mgK〇H/g、羥基= 74mgKOH/g、玻璃轉移溫度—1(rc、重量平均分子^ 150,000之樹脂之溶液。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基}莫耳，環狀酯（b)成為約 1 · 8莫耳/之比率。 _ _ <步驟（3):藉由矽烷化劑（cl)而進行之封閉反應> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟（2)所得之加成型聚酯前驅物（C1)溶液、矽烷化劑（cl)、觸媒、以及有機溶劑。 [聚合槽] — ‘ . ' · ' 加成型聚酯前驅物(C1)溶液 200份 [滴下裝置] 六甲基二石夕氮烧（cl) 16份四氫硼酸四丁基銨（觸媒） 1.2份 78 319793 200838965 份乙酸乙酯 _將聚合槽内之空氣以氮氣置換後，—邊櫈拌加成型聚酯別驅物（C1)溶液—邊升溫至1⑻。c。其二欠，於授拌中之溶液中，藉由滴下裳置而將上述概劑㈣混合 ! 小時以等速滴下。滴士 $ # ^ 同、下滴下凡畢後，再-邊㈣-邊使其熟成、$ α後添加3份乙酸乙酯並冷卻至室溫，而獲得加成型聚I旨樹脂（D1)溶液。 ’ 、旦此反應溶液係淡黃色透明、且其不揮發成分為的.3重罝％、，度為18,〇〇〇mPa. s’該樹脂(D1)之側鏈含有率為 53重量％、芳香環含有率為約17重量％，並且其酸價為。mgKOH/g、纟！基價為5mgK〇H/g、玻璃轉移溫度為— 1(TC、重量平均分子量為16〇,〇〇〇。 ’、、 (合成例2) •將合成例1之步驟（1)中所用之二元酸（a-Ι)變更成異 830知，並將二環狀醚化合物（a_2)變更成新戊二醇二壤乳丙基醚1449份，且在步驟⑺中使用以乙酸乙醋調整 =揮發成分濃度至約6〇重量％之聚酯樹脂（B)溶液2⑽ =，除此以外與合成例丨同樣地操作進行調製，而獲得淡黃色透明、且其不揮發成分濃度為60.0重量％、黏度為 ’、OmPa s之加成型聚酯樹脂(D1)溶液。該樹脂(⑴）之酸仏為。〇.5mgK〇H/g、羥基價為3mgK〇H/g、玻璃轉移溫度為 3〇C、重1平均分子量為80,000。又，在上述配方中，相對於源自二環狀醚化合物(a-2)之二級羥基1莫耳，環狀酯(b)成為約i.3莫耳之比率。 319793 79 200838965 (合成例3) 將合成例1之步變更成ι，4·雙{[(3_乙;^):㈣之：環賴化合物㈣份及雙紛Α二環氧丙：歸環丁基）甲氧基]曱幻苯670 乙酸乙醋調整 ⑻溶液戰，重說聚醋樹脂 w ^ 外興合成例1同樣地操作進行調衣’以乙I乙酯調整不揮八曲早嗌成刀〉辰度至約60重量％，而獲The AM iron-conducting compound 0 is an organic cobalt compound, and examples thereof include cobalt acetate, cobalt benzoate, and 2-ethylhexanoic acid. Examples of the organozinc compound include zinc, zinc oxalate, zinc naphthenate, and zinc 2-ethylhexanoate. ^ As the metal tooth compound, for example, tin (II) chloride, tin (漠), tin (II) iodide, etc. may be mentioned. In addition to the above, a Lewis acid such as boron trifluoride, aluminum trichloride, zinc chloride or titanium chloride can also be used as a catalyst for the polyaddition reaction. The catalyst for the addition reaction is not limited to the above examples, and only one type may be used, or two or more types may be used in combination. The amount of the catalyst to be used is preferably about 1 part by weight or less based on 100 parts by weight of the reaction component. When the amount is more than 10 parts by weight, the product may be colored or may act as a negative catalyst during the ring-opening addition reaction of the cyclic ester (b). The polyaddition reaction is carried out at a temperature in the range of from .20 to 220 ° C, and is from 50 to 200 C in t. The reaction time can usually be from about 1 to about 6 hours. Solvents may be used or not. Examples of the solvent that can be used include hydrocarbon-based solvents such as toluene, xylene, hexane, and heptane; ester solvents such as ethyl acetate and butyl acetate; and ketone solvents such as acetone and methyl ethyl ketone; A halogenated hydrocarbon solvent such as chloroform or chloroform; an ether solvent such as diethyl ether, methoxytoluene or 319793 63 200838965, which may be used singly or in combination of two or more. However, since the solvent containing a radical is greatly reduced in the reaction rate in the subsequent reaction with the cyclic group (8), such a solvent cannot be used. The ring-opening addition reaction of the warp group of the polyacetic acid main chain (I) with the cyclic vinegar (8) can be carried out using known reaction conditions. Specifically, the reaction temperature is preferably increased to 220 C ' and 6 G to 18 ° C:. The reaction time can usually be set to about 30 hours. In addition, although it is possible to use a sputum medium or a catalyst, it is preferable to use it. For the catalyst for ring-opening addition, a catalyst for the upper f-addition reaction used in the reaction of the dibasic acid (a-1) with the dicyclic compound (a_2) can be similarly used. In particular, the quaternary ammonium salt is more suitable as a catalyst from the viewpoint of the difficulty in coloring the resin (D). The catalyst when the blocking compound (4) is reacted with the ith side chain (11) having a terminal radical to obtain an addition-molded polyester resin (Db D3) is characterized by the fact that the reactivity and the addition of the polyester resin (9) are not easily colored. Look, it is more suitable to use quaternary ammonium salts. In the case where the addition-forming resin (D2) is obtained, for the same reason, in the respective steps, the quaternary salt is also suitable as a catalyst. To: make the composition of the adhesive to play the role of a good bond as a balance of the adhesive (especially the adhesion and cohesive force at the same time add to the _ with its glass transfer Qing ^ ^ ^ soil price if added The glass transition temperature of the polyester resin (D1 to D3) ^, the adhesive composition prepared by the polyester resin (D1 to D3) of the shell 1H吏 is thermally applied to the agglutinating force of the adhesive and becomes easy to produce. In the other way, if the glass transition temperature exceeds the order = 319793 64 200838965: sensation, the adhesive contacts the body, and the adhesive layer does not sufficiently wet the body, and there is no way to get enough. The possibility of producing an addition polyester resin (D1 to D3) having a Tg of preferably 80 to 10 〇c, more preferably _6 〇 to -1 ,, as a dibasic acid (d), The selection of each component used for the two cyclic compound (', the cyclic ester (8), and the blocking compound (4) is appropriately considered. From the viewpoint of adhesion, the weight average molecular weight (Mw) of the added polyester resin is In), the range of GGG to 1, _, _ is better, and at 8, _ to 5〇〇, the range of _ is more preferable. If the MW is less than 2,0〇〇, the added method of the addition of the polyester resin of the present invention (Di to the unique cohesive force, heat resistance and heat and humidity resistance are reduced. On the other hand, when the Mw exceeds 1,000,000, the fluidity of the adhesive composition containing the addition-form polyester resin (1)} is deteriorated, and it becomes difficult to produce a pressure-sensitive adhesive sheet. - The adhesive composition of the present invention Containing a crosslinking agent (£) capable of reacting with a functional group of the above-mentioned addition polyester tree _lipid (〇1 to D3), the addition polyester resin is hardened by a crosslinking reaction with a functional group to form an adhesive The crosslinking agent (E) used in the present invention is a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group in the addition-molded polyester resin (D1 to D3) in the molecule, and The crosslinking agent is preferably a compound having two or more functional groups capable of reacting with a hydroxyl group or a carboxyl group in the molecule. Examples of such a compound include a polyisocyanate compound and a polyfunctional rock-burning compound. , compound containing N-thiol group, epoxidation Compound, amine compound, aziridine compound, Shihu 24~ 319793 65 200838965 (carbodiimide) compound, phthalocyanine compound, melamine compound and metal chelate compound, etc. These are followed by crosslinking reaction The composition of the agent is excellent in adhesion to the substrate or the substrate. The crosslinking agent (E) which can react with the base is, for example, a polyisocyanate compound or a polyfunctional decane compound. a compound containing an N-hydroxyindole group, an amine compound, and a melamine compound; a crosslinking agent (E) reactive with a carboxyl group, such as an aziridine compound, an epoxy compound, a phosphonium compound, a carbodiimide compound, and Metal chelate compound. As described above, since the acid value or the hydroxyl value of the addition type polyester resin (D) exists in an appropriate range depending on the type of the crosslinking agent (E), when the polyester resin (D1 to D3) is added, When the hydroxyl group is 0.1 to 50 mgKOH/g, the combined crosslinking agent (E) may be of a type which can react with any of a hydroxyl group and a carboxyl group; if the hydroxyl group of the polyester resin (D1 to D3) is added When it is more than 50 mgKOH/g and is 100 mgKOH/g or less, the combined crosslinking agent (E) / is a type capable of reacting with a carboxyl group; further, from the viewpoint of pot life, an addition molding polyester resin (D1 to The acid value of D3) is preferably from 0.1 to 50 mgKOH/g I. The polyisocyanate compound used as the crosslinking agent (E) is, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate or an alicyclic polyisocyanate. a compound. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. , 2,4-extended phenyl diisocyanate, 2,6-extended phenyl diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate Toluene, 1,3,5-triiso 66 319793 200838965 Cyanate S, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4''-triphenyldecane triisocyanate and the like. Examples of the aliphatic polyisocyanate include tridecyl diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, and 1,2-propyl group. Diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecyl diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, and the like. Examples of the aromatic aliphatic polyisocyanate include ω,ω diisocyanate-1,3-didecylbenzene, 6 ι), 6 ϋ diiso-succinic acid-1,4-dimercaptobenzene, oxime, ω The diisocyanate g is -1,4-diethylbenzene, 1,4-tetramethyl-decyldiisocyanate, 1,3-tetramethyl-decyldiisocyanate or the like. The alicyclic polyisocyanate may, for example, be 3-isocyanatomethyl-3,5,5·trimethylcyclohexyl isocyanate (IPDI), 1 , 3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, fluorenyl-2,6-ring Hexane diisocyanate, 4,4'-fluorenylene bis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, and the like. • '. - It is also possible to use a tri-methyl-propylated adduct of the above polyisocyanate compound or a trimer having a trimeric isocyanate ring. Further, polyphenylmethane polyisocyanate (PAPI) - # # ^ ^ 67 319793 200838965, and the polyisocyanate g-modified substance may be used. Further, in the case of a smear-reducing substance, it is possible to use a condensed egg having a reaction selected from the group consisting of diimide, yttrium (Uretedi〇ne), ureaimine, and water. Any one or two or more kinds of modified substances of a group or an isocyanate group. Further, the polyol and the diiso-(4) reaction product can also be used as a polyisocyanate. In the above polyisocyanate compound, if 4,4, diphenyldecane diisocyanate, hexamethylene diisocyanate, 3-isocyanatomethyl_3,5,^_ ♦ trimethylcyclohexyliso is used. Cyanic acid vinegar (alias: isophora _ diisocyanate), f-diisocyanate, 4,4,_methylene bis (cyclohexyl isocyanate X alias: sulphurized MDI), etc. The polyisocyanate compound is particularly preferred from the viewpoints of weather resistance, heat resistance, and moist heat resistance. When a polyisocyanate compound is used as a crosslinking agent, a known catalyst can be used as needed to promote the reaction. Examples of the catalyst that can be used include a tertiary amine compound and an organometallic compound. The epoxy compound to be used as the crosslinking agent (E) may be exemplified by an epoxy compound such as bisphenol winter epichlorohydrin type or ethylene glycol. Epoxypropyl ether, polyethylene glycol diepoxypropyl ether, glycerol diepoxypropyl ether, glycerol triepoxypropyl sulfonate, 丄6-hexanediol diepoxypropyl ether, trimethylolpropane Triepoxypropyl ether, diepoxypropyl aniline, N,N,N,,N,tetraepoxypropyl/m-decyldiamine, bis(N,N,-diepoxypropylamino) Methyl)cyclohexane, etc. The aziridine compound used as the crosslinking agent (E) may, for example, be -diphenylmethane-4,4'-bis(1-azetidine carbonyl) (ie 319793 68 200838965 N, N'-diphenyl propane -4,4'_bis(l-aziridine carboxide)), N,N'-toluene-2,4-bis(1-aziridine carbonyl;), double Mercapto-1-(2-methylaziridine), tris-l-aziridine phosphine, N,N,-hexamethylene-1,6-bis(1-aziridine carbonyl) ), trimethylolpropane-tri-β-aziridine propionate, tetramethylol decane-tri-/3-aziridine propionate, gin-2,4,6_(1- Aziridine)-1,3,5_three tillage, trimethylolpropane-indole-(1-aziridine)propionate], trihydrocarbylpropane ginseng [3-(1-Azide-B) Pyridyl)butyrate], trimethylolpropane ginseng [3-(1_(2-methyl)aziridine)propionate], trimethylolpropane ruthenium [3-(1-Azide-B) Pyridyl)-2-methylpropionate], 2,2,-bishydroxymethylbutanol gin[3-(1-aziridine)propionate], pentaerythritol tetra[^(^ aziridine Propionate], diphenylmethane-4,4-bis-N,N'-extended ethylurea, 1,6-hexamethylene bis-N,N'-extended ethylurea, 2, 4,6_(tri-ethylethylenimine)_symmetric triterpenoid, bis[1-(2-ethyl)azetidine]benzene-i,3-oroxylamine, etc. as a parent two bismuth ( Xi) The carbodiimide compound used is a compound having two or more carbon-imido groups (_n=C=N_) in the molecule, and a known polycarbon can be used. a diimine or a high molecular weight polycarbodiimide formed by decarbonation condensation reaction of a diisocyanate in the presence of a carbodiimidation catalyst, and a high molecular weight polycarbodiene is formed. The raw material isocyanate of the amine may, for example, be 4,4-dicarboxylic acid diisocyanate, 3,3,-dimethoxy-4-4, mono-methane diisocyanate, 3,3,-dimethyl 4,4'-diphenylmethane 'isocyanide: ester, 4,4-diphenyl ether diisocyanate, 3,3,-didecyl·4 4, one #* _ ^ , _ —benyl ether Cyanate, 2,4-toluene diisocyanate, 2 6_extension, 丨τ τ, monoisocyanate, 1 methoxyphenyl-2,4-diisocyanate, isophorone Diisocyanate, 319793 69 200838965 4,4'-dicyclohexyldecane diisocyanate, tetramethyl decyl diisocyanate - one or a mixture of two or more of these may be used. The carbodiimide catalyst may, for example, be a phenylene-2-cyclophosphene oxide (1-Phenyl-2-Ph〇Spli〇lene-l-oxide) or a thiol-2-ring. Phosphenene-1-oxide, 1-ethyl-3-methyl-2-cyclophosphene oxide, ethyl-2-cyclophosphene-1-oxide, and these 3_cyclophosphene iso a structure such as a cyclophosphene oxide. For the commercially available high molecular weight polycarbodiimide available, the Carb〇dilite series manufactured by Minqing Textile Co., Ltd. can be listed. Among them, CarbodiHte V-01, 03, 05, 〇7, and 〇9 are preferred because they are excellent in compatibility with an organic solvent. The oxazoline compound used as the crosslinking agent (E) is preferably a compound having two or more fluorenyl groups in the molecule, and specifically, for example, 2,-methylene double (2· Oxazoline), 2,2, _ethylidene (2_carbazole), 2,2, _ ethyl bis(4-mercapto-2-oxazoline), 2,2, _ Propyl bis (2_oxazoline _ 2,2'·tetramethylene bis (2-conductine), 2,2, hexamethylene double (2_salin), 2,2, '· octamethyl bis (2 曙曙 porphyrin), 2, 2, _ phenyl bis(2 曙曙曙), 2, 2 pairs of phenyl bis (4, 4 ' dimethyl) _2-carbazolidine, 2,2,_p-phenylene bis(4-mercapto-2-[oxazoline), 2,2'-p-phenylene bis(4_phenyl_2_噚Oxazoline), (4)), 2,2,-inter-phenylene bis(4,4,_dimethyl-2_salt), decyl bis (4-phenylene double _2 sitting ), 2, 2: o-phenyl bis(2_卩 et al), 2,2-o-phenylene bis(4-methyl-2-oxazoline), 2,2, _bis (2_ Oxazoline) 2,2-bis(4-mercapto-2-indolyl salicyl), 2,2,_bis (4-ethyl-2-isophilic. sitting 319793 70 200838965 porphyrin), 2, 2, - double (4_phenyl-2-indole) Morpholine) and so on. In addition, it is also possible to use, for example, 2_isopropenyl-2_oxazoline or 2-isopropenyl-4,4-dimethyl-2-oxazoline, and the like, a vinyl monomer, an energy source, and a vinyl monomer. Copolymerized copolymer of other monomers. ^ As a metal chelate compound used as a parent (E), for example, ethyl bromide or ethyl acetate is placed in aluminum, iron, copper, rhodium, tin, chin, nickel, bismuth, magnesium. a compound of a polyvalent metal such as vanadium, chromium or ruthenium. The above crosslinking agent (E) may be used singly or in combination of plural kinds. The adhesive composition of the invention of the present invention contains a polyester resin (D) as a curable resin component and a crosslinking agent (E). For the polyester resin (D), the above-mentioned addition molding resin (D1) can be used. To D3). The composition ratio is 〇〇〇1 to 2 〇, based on the weight of the crosslinking agent (E) of the polyester resin (D), and is 佺1 to 10 parts by weight. For better. When the amount of the crosslinking agent (E) exceeds 2 G by weight, the adhesiveness (wetting property, adhesion) of the obtained adhesive composition as a pressure-sensitive adhesive tends to decrease, and the resin The layer has a low cohesive force and is poor in shape retention or durability when used repeatedly. It can be used as an adhesive for subsequent fixation due to hardening of the resin. Further, when the amount of G.GG is less than 1 part by weight, a sufficient crosslinked structure cannot be obtained, so that the cohesive force is lowered and the heat resistance and the moist heat resistance tend to be lowered. When it is used as an adhesive composition or a coating composition other than the composition of the pressure-sensitive adhesive, the functional group of the main financial property is reacted with the crosslinked resin to form a hardened adhesive layer or a hardened coating film. However, when it is used as a pressure sensitive layer followed by a composition of y, in order to make the pressure-sensitive layer which has been hardened by the adhesive layer to wet the surface of the object, it is necessary to make the hardened pressure-sensitive adhesive layer have a surface 319793 71 200838965: : (adhesive) semi-solid state. Therefore, it is a step of forming a hardened pressure-sensitive adhesive layer by reacting a part of the above-mentioned addition polyester resin (D1 to D3) with a crosslinking functional group (10) fluorenyl group. The reaction of the mouth-shaped polyacetate tree (9) to the base or a group of the base and the S-energy group of the cross-linking agent can make the resin cross-link three-dimensionally and improve the shape, because the uncrosslinked The side chain enhances the tightness of the resin with various substrates or bodies. Further, the lowering of the compound (4) reduces the base price of the resin, and even under the stricter conditions than before, the acid heat resistance can be improved, so it can be applied to the component. Pressure contact agent. Without impairing the effects of the present invention, the adhesive of the present invention may be formulated with various resins, couplers, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weathering stabilizers, and tackifiers. Agent (taCkifier), plasticizer, filler, anti-aging agent, etc. The layer of the agent layer and the thin layer and the soil material can be used as a continuous sheet. The sheet is obtained, for example, by applying the adhesive composition of the present invention to various sheet-like substrates, drying and hardening. In order to improve the robustness, an organic solvent such as an alcohol or another hydrocarbon-based solvent or water may be added to adjust the viscosity of the adhesive composition, and the adhesive composition may be heated to make the viscosity. reduce. However, if water or alcohol is added in a large amount, it may cause the reaction of the addition polyester resin (D1 to D3) 319793 72 200838965 and the crosslinking agent (E) to inhibit tl -3⁄4 Μ 々 & & 性性性 , , , , , , , , , , , , the amount. For the moon-shaped substrate, enamel, plastic, rubber, foam, tip = material such as Cen〇phane, wood, etc., formed into a flexible flat shape, a sheet-like substrate can be used. In the case of a separate material, it is also possible to use a plurality of layers of material (four) as the surface of the substrate. In addition, 'the substrate made of flaky plastic can be used for long-term insertion of the lake--wall", a... there are various plastic enamel films, such as polyethylene glycol X reed, pancreas, polypropylene, Polyethylene, polycycloolefin, ethylene-vinyl acetate copolymer, etc. - 缂焱糸缂焱糸缂焱糸曰 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Ethylene vinegar and other vinegar-based tree film, polyarylate vinegar-based resin _ gift · eucalyptus fine enamel film, acrylic resin film; polyphenyl sulphur SI resin film · learning scent - 寻, 来本乙A film of a vinyl resin; a film of a vinyl resin; a film of a polyamide resin; a film of a polyimide film; a film of an epoxy resin. The coating method of applying the adhesive composition to the above-mentioned sheet-like base material is not particularly limited, and can be carried out according to a usual method and selecting an appropriate coating means. The coating means may, for example, be a wrap bar, an applicator, a bristles, a spray, a roller, a gravure coater, a die coater, a lip coater, a comma coater, Knife coaters, reverse coaters, suspected coating benefits, etc. When the adhesive composition contains a liquid medium such as an organic solvent or water, an adhesive layer can be formed on the sheet-like substrate by drying and removing the liquid medium after coating; when the adhesive composition does not contain 319793 73 200838965 In addition to the liquid medium, and the layer of the adhesive layer due to the twisted (four) state is cold; = the method of the degree W is not particularly limited, and a method of shouting the outside line or decompressing may be cited. Dry welding is not used.,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Different, but usually to (10) the substrate, the thickness of the adhesive layer is preferably 0.1 m to 1 〇〇 Am. If it does not reach 〇._, ♦, there is no sufficient adhesion, and the characteristics such as force cannot be further improved to exceed 200_. By using the adhesive composition of the present invention, it is possible to provide an adhesive body. The laminate formed by laminating the optical member can be used for assembling and manufacturing parts of the optical device. For example, 2 Yangding optical property m or a film-like optical member is laminated with a layer of a carrier layer, which is obtained by adhering an adhesive layer to a liquid crystal cell box member. A member for a liquid crystal cell formed by pressing an adhesive layer/glass. These optical members which can be used for the laminated body of the optical machine, such as a polarizing film, a phase difference film, a transparent polarizing film, an antireflection film, a film for improving brightness, and the like can be used. film. The laminate may also have a release-treated sheet-like substrate for protecting the other side of the front adhesive layer. The 'θ layered body can be obtained by applying the adhesive composition to the release-treated surface of the sheet-like substrate which is subjected to the release treatment and drying to form a carrier sheet, and then the surface layer layer of the adhesive layer. Optical structure 319793 74 200838965 〇 or 疋 directly coated with an adhesive composition in a sheet-like optical member and dried, ore:,:, after peeling off the surface layer of the adhesive layer Processing surface. The laminate obtained by the operation of the crucible is peeled off by the phase-treated sheet-like substrate covering the surface of the adhesive layer, and is adhered to the optical member to be assembled and manufactured in various optical machines or parts. The adhesive composition of the present invention is composed of a polyester resin, so that it is excellent in a plastic ship or a m-type. Therefore, it is also applicable to the use of the adhesion to a substrate such as a foam. The material is another Lr member film or glass tearing material, and its refractive index is about! 5〇^ 7 The use of the connection to the Bo ~ ~ right 'If in the optical parts, etc., then the refractive index after thinning with the optical does not reach the sword layer design; ^ material difference becomes larger, when the radiation, And reduce the effective utilization of light. Second, the refractive index of the total anti- or hardened ^5 敕 helmet piece. And the dryness of the product and / (4) sheep (four) is the preferred value of the amount of the resin to maintain the refractive index of the resin in the introduction of the aromatic ring into the main skeleton, especially in the upper can be easily adjusted / or hardened After the refractive index is adjusted into a mouth (four) for a refractive index of 1.50 to! 55. The dry perimeter, and the adhesive layer of the dry circumference can be mentioned. • > . 319793 75 200838965 (Embodiment) Hereinafter, specific embodiments of the present invention will be described together with comparative examples, but the present invention is not limited to the following embodiments. In the following examples and comparative examples, ""parts" and "%" indicate "parts by weight" and "weight." "First closed form: using a decylating agent (Cl) as a blocking compound (c) In the following Synthesis Examples 1 to 20, a decylating agent (ci) was used as the blocking compound (c) to prepare a polyester resin. The synthesis examples 丨 to 6 are based on the three-stage production method, the synthesis example 7 is based on the pseudo-two-stage production method, and the synthesis _ examples 8 to 18 are based on the two-stage production method, and the synthesis examples 19 and 20 are in the second. The cyclic ester (b) or the blocking compound (4) is omitted in the stage-type manufacturing method. [Production of Additive Polyester Resin (D1) by Three-Step Manufacturing Method] (Synthesis Example 1) <Step (1): Formation of polyester main chain; > , Mixer, thermometer, reflux cooler, dripping The apparatus and the nitrogen introduction tube are disposed in the polymerization tank to constitute a polymerization reaction device, and the dibasic acid (a-fluorene) and the compound having two cyclic ether groups (a- are respectively added in the polymerization tank and the dropping device at the following ratios. 2), catalyst, and organic solvents. [Polymerization tank] Adipic acid (a-1) 438 parts. Isodecanoic acid (a-1) 332 parts of ethyl acetate 135 parts of toluene 135 parts [Dropping device] 319793 76 200838965 1995 5.5 parts 135 parts 135 parts bisphenol A diglycidyl ether (heart 2) tetrabutylammonium tetrahydroborate (catalyst) Ethyl acetate toluene After the air in the polymerization tank is replaced with nitrogen, the temperature is raised to 100 while stirring the dibasic acid solution in the tank. it. Next, the dibasic acid mixture of the mixture was stirred at a constant rate by taking a mixture of the dicyclic ether compounds by means of a dropping device. After the completion of the dropwise addition, 5:5 parts of the catalyst was added every s. while stirring, and then added for 2 times, and then matured for 24 hours, then 1307 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. . The reaction solution was light yellow transparent and had a nonvolatile content of 6 〇.5 wt%/〇, viscosity 20, 〇〇〇mpa·s, acid value ojmgKOH/g, base price 155 mgKOH/g, glass transition temperature 60. °c, weight average molecular weight 5 〇, 聚酯 polyester resin (B) solution. <Step (2): Ring-opening addition reaction of cyclic ester (b)> A polymerization reaction apparatus prepared with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube in a polymerization tank, and The polyester resin (B) solution for the main chain, the cyclic ester (b), the catalyst, and the organic solvent obtained in the step (1) are added to the polymerization tank and the sublimation apparatus at the following ratios. [Polymerization tank] Polyester resin (B) solution 219 parts Ethyl acetate 3 3 parts [Dropping device] ... ε Caprolactone (b) 114 parts 319793 77 200838965 Tetrabutylammonium tetrahydroborate (catalyst) 13 parts acetic acid After 66 parts of the ethyl ester was replaced with nitrogen in the polymerization tank, the temperature was raised to 100 C while the tree was transferred. Next, in the stirring resin solution, the mixture of the cyclic ester (b) was dripped for 1 hour at a constant rate, and after completion, the mixture was stirred for 12 hours while stirring, and then added: 66 parts. The ethyl acetate was cooled to room temperature, and the reaction was terminated to obtain a solution of the addition-formed polyester precursor (C1) to which the cyclic ester (b) was added. The reaction solution is light yellow transparent, and its nonvolatile content is 6 〇 2 wt%, viscosity 15,000 mPa · s, acid value 〇〇 5 mg K 〇 H / g, hydroxyl group = 74 mg KOH / g, glass transition temperature - 1 (rc a solution of a resin having a weight average molecular weight of 150,000. Further, in the above formulation, the cyclic ester (b) becomes about 1 with respect to the secondary hydroxyl group derived from the dicyclic ether compound (a-2). 8 mole/rate ratio. _ _ <Step (3): Blocking reaction by decylating agent (cl)> Prepared in a polymerization tank with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction The polymerization apparatus of the tube is added to the addition type polyester precursor (C1) solution, the alkylating agent (cl), the catalyst, and the organic solvent obtained in the step (2) in the polymerization tank and the dropping device, respectively. [Polymerization tank] — ' . ' · ' Addition of polyester precursor (C1) solution 200 parts [Drip device] Hexamethyl diazepine (cl) 16 parts of tetrabutylammonium tetrahydroborate (catalyst) 1.2 parts 78 319793 200838965 parts of ethyl acetate _ After replacing the air in the polymerization tank with nitrogen, the side stool is mixed The formed polyester paste (C1) solution is heated to 1 (8). c. In the solution, the above mixture (4) is mixed by dropping the spray! The hour is dropped at a constant rate.士$#^, after the next drop, then the side (four) - while making it mature, add 3 parts of ethyl acetate after $α and cool to room temperature to obtain a solution of the addition polymer (D1). ', the reaction solution is light yellow transparent, and its non-volatile content is .3% by weight, the degree is 18, 〇〇〇mPa. s' The side chain content of the resin (D1) is 53% by weight. The aromatic ring content is about 17% by weight, and the acid value thereof is .mgKOH/g, the base price is 5 mgK〇H/g, and the glass transition temperature is -1 (TC, weight average molecular weight is 16〇, 〇〇、. ', (Synthesis Example 2) • The dibasic acid (a-Ι) used in the step (1) of Synthesis Example 1 was changed to 830, and the dicyclic ether compound (a_2) was changed to a new one. 1449 parts of pentanediol diamyl propyl ether, and in step (7), a polyester resin (B) solution 2 (10) = adjusted with ethyl acetate adjusted to a volatile component concentration of about 6 〇 wt%, except The preparation was carried out in the same manner as in the synthesis example, and a solution of a modified polyester resin (D1) having a pale yellow transparency and a nonvolatile content concentration of 60.0% by weight and a viscosity of ', OmPa s was obtained. The resin ((1)) The acid hydrazine is 〇. 5 mg K 〇 H / g, the hydroxyl value is 3 mg K 〇 H / g, the glass transition temperature is 3 〇 C, and the weight 1 average molecular weight is 80, 000. Further, in the above formula, relative to the second ring The secondary hydroxyl group of the ether compound (a-2) is 1 mol, and the cyclic ester (b) is a ratio of about i.3 mol. 319793 79 200838965 (Synthesis Example 3) The procedure of Synthesis Example 1 was changed to ι, 4·double {[(3_B; ^): (4): cyclized compound (four) and double bismuth diepoxy acrylate: Butyl) methoxy] fluorene benzene 670 acetic acid vinegar adjustment (8) solution warfare, re-speaking of polyacetate resin w ^ external synthesis of the same example 1 operation of the adjustment of the 'E-ethyl ester adjustment does not swing eight early Chengdao> Chen degree to about 60% by weight, and

得淡貫色透明、且J：點*支Q ，一、又為8,500mPa · s之加成型聚酯樹 .10 νίΛττ, ) κ貝為 0.5mgKOH/g、經基價為12mgK0H/g、破璃轉移溫度為，、重量平均分子量為65,000。又，在上沭舾士山丁 J刀丁里配方中，相對於源自二環狀醚化合物（a-2)之一級經基i莫耳，環狀醋⑻成為約口莫耳之比率。 '(合成例4) · /將合成们之步驟⑴中所用之二環狀鍵化合物㈣) 暴變更成雙㈣二環氧丙基鱗(大阪瓦斯化學股份公司製之 BPFG ’ 分子量 462.5 ’ 環氧價 3.89(eq/Kg))3203 份，且在步驟（2)中使甩以乙酸乙醋調整不揮發成分漠度至約的重量％之聚醋樹脂（B)溶液315份，除此以外與合成例丄同樣地操作進行調製’卩乙酸乙醋調整不揮發成分濃度至約的重量％’而獲得淡黃色透明、且其黏度為i8,5〇〇mpa . s之加成型聚酯掛脂（D1)之溶液。該掛脂（D1)之酸價為 1.2mgKOH/g、羥基價為llmgK〇H/g、玻璃轉移溫度為— 2(TC、重量平均分子量為15G,_。又，在上述配方中， 319793 80 200838965 相對於源自二環狀醚化合物（a_2)之二級羥基1莫耳，環狀酯（b)成為約1 ·5莫耳之比率。 (合成例5 ) 將合成例1之步驟(2)中所用之環狀酯（b)變更成戊二S曰100份，且在步驟（3)中使用步驟⑺所得之加成型聚醋前驅物（c 1)溶液（不揮發成分6〇.〇重量％)2〇〇份，除此以外與合成例1同樣地操作進行調製，而獲得淡黃色透明、且其不揮發成分為60.1重量％、黏度為9,〇〇〇mpa . s之加成 ♦型聚醋樹脂（m )之溶液。該樹脂（D1)之酸價為。gKOH/g、每基價為12mgK〇H/g、玻璃轉移溫度為— 30C、重量平均分子量為11〇,〇〇〇。又，在上述配方中，相對於源自一壤狀驗化合物(a_2)之二級羥基」莫耳，環狀酉曰(b)成為約1 · 7莫耳之比率。 (合成例6) 二將合成例1之步驟（3)中所用之矽烷化劑(cl)變更成三甲土夕燒醇18伤’除此以外與合成例j同樣地操作進行調製’而獲得淡黃色透明、且其不揮發成分為6〇·2重量％、黏度為 13，〇0OniPa · s 夕 a ju、n 甘 a s之加成型聚酯樹脂(D1)之溶液。該樹月曰（1)之酉夂仏為i.〇mgKOH/gm價為玻璃轉移溫度為―聊、重量平均分子量為⑽，_。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級幾基1莫耳，環狀酷（b)成為約1.8莫耳之比率。 [以擬似二階段型劁#古、义細f ^方去製造加成型聚酯樹脂（1)1乃 (合成例7). 319793 81 200838965 〈步驟（4)(5):加成型聚酯前驅物（C1)之生成〉準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入二元酸（心丨）、二環狀醚化合= (a-2)、環狀酯（b)、觸媒、以及有機溶劑。知 [聚合槽] 73份 404份 875份 1950 份己二酸（a-l) 癸二酸（a-1) 雙酚F二環氧丙基醚（a_2) 雙酚A系苯氧基樹脂（a_2) (曰本環氧樹脂公司製，商品名rjERi256 環氧丙基當量7800g/eq，Mw為51000) 四氫彌酸四丁基銨（觸媒）乙酸乙酯 - 曱苯 [滴下裝置] 四氫硼酸四丁基銨（觸媒） ε -己内酯（b) 乙酸乙酯曱苯 6.6份 210份 210份 6.6份 800份 420份 420份將聚合槽内之空氣以氮氣置換後，一邊攪拌二元> 液一邊升溫至1O(TC。再使其反應8小時，而獲得酸^ 5(mgKOH/g)以下之聚酯主鏈（工，）焉其次’ 一邊攪拌上述反應物，一邊藉由滴下敦置而將 319793 82 200838965 環狀酯（b)混合物耗費1 和小時，添加四氫二滴下完畢後’再 :透卜、+一 gr„平知成刀59.8重置％、黏度30,〇〇〇mPa.s，上圮别驅物（C1)係酸價〇.〇2mgK〇H/g、羥基價％邮 ΚΟΗ/g、玻璃轉移溫度—15 ^ 之樹腊。又，在上述配方中,f里千均分子1 200，_ ^夕έ 方中，相對於源自二環㈣化合物 _)之-、，及經基i莫耳，環狀醋⑻成為約〇 6莫耳之比率。〈步驟（6):藉由㈣化劑㈣而進行之封閉反應> 下於Γ槽附有授摔機、溫度計、回流冷卻器、滴 H 入管的聚合反應裝置，並在聚合槽及滴下裝物比率加人步驟（5)所得之加成型聚酯前驅洛液（不择·發成分59.8重量％)、㈣化劑( 媒、以及有機溶劑。 [聚合槽] 加成型聚酯前驅物（C1)溶液 2〇〇份 [滴下裝置] 刀 22.5 份 6·6份 10份一乙基甲基梦燒（cl) 四氫调酸四丁基銨(觸媒) 乙酸乙酯將聚合_之空氣以氮氣置換後，—邊㈣溶液一邊升溫至HKTC。其次，於授拌中之溶液，藉由滴下装置而將上述矽烷化劑（cl)混合物耗費丨.小時以等速滴下。滴下 319793 83 200838965 完畢後，再—邊攪拌—邊使其熟成6小時，然後添加$份乙酸乙酉旨並冷卻至室溫，而獲得加成型聚酉旨樹脂_之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇5重量 %、黏度為35,000mPa· s，該樹脂(D1)之側鏈含有率為重量％、芳香環含有率為肖17重量％，並且其酸價為 0.02mgKOH/g、經基價為8‘5mgK〇H/g、玻璃轉移溫度為一 15 C、重量平均分子量為22〇,〇〇〇。鬱[以二階段型製造方法製造加成型聚酯樹脂（D1)] (合成例8) 準備於聚合槽附有攪拌機、溫度計、回流冷卻器及氮導入管的聚合反應裝置，並在聚合槽中分別以下述比率加入二元酸（a-Ι)、二環狀醚化合物（a_2)、環狀酯（b)、觸媒、以及有機溶·劑。 [聚合槽] 己二酸（a-1) 159份異酞酸（a-1) 120份雙酚A二環氧丙基醚（a_2) 721份 ε 己内酯(b) 871份乙酸乙酯 200份甲苯 200份 <步驟（7):加成型聚酯前驅物(C1)之生成〉氣將聚合槽内之空氣以氮氣置-換後，一邊攪拌混合物一邊升溫至：100。(： ’添加四氫硼酸四丁基銨2〇份以起始反 319793 84 200838965 應。-邊授拌混合物，一邊每隔8小時添加一次四氮喊四丁基按2 · 0份，i£禾士 9 一七，、隹/-人 ^ ，、/+力2-人進仃合計24小時之反應及熟成，而獲得加成型聚酉旨前驅物（C1)溶液。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級經基i莫耳’環狀酯（b)成為約ι·8莫耳之比率。 <步驟（8) ··藉由矽烷化劑（c丨）而進行之封閉反應〉在前述加成型聚酯前驅物（C1)溶液令，添加乙酸乙酯：6^0份、作為矽烷化劑（cl)之六甲基二矽氮烷：245份，使/、无、成6小日守。然後，添加乙酸乙酯3⑽份並冷卻至室溫，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇·4重量 %、黏度為15,000mpa . s，該樹脂（m)之酸價為 UmgKOH/g、羥基價為6mgK〇H/g、玻璃轉移溫度為—j 〇 °C、重i平均分子量為15〇,〇〇〇。 ·· (合成例9) 將合成例8所使用之觸媒變更成溴化四丁基銨，除此之外與合成例8同樣地操作進行調製，而獲得淡黃色透明、且其不揮發成分為60·2重量❹/〇、黏度為9,000mPa · s 之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為〇.8mgKOH/g、羥基價為i〇mgK〇H/g、玻璃轉移溫度為一 l〇°C、重量平均分子量為120,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級經基1莫耳，環狀酯（b)成為約1·8莫耳之比率。 (合成例10) 85 319793 200838965 將合成例8之步驟（7)中所用之二元酸（a_1；)變更成丁二酸：322份、將二環狀醚化合物（a_2)變更成新戊二醇二環氧丙基醚：678份、將環狀酯（b)變更成ε、己内酯：456 伤、將作為觸媒之硝酸四丁基按每次使用2份共使用3次、將步驟(8)所用之矽烷化劑（cl)變更成甲氧基三甲基矽烷: 118份、並調整乙酸乙酯之量，除此以外與合成例8同樣地操作進行調製，而獲得淡黃色透明、且其不揮發成分為約60重i %、黏度為i5,〇〇〇mpa · s之加成型聚酯樹脂（叫) φ之溶液。該樹·脂（D1)之酸價為〇.5mgK〇H/g、經基價為 12mgK〇H/g、玻璃轉移溫度為—3 5 °C、重量平均分子量為 80,000。又，在上述配方中，相對於源自二環狀醚化合物 (a-2)之二級羥基1莫耳，環狀酯（b)成為約〇·6莫耳之比率。 (合成例11) -將合成例8所使用之觸媒變更滅四丁基鈦酸酯，除此之外與合成例8同樣地操作進行調製，而獲得黃色透明、 •且其不揮發成分為60.1重量％、黏度為8,5〇〇mPa · s之加成型聚醋樹脂（D1)之溶液。該樹脂（D1)之酸價為〇.6mgKOH/g、羥基償為2511^[0114、玻璃轉移溫度為一 10°C、重量平均分子量為110,000。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級經基〗莫耳，環狀酯（b)成為約1·8莫耳之比率。 (合成例12) 將合成例8所使甩之觸媒變更成氧化二丁基錫，除此之外與合成例8同樣地操作進行調製，而獲得淡黃色半透 319793 86 200838965 明、且其不揮發成分為60.3重量％、黏度為8,000mPa · s 之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為 2.5mgK〇H/g、羥基價為AOingKOIi/g、玻璃轉移溫度為— i〇c、重量平均分子量為125,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約ο莫耳之比率。 (合成例13)It has a clear color and is transparent, and J: point * branch Q, one is 8,500 mPa · s plus shaped polyester tree. 10 νίΛττ, ) κ shell is 0.5 mg KOH / g, base price is 12 mg K0H / g, broken The glass transition temperature was 6, and the weight average molecular weight was 65,000. Further, in the formula of the Shangyushan Ding J knives, the cyclic vinegar (8) is a ratio of about the mouth molar relative to the one derived from the bicyclic ether compound (a-2). '(Synthesis Example 4) · / Change the two ring-bonding compound (4) used in the step (1) of the synthesis to a double (tetra) diepoxypropyl scale (BPFG of Osaka Gas Chemical Co., Ltd.) Molecular Weight 462.5 'Epoxy The price is 3.89 (eq/Kg)) 3203 parts, and in the step (2), 315 parts of the polyacetate resin (B) solution in which the non-volatile component is adjusted to a weight % of the non-volatile content by using acetic acid ethyl acetate, and the like The synthesis example was similarly operated to prepare ''acetic acid ethyl acetate to adjust the concentration of the non-volatile component to about % by weight' to obtain a pale yellow transparent, and its viscosity was i8,5 〇〇mpa. Solution of D1). The grease (D1) has an acid value of 1.2 mgKOH/g, a hydroxyl group value of llmgK〇H/g, a glass transition temperature of -2 (TC, a weight average molecular weight of 15 G, _. Further, in the above formulation, 319793 80 200838965 The cyclic ester (b) is a ratio of about 1.25 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a_2). (Synthesis Example 5) The procedure of Synthesis Example 1 (2) The cyclic ester (b) used in the process is changed to 100 parts of pentane s, and the addition of the condensed precursor (c 1) solution obtained in the step (7) is used in the step (3) (nonvolatile component 6 〇. In the same manner as in Synthesis Example 1, except that the weight %) was adjusted to 2 parts by weight, a yellowish transparent color was obtained, and the nonvolatile content was 60.1% by weight, the viscosity was 9, and the addition of 〇〇〇mpa.s was obtained. a solution of the type polyacetal resin (m). The acid value of the resin (D1) is .gKOH/g, the base price is 12 mg K〇H/g, the glass transition temperature is -30 C, and the weight average molecular weight is 11 〇, 〇 Further, in the above formulation, the cyclic enthalpy (b) becomes a ratio of about 1.7 mol relative to the secondary hydroxyl group "mol" derived from a test compound (a_2). (Synthesis Example 6) The decylating agent (cl) used in the step (3) of the synthesis example 1 was changed to the trimethyl sulphate 18-inhibition, except that the preparation was carried out in the same manner as in the synthesis example j. a yellow transparent, non-volatile component of 6 〇 2 wt%, a viscosity of 13, 〇0OniPa · s 夕 a ju, n 甘as of the addition of a polyester resin (D1) solution. The tree 曰 (1) Thereafter, the price of i.〇mgKOH/gm is the glass transition temperature of “Liao, the weight average molecular weight is (10), _. Further, in the above formula, relative to the secondary derived from the dicyclic ether compound (a_2) A few bases are 1 mole, and the ring is cool (b) is a ratio of about 1.8 moles. [Make a two-stage type of 劁#古,义细f^ square to make an additive polyester resin (1) 1 (synthesis example) 7). 319793 81 200838965 <Step (4) (5): Formation of Additive Polyester Precursor (C1)> Preparation of polymerization in a polymerization tank with a mixer, thermometer, reflux cooler, dropping device, and nitrogen inlet tube a device, in which a dibasic acid (heart palpitations), a dicyclic ether compound = (a-2), a ring are added in a polymerization tank and a dropping device, respectively. Ester (b), catalyst, and organic solvent. Know [polymerization tank] 73 parts 404 parts 875 parts 1950 parts adipic acid (al) sebacic acid (a-1) bisphenol F diglycidyl ether (a_2 Bisphenol A-based phenoxy resin (a_2) (manufactured by Epoxy Epoxy Co., Ltd., trade name rjERi256 epoxy propyl equivalent 7800 g/eq, Mw 51000) tetrabutylammonium tetrahydrofuran (catalyst) acetic acid Ethyl ester - toluene [dropping device] tetrabutylammonium tetrahydroborate (catalyst) ε-caprolactone (b) ethyl acetate benzene 6.6 parts 210 parts 210 parts 6.6 parts 800 parts 420 parts 420 parts polymerization tank After the inside air was replaced with nitrogen, the temperature was raised to 10 (TC) while stirring the binary > Further, the reaction was carried out for 8 hours to obtain a polyester backbone having an acid of 5 (mgKOH/g) or less. Next, while stirring the above reactant, 319793 82 200838965 cyclic ester was added by dropping. (b) The mixture takes 1 hour and an hour. After the addition of tetrahydrogen and two drops, 're:pass, +1 gr, knowing that the knife is 59.8 reset %, viscosity 30, 〇〇〇mPa.s, (C1) is the acid value 〇.〇2mgK〇H/g, hydroxyl price% mail/g, glass transition temperature—15^ of the tree wax. Also, in the above formula, the average molecular weight of 1 is 1,200, _ ^ In the evening, the cyclic vinegar (8) is a ratio of about 6 moles relative to the -, and, and the base of the compound derived from the bicyclic (tetra) compound _). <Step (6): by (iv) a chemical agent (4) The closed reaction carried out> The polymerization reaction device attached to the gutter, the thermometer, the reflux cooler, and the drop H inlet tube is added to the gutter, and the addition ratio of the polymerization tank and the dropping ratio is added to the step (5). Molded polyester precursor liquid (59.8% by weight of the component), (4) agent (media, and organic solvent. [Polymerization tank] Addition of polyester precursor (C1) solution 2 parts [dropping device] knife 22.5 parts 6·6 parts 10 parts monoethyl methyl monoxide (cl) tetrahydroammonium tetrahydroammonium (catalyst) ethyl acetate polymerized air was replaced by nitrogen Thereafter, the side (4) solution is heated to HKTC. Secondly, the solution of the above-mentioned decylating agent (cl) is dripped at a constant rate by dropping the solution in the mixing device. After dropping 319793 83 200838965, Further, while stirring, the mixture was aged for 6 hours, and then added with a portion of acetic acid and cooled to room temperature to obtain a solution of the addition-polymerized resin. The solution was light yellow transparent and its non-volatile content was 6〇5% by weight, viscosity 35,000 mPa·s, the side chain content of the resin (D1) is % by weight, the aromatic ring content is 17% by weight, and the acid value is 0.02 mgKOH/g. It is 8'5 mgK〇H/g, the glass transition temperature is 15 C, and the weight average molecular weight is 22 〇, 〇〇〇. [The two-stage manufacturing method is used to manufacture the modified polyester resin (D1)] (Synthesis Example 8) Preparation of polymerization in a polymerization tank with a mixer, thermometer, reflux cooler, and nitrogen inlet tube The apparatus should be installed, and a dibasic acid (a-fluorene), a dicyclic ether compound (a_2), a cyclic ester (b), a catalyst, and an organic solvent are respectively added in the polymerization tank at the following ratios. Adipic acid (a-1) 159 parts isodecanoic acid (a-1) 120 parts bisphenol A diglycidyl ether (a_2) 721 parts ε caprolactone (b) 871 parts ethyl acetate 200 parts toluene 200 parts <Step (7): Formation of addition-formed polyester precursor (C1)> After the air in the polymerization tank was replaced with nitrogen, the mixture was heated to 100 while stirring the mixture. (: 'Add 4 parts of tetrabutylammonium tetrahydroborate to start the reverse 319793 84 200838965. - Mix the mixture while adding 4 times every 4 hours to call tetrabutyl 2 / 0, i £禾士9一七,,隹/-人^,,/+力2-人进仃24 hours of reaction and ripening, and the addition of the precursor of the pre-formed precursor (C1) is obtained. Also, in the above formula And a ratio of about 2 to 8 moles relative to the secondary mercapto-i-ring cyclic ester (b) derived from the dicyclic ether compound (a_2). <Step (8) ·· By alkylation Blocking reaction by the agent (c丨)> Adding ethyl acetate: 6^0 parts of hexamethyldioxane as a decylating agent (cl) in the above-mentioned addition of a polyester precursor (C1) solution : 245 parts, make /, no, into 6 small days. Then, add 3 (10) parts of ethyl acetate and cool to room temperature to obtain a solution of the addition polyester resin (D1). This solution is light yellow transparent, and The nonvolatile content is 6〇·4% by weight and the viscosity is 15,000mpa. s, the acid value of the resin (m) is UmgKOH/g, the hydroxyl value is 6mgK〇H/g, and the glass transition temperature is -j. In the same manner as in Synthesis Example 8, except that the catalyst used in Synthesis Example 8 was changed to tetrabutylammonium bromide. The operation is carried out to obtain a solution of the addition-molded polyester resin (D1) which is light yellow transparent and has a nonvolatile content of 60·2 weight ❹/〇 and a viscosity of 9,000 mPa·s. The acid value of the resin (D1) It is 88 mgKOH/g, the hydroxyl value is i〇mgK〇H/g, the glass transition temperature is 1°C, and the weight average molecular weight is 120,000. Further, in the above formulation, relative to the dicyclic ether compound The secondary radical of (a-2) is 1 molar, and the cyclic ester (b) is a ratio of about 1.8 mole. (Synthesis Example 10) 85 319793 200838965 The same is used in the step (7) of Synthesis Example 8. The dibasic acid (a_1;) was changed to dicetic acid: 322 parts, the dicyclic ether compound (a_2) was changed to neopentyl glycol diepoxypropyl ether: 678 parts, and the cyclic ester (b) was changed to ε, caprolactone: 456 injury, tetrabutyl nitrate as a catalyst was used 3 times for each use, and the decylating agent (cl) used in the step (8) was changed to methoxytrimethyl In the same manner as in Synthesis Example 8, except that the amount of the ethyl acetate was changed to 118 parts, and the mixture was adjusted to obtain a pale yellow transparent material, and the nonvolatile content was about 60% by weight and the viscosity was i5. 〇mpa · s addition of a polyester resin (called) φ solution. The acid value of the tree fat (D1) is 〇.5mgK〇H/g, the base price is 12mgK〇H/g, and the glass transition temperature is - 3 5 ° C, weight average molecular weight of 80,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 〇6 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a-2). (Synthesis Example 11) - The same procedure as in Synthesis Example 8 was carried out except that the catalyst used in Synthesis Example 8 was changed to tetrabutyl titanate to obtain a yellow transparent color, and the nonvolatile content thereof was A solution of 60.1% by weight, a viscosity of 8,5 〇〇 mPa · s of the formed polyacetal resin (D1). The resin (D1) had an acid value of mg6 mgKOH/g, a hydroxyl group of 2511^[0114, a glass transition temperature of 10 ° C, and a weight average molecular weight of 110,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1.8 mol with respect to the secondary mercapto group derived from the dicyclic ether compound (a_2). (Synthesis Example 12) The same procedure as in Synthesis Example 8 was carried out except that the catalyst of ruthenium in the synthesis example 8 was changed to dibutyltin oxide, and pale yellow translucent 319793 86 200838965 was obtained, and it was non-volatile. A solution of the addition-molded polyester resin (D1) having a composition of 60.3 wt% and a viscosity of 8,000 mPa·s. The resin (D1) had an acid value of 2.5 mg K 〇 H / g, a hydroxyl group value of AOing KOIi / g, a glass transition temperature of - i 〇 c, and a weight average molecular weight of 125,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about ο mol to the secondary hydroxy oxime derived from the dicyclic ether compound (a-2). (Synthesis Example 13)

將合成例8之步驟（7)所使用之環狀酯作)之重量變更成644份，除此之外與合成例8同樣地操作進行調製，而獲得淡黃色透明、且其不揮發成分為6〇·2重量％、黏度為 ll，500mPa · s之加成型聚酯樹脂（D1)之溶液。該樹脂（Di) 之酸價為CK4mgKOH/g、羥基價為〇〇5mgK〇H/g、玻璃轉移溫度為一 io°c、重量平均分子量為ι8〇,〇〇〇。又，在上述配方中，相對於源自二環狀爾化合物(a_2)之二級經基1 莫耳，環狀酯（b)成為約ι·3莫耳之比率。 (合成例14) 將合成例8之步驟（7)所使用之環狀酯卬）之重量變_ 成16伤、並將乙酸乙酯之量從65〇份變更成〗⑽份，除】之外與合成例8同樣地操作進行調製，而獲得淡黃色透明、且其不揮發成分為6〇·5重量％、黏度為 7,000mPa · s 之加成型聚酯樹脂（D1)之溶液。談樹脂（D1)之酸價為 •8mgK〇H/g、羥基價為57 8mgK〇H/g、玻璃轉移溫度為 ίοc、重里平均分子量為12〇,〇〇〇。又，在上述配方中，相對於源自二環狀_化合物（a_2)之二級經基〗莫耳，環狀 319793 87 200838965 酯（b)成為約0.03莫耳之比率。 (合成例15) 分別將合成例8之步驟（7)中所用之二元酸(^1}變更成己二酸：102份及異酞酸：66份、將二環狀醚化合物（a_2) 變更成雙酚A二環氧丙基醚：380份、將環狀酯變更成 ε-己内酯：285份、並將觸媒於反應開始時之使用量及進行中追加里各自’交更成〇·2 <分’除此以外與合成例8同樣地操作，使步驟（7)之反應、熟成於1〇〇〇c進行小時。其 _次，就步驟（8)而言，加入為矽烷化劑（cl)之六甲基二矽氮烷：65份與乙酸乙酯100份並使熟成4小時後，二=乙酸乙酉曰· 90份並冷部至室溫，而獲得加成型聚酯樹脂（ο〗)之溶液。 „ 此溶液係淡黃色透明、且其不揮發成分為59 5重量 %、黏度為3,000mPa.s。該樹脂（m)之酸價為78mgK〇H/g、經基價為20mgKOH/g、玻璃轉移溫度為—1〇c>c、重量平均鲁分子量為40,000。又’在上述配方巾，相對於源自二環狀趟化合物（a-2)之二級經基！莫耳，環狀醋⑼成為約μ莫耳之比率。 (合成例16) 分別將合成例8之步驟(7)中所用之二元酸（a-U變成己二酸：44份及異酖酸：33份、將二環狀難合物(a·: 變更成雙驗A二環氧丙絲：份、將環狀酯⑻變更; ^ •己内酯·· 684份、且不使用觸媒，除此以外與合成例同樣地操作’使步驟⑺之反應、熟成於⑽t進行Μ ^ 319793 88 200838965 日t。其\，就步驟（8)而έ，加入為破统化劑（c 1)之六甲基二矽氮烧·· 290份與乙酸乙酯：665份並使熟成4小時後，加入乙酸乙酯：142份並冷卻至室溫，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為59.7重量 °/〇、黏度為95,000mPa · s。該樹脂（D1)之酸價為 (UmgKOH/g、羥基價為33mgK〇H/g、玻璃轉移溫度為一 8 C、重量平均分子量為20, 〇〇〇。又，在上述配方中，相對籲於源自二環狀醚化合物（a-2)之二級羥基i莫耳，環狀酯（b) 成為約1.3莫耳之比率。 (合成例17) 分別將合成例8之步驟（7)中所用之二元酸（a-i)變更成癸一酸：101份、將二環狀醚化合物（a-2)變更成聚乙二醇一壞氧丙基醚（環氧乙烷加成莫耳數為：22) : 661份、將環狀酯（b)變更成ε _己内酯·· 684份，除此以外與合成例8 馨同樣地操作，使步驟⑺之反應、熟成合計進行24小時。其次’就步驟（8)而言，加入為矽烧化劑（ci)之六曱基 —石夕氮燒245份與乙酸乙酯427份並使熟成4小時後，加入乙酸乙醋：300份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為60.5重量％、黏度為26,000mPa· s之加成型聚醋樹脂（Dl)之溶液。該樹脂之酸價為 l2mgKOH/g、經基價為15mgK〇H/g、玻璃轉移溫度為~ 0 C 重里平均分子量為3()0,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基1莫耳，環狀 89 319793 200838965 酯（b)成為約5莫耳之比率。 (合成例18) 分別將合成例8之步驟（7)中所用之二元酸（a_1}變更In the same manner as in Synthesis Example 8, except that the weight of the cyclic ester used in the step (7) of the synthesis example 8 was changed to 644 parts, the pale yellow crystal was obtained, and the nonvolatile content was A solution of a modified polyester resin (D1) having a viscosity of ll, 500 mPa · s of 6 〇 2 wt%. The resin (Di) had an acid value of CK 4 mgKOH/g, a hydroxyl group value of 〇 5 mg K 〇 H / g, a glass transition temperature of io ° C, and a weight average molecular weight of ι 8 〇. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1⁄3 mol with respect to the secondary mercapto group 1 mol derived from the dicyclic compound (a_2). (Synthesis Example 14) The weight of the cyclic ester oxime used in the step (7) of Synthesis Example 8 was changed to 16 wounds, and the amount of ethyl acetate was changed from 65 parts to (10) parts, except for Further, in the same manner as in Synthesis Example 8, the preparation was carried out to obtain a solution of the addition-molded polyester resin (D1) which was light yellow transparent and had a nonvolatile content of 6 〇·5% by weight and a viscosity of 7,000 mPa·s. The acid value of the resin (D1) is • 8 mg K 〇 H / g, the hydroxyl value is 57 8 mg K 〇 H / g, the glass transition temperature is ίοc, and the average molecular weight of the weight is 12 〇, 〇〇〇. Further, in the above formulation, the ester (b) of the ring 319793 87 200838965 is a ratio of about 0.03 mol with respect to the secondary radical derived from the bicyclic compound (a_2). (Synthesis Example 15) The dibasic acid (^1} used in the step (7) of Synthesis Example 8 was changed to adipic acid: 102 parts and isononic acid: 66 parts, respectively, and a dicyclic ether compound (a_2). Changed to bisphenol A diglycidyl ether: 380 parts, changed cyclic ester to ε-caprolactone: 285 parts, and used the amount of the catalyst at the start of the reaction In the same manner as in Synthesis Example 8, except that the reaction was carried out in the same manner as in Synthesis Example 8, the reaction in the step (7) and the ripening were carried out at 1 ° C for an hour. In the case of the step (8), the addition was carried out. It is a decylating agent (cl) of hexamethyldioxane: 65 parts with 100 parts of ethyl acetate and allowed to mature for 4 hours, and then 2 = ethyl acetate · 90 parts and cooled to room temperature to obtain addition molding A solution of polyester resin (ο). „ This solution is light yellow transparent and has a non-volatile content of 59 wt% and a viscosity of 3,000 mPa·s. The acid value of the resin (m) is 78 mg K〇H/g. The base price is 20 mgKOH/g, the glass transition temperature is -1〇c>c, and the weight average Lu molecular weight is 40,000. Also in the above formula towel, relative to the compound derived from the bicyclic oxime compound (a-2) The secondary base group! Moore, the cyclic vinegar (9) became a ratio of about μmol. (Synthesis Example 16) The dibasic acid (aU used in the step (7) of Synthesis Example 8 was changed to adipic acid: 44 parts, respectively. And isodecanoic acid: 33 parts, a bicyclic hard compound (a·: changed to double A propylene oxide: part, changed cyclic ester (8); ^ • caprolactone · · 684 parts, and In the same manner as in the synthesis example, the reaction of the step (7) was carried out in the same manner as in the synthesis example, and the reaction was carried out at (10) t to carry out Μ ^ 319793 88 200838965 day t. The solution was added to the step (8) and added as a destructurizing agent. (c 1) hexamethyldiazepane·· 290 parts and ethyl acetate: 665 parts and allowed to mature for 4 hours, ethyl acetate: 142 parts, and cooled to room temperature to obtain an addition-form polyester resin Solution of (D1) This solution is light yellow transparent and has a nonvolatile content of 59.7 wt./〇 and a viscosity of 95,000 mPa·s. The acid value of the resin (D1) is (UmgKOH/g, and the hydroxyl value is 33 mgK). 〇H / g, glass transition temperature of 8 C, weight average molecular weight of 20, 〇〇〇. Also, in the above formula, relatively derived from the dicyclic ether compound (a-2) The hydroxy group i mol and the cyclic ester (b) were in a ratio of about 1.3 mol. (Synthesis Example 17) The dibasic acid (ai) used in the step (7) of Synthesis Example 8 was changed to a peracid: 101 parts, the dicyclic ether compound (a-2) was changed to polyethylene glycol monooxypropyl ether (ethylene oxide addition molar number: 22): 661 parts, cyclic ester (b In the same manner as in Synthesis Example 8 except that 684 _caprolactone was changed to 684 parts, the reaction and the ripening of the step (7) were carried out for 24 hours. Next, in the case of step (8), 245 parts of hexamethyl-zeitazine which is a bismuth burning agent (ci) and 427 parts of ethyl acetate were added and matured for 4 hours, and then ethyl acetate: 300 parts was added. After cooling to room temperature, a solution of the addition-formed polyester resin (D1) which was pale yellow transparent and had a nonvolatile content of 60.5 wt% and a viscosity of 26,000 mPa·s was obtained. The acid value of the resin was 12 mg KOH/g, the base price was 15 mg K 〇 H / g, and the glass transition temperature was ~ 0 C. The average molecular weight was 3 () 0,000. Further, in the above formulation, the ester (b) of the cyclic 89 319793 200838965 is a ratio of about 5 moles relative to the secondary hydroxyl group 1 mole derived from the dicyclic ether compound (a-2). (Synthesis Example 18) The dibasic acid (a_1} used in the step (7) of Synthesis Example 8 was changed, respectively.

成異酞I · 83份、將二環狀醚化合物（心2)變更成雙酚A 一袤氧丙基醚· 380伤、將環狀酯（b)變更成ε _己内酯·· μ〕份、且不使用曱笨而只使用乙酸乙酯：200份作為有機溶劑，除此以外與合成例8同樣地操作，使步驟（7)之反應、熟成合計進行24小時。 ♦ 其次，就步驟⑻而言，加入為石夕烧化劑（cl)之六曱基二石夕氮燒·· 245份與乙酸乙酯2⑽份並使熟成4小時後，加入乙酸乙酯300份並冷卻至室温，而獲得淡黃色透明、且其不揮發成分為59·3重量％、黏度為l5,〇〇〇mPa· s之加成i來S日树月日（D1)之溶液。該樹脂（D丨）之酸價為。^rngKOH/g、羥基價為1〇mgK〇ii/g、玻璃轉移溫度為如 c、重量平均分子量為23〇,〇⑽。又，在上述配方中，相馨對於源自―裱狀醚化合物之二級羥基」莫耳，環狀酯 (b)成為約丄3莫耳之比率。 (合成例19) 在合成例8之步驟（7)中不使用環狀酯⑶)、且在步驟（8) 中將使用之乙酸乙g旨之量從65()份變更成⑽份，除此以 :卜與：成例8同樣地進行調製，依據乙酸乙酯之添加量而濃度’而獲得淡黃色透明、且其不揮發成分為60.0重 I % '黏度為3,〇〇〇mPa · s之溶液。此溶液所含有之樹脂，糸為具有聚醋主鏈（1)與源自封閉化合物⑷之側鍵的聚酯 319793 90 200838965 树脂，其酸價為1.5mgKOH/g、羥基價為22mgK〇H/g、玻璃轉移溫度為抑、重量平均分子量為2〇，_。 (合成例20) 在合成例8之步驟（8)中不使用矽烷化劑（cl)而只添加乙酸乙醋266份，除此以外與合成例8同樣地進行調製，而獲得淡黃色透明、且其不揮發成分為6〇〇重量％、黏度為15,〇〇〇mPa. S之溶液。此溶液所含有之樹脂，係為具有聚酉旨主鍵⑴與因環狀酉旨（b)之加成而生成之侧鏈（π)的聚酉旨树脂’其酸價為OhgKOH/g、絲價為93mgK〇H/g、玻璃轉移溫度為-饥、重量平均分子量為135，刪。又，在上述配方中’相對於源白— π 、’、—衣狀驗化合物（a-2)之二級經土1莫耳，環狀酯（b)成為約18莫耳之比率。八、曲=°成μ 1至2G所件之各樹脂溶液之外觀、不揮發成純、以及樹脂之重量平均分子量(Mw)、玻璃轉 ^ =g)、酸價(AV)以及經基價(OHV)囊總顯示於表！。 ,關於㈣項目之評估、測定方法係記載如下。〈溶液外觀〉以目視評估樹脂溶液之外觀。〈不揮發成分濃度（TS)之測定> ，以150。〇之烘爐車以作為不揮發成名祥里树月曰;谷液約1 g於金屬容器中 ^ 20分鐘，秤量殘餘部分並計算殘率濃度（固形成分濃度，罩位：％)。卞〈溶液之黏度（Vis)之測定〉將樹脂溶液之溫度維持於 ^ 于於25C，使用B型黏度計（肩 319793 91 200838965 京計器公司製），以12rpm、1分鐘迴轉之條件測定黏度（單位：mPa · s) 〇〈重量平均分子量（Mw)之測定〉以已溶解於四氳呋喃之樹脂作為試料，藉由使用有東曹股份公司製之GPC(凝膠層析儀）「HPC-8020」的液體層析法，而進行依據分子尺寸差異的分離定量，以聚苯乙烯換算而決定樹脂之重量平均分子量（Mw)。 <玻璃轉移溫度（Tg)之測定〉 • 將「SSC5200 DiscStation」（Seiko Instruments 公司製）連接至robot DSC(示差掃描熱量計，Seiko Instruments公司製之「RDC220」），使用於測定。秤量試料約l〇mg於鋁製秤盤中並組合設置於示差掃描熱量計，又以未置入試料之同型鋁製秤盤作為基準，於 300°C之溫度加熱5分鐘後，使用液體量進行急冷處理至一 120°C。然後，以10°C/分鐘進行升溫，從升溫時所得到之馨DSC圖來決定玻璃轉移溫度（Tg，單位：。〇。〈酸價（AV)之測定> ' 精密地取量試料（聚酯樹脂之溶液：濃度約60%)約lg 於共栓三角燒瓶中，添加曱苯/乙醇（容積比：曱苯/乙醇=2/1) 混合液100ml使其溶解。於其中，加入驗g大（phenolphthalein) 試液作為指示劑，保持30秒後，以〇. IN醇性氫氧化鉀溶液滴定直至溶液呈現淡紅色為止。就乾燥狀態之樹脂之值而言，依據下式求得酸價（單位：mgKOH/g) 〇 92 319793 200838965 酸價（mgK〇H/g)=i(5.611xaxF)/S}/(不揮發成分濃度胸) 惟，S :試料之採取量 a : 0.1N醇性氫氧化鉀溶液之消耗量（mi) F . 0. IN醇性氫氧化鉀溶液之力價 <羥基價（OHV)之測定> 、精密地取量試料（聚酉旨樹脂之溶液：濃度約6〇%)約b 於共栓三角燒瓶中，添加甲苯/乙醇(容積比：甲苯/乙醇混合液HKhni <吏其溶解。更進一纟，準確地添加5mi之乙醯化劑（以吼咬溶解乙酸酐25g並製成容们之溶液）’授拌约i小時。於其中，加入祕試液作為指示劑，保持⑽秒後，以〇.1N醇性氫氧化鉀溶液滴定直至溶液呈現淡紅色為止。依據下式求得經基價（單就乾燥狀態之樹腊之值而言，价·· mgKOH/g)。發成分濃度羥基價（mgKOH/g)=[{(b-a)XFx28.25}S]/(不揮Isomorphic I · 83 parts, the dicyclic ether compound (heart 2) was changed to bisphenol A - oxime propyl ether · 380 wound, and the cyclic ester (b) was changed to ε - caprolactone · · μ In the same manner as in Synthesis Example 8, the reaction and the ripening of the step (7) were carried out for 24 hours in the same manner as in the case of using the ethyl acetate: 200 parts as the organic solvent. ♦ Next, in the case of step (8), after adding 245 parts of hexamethyl sulphate and 245 parts of Eclipidite (cl) and 2 (10) parts of ethyl acetate and aging for 4 hours, 300 parts of ethyl acetate was added. The mixture was cooled to room temperature to obtain a solution which was pale yellow and transparent, and had a nonvolatile content of 59.3% by weight, a viscosity of l5, and an addition of 〇〇〇mPa·s to the day of the tree (D1). The acid value of the resin (D丨) is . ^rngKOH/g, hydroxyl value of 1〇mgK〇ii/g, glass transition temperature such as c, weight average molecular weight of 23〇, 〇(10). Further, in the above formulation, the cyclic ester (b) is a ratio of about 3 moles to the secondary hydroxyl group derived from the "form ether compound". (Synthesis Example 19) The cyclic ester (3) was not used in the step (7) of Synthesis Example 8, and the amount of the acetic acid used in the step (8) was changed from 65 () parts to (10) parts, except This was carried out in the same manner as in Example 8 except that the concentration was 'according to the amount of ethyl acetate added to obtain a pale yellow transparency, and the nonvolatile content was 60.0% by weight. The viscosity was 3, 〇〇〇mPa. s solution. The resin contained in this solution is a polyester 319793 90 200838965 resin having a polyester backbone (1) and a side bond derived from the blocking compound (4), and has an acid value of 1.5 mgKOH/g and a hydroxyl value of 22 mgK〇H/. g, glass transition temperature is suppressed, the weight average molecular weight is 2 〇, _. (Synthesis Example 20) The same procedure as in Synthesis Example 8 was carried out except that the sulfonating agent (cl) was used instead of the chloroalkylating agent (cl) in the step (8) of Synthesis Example 8 to obtain a pale yellow transparent color. And the non-volatile component is 6% by weight, the viscosity is 15, 〇〇〇mPa. S solution. The resin contained in the solution is a polyvalent resin having a side chain (π) formed by addition of a polyfluorene-based primary bond (1) and a cyclic ring (b), and its acid value is OhgKOH/g, silk. The price was 93 mg K 〇 H / g, the glass transition temperature was - hunger, and the weight average molecular weight was 135, deleted. Further, in the above formula, the secondary ester of the compound (a-2) was in a ratio of about 18 moles with respect to the source white-π, ', and the test compound (a-2). 8. The appearance of each resin solution of the piece of the film = 1 to 2G, non-volatile to pure, and the weight average molecular weight (Mw) of the resin, glass rotation = g), acid value (AV), and base price (OHV) capsules are always shown on the table! . The evaluation and measurement methods of the (4) items are described below. <Appearance of Solution> The appearance of the resin solution was visually evaluated. <Measurement of non-volatile content concentration (TS)>, to 150. 〇烘烘以以以以以以以以以以以以以以以以以烘祥祥曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰卞 <Measurement of Viscosity of Solution> The temperature of the resin solution was maintained at 25 C, and the viscosity was measured at a condition of 12 rpm and 1 minute rotation using a B-type viscometer (shoulder 319793 91 200838965 manufactured by Kyoji Co., Ltd.). Unit: mPa · s) 〇 <Measurement of weight average molecular weight (Mw) > A resin which has been dissolved in tetrahydrofuran is used as a sample, and GPC (gel chromatograph) "HPC-" manufactured by Tosoh Corporation is used. The liquid chromatography method of 8020" performs separation and quantification according to the difference in molecular size, and determines the weight average molecular weight (Mw) of the resin in terms of polystyrene. <Measurement of glass transition temperature (Tg)> • "SSC5200 DiscStation" (manufactured by Seiko Instruments Co., Ltd.) was connected to a robot DSC (differential scanning calorimeter, "RDC220" manufactured by Seiko Instruments Co., Ltd.) for measurement. Weigh the sample about l〇mg in the aluminum weighing pan and set it on the differential scanning calorimeter, and use the same type of aluminum weighing pan without the sample as the reference. After heating at 300 °C for 5 minutes, use the liquid amount. Quenching is carried out to a temperature of 120 °C. Then, the temperature was raised at 10 ° C /min, and the glass transition temperature (Tg, unit: 〇. <Measurement of acid value (AV)> was determined from the sweet DSC chart obtained at the time of temperature rise. 'Precision sample ( Solution of polyester resin: concentration: about 60%) about lg in a co-plugged conical flask, adding toluene/ethanol (volume ratio: toluene/ethanol = 2/1) 100 ml of the mixed solution to dissolve it. The phenolphthalein test solution is used as an indicator, and after 30 seconds, it is titrated with 〇. IN alcoholic potassium hydroxide solution until the solution is reddish. For the value of the resin in the dry state, the acid value is obtained according to the following formula. (Unit: mgKOH/g) 〇92 319793 200838965 Acid value (mgK〇H/g)=i(5.611xaxF)/S}/(non-volatile concentration chest) However, S: sample amount a : 0.1N alcohol Consumption of potassium hydroxide solution (mi) F. 0. Strength of the alcoholic potassium hydroxide solution <Measurement of hydroxyl value (OHV)>, Precision sample (polymerization of resin): Concentration about 6〇%) about b in a co-plugged Erlenmeyer flask, adding toluene/ethanol (volume ratio: toluene/ethanol mixture HKhni < Further, add 5mi of the acetalizing agent (25g of acetic anhydride dissolved in a bite and make it into a solution). Allow about 1 hour of mixing. Add the secret test solution as an indicator for (10) seconds. Thereafter, the solution is titrated with a solution of 〇.1N alcoholic potassium hydroxide until the solution is reddish. The base price is obtained according to the following formula (in the case of the value of the wax in a dry state, the price is mgKOH/g). Component concentration hydroxyl value (mgKOH/g) = [{(ba)XFx28.25}S]/(do not wave

/100) +D 惟’ S ·试料之採取量（g) a : 0.1N醇性氳氧化鉀溶液之消耗量（mi) b.空白實驗之01N醇性氫氧化卸溶液之消耗 (ml) F · 〇·IN醇性氫氧化鉀溶液之力償 D :酸價（mglCOH/g) 319793 93 200838965[表1]加成型聚酯樹脂（D1)之合成例：使用矽烷化劑（cl)作為封閉化合物（C)時之情形 OHV (meKOH/g) | ID ΙΩ r— tn eo τ— eg to T·» ΙΟ cd CD o T—* cst O o 0.05 57·Β s η CO m o s CO σ> u> ο 0.05 1 S 〇 ir> 〇 ir> CS4 τ· tr> 〇 ψ"· 0.02 5 寸 d CO 〇 IA K£> 〇 in oi 寸 o CO d 78.0 τ- Ο o’ d in CD 〇 P s To o 丁〇 ? o 了 Ο ? o cp ? iO 丁 -10 〇 IO ? o T o o T o 丁 o 丁 cp § 1 S J CD in ID 雇 Mw § s I 160,000 eo.ooo § ΙΟ CO δ ί § i £ 200,000 220,000 150,000 120,000 i 5 § z J 125.000 160,000 § s § o § 〇 1 δ CJ 230,000 § s o s IO Γ9 VI» ? β Ϊ 20,000 15.000 —18,000 9,000 8,500 18,500 9,000 I to 30,000 i s I 9,000 15,000 8.500 8?000 11,500 7,000 3,000 95,000 26,000 15.000 3,000 o s ID {2 ? 00.5 60.2 60.3 60.0 59.8 59.5 i 60.2 59.8 60.5 60,4 60.2 59,5 60.1 60.3 60.2 60.5 59.5 59.7 60,5 &Θ.3 eo.o 60.0 溶液外觀 m 梅 u 籌 m n 澳黄色透明谀黄色进明淡黄色透明谀黄色透明淡黄色透明 m H « K 灌演黄色透明演黄色透明 w m φ K m 決黄色通明梅 K 黄色透明淡黄色半透明淡黄色通明浃黄色S明嫌黄色通明 m m φ K m m 96 « m Q 婴觸媒 TBABj tbabI ΤΒΑΒ] ΤΒΑΒ] tbabI ΤΒΑΒ I ΤΒΑΒ ! TBABl TBABi TBABl TBABl TBABrl TBAN | TBT I DBSnOl ΤΒΑΒ i 了 BAB ΤΒΑΒ 1 TBAB TBAB TBAB TBAB 〇 r- GO CO 卜 ΙΟ •ψ^ 卜 00 CD d cx> α> to CO CO C9 s o 1:1.3 in CO T— o T- oq T"· 1— X 0 T1 _ T— T— r _ τ— T— ΐίί) <〇 CO S 00 CM η C0 卜 to CO 〇> CM 卜卜 o 卜 τ— 卜 α> 〇> CM 〇> o 〇> σ> CM a> 側鏟含 Cwt%) 1 IJ- CO \α ir> ir> csi ID in CM in eo ir> s CSI CO in ΓΟ to CD CO - CO ιο CO ta 5 β) CO l〇 ID CD lO s 'M 避封閉化 fco I I HMSZ HMSZ ΜΜ5Ζ HMSZ HMSZ TMSiOH 1 DEMSi HMSZ MMSZ TMMtSi HMSZ HMSZ HMSZ MMSZ HMSZ HMSZ MMSZ HMSZ HMSZ 1 〇 S—/ 驊桓溜 2 ! eOL l^VL eCL eCL eCL I eCL S i 率避 m _^_ ifr ifr Jc ¢( f ¥ NPQ-Ep Ο α, % !< BPF-Ep CL i&i m Jc •I έ \ til li ¥ ai UJ li t& Jc Mj ψ\ ifr m 1 I& Jc ¥ I& 1 < a. IU Jc I& 4: 象( 雙 Α-Ερ |S* Jc PEQ-Ep I& 塑雙 A-Ep tu i (a-1H) AdA/IPA AdA/IPA AdA/IPA | AdA/IPA AdA/IPA AdA/IPA AdA/IPA AdA/SbA AdA/SbA AdA/IPA AdA/IPA SuA AdA/IPA AdA/IPA AdA/IPA AdA/IPA AdA/IPA AdA/IPA SbA s 合成例丨 1 (1X2) ! U δ .二 (1X2X3) ! 0X2X3)] (1X2X3) I (1X2X3) ! 0X2X3) i :3 u s (7X8) ! (7X8) | (7ΧΘ) | (7X8) ! (7ΧΘ) ! (7X8) (7X8) (7X8) (7)(8) (7X8) (7)(θ) 00 >< CM CQ a a |卜 s a 3 T— a in CD 'f· 00! 〇> 1 (ο/ΟΪΛνί^^^Γ (％|)齋杷命>令命 hqqs : ο— 餵邈赛.Hs : IgH 缵讀hs^l^: MveH •爾hsqT«:avPQH 鑤4卜0齧襃碱0 : gvfflH ^s^pfn - 1WQ ^^: HOiSRI ^^^U_S-HC: ZSSH f V丨P : ΊΛΡ 施 seto-co: dco (％£##伞莜/100) +D Only 'S · Sample taken (g) a : Consumption of 0.1N alcoholic potassium oxyhydroxide solution (mi) b. Consumption of 01N alcoholic hydrogen hydroxide solution in blank test (ml) F · 〇·IN alcoholic potassium hydroxide solution for the compensation of D: acid value (mglCOH / g) 319793 93 200838965 [Table 1] Synthesis of modified polyester resin (D1): using a decylating agent (cl) as When the compound (C) is blocked, OHV (meKOH/g) | ID ΙΩ r - tn eo τ — eg to T·» ΙΟ cd CD o T—* cst O o 0.05 57·Β s η CO mos CO σ> u&gt ; ο 0.05 1 S 〇ir>〇ir> CS4 τ· tr>〇ψ"· 0.02 5 inch d CO 〇IA K£> 〇in oi inch o CO d 78.0 τ- Ο o' d in CD 〇P s o o 〇 o o o cp i i 丁〇〇 IO IO o o o o o o o o cp § 1 SJ CD in ID hire Mw § s I 160,000 eo.ooo § ΙΟ CO δ ί § i £ 200,000 220,000 150,000 120,000 i 5 § z J 125.000 160,000 § s § o § 〇1 δ CJ 230,000 § sos IO Γ9 VI» ? β Ϊ 20,000 15.000 —18,000 9,000 8,500 18,500 9,000 I to 30,000 is I 9,000 15,000 8.500 8? 000 11,500 7,000 3,000 95,000 26,000 15.000 3,000 os ID {2 ? 00.5 60.2 60.3 60.0 59.8 59.5 i 60.2 59.8 60.5 60,4 60.2 59,5 60.1 60.3 60.2 60.5 59.5 59.7 60,5 &Θ.3 eo.o 60.0 Solution appearance m Mei u mn 澳澳澳澳澳澳澳澳澳澳澳澳澳澳澳 « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « «浃Yellow S is obviously yellow bright mm φ K mm 96 « m Q baby catalyst TBABj tbabI ΤΒΑΒ] ΤΒΑΒ] tbabI ΤΒΑΒ I ΤΒΑΒ ! TBABl TBABi TBABl TBABl TBABrl TBAN | TBT I DBSnOl ΤΒΑΒ i BAB ΤΒΑΒ 1 TBAB TBAB TBAB TBAB 〇 R- GO CO ΙΟ ΙΟ ψ 00 00 CD d cx>α> to CO CO C9 so 1:1.3 in CO T- o T- oq T"· 1 — X 0 T1 _ T— T — r _ τ — T— ΐίί) <〇CO S 00 CM η C0 卜 to CO 〇> CM 卜卜o 卜τ— 卜α>〇> CM 〇> o 〇>σ> CM a> Side shovel containing Cwt% ) 1 IJ- CO \α ir> ir> csi ID in C M in eo ir> s CSI CO in ΓΟ to CD CO - CO ιο CO ta 5 β) CO l〇ID CD lO s 'M Avoiding blocking fco II HMSZ HMSZ ΜΜ5Ζ HMSZ HMSZ TMSiOH 1 DEMSi HMSZ MMSZ TMMtSi HMSZ HMSZ HMSZ MMSZ HMSZ HMSZ MMSZ HMSZ HMSZ 1 〇S—/ 骅桓 2 2 ! eOL l^VL eCL eCL eCL I eCL S i rate avoids m _^_ ifr ifr Jc ¢( f ¥ NPQ-Ep Ο α, % !< BPF -Ep CL i&im Jc •I έ \ til li ¥ ai UJ li t& Jc Mj ψ\ ifr m 1 I& Jc ¥ I& 1 < a. IU Jc I& 4: 象(双Α-Ερ | S* Jc PEQ-Ep I& Plastic Double A-Ep tu i (a-1H) AdA/IPA AdA/IPA AdA/IPA | AdA/IPA AdA/IPA AdA/IPA AdA/IPA AdA/SbA AdA/SbA AdA/ IPA AdA/IPA SuA AdA/IPA AdA/IPA AdA/IPA AdA/IPA AdA/IPA AdA/IPA SbA s Synthesis Example (1 (1X2) ! U δ .2 (1X2X3) ! 0X2X3)] (1X2X3) I (1X2X3 ! ! 0X2X3) i :3 us (7X8) ! (7X8) | (7ΧΘ) | (7X8) ! (7ΧΘ) ! (7X8) (7X8) (7X8) (7)(8) (7X8) (7)( θ) 00 >< CM CQ aa | 卜sa 3 T— a in CD 'f· 00! 〇> 1 (ο/ΟΪΛνί^^^Γ (%|) 斋杷命>令命hqqs : ο — feeding 邈赛.Hs : IgH hhs^l^: MveH 尔hsqT«: avPQH 鑤4 卜 0 襃襃 0 : gvfflH ^s^pfn - 1WQ ^^: HOiSRI ^^^U_S-HC: ZSSH f V丨P : ΊΛΡ seto-co: dco (%£## umbrella 莜

(CNCN:碱：kr^^^^'to^fi)!砩肊嘁fiM^Mto^: dH03d fw^^tiM 鮏：dH0dN ti4^^fr^»龠^: dardPHa^ s ^ sd ^ '»砩vr^fiM j 螽制：^13^^ »硪《^V 龕制：dPQ-v 制^si^ss .. ^ 06 30 羞Λ :06 so : Vdl 盔 : vqs盔 Mro: vpv ^-rh: V口 S 94 319793 200838965 (比較例1) 在合成例1之步驟（1)所得之乂γ/τ仟爻主鏈用聚酯樹脂（溶液 100重量份中添加曱苯5〇份，更進又運步，添加TDI/TMP(伸甲本二異氰酸酉旨之三經甲基丙燒加成物）25 聯劑⑻，仔細授拌，而獲得接著劑組成物。欲將其塗= =]二處理之聚醋薄膜(以下，稱為「剝離薄膜」)上以獲付感壓接著薄片，但因接著劑組成物之黏度急速上升，故無法進行塗佈。 (比較例2) =用合成例1之步驟⑺所得之加成型聚_前驅物（叫洛液曰代主鏈用聚酯樹脂⑻溶液，除此之外與比較例^進 :::樣操作，而獲得接著劑組成物。然而，與比較例i同 =由Γ著劑組成物之黏度急速上升，故無法對剝離溥膜進行塗佈。 / (實施例1) 100二合1之步驟(3)所得之加成型聚酯樹脂(D1)溶液甲I -… 步，添加TDI/TMP(伸 ’、氰-文-曰之二羥曱基丙烷加成物）2 5重量份作為聯劑⑻，仔細攪拌，而獲得接著劑組成物（第！封閉型態）。 ^將其塗佈於㈣薄膜上，於⑽t使其錢2分鐘，猎形成厚度25#m之接著劑層而獲得接著薄片。(CNCN: base: kr^^^^'to^fi)!砩肊嘁fiM^Mto^: dH03d fw^^tiM 鮏:dH0dN ti4^^fr^»龠^: dardPHa^ s ^ sd ^ '»砩Vr^fiM j 螽 system: ^13^^ »硪 "^V 龛 system: dPQ-v system ^si^ss .. ^ 06 30 Shame : 06 so : Vdl helmet: vqs helmet Mro: vpv ^-rh: V-port S 94 319793 200838965 (Comparative Example 1) The polyester resin for the 乂γ/τ仟爻 main chain obtained in the step (1) of Synthesis Example 1 (5 parts of toluene was added to 100 parts by weight of the solution, and further Step by step, add TDI/TMP (stretching of the diisocyanate, the third methyl methacrylate adduct) 25 joint agent (8), carefully mix and obtain the adhesive composition. The second treated polyester film (hereinafter referred to as "peeling film") was subjected to a pressure-sensitive adhesive sheet, but the viscosity of the adhesive composition was rapidly increased, so that the coating could not be performed. (Comparative Example 2) = The addition-formed poly-precursor obtained in the step (7) of Synthesis Example 1 (a solution of the polyester resin (8) for the main chain of the Loose solution was used, and the same procedure as in the comparative example was carried out to obtain an adhesive composition. However, as with the comparative example i, the viscosity of the composition of the sputum agent rises rapidly, so there is no The release ruthenium film was coated. / (Example 1) The solution of the addition-molded polyester resin (D1) obtained in the step (3) of 100-in-1 (3) was added, and TDI/TMP (extension', cyanide- 25 parts by weight of the dihydroxy hydrazinopropane adduct of the hydrazine, as a crosslinking agent (8), and carefully stirred to obtain an adhesive composition (!! closed form). ^ It is coated on the (four) film, (10) t makes the money for 2 minutes, and hunts to form an adhesive layer having a thickness of 25 #m to obtain a subsequent sheet.

—準備以三乙酸纖維素系保護薄膜（以下，稱為「TAC 涛膜」）夾住聚乙烯醇（PVA)系偏光鏡之兩面而成的多層構造之偏光薄膜，使上械技益一 u 9 、使上述接者溥片之接著劑層貼合在該偏光 319793 95 200838965 薄膜之單面上，而獲得「剝離薄膜/接著劑層/ TAC薄膜/ PVA/ TAC薄膜」之構成之積層體。使所传之積層體於溫度23 C、相對濕度50%之條件下熟成1週，進行接著劑層之反應（暗反應），而獲得經接著加工之偏光板（積層體）。 (實施例2至6) 、分別使用合成例2至6所得之加成型聚酯樹脂（D1)替代合成例1所得之加成型聚酯樹脂（D1)，除此之外與實施例1進行同樣操作，製成經接著加工之偏光板。 (比較例3) ^用合成例7之步驟（4)(5)所得之加成型聚酯前驅物 (C1)溶液替代合成例丨之主鏈用聚酯樹脂⑻溶液，除此之外與比較例1進㈣樣操作，而獲得接著劑組成物。然而，與比較例1同樣地，由於接著劑組成物之黏度急速上升，故無法對剝離薄膜進行塗佈。 > (實施例7) 之步驟⑹所得之加成型聚酯樹脂(di)溶液 —^ t添加以5G份’更進—步’添加Tm/TMp(伸炉歧醋之三經甲基丙烧加成物）2.5重量份作為交 :=二!細授拌’而獲得接著劑組成物(第1封閉型態)。接㈣組成物並與實施们進行同樣操作，而製、、二接者加工之偏光板。 (實施例8) 使用合成例8之步驟⑻所得之加成型聚醋樹脂（di)溶 319793 96 200838965 液替代合成例7所锃 M b 吓传之加成型聚酯樹脂（D1)溶液，除此之外與實施例7進行同样^ 示- Preparing a polarizing film of a multilayer structure in which a cellulose acetate-based protective film (hereinafter referred to as "TAC film") is sandwiched between two sides of a polyvinyl alcohol (PVA)-based polarizer, and the technique is applied. 9. The adhesive layer of the above-mentioned carrier is bonded to one side of the polarized film 319793 95 200838965 to obtain a laminated body of a "peeling film/adhesive layer / TAC film / PVA / TAC film". The layered body to be passed was aged for 1 week under the conditions of a temperature of 23 C and a relative humidity of 50%, and a reaction (dark reaction) of the adhesive layer was carried out to obtain a polarizing plate (layered body) which was subjected to subsequent processing. (Examples 2 to 6) The addition molding polyester resin (D1) obtained in Synthesis Examples 2 to 6 was used in place of the addition molding polyester resin (D1) obtained in Synthesis Example 1, respectively, except that the same procedure as in Example 1 was carried out. The operation is performed to produce a polarizing plate which is subsequently processed. (Comparative Example 3) ^ The solution of the polyester resin (8) for the main chain of the synthesis example was replaced by the addition of the polyester precursor (C1) solution obtained in the step (4) (5) of Synthesis Example 7, except for comparison and comparison. Example 1 was carried out in a (four)-like operation to obtain an adhesive composition. However, in the same manner as in Comparative Example 1, since the viscosity of the adhesive composition rapidly increased, the release film could not be applied. > (Example 7) The addition-molded polyester resin (di) solution obtained in the step (6) is added with 5 parts of 'More Steps' to add Tm/TMp (three-way methyl propyl ketone The adduct) 2.5 parts by weight as a cross: = two! finely mixed 'to obtain an adhesive composition (first closed form). The polarizing plate processed by the (4) composition and processed in the same manner as the implementer. (Example 8) The addition-molded polyester resin (di) obtained by the step (8) of Synthesis Example 8 was dissolved in 319793 96 200838965 instead of the addition-formed polyester resin (D1) solution of the synthetic example 7 The same as in the seventh embodiment

Pu,j At、 ± 仃门检刼作，而獲得接著劑組成物（第1封彳用ϋ亥接著劑組成物並與實施例1進行同樣操作’而製成經接著加卫之偏光板。 ’、 (實施例9、10) π分別使用合成例9(實施例9)或合成Μ 1〇(實施例1〇) 所传之加成型聚醋樹月旨（D1)溶液替代合得加型聚酯樹脂（D1V交、右…，氣巍 /次，除此之外與實施例8進行同樣操作’而製成經接著加工之偏光板。 (比較例4) 使用σ成例19所得之聚酯樹脂溶液替代合成例8所得 ^力I成11來1日树脂（Dl)溶液，除此之外與實施例8進行同樣操作，而獲得接著劑組成物。此接著劑組成物雖然可塗佈於到每隹薄膜，但因接著劑層不具有黏性（初期接著性），故無法使用接著劑層於製作積層體。 •(比較例5). & 合成例20所得之聚酯樹脂溶液替代合成例8所得 =樹，溶液，除此之外與實施例8進行同樣操作，而欲獲得接著劑組成物’但因在添加2.5重量份TDI/TMP並仔細授拌後會急逮地增黏，而使流動性變差，故無法製成劑組成物。 (比較例6) 使用合成例14所得之加成型聚酯樹脂（D1)溶液替代合成例8所得之樹脂（D1)溶液，除此之外與實施例1〇進行 319793 97 200838965 同樣操作，而製成經接著加工之偏光板。 (實施例11、12) 分別將交聯劑(E)從實施例8所使用之TDI/TMP變更成XDI/TMP(伸茬基二異氰酸酯之三羥甲基丙烷加成物）2·5重量份（實施例ιυ、或變更成HMm/縮二脲（六亞甲基二異氰酸酯之縮二脲加成物）·· 2·5重量份（實施例12)，除此之外契貝施例8進行同樣操作，而獲得接著劑組成物。使用該接著劑組成物並與實施例i進行同樣操作，而 _製成經接著加工之偏光板。 (實施例13至19) 刀別使用合成例11至13(實施例13至15)、合成例15 、（貝她例16至19)所得之加成型聚酯樹脂（D1)溶液替 2合成例8所得之加成型聚醋樹脂（D1)溶液，除此之外與貝把例10—進订同樣操作，而製成經接著加工之偏光板。關於Λ〜例及比較例所得之接著劑組成物的適用期及瞻上佈加工性，係依據以下之方法評估。將結果示於表2。孫」外’針對實施例及比較例所得之偏光板（積層體）， ^豕以Τ之方法評估其塗膜之折射率、黏著性（初期接著 :、而、熱性、耐濕熱性、光學特性及再剝離性。將結果示 <適用期之評估方法> 小日士 Μ _及比較例所得之接著劑組成物，每隔1 小％測定於25〇c之對奋古u，段來評估可使用,f 小時為止，独1Γ述三階日守間（適用期）。黏度之測定係使用Β型 319793 98 200838965 黏度計（東京計器公司,、行。 D於apm'U鐘迴轉之條件下進The Pu, j At, and the 仃刼 , , , 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 ', (Examples 9, 10) π, respectively, using Synthetic Example 9 (Example 9) or Synthetic Μ 1〇 (Example 1〇), the addition of the shaped vinegar tree (D1) solution to replace the combined addition type A polarizing plate which was subjected to subsequent processing was prepared by using a polyester resin (D1V, right, and gas/time, except that the same operation as in Example 8) was carried out. (Comparative Example 4) The polymerization obtained by using σ in Example 19 The adhesive resin solution was replaced with the resin (D1) solution obtained in the same manner as in Example 8 except that the ester resin solution was used in the same manner as in Example 8. The adhesive composition was obtained. In the case of the film, the adhesive layer was not viscous (initial adhesion), so that the laminate layer could not be used to form the laminate. (Comparative Example 5). & The polyester resin solution obtained in Synthesis Example 20 The same procedure as in Example 8 was carried out instead of the obtained = tree, solution obtained in Synthesis Example 8, and the adhesive group was obtained. The product was formed as a composition because it was added with 2.5 parts by weight of TDI/TMP and carefully mixed, and the fluidity was deteriorated, so that the composition of the agent could not be obtained. (Comparative Example 6) Using Synthesis Example 14 The addition of the modified polyester resin (D1) solution in place of the resin (D1) solution obtained in Synthesis Example 8 was carried out in the same manner as in Example 1 of 319793 97 200838965 to prepare a polarizing plate which was subsequently processed. Examples 11 and 12) The crosslinking agent (E) was changed from TDI/TMP used in Example 8 to XDI/TMP (trimethylolpropane adduct of decyl diisocyanate) in an amount of 2.5 parts by weight ( Example υ, or changed to HMm/biuret (biuret adduct of hexamethylene diisocyanate) ······ parts by weight (Example 12), except for Example 8 The same operation was carried out to obtain an adhesive composition. The adhesive composition was used and subjected to the same operation as in Example i, to prepare a polarizing plate which was subsequently processed. (Examples 13 to 19) Using the synthesis example 11 to 13 (Examples 13 to 15), Synthesis Example 15, and the addition of a polyester resin (D1) solution obtained by (Bei's Examples 16 to 19) The addition of the polyacetal resin (D1) solution obtained in Example 8 was carried out in the same manner as in the case of Example 10, to prepare a polarizing plate which was subsequently processed. The pot life of the composition of the agent and the processability of the coating were evaluated according to the following methods. The results are shown in Table 2. Sun's external polarizing plate (layered body) obtained for the examples and comparative examples, ^豕The method is to evaluate the refractive index and adhesion of the coating film (initial::, heat, humidity resistance, optical properties, and re-peelability. The results are shown in <evaluation method of pot life>> The composition of the adhesive obtained in the comparative example was measured at 25 ° C for every 2 %, and the evaluation was used for the period. The f-hour was used to describe the third-order day-to-day interval (applicable period). Viscosity is measured using Β 319793 98 200838965 Viscometer (Tokyo Keiki Co., Ltd., D. Under the conditions of apm'U clock revolving

Ο ·元全;又有問題。到8丨R士炎L 達2倍」硬到“，為止之黏度上升率係未 △ :「確認到少許黏度上升率係未達2倍」寸為止之黏度上Ο · Yuan Quan; there are problems. To 8丨R Shiyan L up to 2 times "hard to", the viscosity increase rate is not △: "Confirm that a slight viscosity rise rate is less than 2 times"

X 確5忍到急速之點声卜4 Ϊ ,. 於與用卜、“、'升’未達5小時即已凝膠化。於貝用上造成問題」 <塗佈加工性之評估方法> 以使各實施例及比較例 + 戸洚#兔％〃 & 所侍之接者劑組成物乾燥後之 /子度成為25 // in之方夫《χ田#、_ 万式调整逗號塗佈器之供給量，並以祙度2m/min將該等接著匈里工乂速〇c. r J、、且成物塗佈於剝離薄膜上，於1 ο ο C之烘爐進仃乾燥而形成柢觉甘 —Μ , 或接者劑層’再黏貼厚度50am之聚酯薄膜並積層，而製成予度卿m之之狀態，並以三階段作二目視觀察該塗佈面者，則不進行塗佈加下又’料適關之評價為Γχ」 Ο Δ X · 久从下之評估。 ^ ·「完全沒有問題」雖然在塗佈面之姓 pi/ 可確認到少許撓曲或發泡，但於只用上不成問題」在塗佈面之端部可 . 用上造成_ 到撓曲、發泡射絲，於實 <塗膜之折射率之評估方法> 將各實施例及比較例薄膜上，於120t之扭擔、/传之接著劑組成物塗佈於剝離 /、显進行乾燥而設置厚度25#m之接 319793 99 200838965 者姓=，再與聚轉賴合並積層，而製成接著薄片。在2；；後，以ATAG〇公司製之阿貝折射率計「DR-M2」層之折竟中照射納〇線，而測定接著薄片上之接著劑 <光學特性之評估方法> 薄膜：各=以比較例所得之接著劑組成物塗佈職 ;、C之烘爐進行乾燥而設置厚度25/zm之指者劑層後，再與厚度5〇㈣之聚g旨薄膜貼合。使以剝㈣ ,::二成1週後，除去剝離薄膜，以目視判定接著劑 fir同時以日本電色卫業股份公司製之測定裝置NDH-300A」測定HAZE值（霧值）。〇··「於實用上完全沒有問題」 △:「沒有確認到霧狀等情形，HAZE值為i以上且未 3」 _ X:「確認❹許霧狀，或HAZE值為3以上（於實用上造成問題）」〈黏著性（初期接著性）之評估方法> …將各貫施例及比較例所得之接著劑組成物塗佈於剝離 f膜上’於12G°C之烘爐進行乾燥而設置厚度25 # m之接 =劑層後，再與厚度5G/Zm之聚g旨薄膜貼合。使以剝離薄馭與聚醋薄膜挾持的接著劑層在溫度23t：、相對濕度5〇% 之條件下熟成1週後，除去剝離薄膜，依據了，d〇w式滾球法在23t、65%RH之條件下測定接著劑層。又，黎性 319793 100 200838965 之評估結果為「X」纟，不進行此項之後的評估。〇：「顯現充足之黏性。球值為# 8以上」 △:「雖然黏性為弱，但於實用上不成問題。球值為#3 至#8」 X:「幾乎沒有黏性，初期接著性不良。球值未達#3」 <耐熱性、耐濕熱性（1)之評估方法> 將經接著加X之偏光板（積層體）剪裁成15Gmmx8〇mm 之大小，剝去該剝離薄膜’在厚度l lmm之浮式玻璃⑽扣 • glass)板之兩面上以使各自之偏光板之吸收軸呈垂直之方式使用積層機進行黏貼。其次，將此經貼附有偏光板之玻璃板在5Gt：、5大氣壓之條件下於高終内保持2〇分鐘，使偏光板強力地密著於玻璃板上，而獲得偏光板與玻璃板之積層物。 •。就耐熱性之評估而言，以目視觀察將上述積層物於 120 C放置1000小時後之浮起剝離、偏斜、以及使光透過着積層物時之漏光（白點）。另外，就耐濕熱性之評估而言，以目視觀察將上述積層物於8CTC、相對濕度90%中放置1000小時後之浮.起剝 •偏斜、以及使光透過積層物時之漏光（白點）。又，「偏 "牛」係私因偏光板之收縮，而使在黏貼於玻璃板之偏光板的周圍所可觀察到的黏貼位置之改變。關於耐熱性、耐濕熱性，係依據下述四階段之基準而進行評估。 ◎ ·「完全沒有確認到浮起剝離、白點、偏斜等情形，於 319793 101 200838965 實用上完全沒有問題」〇元全〉又有確s忍到浮起剝離、白點望卜主 Λ， — …寻4形’偏斜為未 Δ 達0.2mm，於貫用上完全沒有問題厂雖然確認到少許浮起剝離、白點 ^ A _ 一扁斜為 0.2mm 至未達0.5mm，於實用上沒有問題 X:「全©性地有浮起剝離、白點等情形，無法〈而才濕熱性（2)之評估方法 > 貝」以目視觀察上述耐濕熱性（1)試驗前後的經接之偏光板（積層體）之變色（著色）狀態。口工 0·「凡全沒有確認到黃變等變色情形，於實用上^入々有問題」、' 凡王汶 △ •「雖然確認到少許黃變，但於實用上不成問題 X:「確認到黃變等之明顯變色，於實用上造成問題^ ' <再剝離性（重工（rework)性）之評估方法 > 、」將經接著加卫之偏光板（積層體）剪裁成25軸咖麵之大小，剝去該剝離薄膜，使用積層機黏貼在厚度】之=式玻璃板上，在坑、5大氣壓之條件下於高壓爸内保& 20分鐘，使偏光板強力地密著於玻璃板上片於坑、相對濕度5〇%中放置1週後，往18〇度方匕向^ 300mm/分鐘之速度進行拉剝，實施18〇。剝離試驗，並以目視觀祭剝離後之剝離表面之霧狀，以下述三階段來評估。〇^無霧狀，於實用上完全沒有問題」 △「’二雖然可確認到少許霧狀，但於實用上不成問題」 X.「全面性地可確認到接著劑層之轉黏，無法作為實用」 319793 102 200838965 [表2]使甩第1型態之加成型聚酯樹脂（D1)的接著劑組成物：使用矽烷化劑（cl)作為封閉化合物（C)時之情形 W 球珠 \ \ \\ Η 侧 \ 1 o Ο ο 0 〇 Ο I Ο Ο ο Ο 1 1 < o ο < < < < < < < Ν 1 1 o Ο ο 〇〇 ο I ο Ο ο ο i 1 〇 o ο < < Ο Ο ο 〇 ο τ— J 1 o ο ο 〇〇 ο 1 ο ο ο 0 1 1 <1 o ο Ο < < < <3 < < t 1 I o ο ο 〇〇 ο i ο ο ο ο 1 1 <1 o ο ο < < < < < <3 砌邾璲鐵脚怒 *jlQ 1 1 o ο ο 〇〇 ο i ο ο ο < X I < o ο ο Ο Ο Ο Ο 〇 < 1 1 o ο ο 〇〇 ο \ ο ο ο 0 < 1 < o ο < <J <1 ο < 〇 Ο 齋 1 ! o in S CO CM CO S «α ea 8 ΙΓ> S ιη 1 % % S S CM ΙΟ S 要 CM S IO 1 £ in 宝 s S m S to s ο ΙΟ ΙΟ i S to » ΚΑ 挺，轶蘅雄 is «Η 1 i o ο ο ο ο ο l ο ο ο 0 X 1 < o ο < 0 <1 ο < ο Ο 田Λ X X o ο ο ο ο ο X ο ο ο ο o X < o ο ο < ο ο < ο Ο fs h- h- h- Η Η- Η Η 卜 H Η 1- 1- Η 卜 Η H X 工 1- H μ- Η Η h- Η 率磲髮 2 m. 2 礤 > I 0 <1— JC ip ο C4 » s ΙΑ 00’ CD ο CW S s CO to <〇 *〇 ο o ο ο ο ir> ο ir> g O g d ID Ιί> C4 ΙΟ 〇. g O 3 S CO u> KO CO d CO 5 寸· CD iq 甘 ο ο CO d CM ΙΟ ο g o T o ? ο ο ι § i ο 1 IO T ια τ ο τ ο τ 8 s ID 丁〇 7 o T ο τ ο τ O T ο τ ο τ GO § g Σ 1 s o s g i cT o 1 § I ΙΟ CD I S I ο § S 1 8 €Hi 1 ο 04 1 S· τ— I ο* τ— 1 § i o i » Λ i O i g· Ύ^· 1 S 1 ο i s 塞 cT «0 ο S S ο s s I 1 1 g CM X ο O t— a y· 3· ο ι^； in ψ"· 卜 C0 V <〇 o 00 GO <θ o r* CO s d eq 60 to *·— CD· e> CO IO τ— τ— ^丨 — 齋A ίί <D CO s 卜 CO CM r? GO 卜 m r> 卜卜 ο S m s 卜卜卜卜〇> ; κ 〇> o β> Ϊ§ 萃齋 1 co ΙΛ ΙΟ ιο CM in JO CS* ιη CO m s g S S 5 O s 5 5 δ S s !g s CM CO 寸 ιχ> CD 卜 GO α> ο 〇> S 00 CD τ— csl CO ΙΟ ς〇卜 00 r- 馨 CM t- 4¾ Μ CO ID CD C9 ¥ 馨 Ν 00 :知 α> ο τ— 寸馨 ID 馨 £ CD u τ- r- CSi τ— TO r- 军寸 ID i 嫁 Μ (0 τ— ¥ τ- 00 5 σ> τ- 築-:Tg7iQSH"Hdsi/lolx^ (3)蘅箨扮 ϋ"1 . 鐵本绛 k 蓀键 04 戚 1 103 319793 200838965 《第1封閉型態··使用酸酐（C2)作為封閉化合物（c)》在下述合成例21至43中，使用酸酐（c2)作為封閉化合物（c)以調製聚酯樹脂。合成例21及23至27係依據三階段型製造方法、合成例28係依據擬似二階段型製造方法、合成例29至43係依據二階段型製造方法而調製，而合成例22及40係省略環狀酯（b)。 [以二階段型製造方法製造加成型聚酯樹脂（D j)] (合成例21) _<步驟（1):聚酯主鏈之形成〉將攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管設於聚合槽構成聚合反應裝置，並在聚合槽及滴下裝置X is indeed 5 to endure the speed of the sound of the sound of 4 Ϊ,. With the use of Bu, ", 'L" has not been gelled for 5 hours. The problem is caused by the use of the shell" < evaluation method of coating processability > In order to make each embodiment and the comparative example + 戸洚#兔%〃 & the composition of the stalker after drying, the sub-degree becomes 25 // in the Fangfu "χ田#, _ 10,000 adjustment The supply amount of the comma applicator is applied to the peeling film at a twist of 2 m/min, and the product is applied to the peeling film, and the oven is placed at 1 ο ο C仃 drying to form a 柢甘 Μ Μ 或或或或或或或或或或或或或或或或接接 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 If you do not apply the coating, the evaluation of the material is Γχ Γχ Δ X · The evaluation from the next. ^ · "There is no problem at all" Although the surname pi/ on the coated surface can be confirmed to be slightly deflected or foamed, it is not a problem in use only." At the end of the coated surface, it can be used to cause _ to deflection. , foaming, and the actual <evaluation method of the refractive index of the coating film> On the film of each of the examples and the comparative examples, the composition of the twisting agent/passing agent at 120 t was applied to the peeling/discharging Drying is carried out to set the thickness of 25#m to 319793 99 200838965. The surname is =, and then the laminate is combined with the poly-transfer to form a subsequent sheet. After 2;;, the nano-wire was irradiated by the "A-R2" layer of the Abbé refractometer manufactured by ATAG Co., Ltd., and the adhesive on the sheet was measured. <Method for evaluating optical characteristics> Film : Each of the adhesive composition obtained in the comparative example was coated; and the oven of C was dried to form a finger layer having a thickness of 25/zm, and then bonded to a film of a thickness of 5 〇 (4). After the peeling (four), and the like, the peeling film was removed, and the HAZE value (haze value) was measured by visually determining the adhesive fir and measuring device NDH-300A manufactured by Nippon Denshoku Co., Ltd. 〇·· "There is no problem in practical use" △: "If the fog is not confirmed, the HAZE value is i or more and is not 3" _ X: "Check the fog shape, or the HAZE value is 3 or more (for practical use) "Improved problem") "Adhesiveness (initial adhesion) evaluation method] - Applying the adhesive composition obtained in each of the examples and the comparative examples to the peeling film to dry at 12 ° C in an oven at 12 ° C On the other hand, after the thickness of 25 #m is connected to the agent layer, it is bonded to a film having a thickness of 5 G/Zm. The adhesive layer held by the peeling thin crucible and the polyester film was immersed for one week under the conditions of a temperature of 23 t: and a relative humidity of 5 〇 %, and then the release film was removed. According to the d〇w ball method at 23 t, 65 The adhesive layer was measured under the conditions of %RH. In addition, the evaluation result of Li sex 319793 100 200838965 is "X"纟, and the subsequent evaluation is not carried out. 〇: "There is sufficient viscosity. The ball value is #8 or more" △: "Although the viscosity is weak, it is not a problem in practical use. The ball value is #3 to #8" X: "There is almost no stickiness, initial The ball value is not up to #3" <Evaluation method of heat resistance and moist heat resistance (1)> The polarizing plate (layered body) which is subsequently added with X is cut into a size of 15 Gmm x 8 mm, and the stripping is performed. The release film was adhered on both sides of a floating glass (10) buckle glass plate having a thickness of l mm so that the absorption axes of the respective polarizing plates were perpendicular to each other using a laminator. Next, the glass plate to which the polarizing plate is attached is held in the high end for 5 minutes at 5 Gt: and 5 atm, so that the polarizing plate is strongly adhered to the glass plate to obtain a polarizing plate and a glass plate. The laminate. •. For the evaluation of the heat resistance, the above-mentioned laminate was allowed to float, peel, deflect, and leak light (white spots) when the laminate was allowed to stand at 120 C for 1000 hours. In addition, in the evaluation of the heat and humidity resistance, the above-mentioned laminate was placed in 8 CTC and a relative humidity of 90% for 1000 hours, and floated, peeled, deflected, and leaked when the light was transmitted through the laminate (white) point). Further, "bias" is a change in the position of the adhesive which can be observed around the polarizing plate adhered to the glass plate due to the shrinkage of the polarizing plate. The heat resistance and the heat and humidity resistance were evaluated based on the following four stages. ◎ · "There is no confirmation of floating, peeling, white spots, skewing, etc., and there is no problem in practical use at 319793 101 200838965" 〇元全〉确忍忍浮浮浮浮、、、、、、、、、、、、、、、、、 — ... Looking for 4 shape's skew is not Δ up to 0.2mm, there is no problem in the use of the factory. Although it is confirmed that a little float and peel off, the white point ^ A _ a flat slope is 0.2mm to less than 0.5mm, practical There is no problem in the above-mentioned X: "There is a situation in which the peeling and peeling, white spots, etc. are all available, and the evaluation method of the heat and humidity (2) cannot be performed.] The above-mentioned heat and humidity resistance (1) The color change (coloring) state of the polarizing plate (layered body). Oral worker 0. "Where there is no color change such as yellowing, there is a problem in practical use.", "Wang Wang Wen △" "Although a little yellowing is confirmed, it is not practically problematic X: "Confirm Obvious discoloration to yellowing, etc., causing problems in practical use ^ ' < evaluation method of re-peelability (rework)>, cutting the polarizing plate (layered body) which is subsequently reinforced into 25 axes The size of the coffee surface, peel off the peeling film, use a laminator to adhere to the thickness of the glass plate, in the pit, 5 atmospheres under the pressure of high pressure dad & 20 minutes, the polarizing plate is strongly sealed After placing on a glass plate in a pit and a relative humidity of 5〇% for one week, the film was pulled at a speed of 300 mm/min at a temperature of 18 ,, and 18 实施 was performed. The peeling test was carried out, and the mist of the peeling surface after peeling off by visual observation was evaluated in the following three stages. 〇^ No fogging, there is no problem in practical use. △ "' Although it can be confirmed that there is a little mist, it is not a problem in practical use." X. "Comprehensively, it can be confirmed that the adhesive layer is sticky and cannot be used. Practical use 319793 102 200838965 [Table 2] Adhesive composition of the addition type polyester resin (D1) of the first type: the case when the alkylating agent (cl) is used as the blocking compound (C) W ball\ \ \\ Η side \ 1 o Ο ο 0 〇Ο I Ο Ο ο Ο 1 1 < o ο <<<<<<<<<< lt 1 1 o Ο ο 〇〇ο I ο Ο ο ο i 1 〇o ο << Ο Ο ο 〇ο τ — J 1 o ο ο 〇〇ο 1 ο ο ο 0 1 1 <1 o ο Ο <<<<3<<t 1 I o ο ο 〇〇ο i ο ο ο ο 1 1 <1 o ο ο <<<<<<3 邾璲邾璲邾璲脚 j j j j j j j j j j j j j j j j j j j j j j j j 〇〇ο i ο ο ο < XI < o ο ο Ο Ο Ο Ο 〇 < 1 1 o ο ο 〇〇ο \ ο ο ο 0 < 1 < o ο <<J<1 ο < 〇Ο 斋 1 ! o in S CO CM CO S «α ea 8 ΙΓ> S ιη 1 % % SS CM ΙΟ S CM S IO 1 £ in 宝 s S m S to s ο ΙΟ ΙΟ i S to » 挺 ,, 轶蘅雄 is «Η 1 io ο ο ο ο ο ο ο ο ο 0 X 1 < o ο < 0 <1 ο < ο Ο Λ XX XX o ο ο ο ο ο X X X X X X X X X X X s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s H Η 1- 1- Η Η Η HX work 1- H μ- Η Η h- Η rate burst 2 m. 2 礤> I 0 <1—JC ip ο C4 » s ΙΑ 00' CD ο CW S s CO to <〇*〇ο o ο ο ο ir> ο ir> g O gd ID Ιί> C4 ΙΟ 〇. g O 3 S CO u> KO CO d CO 5 inch · CD iq ganο ο CO d CM ο ο go T o ο ο ι § i ο 1 IO T ια τ ο τ ο τ 8 s ID 〇〇 7 o T ο τ ο τ OT ο τ ο τ GO § g Σ 1 sosgi cT o 1 § I ΙΟ CD ISI ο § S 1 8 €Hi 1 ο 04 1 S· τ— I ο* τ— 1 § ioi » Λ i O ig· Ύ^· 1 S 1 ο is 塞 cT «0 ο SS ο ss I 1 1 g CM X ο O t— ay· 3· ο ι^; in ψ"· Bu C0 V <〇o 00 GO <θ or* CO sd eq 60 to *·- CD· e> CO IO Τ— τ—^丨—Isa A ίί <D CO s 卜 CO CM r? GO 卜 m r> 卜卜ο S ms 卜卜卜〇>; κ 〇> o β> Ϊ§ Co ΙΛ ι ιο CM in JO CS* ιη CO msg SS 5 O s 5 5 δ S s !gs CM CO inch ιχ> CD 卜 GO α> ο 〇> S 00 CD τ- csl CO ΙΟ ς〇 00 r - Xin CM t- 43⁄4 Μ CO ID CD C9 ¥ Ν Ν 00 :知α> ο τ— 寸馨ID 馨 £ CD u τ- r- CSi τ— TO r- 军ID ID i Μ (0 τ— ¥ Τ- 00 5 σ> τ- 筑-:Tg7iQSH"Hdsi/lolx^ (3)蘅箨 Dressing"1. 铁本绛k 荪 key 04 戚1 103 319793 200838965 "1st closed type · use anhydride ( C2) as a blocking compound (c) In the following Synthesis Examples 21 to 43, an acid anhydride (c2) was used as a blocking compound (c) to prepare a polyester resin. Synthesis Examples 21 and 23 to 27 are based on a three-stage production method, Synthesis Example 28 is based on a pseudo-two-stage production method, and Synthesis Examples 29 to 43 are based on a two-stage production method, and Synthesis Examples 22 and 40 are omitted. Cyclic ester (b). [Production of Additive Polyester Resin (D j) by Two-stage Manufacturing Method] (Synthesis Example 21) _<Step (1): Formation of polyester main chain> Mixer, thermometer, reflux cooler, dropping device, and nitrogen The introduction tube is disposed in the polymerization tank to form a polymerization reaction device, and is in the polymerization tank and the dropping device

化合物（a-2)、觸媒、以及有機溶劑。 [聚合槽] 己二酸(a-1) 異酞酸（a-1) 乙酸乙酯甲苯 43 8份 332份 135份 135份 [滴下裝置] 雙酚A二環氧丙基醚（心2) 四氫硼酸四丁基銨（觸媒) 乙酸乙酯甲苯 1995 份 5.5份 135份 135份 319793 104 200838965 將聚合槽内之空氣以氮氣置換後，一邊攪拌二元酸 (a-l)混合物一邊升溫至10(rc。其次，於攪拌中之二元酸混合物中，藉由滴下裝置而將二環狀醚化合物（a-2)混合物耗費1小時以等速滴下。滴下完畢後，再一邊攪拌一邊每隔8小時加入觸媒5·5份，共加入2次後，再使其進行合計24小時之反應、熟成，然後添加13〇7份乙酸乙酯並冷部至至·，結束反應，獲得主鏈用聚酯樹脂（Β)溶液。此溶液係淡黃色透明、且其不揮發成分為6〇·5重量 _ %、黏度為20,〇〇〇mpa· s，該樹脂之酸價為〇5mgK〇H/g、羥基價為155mgKOH/g、玻璃轉移溫度為6〇°c、重量平均分子量為50,000。 <步驟（2):環狀酉旨^^之開環加成反應〉準備於聚合槽附有擾拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟（1)所得之主鏈用聚酯樹脂擊⑻溶液、環狀酯（b)、觸媒、以及有機溶劑。 [聚合槽] 聚酯樹脂（B)溶液 219份乙酸乙酯 33份 [滴下裝置] ε -己内醋（b) 114份四氫硼酸四丁基銨（觸媒） 1.3份乙酸乙酯 66份 319793 200838965 將聚合槽内之空氣以氮氣置換後，—邊攪拌樹脂溶液二邊升溫至航。其次’藉由滴下|置而將環狀醋⑻混 1:ϊ費1小時以等速滴下。滴下完畢後，再-邊授拌-邊使其騎η小時之反應、熟成、然後添力口 66份乙酸乙酉旨並冷卻至室溫，結束反應’而製得加成型聚酉旨前驅物之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇·2重量 %、黏度為15,000mPa. s，該樹脂之酸價為〇〇5mgK〇H/g、 _羥基價為74mgKOH/g、玻璃轉移溫度為—1〇。〇、重量平均分子量為150,000。又，在上述配方中，相對於源=二環狀醚化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約i ^ 莫耳之比率。 <步驟(3) ··藉由酸酐（C2)而進行之封閉反應> 準備於水合槽附有授拌機、溫度計、回流冷卻器、滴下I置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝鲁置中分別以下述比率加入步驟（2)所得之加成型聚酯前驅物（C1)溶液、酸酐（C2)、觸媒、以及有機溶劑。 [聚合槽] 步驟（2)所得之加成型聚酯前驅物（Cl)溶液 200份 [滴下裝置] 酞酸酐（c2) 3·6份四氫硼酸四丁基銨（觸媒） 1·2份乙酸乙酯 1份 319793 106 200838965 义將聚合槽内之线以氮氣置換後，—邊_加成型聚Compound (a-2), a catalyst, and an organic solvent. [Polymerization tank] Adipic acid (a-1) Isophthalic acid (a-1) Ethyl acetate toluene 43 8 parts 332 parts 135 parts 135 parts [Drip device] Bisphenol A diglycidyl ether (heart 2) Tetrabutylammonium tetrahydroborate (catalyst) Ethyl acetate toluene 1995 parts 5.5 parts 135 parts 135 parts 319793 104 200838965 After replacing the air in the polymerization tank with nitrogen, the temperature is raised to 10 while stirring the dibasic acid (al) mixture. (rc. Secondly, in the dibasic acid mixture under stirring, the mixture of the dicyclic ether compound (a-2) was dropped by a dropping device for 1 hour at a constant rate. After the dropwise addition, the mixture was stirred again. After adding 5 parts of the catalyst for 5 hours, the mixture was added for 2 times, and then subjected to a total of 24 hours of reaction and aging. Then, 13 〇 7 parts of ethyl acetate was added and the mixture was cooled to the end to complete the reaction to obtain a main chain. A polyester resin (Β) solution is used. This solution is light yellow transparent, and its nonvolatile content is 6 〇·5 wt%, viscosity 20, 〇〇〇mpa·s, and the acid value of the resin is 〇5 mgK〇. H/g, a hydroxyl group value of 155 mgKOH/g, a glass transition temperature of 6 ° C, and a weight average molecular weight of 50,000. <Step (2) : ring-opening addition reaction of ring-shaped ^^^> Prepared in a polymerization tank equipped with a scrambler, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, and in the polymerization tank and the dropping device, respectively The (8) solution of the polyester resin for the main chain obtained in the step (1), the cyclic ester (b), the catalyst, and the organic solvent were added in the following ratio. [Polymerization tank] Polyester resin (B) solution 219 parts of ethyl acetate 33 parts [dropping device] ε - caprolactone (b) 114 parts of tetrabutylammonium tetrahydroborate (catalyst) 1.3 parts of ethyl acetate 66 parts 319793 200838965 After the air in the polymerization tank was replaced with nitrogen, stirring The resin solution is heated to the air on both sides. Secondly, the ring vinegar (8) is mixed by dropping: the vinegar is mixed for 1 hour at a constant rate. After the dropping is completed, the mixture is stirred again. After reacting, aging, and then adding 66 parts of ethyl acetate and cooling to room temperature, the reaction is terminated to obtain a solution of the precursor of the addition polymerization. The solution is light yellow transparent and has a nonvolatile content of 6 〇. · 2% by weight, viscosity is 15,000 mPa. s, the acid value of the resin is 〇 5 mg K 〇 H / g, _ hydroxyl value of 74 mg KOH / g, glass transition temperature of -1 〇. 〇, weight average molecular weight of 150,000. Also, in the above formula, relative to the source = dicyclic ether compound (a-2 The secondary hydroxy oxime, the cyclic ester (b) becomes a ratio of about i ^ mol. <Step (3) · The blocking reaction by the acid anhydride (C2) > Prepared in the hydration tank a polymerization reactor having a mixer, a thermometer, a reflux condenser, a drop I, and a nitrogen introduction tube, and adding the addition polyester precursor obtained in the step (2) in the polymerization tank and the dropping device, respectively, at the following ratios (C1) a solution, an acid anhydride (C2), a catalyst, and an organic solvent. [Polymerization tank] 200 parts of the addition-formed polyester precursor (Cl) solution obtained in the step (2) [Dropping device] Phthalic anhydride (c2) 3·6 parts Tetrabutylammonium tetrahydroborate (catalyst) 1·2 parts Ethyl acetate 1 part 319793 106 200838965 After the line in the polymerization tank is replaced by nitrogen, the side-additional polymerization

酯月il驅物（C1)溶液一邊升溫至1〇〇。0。复·A /、A，於其中，藉由滴下裝置而將酸酐混合物混合物耗費 ★ 貝1小時以等速滴了。滴下完畢後，再一邊攪拌一邊使其進行8小時之反應、 #成’然後添加5份乙酸乙酯並冷卻至宮 . f 至，现，而獲得加成型聚酯樹脂（D1)之溶液。 T % 此溶液係淡黃色透明、且其不揮發成分為6G2重量 %、黏度為22,000mPa.s，該樹脂（D1)之酸價為 ΚΟΗ/g、羥基價為65mgK〇H/g、玻璃轉移溫度為—切。c、重量平均分子量為180,000。 (合成例22) 在合成例2!中’省略步驟⑺，並在步驟⑺中使用步驟⑴所得之主鏈用聚醋樹轉)溶液（不揮發成分6〇 2重量 %)200份替代步驟⑺所得之加成型聚醋前驅物⑹）溶液，除此以外與合成例21同樣地操作進行調製，而獲得淡黃色鲁透明、且其不揮發成分為6〇1重量％、黏度為Μ，刪 s之聚酯樹脂之溶液。該溶液中所含有之樹脂的酸價為〇35mgK=H/g、經基價為98mgK〇H/g、玻璃轉移溫度為 C、重量平均分子量為60,000。 (合成例23) 、刀別將口成例21之步驟（1)中所用之二元酸（a-1)變更成:· 830份、將二環狀醚化合物（&_2)變更成新戊二蜂二環氧丙_: 1449份’且在步驟⑺中使用將所得之主鍵用承酉曰树月曰⑻浴液以乙酸乙醋調整不揮發成分至約⑽ 319793 107 200838965 重量％而成的溶液20G份’除此以外與合成例21同樣地操作進行調製，以乙酸乙酯調整不揮發成分至約。/，而獲得淡黃色透明、且其黏度為14,〇〇〇mPa s之加成型0聚酯樹脂（D1)之溶液。該樹脂（m)之酸價為165够⑽了羥基價為68mgKOH/g、玻璃轉移溫度為—25。〇、重量平均分子量為U0，_。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級經基i莫耳，環狀酉旨⑻成為約u 莫耳之比率。鑤（合成例24) ▲將合成例之步驟⑴中所用之二環狀鱗化合物卜2) 變更成1,4-雙{[(3-乙基j氧雜環丁基）甲氧基]甲基}苯： 670伤及雙驗A二環氧丙基醚：1385份，且在步驟（2)中使用將所知之主鏈用聚I旨樹脂⑻溶液以乙酸乙_調整不揮發成分至約6〇重量％而成的溶液224份，除此以外與合成 ]同木^地作進行调製，以乙酸乙酯調整不揮發成分至鲁約60重量％，而獲得淡黃色透明、且其黏度為η，卿mPa· S之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為。mgKOH/g、羥基價為72mgK〇H/g、玻璃轉移溫度為— 35C、重i平均分子量為142,〇〇〇。又，在上述配方中，相對於源自—％、狀_化合物（a])之二級經基工莫耳，環狀酉曰（b)成為約ι·7莫耳之比率。 (合成例25) ^將合成例21之步驟（1)中所用之二環狀醚化合物（a_2) 變更成雙齡棻-ϊ夢弗—衣虱丙基醚（大阪瓦斯化學股份公司製之 108 319793 200838965 BPFG，別名為9,9-雙[4-(環氧丙氧基）苯基]-9H-苐，分子量：462.5，環氧價：3.89(eq/Kg)) : 3203 份，且在步驟（2) 中使用將所得之主鏈用聚酯樹脂（B)溶液以乙酸乙酯調整不揮發成分至約60重量％而成的溶液3 15份，除此以外與合成例21同樣地操作進行調製，以乙酸乙酯調整不揮發成分至約60重量％，而獲得淡黃色透明、且其黏度為 35,000mPa · s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1) 之酸價為13.2mgKOH/g、羥基價為71mgK〇H/g、玻璃轉移 _溫度為一 15°C、重量平均分子量為165,〇〇〇。又，在上述配方中，相對於源自二環狀_化合物（a_2)之二級經基1莫耳，環狀酯（b)成為約ι·3莫耳之比率。 (合成例26) 、將合成例21之步驟(2)中所用之環狀酯（b)變更成戊内醋.100份，且在步驟（3).中使用將所得之主鍵用聚醋樹脂⑻溶液以乙酸乙酉旨調整不揮發成分至約6〇重量％而鲁成的溶液綱份’除此以外與合成例21同樣地操作進行調製’以乙酸乙酉旨調整不揮發成分至約6〇重量％，而獲得淡黃色透明、黏度為1G，_mPa· s之加成型聚韻脂（di) 之溶液。該樹脂（m)之酸價為15 8mgK〇H/g、經基價為 70mgKOH/g、玻璃轉移溫声糸秒，里度為〜25 C、重量平均分子量為 120,000。又，在上述配方中，相 Ύ 相對於源自二環狀醚化合物 (a_2)之二級經基1莫耳，擇你而匕丄、斗衣狀§日（b)成為約1 ·6莫耳之比率。 (合成例27) τ 將合成例21之步驟（3)中【）干所用之酸酐（C2)變更成海米 319793 109 200838965 克酸酐（Himic anhydride) : 4份，除此以外與合成例2ι石樣地操作進行調製，而獲得淡黃色透明、且其°不揮發成S 為60.1重量％、黏度為i4，_mPa. s之加成型聚酉旨樹脂之溶液。該樹脂（D1)之酸價為13.9mgK〇H/g、羥基價為 65mgKOH/g、玻璃轉移溫度為—15χ：、重量平均分為 170,000。又，在上述配方中，相對於源自二環狀二化:物 (a-2)之二級羥基1莫耳，環狀酯（b)成為約18莫耳之比率。 [以擬似二階段型製造方法製造加成型聚酯樹脂①1)]、拳（合成例28) <步驟（4)(5):加成型聚酯前驅物（ci)之生成> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入二元酸（a_〗）、二環狀醚化合物 (a_2)、環狀酯（b)、觸媒、/以及有機溶劑。 [聚合槽] 己二酸（a-1) 73份癸二酸（a-1) 404份雙酴F二環氧丙基_ (a-2) 875份雙酚A系苯氧基樹脂（a_2) 1950 份 (曰本環氧樹脂公司製，商品名「jER1256」，環氧丙基當量7800g/eq， Mw 為 51000) 四氫硼酸四丁基銨（觸媒） 6·6份乙酸乙酯 210份甲苯 210份 319793 110 200838965 [滴下裝置] 6.6份 3500 份 210份 210份四氫硼酸四丁基銨（觸媒） ε -己内酯（b) 乙酸乙酯甲苯將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物— 邊升溫至100 °C。再使其反應8小時，而獲得酸價為 5mgKOH/g以下之主鏈(1，）用聚酯樹脂。 _ 其次，藉由滴下裝置而將環狀酯（b)混合物耗費1小時以等速滴下。滴下完畢後，一邊攪拌一邊於8小時後添加四氫硼酸四丁基銨6.6份，並再使其進行8小時之反應、熟成，然後添加350G份乙酸乙酯並冷卻至室溫，結束反應，而獲得加成型聚酯前驅物（Cl)。此溶液係淡黃色透明、且其不揮發成分59·8重量％、黏度30,0〇〇mpa.s，上述前驅物（C1)係酸價〇〇2mgK〇H/g、鲁羥基價92mgKOH/g、玻璃轉移溫度_15t、重量平均分子里200,〇〇〇之樹脂。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基丨莫耳，環狀酯（b)成為約of 莫耳之比率。〈步驟（6):藉由酸酐（c2)而進行之封閉反應> 準備於聚合槽附有攪拌機、温度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟（5)所得之加成型聚酯前驅物（ci)溶液（不揮發成分59 8重量％)、酸酐（c2)、觸媒、以 319793 111 200838965 及有機溶劑。 [聚合槽] 加成型聚酯前驅物（ci)溶液 [滴下裝置] 丁二酸酐（C2) 四氫硼酸四丁基銨（觸媒）乙酸乙酯將聚合槽内之空氣以氮氣置換後 200份 5.0份 6.6份 10份、一邊攪拌槽内溶液一 4升溫至100 C。其次，於其中，葬由、T 错由滴下裝置而將酸酐混合物耗費H、時以等速滴下。滴下完畢後，再一邊擾拌-邊使其進行6小時之反應、熟成，然後添加5份乙酸乙酯並冷卻至室温，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為60·5重量 %、黏度為30,000mpa . s ’該樹脂（D1)之酸價為 15mgKOH/g、羥基價為62mgKOH/g、玻璃轉移溫度為—1〇 °C、重量平均分子量為170,000。 [以一階段型製造方法製造加成型聚酯樹脂①工）] (合成例29) 準備於聚合槽附有攪拌機、溫度計、回流冷卻器及氮導入管的^^合反應裝置，並在聚合槽中分別以下述比率加入二元酸（a-1)、二環狀鍵化合物（a_2)、環狀酯（b)、觸媒、以及有機溶劑。 [聚合槽] 159份己二酸（a-1) 159份 319793 112 200838965 異酞酸(a-1) 120份雙酚A二環氧丙基醚〇-2) 721份 ε -己内酯（七） 871份乙酸乙酯 200份甲苯 200份 <步驟（7):加成型聚酯前驅物（C1)之生成〉、將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物一邊升溫至lGGt，添加四氫酸四丁基銨2()份以起始反應。一邊攪拌混合物’―邊每隔8小時添加—次四氯棚酸四丁基銨2.G份，共添加2次，進行合計24小時之反應及熟成，而獲得加成型聚酯前驅物（C1)溶液。又，在上^配方中，相對於源自二環狀醚化合物（a_二耳’環㈣⑻成為約L8莫耳之比率。 &基1莫 <步驟（8):藉由酸酐（c2)而進行之封閉反應> 在前述加成型聚酯前驅物（C1)溶液中，添加乙酉旨:500份、作為酸酐（c2)找酸酐：兄份，使其熟成〇小時::然後，添加乙酸乙酯以使不揮發成分成為約重 /〇亚冷郃至室溫，而獲得加成型聚酯樹腊①1)之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇4重1 %、黏度為37,000mPa.s，該樹脂（m)之酸價為n7m KOf/g、幾基價為94mgK〇H/g、玻璃轉移溫度為—〗〇<t 重量平均分子量為150,〇〇〇。 (合成例30) 將合成例 29之步驟（7)中所用之二元酸變更成丁 319793 113 200838965 二l : 322份、將二環狀醚化合物（a_2)變更成新戊二醇二環氧丙基醚：678份、將環狀酯（b)變更成ε _己内酯：143 份、將添加3次之觸媒變更成硝酸四丁基銨：各2份、將步驟（8)所用之酸酐（c2)變更成丁二酸酐：38份，除此以外與合成例29同樣地操作進行調製，而獲得淡黃色透明、且其不揮發成分為59.7重量％、黏度為15,000mPa · s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為 19.6mgKOH/g、羥基價為75mgKOH/g、玻璃轉移溫度為一馨35 C、重置平均分子量為16〇,〇〇〇。又，在上述配方中，相對於源自二環狀鍵化合物（a-2)之二級經基1莫耳，環狀酯（b)成為約〇·2莫耳之比率。 (合成例31) 將合成例29所使用之觸媒變更成溴化四丁基銨，除此之外與哈成例29同樣地操作進行調製，，而獲得淡黃色透明、且其不揮發成分為60 2重量％、黏度為19,〇〇〇mPa · s 鲁之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為 13.8mgKOH/g、羥基價為88mgKOK[/g、玻璃轉移溫度為— 10C、重f平均分子量為丨3〇5〇〇〇。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級經基！莫耳，環狀 S旨（b)成為約1 · 8莫耳之比率。 ‘（合成例32) 」將合成例29所使用之觸媒變更成四丁基鈦酸酯，除此之外與合成例29同樣地操作進行調製，而獲得黃色透明、且其不揮發成分為60·2重量％、黏度為9,5〇〇mPa · s之加 319793 114 200838965 成型聚酯樹脂（D〇之溶液。該樹脂（D1；)之酸價為8坊运 KOH/g、羥基價為MmgKOH/g、玻璃轉移溫度為—1〇〇c g 重量平均分子量為80,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基}莫耳，環狀酯（b)成為約1 · 8莫耳之比率。' (合成例33) 將合成例29所使用之觸媒變更成氧化二丁基錫，除此之外與合成例29同樣地操作進行調製，而獲得淡黃色半透 _明、且其不揮發成分為601重量％、黏度為6，_mPa · $ 之加成型聚酯樹脂（D1)之溶液。該樹脂①1；)之酸價為 14.2mgKOH/g、羥基價為80mgK〇H/g、玻璃轉移溫度為— l〇°C、重量平均分子量為15，_。又，在上述配方中，相對於源自二環狀醚化合物（心2)之二級羥基〗莫耳，環狀酯 (b)成為約1.8莫耳之比率。 (合成例34) 馨將合成例29之步驟（8)所使用之作為酸酐（c2)的酞酸酐^重量變更成3份，除此之外與合成例29同樣地操作進行調製，更藉由添加乙酸乙酯，而獲得淡黃色透明、且其不揮發成分為59.8重量％、黏度為5〇,〇〇〇mPa· s之加成型 ♦ 1曰树知（D1)之溶液。該樹脂（D1)之酸價為〇〇5邮 KOH/g、羥基價為133 5mgK〇H/g、玻璃轉移溫度為一 ι〇 C、重量平均分子量為250,000。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基丨莫耳，環狀酯 (b)成為約ι ·3莫耳之比率。 319793 115 200838965 (合成例35) 將合成例29之步驟（8)所使用之作為酸酐（c2)的酞酸酐之重1變更成2 8 5份、並將與g太酸酐一起添加之乙酸乙醋之量變更成237份，除此之外與合成例29同樣地操作進行調製，更藉由添加乙酸乙酯300份，而獲得淡黃色透明、且其不揮發成分為60.4重量％、黏度為6,000mPa · s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為80.8mg K〇H/g、經基價為7.8mgKOH/g、玻璃轉移溫度為一 10°c、 _重里平均分子量為110,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基1莫耳，環狀酯沙) 成為約1 · 8莫耳之比率。 (合成例3 6) 分別將合成例29之步驟（7)中所用之二元酸(a·〗）變更 -成己二酸·· 102份及異酞酸·· 66份、將二環狀醚化合物（&_2) 全更成雙酴A 一環氧丙基醚：3 80份、將環狀醋（b)變更成鬱ε-己内酯：285份、並將觸媒於反應開始時之使用量及進行中追加量各自變更成〇·2份，除此以外與合成例29同樣地操作，使步驟（7)之反應、熟成於100°C進行24小時。其次，就步驟（8)而言，加入為酸酐（C2)之酞酸酐：13份與乙酸乙酯：1〇0份並使熟成4小時後，加入乙酸乙酯：64份並/々部至至溫，而獲得加成型聚i旨樹脂（D1)之溶液。。此溶液係淡黃色透明、且其不揮發成分為59·6重量 %黏度為3,500mPa· s，該樹脂（D1)之酸價為24 5mg K〇H/g、羥基價為9〇mgK〇H/g、玻璃轉移溫度為一、 319793 116 200838965 重量平均分子量為45,000。又，在上述配方中，栢對於源自二環狀醚化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約1·1莫耳之比率。 (合成例37) 分別將合成例29之步驟（7)中所用之二元酸^])變更成己二酸：44份及異酞酸：33份、將二環狀醚化合物（a_2) 變更成雙酚A二環氧丙基醚：76〇份、將環狀酯（b)變更成 ε _己内酯：684份、且不使用觸媒，除此以外與合成例29 馨同樣地操作，使步驟（7)之反應、熟成於1〇(rc進行24小 B守。其次，就步驟（8)而言，加入為酸酐（C2)之酿酸酐65 份與乙酸乙酯280份並使熟成4小時後，加入乙酸乙酯377 份並冷卻至室溫，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇〇重量 %、黏度為98,00〇mpa ·- s，該樹脂（D1)之酸價為2.5mg KOH/g、羥基價為98.3mgKOH/g、玻璃轉移溫度為_ 5。〇、鲁重量平均分子量為21，_。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約1·3莫耳之比率。 (合成例38) 分別將合成例29之步驟（7)中所用之二元酸（a_1}變更成癸二酸：101份、將二環狀醚化 ?二環氧丙基鴨乙院加成莫耳數為= 壤狀醋（b)變更成ε •己㈣：684份，除此以外盘合成例 29同樣地操作，使步驟（7)之反應、熟成合計進行24小時。 319793 117 200838965 其次’就步驟（8)而言，加入為酸酐（c2)之酞酸酐56 份與乙酸乙酯500份並使進行6小時之反應、熟成後，再加入乙酸乙酯300份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為60·2重量％、黏度為27,〇〇〇mPa· s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為i2.2mg KOH/g、羥基價為75mgK〇K[/g、玻璃轉移溫度為一⑽艺、重量平均分子量為350,0〇〇。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基1莫耳，環狀酯（b) 成為約5莫耳之比率。 (合成例39) 分別將合成例29之步驟（7)中所用之二元酸（a_1}變更成異酞酸：83份、將二環狀醚化合物（a_2)變更成雙酚A 二環氧丙基醚：380份、將環狀酯（b)變更成ε_己内酯：342 份，除此以外與合成,29同樣地操作，使步驟（7)之反應、熟成合計進行24小時。其次，就步驟（8)而言，加入為酸酐（c2)之酞酸酐56 份與乙酸乙酯1〇〇份並使進行6小時之反應、熟成後，加入乙酸乙酯74份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為59.5重量％、黏度為i3,000mPa· s之加成型聚醋樹脂（D1)之溶液。該樹脂（D1)之酸價為18.5mg KOH/g、羥基價為7〇.5mgK〇H/g、玻璃轉移溫度為3〇它、重量平均分子量為250,000。又，在上述配方中，相對於源自一環狀醚化合物（a_2)之二級羥基1莫耳，環狀酯（七) 成為約1·3莫耳之比率。 319793 118 200838965 (合成例40) 在合成例29之步驟（7)中不使用環狀酯（b)、且在步驟 (8)中將與酞酸酐（c2)—起添加之乙酸乙酯之量從500份變更成204份，除此以外與合成例29同樣地進行調製，添加乙酸乙酯100份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為60.0重量％、黏度為5,000mPa · s之聚i旨樹脂溶液。此溶液所含有之樹脂，其酸價為48.5mgKOH/g、羥基價為102mgKOH/g、玻璃轉移溫度為60°C、重量平均 •分子量為25,000 〇 (合成例41) 將合成例29之步驟（8)所使用之酸酐（c2)之重量變更成562份，除此之外與合成例29同樣地操作進行調製，並添加乙酸乙酯，而獲得淡黃色透明、且其不揮發成分為60.4 重量％、黏度為/40,000mPa · s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為120mgKOH/g、羥基價為0.02mg 0 KOH/g、玻璃轉移溫度為一 5 °C、重量平均分子量為 220,000 °又，在上述配方中，相對於源自二環狀醚化合物 (a-2)之二級羥基1莫耳，環狀酯（b)成為約1.8莫耳之比率。 (合成例42) 對於合成例29之步驟（8)所得之加成型聚酯樹脂（D1) 溶液100重量份，再使作為封閉化合物（c)之異氰酸苯酯進行反應，藉此而獲得羥基價從94mgKOH/g減少至9.5mg KOH/g、且不揮發成分為60.2重量％、$占度為37,000mi>a · s之加成型聚酯樹脂（D1)之溶液。 119 319793 200838965 (合成例43) 對於合成例29之步驟（8)所得之加成型聚酯樹脂（Dl) 溶液100重量份，再使作為封閉化合物（c)之二乙基曱基矽烷進行反應，藉此而獲得羥基價從94mgKOH/g減少至 11.5mgKOH/g、且不揮發成分為59·9重量％、黏度為37,000 mPa · s之加成型聚酯樹脂（D1)之溶液。將合成例21至43所得之各樹脂溶液之外觀、不揮發成分濃度、黏度、以及樹脂之重量平均分子量（Mw)、玻璃參轉移溫度（Tg)、酸價（AV)以及羥基價（OHV)彙總顯示於表 120 319793 200838965 [表3]加成型聚酯樹脂（D1)之合成例：使用酸酐（c2)作為封閉化合物（C)時之情形 121 319793 200838965 (比較例7) 在合成例21之步驟⑴所得之主鍵用聚醋樹脂⑻溶液 100重量份t添加甲苯5()份’更進—步，添加謂TMp(伸 f笨- /、氰酉夂酉曰之二每甲基丙烧力口成物）2 5 i量份作為交聯劑⑻，仔細授拌，而獲得接著劑組成物。雖欲將其塗佈於剝離薄膜上以雈;^呈& f @ u . 以獲侍接者溥片，但因接著劑組成物之黏度急速上升，故無法進行塗佈。 (比較例8) ♦〜使用合成例21之步驟⑺所得之加成型聚醋前驅物（ci) 溶液，除此之外與比較例7進行同樣操#，而獲得接著劑組成物。將其塗佈於剝離薄膜上之時，雖然在形成之接^ 劑層表面產生發泡等現象，但以與實施例丨至19同樣之方式操作，獲得「剝離薄膜/接著劑層/ TAC薄膜/ pva/ tac 薄膜」之構成之積層體’並進行接.著劑層之反應，而得到經接著加工之偏光板（積層體）。然而，由於塗佈面為明顯 •地不良，故不進行其後之評估。、 (實施例20) 在合成例21之步驟（3)所得之加成型聚酯樹脂①丨）溶液100重量份中添加甲苯5〇份，更進一步，添加 (2’2 _雙良基曱基丁醇參[3_(ι_氣丙咬基）丙酸酯]重量份作為交聯劑（E)，仔細攪拌，而獲得接著劑組成物（第1 封閉型態）。以下，以與實施例1至19同樣之方式操作，製作由「剥離薄膜/接著劑層/TAC薄膜/PVA/TAC薄膜」所構成之 ί貝 319793 122 200838965 層體，並進行接著劑層之反應，而得到經接著加工之偏光板（積層體）。 (比較例9) 使用合成例22所得之加成型聚醋樹脂溶液替代合成例2】所得之加成型聚醋樹脂（D1)溶液，除此之外與實施例 2〇進行同樣操作，而獲得接著劑組成物。雖然其係可塗佈於剝離薄膜上，但由於接著劑層不具有黏著性（初期接著 =)’故無法以「TAC薄膜/ PVA/ TAC薄膜」之構成來積層於接著劑層。、 (實施例21至25) 二別使用σ成例22 i 23所得之樹脂溶液#代合成例、斤得之加成型聚酉旨樹脂_溶液，除此之外與實施例進仃同樣刼作，雨製成經接著加工之偏光板。 ’（實施例26) ^ 在口成例28之步驟⑹所得之加成型聚醋樹脂（叫溶麄液10 〇重詈份φ、太决田# ^ (2 2，-雔f 本0份，更進一步，添加〜t &殘土甲基丁醇參[Μ1，氮丙咬基）丙酸酯])0.25重量伤作為交聯劑（Ε)，仔 ^设仔、，，田攪拌，雨獲得接著劑組成物（第2 封閉型態）。使用該接著劑摔作，&制a Mj、、且成物亚與貫鉍例20進行同樣 ^作’而製成經接著加卫之偏光板。 (貫施例27) 例28使所用，成例29所得之加成型《樹脂（D1)替代合成 %細謂），除㈣與實施例 &件接著劑組成物。使用該接著劑組 319793 123 200838965 成物並與實施例26進行同樣操作，而製成經接著加工之偏光板。 (比較例10) 使用合成例40所得之加成型聚酯樹脂溶液替代合成例28所得之加成型聚酯樹脂溶液（D1)，除此之外與實施例 27進行同樣操作，而獲得接著劑組成物。雖然其係可塗佈於剝離薄膜上，但由於接著劑層不具有黏著性（初期接著性），故無法以「TAC薄膜/ PVA/ TAC薄膜」之構成來積 Φ層於接著劑層。 (實施例28至35) 分別使用合成例30至33(實施例28至31)及合成例36 至39(實施例32至35)所得之加成型聚酯樹脂（D1)替代合成例2 8所得之加成型聚酯樹脂（D1)溶液，除此之外與實施例26進行同樣操作，而製成經接著加工之偏光板。 -· (比較例11、12) 0 分別使用合成例34(比較例11)或合成例35(比較例12) 所得之加成型聚酯樹脂（D1)替代合成例28所得之加成型聚酯樹脂（D1)溶液，除此之外與實施例26進行同樣操作，而製成經接著加工之偏光板。 (實施例36至39) 分別使用TGMXDA(N，N，N’，N，·四環氧丙基間伸茬基二胺）（實施例36)、Carbodilite V-05(曰清紡積股份公司製之碳二亞胺系交聯劑）（實施例37)、TMBOX[2,2’-四亞曱基雙（2-噚唑啉）](實施例38)、或A1AA[參（乙醯丙酮）鋁](實施 124 319793 200838965 例39)0.25重量份替代實施例27所用之交聯齊 HBAP，除此之外與實施例27進行同樣操作，而獲得接著劑組成物。使用該接著劑組成物並與實施例28進行同樣作，而製成經接著加工之偏光板。 7 (實施例40、41) 將實施例21所用之加成型聚醋樹脂（Dl)變更成例35(實施例4〇)或合成例41(實❹j4i)所得之加成型_ 樹脂P1)，並❹Tm/TMP(伸f苯二異級§旨之三經甲^ 丙烧加成物）2.5重量份作為交聯劑⑻，除此之外與實施: 21進行同樣操作，而製成經接著加工之偏光板。、 (實施例42、43) 將實施例28所用之加成型聚醋樹脂(Di)變例42(實施例42)或合成例43(實施例43)所得之加成型二^ 樹脂_，除此之外編例28進行同樣操作，而_ 了劑組成物。使用該接著劑組成物並與實施例27進行刼作，而製成經接著加工之偏光板。办關於實施似比較朗得之接著”·絲的適用期及塗佈加工性’係依據與實施例1至19同樣之方法進行評估。將結果示於表4。 , 另外，針對實施例及比較例所得之經接著加工之板（積層體）’係依據與實施例丨至19同樣之方法進射;〆，生、耐濕熱性、光學特性及再剝離 (將、、、。果不於表4。又，耐熱性之評估試驗中，杏施例42、43以外之試料係將調整條件從「於12代放置^ 319793 125 200838965 J寸」憂更成「於8〇°C放置1 〇〇〇小時」，除此之外與實施例1至19進行同樣操作。耐濕熱性之評估試驗中，將調整條件從「於8(TC、相對濕度9〇%中放置1〇〇〇小時」變更成「於6(TC、相對濕度9〇%中放置1〇〇〇小 ^卜與實施例1至19進行间婵从此之外 τη松刼作。針對實施例42、43，|丨J 與實施例1至19進行同樣操作。則The ester il il drive (C1) solution was heated to 1 Torr. 0. Complex A /, A, in which the anhydride mixture mixture was consumed by dropping the device ★ The shell was dropped at a constant rate for 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 8 hours, and then added to 5 parts of ethyl acetate and cooled to a palace. f to, to obtain a solution of the addition type polyester resin (D1). T % This solution is light yellow transparent, and its non-volatile content is 6 G 2 wt%, viscosity is 22,000 mPa·s, the acid value of the resin (D1) is ΚΟΗ / g, the hydroxyl value is 65 mg K 〇 H / g, glass transfer The temperature is - cut. c. The weight average molecular weight is 180,000. (Synthesis Example 22) In the synthesis example 2!, the step (7) was omitted, and in the step (7), the step (7) of the main chain with a polyphenolate solution (nonvolatile content: 6 〇 2% by weight) 200 parts was substituted for the step (7). A solution of the obtained addition-formed polyacetic acid precursor (6)) was prepared in the same manner as in Synthesis Example 21, and was obtained in a pale yellow color, and its nonvolatile content was 6 〇 1% by weight, and the viscosity was Μ. a solution of a polyester resin. The resin contained in the solution had an acid value of 〇35 mg K = H / g, a base price of 98 mg K 〇 H / g, a glass transition temperature of C, and a weight average molecular weight of 60,000. (Synthesis Example 23), the dibasic acid (a-1) used in the step (1) of the example 21 was changed to: 830 parts, and the dicyclic ether compound (&_2) was changed to a new one. Ethylene bis(dimethacrylate) _: 1449 parts' and used in step (7) to adjust the non-volatile content of the obtained primary bond with acetaminophen (8) bath to about (10) 319793 107 200838965 wt% The solution was prepared in the same manner as in Synthesis Example 21 except that 20 g of the solution was used, and the nonvolatile content was adjusted to about 100% with ethyl acetate. /, and a solution of the addition-polyester resin (D1) which is light yellow transparent and has a viscosity of 14, 〇〇〇mPa s is obtained. The resin (m) had an acid value of 165 (10), a hydroxyl group value of 68 mgKOH/g, and a glass transition temperature of -25. 〇, weight average molecular weight is U0, _. Further, in the above formulation, the cyclic ring (8) is a ratio of about u mol to the secondary meridyl group derived from the bicyclic ether compound (a-2).鑤 (Synthesis Example 24) ▲ The two cyclic scaly compounds used in the step (1) of the synthesis example 2) were changed to 1,4-bis{[(3-ethylj oxetanyl)methoxy] Benzene: 670 injury and double test A diglycidyl ether: 1385 parts, and in step (2), the known main chain is used to adjust the non-volatile component to the acetic acid 224 parts by weight of about 6% by weight of the solution, in addition to the synthesis of the same wood, the non-volatile content of ethyl acetate was adjusted to about 60% by weight of Lu, to obtain a pale yellow transparent, and A solution of a modified polyester resin (D1) having a viscosity of η, qing mPa·S. The acid value of the resin (D1) is . The mgKOH/g, the hydroxyl value was 72 mg K〇H/g, the glass transition temperature was -35 C, and the weight average molecular weight was 142, 〇〇〇. Further, in the above formulation, the cyclic enthalpy (b) is a ratio of about 1 Å to 7 moles with respect to the secondary base-based mole derived from -%, the compound (a). (Synthesis Example 25) ^ The dicyclic ether compound (a_2) used in the step (1) of Synthesis Example 21 was changed to a double-aged 棻-ϊ梦弗- 虱propyl propyl ether (108 manufactured by Osaka Gas Chemical Co., Ltd.) 319793 200838965 BPFG, alias 9,9-bis[4-(glycidoxy)phenyl]-9H-indole, molecular weight: 462.5, epoxy price: 3.89 (eq/Kg)): 3203 parts, and In the same manner as in Synthesis Example 21, except that the solution of the polyester resin (B) obtained in the main chain was adjusted to have a nonvolatile content of about 60% by weight to about 60% by weight. The preparation was carried out, and the nonvolatile content was adjusted to about 60% by weight with ethyl acetate to obtain a solution of the addition-molded polyester resin (D1) having a pale yellow transparency and a viscosity of 35,000 mPa·s. The resin (D1) had an acid value of 13.2 mgKOH/g, a hydroxyl group value of 71 mgK〇H/g, a glass transition temperature of 15 ° C, and a weight average molecular weight of 165, 〇〇〇. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1⁄3 mol with respect to the secondary radical 1 mol derived from the bicyclic compound (a_2). (Synthesis Example 26) The cyclic ester (b) used in the step (2) of Synthesis Example 21 was changed to 100 parts of vinegar, and the obtained primary bond was used in the step (3). (8) The solution was prepared in the same manner as in Synthesis Example 21 except that the solution was adjusted to a non-volatile content of about 6.0% by weight of acetic acid, and the non-volatile content was adjusted to about 6 Torr by acetic acid. %, and a solution of a pale yellow transparent, viscosity 1G, _mPa·s addition shaped polydip (di) was obtained. The resin (m) had an acid value of 15 8 mg K 〇 H / g, a base price of 70 mg KOH / g, a glass transfer temperature of 糸 seconds, a degree of 〜25 C, and a weight average molecular weight of 120,000. Further, in the above formula, relative to the secondary base group 1 Mo, which is derived from the dicyclic ether compound (a_2), the choice of the 匕丄, the cloak-like § day (b) becomes about 1 · 6 Mo The ratio of the ears. (Synthesis Example 27) τ The acid anhydride (C2) used in the dry step [3] of the synthesis example 21 was changed to a sea rice 319793 109 200838965 amic acid anhydride (Himic anhydride): 4 parts, and other than the synthesis example 2 ι stone sample The operation was carried out to obtain a solution which was light yellow transparent and which was not volatilized to have a S of 60.1% by weight and a viscosity of i4, _mPa.s. The resin (D1) had an acid value of 13.9 mg K 〇 H / g, a hydroxyl group value of 65 mg KOH / g, a glass transition temperature of - 15 Å: and a weight average of 170,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 18 moles with respect to the secondary hydroxyl group 1 mole derived from the dicyclic dimerization product (a-2). [Production of Additive Polyester Resin 11 by a Quasi-Two-Phase Manufacturing Method]], Boxing (Synthesis Example 28) <Step (4) (5): Formation of Additive Polyester Precursor (ci)> Prepared for Polymerization The tank is equipped with a polymerization device of a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, and a dibasic acid (a_) and a dicyclic ether compound (a_2) are respectively added in the polymerization tank and the dropping device at the following ratios. ), cyclic ester (b), catalyst, / and organic solvent. [Polymerization tank] Adipic acid (a-1) 73 parts azelaic acid (a-1) 404 parts of bismuth F epoxide _ (a-2) 875 parts of bisphenol A phenoxy resin (a_2 1950 parts (manufactured by Sakamoto Epoxy Co., Ltd., trade name "jER1256", epoxy propylene equivalent 7800g/eq, Mw 51000) tetrabutylammonium tetrahydroborate (catalyst) 6·6 parts ethyl acetate 210 Part toluene 210 parts 319793 110 200838965 [Dripping device] 6.6 parts 3500 parts 210 parts 210 parts tetrabutylammonium tetrahydroborate (catalyst) ε-caprolactone (b) ethyl acetate toluene The air in the polymerization tank is nitrogen After the replacement, the mixture was stirred while raising the temperature to 100 °C. Further, the mixture was reacted for 8 hours to obtain a polyester resin for the main chain (1,) having an acid value of 5 mgKOH/g or less. _ Next, the cyclic ester (b) mixture was consumed by dropping the device for 1 hour at a constant rate. After the completion of the dropwise addition, 6.6 parts of tetrabutylammonium tetrahydroborate was added thereto after stirring for 8 hours, and the reaction was further carried out for 8 hours, followed by aging, and then 350 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to terminate the reaction. An addition of a polyester precursor (Cl) is obtained. The solution is light yellow transparent, and its non-volatile content is 59.8% by weight, viscosity is 30,0〇〇mpa.s, and the precursor (C1) is acid value 〇〇2mgK〇H/g, and the ruthenium price is 92mgKOH/ g, glass transfer temperature _15t, weight average molecular weight of 200, bismuth resin. Further, in the above formulation, the cyclic ester (b) has a ratio of about of mole relative to the secondary hydroxy oxime derived from the dicyclic ether compound (a_2). <Step (6): Blocking reaction by acid anhydride (c2)> Preparing a polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube in a polymerization tank, and in the polymerization tank and The addition-molded polyester precursor (ci) solution (non-volatile content 598% by weight), acid anhydride (c2), catalyst, 319793 111 200838965 and an organic solvent obtained in the step (5) were respectively added to the dropping device at the following ratios. [Polymerization tank] Addition of polyester precursor (ci) solution [Dropping device] Succinic anhydride (C2) Tetrabutylammonium tetrahydroborate (catalyst) Ethyl acetate was replaced with 200 parts of air in the polymerization tank with nitrogen. 5.0 parts of 6.6 parts of 10 parts, and the temperature of the solution 4 in the stirred tank was raised to 100 C. Next, in which the acid anhydride mixture is consumed by the dripping device and the T-displacement device is consumed by H, and is dropped at a constant rate. After the completion of the dropwise addition, the mixture was further subjected to a reaction for 6 hours while stirring, and then 5 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of the addition-molded polyester resin (D1). The solution was light yellow and transparent, and had a nonvolatile content of 60.5% by weight and a viscosity of 30,000 mPa. s 'The acid value of the resin (D1) was 15 mgKOH/g, the hydroxyl value was 62 mgKOH/g, and the glass transition temperature was - 1 〇 ° C, weight average molecular weight of 170,000. [Production of Additive Polyester Resin by One-Step Manufacturing Method] (Synthesis Example 29) A reaction apparatus equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction tube in a polymerization tank, and a polymerization tank The dibasic acid (a-1), the bicyclic bond compound (a_2), the cyclic ester (b), the catalyst, and the organic solvent are respectively added in the following ratios. [Polymerization tank] 159 parts adipic acid (a-1) 159 parts 319793 112 200838965 isophthalic acid (a-1) 120 parts bisphenol A diglycidyl ether oxime-2) 721 parts ε-caprolactone ( VII) 871 parts of ethyl acetate 200 parts of toluene 200 parts <Step (7): Formation of the addition-formed polyester precursor (C1)> After replacing the air in the polymerization tank with nitrogen, the mixture is heated to lGGt while stirring the mixture. Add 2 parts of tetrabutylammonium tetrahydrogenate to initiate the reaction. While stirring the mixture '- while adding 2. G of tetrabutylammonium tetrachloroammonate every 8 hours, a total of 2 times was added, and a total of 24 hours of reaction and aging were carried out to obtain an additive polyester precursor (C1). ) solution. Further, in the above formula, the ratio derived from the dicyclic ether compound (a-bile' ring (tetra) (8) is about L8 mole. & base 1 Mo <Step (8): by anhydride (c2) The blocking reaction is carried out. In the solution of the addition-formed polyester precursor (C1), 500 parts of ethyl acetate is added, and the acid anhydride (c2) is used as an acid anhydride: the brother is cooked to form an hour:: Then, Ethyl acetate was used to freeze the non-volatile component to about room temperature to obtain a solution of the modified polyester wax 11). This solution is light yellow transparent, and its nonvolatile content is 6〇4 weight 1%, viscosity is 37,000mPa.s, the acid value of the resin (m) is n7m KOf/g, and the base price is 94mgK〇H/g. The glass transition temperature is -〗〖 < t The weight average molecular weight is 150, 〇〇〇. (Synthesis Example 30) The dibasic acid used in the step (7) of Synthesis Example 29 was changed to Ding 319793 113 200838965 Two l: 322 parts, and the dicyclic ether compound (a_2) was changed to neopentyl glycol diepoxide. Propyl ether: 678 parts, the cyclic ester (b) was changed to ε-caprolactone: 143 parts, and the catalyst added three times was changed to tetrabutylammonium nitrate: 2 parts each, and used in the step (8) The acid anhydride (c2) was changed to a succinic anhydride: 38 parts, and the same procedure as in Synthesis Example 29 was carried out to obtain a pale yellow transparent material having a nonvolatile content of 59.7% by weight and a viscosity of 15,000 mPa·s. Add a solution of the polyester resin (D1). The resin (D1) had an acid value of 19.6 mgKOH/g, a hydroxyl group value of 75 mgKOH/g, a glass transition temperature of 35 C, and a reset average molecular weight of 16 Å. Further, in the above formulation, the cyclic ester (b) has a ratio of about 0.2 mol with respect to the secondary mercapto group 1 mol derived from the dicyclic bond compound (a-2). (Synthesis Example 31) The same procedure as in Example 29 was carried out except that the catalyst used in Synthesis Example 29 was changed to tetrabutylammonium bromide to obtain a pale yellow transparent material and a nonvolatile content thereof. It is a solution of 60 2% by weight, a viscosity of 19, and 〇〇〇mPa · s of a modified polyester resin (D1). The acid value of the resin (D1) was 13.8 mgKOH/g, the hydroxyl value was 88 mg KOK [/g, the glass transition temperature was -10 C, and the weight average molecular weight was 丨3〇5〇〇〇. Further, in the above formulation, it is relative to the secondary meridine derived from the dicyclic ether compound (a_2)! Mohr, ring S (b) becomes a ratio of about 1.8 m. (Synthesis Example 32) The same procedure as in Synthesis Example 29 was carried out except that the catalyst used in Synthesis Example 29 was changed to tetrabutyl titanate, and yellowish transparent was obtained, and the nonvolatile content was 60. 2% by weight, viscosity of 9,5〇〇mPa · s plus 319793 114 200838965 Forming polyester resin (D〇 solution. The acid value of the resin (D1;) is 8 square KOH / g, hydroxyl price It is MmgKOH/g, the glass transition temperature is -1〇〇cg, and the weight average molecular weight is 80,000. Further, in the above formulation, the ring is relative to the secondary hydroxyl group derived from the dicyclic ether compound (a-2). In the same manner as in Synthesis Example 29, the ester (b) was prepared in the same manner as in Synthesis Example 29 except that the catalyst used in Synthesis Example 29 was changed to dibutyltin oxide. A solution of a modified polyester resin (D1) having a pale yellow semi-transparent and having a nonvolatile content of 601% by weight and a viscosity of 6, _mPa · $ was obtained. The acid value of the resin 11;) was 14.2 mgKOH/ g, the hydroxyl value is 80 mg K 〇 H / g, the glass transition temperature is - l 〇 ° C, the weight average molecular weight is 15, _. Further, in the above formulation, the cyclic ester (b) became a ratio of about 1.8 moles relative to the secondary hydroxyl group derived from the dicyclic ether compound (heart 2). (Synthesis Example 34) The same procedure as in Synthesis Example 29 was carried out except that the weight of the phthalic anhydride of the acid anhydride (c2) used in the step (8) of Synthesis Example 29 was changed to 3 parts. Ethyl acetate was added to obtain a pale yellow transparent solution having a nonvolatile content of 59.8 wt%, a viscosity of 5 Å, and an addition of 〇〇〇mPa·s to a solution of 曰1知树知(D1). The resin (D1) had an acid value of 〇〇 5 KOH/g, a hydroxyl value of 133 5 mg K 〇 H / g, a glass transition temperature of 1 〇 C, and a weight average molecular weight of 250,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1⁄3 mol relative to the secondary hydroxy oxime derived from the dicyclic ether compound (a_2). 319793 115 200838965 (Synthesis Example 35) The weight 1 of the phthalic anhydride used as the acid anhydride (c2) used in the step (8) of Synthesis Example 29 was changed to 2 8 5 parts, and the ethyl acetate was added together with the g-anhydride. The amount was changed to 237 parts, and the preparation was carried out in the same manner as in Synthesis Example 29, and by adding 300 parts of ethyl acetate, a pale yellow color was obtained, and the nonvolatile content was 60.4% by weight, and the viscosity was 6,000. A solution of mPa · s plus shaped polyester resin (D1). The resin (D1) had an acid value of 80.8 mg K 〇 H / g, a base price of 7.8 mg KOH / g, a glass transition temperature of 10 ° C, and a _ weight average molecular weight of 110,000. Further, in the above formulation, the cyclic ester sand) is a ratio of about 1.8 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a-2). (Synthesis Example 3 6) The dibasic acid (a·) used in the step (7) of Synthesis Example 29 was changed to adipic acid · 102 parts and isononic acid · 66 parts, respectively The ether compound (&_2) was further converted into bis-A-epoxypropyl ether: 3 80 parts, and the cyclic vinegar (b) was changed to εε-caprolactone: 285 parts, and the catalyst was started in the reaction. In the same manner as in Synthesis Example 29, the reaction and the aging were carried out at 100 ° C for 24 hours, except that the amount of use and the amount of the addition were changed to 2 parts. Next, in the case of the step (8), an anhydride (C2) of phthalic anhydride was added: 13 parts and ethyl acetate: 1 〇 0 parts and allowed to mature for 4 hours, and then ethyl acetate was added: 64 parts/々 to At a temperature, a solution of the addition polymer (D1) was obtained. . The solution is light yellow transparent and has a non-volatile content of 59.6% by weight and a viscosity of 3,500 mPa·s. The acid value of the resin (D1) is 24 5 mg K〇H/g, and the hydroxyl value is 9 〇mgK〇H. /g, glass transition temperature is one, 319793 116 200838965 The weight average molecular weight is 45,000. Further, in the above formulation, Cypress is a secondary hydroxyl group derived from the dicyclic ether compound (a-2), and the cyclic ester (b) has a ratio of about 1.1 mole. (Synthesis Example 37) The dibasic acid used in the step (7) of Synthesis Example 29 was changed to adipic acid: 44 parts and isononic acid: 33 parts, and the dicyclic ether compound (a_2) was changed. The operation was carried out in the same manner as in Synthesis Example 29 except that the bisphenol A diglycidyl ether was changed to 76 parts, and the cyclic ester (b) was changed to ε-caprolactone: 684 parts, and no catalyst was used. The reaction of the step (7) is carried out at 1 Torr (rc is carried out at 24 hours B. Next, in the case of the step (8), 65 parts of the anhydride of the acid anhydride (C2) and 280 parts of ethyl acetate are added and After 4 hours of aging, 377 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of the addition-formed polyester resin (D1). This solution was light yellow transparent, and its nonvolatile content was 6 〇〇% by weight, viscosity. The resin (D1) has an acid value of 2.5 mg KOH/g, a hydroxyl group value of 98.3 mgKOH/g, and a glass transition temperature of _ 5. The weight average molecular weight of the ruthenium and ruthenium is 21, _, which is 98,00 〇mpa ·- s. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1.3 mol with respect to the secondary hydroxy oxime derived from the dicyclic ether compound (a-2). ) separately The dibasic acid (a_1} used in the step (7) of Synthesis Example 29 was changed to azelaic acid: 101 parts, and the dicyclic etherified; diepoxypropyl ducks were added to the molar number = soil The vinegar (b) was changed to ε • (4): 684 parts, and the disk synthesis example 29 was operated in the same manner, and the reaction and the ripening of the step (7) were carried out for 24 hours in total. 319793 117 200838965 Next, in the case of the step (8) Then, 56 parts of the anhydride (c2) and 500 parts of ethyl acetate were added and reacted for 6 hours, and after aging, 300 parts of ethyl acetate was further added, and it cooled to room temperature, and it was yellow-yellow transparent, and a solution of a modified polyester resin (D1) having a nonvolatile content of 60. 2 wt% and a viscosity of 27, 〇〇〇mPa·s. The acid value of the resin (D1) is i2.2 mg KOH/g, and a hydroxyl group. The valence is 75 mg K 〇 K [/g, the glass transition temperature is one (10) art, and the weight average molecular weight is 350, 0 〇〇. Further, in the above formulation, relative to the secondary hydroxyl group derived from the dicyclic ether compound (a_2) 1 mol, the cyclic ester (b) becomes a ratio of about 5 mol. (Synthesis Example 39) The dibasic acid (a_1) used in the step (7) of Synthesis Example 29, respectively. Change to isodecanoic acid: 83 parts, change the dicyclic ether compound (a_2) to bisphenol A diglycidyl ether: 380 parts, and change the cyclic ester (b) to ε_caprolactone: 342 parts In the same manner as in the synthesis, 29, the reaction and the ripening of the step (7) were carried out for 24 hours. Next, in the step (8), 56 parts of the anhydride (c2) and acetic acid B were added. After 1 part of the ester was allowed to react for 6 hours and matured, 74 parts of ethyl acetate was added and cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 59.5% by weight and a viscosity of i3,000 mPa. A solution of the formed polyacetal resin (D1). The resin (D1) had an acid value of 18.5 mg KOH/g, a hydroxyl group value of 7 〇.5 mg K 〇 H/g, a glass transition temperature of 3 Torr, and a weight average molecular weight of 250,000. Further, in the above formulation, the cyclic ester (VII) is a ratio of about 1.3 mol with respect to the secondary hydroxyl group 1 mol derived from the cyclic ether compound (a_2). 319793 118 200838965 (Synthesis Example 40) The cyclic ester (b) was not used in the step (7) of Synthesis Example 29, and the amount of ethyl acetate added to the phthalic anhydride (c2) in the step (8) was used. The mixture was prepared in the same manner as in Synthesis Example 29 except that the amount was changed from 500 parts to 204 parts, and 100 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material, and the nonvolatile content was 60.0% by weight, and the viscosity was 5,000 mPa · s is a resin solution. The resin contained in this solution had an acid value of 48.5 mgKOH/g, a hydroxyl group value of 102 mgKOH/g, a glass transition temperature of 60 ° C, and a weight average molecular weight of 25,000 Å (Synthesis Example 41). 8) The weight of the acid anhydride (c2) used was changed to 562 parts, and the same procedure as in Synthesis Example 29 was carried out, and ethyl acetate was added thereto to obtain a pale yellow transparent material and a nonvolatile content of 60.4% by weight. %, a solution of the addition-molded polyester resin (D1) having a viscosity of /40,000 mPa · s. The resin (D1) has an acid value of 120 mgKOH/g, a hydroxyl group value of 0.02 mg 0 KOH/g, a glass transition temperature of 5 ° C, and a weight average molecular weight of 220,000 °, and in the above formula, relative to the second source. The secondary hydroxyl group of the cyclic ether compound (a-2) is 1 mol, and the cyclic ester (b) is a ratio of about 1.8 mol. (Synthesis Example 42) 100 parts by weight of the solution of the addition-form polyester resin (D1) obtained in the step (8) of Synthesis Example 29, and then reacting phenyl isocyanate as the blocking compound (c), thereby obtaining A solution of the addition-molded polyester resin (D1) having a hydroxyl group value of from 9.4 mg KOH/g to 9.5 mg KOH/g and a nonvolatile content of 60.2% by weight and a share of 37,000 mi > a · s. 119 319793 200838965 (Synthesis Example 43) 100 parts by weight of the solution of the addition polyester resin (D1) obtained in the step (8) of Synthesis Example 29, and then reacting diethyl decyl decane as the blocking compound (c). Thus, a solution of the addition-molded polyester resin (D1) having a hydroxyl group value of from 94 mgKOH/g to 11.5 mgKOH/g and a nonvolatile content of 59.9% by weight and a viscosity of 37,000 mPa·s was obtained. The appearance, non-volatile component concentration, viscosity, and weight average molecular weight (Mw) of the resin, glass transition temperature (Tg), acid value (AV), and hydroxyl value (OHV) of each of the resin solutions obtained in Synthesis Examples 21 to 43 The summary is shown in Table 120 319793 200838965 [Table 3] Synthesis Example of Addition Polyester Resin (D1): Case When Acidic Acid (c2) Is Used as Blocking Compound (C) 121 319793 200838965 (Comparative Example 7) In Synthesis Example 21 The primary bond obtained in the step (1) is further added with 100 parts by weight of the polyacetate resin (8) solution, and 5 parts of toluene is added, and the addition is called TMp (extension f stupid - /, cyanogen bromide per methyl propylene burning power) The aliquot of 2 5 i parts was used as a crosslinking agent (8), and the mixture was carefully mixed to obtain an adhesive composition. Although it is intended to be applied to the release film to obtain a film of the contactor, the viscosity of the adhesive composition is rapidly increased, so that the coating cannot be performed. (Comparative Example 8) The same procedure as in Comparative Example 7 was carried out except that the addition of the polyacetal precursor (ci) solution obtained in the step (7) of Synthesis Example 21 was carried out to obtain an adhesive composition. When it was applied to the release film, foaming or the like occurred on the surface of the formed interface layer, but the same procedure as in Examples -19 to 19 was carried out to obtain a "release film/adhesive layer/TAC film. The laminated body of the structure of the /pva/ tac film is subjected to a reaction of the coating layer to obtain a polarizing plate (layered body) which is subsequently processed. However, since the coated surface is obviously poor, no subsequent evaluation is performed. (Example 20) To 100 parts by weight of the solution of the addition-molded polyester resin obtained in the step (3) of Synthesis Example 21, 5 parts of toluene was added, and further, (2'2 _ bis- succinyl butyl amide was added. Alcohol ginseng [3_(ι_acetonyl)propionate] parts by weight as crosslinking agent (E), carefully stirred to obtain an adhesive composition (first closed form). Hereinafter, with Example 1 In the same manner as in 19, a layer of 395793 122 200838965 consisting of a "peeling film/adhesive layer/TAC film/PVA/TAC film" was prepared and subjected to a reaction of an adhesive layer to obtain a subsequent processing. Polarizing plate (layered body) (Comparative Example 9) The addition-molded polyester resin solution obtained in Synthesis Example 22 was used instead of the addition-formed polyester resin (D1) solution obtained in Synthesis Example 2, except that Example 2 The same operation was carried out to obtain an adhesive composition. Although it was applied to the release film, since the adhesive layer did not have adhesiveness (initial follow-up), it was impossible to use "TAC film / PVA / TAC film". It is laminated to form an adhesive layer. (Examples 21 to 25) Using the resin solution obtained in Example 22 i 23 as an example, the synthesis example and the addition of the resin to the solution were used in the same manner as in the example, and the rain was made into a polarizing plate which was subsequently processed. '(Example 26) ^ Addition of a polyacetate resin obtained in the step (6) of the mouth example 28 (called a solvent solution 10 〇 heavy φ 太, Tai tiantian # ^ (2 2, -雔f this 0 parts) Further, add ~t & residue methylbutanol ginseng [Μ1, aziridine base] propionate]) 0.25 weight injury as a cross-linking agent (Ε), aberdeen, set, and, the field stir, The rain obtains an adhesive composition (second closed type). Using this adhesive, it is made, & a Mj, and the product is made in the same way as the example 20 Polarized plate. (Example 27) Example 28 used the addition molding "Resin (D1) instead of Synthetic %) obtained in Example 29, except (4) and Example & This adhesive group 319793 123 200838965 was used and subjected to the same operation as in Example 26 to produce a polarizing plate which was subsequently processed. (Comparative Example 10) The same procedure as in Example 27 was carried out except that the addition-molding polyester resin solution obtained in Synthesis Example 40 was used instead of the addition-molding polyester resin solution (D1) obtained in Synthesis Example 28, to obtain an adhesive composition. Things. Although it can be applied to the release film, since the adhesive layer does not have adhesiveness (initial adhesion), the layer of the "TAC film / PVA / TAC film" cannot be laminated to the adhesive layer. (Examples 28 to 35) The addition molding resin (D1) obtained in Synthesis Examples 30 to 33 (Examples 28 to 31) and Synthesis Examples 36 to 39 (Examples 32 to 35) was used instead of Synthesis Example 28. A polarizing plate which was subjected to subsequent processing was prepared in the same manner as in Example 26 except that the solution of the polyester resin (D1) was added. - (Comparative Examples 11, 12) 0 The addition-molded polyester resin (D1) obtained in Synthesis Example 34 (Comparative Example 11) or Synthesis Example 35 (Comparative Example 12) was used instead of the addition-molded polyester resin obtained in Synthesis Example 28. Except for the solution of (D1), the same operation as in Example 26 was carried out to prepare a polarizing plate which was subjected to subsequent processing. (Examples 36 to 39) TGMXDA (N, N, N', N, · tetraepoxypropyl meta-decyl diamine) (Example 36), Carbodilite V-05 (曰清纺积集公司) were used, respectively. Prepared carbodiimide crosslinker) (Example 37), TMBOX [2,2'-tetradecylbis(2-oxazoline)] (Example 38), or A1AA [Ref. Acetone) aluminum] (Example 124 319793 200838965 Example 39) 0.25 parts by weight of the crosslinked homogeneous HBAP used in the alternative Example 27 was used, except that the same procedure as in Example 27 was carried out to obtain an adhesive composition. Using this adhesive composition, the same procedure as in Example 28 was carried out to prepare a polarizing plate which was subsequently processed. 7 (Examples 40 and 41) The addition molding resin (D1) used in Example 21 was changed to the addition molding_resin P1) obtained in Example 35 (Example 4A) or Synthesis Example 41 (Embodiment j4i), and ❹Tm/TMP (extension of benzene bisexitate § 三甲 ^ 丙丙 ) ) ) ) ) ) ) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Polarized plate. (Examples 42, 43) The addition molding resin (Di) of Example 28 (Example 42) used in Example 28 (Example 42) or Synthesis Example 43 (Example 43) was added. In addition, the same operation was carried out in the case of the example 28, and the composition of the agent was used. This adhesive composition was used and subjected to the same operation as in Example 27 to prepare a polarizing plate which was subsequently processed. The evaluation of the application period and the coating processability of the silk fabrics was carried out in the same manner as in Examples 1 to 19. The results are shown in Table 4. Further, for the examples and comparisons The subsequently processed sheet (layered body) obtained in the same manner was injected in the same manner as in Examples 丨 to 19; 〆, raw, heat and humidity resistance, optical properties, and re-peeling (will, 4. In the heat resistance evaluation test, the test conditions other than the apricots 42 and 43 were adjusted from "12 generations ^ 319793 125 200838965 J inch" to "at 8 ° ° C. 1 〇〇 In the same manner as in the first to the ninth embodiments, the adjustment conditions were changed from "8 (TC, relative humidity 9 〇% for 1 hr)". In the case of "6, TC, relative humidity of 9〇%, 1〇〇〇小^, and Examples 1 to 19, the τ 婵婵婵。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 The same operation was performed in Examples 1 to 19.

319793 126 200838965 [表4]使用第1型態之加成型聚酯樹脂（D1)的接著劑組成物：使用酸酐（c2)作為封閉化合物（C)時之情形璀*¥獾\喫蘅柳埤挺綾i#撕濰 (3)蘅箨祝挺紱(16槳率遛鉍重工性 1 1 0 1 〇〇 o o Ο ο Ο 1 ο 0 ο 〇 o <l < < < < 〇 0 ο 0 < < ο Ο 耐濕熱性 N 1 1 ο I o 1 〇 o o Ο ο Ο 1 °ι 0 < <1 0 O 〇 0 ο Ο 〇 Ο ο Ο Ο o ο Ο 1 1 ο -"1 1 〇 o o o ο ο Ο 1 0 ο ο <1 o < < <J < < 〇 Ο ο ο < < ο ο — 耐熱性 _ i 1 0 ί o o o o ο ο Ο \ ο 0 ο 〇 o < <1 < <j < 〇 Ο ο ο < < 0 ο 黏著性 1 t ο X o o o I o ο ο Ο X 0 0 ο 〇 < < o o ο Ο 〇 Ο ο ο Ο o ο ο SS 1 1 ° < o o o o 0 ο Ο X 0 0 < 〇 < < < < ο ο 〇 Ο ο ο ο < ο ο 折射率 1 1 ] 1.5406 1 1.53β7 1 1.5388 ] 1.4861 | 1.4672 ! 1,5704 | 1.5302 1 1.5534 1 1.5228 ! 1.5401 1.5398 1.5277 1.5298 1.530Z 1.5223 1.524Θ 1.5201 1.6265 1.5187 ί 1.5216 I 1.5365 1.6482 I 1.5298 ! 1.5423 ! 1.5211 1 1.5455 1 1.5228 | 1.5228 塗佈加工性 ] < Ο < o 〇〇 o Ο Ο Ο X 0 Ο < 〇 < < 〇 < Ο Ο 〇 Ο Ο Ο Ο 〇 ό ο 適用期 X X ο Ο o 〇〇 o Ο 闕 Ο Ο 0 Ο < o < o < Ο <3 〇 Ο Ο Ο ο o ο ο 分數 KO IO 0.25 ml 0.25 ιη 圓 1 _Μ5| 〇^5| 0^51 0¾ 025 025 0.25 0.25 0,25 0·25 0.25 0·25 0.25 ΙΓ> LM5 0.25 種類 TDi/TMPl TDl/TMPl ΗΒΑΡ ΗΒΑΡ HBAP HBAP | HBAP 1 HBAP i ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ HBAP HBAP HBAP HBAP HBAP ΗΒΑΡ ΗΒΑΡ TGMXDA V-05 ΤΜΒΟΧ 1 AIM ITDI/TMP lTDi/TMP 1 ΗΒΑΡ [ΗΒΑΡ € m OHV ▼- GO σ> S 'P—1 o ΙΟ CD CM Ο s ιο S § ir> GD S 98.3 ιη tr> ο t t ο s CO s 〇 ΙΟ oi 1 11.5 δ to d 0,05 1 15.3 35.0 10.5 16.8 T3Ji 15.8 α» d τ— ιη 1^· 11.7 48.5 19.6 13.8 12.8 14.2 0.05 80.6 24.5 iq 12.2 18.5 11.7 丄1丄 Τ oq s 10.5 11.2 1? s o yj· ο 丁 s in ia cp ID u> CM t ιη 丁 ΙΟ ό 丁 r1〇j ? -10 -to ο i -to o 丁 -10 in -90 8 -10 Ο ο Ο 丁〇i τ| u> ο 1=11, Mw I 1 g· ί οι -I I i 2· I i s· 1 I ο* ί 1 I 160,000 I βο,οοο I g I rn 1 o | I I1 « 250.000 170,000 1 ϊ Ο ο s 1 o 220,000 ί ο 160,000 OH : (b) o €〇 ο to n e> 00 ΙΟ «0 ο ra CD τ- ”丨 CQ CD CD "Ί CO c> CD τ*. G0 CO CO CO CD C0 to ，二· 产 r- 二* 二’ 二· 二· 二 ψ- Τ 二*1 ! 二 r· τ-； r- •鬌ι ― τ- 二·| Ar 含有率 (wt%) s CM a ir> to τ·-· CM r~ τ- Ύ— ιο σ> s Ο j 〇> σ> 〇> τ-· 〇> 卜 CO ο! CO CM β> σ> τ- 〇> τ- 1 σ> τ- 卜 ir> v- ρ^! 卜 Τ 側鏈含有率 (wt%) I 0 CO s ζ- 〇穿 ο ιη ο ΙΟ α> esi ο CO 3 fj s s rj Ο CO § Ο CO s 〇> ir> Ο (Τ> Ο u> 合成例 CO CM s to csi CD CM S 〇> CM ο g s d I s ΙΛ CO : CO s； σ> CO σ> σ> σ> s ? ? 1.比較例7 1 丨比較例8丨丨實施例2〇| 1比較例9 1 I實施例21 | 丨實施例221 [·贫施例23 | 丨實施例241 ΙΩ CS1 军 (Ο οι 苳 Μ 1實施例27 1比較例ίο 丨實施例2Β| 丨贫施例29 丨贫施例30 br施例31 丨比較例11 比較例12 丨貧施例32 T> ϋ> 貧施例34 丨實施例35 It施例36! Κ CO m 丨贫施例38 贫施例39 |實施例40 軚 Μ 寸军 1宵施例43 亨〇〇 τΗ 〇ik S要 P ' §0〇 •*s 癍·· t 亨〇 r-H 皆令· 〇«ίί S叙 °Ρ ·· 〇〇 Si m t Μ ¥ 實施例42、43 #噶4建“键W遛嬸·w蛛Μ螬δ-朗夂：SM锿/ία目蓥噠4越《蝴&-瘛川》谐镲·w^-r蝴神砮：ds/Iax 紊噶4越苽硪A璁蚪ft-拿：dwi/iai 球(1苽饍0)砵：ννιν (#¥§1112)穸砩fe-SHs-CS3W : X0CO1U <鉍莳<<钽荽第绽#〇1)90—>3二15〇亡3:50丨>» 鸽“硪神拿迓 |硪«^•蛘 s- .Krzs:^: vaxsl 【避嬸苽(砩钐龄卜砩ft-砩《制-hz :dvs一 127 319793 200838965 《第1封閉型態、：使用異氰酸醋化合物（c3)作為封閉化合物(C)》在下述合成例44至63中，使用異氰酸酯化合物（c3) 作為封閉化合物（c)以調製聚酯樹脂。合成例44至49係依據二1¾ &型製造方法、合成例5〇係依據擬似二階段型製造方法、合成例51至61係依據二階段型製造方法而調製，而合成例62及63係省略環狀酯（b)或封閉化合物（c)。 [以二階段型製造方法製造加成型聚酯樹脂（D1)] _(合成例44) <步驟（1):聚酯主鏈之形成> 將攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入官設於聚合槽而構成聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入二元酸（a_i)、具有2個環狀醚基之化合物（a-2)、觸媒、以及有機溶劑。.319793 126 200838965 [Table 4] Adhesive composition using the addition type polyester resin (D1) of the first type: When the acid anhydride (c2) is used as the blocking compound (C) 璀*¥獾\吃蘅柳埤Pretty 绫i# 潍潍 (3) 蘅箨绂绂 (16 paddle rate 遛铋 heavy work 1 1 0 1 〇〇oo Ο ο Ο 1 ο 0 ο 〇o <l <<<< 〇 0 ο 0 << ο Ο resistance to heat and humidity N 1 1 ο I o 1 〇oo Ο ο Ο 1 °ι 0 <<1 0 O 〇0 ο Ο 〇Ο ο Ο Ο o ο Ο 1 1 ο -"1 1 〇ooo ο ο Ο 1 0 ο ο <1 o <<<J<< 〇Ο ο ο << ο ο — Heat resistance _ i 1 0 ί oooo ο ο Ο \ ο 0 ο 〇o <<1<<j< 〇Ο ο ο << 0 ο Adhesive 1 t ο X ooo I o ο ο Ο X 0 0 ο 〇 << Oo ο Ο 〇Ο ο ο Ο o ο ο SS 1 1 ° < oooo 0 ο Ο X 0 0 <〇<<<< ο ο 〇Ο ο ο ο < ο ο Refractive index 1 1 ] 1.5406 1 1.53β7 1 1.5388 ] 1.4861 | 1.4672 ! 1,5704 | 1.5302 1 1.5534 1 1.5228 ! 1.5401 1.5398 1.5277 1.5298 1.530Z 1 .5223 1.524Θ 1.5201 1.6265 1.5187 1.5 1.5216 I 1.5365 1.6482 I 1.5298 ! 1.5423 ! 1.5211 1 1.5455 1 1.5228 | 1.5228 Coating processability] < Ο < o 〇〇o Ο Ο Ο X 0 Ο <〇<<〇< Ο Ο 〇Ο Ο Ο Ο 〇ό ο Applicable period XX ο Ο o 〇〇o Ο 阙Ο Ο 0 Ο < o < o < Ο <3 〇Ο Ο Ο ο o ο ο KO IO 0.25 ml 0.25 ιη Round 1 _Μ5| 〇^5| 0^51 03⁄4 025 025 0.25 0.25 0,25 0·25 0.25 0·25 0.25 ΙΓ> LM5 0.25 Type TDi/TMPl TDl/TMPl ΗΒΑΡ ΗΒΑΡ HBAP HBAP | HBAP 1 HBAP i ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ ΗΒΑΡ HBAP HBAP HBAP HBAP HBAP ΗΒΑΡ TG TGMXDA V-05 ΤΜΒΟΧ 1 AIM ITDI/TMP lTDi/TMP 1 ΗΒΑΡ [ΗΒΑΡ € m OHV ▼- GO σ> S 'P—1 o ΙΟ CD CM Ο s ιο S § ir> GD S 98.3 ιη tr> ο tt ο s CO s 〇ΙΟ oi 1 11.5 δ to d 0,05 1 15.3 35.0 10.5 16.8 T3Ji 15.8 α» d τ— ιη 1^· 11.7 48.5 19.6 13.8 12.8 14.2 0.05 80.6 24.5 iq 12.2 18 .5 11.7 丄1丄Τ oq s 10.5 11.2 1? so yj· ο丁s in ia cp ID u> CM t ιη 丁ΙΟ ό丁r1〇j ? -10 -to ο i -to o Ding-10 in - 90 8 -10 Ο ο Ο 〇〇 i τ| u> ο 1=11, Mw I 1 g· ί οι -II i 2· I is· 1 I ο* ί 1 I 160,000 I βο,οοο I g I rn 1 o | I I1 « 250.000 170,000 1 ϊ Ο ο s 1 o 220,000 ί ο 160,000 OH : (b) o €〇ο to n e> 00 ΙΟ «0 ο ra CD τ- ”丨CQ CD CD "Ί CO c> CD τ*. G0 CO CO CO CD C0 to , II · Production r- 2* 2' 2 · 2 · 2ψ - Τ 2*1 ! 2r· τ-; r- • 鬌ι ― τ- 2 · Ar content rate (wt%) s CM a ir> to τ·-· CM r~ τ- Ύ- ιο σ> s Ο j 〇>σ>〇> τ-· 〇> Bu CO ο! CO CM β > σ > τ - 〇 > τ - 1 σ > τ - 卜 ir > v - ρ ^! Τ 侧 side chain content rate (wt%) I 0 CO s ζ - 〇 wear ο ιη ο ΙΟ α> Es ο 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 CO s; σ > CO σ > σ > σ > s ? 1. Comparative Example 7 1 丨 Comparative Example 8 丨丨 Example 2 〇 | 1 Comparative Example 9 1 I Example 21 | 丨 Example 221 [· Poor Example 23 | 丨 Example 241 Ι Ω CS1 军 (Ο οι 苳Μ 1 Example 27 1 Comparative Example ίο 丨 Example 2 Β | 丨施 29 29 29 丨施 30 30 30 施 Example 31 丨 Comparative Example 11 Comparative Example 12 丨Lean Application 32 T>ϋ> Lean Example 34 丨Example 35 It Example 36! Κ CO m 丨 Poor Example 38 Poor Example 39 | Example 40 軚Μ 寸宵 1 宵 Example 43 亨〇〇τΗ 〇ik S要 P ' §0〇•*s 癍·· t 亨〇rH 令令·〇«ίί S叙°Ρ ··〇〇Si mt Μ ¥ Example 42, 43 #噶4Build "Key W遛婶·w spider Μ螬 - 夂夂锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿锿蝴蝴蝴蝴蝴蝴蝴蝴蝴蝴蝴蝴蝴蝴蝴 ds蚪ft-take: dwi/iai ball (1 苽 meal 0) 砵: ννιν (#¥§1112)穸砩fe-SHs-CS3W : X0CO1U <铋莳<<钽荽第绽#〇1)90 —>3二15〇死3:50丨>» Pigeon "硪神迓迓|硪«^•蛘s-.Krzs:^: vaxsl [After 砩钐 (砩钐龄砩 ft-砩" -hz :dvs 127 319793 200838965 "First closed type: using isocyanate compound (c3) as blocking compound (C)" In the following Synthesis Examples 44 to 63, an isocyanate compound (c3) was used as a blocking compound (c) to prepare polyester resin. Synthesis Examples 44 to 49 were prepared according to the two-stage type manufacturing method, the synthesis example 5 based on the pseudo-two-stage type production method, and the synthesis examples 51 to 61 according to the two-stage type production method, and the synthesis examples 62 and 63 were prepared. The cyclic ester (b) or the blocking compound (c) is omitted. [Production of Additive Polyester Resin (D1) by Two-Step Manufacturing Method] _ (Synthesis Example 44) <Step (1): Formation of Polyester Main Chain> Agitator, thermometer, reflux cooler, dropping device, and The nitrogen introduction unit is provided in the polymerization tank to constitute a polymerization reaction device, and the dibasic acid (a_i), the compound (a-2) having two cyclic ether groups, and the catalyst are respectively added to the polymerization tank and the dropping device at the following ratios. And organic solvents. .

[聚合槽] 己二酸（a_l) 438份異酞酸（a-1) 332份乙酸乙酯 135份曱苯 135份 [滴下裝置] 雙盼A 一％氣丙基謎（a-2) 1995 份四氫硼酸四丁基銨（觸媒） 5.5份乙酸乙酯 135份曱苯 135份 319793 128 200838965 將承“曰内之空氣以氮氣置換後，—邊授摔二元酸混合物-邊升…，c。其次，於其中，藉由滴下裝置而將二環狀醚化合物混合物耗費！小時以等速滴下。再一邊攪拌一邊每隔8小時加入觸媒5.5份，共加入2次後，：使其進行合計24小時之反應、熟成，然後添加⑽7份乙酸乙酯並冷卻至室溫，結克及靡，獾p + Μ 末夂應獲侍主鏈用聚酯樹脂（Β) 溶液。此溶液係淡黃色透明、且其不揮發成分為60.5重量 • %、黏度為2〇，_mPa· s，而溶液中所含之樹脂（β)之酸價為〇.5mgK〇H/g、M基價為155mgK⑽g、玻璃轉移溫度為 6〇°C、重量平均分子量為5〇,〇〇〇。 <步驟（2) ·環狀醋（b)之開環加成反應> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟（1)所得之主鏈用聚醋樹脂 _ (B)溶液、環狀酯⑻、觸媒、以及有機溶劑。 [聚合槽] 聚酯樹脂（B)溶液 219份乙酸乙酯 3 3份 [滴下裝置] ε -己内酯（b) 114份四氫硼酸四丁基銨（觸媒） 1·3份乙酸乙醋 66份將聚合槽内之空氣以氮氣置換後，一邊攪拌樹脂溶液 319793 129 200838965 一邊升溫至10(rc。其次，於其中，藉由滴下裝置而將環狀酯（b)混合物耗費1小時以等速滴下。再一邊攪拌一邊使其進行12小時之反應、熟成，然後添加66份乙酸乙酯並〜部至至溫，結束反應，而製得加成型聚酯前驅物（c丨）之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇2重量 %、黏度為15,000mPa· s ’該加成型聚酯前驅物（ci)之酸價為0.05mgKOH/g、羥基價為74mgK〇H/g、玻璃轉移溫度為、重量平均分子㈣15G，_。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基1莫耳，環狀酯（b)成為約1.8莫耳之比率。 <步驟（3):藉由異氰酸酯化合物（c3)而進行之封閉反應〉準備於聚合槽附有授拌機、温度計、回流冷卻器、滴下裝置及氮導人管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟⑺所得之加成型聚酿前驅物（C1)溶液、異氰酸醋化合物（c3)、觸媒、以及有機溶劑。 200份加成型聚酯前驅物（C1)溶液 [滴下裝置] 異氰酸苯醋（c3) 四氫硼酸四丁基銨（觸媒）乙酸乙酯將聚合槽内之空氣以氮氣升溫至100°C。其次，於其中 21份 5份置換後，一邊攪拌溶液一邊，藉由滴下裝置而將異氰酸 319793 130 200838965 酉曰化合物之混合物耗費1小時以等速滴下。再一邊攪拌一邊使其進行8小時之反應、熟成，然後添加8份乙酸乙酯亚冷部至室溫，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇·4重量 %、黏度為19,〇〇〇mPa.s，該樹脂（D1)之酸價為〇〇5邮 KOH/g、羥基價為5mgK〇fI/g、玻璃轉移溫度為—⑺亡、重量平均分子量為170,000。 (合成例45) • 分別將合成例44之步驟⑴中所用之二元酸㈤）變更成/、酞I . 830伤、將二環狀醚化合物（心2)變更成新戊二醇二環氧丙基鍵：1449份，且在步驟(2)中使用所得之主鏈用聚醋樹脂⑻溶液（不揮發成分為60.2重量％)200份，除此以外與合成例44同樣地操作進行調製，並添加乙酸乙醋，整濃度，而獲得淡黃色透明、且其不揮發成分為㈤重 Ϊ %、黏度為9,50〇mPa · s之加成型聚醋樹脂则之溶液。 •該樹脂则之酸價為。.6mg職/g、祕價為㈣讓&、玻璃轉移溫度為-3(TC、重量平均分子量為Μ，刪。又，在上述配方:’相對於源自二環狀峻化合物㈣之二級經基1莫耳，環狀酯（b)成為約15莫耳之比率。 (合成例46) '、將合成例44之步驟（η中新 Λ )中所用之二環狀醚化合物（a-2) 變更成1，4-雙{[(3-乙基_3_氧雜乳丁基）曱氧基]曱基}苯： 67Θ份及雙驗A 一環氧丙基_ : 13 ^ 1385份，且在步驟（2)中使用所得之主鏈用聚酯樹脂玄、、存 1 j/合/夜（不揮發成分為60.0重量 319793 131 200838965 %)224份’除此以外與合成例44同樣地操作進行調製，添加乙酸乙醋調整濃度，而獲得淡黃色透明、且其不揮發成[Polymerization tank] Adipic acid (a_l) 438 parts of isophthalic acid (a-1) 332 parts of ethyl acetate 135 parts of benzene 135 parts [Drip device] Double-awaiting A-% gas propyl mystery (a-2) 1995 Part of tetrabutylammonium tetrahydroborate (catalyst) 5.5 parts of ethyl acetate 135 parts of benzene 135 parts 319793 128 200838965 After the air in the crucible is replaced by nitrogen, the mixture of diacids is added... Next, in which the dicyclic ether compound mixture is consumed by dropping the device, and the mixture is dropped at a constant rate. After stirring, 5.5 parts of the catalyst is added every 8 hours, and after a total of 2 times, It is subjected to a total of 24 hours of reaction, ripening, and then (10) 7 parts of ethyl acetate is added and cooled to room temperature, and the mixture of gram and 靡, 獾p + Μ 夂获 should be obtained as a polyester resin (Β) solution for the main chain. It is light yellow and transparent, and its non-volatile content is 60.5 wt•%, viscosity is 2〇, _mPa·s, and the acid value of the resin (β) contained in the solution is 〇.5mgK〇H/g, M base price. It is 155 mg K (10) g, the glass transition temperature is 6 〇 ° C, and the weight average molecular weight is 5 〇, 〇〇〇. <Step (2) Open-loop addition reaction of vinegar (b)> A polymerization reaction apparatus equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube in a polymerization tank, and the following ratios in the polymerization tank and the dropping device, respectively The main chain obtained by the step (1) is a polyester resin _ (B) solution, a cyclic ester (8), a catalyst, and an organic solvent. [Polymerization tank] Polyester resin (B) solution 219 parts Ethyl acetate 3 3 parts [Dropping device] ε-caprolactone (b) 114 parts of tetrabutylammonium tetrahydroborate (catalyst) 1 part of 3 parts of ethyl acetate vinegar 66 parts of the air in the polymerization tank was replaced with nitrogen, and the resin solution was stirred while stirring 319,793 129 200838965 While raising the temperature to 10 (rc. Secondly, the mixture of the cyclic ester (b) was dropped at a constant rate by dropping the device for one hour, and then reacted for 12 hours while stirring, and then cooked. A solution of the addition-formed polyester precursor (c丨) was prepared by adding 66 parts of ethyl acetate and heating to the temperature to complete the reaction. The solution was light yellow transparent and had a nonvolatile content of 6.2% by weight. , the viscosity is 15,000mPa·s 'the addition of poly-forming The precursor (ci) has an acid value of 0.05 mg KOH/g, a hydroxyl group value of 74 mg K〇H/g, a glass transition temperature of, a weight average molecule (tetra) 15 G, _. Further, in the above formulation, relative to the dicyclic ether derived from The secondary hydroxyl group of the compound (a_2) is 1 mol, and the cyclic ester (b) is a ratio of about 1.8 mol. <Step (3): blocking reaction by the isocyanate compound (c3)> Prepared in the polymerization tank A polymerization reaction device equipped with a mixer, a thermometer, a reflux cooler, a dropping device, and a nitrogen guiding tube, and the addition polymerization precursor (C1) obtained in the step (7) is added to the polymerization tank and the dropping device at the following ratios respectively. a solution, an isocyanate compound (c3), a catalyst, and an organic solvent. 200 parts of modified polyester precursor (C1) solution [dropping device] phenylacetic acid isocyanate (c3) tetrabutylammonium tetrahydroborate (catalyst) ethyl acetate heated the air in the polymerization tank to 100 ° with nitrogen C. Next, after disposing 21 parts of 5 parts, the mixture of isocyanic acid 319793 130 200838965 hydrazine compound was dropped for 1 hour at a constant rate by a dropping device while stirring the solution. Further, the mixture was stirred for 8 hours, and aged, and then 8 parts of ethyl acetate subcooling portion was added to room temperature to obtain a solution of the addition-molded polyester resin (D1). The solution is light yellow transparent, and its nonvolatile content is 6〇·4% by weight, viscosity is 19, 〇〇〇mPa.s, and the acid value of the resin (D1) is 〇〇5 post KOH/g, and the hydroxyl value is It is 5 mg K〇fI/g, the glass transition temperature is -(7), and the weight average molecular weight is 170,000. (Synthesis Example 45) • The dibasic acid (five) used in the step (1) of Synthesis Example 44 was changed to /, 酞I. 830, and the dicyclic ether compound (heart 2) was changed to neopentyl glycol bicyclic. The oxypropyl group was prepared in the same manner as in Synthesis Example 44 except that the oxypropyl group was used in the same manner as in Synthesis Example 44 except that the obtained polyester resin (8) solution (60.2% by weight of a nonvolatile component) was used in the step (2). And adding ethyl acetate to the whole concentration, and obtaining a solution which is light yellow transparent and whose non-volatile content is (5) heavy Ϊ %, viscosity is 9,50 〇 mPa · s, and the formed polyacetal resin is obtained. • The resin has an acid value of . .6mg job / g, the secret price is (four) let &, glass transfer temperature is -3 (TC, weight average molecular weight is Μ, delete. Also, in the above formula: 'relative to the two ring derived from the compound (four) The mercapto group 1 mol, the cyclic ester (b) is a ratio of about 15 mol. (Synthesis Example 46) ', the dicyclic ether compound used in the step of Synthesis Example 44 (n=in the new oxime) (a -2) Change to 1,4-double {[(3-ethyl_3_oxalactobutyl) decyloxy] fluorenyl} benzene: 67 Θ and double-test A-epoxypropyl _ : 13 ^ 1385 parts, and in the step (2), the obtained polyester resin for the main chain is used, and 1 j/h/night (nonvolatile content is 60.0 weight 319793 131 200838965%) 224 parts' is used in addition to the synthesis example. 44, the same operation was carried out, and the concentration of acetic acid was added to adjust the concentration to obtain a pale yellow transparent, and it was not volatilized.

分為59·9重量％、黏唐兔q nnn D 里功戾為9,00〇mPa· s之加成型聚酯樹脂 (D1)之溶液。該樹脂（D1)之酸價為〇 5mgK〇H/g、羥基價為 12.5mgKOH/g、玻璃轉移溫度為—4〇。〇、重量平子量為68,000。又，在上述配方中，相對於源自二環狀趟化: 物（a-2)之二級羥基1莫耳，環狀酯(b)成為約莫耳之比率。 (合成例47) ! ▲將合成例44之步驟⑴中所用之二環_化合物（ k更成雙紛苐一壞氧丙基越（大阪瓦斯化學股份公司制之刪G’別名為9,9-雙[4_(環氧丙氧基）苯基]*第，:子量·· 462.5，環氧價：3.89(eq/Kg)) : 32〇3份，且在步驟⑺ 中使用所狀线Μ崎脂（B)料（㈣發成分為6〇〇重量仰B份，除此以外與合成例料同樣地操作進行調製，添加乙酸乙酉旨調整濃度，而獲得淡黃色透明、且其不揮發成分為59.8重量％、黏度為!9,5〇〇mpa . s之加成型聚醋樹脂(D1)之溶液。該樹脂（D丨）之酸價為丨.5够〇阶、經基償為12mgKOH/g、玻璃轉移温度為—2〇它、重量平均= 子量為_，_。又，在上述配方中，相對於源：二環：鍵化合物（a-2)之二級經基】莫耳，環狀酉旨⑻成為約13莫耳之比率。 (合成例48) 將合成例44之步驟（2)中所用之環狀醋⑻化合物變更 319793 132 200838965 ί:=:1〇°份’且在步驟⑺中使用所得之加 60.0 ^〇/o)200 #^,b 曲…/例44同樣地操作進行調製，添加乙酸乙酯調整痕度，、而獲得淡黃色透明、且其不揮發成分為㈤重量％、 :度為9’50〇mpa . s之加成型聚酯樹脂⑼)之溶液。該樹脂(D1)之酸價為L8mgK⑽g、經基價為125啦嘴、玻璃轉移溫度為-抓、重量平均分子量為ιΐ5，_。又，在上述配方中’相對於源自二環狀㈣化合物㈣)之二級經基1莫耳，環狀酯（b)成為約16莫耳之比率。 (合成例49) 將合成例44之步驟⑺中所用之異氰酸醋化合物(c3) 變更成對-曱苯石黃酸基異氰酸酉旨（咖1):36份，除此以外與口成例44同木；^地刼作進行調製，添加乙酸乙酯調整濃度，而獲得淡黃色透明、且其不揮發成分為6〇 3重量％、黏度為13,500mPa· s之加成型聚酯樹脂（D1)之溶液。該樹脂（Di) 為 1.2mgK0H/gm價為 15 4mgK〇H/g、玻璃轉移溫度為H、重量平均分子量為165，_。又，在上述配方中’相對於源自二環狀醚化合物（a_2)之二級羥基1 莫耳，環狀酯（b)成為約18莫耳之比率。 [以擬似二階段型製造方法製造加成型聚酉旨樹脂(D1)] (合成例50) <步驟（4)(5):加成型聚酯前驅物（C1)之生成〉準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裴置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝 133 319793 200838965 置中分別以下述比率加入二元酸（aq) 、二環狀醚化合物 (a-2)、環狀酯（b)、觸媒、以及有機溶劑。 [聚合槽] 己二酸（a-l) 73份癸二酸（a-l) 404份雙酚F二環氧丙基醚（a_2) 875份雙龄A系苯氧基樹脂（a-2) 1950 份 (曰本環氧樹月旨公司製，商品名「jERl256」，環氧丙基當量7800g/eq，Mw為51000) 四氫硼酸四丁基銨（觸媒） 6·6份乙酸乙酯 210份曱苯 210份 [滴下裝置] 四氫硼酸四丁基銨（觸媒） 6.6* 份 ε -己内酯（b) 800份乙酸乙酯 210份甲苯 210份將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物— 邊升溫至100 °c。再使其反應8小時，而獲得酸價為 5mgKOH/g以下之主鏈（1，）用聚酯樹脂。其次，藉由滴下裝置而將環狀酯(b)混合物耗費、小時以等速滴下。滴下完畢後，一邊擾拌一邊於8.小時後添加四氫硼酸四丁基銨6.6份，並再使其進行8小時之反應、 #成’然後添加140Ό份乙酸乙酯並冷卻至室溫，結束反 319793 134 200838965 應，而獲得加成型聚酯前驅物（C1)。决此溶液係淡黃色透明、且其不揮發成分59.8重量％、黏度30,〇〇〇mPa.s，上述前驅物（C1)係酸價⑽邮⑽^ 羥基彳貝92mgKOH/g、玻璃轉移溫度_15。〇、重量平均分子量200,〇〇〇之樹脂。又，在上述配方中，相對於源自二環狀驗化合物（a_2)之二級經基！莫耳，環狀醋⑻成為約〇 ι 莫耳之比率。 v驟（6) ·猎由異氧酸酯化合物（^)而進行之封閉反應> 鲁帛備於聚合槽附有擾拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟（5)所得之加成型聚酯前驅物（ci)溶液（不揮發成分59·8重量％)、異氰酸酯化合物 (c3)、觸媒、以及有機溶劑。 [聚/合槽] / 加成型聚酯前驅物（C1)溶液 200份 •[滴下裝置] 異氰酸環己酯（c3) 23份四氫硼酸四丁基銨（觸媒） 6·6份乙酸乙酯 10份將聚合槽内之空氣以氮氣置換後，一邊攪拌槽内溶液一邊升溫至100它。其次，於其中，藉由滴下裝置而將異氰酸酯北合物之混合物耗費1小時以等速滴下。滴下完畢後，再一邊攪拌一邊使其進行6小時之反應、熟成，然後添加4份乙酸乙酯並冷卻至室溫，而獲得加成型聚酯樹脂 135 319793 200838965 (D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇·2重量 %、黏度為36,0〇〇mpa · s，該樹脂（1)1)之酸價為1〇邮 KOH/g、羥基價為8.2mgKOH/g、玻璃轉移溫度為〜15。〇、重量平均分子量為225,000。 [以二階段型製造方法製造加成型聚酯樹脂（D1)] (合成例51) 準備於聚合槽附有攪拌機、溫度計、回流冷卻器及氮入管的聚合反應裝置，並在聚合槽中分別以下述比率加入二元酸（a-Ι)、二環狀醚化合物（a_2)、環狀酯（b)、觸媒、以及有機溶劑。 [聚合槽] 己一酸（a-1) 159份兴酜酸（a-Ι) - 120份 :又齡A —私氧丙基鍵（a-2) 721份 871份 200份 200份 ε -己内酯(b) 乙酸乙酯曱苯 <步驟（7):加成型聚酯前驅物（C1)之生成〉將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物一邊升溫至loot:，添加四氫硼酸四丁基銨2 0份以起始反應。一邊攪拌混合物，一邊每隔8小時添加一次四氫硼酸四丁基銨2·0份，共添加2次，進行合計24小時之反應及熟成’而獲得加成型聚酯前驅物（C1)溶液。 319793 136 200838965 <步驟（8) ·藉由異氰酸酷化合物（C3)而進行之封閉反應〉在前述加成型聚酯前驅物（C1)溶液中，添加乙酸乙酯：600份、作為異氰酸酯化合物（C3)之異氰酸酯：2〇〇份，使其熟成6小時。然後，添加乙酸乙酯38〇份並冷卻至室溫，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為6〇·5重量 %、黏度為16,000mpa.s，該樹脂（D1)之酸價為〇5mg KOH/g、羥基價為5.8mgKOH/g、玻璃轉移溫度為—丨代、 ♦重量平均分子量為16G，_。又’在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基〗莫耳，環狀酯（成為約1.8莫耳之比率。曰 (合成例52) 將合成例51所使用之觸媒變更成溴化四丁基銨，除赴之外與合成例51同樣地操作·進行調製，並添加乙酸乙醋铸整濃度，而獲得淡黃色透明、且其不揮發成分為6〇3重量月曰之酉文價為0.6mgK〇H/g、經基價為9 、移溫度為-驚、重量平均分子量…^ ，配方中，相躲源自二環_化合物㈣之二級窥基】吴耳，環狀酯（b)成為約；[.8莫耳之比率。 (合成例53) 、分別將合成例51之步驟⑺中所用之二元酸成丁二酸：322份、验-與山 J又文孚一衣狀醚化合物（a-2)變更成新戊二衣氧丙基鍵：678份、將環狀酯⑻變更成ε -己内醋： 319793 137 200838965 143份、將觸媒變更成硝酿、， ^ -四丁基叙、並將步驟(8)中所用之兴氰酸酯化合物（c 3)鬱p 士 s〆 1 )又更成異氰酸丁酯·· 113份，除此以曲兵5成例51同樣地操作進行調製，1添加乙酸乙醋調整浪度，、而獲得淡黃色透明、且其不揮發成分為59.6重量％、黏度為 16,000niPa · s 夕 */?rT 4、λ丨 w 成良聚酯樹脂（D1)之溶液。該樹月日（D1)之酸價為0.3mgK〇H/s、叙：a：抑达1 ο c swn/g、經基價為 i2 5mgK〇H/、玻璃轉移溫度為—35°C、重量平均分子量為85，_。又，在上述配方中，相對於源自二環狀_化合物㈣)之二級經基1莫耳，環狀酯（b)成為約0·2莫耳之比率。 (合成例54) 將合成例51所使用$總上甘@ 用之觸媒鉍更成四丁基鈦酸酯，除此之外與合成例51同樣地操作進行調製，並添加乙酸乙醋調整濃度，而獲得黃色透明、且其不揮發成分為6〇2重量％、黏度為9,谓mPa · s之加成型聚酉旨樹脂（m)之溶液。該樹脂_之酸價為〇.5mgK〇H/g、經基價為26 2mgK〇H/g、 •玻璃轉移溫度為-HTC、重量平均分子量為12〇，_。又，在上述配方中，相對於源自二環狀轉化合物卜2)之二級經基1莫耳，環狀酯（b)成為約18莫耳之比率。 (合成例55) 將合成例51所使用之觸媒變更成氧化二丁基錫，除此之外與合成例51同樣地操作進行調製，並添加乙酸乙酉旨調整濃度’而€得淡黃色半透明、且其不揮發成分為6〇 4重量％、黏度為8,5〇〇mPa.S之加成型聚醋樹月旨_之溶液。該樹脂（D1)之酸價為〇.lmgK〇H/g、_呈基價為412叫 319793 138 200838965 KOH/g、玻璃轉移溫度為—⑺它人重量平均分子量為 πο,οοο。又，在上述配方中，相對於源自二環狀趟化合物 (a-2)之二級羥基丨莫耳，環狀醋（b)成為約18莫耳之比率。 (合成例56) 將合成例51之步驟（7)所用之環狀酯化合物（b)之重量變更成644份，除此之外與合成例51同樣地操作進行調製，並添加乙酸乙酯調整濃度，而獲得淡黃色透明、且^ 不揮發成分為60.3重量％、黏度為12,5〇〇mPa· s之加成^ 籲聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為〇5mgK〇H/g、羥基價為O.OSmgKOH/g、玻璃轉移溫度為—忉它、重量均分子量為185,000。又，在上述配方中，相對於源=二環狀醚化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為: 1.3莫耳之比率。 ''' (合成例57) - 將合成例51之步驟（7)所用之環狀酯化合物卬）之重量書變更成16份，除此之外與合成例η同樣地操作進行調^ 並添加乙酸乙酯調整濃度，而獲得淡黃色透明、且其不^軍务成为為60.7重里％、黏度為8,〇〇〇mPa · s之加成型取酉匕樹脂（D1)之溶液。該樹脂（D1)之酸價為〇 6mgK〇H/g、_大價為58.8mgKOH/g、玻璃轉移溫度為—1(rc、重量平均: 子里為125,000。又’在上述配方中，相對於源自二學狀醚化合物（a-2)之二級羥基1莫耳，環狀酯（b)成為約〇“ 莫耳之比率。 (合成例58) 319793 139 200838965 分別將合成例51之步驟（7)中所用之二元酸（ad)變更成己二酸：102份及異酞酸：66份、將二環狀醚化合物（a_2) 變更成雙齡A二環氧丙基峻：38〇份、將環狀醋⑻變更成卜己内酿：285份、且將反應開始後每8小時追加一次共追加2次之四氫㈣四丁基銨之追加量變更成各0.2份了除此以外與合成例51同樣地操作，進行步驟（7)之於1〇〇 °C進行24小時的反應，就步驟（8)而言，再加入作為異氰酸酉士旨化合物⑽之異氰㈣醋54份與乙酸乙酉旨並使熟成4 小時後，添加乙酸乙酯調整不择發成分之濃度，並冷卻至室溫，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為59 6重量 %、黏度為2,500mPa . s，該樹脂（m)之酸價為79 2mg KOH/g、經基價為2〇.lmgK：〇H/g、玻璃轉移溫度為一 1〇〇c、重量平均分子量為38，_。χ，在上述配方中，相對於源自二環狀_化合物㈣之二⑽基丨莫耳，環㈣旨⑻成為 •約1·1莫耳之比率。 (合成例59) 分別將合成例51之步驟(7)中所用之二元酸變更成己二酸：44份及異酞酸：3 3份、將二環狀醚化合物（a_2) 變更成雙酚A二環氧丙基醚：76〇份、將環狀酯(b)變更成卜己内酯：684份、且不使用觸媒，除此以外與合成例51 同樣地操作’進行步驟⑺之於1〇(rc進行24小時的反應，，步驟（8)而言，再加入作為異氰酸酯化合物（c3)之異氰酸苄酯660份與乙酸乙酯6〇〇份並使熟成4小時後，添加乙 319793 140 200838965 酸乙醋調整不揮發成分夕、、曹诤、，" 平知风刀之/辰度，亚冷卻至室溫，而成型聚酯樹脂（D1)之溶液。 ^ 此反應溶液係淡黃色透明、且其不揮發成分為％量％、黏度為96,〇〇〇mPa . s，兮抖日匕，⑴、 s，該樹脂（Dl)之酸價為 .mg H/g、經基價$ 33 5mgK〇H/g、玻璃轉移溫度為 -8C、、重量平均分子量為22,3〇〇。又，在上述配方中，相對於源自二環狀轉化合物（a_2)之二級經基i莫耳，環狀酯（b)成為約1·3莫耳之比率。 ·(合成例60) 、分別將合成例51之步驟（7)中所用之二元.（a-1)變更成癸二酸：101份、將二環狀醚化合物（a_2)變更成聚乙二醇二環氧丙基醚（環氧乙烷加成莫耳數·· 22) : 661份、將環狀酉曰(b)、又更成ε _己内酯·· M4份，除此以外與合成例5工同樣地操作，進行步驟（7)之24小時的反應I、熟成。然後，就步驟(8)而言，加入作為異氰酸酯化合物（c3)之異氰酸节書酯200份與乙酸乙酯5〇〇份並使進行6小時之熟成後，添加乙酸乙酯調整濃度，並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為60·6重量％、黏度為26,500mPa· s之加成型聚醋樹脂（D1)之溶液。該樹脂(D1)之酸價為〇2mg K〇Ii/g、經基價為H6mgKOH/g、玻璃轉移溫度為—9〇t：、重I平均分子量為310,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基1莫耳，、環狀酯（b) 成為約5莫耳之比率。 (合成例01) 141 319793 200838965 分別將合成例之步驟⑺中所用之二元酸㈣變更成異酜酸.83份、將二環狀鍵化合物（a_2)變更成雙酚a 二環氧丙基醚：380份、將環狀醋（b)變更成^ _己内酯：342 份，除此以外與合成例50同樣地操作，使步驟（巧之反應、熟成進行24小時。然後，就步驟⑻而言，加人作為異氮酸酯化合物（C3)之異氰酸节酯2〇〇份與乙酸乙酯17〇份並使進行6小時之熟成後，添加乙酸乙酯成之濃度，並冷卻至室溫，而獲得淡黃色透明、且其軍= •分為59.4重量％、黏度為，5,5〇〇mPa . s之加成型聚酯樹脂 (D1)之溶液。該樹脂（D1)之酸價為〇 6mgK〇H/g、羥基價為 10.5mgKOH/g、玻璃轉移溫度為3〇。〇、重量平均分子量為 235,000。又，在上述配方中，相對於源自二環狀醚化合物 (a_2)之二級羥基1莫耳，環狀酯（b)成為約^莫耳之比率。 (合成例62) ·· 在合成例51之步驟（7)中不使用環狀酯（b)、且在步驟鲁（8)中將與異氰酸酯化合物〇3) 一起添加之乙酸乙酯之量從 600份變更成200份，除此以外與合成例51同樣地進行調製，添加乙酸乙酯調整不揮發成分之濃度，並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為6〇1重量％、黏度為3,500mPa · s之聚醋樹脂溶液。此溶液所含有之樹脂，其酸價為1.6mgKOH/g、羥基價為22.5nigK〇H/g、玻璃轉移溫度為56°C、重量平均分子量為21，〇〇〇。 (合成例63) 在合成例51之步驟（8)中將乙酸乙酯之量變更成847 319793 142 200838965 份、且不添加異氰酸酯化合物03)、並在添加乙酸乙酯後 4部至至bHL，除此以外與合成例5〗同樣地進行調製，而獲得淡黃色透明、且其不揮發成分為6〇1重量％、黏度為 l^=〇〇mpa · s之聚酯樹脂溶液。此溶液所含有之樹脂，其酉夂f貝為0、7mgK〇H/g、經基價為94mgK〇H/g、玻璃轉移溫 :為15 C、重！平均分子量為ΗΟ,ΟΟΟ。又，在上述配相對於源自二環狀醚化合物（a-2)之二級經基1莫耳，環狀酯（b)成為約h8莫耳之比率。、之外t對合f例44至63所得之各樹脂溶液，將該等溶液破螭轉移：1二成、分巧、樹脂之重量平均分子量(Mw)、例1至20间二g、酸價（AV)以及羥基價（0HV)以與合成 5水之方式評估，彙總顯示於表5。 319793 143 200838965It is a solution of the addition-molded polyester resin (D1) which is divided into 59.9% by weight and viscous rabbit q nnn D with a work weight of 9,00 〇 mPa·s. The acid value of the resin (D1) was mg 5 mg K 〇 H / g, the hydroxyl value was 12.5 mg KOH / g, and the glass transition temperature was -4 Torr. The weight and weight are 68,000. Further, in the above formulation, the cyclic ester (b) is about a molar ratio with respect to the secondary hydroxyl group 1 mol derived from the dicyclic deuterated product (a-2). (Synthesis Example 47) ! ▲ The bicyclic _ compound used in the step (1) of Synthesis Example 44 (k is a double 苐苐坏坏坏 ( ( (Osaka Gas Chemical Co., Ltd. deleted G' alias 9,9 - bis [4_(glycidoxy)phenyl]*,:, sub-quantity · · 462.5, epoxy price: 3.89 (eq/Kg)): 32 〇 3 parts, and the desired line is used in the step (7) The product was prepared in the same manner as in the synthesis example except that the composition of the product was (6), and the composition of the product was (6), and the composition was adjusted in the same manner as in the synthesis example, and the concentration was adjusted to obtain a light yellow transparent color, and it was non-volatile. The composition is a compound solution of the addition of a polyester resin (D1) having a viscosity of 59.8 wt% and a viscosity of 9,9 〇〇mpa. s. The acid value of the resin (D丨) is 丨.5 enough, and the basis is 12 mg KOH / g, glass transition temperature is -2 〇 it, weight average = sub-quantity _, _. Also, in the above formula, relative to the source: bicyclic: bond compound (a-2) secondary base] Mohr, ring-shaped (8) is a ratio of about 13 moles. (Synthesis Example 48) The cyclic vinegar (8) compound used in the step (2) of Synthesis Example 44 is changed 319793 132 200838965 ί:=:1〇° 'And in In step (7), the obtained addition of 60.0 ^ 〇 / o) 200 # ^, b 曲 ... / Example 44 was prepared in the same manner, adding ethyl acetate to adjust the trace, to obtain a light yellow transparent, and its non-volatile content is (5) A solution of the weight-formed %: degree of 9'50 〇mpa.s plus shaped polyester resin (9)). The acid value of the resin (D1) was L8 mgK (10) g, the base price was 125, the glass transition temperature was - scratched, and the weight average molecular weight was ιΐ5, _. Further, in the above formula, the cyclic ester (b) has a ratio of about 16 moles relative to the secondary radical 1 mole derived from the dicyclic (tetra) compound (tetra). (Synthesis Example 49) The isocyanate compound (c3) used in the step (7) of Synthesis Example 44 was changed to p-terbepyric acid isocyanate (cafe 1): 36 parts, and The mouth of the example 44 is the same as the wood; the ground is prepared, and the ethyl acetate is added to adjust the concentration to obtain a modified polyester which is light yellow transparent and has a nonvolatile content of 6〇3 wt% and a viscosity of 13,500 mPa·s. A solution of the resin (D1). The resin (Di) had a valence of 1.2 mg K0H/gm of 15 4 mg K 〇 H/g, a glass transition temperature of H, and a weight average molecular weight of 165, _. Further, in the above formulation, the cyclic ester (b) has a ratio of about 18 moles relative to the secondary hydroxyl group 1 mole derived from the dicyclic ether compound (a_2). [Production of the addition-molding resin (D1) in a pseudo-two-stage manufacturing method] (Synthesis Example 50) <Step (4) (5): Formation of addition-formed polyester precursor (C1)> Preparation in polymerization tank A polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and a dibasic acid (aq) and a dicyclic ether are respectively added in the following ratios in the polymerization tank and the dropping device 133 319793 200838965 Compound (a-2), cyclic ester (b), catalyst, and organic solvent. [Polymerization tank] Adipic acid (al) 73 parts azelaic acid (al) 404 parts bisphenol F diglycidyl ether (a_2) 875 parts of two-year-old A-type phenoxy resin (a-2) 1950 parts (曰本环氧 epoxy resin company, the trade name "jERl256", epoxy propylene equivalent 7800g / eq, Mw is 51000) tetrabutylammonium tetrahydroborate (catalyst) 6 · 6 parts ethyl acetate 210 parts 曱210 parts of benzene [dropping device] tetrabutylammonium tetrahydroborate (catalyst) 6.6* parts ε-caprolactone (b) 800 parts of ethyl acetate 210 parts of toluene 210 parts After the air in the polymerization tank was replaced with nitrogen, While stirring the mixture - warm to 100 °c. Further, the mixture was reacted for 8 hours to obtain a polyester resin for the main chain (1,) having an acid value of 5 mgKOH/g or less. Next, the cyclic ester (b) mixture was dropped at a constant rate by dropping the apparatus at a low cost. After the completion of the dropwise addition, 6.6 parts of tetrabutylammonium tetrahydroborate was added after 8 hours, and the reaction was further carried out for 8 hours, then #1.4', then 140 parts of ethyl acetate was added and cooled to room temperature. End anti-319793 134 200838965 should be obtained, and the addition of polyester precursor (C1). The solution is light yellow transparent, and its non-volatile content is 59.8 wt%, viscosity 30, 〇〇〇mPa.s, the precursor (C1) is acid value (10) post (10) ^ hydroxy mussel 92 mg KOH / g, glass transition temperature _15. 〇, weight average molecular weight 200, 〇〇〇 resin. Further, in the above formulation, it is relative to the secondary base derived from the bicyclic test compound (a_2)! Mohr, ring vinegar (8) becomes the ratio of about ι ι Mo. v (6) · Hunting reaction by isophthalic acid ester compound (^)> Rugao prepared in a polymerization tank with a scrambler, thermometer, reflux cooler, dropping device and nitrogen introduction tube polymerization And adding, in the polymerization tank and the dropping device, the addition polyester precursor (ci) solution obtained in the step (5) (nonvolatile content: 59.8% by weight), isocyanate compound (c3), catalyst And organic solvents. [Poly/glot] / Addition of polyester precursor (C1) solution 200 parts • [Drip device] Cyclohexyl isocyanate (c3) 23 parts Tetrabutylammonium tetrahydroborate (catalyst) 6·6 parts After 10 parts of ethyl acetate was replaced with nitrogen in the polymerization tank, the temperature was raised to 100 while stirring the solution in the tank. Next, in which the mixture of isocyanate bead compounds was consumed by dropping the apparatus for 1 hour to drip at a constant rate. After the completion of the dropwise addition, the mixture was reacted for 6 hours while stirring, and then matured, and then 4 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of the addition-molded polyester resin 135 319793 200838965 (D1). This solution is light yellow transparent, and its nonvolatile content is 6 〇 2 wt%, viscosity is 36,0 〇〇 mPa · s, and the acid value of the resin (1) 1) is 1 〇 KOH / g, hydroxyl The price was 8.2 mgKOH/g, and the glass transition temperature was -15. 〇, weight average molecular weight is 225,000. [Production of Additive Polyester Resin (D1) by Two-Step Manufacturing Method] (Synthesis Example 51) A polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube in a polymerization tank, and the following in the polymerization tank The ratio is added to a dibasic acid (a-fluorene), a dicyclic ether compound (a_2), a cyclic ester (b), a catalyst, and an organic solvent. [Polymerization tank] Hexanoic acid (a-1) 159 parts of decanoic acid (a-Ι) - 120 parts: Aging A - oxypropyl bond (a-2) 721 parts 871 parts 200 parts 200 parts ε - Caprolactone (b) ethyl acetate hydrazine <Step (7): Formation of addition-formed polyester precursor (C1)> After the air in the polymerization tank is replaced with nitrogen, the mixture is heated to a loot: while stirring the mixture. 20 parts of tetrabutylammonium tetrahydroborate was added to initiate the reaction. While the mixture was stirred, 2·0 parts of tetrabutylammonium tetrahydroborate was added every 8 hours, and the mixture was added twice, and a total of 24 hours of reaction and ripening was carried out to obtain a solution of the addition-formed polyester precursor (C1). 319793 136 200838965 <Step (8) · Blocking reaction by isocyanic acid compound (C3)> In the above-mentioned addition polyester precursor (C1) solution, ethyl acetate: 600 parts is added as isocyanate The isocyanate of the compound (C3): 2 parts, which was aged for 6 hours. Then, 38 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of the addition-molded polyester resin (D1). The solution is light yellow and transparent, and has a nonvolatile content of 6 〇 5% by weight and a viscosity of 16,000 mPa.s. The acid value of the resin (D1) is mg5 mg KOH/g, and the hydroxyl value is 5.8 mg KOH/g. The glass transition temperature is - deuterated, ♦ weight average molecular weight is 16G, _. Further, in the above formulation, the cyclic ester (which is a ratio of about 1.8 moles) relative to the secondary hydroxyl group derived from the dicyclic ether compound (a_2). 曰 (Synthesis Example 52) Synthesis Example 51 The catalyst used was changed to tetrabutylammonium bromide, and the same procedure as in Synthesis Example 51 was carried out, and preparation was carried out, and the concentration of ethyl acetate was added to obtain a pale yellow transparent material, and the nonvolatile content was 6 〇3 weight 曰曰酉 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6窥基] Wu Er, cyclic ester (b) becomes about; [.8 molar ratio. (Synthesis Example 53), the dibasic acid used in the step (7) of Synthesis Example 51 is separately formed into dicetic acid: 322 parts , test - and mountain J and Wenfu a flavonoid compound (a-2) changed to a neopentyl oxypropyl bond: 678 parts, the cyclic ester (8) was changed to ε - caprolactone: 319793 137 200838965 143 And change the catalyst to nitrate, ^-tetrabutyl, and use the cyanate compound (c 3) used in step (8) to become more different. 113 parts of butyl acrylate, and the same operation was carried out in the same manner as in Example 51 of the squad, and the viscosity was adjusted by adding ethyl acetate to obtain a pale yellow transparent, and the nonvolatile content was 59.6% by weight. It is a solution of 16,000 niPa·s s*/?rT 4, λ丨w into a polyester resin (D1). The acid value of the tree date (D1) is 0.3 mg K 〇 H / s, a: a: inhibited 1 ο c swn / g, the base price is i2 5 mg K 〇 H /, the glass transition temperature is -35 ° C, The weight average molecular weight is 85, _. Further, in the above formulation, the cyclic ester (b) has a ratio of about 0.2 mol with respect to the secondary radical 1 mol derived from the bicyclic compound (tetra). (Synthesis Example 54) The same procedure as in Synthesis Example 51 was carried out except that the total amount of the catalyst used in Synthesis Example 51 was changed to tetrabutyl titanate, and adjustment was carried out by adding ethyl acetate. At the concentration, a solution which is transparent to yellow, has a nonvolatile content of 6.2% by weight, and has a viscosity of 9, which is mPa·s, is added to the resin (m). The acid value of the resin was 〇. 5 mg K 〇 H / g, the base price was 26 2 mg K 〇 H / g, • the glass transition temperature was -HTC, and the weight average molecular weight was 12 〇, _. Further, in the above formulation, the cyclic ester (b) has a ratio of about 18 moles with respect to the secondary radical 1 mole derived from the bicyclic compound 2). (Synthesis Example 55) The same procedure as in Synthesis Example 51 was carried out except that the catalyst used in Synthesis Example 51 was changed to dibutyltin oxide, and acetic acid was added to adjust the concentration ', and pale yellow translucent was obtained. The solution has a non-volatile content of 6.4% by weight and a viscosity of 8,5 〇〇mPa.S. The acid value of the resin (D1) is 〇.lmgK〇H/g, the base price is 412 is 319793 138 200838965 KOH/g, and the glass transition temperature is - (7) its weight average molecular weight is πο, οοο. Further, in the above formulation, the cyclic vinegar (b) has a ratio of about 18 moles with respect to the secondary hydroxy oxime derived from the dicyclic guanidine compound (a-2). (Synthesis Example 56) The same procedure as in Synthesis Example 51 was carried out except that the weight of the cyclic ester compound (b) used in the step (7) of the synthesis example 51 was changed to 644 parts, and ethyl acetate was added thereto. At the concentration, a solution of a polyester resin (D1) which was light yellow transparent and had a nonvolatile content of 60.3 wt% and a viscosity of 12,5 〇〇 mPa·s was obtained. The resin (D1) had an acid value of mg5 mgK〇H/g, a hydroxyl group value of O.OSmgKOH/g, a glass transition temperature of 忉, and a weight average molecular weight of 185,000. Further, in the above formulation, the cyclic ester (b) was a ratio of 1.3 mol with respect to the secondary hydroxy oxime of the source = dicyclic ether compound (a-2). ''' (Synthesis Example 57) - The same procedure as in the synthesis example η was carried out except that the weight of the cyclic ester compound 卬) used in the step (7) of Synthesis Example 51 was changed to 16 parts. Ethyl acetate was adjusted to a concentration to obtain a pale yellow transparent, and it was not treated as a solution of 60.7 wt%, a viscosity of 8, and 〇〇〇mPa·s was added to the resin (D1). The resin (D1) has an acid value of 〇6 mg K〇H/g, a large price of 58.8 mgKOH/g, and a glass transition temperature of -1 (rc, weight average: 125,000 in the sub-ratio. The secondary hydroxyl group 1 mol derived from the di-ether ether compound (a-2), and the cyclic ester (b) is a ratio of about 〇 "mole. (Synthetic Example 58) 319793 139 200838965 The dibasic acid (ad) used in the step (7) is changed to adipic acid: 102 parts and isodecanoic acid: 66 parts, and the dicyclic ether compound (a_2) is changed to a double-aged A diepoxypropyl group: 38 parts, the ring vinegar (8) was changed to 285 parts, and the additional amount of tetrahydrotetrakis(tetra)ammonium added to the total of 2 times was added to each 0.2 parts after the start of the reaction. Otherwise, in the same manner as in Synthesis Example 51, the reaction of the step (7) at 1 ° C for 24 hours was carried out, and in the case of the step (8), the addition of the compound (10) as the isocyanate was further added. After cyanide (iv) vinegar 54 parts and ethyl acetate were prepared and allowed to mature for 4 hours, ethyl acetate was added to adjust the concentration of the unselected components, and cooled to room temperature to obtain addition polymerization. a solution of the ester resin (D1). The solution is light yellow transparent and has a nonvolatile content of 596% by weight and a viscosity of 2,500 mPa.s. The acid value of the resin (m) is 79 2 mg KOH/g. The price is 2〇.lmgK: 〇H/g, the glass transition temperature is 1〇〇c, and the weight average molecular weight is 38, χ. χ, in the above formula, relative to the second ring derived from the compound _ compound (4) (10) Based on the molars, the ring (4) is (8) is a ratio of about 1·1 mole. (Synthesis Example 59) The dibasic acid used in the step (7) of Synthesis Example 51 is changed to adipic acid: 44 parts and Isophthalic acid: 33 parts, the dicyclic ether compound (a_2) was changed to bisphenol A diglycidyl ether: 76 parts, and the cyclic ester (b) was changed to 848 parts of bisperactone. In the same manner as in Synthesis Example 51 except that the catalyst was not used, the operation of the step (7) was carried out in 1 (the reaction was carried out for 24 hours in rc, and the addition of the isocyanate compound (c3) in the step (8). After 660 parts of benzyl cyanate and 6 parts of ethyl acetate and allowed to mature for 4 hours, add 319793 140 200838965 acid vinegar to adjust non-volatile components, 诤, Cao,, " Know the wind knife / Chen degree, sub-cooling to room temperature, and forming a solution of polyester resin (D1). ^ This reaction solution is light yellow transparent, and its non-volatile content is %%, viscosity is 96, 〇〇〇mPa. s, trembling sundial, (1), s, the acid value of the resin (Dl) is .mg H/g, the base price is $33 5mgK〇H/g, the glass transition temperature is -8C, and the weight average The molecular weight is 22, 3 Torr. Further, in the above formulation, the cyclic ester (b) becomes about 1.3 mol with respect to the secondary mercapto group derived from the bicyclic compound (a_2). ratio. (Synthesis Example 60) The binary (a-1) used in the step (7) of Synthesis Example 51 was changed to azelaic acid: 101 parts, and the dicyclic ether compound (a_2) was changed to polyethylene. Diol diglycidyl ether (ethylene oxide addition mole number · 22): 661 parts, ring 酉曰 (b), and further ε _ caprolactone · · M4 parts, in addition to this The reaction was carried out in the same manner as in the synthesis example 5 except that the reaction I and the ripening were carried out for 24 hours in the step (7). Then, in the step (8), 200 parts of isocyanate ester as the isocyanate compound (c3) and 5 parts of ethyl acetate were added thereto, and the mixture was aged for 6 hours, and then ethyl acetate was added to adjust the concentration. The mixture was cooled to room temperature to obtain a solution of the addition-formed polyester resin (D1) which was light yellow and transparent, and had a nonvolatile content of 60.6% by weight and a viscosity of 26,500 mPa·s. The acid value of the resin (D1) was 〇2 mg K〇Ii/g, the base price was H6 mgKOH/g, the glass transition temperature was -9 〇t:, and the weight I average molecular weight was 310,000. Further, in the above formulation, the cyclic ester (b) is a ratio of about 5 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a-2). (Synthesis Example 01) 141 319793 200838965 The dibasic acid (tetra) used in the step (7) of the synthesis example was changed to 83 parts of isodecanoic acid, and the dicyclic bond compound (a_2) was changed to bisphenol a diepoxypropyl group. The procedure was carried out in the same manner as in Synthesis Example 50 except that the ether was changed to 380 parts, and the cyclic vinegar (b) was changed to _caprolactone: 342 parts. The reaction was carried out for 24 hours. (8) Addition of human isocyanate compound (C3) 2 parts of isocyanate ester and ethyl acetate 17 parts, and after 6 hours of aging, ethyl acetate is added to a concentration, and Cooled to room temperature to obtain a solution of the addition-molded polyester resin (D1) which is light yellow transparent and has a weight of 59.4% by weight and a viscosity of 5,5〇〇mPa.s. The acid value is 〇6 mg K〇H/g, the hydroxyl value is 10.5 mgKOH/g, the glass transition temperature is 3 〇, and the weight average molecular weight is 235,000. Further, in the above formulation, relative to the dicyclic ether compound The secondary hydroxyl group of (a_2) is 1 mol, and the cyclic ester (b) is a ratio of about 2 mol. (Synthesis Example 62) ·· In the step of Synthesis Example 51 The cyclic ester (b) is not used in the step (7), and the amount of ethyl acetate added together with the isocyanate compound 〇3) is changed from 600 parts to 200 parts in the step (8), and the synthesis is carried out. Example 51 was prepared in the same manner, and ethyl acetate was added to adjust the concentration of the nonvolatile matter, and cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 6.1% by weight and a viscosity of 3,500 mPa·s. Vinegar resin solution. The resin contained in this solution had an acid value of 1.6 mgKOH/g, a hydroxyl value of 22.5 nig K〇H/g, a glass transition temperature of 56 ° C, and a weight average molecular weight of 21, 〇〇〇. (Synthesis Example 63) In the step (8) of Synthesis Example 51, the amount of ethyl acetate was changed to 847 319793 142 200838965 parts, and the isocyanate compound 03) was not added, and after adding ethyl acetate, 4 parts to bHL, Otherwise, it was prepared in the same manner as in Synthesis Example 5 to obtain a polyester resin solution which was light yellow transparent and had a nonvolatile content of 6.1% by weight and a viscosity of l^=〇〇mpa·s. The resin contained in this solution has a 酉夂f shell of 0, 7 mg K 〇 H / g, a base price of 94 mg K 〇 H / g, a glass transfer temperature: 15 C, heavy! The average molecular weight is ΗΟ, ΟΟΟ. Further, in the above-mentioned formula, the cyclic ester (b) has a ratio of about h8 mol with respect to the secondary radical 1 mol derived from the dicyclic ether compound (a-2). And t to the respective resin solutions obtained in the examples 44 to 63, the solutions are broken and transferred: 1%, fractional, weight average molecular weight (Mw) of the resin, 1 to 20 g, acid The valence (AV) and the hydroxyl value (0 HV) were evaluated in the same manner as in the synthesis of 5 water, and are collectively shown in Table 5. 319793 143 200838965

[表5]加成型聚酯樹脂（D1)之合成例：使用異氰酸酯化合物 (c3)作為封閉化合物（C)時之情形 X 0 \ X 〇 1 s JJ in ir> Csf CM λ csi Mi IO s— s N 00 00 u> 60 e> Ift c4 CM s ca η §| 2 in 5 to s> CD lf> in O ID e4 rsi s u> 〇 d g d J § ID ΙΩ 00 CNI J PI 〇 2 o o o o 5 ΙΟ <E> o CM 〇> 卜 s! 〇 QP V-» s 0 1 o § § t S o ? r to '•JP IO o o：丁 s o 丁〇丁 ο 丁 0 1 〇 o s t S ir> 1 0 1 IO § g 产 o § o' 〇 δ IO 00 〇 8 t Ο s g 严 Ϊ IO § n CD I g i s C4 § §· § u> § s Ϊ o Ϊ s § 严 I I CO I rj CM 1 I 〇 1 i § « > ? β Ql E I o o I s I 5 g in oeT ί 〇» I ΙΟ m o in oT a s ri 1 s o § 1 9 o s a> I 8 u> a» 8 » «Γ I 1 i in 1 s I U> s I to IO ▼— I in ci | £ tt> s s s 5 CO 9k S m s csi s « o m s csl s to CD CO s «» s i s 卜 ο <D s CD s Φ s of in i I 姨 s m & m m s ffi « m 箱 5 m φ « 眾 5 IS « « 崁 S 癩 «] « 薄 5 K ¢3 K fk s IB « 裹 w m & « m 9 m 氣 f$S w m «3 K m m m & K m 酱 fS Φ m m 梅珀 m m m «1 « 梅 «3 K m R 餌 K 嵌 s 1β «3 « 琪 s IS «3 K 热 9 m m m M S ΙΘ 珀 K 系 _ tt 獎率避辕 W < DQ CD < m m H m h- < m m 芝 H m < m is 各 < m < CD < m I m I m K ο Μ g 5 φ 5 e 1 1 i ffi ED A | 2 a 〇 r- e» iq eq r> 2 2 g flO CD csl ec» ea r> § :· CO T- ID T- c*> o 严 CD X 0 r» r* T- ^r- T- f • r· r- r— 产 t— ♦δ $齋 S Oi s 卜 σ> « 卜 IO m o 〇 : o : CO ico IO » 姦 CD % l $ s CD IO s S s s s S S g S s p s ID IO S s €0 s CD 矣# CT? S命 /-N CO \ \ o 0 1 〇 ϋ z £ O 0 1 o o Z έ o o z έ v> 1 o 0 1 o 1 1 o 0 1 0 1 iS 8 1 ο ο 1 o o Έ 0 B z iS 〇 o z £ o o ? ffi o O οι 8 m o o 0 1 〇 ¥ m Μ 丟 2 1 d > «〇 d U> o y (U ί u> a \w/ 避 m 絜 Μ i I& ¥ LU Jc ¥ iS £ ά a ω 1& f □L m ifr ifr K 1 、 iS Jc 2 i 、 I& Jc ¥ I& iS ¥ iS ώ 窆 1& iff Jc I& Jc ¥ I& Jc Ψ I& Jc I& Jc ¥ iS σ UJ I& ¢( iS* Jc Ψ I& I < CL i < a. 5 5 < 1 < ：& ί 1 < CL 1 i< !〇. I !5 | t l < I < 1 < ί i ί 1 < I 1 1 t 1 I Ϊ < 5 φ ξ & S < 1 噠鎵 Φν i 3 s iS s i^N :二 1 s δ r> IS 丨 § s tB ym^ s s s § s s » δ $ X D s 00 >< B〇 >< CO 泛 00 g p 要 s s IO CO IO s Ια ΙΟ o LO 5 CD in » in I T— CD e3 CD CO 餵蚪翹碱畹：ouMqd ^^^fr-^OM::ss3a ff^hqqf^: ousPQa 餵齧^硪卜0:131 鎳-fhs^'赏：MVSl 綠補hsqT^:占 vffll 鑛砩卜 0^f^s : gvml 遛h盔碱蜱：ouMtla 餵私翹碱畹：OQNZPQ 迦 srofi^^畹：oaMHu 餵盔緘畹砩：IS1PH 餵蚪齧臧畹：ooM-qp-l i v-心：ΊΛΡ 遛 sto-cod ω (s :碱：t^^^^o^ti)富補^r^fiM 螽 40龄： f砩vr^liu 歡 4^^: dpq-odM f_ «碱鲦-^械鍪^澈^--^寸-^卜？^-:^£:0(3-^81 當^肊碱鲦“滩翕粼：da-PHPHPQ 蚪{砩&-.【^碱‘(^卜酴難碱-7砩0^)】}^_气1:1:^03 t^^^fiMd;螽制：dalj 制 t4vr^fiH V 螽鹌：d3-v^ 06IWO §ρίΛ : 06IMO 毽銮畹：VdI 盔"你：vqs WIMVO: VPV 餾4卜：ν口s 144 319793 200838965 (比較例13) H)0重量份中添主鍵用來酉曰樹脂⑻溶液甲茉-昱二缺本伤，更進一步，添加丁DI/TMP(伸甲本，、魏酿之三羥甲基丙烷加成物)2 子細授摔’而獲得接膜上以獲得接著薄片，但因接著劑組成物々又心、k上升，故無法進行塗佈。 (比較例14) 〜=用S成例44之步驟（2)所得之加成型聚醋前驅物(c ι) 〉谷液替代主鏈用聚醋樹脂⑻溶液，除此之外與比較例π 知同樣操作，而獲得接著齡成物。^，與比較例ΐ3 :樣，，因接著劑組成物之黏度急速上升，故無法塗佈於剝離薄膜上。 (實施例44) . 、在合成例44之步驟（3)所得之加成型聚酯樹脂（1)1；)溶液1 〇〇重買份中添加甲苯50份，更進一步，添加Tm/TMp (伸甲苯二異氰酸酯之三羥曱基丙烷加成物）25重量份作為交聯劑（E )，仔細攪拌，而獲得本發明之接著劑組成物。使用該接著劑組成物，以與實施例1至19同樣之方式作’獲得「剝離薄膜/接著劑層/ TAc薄膜/ pvA/ TAC薄膜」之構成之積層體，並進行接著劑層之反應，而製得經接著加工之偏光板（積層體）。 (貫施例45至49) 分別將使用之加成型聚酯樹脂（D1)溶液變更成實施例 145 319793 200838965 45至49所得之加成型聚醋樹脂（m)溶液，除此之外盘實施^4進行同樣操作，而製成經接著加工之偏光板。、 (比較例15) 、、六、、广，用口成例5〇之步驟（5)所得之加成型聚酯前驅物（C1) Ο)曰代合成命J 44之步驟⑺所得之加成型聚醋樹脂（D1) 合液除此之外與霄施例44進行同樣操作，而獲得接著劑 :广然而，與比較例13同樣地，因接著劑、_ 度心速上升，故無法塗佈於剝離薄膜上。 _ (實施例50) …使用合成例50之步驟⑹所得之加成型聚醋樹脂_ =液替代合成例44之步驟（3)所得之加成型聚酯樹脂（di) /合液除此之外與貫施例44進行同樣操作，而調製接著劑組成物，並製成經接著加工之偏光板。 (實施例51) - 讀* 使用合成例51所得之加成型聚酯樹脂（D1)溶液替代 §合成例50所得之加成型聚酯樹脂（Dυ溶液，除此之外與實 f例44進行同樣操作，而調製接著劑組成物，並製成經ς 著加工之偏光板。工 (比較例16) 使用合成例62所得之樹脂溶液替代合成例51所得之加成型聚酯樹脂（D1)溶液，除此之外與實施例5丨.進行同樣操作，而獲得接著劑組成物。雖然其係可塗佈於剝離薄= 上，但由於接著劑層不具有黏著性（初期接著性），故盔法以「TAC薄膜/ PVA/ TAC薄膜」之構成來積層於接著劑層。 319793 146 200838965 (比較例17)[Table 5] Synthesis Example of Addition Polyester Resin (D1): When Isocyanate Compound (c3) Is Used as Blocking Compound (C) X 0 \ X 〇1 s JJ in ir > Csf CM λ csi Mi IO s - s N 00 00 u> 60 e> Ift c4 CM s ca η §| 2 in 5 to s> CD lf> in O ID e4 rsi s u> 〇dgd J § ID ΙΩ 00 CNI J PI 〇2 oooo 5 ΙΟ &lt ;E> o CM 〇> 卜s! 〇QP V-» s 0 1 o § § t S o ? r to '•JP IO oo: Ding so Ding ding ding Ding 0 1 〇ost S ir> 1 0 1 IO § g production o § o' 〇δ IO 00 〇8 t Ο sg strict IO § n CD I gis C4 § § § u> § s Ϊ o Ϊ s § strict II CO I rj CM 1 I 〇1 i § « > ? β Ql EI oo I s I 5 g in oeT ί 〇» I ΙΟ mo in oT as ri 1 so § 1 9 os a> I 8 u> a» 8 » «Γ I 1 i in 1 s I to IO ▼ — I in ci | £ tt> sss 5 CO 9k S ms csi s « oms csl s to CD CO s «» sis οο <D s CD s Φ s of in i I姨sm & mms ffi « m box 5 m φ « public 5 IS « « 崁S 癞«] « thin 5 K ¢3 K fk s IB « Wrap wm & « m 9 m gas f$S wm «3 K mmm & K m sauce fS Φ mm Meppem mm «1 « 梅«3 K m R bait K embedded s 1β «3 « 琪 s IS «3 K 热 9 mmm MS ΙΘ 珀 K _ tt Award rate avoidance W < DQ CD < mm H m h- < mm 芝 H m < m is each < m &lt CD < m I m I m K ο Μ g 5 φ 5 e 1 1 i ffi ED A | 2 a 〇r- e» iq eq r> 2 2 g flO CD csl ec» ea r> § :· CO T-ID T-c*> o Strict CD X 0 r» r* T- ^r- T- f • r· r- r—production t— ♦δ $斋 S Oi s 卜σ> « 卜IO mo 〇: o : CO ico IO » 奸 CD % l $ s CD IO s S sss SS g S sps ID IO S s €0 s CD 矣# CT? S life/-N CO \ \ o 0 1 〇ϋ z £ O 0 1 oo Z έ ooz έ v> 1 o 0 1 o 1 1 o 0 1 0 1 iS 8 1 ο ο 1 oo Έ 0 B z iS 〇oz £ oo ? ffi o O οι 8 moo 0 1 〇¥ m丢 Lose 2 1 d > «〇d U> oy (U ί u> a \w/ avoid m 絜Μ i I& ¥ LU Jc ¥ iS £ ά a ω 1& f □L m ifr ifr K 1 , iS Jc 2 i , I& Jc ¥ I& iS ¥ iS ώ 窆1& iff Jc I& Jc ¥ I& Jc Ψ I& Jc I& Jc ¥ iS σ UJ I& ¢( iS* Jc Ψ I& I < CL i < a. 5 5 < 1 <:& ί 1 < CL 1 i< !〇. I !5 | tl < I < 1 < ί i ί 1 < I 1 1 t 1 I Ϊ < 5 φ ξ & S < 1 哒 gallium Φν i 3 s iS si^N : two 1 s δ r> IS 丨§ s tB ym^ sss § ss » δ $ XD s 00 ><B〇>< CO泛 00 gp want ss IO CO IO s Ια ΙΟ o LO 5 CD in » in IT- CD e3 CD CO Feed 蚪畹畹 ou: ouMqd ^^^fr-^OM::ss3a ff^hqqf^: ousPQa Feeding ^硪卜0:131 Nickel-fhs^'review: MVSl Green supplement hsqT^: accounted for vffll mine 砩 0^f^s : gvml 遛h helmet alkali 蜱: ouMtla 私私翘碱畹: OQNZPQ 迦 srofi^^畹: oaMHu Feeding helmet IS: IS1PH Feeding 蚪臧畹: ooM-qp-l i v-心: ΊΛΡ 遛sto-cod ω (s: base: t^^^^o^ti) rich complement ^r^fiM螽40 age: f砩vr^liu Huan 4^^: dpq-odM f_ «Alkaline 鲦-^鍪鍪^^^^^^^^^^? ^-:^£:0(3-^81 When 肊肊鲦翕粼翕粼翕粼翕粼 da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da da ^_气1:1:^03 t^^^fiMd; 螽: dalj system t4vr^fiH V 螽鹌:d3-v^ 06IWO §ρίΛ : 06IMO 毽銮畹:VdI Helmet"You:vqs WIMVO: VPV Distillation 4 Bu: ν mouth s 144 319793 200838965 (Comparative Example 13) H) 0 parts by weight of the primary key used for the bismuth resin (8) solution, the jasmine- 昱2 lack of this injury, and further, add Ding DI/TMP (stretching armor) This, the fermented trimethylolpropane adduct) 2 is finely imparted and the film is obtained to obtain the subsequent sheet. However, since the composition of the adhesive is increased in heart and k, it is impossible to apply. Comparative Example 14) ~ = Addition of a polyacetate precursor (c ι) obtained by the step (2) of S Example 44, and a solution of a polyester resin (8) for the main chain, in addition to the comparative example π In the same manner, the age-related product was obtained. In the same manner as in Comparative Example 3, the viscosity of the adhesive composition was rapidly increased, so that it could not be applied to the release film. (Example 44) . In Synthesis Example 44 Addition of the polyester resin (1) 1 obtained in the step (3); 50 parts of toluene was added to the repurchase portion, and further, 25 parts by weight of Tm/TMp (trihydroxydecyl propane adduct of toluene diisocyanate) was added as a crosslinking agent (E), and the mixture was carefully stirred to obtain the present invention. In the same manner as in Examples 1 to 19, the laminate of the composition of the "release film/adhesive layer/TAc film/pvA/TAC film" was carried out in the same manner as in Examples 1 to 19, and was carried out. Following the reaction of the agent layer, a polarizing plate (layered body) which is subsequently processed is obtained. (Examples 45 to 49) The solution of the addition-molded polyester resin (D1) used was changed to the solution of the addition-formed polyester resin (m) obtained in Example 145 319793 200838965 45 to 49, respectively. The same operation was carried out to prepare a polarizing plate which was subsequently processed. (Comparative Example 15), 6, and wide, and the addition molding of the addition-formed polyester precursor (C1) obtained by the step (5) of the example (5) In the same manner as in Example 44, except that the polyacetal resin (D1) was mixed, the adhesive was obtained. However, in the same manner as in Comparative Example 13, the adhesive was not able to be coated due to an increase in the rate of the adhesive. On the release film. _ (Example 50) - The addition molding resin (di) / liquid obtained by the step (3) of Synthesis Example 44 was used instead of the addition molding resin obtained in the step (6) of Synthesis Example 50. The same operation as in Example 44 was carried out to prepare an adhesive composition, and a polarizing plate which was subjected to subsequent processing was prepared. (Example 51) - Reading * The addition-molded polyester resin (D1) solution obtained in Synthesis Example 51 was used instead of the addition-molded polyester resin (Dυ solution obtained in Synthesis Example 50, except that the same procedure as in Example 44 was carried out. The composition of the adhesive was prepared and prepared into a polarizing plate which was subjected to the processing. (Comparative Example 16) The resin solution obtained in Synthesis Example 62 was used instead of the addition-molded polyester resin (D1) solution obtained in Synthesis Example 51, except In the same manner as in Example 5, the same procedure was carried out to obtain an adhesive composition. Although it can be applied to the peeling thin =, since the adhesive layer does not have adhesiveness (initial adhesion), the helmet method The layer of the "TAC film / PVA / TAC film" is laminated on the adhesive layer. 319793 146 200838965 (Comparative Example 17)

51所得之得可使用之接著劑組成物。又除此之外與實施例51進行同樣物，但在添加TDI/TMP2.5重黏並使流動性變差，故無法獲 (實施例52、53) _、刀別使用合成例52、53所得之加成型聚酯樹脂（Dl) 溶液替^合成例51所得之加成型聚醋樹脂（D1)溶液，除此之外與貫施例51進行同樣操作，而調製接著劑組成物，並製成經接著加工之偏光板。 (實施例54、55) 分別在實施例54使用伸茬基二異氰酸酯之三羥甲基丙烷加成物（以下，稱為XDI/TMP)2.5份、在實施例55使用，、亞曱基二異氰酸酯之縮二脲加成物（以下，稱為hmdi/ _鈿二脲）2·5份，以替代於實施例51中作為交聯劑（E)使用之TDI/TMP，除此之外與實施例51進行同樣操作，而獲得接著劑組成物。使用該接著劑組成物並與實施例51進行同樣操作，而製成經接著加工之偏光板。 (實施例56至58、59至62，比較例18) 分別在實施例56至58中使用合成例54至56所得之加成型聚酯樹脂（D1)溶液、在比較例18中使用合成例5 7 所得之加成型聚酯樹脂（D1)溶液、在實施例59至62中使用合成例58至61所得之加成型聚酯樹脂（D1)溶液，以替 147 319793 200838965 代合成例”所得之加成型實施例5!進行同樣操作，而計曰丄，谷液，除此之外與比較例18之情形中，因接著齊無法塗佈於剝離薄膜上。關於實製成經接著加工之偏光板。 1進仃同樣操作，而了於實_及比較例所得之接著·絲佰將結果不於表6 〇另外，針對實施例及比較例所得之經接著加工之偏光 ^積層體）’係依據與實施例i至22同樣之方法進行評估其塗膜之折射率、耐熱性、耐濕熱性、光學特性及再剝離性。將結果示於表6。 319793 148 200838965 [表6]使用第1型態之加成型聚酯樹脂(D1)的接著劑組成物使用異氰酸酯化合物（c3)作為封閉化合物（C)時之情形 # 蝴荽 &- Φ- 磔锯 π! Μ 避避避 K »1 »1 »1 蛾 Β- &- 〇. t： Q. 辑 »1 5 Ω s X Η a X Q m m 149 _ 319793 200838965 《第1封閉型態：使用聚醯胺二羧酸（a-l-4)作為二元酸 (a_l)》在下述合成例63中調製聚醯胺二羧酸，在合成例64 至66中調製使用聚醯胺二羧酸（a-1-4)作為二元酸（a-1)的聚酯樹脂。 (合成例03) 〈聚醯胺二羧駿之合成反應> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器及氮 _導入管的聚合反應裝置，並在聚合槽中分別加入作為二元酸之癸二酸：462.7份、壬二酸：430.7份、己二酸·· 345.1 份以及作為二胺之六亞曱二胺：350.9份、間伸茬二胺： 410.7份，將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物一邊升溫至250°C，添加乙酸鋅：2.0份作為觸媒，一邊進行減壓脫水一邊使其反應1 〇·小時。然後使其冷卻，而獲得f醯胺二羧酸。此樹脂為淡黃色、且其酸價為39mgKOH/g、胺價為 0.26mgKOH/g、重量平均分子量為30,000。 [以三階段型製造方法製造加成型聚酯樹脂（D1)] 〈使用石夕烧化劑（cl)作為封閉化合物（c)而成的加成型聚酯樹脂（Dl)> (合成例64) 使用合成例63所得之聚醯胺二羧酸：1435份及異酞酸：747份替代合成例1之步驟（1)所得之二元酸（a-1)，除此之外與合成例1之步驟（1)進行同樣操作，而調製主鏈用 150 319793 200838965 聚醋樹脂⑻料揮發成分為 60·0重量％)173份，使用，亚與合成例i之步驟（2)進行同樣操作及反應，而獲得淡汽色透明、且其不揮發成分為60.2重量％、黏度為 45,00〇mpa · s之加成型聚酯樹脂⑴1)之溶液。該樹脂⑴i) 貝為O.SmgKOH/g、經基價為心沐⑽仏、玻璃轉移又為5C重畺平均分子量為1 8〇,〇〇〇。又，在上述配方中相對於源自二環狀醚化合物（a_2)之二級羥基」莫耳’環狀酯（b)成為約3莫耳之比率。 φ <使用酸酐（c2)作為封閉化合物⑷而成的加成型聚醋樹脂 (合成例65) 使用合成例63所得之聚醯胺二羧酸：1435份及異酞酸.747份替代合成例21之步驟⑴所得之二元酸㈤)，除此之外與合成例2〇之步驟⑴進行同樣操作，而調製主鍵用聚醋樹脂（B)溶液（不揮發成分為6〇〇重量％)173份，使用θ其並與合成例2G之步驟⑺進行同樣操作及反應，而狻付次κ色透明、且其不揮發成分為6〇 5重量。、、黏度為 40’000mPa s之加成型聚酯樹脂（D1)之溶液。該樹脂①丄）之酸價為16mgKOH/g、羥基價為62mgK〇H/g、玻璃轉移溫度為-5t：、重量平均分子量為17〇，_.。又，在上述配方中，相對於源自二環狀難合物(a_2)之二級經基】莫耳，環狀酯（b)成為約3莫耳之比率。〈使用異氰酸酯化合物(c3)作為封閉化合物⑷的加戒型聚酯樹脂（Dl)> 319793 151 200838965 (合成例66) 使用合成例63所得之聚醯胺二羧酸：1435份及異酞酸：747份替代合成例44之步驟（1)所得之二元酸（a-Ι)，除此之外與合成例44之步驟（1)進行同樣操作，而調製主鏈用聚酯樹脂（B)溶液（不揮發成分為60.0重量％)173份，使用其並與合成例43之步驟（2)進行同樣操作及反應，添加乙酸乙酯調整濃度，而獲得淡黃色透明、且其不揮發成分為60.3重量％、黏度為46,000mPa · s之加成型聚酯樹脂攀（D1)之溶液。該樹脂（D1)之酸價為0.4mgKOH/g、羥基價為 15.5mgKOH/g、玻璃轉移溫度為一 5t：、重量平均分子量為 185,000。又，在上述配方中，相對於源自二環狀醚化合物 (a-2)之二級羥基1莫耳，環狀酯（b)成為約3莫耳之比率。針對合成例64至66所得之各樹脂溶液，將該等溶液之外觀、不揮發成分、樹脂之重量平均分子量（Mw)、玻璃轉移溫度（Tg)、酸價（AV)以及羥基價（OHV)以與合成例1 至19同樣之方式求得，並將結果彙總顯示於表7。 152 319793 200838965 [表7]加成型聚酯樹脂（D1)之合成例：使用低分子量二羧酸 (a-1-l)與聚醯胺二羧酸（a-1-4)作為二元酸（a-1)之情形The resulting adhesive composition is obtained from 51. The same procedure as in Example 51 was carried out, except that the addition of TDI/TMP 2.5 was heavy and the fluidity was deteriorated, so that it was not obtained (Examples 52 and 53) _, and the use of the synthesis examples 52 and 53 The obtained addition-molded polyester resin (D1) solution was subjected to the same operation as in Example 51 except that the solution of the addition-formed polyester resin (D1) obtained in Synthesis Example 51 was used, and the composition of the adhesive was prepared and prepared. A polarizing plate that is subsequently processed. (Examples 54, 55) In Example 54, respectively, 2.5 parts of a trimethylolpropane adduct (hereinafter referred to as XDI/TMP) of a mercapto diisocyanate was used, and in Example 55, an anthracene group II was used. a biuret adduct of an isocyanate (hereinafter referred to as hmdi/ 钿钿 diurea) in an amount of 2.5 parts instead of the TDI/TMP used as the crosslinking agent (E) in Example 51, in addition to Example 51 was carried out in the same manner to obtain an adhesive composition. This adhesive composition was used and subjected to the same operation as in Example 51 to prepare a polarizing plate which was subsequently processed. (Examples 56 to 58, 59 to 62, Comparative Example 18) The addition-molded polyester resin (D1) solution obtained in Synthesis Examples 54 to 56 was used in Examples 56 to 58, and Synthesis Example 5 was used in Comparative Example 18, respectively. 7 The obtained addition-molded polyester resin (D1) solution, and the addition-molded polyester resin (D1) solution obtained in Synthesis Examples 58 to 61 in Examples 59 to 62, for the addition of the synthesis example of 147 319793 200838965 Molding Example 5: The same operation was carried out, and in the case of Comparative Example 18, the same procedure as in Comparative Example 18 was carried out, and it was not possible to apply it to the release film. 1) The same operation was carried out, and the results obtained in the actual and comparative examples were not as shown in Table 6. In addition, the post-processed polarized layered bodies obtained in the examples and the comparative examples were based on The refractive index, heat resistance, moist heat resistance, optical properties, and removability of the coating film were evaluated in the same manner as in Examples i to 22. The results are shown in Table 6. 319793 148 200838965 [Table 6] Using Type 1 Adhesive composition of the addition molding polyester resin (D1) When the isocyanate compound (c3) is used as the blocking compound (C) # 荽荽 &- Φ- 磔 π π! Μ 避 Avoid K »1 »1 »1 moth - &- 〇. t: Q. Series»1 5 Ω s X Η a XQ mm 149 _ 319793 200838965 "1st closed form: using polyamine dicarboxylic acid (al-4) as dibasic acid (a-1)" Modification in the following Synthesis Example 63 For the decylamine dicarboxylic acid, a polyester resin using polyamine dicarboxylic acid (a-1-4) as the dibasic acid (a-1) was prepared in Synthesis Examples 64 to 66. (Synthesis Example 03) Synthesis reaction of amine dicarboxylate> Prepared in a polymerization reactor equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen-introduction tube, and added a sebacic acid as a dibasic acid in the polymerization tank: 462.7 parts , azelaic acid: 430.7 parts, adipic acid · 345.1 parts and hexamethylenediamine as diamine: 350.9 parts, meta-diamine: 410.7 parts, after replacing the air in the polymerization tank with nitrogen, one side While stirring the mixture, the temperature was raised to 250 ° C, and zinc acetate was added: 2.0 parts was used as a catalyst. The mixture was reacted for 1 〇·hr under reduced pressure, and then cooled to obtain f-amined dicarboxylic acid. The resin was pale yellow, and its acid value was 39 mgKOH/g, and the amine value was 0.26 mgKOH/g. The average molecular weight is 30,000. [Production of a modified polyester resin (D1) by a three-stage production method] [Additional polyester resin (Dl) using a Xihua burning agent (cl) as a blocking compound (c)> (Synthesis Example 64) The polydiamine dicarboxylic acid obtained in Synthesis Example 63: 1435 parts and isophthalic acid: 747 parts were used instead of the dibasic acid (a-1) obtained in the step (1) of Synthesis Example 1, except The same operation as in the step (1) of the synthesis example 1 was carried out, and 173 parts of the main chain was prepared by using 150 319793 200838965 polyester resin (8) volatile component (60. 0% by weight), using, sub-synthesis example i (2) The same operation and reaction were carried out to obtain a solution of the addition-molded polyester resin (1) 1) which was transparent in light vapor and had a nonvolatile content of 60.2% by weight and a viscosity of 45,00 〇mpa · s. The resin (1) i) is O.SmgKOH/g, the base price is Xinmu (10) 仏, the glass is transferred, and the 5C heavy 畺 average molecular weight is 18 〇, 〇〇〇. Further, in the above formula, the ratio of the secondary hydroxyl group "roth" cyclic ester (b) derived from the dicyclic ether compound (a_2) is about 3 moles. φ <Additional Polyacetate Resin Using Acidic Acid (c2) as Blocking Compound (4) (Synthetic Example 65) The polyamine carboxylic acid obtained in Synthesis Example 63: 1435 parts and isophthalic acid. 747 parts were used instead of the synthesis example. In the same manner as in the step (1) of Synthesis Example 2, the same procedure as in the step (1) of Synthesis Example 2 was carried out, and the solution of the polyester resin (B) for the primary bond was prepared (the nonvolatile content was 6 〇〇% by weight). 173 parts were subjected to the same operation and reaction as in the step (7) of Synthesis Example 2G using θ, and the κ color was transparent and the nonvolatile content was 6 〇 5 by weight. A solution of the addition-molded polyester resin (D1) having a viscosity of 40'000 mPa s. The resin had an acid value of 16 mgKOH/g, a hydroxyl group value of 62 mgK〇H/g, a glass transition temperature of -5t: and a weight average molecular weight of 17 Å. Further, in the above formula, the cyclic ester (b) has a ratio of about 3 moles with respect to the secondary radical derived from the dicyclic hard compound (a_2). <The addition type polyester resin (D1) using the isocyanate compound (c3) as the blocking compound (4) > 319793 151 200838965 (Synthesis Example 66) The polyamine dicarboxylic acid obtained in Synthesis Example 63: 1435 parts and isophthalic acid The following procedure was carried out in the same manner as in the step (1) of Synthesis Example 44, except that the dibasic acid (a-fluorene) obtained in the step (1) of the synthesis of Example 44 was replaced, and the polyester resin for the main chain was prepared (B). 173 parts of a solution (nonvolatile content: 60.0% by weight), which was used in the same manner as in the step (2) of Synthesis Example 43 and reacted, and ethyl acetate was added thereto to adjust the concentration to obtain a pale yellow transparent material and a nonvolatile content thereof. A solution of a molded polyester resin (D1) of 60.3 wt% and a viscosity of 46,000 mPa·s. The resin (D1) had an acid value of 0.4 mgKOH/g, a hydroxyl value of 15.5 mgKOH/g, a glass transition temperature of 5t: and a weight average molecular weight of 185,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 3 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a-2). The respective resin solutions obtained in Synthesis Examples 64 to 66, the appearance of the solutions, the nonvolatile content, the weight average molecular weight (Mw) of the resin, the glass transition temperature (Tg), the acid value (AV), and the hydroxyl group (OHV) The results were obtained in the same manner as in Synthesis Examples 1 to 19, and the results are collectively shown in Table 7. 152 319793 200838965 [Table 7] Synthesis example of addition molding polyester resin (D1): using low molecular weight dicarboxylic acid (a-1-l) and polydecylamine dicarboxylic acid (a-1-4) as dibasic acid (a-1) situation

性狀 | OHV 1¾ 1 i LO Τ» <N <D IO IA Ί— in o CD T— o f!P ΙΓ5 in to o 0 1 Ϊ o 185.000 Vie (mPe-8) 45,000 40,000 46,000 CM § IO s CO S 溶液外觀加咸型聚酯樹脂（D1) 辕 tbab| tbab| tbab! Z 〇 CO r- o CO CD Oj 側鍵含有率 (wt%) L£> ir> g CD LO 封閉化合物(C) HMSZ AnhPh PhNCO 加成型聚酯前驅物（C1) | S -j O (〇主鏈用聚酯樹脂（B) . 1 <-> S 雙 A-Ep 1 r- 1 ο \ 产 1 r- i sS IPA/PA 合成例 I (1)(2)(3) MM 1 1 避蚪键 t4f:ooMd fe银銮：qjqcv^Ί^Μ4A4C: zsi 避MQ—3 : d3 S4^τ^ιίΜν龠制：p(a丨 v 制 .· £怒瀋畹：Vdl 153 319793 200838965 (實施例63) 在實施例1中，使甩合成例64所得之加成型聚酯樹脂 (D1)溶液替代合成例丨之步驟（3)所得之加成型聚醋樹脂 (D1)溶液，除此之外與實施例丨進行同樣操作，而調製接著劑組成物，使用該接著劑組成物而製成經接著加工之偏光板。將同樣進行之評估結果顯示於表8。 (實施例64) 在實_ 20中，使用合成例65所得之加成型聚醋樹等脂（D1)溶液替代合成例21之步驟（3)所得之加成型聚酉旨樹脂(Di)溶液’除此之外與實施例2Q進行同樣操作而調製接著劑組成物’使用該接著劑組成物而製成經接著加工之偏光板。將同樣進行之評估結果顯示於表8。 (實施例65) 纟實施 <列44中，-使用合成例66所得之加成型聚料月曰（m)溶液替代合成例44之步驟（3)所得之加成型聚酉旨相春脂(m)溶液’除此之外與實施例44進行同樣操作而調者劑組成物，使用該接著劑組成物而製成經接著加工光板。將同樣進行之評估結果顯示於表8。 319793 154 200838965 [表8]使用第1封閉型態之加成型聚酯樹脂(D1)而成的接著劑組成物：使用異氰酸酯化合物(c3)作為封閉化合物(c)之情形Traits | OHV 13⁄4 1 i LO Τ» <N <D IO IA Ί—in o CD T—of!P ΙΓ5 in to o 0 1 Ϊ o 185.000 Vie (mPe-8) 45,000 40,000 46,000 CM § IO s CO S solution appearance with salty polyester resin (D1) 辕tbab| tbab| tbab! Z 〇CO r- o CO CD Oj side bond content (wt%) L£> ir> g CD LO blocking compound (C) HMSZ AnhPh PhNCO Additive Polyester Precursor (C1) | S -j O (Polyester Resin for Polyester Resin (B) . 1 <-> S Double A-Ep 1 r- 1 ο \ Production 1 r- i sS IPA/PA Synthesis Example I (1)(2)(3) MM 1 1 Avoidance key t4f:ooMd fe silver 銮:qjqcv^Ί^Μ4A4C: zsi Avoid MQ-3: d3 S4^τ^ιίΜν龠: p (a 丨制 . 怒怒怒畹畹 V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V The addition of the polyacetal resin (D1) solution obtained in the step (3) was carried out in the same manner as in Example ,, and the adhesive composition was prepared, and the adhesive composition was used to prepare a polarizing plate which was subsequently processed. The same evaluation results will be made In the present invention, in the -20, the addition of the resin (D1) solution such as the addition of the polyacetate obtained in the synthesis example 65 was used instead of the addition of the resin (step) obtained in the step (3) of the synthesis example 21 ( Di) The solution was prepared in the same manner as in Example 2Q except that the same procedure as in Example 2Q was used to prepare a polarizing plate which was subjected to subsequent processing using the adhesive composition. The evaluation results similarly carried out are shown in Table 8. Example 65) 纟Implementation <Column 44, - Addition of the shaped polyurea (m) solution obtained in Synthesis Example 66 in place of the addition of the step (3) of Synthesis Example 44 The solution was prepared in the same manner as in Example 44 except that the composition of the agent was used to prepare a light-receiving sheet. The evaluation results similarly shown in Table 8 are shown in Table 8. 319793 154 200838965 [ Table 8] Adhesive composition using the addition type polyester resin (D1) of the first closed form: the case where the isocyanate compound (c3) is used as the blocking compound (c)

參Reference

% 璩 \ \ 擊柳重工性 Ο Ο o 耐濕熱性 Μ < < < Ο ο o 耐熱性 ο ο o 經乾燥之接著劑層黏性著 ο ο o 先學特性 ο ο o 折射率 | 1.5107 1 | 1.5107 1 1.5142 接著劑溶液塗佈加工性 ο ο 〇 % δ ο ο o 接著劑組成物交聯劑（Ε) 份數 ιη ir> 種類 1 TDI/TMP 1 1 ΗΒΑΡ 1 TDI/TMP 聚酯樹脂（Dl)溶液 OHV ΙΟ CM CD I 15.5 I ΙΑ CD 寸〇· I? ΙΟ bp 1γ Mw 1 180,000 I 170.000 丨 185-000 I OH : (b) W ir· 齋Q s CD CM 側鏈含有率 (wt%) s CO IO 合成例 IT5 CD CD CD |實施例63| |實施例64| |實施例65 【避键«(14智《碱丨 ΪΥΞ砵敏卜4- hz: dvCQH 155 319793 200838965 《第1封閉狀態：使用高分子量二羧酸（a-;U2)作為二元酸 (a-l)>) :一 ^ 在下述合成例67至106中，顯示使用由低分子量二羧酸（a-M)與各種多元醇（ad-α )而成之反應生成物高分子量二羧酸（a-1-2)作為二元酸（a-Ι)時的情形。 [以二階段型製造方法製造加成型聚酯樹脂（D1)] (合成例07) 〈步驟（1):聚酯主鏈之形成> 等將攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管設於聚合槽而構成聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入二元酸（a-1)、多元醇類（a_ 1 _ α )、具有2個環狀醚基之化合物（a-2)、觸媒、以及有機溶劑。 [聚合槽] KURARAY 多元醇 P4010(a-l-a ) 376 份丁二酸酐〇1-1) 甲苯乙酸乙酯四氫硼酸四丁基銨（觸媒） [滴下裝置] 雙酚A二環氧丙基醚（a-2) 四氫硼酸四丁基銨(觸媒）乙酸乙酯 18份 76份 30份 0·5份 34份 1份 3 6份將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物一邊升溫至100°C ’並進行8小時開環加成反應。其次，於 156 319793 200838965 攪拌，之反應物中’藉由滴下裝置而將二環狀醚化合物 (真）此°物耗費1小時以等速滴下。，滴下完畢後，再-邊攪拌「邊每隔8小時加入觸媒〇·5份，共加入2次後，使’、進行合计24小時之反應、熟成，然後添加崩份乙酸乙酯並冷卻至室溫，結束反應。此办液係淡黃色透明、其不揮發成分為5〇·丨重量％、钻度為18,〇〇〇mpa · s，而其中含有酸價為〇、龜=基=為75.2mgKOH/g、玻璃轉移溫度為4〇。〇、重量平均刀子夏為150,000之主鏈用聚酯樹脂（B) 〇 v驟（2) ·環狀酯（b)之開環加成反應> 壯準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下衣置及氮導入官的聚合反應裝置，並在聚合槽及滴下裝置中刀別以下述比率加入步驟所得之主鏈用聚酯樹脂 (B)溶液·、環狀酯（b)、觸媒、以及有機溶劑。 [聚合槽] 500份 20份〇·5份 10份 φ 聚酯樹脂（B)溶液 [滴下裝置] ε-己内酯（b) 四氫硼酸四丁基銨（觸媒） . 乙酸乙酯將聚合槽内之空氣以氮氣置換後，一邊攪拌樹脂溶液一邊升温至loot：。其次，於其中，藉由滴下裝置而將環狀酯（b)混合物耗費1小時以等速滴下。再一邊攪拌一邊使其進行12小時之反應、熟成，然後添加1〇份乙酸乙酯並 319793 157 200838965 冷卻至室溫’結束反應，而製得加成型聚㈣驅物（叫之溶液。此溶液係淡黃色透明、且其不揮發成分為5〇1重量 %、黏度為20,〇〇〇mpa . s，該聚酯前驅物（C1)之酸價為 0.〇5mgK〇H/g、备基價為56 2mgK〇H/g、玻璃轉移溫度為 —2(TC、重量平均分子量為16〇,〇〇〇。又，在上述配方相對於源自二環狀醚化合物（a_2)之二級羥基丨莫耳，環狀酯（b)成為約1 · 5莫耳之比率。 _ <步驟（3) ··藉由異氰酸酯化合物（c3)而進行之封閉反應〉準備於聚合槽附有_機、溫度計、回流冷卻器\滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分、別、以下述比率加入步驟⑺所得之加成型聚醋前驅物（ci)溶液、作為封閉化合物（c)之異氮酸醋化合物㈦）、觸媒、以及有機溶劑。 .% 璩\ \ 柳柳重工性Ο Ο o Heat and humidity resistance Μ <<<< Ο ο o Heat resistance ο ο o The adhesive layer is dry and sticky ο ο o Learn characteristics ο ο o Refractive index | 1.5107 1 | 1.5107 1 1.5142 Adhesive solution coating processability ο ο 〇% δ ο ο o Substance composition crosslinker (Ε) Parts ιη ir> Category 1 TDI/TMP 1 1 ΗΒΑΡ 1 TDI/TMP polyester Resin (Dl) solution OHV ΙΟ CM CD I 15.5 I ΙΑ CD 〇 · I? bp bp 1γ Mw 1 180,000 I 170.000 丨 185-000 I OH : (b) W ir· 斋 Q s CD CM side chain content rate ( Wt%) s CO IO Synthesis Example IT5 CD CD CD | Example 63 | | Example 64 | | Example 65 [Keys « (14) "Alkaline Sensitive Bub 4-hz: dvCQH 155 319793 200838965" 1 closed state: using a high molecular weight dicarboxylic acid (a-; U2) as a dibasic acid (al)>): a compound in the following Synthesis Examples 67 to 106, showing the use of a low molecular weight dicarboxylic acid (aM) and A case where a reaction product of various polyols (ad-α) is a high molecular weight dicarboxylic acid (a-1-2) as a dibasic acid (a-oxime). [Production of Additive Polyester Resin (D1) by Two-stage Manufacturing Method] (Synthesis Example 07) <Step (1): Formation of polyester main chain> Etc. Mixer, thermometer, reflux cooler, dropping device, and nitrogen The introduction tube is disposed in the polymerization tank to constitute a polymerization reaction device, and the dibasic acid (a-1), the polyhydric alcohol (a_1_α), and the two cyclic ethers are respectively added in the polymerization tank and the dropping device at the following ratios. a compound (a-2), a catalyst, and an organic solvent. [Polymerization tank] KURARAY polyol P4010 (ala ) 376 parts succinic anhydride 〇 1-1) Toluene ethyl acetate tetrabutylammonium tetrahydroborate (catalyst) [Drip device] Bisphenol A diglycidyl ether ( A-2) tetrabutylammonium tetrahydroborate (catalyst) ethyl acetate 18 parts 76 parts 30 parts 0·5 parts 34 parts 1 part 36 parts The air in the polymerization tank was replaced with nitrogen, and the mixture was stirred while stirring. The temperature was raised to 100 ° C ' and a ring-opening addition reaction was carried out for 8 hours. Next, the mixture was stirred at 156 319793 200838965, and the dicyclic ether compound (true) was dropped by a dropping device for 1 hour at a constant rate. After the completion of the dropwise addition, stir again and then add 5 parts of the catalyst 每隔················································ The reaction is completed at room temperature. The liquid is light yellow transparent, its non-volatile content is 5〇·丨% by weight, the degree of drilling is 18, 〇〇〇mpa · s, and the acid value is 〇, turtle = base = 75.2 mg KOH / g, glass transition temperature of 4 〇. 〇, weight average knife summer 150,000 polyester resin for the main chain (B) 〇 v (2) · cyclic ester (b) open-loop addition Reaction> It is prepared in a polymerization tank equipped with a stirrer, a thermometer, a reflux cooler, a drip coat, and a nitrogen introduction unit, and is added to the main chain of the step in the polymerization tank and the dropping device at the following ratio. Polyester resin (B) solution, cyclic ester (b), catalyst, and organic solvent [Polymerization tank] 500 parts 20 parts 〇·5 parts 10 parts φ Polyester resin (B) solution [Drip device] ε - caprolactone (b) tetrabutylammonium tetrahydroborate (catalyst). ethyl acetate is used to set the air in the polymerization tank to nitrogen. Thereafter, the mixture was heated to a loot while stirring the resin solution. Next, the mixture of the cyclic ester (b) was dropped at a constant rate by a dropping device for 1 hour, and further reacted for 12 hours while stirring. After aging, then add 1 part of ethyl acetate and 319793 157 200838965 to cool to room temperature' to terminate the reaction, and obtain a shaped poly(tetra)-driven (called a solution. This solution is light yellow transparent, and its non-volatile content is 5 〇1% by weight, viscosity 20, 〇〇〇mpa.s, the acid value of the polyester precursor (C1) is 0. 〇 5 mg K 〇 H / g, the base price is 56 2 mg K 〇 H / g, glass transfer The temperature is -2 (TC, weight average molecular weight is 16 〇, 〇〇〇. Further, in the above formula relative to the secondary hydroxy oxime derived from the dicyclic ether compound (a_2), the cyclic ester (b) becomes a ratio of about 1 · 5 moles. _ <Step (3) · Closed reaction by isocyanate compound (c3) > Prepared in a polymerization tank with a machine, a thermometer, a reflux cooler, a drip device, and nitrogen Introducing the polymerization device of the tube, and dividing it in the polymerization tank and the dropping device. Of the ratio of the added step ⑺ addition-resultant polyester precursor (CI) solution, as a closed compound (c) (vii) The compound isobutyl N Suancu), catalyst, and an organic solvent.

[聚合槽] 參加成型聚酯前驅物（C1)溶液 500份 [滴下裝置] 29份〇·1份 10份異氰酸苯酯（C3；) 四氫硼酸四丁基銨（觸媒）乙酸乙酯將聚合槽内之空氣以氮氣置換後，一邊攪拌溶液-邊升溫至loot：。其攻，认甘丄 · 、於其中，藉由滴下裝置而將封閉化合物（c)之混合物耗費]k 士 —七知 '買1小蚪以等速滴下。滴下完畢後，再一邊攪拌一邊使其進杆s丨士 ^ 订8小％之反應、熟成，然後添加19 158 319793 200838965 份乙酸乙醋並冷卻至室溫’而獲得加成型[Polymerization tank] 500 parts of the molded polyester precursor (C1) solution [dropping device] 29 parts 〇·1 part of 10 parts of phenyl isocyanate (C3;) tetrabutylammonium tetrahydroborate (catalyst) After the ester was replaced with nitrogen in the polymerization tank, the solution was heated to a loot: while stirring the solution. In the attack, it is recognized that the mixture of the compound (c) is consumed by dripping the device] k _ _ _ _ ' buy 1 small 蚪 to drop at a constant rate. After the dripping is completed, the mixture is stirred and allowed to enter the s gentleman's ^ 8 small % of the reaction, ripening, and then added 19 158 319793 200838965 parts of ethyl acetate and cooled to room temperature ' to obtain the addition molding

溶液。 V 此溶液係淡黃色透明、且其不揮發成分為5㈣重量 %、黏度為18,000mpa.s，該樹脂（m)之酸價 KOH/g、羥基價為25mgK〇H/g、玻璃轉移溫度為—贼、重量平均分子量為165,〇〇〇。 (合成例08) 省略合成例67之步驟（2)、並使用步驟⑴所得之主鏈 ♦用聚㈣脂⑻溶液（不揮發成分為5()1重量邱⑼份替代步驟（3).之加成㈣酉旨前驅物（C1)溶液、且再將異氰酸苯醋 ⑷，之篁變更成27份，除此之外與合成例67同樣操作而進行調製’並添加乙酸乙醋17份，冷卻至室溫，而獲得淡黃色透月且其不揮發成分為5〇 2重量％、黏度為U，〇O〇 mPa . s ,之聚醋樹脂之溶液。，樹脂之酸價為〇〇5mg KOH/g、經基價為28mgK〇H/g、玻璃轉移溫度為仙。c、重儀量平均分子量為155,〇〇〇。 (合成例69) 將合成例67之步驟（3)中所用之封閉化合物（c)變更成㈣化劑(el)之二乙基甲基錢：23❾，除此之外與合成例67同松‘作而進行調製，並添加乙酸乙醋u份，冷卻至至，而獲侍淡黃色透明、且其不揮發成分為5〇〇重量 /〇黏度為13,0〇〇mpa · $之加成型聚酯樹脂⑴丨)之溶液。該樹扁（D1)之酸價為〇.〇5mgKOH/g、羥基價為 18.5mgKOH/g、玻璃轉移溫度為一 2〇。〇、重量平均分子量 159 319793 200838965 為120,000。χ ’在上述配方中，相對於源自二環狀鱗化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約15莫耳之比率。 (合成例70) 將合成例67之步驟（3)中所用之封閉化合物（c)變更成酸酐（c2)之酞酸酐：34份，除此之外與合成例67同樣操作而進行凋製，並添加乙酸乙酯24份，冷卻至室溫，而獲得淡貫色透明、且其不揮發成分為5〇 3重量％、黏度為鲁17’500mPa s之加成型聚醋樹脂(叫之溶液。該樹脂⑽) 之酸價為85.1mgK〇H/g、羥基價為16 8mgK〇H/g、玻璃轉移溫度為-20°C、重量平均分子量為175，綱。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基】莫耳，環狀酯（b)成為約1.5莫耳之比率。 (合成例71) .. 將合成例67之步驟（3)中所用之封閉化合物（〇變更成癱酉夂酐(c2)之敵酉夂_ . 5份，除此之外與合成例同樣操作而進行調製，不添加乙酸乙酯，冷卻至室溫，而獲得淡普色透明、且其不揮發成分為>4重量％、黏度.為 11’OOOmPa· s之加成型聚酯樹脂(Di)之溶液。該樹脂（di) 之酸價為5為gK0H/g、絲價為51 5mgK〇H/g、玻璃轉私酿度為—20C、重量平均分子量為1〇5，_。又，在上述配方中，相對於源自二環狀難合物（a_2)之二級經基ι 莫耳，環狀醋（b)成為約1.5莫耳之比率。 [以二階段型製造方法製造加成型聚酯樹脂(D1)] 319793 160 200838965 〈聚酯多元醇之合成〉 (合成例A) 準備於聚合槽附有攪拌機、溫度計、回流冷卻器及氮導入管的聚合反應裝置，並在聚合槽中分別以下述比率加入二羧酸、二元醇、以及觸媒。 [聚合槽] 癸二酸 606份異酜酸 332份新戊二醇 210份 1，4-丁二醇 140份 1，6-己二醇 180份乙酸辞〇·5份將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物一邊升溫至200°C，一邊脫水，一邊反應至使酸價成為2·以下。其次，冷卻至50°C以下並結束反應，而獲得聚酯多元醇。 . 此聚酯多元醇係淡黃色透明，且樹脂之酸價為 0.3mgKOH/g、羥基償為21.5mgKOH/g、玻璃轉移溫度為 —20°C、數平均分子量(Μη)為4,200。 (合成例Β) 使用丁二酸354份、己二酸292份、ί，4-丁二醇470 份替代合成例Α中所用之二羧酸及二元醇，除此之外與合成例A同樣操作而進行調製，而獲得淡黃色透明、且樹脂之酸價為〇.5mgKOH/g、羥基價為22.3mgKOH/g、玻璃轉 161 319793 200838965 私狐度為20 C、數平均分子量（Μη)為4,000的聚酯多元醇。 (合成例72) [以二階段型製造方法製造加成型聚酯樹脂（D1)] 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下衣置及氮‘入言的聚合反應裝置，並在聚合槽及滴下裳置中分別以下述比率加入低分子量二羧酸類（a_lel)、多元醇類（a-1-α )、二環狀醚化合物（a-2)、環狀酯（b)、觸媒、鲁以及有機溶劑。 [聚合槽] KURARAY 多元醇 p4010(a-l-a) 376份丁二酸酐（a-1-1) 18份曱苯 76份乙酸乙酯 ·， 30份四氫硼酸四丁基銨（觸媒）〇·5份 [滴下裝置] 雙酚A二環氧丙基醚（a_2) 34份 ε ·己内酯（b) 32份四氫硼酸四丁基銨（觸媒） 1份乙酸乙酯 47份 <步驟（7):加成型聚酯前驅物（ci)之生成〉將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物〜邊升溫至100°C，使其反應8小時，而獲得為二元酸（ip 之高分子量二羧酸（a-1-3)。 319793 162 200838965 其次，藉由滴下裝置而將上述混合物耗費丨小時以等速滴下。滴下完畢後，-邊擾拌-邊於8小時後添加四氮棚酸四丁基銨1份，再使其熟成8小時後，添加乙酸乙酯307 伤並~部至至溫，結束反應，而獲得經加成環狀酯化合物 (b)之加成型聚酯前驅物（C1)之溶液。此溶液係淡黃色透明、且其不揮發成分為5〇 2重量 %、黏度為22,0〇〇mPa.s，該樹脂（C1)之酸價為〇〇5mg 鲁KOH/g、羥基價為52.6mgK〇H/g、玻璃轉移溫度為一 2〇t>c、重1平均为子量為17〇,〇〇〇。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基】莫耳，環狀酯（b) 成為約1 · 4莫耳之比率。 <步驟（8):藉由異氰酸酯化合物（c3)而進行之封閉反應> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝鲁置中分別以下述比率加入步驟所得之加成型聚酯前驅物（C1)溶液（不揮發成分為502%)、單官能異氰酸酯化合物 (c3)、觸媒、以及有機溶劑。 [聚合槽] 加成型聚酯前驅物（C1)溶液 500份 [滴下裝置] 異氰酸苯酯（c3) 21份四氫硼酸四丁基銨（觸媒）〇·1份乙酸乙酯 10份 163 319793 200838965 將聚合槽内之空氣以氮氣置換後，一邊攪拌溶液一邊升溫至100°C。其次，於其中，於其中將滴下裝置之混合物耗費1小時以等速滴下。滴下完畢後，一邊攪拌一邊使其進行6小時之反應、熟成，然後添加11份乙酸乙酯並冷卻至室溫，而獲得加成型聚酯樹脂（D1)之溶液。此溶液係淡黃色透明、且其不揮發成分為50.3重量 %、黏度為19,000mPa · s，該樹脂（D1)之酸價為0.2mg ΚΟΠ/g、羥基價為22.8mgKOH/g、玻璃轉移溫度為-20。。、馨重量平均分子量為170,000。 (合成例73) 使甩376份之KURARAY多元醇P4090替代合成例72 之步驟（7)所用之多元醇類（a-l_a )，除此之外與合成例72 同樣操作而進行調製，而獲得淡黃色透明、且其不揮發成分為49/7重量％、黏度為16,000mPa· s之加成型聚酯樹脂 (D1)之溶液。該樹脂（D1)之酸價為0.5mgKOH/g、羥基價為 • 20.5mgKOH/g、玻璃轉移溫度為一20°C、重量平均分子量為150,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基1莫耳，環狀酯（b)成為約1.4莫耳之比率。 (合成例74) 使用376份之KURARAY多元醇P4011替代合成例72 之步驟（7)所用之多元醇類（a-1-α )，除此之外與合成例72 同樣操作而進行調製，而獲得淡黃色透明、且其不揮發成分為50.2重量％、黏度為12,000mPa· s之加成型聚酯樹脂 164 319793 200838965 (D1)之溶液。該樹脂（D1)之酸價為〇lmgK〇H/g、羥基價為 22.8mgK〇H/g、玻璃轉移溫度為—1〇。。、重量平二:子量為11〇，_。又，在上述配方中，相對於源自二環：醚：合物（a-2)之二級羥基1莫耳，環狀酯（b)成為約莫耳之比率。、 (合成例75) 使用376份之KURARAY多元醇P4050替代合成例72 之步驟⑺所用之多το醇類，除此之外與合成例^ 同樣操作而進行調製，而獲得淡黃色透明、且其不揮發成分為50.0重量％、黏度為18,5〇〇mPa·^加成型聚醋樹月旨 (D1)之溶液。該樹脂（D1)之酸價為〇 8mgK〇H/g、羥基價為 21.4mgKOH/g、玻璃轉移溫度為—菸它、重量平均分子量為140,000。又，在上述配方中，相對於源自二環狀醚化合物(a-2)之二級羥基丨莫耳，環狀酯（b)成為約丨.4莫耳之比率。、Solution. V This solution is light yellow transparent, and its non-volatile content is 5 (four) wt%, viscosity is 18,000 mpa.s, the acid value of the resin (m) is KOH/g, the hydroxyl value is 25 mg K〇H/g, and the glass transition temperature is - Thieves, weight average molecular weight is 165, 〇〇〇. (Synthesis Example 08) The step (2) of Synthesis Example 67 was omitted, and the main chain obtained by the use of the step (1) was a solution of a poly(tetra)lipid (8) (the nonvolatile content was 5 () 1 weight by weight (9) parts instead of the step (3). Addition of (4) acetic acid precursor (C1) solution, and further changing the isocyanate benzene vinegar (4) to 27 parts, and preparing in the same manner as in Synthesis Example 67, and adding 17 parts of ethyl acetate. After cooling to room temperature, a pale yellow permeable moon having a non-volatile content of 5.2 wt% and a viscosity of U, 〇O〇mPa·s, a solution of the polyester resin is obtained. The acid value of the resin is 〇〇 5 mg KOH / g, base price 28 mg K 〇 H / g, glass transition temperature is sen. c, weight average molecular weight is 155, 〇〇〇. (Synthesis Example 69) In the step (3) of Synthesis Example 67 The blocking compound (c) used was changed to a diethyl group of (4) anion (el): 23 Å, and otherwise prepared in the same manner as in Synthesis Example 67, and ethyl acetate was added thereto to be cooled. As a result, it is a solution which is light yellow transparent and has a non-volatile content of 5 〇〇 / 〇 viscosity of 13,0 〇〇mpa · $ of modified polyester resin (1) 丨)The acid value of the tree flat (D1) was 〇.〇5 mgKOH/g, the hydroxyl value was 18.5 mgKOH/g, and the glass transition temperature was one 〇. 〇, weight average molecular weight 159 319793 200838965 is 120,000. χ ' In the above formulation, the cyclic ester (b) has a ratio of about 15 moles relative to the secondary hydroxy oxime derived from the bicyclic scaly compound (a-2). (Synthesis Example 70) The blocking compound (c) used in the step (3) of Synthesis Example 67 was changed to the phthalic anhydride of the acid anhydride (c2): 34 parts, and the same procedure as in Synthesis Example 67 was carried out to carry out the crystallization. And 24 parts of ethyl acetate was added, and it cooled to room temperature, and the addition-formation of the polyacetal resin (called a solution) which is transparent, and the non-volatile content is 5 3 3 % by weight, and the viscosity is 17 '500 mPas. The resin (10)) had an acid value of 85.1 mg K 〇 H / g, a hydroxyl group value of 16 8 mg K 〇 H / g, a glass transition temperature of -20 ° C, and a weight average molecular weight of 175. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1.5 mol with respect to the secondary hydroxyl group derived from the dicyclic ether compound (a_2). (Synthesis Example 71): The same procedure as in the synthesis example was carried out except that the blocking compound used in the step (3) of Synthesis Example 67 was changed to oxime of phthalic anhydride (c2). The preparation was carried out without adding ethyl acetate, and the mixture was cooled to room temperature to obtain an addition-molded polyester resin having a pale color and a nonvolatile content of > 4% by weight and a viscosity of 11 OO mPa·s. The resin (di) has an acid value of 5 gK0H/g, a silk price of 51 5 mg K〇H/g, a glass conversion degree of -20 C, and a weight average molecular weight of 1〇5, _. In the above formulation, the cyclic vinegar (b) has a ratio of about 1.5 moles relative to the secondary methoxyl group derived from the dicyclic hard compound (a_2). [Manufactured in a two-stage manufacturing process Molded Polyester Resin (D1)] 319793 160 200838965 <Synthesis of Polyester Polyol> (Synthesis Example A) A polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube in a polymerization tank, and in an polymerization tank Dicarboxylic acid, diol, and catalyst were added in the following ratios. [Polymerization tank] 636 parts of azelaic acid 332 parts by weight Pentylene glycol 210 parts 1,4-butanediol 140 parts 1,6-hexanediol 180 parts of acetic acid 〇5 parts After the air in the polymerization tank was replaced with nitrogen, the mixture was heated to 200 ° C while stirring the mixture. The reaction is carried out until the acid value is 2 or less. Next, the reaction is cooled to 50 ° C or lower, and the reaction is terminated to obtain a polyester polyol. The polyester polyol is light yellow transparent, and the acid value of the resin is 0.3 mgKOH/g, hydroxyl group 21.5 mgKOH/g, glass transition temperature of -20 ° C, and number average molecular weight (Μη) of 4,200. (Synthesis Example) 354 parts of succinic acid, 292 parts of adipic acid, ί Further, 470 parts of 4-butanediol were used instead of the dicarboxylic acid and the diol used in the synthesis example, and the same procedure as in Synthesis Example A was carried out to obtain a pale yellow transparent, and the acid value of the resin was 〇. .5 mg KOH / g, hydroxyl value of 22.3 mg KOH / g, glass to 161 319793 200838965 Polyester polyol having a private fox of 20 C and a number average molecular weight (?η) of 4,000. (Synthesis Example 72) [Manufactured in a two-stage type Method for manufacturing addition-molded polyester resin (D1)] Prepared in a polymerization tank with a mixer, thermometer, reflux a low-molecular-weight dicarboxylic acid (a-lel), a polyhydric alcohol (a-1-α), and a polymerization device in which the nitrogen and the nitrogen are introduced into the polymerization tank and the dropping skirt, respectively. Dicyclic ether compound (a-2), cyclic ester (b), catalyst, ruthenium and organic solvent [polymerization tank] KURARAY polyol p4010 (ala) 376 parts succinic anhydride (a-1-1) 18 Benzene 76 parts ethyl acetate·, 30 parts tetrabutylammonium tetrahydroborate (catalyst) 〇·5 parts [dropping device] bisphenol A diglycidyl ether (a_2) 34 parts ε·caprolactone (b) 32 parts of tetrabutylammonium tetrahydroborate (catalyst) 1 part of ethyl acetate 47 parts <Step (7): Formation of addition-formed polyester precursor (ci)> Air in the polymerization tank was nitrogen After the substitution, the mixture was heated to 100 ° C while stirring, and allowed to react for 8 hours to obtain a dibasic acid (ip high molecular weight dicarboxylic acid (a-1-3). 319793 162 200838965 Secondly, the above mixture was consumed for a few hours by dropping the device to drip at a constant rate. After the completion of the dropwise addition, 1 part of tetrabutylammonium arsenate was added after 8 hours, and then it was aged for 8 hours, and then ethyl acetate 307 was added and the mixture was warmed to the end to complete the reaction. A solution of the addition-formed polyester precursor (C1) to which the cyclic ester compound (b) was added was obtained. The solution is light yellow transparent, and its nonvolatile content is 5.2 wt%, viscosity is 22,0 〇〇 mPa.s, the acid value of the resin (C1) is 〇〇5 mg KOH/g, and the hydroxyl value is 52.6 mg K 〇 H / g, glass transition temperature of 1 2 〇 t > c, weight 1 average of 17 〇, 〇〇〇. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1.4 mol with respect to the secondary hydroxyl group derived from the dicyclic ether compound (a_2). <Step (8): Blocking reaction by isocyanate compound (c3)> Preparation of a polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube in a polymerization tank, and in a polymerization tank And a solution of the addition-formed polyester precursor (C1) obtained by the step (non-volatile component: 502%), a monofunctional isocyanate compound (c3), a catalyst, and an organic solvent were added to the dropping apparatus in the following ratios. [Polymerization tank] 500 parts of a modified polyester precursor (C1) solution [Dropping device] Phenyl isocyanate (c3) 21 parts of tetrabutylammonium tetrahydroborate (catalyst) 〇·1 part of ethyl acetate 10 parts 163 319793 200838965 After replacing the air in the polymerization tank with nitrogen, the temperature was raised to 100 ° C while stirring the solution. Next, in which the mixture of the dropping device was used for 1 hour to drip at a constant rate. After the completion of the dropwise addition, the mixture was reacted for 6 hours while stirring, and then matured, and then 11 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of the addition-molded polyester resin (D1). The solution was light yellow and transparent, and had a nonvolatile content of 50.3 wt% and a viscosity of 19,000 mPa·s. The acid value of the resin (D1) was 0.2 mg ΚΟΠ/g, the hydroxyl value was 22.8 mgKOH/g, and the glass transition temperature was obtained. For -20. . The sweet weight average molecular weight is 170,000. (Synthesis Example 73) The same procedure as in Synthesis Example 72 was carried out except that 376 parts of KURARAY polyol P4090 was used instead of the polyol (a-l_a) used in the step (7) of Synthesis Example 72. A solution of the addition-molded polyester resin (D1) which is light yellow transparent and has a nonvolatile content of 49/7 wt% and a viscosity of 16,000 mPa·s. The resin (D1) had an acid value of 0.5 mgKOH/g, a hydroxyl group value of 20.5 mgKOH/g, a glass transition temperature of 20 ° C, and a weight average molecular weight of 150,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1.4 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a-2). (Synthesis Example 74) Modification was carried out in the same manner as in Synthesis Example 72 except that 376 parts of KURARAY polyol P4011 was used instead of the polyol (a-1-α) used in the step (7) of Synthesis Example 72. A solution of an addition-molded polyester resin 164 319793 200838965 (D1) having a pale yellow transparency and a nonvolatile content of 50.2% by weight and a viscosity of 12,000 mPa·s was obtained. The acid value of the resin (D1) was 〇lmgK〇H/g, the hydroxyl value was 22.8 mg K〇H/g, and the glass transition temperature was -1 Torr. . The weight is two: the amount is 11〇, _. Further, in the above formulation, the cyclic ester (b) is in a ratio of about mol with respect to the secondary hydroxyl group 1 mol derived from the bicyclo:ether compound (a-2). (Synthesis Example 75) The 376 parts of KURARAY polyol P4050 was used instead of the polyhydrazol used in the step (7) of Synthesis Example 72, except that it was prepared in the same manner as in Synthesis Example, to obtain a pale yellow transparency, and The non-volatile component was 50.0% by weight, and the viscosity was 18,5 〇〇mPa·^. The solution of the polyacetate tree (D1) was added. The resin (D1) had an acid value of 〇 8 mg K 〇 H / g, a hydroxyl group value of 21.4 mg KOH / g, a glass transition temperature of - smoke, and a weight average molecular weight of 140,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 丨4 mol with respect to the secondary hydroxy oxime derived from the dicyclic ether compound (a-2). ,

(合成例76) 使用478份之Kyowapol 5〇〇〇pA替代合成例72之步驟(7)所用之多元醇類（a_丨· α )、且將加入聚合槽中之甲苯之里變更成103份，除此之外與合成例72同樣操作而進行調製，並添加乙酸乙酯35〇份，而獲得經加成環狀酯化合物（b)之加成型聚酯前驅物（C1)之溶液。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基丨莫耳，環狀酯（b)成為約1.4莫耳之比率。其次’使用所得之加成型聚酯前驅物（C1)溶液（不揮發 319793 165 200838965 成分為50.2重量。/。)500份、且將異氰酸苯醋（c3)之量變更成15份，除此之外與合成例72之步驟進行同樣反應，而獲得淡黃色透明、且其不揮發成分為5〇1重量％、黏度為15,500mPa.s之加成型聚酯樹脂（m)之溶液。該樹脂（di) 之酸價為1.2mgKOH/g、絲價為19 5mgK〇H/g、玻璃轉移溫度為-2G°C、重量平均分子量為135，_。 (合成例77) 將合成例72之步驟（7)所用之多元醇類^-^^ )變更成 • m份之KURARAY多元醇P60! 0以及1 δ8份之kuraray 多元醇P20H)，除此之外與合成例72同樣操作而進行調製，而獲得淡黃色透明、且其不揮發成分為5〇2重量％、黏度為22,500mPa . s之加成型聚酯樹脂（D丨）之溶液。該樹脂（D1)之酸價為〇.imgK〇H/g、羥基價為 '玻璃轉移溫度為一25¾、重量平均分子量為17〇,〇〇〇。又，在上述配方中’相對於源自二環狀醚化合物（a_2’)之二級羥 _基1莫耳，環狀酯（b)成為約i ·4莫耳之比率。 (合成例78) 使甩658份之ΤΡΑΕ_617替代合成例72之步驟（7)所用之多元醇類（a-l· α )、且將加入聚合槽中之甲苯之量變更成 152份，除此之外與合成例72之步驟（7)同樣操作而進行調製L並添加乙酸乙酯447份，而獲得加成型聚酯前驅物（^) 之溶液。X ’在上述配方中’相對於源自二環狀趟化合物 (a-2)之二級羥基〗莫耳，環狀酯（b)成為約14莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發 319793 166 200838965 成分為50.0重量％)500份、且將異氰酸苯酯（c3)之量變更成13份，除此之外與合成例8之步驟（8)同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為50.2重量％、黏度為20,500mPa· s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1) 之酸價為O.lmgKOH/g、羥基價為22.6mgKOH/g、玻璃轉移溫度為一 10°C、重量平均分子量為175,000。 (合成例79) 使用277份之KURARAY多元醇P6010替代合成例72 _之步驟（7)所用之多元醇類（a-1-α )、且將酞酸酐之量變更成11份、將加入聚合槽中之曱苯之量變更成30份、並於聚合槽中添加癸二酸12份作為二羧酸，除此之外與合成例 72之步驟（7)同樣操作而進行調製，並添加乙酸乙酯226 份，而獲得加成型聚酯前驅物（C1)之溶液。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基1莫耳，環狀酯（b)成為約1.4莫耳之比率。龜其次，使用所得之樹脂（C1)溶液（不择發成分為50.0 重量％)500份、且將異氰酸苯酯（c3)之量變更成17份，除此之外與合成例72之步驟（8)進行同樣反應，而獲得淡黃色透明、且其不揮發成分為50.3重量％、黏度為13,500 mPa · s之加成型聚酯樹脂(D1)之溶液。該樹脂（D1)之酸價為O.lmgKOH/g、羥基價為21.7mgKOH/g、玻璃轉移溫度為一 20°C、重量平均分子量為120,000。 (合成例80) 使用合成例A製造之聚酯多元醇375份替代合成例72 167 319793 200838965 之步驟⑺所用之多元醇類㈤·α)，除此之外與合同樣操作而進行調製，而獲得淡黃色透明分為5 0 2重詈〇/„、斑疮去，， …不揮备成 =二2重里/0 #占度為14,〇〇〇ιηρ"之加成型聚醋樹脂 )之洛液。該樹脂（D1)之酸價為〇5mgK〇H/g、羥基價 19.7mgKOH/g、玻璃轉移溫度為-lot：、重量平^子I =r25,000。又，在上述配方中，相對於源自二環狀』 5物（a-2)之二級經基i莫耳，環狀g|(b)成為約比率。 ·矢寸心 (合成例δΐ) 使用合成例Β製造之聚酯多元醇3 7 7份替代合 2 之步驟⑺所用之多元醇類㈤…，除此之外與合成例Μ 同樣操作而進行調製，而獲得淡黃色透明、且其不揮發成分為50.0重量。/。、黏度為12，_mPa.s之加成型聚醋樹脂 (D1)之溶液。該樹脂（D1)之酸價為〇5mgK〇H/g、羥基價為 13.5mgKOH/g、玻璃轉移溫度為—4〇〇c、重量平均分子量為115,000。又，在上述配方中，相對於源自二環狀鍵化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約14莫耳之比率。、 (合成例δ2) •使用駄酸酐27份替代合成例72之步驟（7)所用之低分子量二羧酸類（a-1-l)、且將加入聚合槽中之甲苯之量變更成78份’除此之外與合成例72之步驟（7)同樣地進行反應，並添加乙酸乙酯281份，而獲得加成型聚酷前驅物（ci) 之溶液。又’在上述配方中’相對於源自二環狀醚化合物 319793 168 200838965 (a-2)之二級羥基丨莫耳，環狀酯（b)成為約14莫耳之比率。其次，使用所得之樹脂（C1)溶液（不揮發成分為5〇〇重量％)500份、且將異氰酸苯醋（c3)之量變更成⑴分，除此之外與合成例8之步驟（8)進行同樣反應，而獲得淡黃色透明、且其不揮發成分為5〇2重量％、黏度為i5,〇〇〇mPa. s之加成型聚酯樹脂（D1)之溶液。該樹脂①丨）之酸價為 MmgKOH/g、羥基價為18.8mgK〇H/g、玻璃轉移溫度為 — 20°C、重量平均分子量為142,000。魯（合成例8 3 ) 使用海米克酸酐（Himic anhydride)30份替代合成例72 t步驟⑺所用之低分子量二叛酸類（a-H)、且將加入聚合槽中之甲苯之量變更成8〇份，除此之外與合成例72之步，（7)同樣地操作進行調製，並添加乙酸乙酯份，而獲得加成型聚酯前驅物（C1)之溶液。又，在上述配方中，相 v ;源自—環狀驗化合物（&_2)之二級經基1莫耳，環狀酯鲁（b)成為約1.4莫耳之比率。、其次’使用所得之加成型聚醋前驅物（C1)溶液（不揮發成刀為50· 1重量％)5〇〇份、且將異氰酸苯酯（c3)之量變更成22伤，除此之外與合成例72之步驟（8)同樣地進行反 :而獲得淡黃色透明、且其不揮發成分為50.0重量％、 j度為l7,5〇〇mPa· s之加成型聚酯樹脂⑴1)之溶液。該樹月曰（Dl)之酸價為〇〗mgK〇H/g、羥基價為l6 5mgK〇H/g、破离付移溫度為一 2〇°C、重量平均分子量為165,〇〇〇。 (合成例84) 169 319793 200838965 使用又苯氧基第二環氧丙基醚（大阪瓦斯化學股份公 *司衣之BPEFG，別名為9,9_雙乙氧基環氧丙氧基）苯基]9H苐刀子1 : 550·5，環氧價：3.26(eq/Kg))55份替代合成例72之步驟⑺所用之二環狀醚化合物㈣、且將加入滴下裝置中之乙酸乙酯之量變更成54份，除此之外 14 〇成例72之步驟（7)同樣地操作進行調製，並添加乙酸乙醋321份，而獲得加成型聚酯前驅物（C1)之溶液。又，在上述配方中，相對於源自二環狀ϋ化合物（a-2)之二級經基1莫耳，環狀_)成為約14莫耳之比率。胃其次，使用所得之樹脂（C1)溶液（不揮發成分為5〇·ΐ 重里/〇)500伤、且將異氰酸苯醋（c3)之量變更成22份，除 =之外與合成例73之㈣（8)同樣地進行反應，而獲得淡 ’、色透月且其不揮發成分為5〇·2重量％、黏度為21，000 mPa S之加成型聚醋樹脂(D1)之溶液。該樹脂（D1)之酸價為〇.lmgK〇H/g、經基價為mmgKOH/g、玻璃轉移溫度為-20°C、重量平均分子量為17〇，_。 (合成例85) 使用1，4·雙{[(3-乙基_3_氧雜環丁基）甲氧基]甲基}苯別伤以及間苯一紛二環氧丙基酸(別名為苯基雙（環氧丙基醚），分子量為222·2)1〇份替代合成例72之步驟（7) 在刀子内具有2個環狀醚基之化合物（a_2)、且將加入滴下衣置中之乙酸乙醋之量變更成46份，除此之外與合成例72之步驟（7)同樣地進行反應，並添加乙酸乙醋3〇4 份，而獲得加成型聚酯前驅物（C1)之溶液。又，在上述配 319793 170 200838965 方中，相對於源自二環狀醚化合物（a_2)之二級羥基丨莫耳’環狀酯（b)成為約1·7莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為49·8重量％)5⑽份，除此之外與合成例72之步驟 (8)同松地進行反應，而獲得淡黃色透明、且其不揮發成分為49·7重里％、黏度為n，〇〇〇mPa.s之加成型聚酯樹脂①1) 之溶液。該樹脂（D1)之酸價為〇.5mgK〇H/g、羥基價為 25,3mgKOH/g、玻璃轉移溫度為_25。〇、重量平均分子 ♦為 100,000 〇 (合成例86) 成使用雙紛A “分子量環氧丙基樹脂「皿⑽2」（日本環氧樹脂公司製，環氧當量：635(g/eq)，每—分子之斗均OH: 3.3個）130份替代合成例72之步驟⑺所用之二拜狀鱗化合物㈣、且將加人滴下裝置中之乙酸乙酯之量變更成,80份，除此之外與合成例72之步驟⑺同樣地進行及應’並添加乙酸乙酯370份，而痛π 4上、π 切而獲侍加成型聚酯前驅物（Cl 之溶液。又’在上述配方中’相對於源自二環狀醚化合物 (a-2)之二級㈣！莫耳，環狀§旨⑼成為約Q 5料之比率士'、^一人使用所狀加成型聚醋前驅物（C1)溶液（不揮發成为為50.2重量％)500份、且將異氛酸苯酉旨之量變更成^ 份，除此之外與合成例72之步驟_樣反獲得淡黃色透明、且其不揮發成分為丁汉應而 p 為〇·2重1%、黏度為 25,000mPa · s之加成型聚酯樹脂① 之酸價為〇.5m⑽H/g、^液。該樹脂则 s 土 1貝马12.1mgK〇H/g、玻璃轉 319793 171 200838965 移溫度為一15°C、重量平均分子量為18〇,〇〇〇。 (合成例87) 使用新戊二醇二環氧丙基醚28份替代合成例72之步驟（7)所用之二環狀醚化合物（a_2)、且將加入滴下襞置中: 乙酸乙酯之量變更成45份，除此之外與合成例72之步驟 (7) 同樣地進行反應，並添加乙酸乙酯3〇3份，而獲得二成型聚酯前驅物（C1)之溶液。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基i莫耳，環狀酯（b)成為' •約1.1莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為50.0重量％)500份，除此之外與合成例72之步驟 (8) 同木k地進行反應，而獲得淡黃色透明、且其不揮發成分為50·2重量％、黏度為i2,50〇mpa· s之加成型聚酯樹脂（m) 之溶液。該樹脂（D1)之酸價為0.2mgK〇H/g、羥基價為 23.4mgKOH/g、玻璃轉移溫度為一 5〇〇c、重量平均分子量 •為 120,000 〇 (合成例δ8) 使用雙_(3,4_環氧基環己基）己二酸醋（分子量為 366.5)100份替代合成例72之步驟（7)所用之二環狀醚化合物(a-2)、且將加入滴下裝置中之乙酸乙酯之量變更成8〇份，除此之外與合成例72之步驟（7)同樣地進行反應，並添加乙酸乙酯370份，而獲得加成型聚酯前驅物（C1)之溶液。又，在上述配方中，相對於源自二環狀醚化合物（a_2) 之一級羥基1莫耳，環狀酯（b)成為約〇.5莫耳之比率。 319793 172 200838965 其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為50.0重量％)5〇〇份、且將異氰酸苯酯之量變更成25 份，除此之外與合成例72之步驟(8)同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為5〇·5重量％、黏度為 19,000mPa · s之加成型聚酯樹脂（m)之溶液。該樹脂⑼) 之酸價為0.5mgKOH/g、羥基價為13 5mgK〇H/g、玻璃轉移溫度為一20°C、重量平均分子量為165,〇〇〇。 (合成例89) 使用聯笨-4,4’-二環氧丙基醚(別名為雙（環氧丙氧基）-1，Γ-聯苯，分子量·· 298·3)30份替代合成例72之步驟（7)所用之一環狀_化合物（a-2)、且將加入滴下裝置中之乙酸乙酯之量變更成44份，除此之外與合成例72之步驟 (7)同樣地進行反應，並添加乙酸乙酯3〇〇份，而獲得加成型聚醋前驅物（C1)之溶液。又，在上述配方中，相對於源自二環狀醚化合物(a-2)之二級羥基丨莫耳，環狀酯（b)成為 •約1·4莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為50·1重量％)5〇〇份、且將異氰酸苯酯之量變更成2〇份’徐此之外與合成例72之步驟⑻同樣地進行反應.，而獲得淡黃色透明、且其不揮發成分為5〇〇重量％、黏度為 15,000mPa · s之加成型聚酯樹脂pi)之溶液。該樹脂（Dl) 之酸價為O.lmgKOH/g、羥基價為i7.2mgKOH/g、玻璃轉移溫度為一 20。(：、重量平均分子量為145,000。 (合成例90；) 319793 173 200838965 使用占-戊内酷28份替代合成例72之步驟⑺所用之環狀醋（b)、且將加入滴下裝置中之乙酸乙醋之量變更成私份，除此之外與合成例72之步驟（7)同樣地進行反應，並添加乙酸乙酯304份，而獲得加成型聚酯前驅物（ci)之溶液。又，在上述配方中，相對於源自二環狀鍵化合物（Μ) 之二級羥基1莫耳，環狀醋（b)成為約14莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為50.0重量％)50(M分，除此之外與合成例72之步驟 ♦⑻同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為50.2重篁。/〇、黏度為21，〇〇〇mPa.s之加成型聚醋樹脂则之溶液。該樹脂（D1)之酸價為〇 5mgK〇H/g、羥基價為 18.9mgKOH/g、玻璃轉移溫度為一 2〇c>c、重量平均分子量為 195,000 〇 (合成例91) . 使用r _T㈣24份替代合成例72之步驟⑺所用之鲁環狀醋⑻、且將加入滴下裝置中之乙酸乙醋之量變更成45 份，除此之外與合成例72之步驟⑺同樣地進行反應，並添加乙酸乙酉旨30H分，而獲得加成型聚醋前驅物（ci)之溶液。又，在上述配方中，相對於源自二環狀驗化合物（a·]) 之二級經基1莫耳，環狀醋（b)成為約1.4莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為50,1重量％)5〇〇份，除此之外與合成例72之步驟 ⑻同樣地f行反應，而獲得淡黃色透明、且其不揮發成分為50.1重里/〇黏度為22,5〇〇mpa.s之加成型聚酯樹脂（D1) 319793 174 200838965 之々;夜。e亥樹脂（Dl)之酸價為〇.5mgK〇H/g、經基價為 24.3mgKOH/g、破璃轉移溫度為—15它、重量平均分子量為 200,〇〇〇〇 (合成例92) 將合成例72之步驟（7)所用之環狀酯（b)之量變更成ι〇伤、且將加入滴下農置中之乙酸乙酯之量變更成4〇份，除 Λ之外與合成例72之步驟⑺同樣地進行反應，並添加乙酉夂乙酉日292伤’而獲得加成型聚醋前驅物（c工）之溶液。又， ♦在上述配方中，4目對於源自二環狀·合物（a_2)之二級經基1莫耳，環狀酯（b)成為約0.4莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為50」重量％)500份，除此之外與合成例72之步驟 (8)同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為50.0重篁％、黏度為-’32,〇〇〇mPa.s之加成型聚酯樹脂①丄) 之溶液。該樹脂（D1)之酸價為〇 6mgK〇H/g、經基價為籲48.4mgKOH/g、玻璃轉移溫度為—15t、重量平均分子量為 290,000 〇 (合成例93) 將合成例72之步驟（7)所用之環狀酯化合物（b)之量變更成80份、且將加入滴下裝置中之乙酸乙酯之量變更成 63份，除此之外與合成例72之步驟（7)同樣地進行反應，並添加乙酸乙醋339份，而獲得加成型聚醋前驅物（cl)之溶液。又，在上述配方中，相對於源自二環狀醚化合物之二級羥基1莫耳，環狀酯（b)成為約35莫耳之比率。 319793 175 200838965 、:、人*用所*之加成型聚醋前驅物（ci)溶液（不揮發成分為50·5重量八 a x 里/。）5〇〇份，除此之外與合成例72之(Synthesis Example 76) The polyol (a_丨·α ) used in the step (7) of Synthesis Example 72 was replaced with 478 parts of Kyowapol 5〇〇〇pA, and the toluene added to the polymerization tank was changed to 103. A solution of the addition-formed polyester precursor (C1) to which the cyclic ester compound (b) was added was obtained by preparing the same procedure as in Synthesis Example 72, and adding 35 parts of ethyl acetate. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1.4 mol with respect to the secondary hydroxy oxime derived from the dicyclic ether compound (a_2). Next, 'using the obtained addition-formed polyester precursor (C1) solution (non-volatile 319793 165 200838965 component 50.2 wt%) 500 parts, and changing the amount of isocyanate vinegar (c3) to 15 parts, except Further, in the same manner as in the step of Synthesis Example 72, a solution of the addition-molded polyester resin (m) which was light yellow transparent and had a nonvolatile content of 5% by weight and a viscosity of 15,500 mPa·s was obtained. The resin (di) had an acid value of 1.2 mgKOH/g, a silk price of 19 5 mg K〇H/g, a glass transition temperature of -2 G ° C, and a weight average molecular weight of 135, _. (Synthesis Example 77) The polyols used in the step (7) of Synthesis Example 72 were changed to K-ray KURARAY polyol P60! 0 and 1 δ 8 parts of kuraray polyol P20H). Further, it was prepared in the same manner as in Synthesis Example 72, and a solution of an addition-molded polyester resin (D丨) having a pale yellow transparency and a nonvolatile content of 5.2 wt% and a viscosity of 22,500 mPa·s was obtained. The acid value of the resin (D1) was 〇.imgK〇H/g, and the hydroxyl value was 'glass transition temperature was 253⁄4, and the weight average molecular weight was 17〇, 〇〇〇. Further, in the above formula, the cyclic ester (b) is a ratio of about i · 4 moles with respect to the secondary hydroxyl group 1 mole derived from the dicyclic ether compound (a_2'). (Synthesis Example 78) 658 parts of ΤΡΑΕ_617 was used instead of the polyol (al·α ) used in the step (7) of Synthesis Example 72, and the amount of toluene added to the polymerization tank was changed to 152 parts, and A solution L was prepared in the same manner as in the step (7) of Synthesis Example 72, and 447 parts of ethyl acetate was added to obtain a solution of the modified polyester precursor (^). X ' in the above formula' is relative to the secondary hydroxyl group derived from the dicyclic quinone compound (a-2), and the cyclic ester (b) becomes a ratio of about 14 moles. Next, 500 parts of the obtained addition-formed polyester precursor (C1) solution (non-volatile 319793 166 200838965 component: 50.0% by weight) was used, and the amount of the phenyl isocyanate (c3) was changed to 13 parts, and the Further, a reaction was carried out in the same manner as in the step (8) of Synthesis Example 8 to obtain a solution of the addition-molded polyester resin (D1) which was pale yellow transparent and had a nonvolatile content of 50.2% by weight and a viscosity of 20,500 mPa·s. The resin (D1) had an acid value of 0.1 mg KOH/g, a hydroxyl value of 22.6 mgKOH/g, a glass transition temperature of 10 ° C, and a weight average molecular weight of 175,000. (Synthesis Example 79) The 277 parts of KURARAY polyol P6010 was used instead of the polyol (a-1-α) used in the step (7) of Synthesis Example 72, and the amount of the phthalic anhydride was changed to 11 parts, and the polymerization was carried out. The amount of benzene in the tank was changed to 30 parts, and 12 parts of sebacic acid was added to the polymerization tank as a dicarboxylic acid, and the same procedure as in the step (7) of Synthesis Example 72 was carried out, and acetic acid was added thereto. A solution of the addition-formed polyester precursor (C1) was obtained from 226 parts of ethyl ester. Further, in the above formula, the cyclic ester (b) has a ratio of about 1.4 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a-2). The turtle was used in an amount of 500 parts of the obtained resin (C1) solution (50.0% by weight of the component), and the amount of the phenyl isocyanate (c3) was changed to 17 parts, and the synthesis example 72 was used. The same reaction was carried out in the step (8) to obtain a solution of the addition-molded polyester resin (D1) which was pale yellow transparent and had a nonvolatile content of 50.3 wt% and a viscosity of 13,500 mPa·s. The resin (D1) had an acid value of 0.1 mg KOH/g, a hydroxyl value of 21.7 mgKOH/g, a glass transition temperature of 20 ° C, and a weight average molecular weight of 120,000. (Synthesis Example 80) The 375 parts of the polyester polyol produced in Synthesis Example A was used instead of the polyol (5)·α) used in the step (7) of Synthesis Example 72 167 319793 200838965, except that the same operation was carried out in the same manner as in the case of the combination. Obtained a light yellow transparent divided into 5 0 2 heavy 詈〇 / „, spot sore, ... not sway into = 2 2 zhongli / 0 #占度14, 〇〇〇ιηρ" added molding polyester resin) The acid value of the resin (D1) is 〇5 mgK〇H/g, the hydroxyl value is 19.7 mgKOH/g, the glass transition temperature is -lot:, and the weight is flat I = r25,000. Further, in the above formula The ring g|(b) becomes an approximate ratio with respect to the secondary meridine i mole derived from the dicyclic quinone (a-2). · Sagittacentric (synthesis example δ ΐ) Manufactured using a synthesis example The polyester polyol (37) was replaced with the polyol (5) used in the step (7) of the second step, except that it was prepared in the same manner as in the synthesis example, to obtain a pale yellow transparent material and a nonvolatile content of 50.0 by weight. a solution of the addition-molded polyester resin (D1) having a viscosity of 12, _mPa.s. The acid value of the resin (D1) is mg5 mgK〇H/g, and the hydroxyl value is 13.5 mgKOH/g. The glass transition temperature is -4 〇〇c, and the weight average molecular weight is 115,000. Further, in the above formulation, the cyclic ester (b) relative to the secondary hydroxy oxime derived from the dicyclic bond compound (a-2) ) is a ratio of about 14 moles. (Synthesis Example δ2) • 27 parts of phthalic anhydride is used instead of the low molecular weight dicarboxylic acid (a-1-l) used in the step (7) of Synthesis Example 72, and will be added to the polymerization tank. In the same manner as in the step (7) of Synthesis Example 72 except that the amount of toluene in the mixture was changed to 78 parts, a solution of the addition of the polycondensation precursor (ci) was obtained by adding 281 parts of ethyl acetate. Further, in the above formulation, the cyclic ester (b) is a ratio of about 14 moles relative to the secondary hydroxy oxime derived from the dicyclic ether compound 319793 168 200838965 (a-2). 500 parts of the resin (C1) solution (nonvolatile content: 5% by weight), and the amount of the isocyanate benzene vinegar (c3) was changed to (1), and the step (8) of Synthesis Example 8 was used. The same reaction was carried out to obtain a pale yellow transparent, and its nonvolatile content was 5.2 wt%, the viscosity was i5, and 〇〇〇mPa.s A solution of the molded polyester resin (D1) having an acid value of MmgKOH/g, a hydroxyl value of 18.8 mg K〇H/g, a glass transition temperature of -20 ° C, and a weight average molecular weight of 142,000. Synthesis Example 8 3) Using 30 parts of Himic anhydride instead of the low molecular weight direxate (aH) used in the step 72 (7) of Synthesis Example 72, and changing the amount of toluene added to the polymerization tank to 8 parts, Otherwise, the same procedure as in the synthesis of Example 72, (7), and the ethyl acetate fraction were added to obtain a solution of the addition-formed polyester precursor (C1). Further, in the above formulation, the phase v; the secondary radical of the ring-like compound (&_2) was 1 molar, and the cyclic ester (b) became a ratio of about 1.4 mole. Next, using the obtained addition-formed polyacetic acid precursor (C1) solution (non-volatile forming knives: 50.1% by weight) 5 parts, and changing the amount of phenyl isocyanate (c3) to 22 wounds, Otherwise, in the same manner as in the step (8) of Synthesis Example 72, an inversely colored polyester having a pale yellow transparency and a nonvolatile content of 50.0% by weight and a j degree of 1,7 〇〇mPa·s was obtained. A solution of the resin (1) 1). The acid value of the tree (Dl) is 〇mgK〇H/g, the hydroxyl value is l6 5mgK〇H/g, the breaking temperature is 1〇°C, and the weight average molecular weight is 165. . (Synthesis Example 84) 169 319793 200838965 Use of phenoxy second epoxy epoxide (BPEFG, Osaka Gas Chemical Co., Ltd., alias 9,9_bisethoxyoxypropyloxy) phenyl ] 9H 苐 knife 1 : 550·5, epoxy price: 3.26 (eq/Kg)) 55 parts of the dicyclic ether compound (IV) used in place of the step (7) of Synthesis Example 72, and added to the ethyl acetate in the dropping device The amount was changed to 54 parts, and the same procedure as in the step (7) of Example 72 was carried out, and 321 parts of ethyl acetate was added to obtain a solution of the addition-formed polyester precursor (C1). Further, in the above formulation, the ring_) is a ratio of about 14 moles with respect to the secondary radical 1 mole derived from the dicyclic quinone compound (a-2). The stomach was used, and the obtained resin (C1) solution (nonvolatile content was 5 〇·ΐ 重里/〇) was used for 500 injuries, and the amount of isocyanate vinegar (c3) was changed to 22 parts, except for = and synthesis. (4) (8) of Example 73 was reacted in the same manner to obtain an addition-formed polyester resin (D1) having a light color, a color-transparent month, a nonvolatile content of 5 〇 2 % by weight, and a viscosity of 21,000 mPa s. Solution. The resin (D1) had an acid value of 〇.lmgK〇H/g, a base price of mmgKOH/g, a glass transition temperature of -20 ° C, and a weight average molecular weight of 17 Å. (Synthesis Example 85) Using 1,4·bis{[(3-ethyl-3-(oxetanyl)methoxy]methyl}benzene and benzoic acid (alias) a phenyl bis(epoxypropyl ether) having a molecular weight of 222·2) 1 liter instead of the step (7) of Synthesis Example 72. A compound (a_2) having two cyclic ether groups in a knives, and added to the dropping The amount of the ethyl acetate in the clothes was changed to 46 parts, and the reaction was carried out in the same manner as in the step (7) of Synthesis Example 72, and then 4 parts of ethyl acetate was added to obtain an additive polyester precursor. Solution of (C1). Further, in the above-mentioned formula 319793 170 200838965, the ratio of the secondary hydroxy 丨mol' cyclic ester (b) derived from the dicyclic ether compound (a_2) is about 1.7 mol. Next, 5 (10) parts of the obtained addition-formed polyester precursor (C1) solution (49.8% by weight of a nonvolatile component) was used, and the reaction was carried out in the same manner as in the step (8) of Synthesis Example 72. A solution of a modified polyester resin 11) which is light yellow transparent and has a nonvolatile content of 49.7% by weight, a viscosity of n, and 〇〇〇mPa.s. The resin (D1) had an acid value of mg. 5 mg K 〇 H / g, a hydroxyl value of 25, 3 mg KOH / g, and a glass transition temperature of _25. 〇, weight average molecular weight ♦ 100,000 〇 (Synthesis Example 86) The use of double A "molecular weight epoxy propyl resin "Dish (10) 2" (made by Nippon Epoxy Co., Ltd., epoxy equivalent: 635 (g / eq), per - Molecular OH: 3.3) 130 parts of the quaternary compound (4) used in the step (7) of Synthetic Example 72, and the amount of ethyl acetate in the dropping device was changed to 80 parts. Further, in the same manner as in the step (7) of Synthesis Example 72, 370 parts of ethyl acetate were added and added, and the solution of the polyester precursor (solution of Cl) was obtained by the π cut and the π cut. 'relative to the secondary (four) derived from the dicyclic ether compound (a-2)! Moore, the ring § (9) becomes the ratio of the Q 5 material, and the one used for the addition of the shaped polyurethane precursor ( C1) 500 parts of a solution (non-volatile content: 50.2% by weight), and the amount of the benzoic acid benzoquinone was changed to a portion, and the step of the synthesis example 72 was obtained as a pale yellow transparent, and The non-volatile content is Ding Han Ying and p is 〇·2 weight 1%, viscosity is 25,000 mPa · s. The acid value of the added polyester resin 1 is 〇.5m. H/g, liquid. The resin is s soil 1 beta horse 12.1 mg K 〇 H / g, glass to 319793 171 200838965 transfer temperature of a 15 ° C, weight average molecular weight of 18 〇, 〇〇〇. (Synthesis Example 87 Using 28 parts of neopentyl glycol diepoxypropyl ether instead of the dicyclic ether compound (a_2) used in the step (7) of Synthesis Example 72, and adding it to the dropping device: The amount of ethyl acetate was changed to 45 In addition, the reaction was carried out in the same manner as in the step (7) of Synthesis Example 72, and ethyl acetate (3 〇 3 parts) was added to obtain a solution of the two-molded polyester precursor (C1). Further, in the above formulation The cyclic ester (b) becomes a ratio of about 1.1 moles relative to the secondary hydroxyl group i mole derived from the dicyclic ether compound (a-2). Next, the resulting addition-formed polyester precursor is used. (C1) 500 parts of a solution (nonvolatile content: 50.0% by weight), and otherwise reacted with the step (8) of Synthesis Example 72 to obtain a pale yellow transparent material and a nonvolatile content of 50· 2% by weight, a solution of the addition-molded polyester resin (m) having a viscosity of i2, 50 〇 mpa·s. The acid value of the resin (D1) is 0.2 mg K〇H/g, and the hydroxyl value is 2 3.4 mg KOH / g, glass transition temperature of 5 〇〇 c, weight average molecular weight • 120,000 〇 (synthesis example δ8) using bis (3,4-epoxycyclohexyl) adipic acid vinegar (molecular weight 366.5) 100 parts of the dicyclic ether compound (a-2) used in the step (7) of the synthesis example 72, and the amount of ethyl acetate added to the dropping device was changed to 8 parts, and the synthesis example 72 was used. Step (7) was carried out in the same manner, and 370 parts of ethyl acetate was added to obtain a solution of the addition-formed polyester precursor (C1). Further, in the above formulation, the cyclic ester (b) has a ratio of about 0.5 mol with respect to 1 mol of the hydroxyl group derived from the monocyclic ether compound (a_2). 319793 172 200838965 Next, using the obtained addition molding polyester precursor (C1) solution (nonvolatile content: 50.0% by weight) 5 parts, and changing the amount of phenyl isocyanate to 25 parts, The reaction was carried out in the same manner as in the step (8) of Synthesis Example 72 to obtain a solution of the modified polyester resin (m) which was pale yellow transparent and had a nonvolatile content of 5 〇 5% by weight and a viscosity of 19,000 mPa · s. . The resin (9)) had an acid value of 0.5 mgKOH/g, a hydroxyl group value of 13 5 mg K〇H/g, a glass transition temperature of 20 ° C, and a weight average molecular weight of 165, 〇〇〇. (Synthesis Example 89) Substituting 30 parts of LBP-4,4'-diepoxypropyl ether (also known as bis(glycidoxy)-1, fluorene-biphenyl, molecular weight · 298·3) One of the cyclic _ compounds (a-2) used in the step (7) of Example 72, and the amount of ethyl acetate added to the dropping device was changed to 44 parts, and the step (7) of Synthesis Example 72 was used. The reaction was carried out in the same manner, and ethyl acetate (3 parts) was added to obtain a solution of the addition-formed polyester precursor (C1). Further, in the above formulation, the cyclic ester (b) is a ratio of about 1.4 mol with respect to the secondary hydroxy oxime derived from the dicyclic ether compound (a-2). Next, the obtained addition-formed polyester precursor (C1) solution (non-volatile content: 50. 1% by weight) was used in an amount of 5 parts, and the amount of phenyl isocyanate was changed to 2 parts. The reaction was carried out in the same manner as in the step (8) of Synthesis Example 72 to obtain a solution of a modified polyester resin pi) which was pale yellow transparent and had a nonvolatile content of 5% by weight and a viscosity of 15,000 mPa·s. The resin (Dl) had an acid value of 0.1 mgKOH/g, a hydroxyl group value of i7.2 mgKOH/g, and a glass transition temperature of 20%. (:, weight average molecular weight was 145,000. (Synthesis Example 90;) 319793 173 200838965 The use of the quaternary vinegar (b) used in the step (7) of Synthesis Example 72, and the acetic acid to be added to the dropping device, was used. The reaction was carried out in the same manner as in the step (7) of Synthesis Example 72 except that the amount of the ethyl acetate was changed to a portion, and a solution of the addition of the polyester precursor (ci) was obtained by adding 304 parts of ethyl acetate. In the above formulation, the cyclic vinegar (b) is a ratio of about 14 moles relative to the secondary hydroxyl group 1 mole derived from the dicyclic bond compound (Μ). Next, the resulting addition molded polyester precursor is used. In the same manner as in the step ♦ (8) of Synthesis Example 72, the solution (C1) (non-volatile content: 50.0% by weight) was obtained in the same manner as in the step (8) of Synthesis Example 72 to obtain a pale yellow transparent material and a nonvolatile content of 50.2.篁./〇, viscosity 21, 〇〇〇mPa.s addition of a solution of a polyacetal resin. The acid value of the resin (D1) is mg5mgK〇H/g, the hydroxyl value is 18.9mgKOH/g, glass The transfer temperature was 1 〇c>c, and the weight average molecular weight was 195,000 Å (Synthesis Example 91). Using r _T The reaction was carried out in the same manner as in the step (7) of Synthesis Example 72, except that the amount of the vinegar (8) used in the step (7) of the synthesis example 72 was changed to 45 parts, and the amount of the ethyl acetate to be added to the dropping apparatus was changed to 45 parts. And adding a solution of ethyl acetate to 30H to obtain a solution of the addition-formed polyester precursor (ci). Further, in the above formula, relative to the secondary base 1 derived from the two-ring test compound (a·]) The ear, the annular vinegar (b) is a ratio of about 1.4 moles. Next, the obtained addition-formed polyester precursor (C1) solution (non-volatile content of 50, 1% by weight) is used in 5 parts, in addition to this. Further, in the same manner as in the step (8) of Synthesis Example 72, the reaction was carried out in the same manner to obtain an addition-molded polyester resin (D1) 319793 which was light yellow transparent and had a nonvolatile content of 50.1 mils/〇 viscosity of 22,5 〇〇mpa.s. 174 200838965; night. The acid value of ehai resin (Dl) is 〇.5mgK〇H/g, the base price is 24.3mgKOH/g, the glass transition temperature is -15, and the weight average molecular weight is 200. 〇〇〇 (Synthesis Example 92) The amount of the cyclic ester (b) used in the step (7) of Synthesis Example 72 was changed to ι 〇, and the drop was added. The amount of ethyl acetate in the agricultural setting was changed to 4 parts, and the reaction was carried out in the same manner as in the step (7) of Synthesis Example 72 except that hydrazine was added, and acetonitrile was added to the 292 wound to obtain an addition-formed polyester precursor (c). Further, ♦ In the above formulation, 4 meshes are the molar ratio of the cyclic ester (b) to about 0.4 moles for the secondary radical 1 mole derived from the dicyclic compound (a_2). Next, the reaction was carried out in the same manner as in the step (8) of Synthesis Example 72 except that 500 parts of the obtained addition-formed polyester precursor (C1) solution (50% by weight of the nonvolatile component) was used, and a pale yellow color was obtained. A solution which is transparent and has a nonvolatile content of 50.0% by weight and a viscosity of -'32, 〇〇〇mPa.s of the addition-molded polyester resin 1). The acid value of the resin (D1) was 〇6 mgK〇H/g, the base price was 48.4 mgKOH/g, the glass transition temperature was -15 Torr, and the weight average molecular weight was 290,000 〇 (Synthesis Example 93). (7) The amount of the cyclic ester compound (b) to be used is changed to 80 parts, and the amount of ethyl acetate added to the dropping device is changed to 63 parts, and otherwise the same as the step (7) of Synthesis Example 72. The reaction was carried out, and 339 parts of ethyl acetate was added to obtain a solution of the addition-formed polyester precursor (cl). Further, in the above formulation, the cyclic ester (b) has a ratio of about 35 moles relative to the secondary hydroxyl group 1 mole derived from the dicyclic ether compound. 319793 175 200838965 , :, person * using the addition of the formed polyacetate precursor (ci) solution (non-volatile content is 50 · 5 weight eight ax / /) 5 parts, in addition to the synthesis example 72 It

(8)同樣地進行反應，而班俨 ” A 或们杳旦。/、私二更色透明、且其不揮發成分 '、、、里0 —又為6,500mPa.s之加成型聚酯樹脂（Dl) 之溶液。該樹脂（D1)之酸價為1.2mgKOH/g、經基價為 3.5mgK〇H/g、玻璃轉移溫度為_35t：、重量平均分子量為 80,000 〇匈 (合成例94) • 錢為單官能異氰酸酯化合物（c3)之對_甲苯瑞酸美異氰酸酉旨35份替代合成例72之步驟⑻所用之封閉化合ς (c)、且將加入滴下裝f中之乙酸乙醋之量變更成u份，除此之外與合成例72之步驟⑺同樣地進行反應，並添加乙酸乙，13份，而獲得淡黃色透明、且其不揮發成分為 50.3重篁％、黏度為12,〇〇〇1111^ .3之加成型聚酯樹脂（叫）之溶液。該樹脂（D1)之酸價為21.3mgK〇H/g、羥基價為 _ 14.2mgKOH/g、玻璃轉移溫度為—2〇t：、重量平均分子量為105,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約14莫耳之比率〇 (合成例9 5) 使用為矽烧化劑（cl)之三甲基氯矽烷19份替代合成例 72之步驟（8)所用之封閉化合物（c)、且將加入滴下裝置中之乙酸乙酯之量變更成9份，除此之外與合成例72同樣地進行反應，並添加乙酸乙酯10份，而獲得淡黃色透明、且 319793 176 200838965 不揮1成分為50.1重量％、黏度為l2,500mPa · s之加成型聚醋樹脂（D1)之溶液。該樹脂（D1)之酸價為〇.5mg KOH/g、故基價為15 8mgK〇H/g、玻璃轉移溫度為一 2〇它、重i平均分子量為11〇,〇〇〇。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基1莫耳，環狀酯（b) 成為約1 · 4莫耳之比率。 (合成例96) 使用為矽烷化劑（cl)之三乙基矽烷醇13份替代合成例 _ 72之步驟⑻所用之封閉化合物⑷、且將力口人滴下裝置中之乙酸乙醋之量變更成6份，除此之外與合成例72同樣地進仃反應’並添加乙酸乙酯7份，而獲得淡黃色透明、且其不揮發成分為50·2重量％、黏度為n，5〇〇mPa· s之加成型聚醋樹脂（D1)之溶液。該樹脂（D1)之酸價為〇.5mg KOH/g、羥基，價為172mgK〇H/g、玻璃轉移溫度為一 2〇艺、重量平均分子量為98,〇〇〇。又，在上述配方中，相對於源 _自二環狀醚化合物（a_2)之二級羥基i莫耳，環狀酯（b)成為約1.4莫耳之比率。 (合成例97) 使用為矽烷化劑（CO之六甲基二矽氮烷20份替代合成例72之步驟（8)所用之封閉化合物（c)，除此之外與合成例 72同樣地進行反應，並添加乙酸乙酯10份，而獲得淡普色透明、且其不揮發成分為50.2重量％、黏度為9,5〇〇mPa· S之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為〇’5mgK〇H/g、羥基價為2〇.5mgK〇H/g、玻璃轉移溫度為 319793 177 200838965 20C、重量平均分子量為85,〇〇〇。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基1莫耳，環狀 _ (b)成為約L4莫耳之比率。 (合成例98) 使用為酸酐（C2)之酞酸酐15份替代合成例72之步驟 (8)所用之封閉化合物（c)、且將加入滴下裝置中之乙酸乙酯里受更成12伤’除此之外與合成例72同樣地進行反應，亚添加乙酸乙酯13份，而獲得淡黃色透明、且其不揮發成 _刀為50·5重量％、黏度為i5,5〇〇mpa · s之加成型聚酯樹脂 (D1)之溶液。該樹脂（D1)之酸價為78.5mgK〇H/g、羥基價為15.7mgKOH/g、玻璃轉移溫度為一 2(rc、重量平均分子量為 160,〇〇〇〇 (合成例99) 使用為酸酐（c2)之酞酸酐2份替代合·成例72之步驟（8) 所用之封閉化合物（c)、且於谪下裝置中不加入乙酸乙酯， _除此之外與合成例72同樣地進行反應，並添加乙酸乙酯2 份，而獲得淡黃色透明、且其不揮發成分為5〇·3重量％、黏度為10,500mPa· s之加成型聚酯樹脂（D1)之溶液。該樹月曰（D1)之酸價為6.2mgKOH/g、羥基價為52.7mgKOH/g、玻璃轉移溫度為一 20°C、重量平均分子量為i⑽，〇〇〇。又，在上述配方中，相對於源自二環狀醚化合物（a_2)之二級羥基1莫耳，環狀酯（b)成為約1 ·4莫耳之比率。 (合成例100) 使用為酸酐（C2)之海米克酸酐（Himic anhydride)2份替 319793 178 200838965 代合成例72之步驟（8)所用之封閉化合物（c)、且於滴下裝置中不加入乙酸乙酯，除此之外與合成例72同樣地進行= 應，並添加乙酸乙酯2份，而獲得淡黃色透明、且其不揮發成分為50.3重量％、黏度為uwoompa· s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為5 2mgK〇H/g、羥基價為54.2mgKOH/g、玻璃轉移溫度為—2〇〇c、重量平均分子罝為95,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基〗莫耳，環狀酯（b)成為約14莫耳攀之比率。 (合成例101) 使用合成例A製造之聚酯多元醇276份替代合成例72 之步驟（7)所用之多元醇類α )、且將丁二酸酐之量變更成11份、將甲苯之量變更成3〇份、並於聚合槽中添加己二酸5份及異酞酸5份作為二羧酸，除此之外與合成例72之步驟（7)同樣地進行反應，並添力口乙酸乙酯226 擊伤’而獲得加成型聚酯前驅物（C1)之溶液。又，在上述配方中’相對於源自二環狀醚化合物（a_2)之二級羥基1莫耳，環狀酯（b)成為約ι·4莫耳之比率。其次，使用所得之加成型聚酯前驅物（C1)溶液（不揮發成分為50.1重量％)5〇〇份、並使用為酸酐（c2)之酞酸酐2 份替代步驟（8)所用之封閉化合物（c)，除此之外與合成例 72之步驟（8)同樣地進行反應，以乙酸乙酯進行調整，而獲得淡黃色透明、且其不揮發成分為5〇 4重量％、黏度為 14,000mpa · s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1) 179 319793 200838965 之K貝為5.7mgKOH/g、經基價為58.2mgKOH/g、玻璃轉移溫度為一20°C、重量平均分子量為13〇,〇〇〇。 (合成例102) 使用合成例B製造之聚酯多元醇377份替代合成例72 之步驟（7)所用之多元醇類（a_pa )、且使用匕扣丁二醇二環氧丙基醚24份替代二環狀醚化合物（a_2)、並將於滴下衣置中加入之乙酸乙酯之量變更成丨5份，除此之外與合成例72之步驟（7)同樣地進行反應，並添加乙酸乙酯份，瘳而獲得加成型聚酯前驅物（C1)之溶液。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級經基丨莫耳，環狀醋（b)成為約1 ·2莫耳之比率。田其次，使用所得之樹脂（C1)溶液（不揮發成分為5〇3 重量％)500份、並使用為酸酐（c2)之丁二酸酐2份替代步 -·驟⑻所用之封閉化合物⑷，除.此之外與合成例72同樣地進打反應，以乙酸乙酯進行調整，而獲得淡黃色透明、且拳其不揮發成分為49.7重量％、黏度為9,50〇mPa· s之加成型聚酯樹脂（Di)之溶液。該樹脂（D1)之酸價為8 3mg KOH/g、經基價為16 2mgK〇H/g、玻璃轉移溫度為—^、重量平均分子量為90,〇〇〇。 (合成例103) 將合成例72之步驟(8)所用之異氰酸苯酯（c3)之量變更成30份、並將於滴下裝置中加入之乙酸乙酉旨之量變更成 15份’除此之外與合成例72同樣地進行反應，並添加乙酸乙醋15份，而獲得淡黃色透明、且其不揮發成 319793 180 200838965 重里％、黏度為17,000mPa . s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1)之酸價為〇.5mgK〇H/g、羥基價為 0.05mgKOH/g、玻璃轉移溫度為—15°c、重量平均分子量為155,000。又，在上述配方中，相對於源自二環狀醚化合物（a-2)之二級羥基丨莫耳，環狀酯（b)成為約14莫耳之比率。 (合成例104) 使用為酸酐（C2)之酞酸酐20份替代合成例72之步驟 _ (8)所用之封閉化合物⑷，除此之外與合成例72同樣地進行反應，並添加乙酸乙酯10份，而獲得淡黃色透明、且其不揮發成分為50.4重量％、黏度為28,00〇mpa· s之加成型聚酯樹脂（D1)之溶液。該樹脂（m)之酸價為 86.4mgKOH/g、羥基價為〇〇2mgK〇H/g、玻璃轉移溫度為 — 15t：、重量平均分子量為230,000。又，在上述配方中，〃相對於源自一環狀鱗化合物（a_2)之二級經基1莫耳，環狀目曰（b)成為約1 ·4莫耳之比率。 (合成例105) 將合成例72所用之觸媒變更成硝酸四丁基銨，除此之外與合成例72同樣地進行反應，並添加乙酸乙酯以調整，而獲知淡黃色透明、且其不揮發成分為49·7重量％、黏度為17,00〇mPa.s之加成型聚酯樹脂（D1)之溶液。該樹脂（D1) 之酸彳貝為〇.2mgK〇H/g、羥基價為23.5mgKOH/g、玻璃轉移溫度為一 20°C、重量平均分子量為ι65,〇〇〇。又，在上 ^配方中’相對於源自二環狀醚化合物（a-2)之二級經基1 181 319793 200838965 莫耳，環狀_成為約1.4莫耳之比率。 (合成例106) 逸 > ::成例、72省略觸媒，除此之外與合成例72同樣地且乙酸乙酯以調整’而獲得淡黃色透明、成^ 5 5成分為5(U重量％、黏度為17,500mPa.s之加 ο」| :酯樹脂(D1)之溶⑨。該樹脂_之酸價為、基價為26 5mgK°H/g、玻璃轉移溫度為 •相對於源自量：：分子量為150，_。又，在上述配方中，酉旨合物㈣之二級絲1莫耳，環狀曰（b)成為約1·4莫耳之比率。之外_ Υ成例67至ι〇6所得之各樹脂溶液，將該等溶液轉移〇二揮發成分、樹脂之重量平均分子量(Mw)、玻璃至二同二g)、酸價(AV)以及經基價_V)以與合成例1 水之方式評估·，彙總顯示於表9、表。 319793 182 200838965 [表9]加成型聚酯樹脂（D1)之合成例：使用由低分子量二羧酸（a-1-l)與各種多元醇（a-1-α )而成之反應生成物 [高分子量二羧酸（a-1-2)]作為二元酸（a-Ι)時的情形(8) The reaction is carried out in the same manner, and the 俨俨俨 A A / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / A solution of (Dl) having an acid value of 1.2 mgKOH/g, a base price of 3.5 mg K〇H/g, a glass transition temperature of _35t: and a weight average molecular weight of 80,000 〇Hung (Synthesis Example 94 • The money is a monofunctional isocyanate compound (c3) of p-toluic acid mesocyanate, 35 parts of the blocked compound ruthenium (c) used in the step (8) of Synthesis Example 72, and the acetic acid added to the dropping device f is added. The reaction was carried out in the same manner as in the step (7) of Synthesis Example 72 except that the amount of the acetonitrile was changed to the amount of the acetonitrile, and ethyl acetate and 13 parts were added to obtain a pale yellow transparent material, and the nonvolatile content was 50.3% by weight. A solution of a modified polyester resin having a viscosity of 12, 〇〇〇1111^.3. The acid value of the resin (D1) is 21.3 mg K〇H/g, the hydroxyl value is _ 14.2 mgKOH/g, and the glass is transferred. The temperature is -2 〇t: and the weight average molecular weight is 105,000. Further, in the above formulation, relative to the compound derived from the dicyclic ether compound (a-2) The hydroxy oxime and the cyclic ester (b) have a ratio of about 14 moles (Synthesis Example 9 5). Step 19 of the synthesis example 72 was replaced with 19 parts of trimethylchloromethane as a hydrazine burning agent (cl). The reaction was carried out in the same manner as in Synthesis Example 72 except that the amount of the ethyl acetate to be added to the dropping device was changed to 9 parts, and 10 parts of ethyl acetate was added thereto to obtain a light color. A yellow transparent, 319793 176 200838965 solution having a composition of 50.1% by weight and a viscosity of 12,500 mPa·s of the addition-formed polyester resin (D1). The acid value of the resin (D1) is 〇.5 mg KOH/g. Therefore, the base price is 15 8 mg K 〇 H / g, the glass transition temperature is 1 〇, and the average molecular weight of the weight i is 11 〇, 又. Further, in the above formulation, relative to the compound derived from the dicyclic ether ( A-2) The secondary hydroxyl group 1 mol, and the cyclic ester (b) becomes a ratio of about 1 · 4 mol. (Synthesis Example 96) 13 parts of triethyl stanol which is a decylating agent (cl) is used instead. The blocking compound (4) used in the step (8) of the synthesis example _72, and the amount of the ethyl acetate in the drip device is changed to 6 parts, in addition to In the same manner as in Synthesis Example 72, the reaction was carried out in the same manner, and 7 parts of ethyl acetate was added to obtain an addition-formed polyacetate which was pale yellow transparent and had a nonvolatile content of 50.2% by weight and a viscosity of n, 5 〇〇 mPa·s. a solution of the resin (D1) having an acid value of mg.5 mg KOH/g, a hydroxyl group, a valence of 172 mg K〇H/g, a glass transition temperature of 2 Å, and a weight average molecular weight of 98, 〇〇 Hey. Further, in the above formulation, the cyclic ester (b) has a ratio of about 1.4 mol with respect to the source _ from the secondary hydroxyl group i mole of the dicyclic ether compound (a_2). (Synthesis Example 97) The same procedure as in Synthesis Example 72 was carried out, except that the blocking compound (c) used in the step (8) of Synthesis Example 72 was replaced by 20 parts of decylating agent (CO hexamethyldioxane). The reaction was carried out, and 10 parts of ethyl acetate was added to obtain a solution of the addition-molded polyester resin (D1) having a pale pale color and a nonvolatile content of 50.2% by weight and a viscosity of 9,5 〇〇mPa·s. The acid value of the resin (D1) is 〇'5mgK〇H/g, the hydroxyl value is 2〇.5mgK〇H/g, the glass transition temperature is 319793 177 200838965 20C, and the weight average molecular weight is 85, 〇〇〇. In the above formulation, the ring_(b) is a ratio of about L4 molar relative to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a-2). (Synthesis Example 98) Use as an acid anhydride (C2) 15 parts of the phthalic anhydride were replaced by the blocking compound (c) used in the step (8) of Synthesis Example 72, and the amount of the ethyl acetate added to the dropping device was further changed to 12 in the same manner as in Synthesis Example 72. The reaction was carried out, and 13 parts of ethyl acetate was added in the sub-mesh to obtain a pale yellow transparent, which was not volatilized to a knives of 50.5 wt%, and the viscosity was i5, 5 〇〇mpa. · A solution of the addition of the polyester resin (D1). The acid value of the resin (D1) is 78.5 mg K〇H/g, the hydroxyl value is 15.7 mgKOH/g, and the glass transition temperature is 2 (rc, weight average molecular weight) 160, hydrazine (Synthesis Example 99) using 2 parts of phthalic anhydride as the acid anhydride (c2) instead of the blocking compound (c) used in the step (8) of Example 72, and not added in the underarm device The reaction was carried out in the same manner as in Synthesis Example 72 except for ethyl acetate, and ethyl acetate was added in two portions to obtain a pale yellow transparent material, a nonvolatile content of 5 〇 3% by weight, and a viscosity of 10,500 mPa. a solution of the modified polyester resin (D1), which has an acid value of 6.2 mgKOH/g, a hydroxyl value of 52.7 mgKOH/g, a glass transition temperature of 20 ° C, and a weight average molecular weight of i(10), 〇〇〇. Further, in the above formulation, the cyclic ester (b) is a ratio of about 1.4 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a_2). Synthesis Example 100) Using a portion of Himic anhydride as an acid anhydride (C2) for use in the step (8) of Synthesis Example 72, 319793 178 200838965 In the same manner as in Synthesis Example 72, except that ethyl acetate was not added to the dropping apparatus, 2 parts of ethyl acetate was added to obtain a pale yellow transparent material and a nonvolatile content thereof. a solution of 50.3 wt% of a modified polyester resin (D1) having a viscosity of uwoompa·s. The acid value of the resin (D1) is 5 2 mg K〇H/g, the hydroxyl value is 54.2 mgKOH/g, and the glass transition temperature is - 2 〇〇 c, the weight average molecular enthalpy is 95,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 14 moles relative to the secondary hydroxyl group derived from the dicyclic ether compound (a-2). (Synthesis Example 101) 276 parts of the polyester polyol produced in Synthesis Example A was used instead of the polyol (α) used in the step (7) of Synthesis Example 72, and the amount of succinic anhydride was changed to 11 parts, and the amount of toluene was changed. The reaction was carried out in the same manner as in the step (7) of Synthesis Example 72 except that 5 parts of adipic acid and 5 parts of isodecanoic acid were added to the polymerization tank as the dicarboxylic acid, and the reaction was carried out. Ethyl acetate 226 was "injured" to obtain a solution of the addition-formed polyester precursor (C1). Further, in the above formula, the cyclic ester (b) is a ratio of about 1 4 mol with respect to the secondary hydroxyl group 1 mol derived from the dicyclic ether compound (a_2). Next, using the obtained addition-formed polyester precursor (C1) solution (non-volatile content: 50.1% by weight) 5 parts, and using the acid anhydride (c2) phthalic anhydride 2 parts instead of the blocking compound used in the step (8) (c) The reaction was carried out in the same manner as in the step (8) of Synthesis Example 72, and the mixture was adjusted with ethyl acetate to obtain a pale-yellow transparent material having a nonvolatile content of 5% by weight and a viscosity of 14,000. A solution of mpa · s plus shaped polyester resin (D1). The resin (D1) 179 319793 200838965 had a K shell of 5.7 mgKOH/g, a base price of 58.2 mgKOH/g, a glass transition temperature of 20 ° C, and a weight average molecular weight of 13 Å. (Synthesis Example 102) 377 parts of the polyester polyol produced in Synthesis Example B was used instead of the polyol (a_pa) used in the step (7) of Synthesis Example 72, and 24 parts of butyl butyl diglycol diglycidyl ether was used. The reaction was carried out in the same manner as in the step (7) of Synthesis Example 72 except that the di-cyclic ether compound (a_2) was replaced with the amount of ethyl acetate added to the dropping device, and the amount was changed to 5 parts. A solution of the addition-formed polyester precursor (C1) was obtained by taking a portion of ethyl acetate and hydrazine. Further, in the above formulation, the cyclic vinegar (b) has a ratio of about 1.25 mol with respect to the secondary thiol derived from the dicyclic ether compound (a-2). Tianqi, using the obtained resin (C1) solution (non-volatile content of 5〇3 wt%) 500 parts, and using 2 parts of succinic anhydride as the acid anhydride (c2) instead of the blocking compound (4) used in the step (8), In the same manner as in Synthesis Example 72, the reaction was carried out in the same manner as in Synthesis Example 72, and the mixture was adjusted with ethyl acetate to obtain a pale-yellow transparent material, which had a nonvolatile content of 49.7% by weight and a viscosity of 9,50 〇mPa·s. A solution of a shaped polyester resin (Di). The resin (D1) had an acid value of 83 mg KOH/g, a base price of 16 2 mg K 〇 H/g, a glass transition temperature of -^, and a weight average molecular weight of 90 Å. (Synthesis Example 103) The amount of the phenyl isocyanate (c3) used in the step (8) of Synthesis Example 72 was changed to 30 parts, and the amount of the ethyl acetate added to the dropping device was changed to 15 parts. The reaction was carried out in the same manner as in Synthesis Example 72, and 15 parts of ethyl acetate was added to obtain a pale-transparent polyester resin which was light yellow transparent and which did not volatilize to 319793 180 200838965 % by weight and viscosity of 17,000 mPa. Solution of D1). The resin (D1) had an acid value of mg. 5 mg K 〇 H / g, a hydroxyl value of 0.05 mg KOH / g, a glass transition temperature of - 15 ° C, and a weight average molecular weight of 155,000. Further, in the above formulation, the cyclic ester (b) has a ratio of about 14 moles with respect to the secondary hydroxy oxime derived from the dicyclic ether compound (a-2). (Synthesis Example 104) The reaction was carried out in the same manner as in Synthesis Example 72 except that 20 parts of the anhydride of the acid anhydride (C2) was used instead of the blocking compound (4) used in the step _ (8) of Synthesis Example 72, and ethyl acetate was added thereto. 10 parts were obtained, and a solution of a modified polyester resin (D1) having a pale yellow transparency and a nonvolatile content of 50.4% by weight and a viscosity of 28,00 〇mpa·s was obtained. The resin (m) had an acid value of 86.4 mgKOH/g, a hydroxyl group value of 〇2 mgK〇H/g, a glass transition temperature of -15 t: and a weight average molecular weight of 230,000. Further, in the above formulation, 环状 is a ratio of the ring-shaped target (b) to about 1 · 4 moles with respect to the secondary radical 1 mol derived from a cyclic squama compound (a_2). (Synthesis Example 105) The reaction was carried out in the same manner as in Synthesis Example 72 except that the catalyst used in Synthesis Example 72 was changed to tetrabutylammonium nitrate, and ethyl acetate was added thereto for adjustment, and it was found that the pale yellow was transparent and A solution of the addition-molded polyester resin (D1) having a nonvolatile content of 49.7% by weight and a viscosity of 17,00 〇mPa.s. The acid mussel of the resin (D1) was mg. 2 mg K 〇 H / g, the hydroxyl value was 23.5 mg KOH / g, the glass transition temperature was 20 ° C, and the weight average molecular weight was ι 65, 〇〇〇. Further, in the above formula, relative to the secondary radical 1 181 319793 200838965 from the dicyclic ether compound (a-2), the ring_ became a ratio of about 1.4 moles. (Synthesis Example 106) In the same manner as in Synthesis Example 72, except that the catalyst was omitted in the same manner as in Synthesis Example 72, the ethyl acetate was adjusted to obtain a pale yellow transparency, and the composition was 5 (U). % by weight, viscosity is 17,500 mPa.s plus ο"| : ester resin (D1) is dissolved 9. The acid value of the resin is, the base price is 26 5 mg K °H / g, the glass transition temperature is • relative to the source Self-quantity: The molecular weight is 150, _. Further, in the above formula, the secondary filament of the ruthenium complex (4) is 1 mol, and the cyclic oxime (b) becomes a ratio of about 1.4 mu. In each of the resin solutions obtained in Examples 67 to 〇6, the solutions are transferred to the divalent volatile component, the weight average molecular weight (Mw) of the resin, the glass to the second g), the acid value (AV), and the base price. V) was evaluated in the same manner as in Synthesis Example 1, and is shown in Table 9 and Table. 319793 182 200838965 [Table 9] Synthesis example of addition molding polyester resin (D1): a reaction product obtained by using a low molecular weight dicarboxylic acid (a-1-l) and various polyols (a-1-α) [High molecular weight dicarboxylic acid (a-1-2)] as a dibasic acid (a-Ι)

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ίυ 丨9 二：aH 瀹 4h,寸二：a® 鮏 u^審：odz t^^^fiMIg-TJL-气 I : d3-Qg iw^^^tiMISMV 審：PKw-odN /f_«^fiM-,寸 νί4裔·· d3^.&8t 餵毽 uta(爾rofif^fi-l/v制：dg-PVHa (鵷冗<<獎寒碱蛑40)婴率1^碱鲦¥屮令崦％'¥翕鈥：2:〇〇1,^3*-*5t^^^fiM^q^s£:d3-sara s_VE:^tiM 浓瀹 0_龢蚪制：dg>dv« 埏{_®-【硪碱‘(^卜酴罄^^-讀0-2}制-寸二：1XOH 富硪«^^4¥翕制：^3-<制盔銮畹：Vdl 毽"你：vqs ^Mro: VPV 183 319793 200838965 [表10]加成型聚酯樹脂（D1)之合成例：使用由低分子量二羧酸（a-1-1)與各種多元醇（a-1- α )而成之反應生成物 [高分子量二羧酸（a-1-2)]作為二元酸（a-Ι)時的情形 0 έ 1 Μ 1 I « tmrnrn 臂 S ID «·>· N m O S’ 彎 ? Ki> 3 i 严 *s ΙΟ s U> s s 2 1ft 2 〇 § ll> w CSI ID s 5 § o 3 § 5 te> O s 5 s 1 iq to IO » esj 卜· Λ in 气 s c%i 6 d Ρ 早 in in T S 1 S 1 〇 0 1 IO T g I 〇 1 0 1 ο ? 1 o 丁 ΙΟ 1 m 丁 in T 0 1 0 1 I f 1 卜 I 严 I 豸 ϊ 〇 Ϊ t ▼— 1 V— 1 产 I CM 1 s· N I I I I m ΰ 1 1 O* T" 1 s i in il d φ § sf 1 s· Ϊ S Ϊ 莒 I N 1 s r· Ϊ s «i _ φ S > i £ E I T «» I 筘 S tf> 轉 1 oT wm I I O s I 1 s to 一 s s ID 0» s u> ici — 1 I ¥ ir> 〇» ϊ i m Ϊ i IO ? CM t 卜 i IO I I s 1 n s i 1 i lf> s » s i 卜 I s 卜 i 癍 m m «3 m m "¥ 鷉 ¢3 m 灌 m ¢3 魏翥 ff » Φ K 薄霧 Η Φ 氣 m » ¢1 氣 s m 珀 K M m 氣裹 s 5 i § s s：纗 ¢1 m m i：梅 40 « m m ¢3 m m K «1 K 涣 s： « m « 盔 m φ m m 鰣 m m w m 如 m m m m m m W m «3 獻涣旺 m 却 u m — Μ 避 Μ •S ~ 邂 GO < m K m H m H a H ο m < m "m m f < s \ X 〇气严 IO ¥·* m o ψ- •· ▼— τ-丨气 <r· r· d ▼— 气 r· 气 Λί ， Ψ· .r :· m ub ir> 哧 m CO CO m 卜卜 rs Γ> Γ9 哧 rt Κ» 〇 a» 卜卜卜 l；f 每 ^ • ♦ CO Γ» u j o 〇> 2 60 » o 00 口 J ，脅 o 0 1 〇 % f 8 z t 2 1 1 I ►: »« s J 1 [ e *c έ •c 1 •C i I I £ JC £ § z έ r^\ 槳 % % 嗜遛 |芻 3 d u> -j o «0 •j o K 〇 ta U) M3 y^N -Hi 賭 r L & i m ά〇 S® 蛋 8： ω l5 ώ z ω 4> < g & k m & k ¥ ω k 彰 £ < i ω L· m Ϊ 制 (NI τ«Η L· ’丨1 .婭 is 1 l ο ο s o o ai o s Q. 〇 i CL < 軍 « m 霉 « 0 1 0. 丄 i 1 I I 1 1 1 I 1 — 1 l 1 1 1 1 1 1 < ^ \ 1 1 i 1 m 3 2 3 ! 3 2 1 < 1 噠 ! s 匕 3 « €0 D 1 u 2 丨 lb £ s Sm^ a £ S 5 n S ^s ο 2 N » N s a N » t D 2 3 S u> 00 «ο 00 1 S CO CO i 〇> c7 σ> 〇> O) Ia 03 co σ> 03 a 〇> a> o r— 〇 "g T— s ^F· "g "g "g t—· ^_hs^lf:MVPQl 壤^hs^f^s : gvCQl (9ρμρχψΙΒ.2ms)fe^*^呆螋：qM^IVfe^-rh: ηοοψχν ^ί^μϋ®--^: ZSSK ^^¾、砩S-M : Isosl^^^s~_oM : issHa 餵嬸誠毗_饍臀鉍s--歙： ISld 施 Si4^^畹：ooNqd餹 Mh二：一ux 皿 «: ΊΛ60 施 S Mro-co- d ω 富^s^fiMIg-rh-VI :dw-ag 富^s^tiuisHV審：da-odM fw^^^M-,寸 Vi4蔡：dg-qds 施B^Mvoc^TOfi 砩^fi4d:·-^: dg-PVHu (誠砣<<lsrwfi4B)迴奪 Ϋ®^ΙίΛ+φ«%'ν^^:(Ν00ΤΉ3Γ n^^^fiM 翕 Mi4SE:d3-sara 當^肊碱鲦4辘歡04^蚪制：dw-lxiva ^{ws-tw^^^hfiw^rA-^o-s}^-寸二：1XOS ，‘富4VE:^fiM V 畲鰂：d3-v^ 盔銮畹：VPHI 德：vqs ^qro':vpv 184 319793 200838965 (比較例19) 在合成例67之+ _ α β 1 、广· 1πη舌曰八士 ^驟（）所侍之主鏈用聚酯樹脂（Β)溶液· 100重虿份中添加甲苯5 推 ,,w ^田卜^ T本〇仂更進一步，添加TDI/TMP (伸甲本二兴亂酸酉旨之三經甲基丙燒加成為交聯劑⑻’仔細授拌，而獲得接著劑組成物。欲將= 佈於剝離薄膜上以獲得咸厭妓芏键 /、獲件感昼接者涛片，但因接著劑組成物之站度心速上升，故無法進行塗佈。 (比較例20) _…制合成例67之步驟⑺所得之加成型聚g旨前驅物㈣洛液，除此之外與比較例16進行同樣操作，而獲得接著劑 :且=。然而’與比較例16同樣地，由於接著劑組成物之黏度μ速上升，故無法塗佈於剝離薄膜上。 (實施例63) 在合成例67之步驟（3)所得之加成型聚醋樹液1〇0重量份中添加甲苯25份，更進一步，添)加 Tm/TMP(伸甲苯：異氰酸m甲基丙燒加成物）^ 重量份作為交·⑻，仔細㈣，㈣得本發明之接著巧組成物。將其以使乾燥後之厚度成為^m之方式塗佈^ 剝離溥膜上’於1’乾燥2分鐘，而形成接著劑層。再者，以與實施例1至19同樣之方式操作，/得「剝離薄膜/接著劑層/TAC薄膜/PVA/TAC薄膜」之^成之積層體，並進行接著劑層之反應，而得到經接著加工板（積層體）。 (比較例21) 319793 185 200838965 ^合錢68所得讀脂溶”代合成例67之步驟 -门^加成型聚酉1樹脂（D1)，除此之外與實施例63進 I二=二Γ接著劑組成物。使用該接著劑組成物著^ /時’雖然其係可進行塗佈，但由於接黏著性(初期接著性)，故無法製作經接著加丄·^偏光板0 (實施例64、65) •所r °成例69(實施例64)或合成例70(實施例65) =者劑溶液替代合成例67之步驟(獅之加成型來S日树脂（D1)溶液，除此之外盘而調製接著劑組成物，製上; (比較例22) 衣成-接耆加工之偏光板。 _^用合成例71所得之樹脂溶液替代合成例67之步驟成型聚除此之外與實施例之值Μ # 成物，並欲製作經接著加工υ 丨 9 2: aH 瀹 4h, inch 2: a® 鮏u^ 审:odz t^^^fiMIg-TJL-gas I : d3-Qg iw^^^tiMISMV Review: PKw-odN /f_«^fiM- , inch νί4 ...... d3^.&8t feed 毽uta (r rofif^fi-l/v system: dg-PVHa (鹓 &<<奖寒碱40) infant rate 1^ alkali 鲦¥屮崦%'¥翕鈥:2:〇〇1,^3*-*5t^^^fiM^q^s£:d3-sara s_VE:^tiM 瀹0_ and 蚪 system: dg>dv« 埏{_®-[硪碱'(^卜酴罄^^-read 0-2} system-inch two: 1XOH rich 硪«^^4¥翕 system: ^3-< Helmet: Vdl 毽&quot ; you: vqs ^Mro: VPV 183 319793 200838965 [Table 10] Synthesis example of addition molding polyester resin (D1): using low molecular weight dicarboxylic acid (a-1-1) and various polyols (a-1- The case where α ( ) is a reaction product [high molecular weight dicarboxylic acid (a-1-2)] as a dibasic acid (a-Ι) 0 έ 1 Μ 1 I « tmrnrn arm S ID «·>· N m O S' Bend? Ki> 3 i Strict*s ΙΟ s U> ss 2 1ft 2 〇§ ll> w CSI ID s 5 § o 3 § 5 te> O s 5 s 1 iq to IO » esj Bu· Λ in gas sc%i 6 d 早 early in in TS 1 S 1 〇0 1 IO T g I 〇1 0 1 ο ? 1 o Ding ΙΟ 1 m D In T 0 1 0 1 I f 1 卜 I 严 I 豸ϊ 〇Ϊ t ▼— 1 V— 1 I CM 1 s· NIIII m ΰ 1 1 O* T" 1 si in il d φ § sf 1 s· Ϊ S Ϊ 莒IN 1 sr· Ϊ s «i _ φ S > i £ EIT «» I 筘S tf> Turn 1 oT wm IIO s I 1 s to 1 ss ID 0» s u> ici — 1 I ¥ Ir> 〇» ϊ im Ϊ i IO CM t ib i IO II s 1 nsi 1 i lf> s » si 卜 I s ib i 癍mm «3 mm "¥ 鷉¢3 m irrigation m ¢3 Wei ff » Φ K mist Η Φ gas m » ¢1 gas sm 珀 KM m air wrap s 5 i § ss: 纗¢1 mmi: plum 40 « mm ¢3 mm K «1 K 涣s: « m « helmet m φ Mm 鲥mmwm such as mmmmmm W m «3 献涣旺 m but um — Μ Μ Μ • S ~ 邂GO < m K m H m H a H ο m < m "mmf < s \ X 〇 IO ¥·* mo ψ- •· ▼— τ-丨气<r· r· d ▼—gas r·gas Λί , Ψ· .r :· m ub ir> 哧m CO CO m 卜卜rs Γ> Γ9 哧rt Κ» 〇a» 卜卜卜;f per ^ • ♦ CO Γ» ujo 〇 > 2 60 » o 00 mouth J , threat o 0 1 〇% f 8 zt 2 1 1 I ►: »« s J 1 [ e *c έ •c 1 •C i II £ JC £ § z έ r^ \ paddle % % 遛遛 |刍3 d u> -jo «0 •jo K 〇ta U) M3 y^N -Hi bet r & im ά〇S® egg 8: ω l5 ώ z ω 4> &lt g & km & k ¥ ω k £ £ < i ω L· m Ϊ (NI τ«Η L· '丨1 .娅is 1 l ο ο soo ai os Q. 〇i CL < « m 霉 « 0 1 0. 丄i 1 II 1 1 1 I 1 — 1 l 1 1 1 1 1 1 < ^ \ 1 1 i 1 m 3 2 3 ! 3 2 1 < 1 哒! s 匕3 « €0 D 1 u 2 丨lb £ s Sm^ a £ S 5 n S ^s ο 2 N » N sa N » t D 2 3 S u> 00 «ο 00 1 S CO CO i 〇> c7 σ&gt ;〇> O) Ia 03 co σ> 03 a 〇>a> or- 〇"g T- s ^F· "g "g "gt-· ^_hs^lf:MVPQl soil^hs ^f^s : gvCQl (9ρμρχψΙΒ.2ms)fe^*^ 螋: qM^IVfe^-rh: ηοοψχν ^ί^μϋ®--^: ZSSK ^^3⁄4, 砩SM: Isosl^^^s~_oM : issHa 喂婶诚彼_食臀铋s- -歙: ISld Shi Si4^^畹:ooNqd餹Mh two: one ux dish«: ΊΛ60 application S Mro-co-d ω rich ^s^fiMIg-rh-VI :dw-ag rich ^s^tiuisHV review:da -odM fw^^^M-, inch Vi4 Cai: dg-qds Shi B^Mvoc^TOfi 砩^fi4d:·-^: dg-PVHu (sincerely <<lsrwfi4B) Ϋ Ϋ®^ΙίΛ+φ «%'ν^^:(Ν00ΤΉ3Γ n^^^fiM 翕Mi4SE:d3-sara When ^肊碱鲦4辘欢04^蚪 system: dw-lxiva ^{ws-tw^^^hfiw^rA-^os }^-inch 2: 1XOS, 'Fu 4VE: ^fiM V 畲鲗: d3-v^ Helmet 銮畹: VPHI De: vqs ^qro': vpv 184 319793 200838965 (Comparative Example 19) + _ in Synthesis Example 67 α β 1 , 广 · 1πη 曰曰 ^ ^ ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) 聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯聚酯Further, an additive composition was obtained by adding TDI/TMP (three kinds of methyl methacrylate added to the cross-linking agent (8)'. If it is desired to apply the = on the release film to obtain the salty anodic bond / and obtain the sensation of the splicer, the coating cannot be applied due to the increase in the heart rate of the adhesive composition. (Comparative Example 20) The same procedure as in Comparative Example 16 was carried out except that the precursor of the addition of the precursor (4) obtained in the step (7) of Synthesis Example 67 was used to obtain an adhesive: and =. However, in the same manner as in Comparative Example 16, since the viscosity of the adhesive composition was increased at a μ speed, it could not be applied to the release film. (Example 63) To 1 part by weight of the addition-formed polyvinyl vinegar obtained in the step (3) of Synthesis Example 67, 25 parts of toluene was added, and further, Tm/TMP was added (toluene: isocyanate m-methyl) The base propylene burn adduct) ^ parts by weight as the intersection (8), careful (four), (d) to obtain the composition of the present invention. This was applied to the peeling of the ruthenium film by drying at a thickness of 2 m for 2 minutes to form an adhesive layer. Further, in the same manner as in Examples 1 to 19, a laminate of "release film/adhesive layer/TAC film/PVA/TAC film" was obtained, and a reaction of the adhesive layer was carried out to obtain a laminate. The plate (layered body) is then processed. (Comparative Example 21) 319793 185 200838965 ^The result of the reading of the fat-soluble "Synthesis of 67" - the addition of the poly(1) resin (D1), in addition to the example 63, I = 2 The composition of the adhesive is used. Although the composition of the adhesive is used, it can be applied, but the adhesive property (initial adhesion) cannot be produced by the subsequent addition of the polarizing plate 0 (Example) 64, 65) • r ° Example 69 (Example 64) or Synthesis Example 70 (Example 65) = the agent solution instead of the synthesis example 67 step (the addition of the lion to the S-day resin (D1) solution, except The adhesive composition was prepared by the above-mentioned disk, and was prepared. (Comparative Example 22) A polarizing plate which was subjected to the coating process. The resin solution obtained in Synthesis Example 71 was replaced by the resin of the synthesis example 67. And the value of the embodiment Μ #成物, and want to make the subsequent processing

H攝无板。然而，因接莫添I •法塗佈於剥離薄琪:相成物之黏度急速上升’故無 (比較例23) 溶液之㈣（7)所得之加成型聚酉旨前驅物（叫、容、夜’ r ‘之：:2之步驟(2)所得之加成型聚醋前驅物(C1) 组成m V 行同樣操作，而獲得接著劑产备速上弁，从例20同樣地’因接著劑組成物之黏 ϋ样曲不但無法進行塗佈，且在塗佈面上會產生或撓曲’而無法製成經接著加卫之偏光板。 319793 186 200838965 (實施例66) 在合成例72之步驟（8)所得之加成型聚酯樹脂（D1)溶液100重量份中添加曱苯25份，更進一步，添加TDI/TMP (伸曱苯二異氰酸酯之三羥曱基丙烷加成物）2,5重量份作為交聯劑（E)，仔細攪拌，而獲得本發明之接著劑組成物。使用該接著劑組成物並以與實施例63同樣之方式操作，而製成經接著加工之偏光板。 (實施例07至92) _ 分別使用合成例72至98所得之樹脂（D1)溶液替代合成例72之步驟（8)所得之樹脂（D1)溶液，除此之外與實施例66進行同樣操作而調製接著劑組成物，而製成經接著加工之偏光板。 (實施例93至97)H has no board. However, due to the addition of the method, the method is applied to the stripping of the thin film: the viscosity of the phase is rapidly increased, so there is no (comparative example 23) the addition of the precursor of the solution (4) (7). , the night 'r':: 2 step (2) obtained by adding the shaped polyester precursor (C1) to form the m V line to operate the same, and obtain the adhesive production speed of the upper sputum, from the same example 20 The viscous smear of the composition of the agent can not only be coated, but also produces or flexes on the coated surface and cannot be made into a polarizing plate which is subsequently cured. 319793 186 200838965 (Example 66) In Synthesis Example 72 To 100 parts by weight of the solution of the addition-molded polyester resin (D1) obtained in the step (8), 25 parts of toluene was added, and further, TDI/TMP (trihydroxydecyl propane adduct of phenylene diisocyanate) was added. 5 parts by weight as a crosslinking agent (E), which was carefully stirred to obtain an adhesive composition of the present invention. The adhesive composition was used and operated in the same manner as in Example 63 to prepare a polarized film which was subjected to subsequent processing. (Examples 07 to 92) _ Replacing the resin (D1) solution obtained in Synthesis Examples 72 to 98, respectively Step (8) obtained from Example 72 of Resin (D1) solution, except for Example 66 in the same manner to prepare adhesive composition, followed by a polarizing plate made of processed (Examples 93-97)

分別使用合成例102至106所得之樹脂（D1)溶液替代合成例72之步驟（8)所得之樹脂（D1)，除此之外與實施例 66進行同樣操作而調製接著劑組成物，而製成經接著加工之偏光板。 (比較例24至26) 分別使用合成例99至101所得之樹脂（D1)溶液替代合成例72之步驟（8)所得之樹脂（D1)溶液，除此之外與實施例66進行同樣搡作而調製接著劑組成物，並欲製作經接著加工之偏光板。然而，因接著劑組成物之黏度急速上升，故無法塗佈於剝離薄膜上。 (實施例98、99) 187 319793 200838965 分別將實施例66所使用之交聯劑（£)從TDI/TMp變更成xm/TMP(伸茗基二異氰酸醋之三羥甲基丙烷加成物）2.5重量份（實施例％)、或變更成HMm/縮二脲（六亞甲基二異氰酸酯之縮二脲加成物）2.5重量份（實施例99)，除此之外與貫施例66進行同樣操作，而獲得接著劑組成物。使用該接著劑組成物並與實施例66進行同樣操作，而製成經接著加工之偏光板。 (實施例100) _ 在合成例99所得之加成型聚酯樹脂（D1)溶液100重量伤中添加甲苯25份，更進一步，添加hbap(2,2、雙經基曱基丁醇参[3-(1-氮丙淀基）丙酸醋])〇·25重量份作為交聯劑⑻，仔細擾拌，而獲得接著劑組成物。使用該接著劑包成物並與實施例66進行同樣操作，而製成經接著加工之偏光板。 / (比較例27、28) 擎分別使用合成例9 8或合成例丨G 4所得之加成型聚酉旨樹脂则溶液替代合成例99所得之加成型聚酯樹脂（m)溶液’除此之外與實施例100進行同樣操作而調製接著劑組成物。此時，雖然接著劑組成物之黎度上升，但仍可進行塗佈，而製成經接著加工之偏光板。 (實施例101至103) 刀別使用合成例100至1〇2所得之樹脂则溶液替代合成例99所得之加成型聚醋樹脂（m)溶液，除此之外與實施例100進行同樣操作’調製接著劑組成物，而製成經接 319793 188 200838965 者加工之偏光板。 (實施例104) 在合成例99所得之加成型聚酯樹脂（D1)溶液1〇〇重量份中添加甲苯25份，更進一步，添加TGMXDA(N，N，N，，N，- 四環氧丙基-間伸茬基二胺）〇·25重量份作為交聯劑（e)，仔細攪拌，而獲得本發明之接著劑組成物。使用該接著劑組成物並與實施例1〇〇進行同樣操作，而製成經接著加工之偏光板。 _ (比較例29、30) 分別使用合成例98、99所得之樹脂（D1)溶液替代合成例99所得之加成型聚酯樹脂（m)溶液，除此之外與實施例刚進行同樣操作而調製接著劑組成物。然而，因接著劑組成物之黏度急速上升，故無法塗佈於剝離薄膜上。 (實施例105至1〇7)- 、分別❹合成例丨⑽至1()2所狀樹脂（di)溶液替代 .合成99所得之加成型聚醋樹腊（m)溶液，除此之外與實，例104進行同樣操作，調製接著劑組成物，而製成經接著加工之偏光板，並進行評估。 (實施例108) 在。成例99所得之加成型聚酯樹脂①u溶液丨重「中：力甲苯25伤’更進一步，添加為碳二亞胺化合物、山」llte Ve〇5」（日清紡積股份公司製）0·25重量份仔細攪拌，而獲得本發明之接著劑組成物者触成物並與實施例1⑻進行同樣操作，而 319793 189 200838965 成經接著加工之偏光板。 (比較例31、32) 成例t:二合广例：或99所得之卿^ 于σ成型聚酯樹脂（D1)溶液，除此之外盘實二、、二二黏度急速上升，故無法塗佈於剝離薄膜上。 (貫施例109至1U) ί另 1 使用合成例100至102所得之樹脂（di)溶液替代。成彳所得之加成型聚醋樹脂_溶液，除此之外盘實了08進行同樣操作，調製接著劑組成物，而製成經接著加工之偏光板。 (實施例112) 在口成例99所得之加成型聚酯樹月旨（D1)溶液工⑻重量 i中添;^甲本25«份’更進一步’添加聰〇邱，2人六亞甲基雙（2·%唾琳）)0.25重量份作為交聯劑⑻，仔細擾摔，而獲得本發明之接著劑組成物。使用該接著劑組成物並與實施例100進行同樣操作，”成轉著加玉之偏光板。 (比較例33、34) 分別使用合成例98、99所得之樹脂（m)溶液替代合成例99所得之加成型聚酯樹脂（m)溶液，除此之外盘實施例 112進行同樣操作而調製接著劑組成物。然而，因接著劑組成物之黏度急速上升，故無法塗佈於剝離薄膜上。 (實施例113至116) ' 分別制合成例⑽至⑽所得之樹脂（D1)溶液替代 319793 190 200838965 合成例99所得之加成型聚酯樹脂（D1)溶液，除此之外與實施例112進行同樣操作，調製接著劑組成物，而製成經接著加工之偏光板，並進行評估。 (實施例118) 在合成例99所得之加成型聚酯樹脂（D1)溶液1〇〇重量份中添加異丙醇25份，更進一步，添加A1AA(參（乙醯丙酮）鋁）0·25重量份作為交聯劑（E)，仔細攪拌，而獲得本發明之接著劑組成物。使用該接著劑組成物並與實施例1〇〇骞進行同樣操作，而製成經接著加工之偏光板。 (比較例35、36) 分別使用合成例98、99所得之樹脂溶液替代合成例99所得之加成型聚酯樹脂（D1)溶液，除此之外與實施例 118進行同樣操作而調製接著劑組成物。然而，因接著劑組成物之黏度急速上升，故無法塗佈於剝離薄膜上。 (實施例119至121) •、分別使用合成例_至102所得之樹脂(D1)溶液替代合成例99所得之加成型聚酯樹脂（D1)溶液，除此之外與與施例118進行同樣操作，調製接著劑組成物，使用該接二劑組成物而製成經接著加工之偏光板。人組成物的適用期及同樣之方法進行評關於實施例及比較例所得之接著劑塗佈加工性，係依據與實施例1至19 估。將結果示於表11至13。另外，針對實施例及比較例所得之經接板(積層體），係依據與實施们至22同樣之方法進== 319793 191 200838965 其塗膜之折射率、耐熱性、耐濕熱性、光學特性及再剝離性。將結果示於表11至13。The resin (D1) obtained in Synthesis Examples 102 to 106 was used in place of the resin (D1) obtained in the step (8) of Synthesis Example 72, except that the same procedure as in Example 66 was carried out to prepare an adhesive composition. A polarizing plate that is processed into a film. (Comparative Examples 24 to 26) The same procedure as in Example 66 was carried out except that the resin (D1) solution obtained in Synthesis Examples 99 to 101 was used instead of the resin (D1) solution obtained in the step (8) of Synthesis Example 72. The adhesive composition is prepared, and a polarizing plate which is subsequently processed is prepared. However, since the viscosity of the adhesive composition rapidly rises, it cannot be applied to the release film. (Examples 98, 99) 187 319793 200838965 The crosslinking agent (£) used in Example 66 was changed from TDI/TMp to xm/TMP (trimethylolpropane addition of thioglycolic acid diisocyanate, respectively). 2.5 parts by weight (Example %) or changed to HMm/biuret (biuret adduct of hexamethylene diisocyanate) 2.5 parts by weight (Example 99), in addition to Example 66 was carried out in the same manner to obtain an adhesive composition. This adhesive composition was used and subjected to the same operation as in Example 66 to prepare a polarizing plate which was subsequently processed. (Example 100) _ 25 parts of toluene was added to 100 parts of the weight of the addition-molded polyester resin (D1) solution obtained in Synthesis Example 99, and further, hbap (2, 2, bis-mercaptobutanol ginseng [3] was added. -(1-Aziridine-based) propionic acid vinegar]) 25 parts by weight as a crosslinking agent (8), which was carefully disturbed to obtain an adhesive composition. The adhesive package was used and the same operation as in Example 66 was carried out to prepare a polarizing plate which was subsequently processed. / (Comparative Examples 27 and 28) The addition molding resin of the synthesis example 9.8 or the synthesis example 丨G 4 was used in place of the addition-molded polyester resin (m) solution obtained in Synthesis Example 99, except for this. The same procedure as in Example 100 was carried out to prepare an adhesive composition. At this time, although the degree of susceptibility of the adhesive composition is increased, coating can be carried out to form a polarizing plate which is subsequently processed. (Examples 101 to 103) The same procedure as in Example 100 was carried out except that the resin obtained in Synthesis Examples 100 to 1 2 was used instead of the addition-formed polyester resin (m) solution obtained in Synthesis Example 99. The adhesive composition was prepared to prepare a polarizing plate processed by 319793 188 200838965. (Example 104) 25 parts of toluene was added to 1 part by weight of the solution of the addition-molded polyester resin (D1) obtained in Synthesis Example 99, and further, TGMXDA (N, N, N, N, - tetraepoxy was added). As a crosslinking agent (e), 25 parts by weight of propyl-m-decyldiamine diamine) was carefully stirred to obtain an adhesive composition of the present invention. The adhesive composition was used and subjected to the same operation as in Example 1 to prepare a polarizing plate which was subsequently processed. (Comparative Examples 29 and 30) The resin (D1) solution obtained in Synthesis Examples 98 and 99 was used in place of the addition-molded polyester resin (m) solution obtained in Synthesis Example 99, except that the same operation as in the Example was carried out. The adhesive composition is modulated. However, since the viscosity of the adhesive composition rapidly rises, it cannot be applied to the release film. (Examples 105 to 1〇7)-, respectively, the resin (di) solution of the synthesis example (10) to 1 () 2 was replaced by the addition of the formed polyacetate wax (m) solution obtained by the synthesis of 99, except The same procedure as in Example 104 was carried out to prepare an adhesive composition, and a polarizing plate which was subsequently processed was prepared and evaluated. (Example 108) In. Addition of the polyester resin 1u solution obtained in the example 99 is carried out in the weight of the medium: the strength of the toluene 25 is further increased, and it is added as a carbodiimide compound or a mountain llte Ve〇5 (manufactured by Nisshin Textile Co., Ltd.) 0·25 The parts by weight were carefully stirred to obtain the contact of the adhesive composition of the present invention and the same operation as in Example 1 (8) was carried out, and 319793 189 200838965 was passed through a processed polarizing plate. (Comparative Examples 31, 32) Example t: a wide variety of cases: or 99 obtained by the method of forming a polyester resin (D1) solution in σ, in addition to the second, second and second viscosity of the plate is rapidly increased, so it is impossible to apply Spread on the release film. (Examples 109 to 1U) ί 1 The resin (di) solution obtained in Synthesis Examples 100 to 102 was used instead. The addition of the formed polyacetal resin _ solution obtained by the formation of the crucible was carried out in the same manner as in the case of 08, and the composition of the adhesive was prepared to prepare a polarizing plate which was processed. (Example 112) Addition molding polyester tree obtained in the mouth example 99 (D1) solution (8) weight i was added; ^ Aben 25 « parts 'further further' added Cong Yuqiu, 2 persons Liu Yajia The base double (2%% salicin)) 0.25 parts by weight as a crosslinking agent (8) was carefully disturbed to obtain the adhesive composition of the present invention. Using this adhesive composition, the same operation as in Example 100 was carried out, and the polarizing plate was added to the jade. (Comparative Examples 33 and 34) The resin (m) solution obtained in Synthesis Examples 98 and 99 was used instead of Synthesis Example 99, respectively. The obtained addition-molding polyester resin (m) solution was subjected to the same operation as in Example 112, except that the adhesive composition was prepared in the same manner. However, since the viscosity of the adhesive composition rapidly increased, it could not be applied to the release film. (Examples 113 to 116) The resin (D1) solution obtained in Synthesis Examples (10) to (10) was replaced with the solution of the addition-molding polyester resin (D1) obtained in Synthesis Example 99 of 319793 190 200838965, except that it was carried out in the same manner as in Example 112. In the same manner, the adhesive composition was prepared to prepare a polarizing plate which was subsequently processed, and evaluated. (Example 118) Addition of 1 part by weight of the solution of the addition-form polyester resin (D1) obtained in Synthesis Example 99 25 parts of isopropyl alcohol, and further, 0. 25 parts by weight of A1AA (e (acetonitrile) aluminum) was added as a crosslinking agent (E), and the mixture was carefully stirred to obtain an adhesive composition of the present invention. Composition and reality Example 1 〇〇骞 The same operation was carried out to prepare a polarizing plate which was subsequently processed. (Comparative Examples 35 and 36) The resin solution obtained in Synthesis Examples 98 and 99 was used instead of the addition-molded polyester resin obtained in Synthesis Example 99 (D1). In the same manner as in Example 118, the adhesive composition was prepared in the same manner as in Example 118. However, since the viscosity of the adhesive composition rapidly increased, it could not be applied to the release film (Examples 119 to 121). The same procedure as in Example 118 was carried out, except that the resin (D1) solution obtained in Synthesis Examples _ to 102 was used instead of the solution of the addition-molding polyester resin (D1) obtained in Synthesis Example 99, and the composition of the adhesive was prepared. The second polarizer composition was used to prepare a polarizing plate which was subsequently processed. The pot life of the human composition and the same method were evaluated for the adhesive coating processability obtained in the examples and the comparative examples, based on Example 1 The results are shown in Tables 11 to 13. In addition, the delamination sheets (layered bodies) obtained in the examples and the comparative examples were subjected to the same method as in the embodiment 22 to == 319793 191 200838965 Fold Rate, heat resistance, wet heat resistance, optical characteristics and removability. The results are shown in Tables 11-13.

192 319793 200838965 [表11]使用第1型態之加成型聚酯樹脂（D1)的接著劑組成物：使用由低分子量二羧酸（a-1-l)與各種多元醇 (a-1-α )而成之反應生成物[高分子量二羧酸（a-1-2)] 作為二元酸（a-1)時的情形192 319793 200838965 [Table 11] An adhesive composition using the addition type polyester resin (D1) of the first type: using a low molecular weight dicarboxylic acid (a-1-l) and various polyols (a-1- Reaction product formed by α) [high molecular weight dicarboxylic acid (a-1-2)] as a dibasic acid (a-1)

mam $ it \ ‘镩 \ 触 — 重工性 | I I 〇 1 ο Ο < mmm Ο mmm Ο 〇〇 Ο 0 〇〇 ο Ο 〇〇 Ο ο ο ο 〇 ο 耐濕熱性 CS2 l o 1 ο Ο 〇 1 Ο Ο 5 0 ο Ο 〇 0 ο Ο 〇〇 Ο 〇 ο ο 〇 ο T-" 1 I @ I < X 1 & ο & © & 0 & ® ◎ ◎ ◎ ο ο ◎ @ 耐熱性 1 I @ 1 © Ο < 1 © 0 Θ © @ 0 © ® ◎ ◎ @ ο ◎ ο @ ◎ 經乾燥之接著劑層黏著性 1 I o X ο < 〇 1 Ο < <1 〇 ο 0 0 0 < ο 〇〇 <1 ο < ο 〇 < 光學特性 ! i 〇 < ο ο < 1 ο ο 〇〇 < 〇〇〇 ο ο 〇〇 ο < ο ο 〇 ο 折射率 1 I 1.523Θ 1.5312 1.5222 1.5216 1.5233 i 1.5245 1.5287 1.5246 1.5221 ；1.5223 1 1.5256 I 1.5122 | 1.5277 I 1.5282 1 1.5201 | 1.5198 [1.5304 1 1.5465 1 14764 1 1.5033 1 1.4829 | 1.4965 1 1.5288 接著劑溶液塗佈加工性 1 I 〇 < Ο Ο < X Ο Ο 〇〇 Ο 0 〇〇 Ο < 〇 <1 Ο <1 Ο < < Ο 適用期 X X 〇〇 Ο Ο < X Ο Ο 〇〇 Ο 〇〇〇 Ο Ο 〇〇 Ο ο Ο Ο 〇 Ο 審滅 W 钟? 雄交聯劑 (Ε) TDIAMP TDI/TMP 0 2 Ε 聚酯樹脂（D1)溶液 ν (W(o>無 I (c)無 I ⑹無1 OHV 56.2 m 18,5 Ίμ 51.5 52·β 22.8 20.5 22.8 21.4 10.5 23.8 22.6 2U I tr> r> 1S.8 ΙΟ to 15.2 25·3 23.4 13.5 €*4 0.07 0.05 CSI 0.05 0.05 85.1 9 U> 0.05 e^i ΙΑ Ο 5 CO ο CSf 〇〇 d ιη IC> 〇 5 5 ΙΟ ιη οα in 〇 5 5 o ? o «ΝΙ ο ο ί ο ! Έ 1 r σ Ύ Ο 1 〇 T u> 1 ο 1 !£> CSI \ -10 一 20 ο Ο τ Έ \ ο -20 ΙΟ ιη ¥ 1 〇 CSI Ο CSI Mw 150,000 160,000 165,000 155,000 ο S ο 175,000 105,000 170,000 170,000 150,000 110,000 140,000 135,000 170,000 175,000 120,000 125,000 115,000 142,000 105,000 170,000 100,000 180.000 120,000 165,000 145,000 OH : (b) 〇 to t— Ο τ- &ο ΙΟ t— U» 寸 τ- r· Ρ-* τ- ΙΟ in τ— r- τ— τ- 产 τ- τ— -feif to ro σ> η Ο CO to to to to η CM r> CM ο ΓΟ ο Ι 00 ιο «Ο ο» 側鏈含有率 (wt%) I 卜卜 Ο ιο α> σ> 卜寸寸 'r· CO 寸 CM »— CD τ-· ί 寸寸 τ- 寸 -寸 τ— ο 寸寸合成例 ο C0 CD σ> to ο to jr ΙΟ Ο β m ΐ m CM CO Ο GO S u> 9 to CO CO σ> to I比較例191 I比較例2〇l 1實施例63| r- Ν 累 * 1實施例β4ΐ ID to 比較例221 比較例23! (D Φ 卜 (D ¥ 00 (D (D 1實施例*70丨 I實施例71 €ϋ 卜 to rv 累 1實施例74 "i〇| Ν (D Γ- 1實施例77 οο σ> 卜 ¥ ω 产 CO 荽噠矣键 W 避溆祐«lc-:r^A«*l<:fif“sl7Ia_ #^^^®4A^*HW^tift4^^4rdwJ7Iax #噶4返把'fs-^-HW 谐嬸一I 蜱”柃.奪：CUM/IalMam $ it \ '镩\ Touch - Heavy work | II 〇1 ο Ο < mmm Ο mmm Ο 〇〇Ο 0 〇〇ο Ο 〇〇Ο ο ο ο 〇 ο Moisture resistance CS2 lo 1 ο Ο 〇1 Ο Ο 5 0 ο Ο 〇 0 ο Ο 〇〇Ο 〇ο ο 〇ο T-" 1 I @ I < X 1 & ο & © & 0 & ® ◎ ◎ ◎ ο ο ◎ @ Heat resistance 1 I @ 1 © Ο < 1 © 0 Θ © @ 0 © ® ◎ ◎ @ ο ◎ ο @ ◎ Adhesive layer adhesion to dry 1 I o X ο < 〇1 Ο <1 〇ο 0 0 0 < ο 〇〇<1 ο < ο 〇< Optical characteristics! i 〇< ο ο < 1 ο ο 〇〇< 〇〇〇ο ο 〇〇ο < ο ο 〇ο Refractive index 1 I 1.523 Θ 1.5312 1.5222 1.5216 1.5233 i 1.5245 1.5287 1.5246 1.5221 ; 1.5223 1 1.5256 I 1.5122 | 1.5277 I 1.5282 1 1.5201 | 1.5198 [1.5304 1 1.5465 1 14764 1 1.5033 1 1.4829 | 1.4965 1 1.5288 Substrate solution coating processability 1 I 〇< Ο Ο < X Ο Ο 〇〇Ο 0 〇〇Ο <〇<1 Ο <1 Ο << Ο Applicable period XX 〇〇Ο Ο < X Ο Ο 〇〇Ο 〇〇〇Ο Ο 〇〇Ο ο Ο Ο 〇Ο Trial W clock? Male crosslinker (Ε) TDIAMP TDI/TMP 0 2 Ε Polyester resin (D1) solution ν (W(o>gt ; no I (c) no I (6) no 1 OHV 56.2 m 18,5 Ίμ 51.5 52·β 22.8 20.5 22.8 21.4 10.5 23.8 22.6 2U I tr> r> 1S.8 ΙΟ to 15.2 25·3 23.4 13.5 €*4 0.07 0.05 CSI 0.05 0.05 85.1 9 U> 0.05 e^i ΙΑ Ο 5 CO ο CSf 〇〇d ιη IC> 〇5 5 ΙΟ ιη οα in 〇5 5 o ? o «ΝΙ ο ο ί ο ! Έ 1 r σ Ύ Ο 1 〇T u> 1 ο 1 !£> CSI \ -10 20 ο Ο τ Έ \ ο -20 ΙΟ ιη ¥ 1 〇CSI Ο CSI Mw 150,000 160,000 165,000 155,000 ο S ο 175,000 105,000 170,000 170,000 150,000 110,000 140,000 135,000 170,000 175,000 120,000 125,000 115,000 142,000 105,000 170,000 100,000 180.000 120,000 165,000 145,000 OH : (b) 〇to t— Ο τ- &ο ΙΟ t— U» ττ- r· Ρ-* τ- ΙΟ in τ— r- τ —τ—produce τ- τ—-feif to ro σ> η Ο CO to to to η CM r> CM ο ΓΟ ο Ι 00 ιο «Ο ο» Side chain content rate (wt%) I Bu Bu Ο ιο α>σ> Bu inch inch 'r· CO inch CM » — CD τ-· ί inch inch τ- inch-inch τ — ο inch Synthesis Example ο C0 CD σ> to ο to jr Ο Ο β m ΐ m CM CO Ο GO S u> 9 to CO CO σ> to I Comparative Example 191 I Comparative Example 2〇1 Example 63| r- Ν Tired *1 Example β4ΐ ID to Comparative Example 221 Comparative Example 23! (D Φ 卜 (D ¥ 00 (D (D 1 embodiment * 70 丨 I embodiment 71 ϋ 到 to rv 累 1 embodiment 74 " i〇 | Ν (D Γ - 1 Example 77 οο σ> 卜¥ ω CO 荽哒矣 W « «lc-:r^A«*l<:fif"sl7Ia_ #^^^®4A^*HW ^tift4^^4rdwJ7Iax #噶4回把'fs-^-HW 婶一一蜱柃.柃: CUM/Ial

193 319793 200838965 [表12]使用第1型態之加成型聚酯樹脂（D1)的接著劑組成物：使用由低分子量二羧酸（a-1-l)與各種多元醇 (a-1- α )而成之反應生成物[高分子量二叛酸（a_l-2)] 作為二元酸（a-1)時的情形193 319793 200838965 [Table 12] An adhesive composition using the addition type polyester resin (D1) of the first type: using a low molecular weight dicarboxylic acid (a-1-l) and various polyols (a-1- Reaction product formed by α) [high molecular weight di-oroxic acid (a_l-2)] as a dibasic acid (a-1)

\ 烬 \ Bt® \\ Η W Ο 〇〇 < 0 0 Ο Ο 0 0 < 〇〇 1 J t O ο 戚 m t eg Ο 〇〇 Ο < 〇 ο Ο 〇 ° 0 0 〇 Ο 1 1 ! 0 Ο r* Φ 0 ο o & ◎ ◎ 0 o 0 ◎ ί 1 i ◎ 0 戚 @ © 〇 © © 〇 © ◎ 0 ◎ 0 0 ◎ ◎ 1 I I © © 蘅雄璇 P Ο 〇 0 0 0 〇 ο 0 < 〇 0 0 〇 0 1 1 1 0 Ο m ο 〇 < 0 o 〇 ο Ο 0 ο o < 〇 0 ! 1 1 0 Ο 齋 δ δ m S 1C 5 « i » &τ> £ 3 !q 卜 S ¥ u> IP 5 &〇翠 1 1 1 u> η S 1Γ> 焕 3E 珠 Η Μ ο 0 < < o 〇 < 0 ο ο < < 〇 0 1 1 1 0 ο Κ Η； ο 0 < ο o 〇 ο 0 0 0 0 0 〇 0 X X X 0 0 審蘅獬雄 g i m η. ΖΕ Ο a. S a Q. Q 1 1 CL s S O i >1 装 S X 娀 /^\ P—< S 避 1 i > X ο 〇> CO CO 5 m ιη ο CSI 00 Ιί> CSI ΙΧ> S 卜 ID eg %ό § I i Ξ 鼸 S 1〇 C0 CM ΙΟ ο CM ΙΟ CM S CM s GO Csi eg ΙΓ> ΙΑ d CD CSI « V> 1ft ο 1ί> ο in » CO eo ID d CM Ο d CM CD CSJ tn 5 eg O S ί ΙΟ 丁 ΙΟ 丁 lf> cp 8 Ο 7 ο ? ο ? ir> T in 丁 S 1 石 s 1 s 1 o 丁 s 1 Έ 1 ιη φ Ο 8 i i cT S i § i 〇 — I 〇 I S § S I i g i s Ο 8 S ϊ 1 Ϊ | ϊ s Ϊ § 1 o I Ο *r— r- 寸· 产兮· r- ΙΟ ο t— 寸， r- CM· τ- 寸· r- ^rQ 伞、✓ CO 00 CO 卜卜 CO CO ο CD Ο σ> 卜卜寸 CO to CO 金齋8 〇 eg CM σ> 1— 寸 CM CM GO 卜 τ— 寸寸 00 CO o s CM 〇> o 〇> 苤 ir> σ> ς〇 CD Si 00 Oi s s τ— S T—· g y^· σ> σ> o T— o Ύ— ί 丨寸 ® 1茗丨婼 1舡 ID 00 Φ GD 卜 CO φ m 荃 ο α> 上 Ο 〇} 恥 τ- Ο a> w GE) 寸 0) to 0> 軍 φ σ> 軍 ao s 窠 ID N 玄 Φ N •a 00 0> σ> σ> #3r4su 紫 W 避tif«i:*r^te-^4c:辑 Η 繫/Ια· 荟噠4螇钇砩6-截蝌潜*W畹神％: il/IS 審噠矣紱肊硪轳墩川丨避澍n砵q^fe-%: ds/lal 194 319793 200838965 [表13]使用第1型態之加成型聚酯樹脂（D1)的接著劑組成物：使用由低分子量二羧酸（a-1-l)與各種多元醇 (a-1-α )而成之反應生成物[高分子量二羧酸（a-1-2)] 作為二元酸（a-1)時的情形 t ¥" \\ 重工性 0 wmm 1 0 〇 wmam Ο 0 1 i Ο < ΜΜ Ο MM o I I <1 <J < 0 I 1 < <J Ο Ο I < < ο 耐濕熱性 Μ ο 1 1 Ο 0 〇。 I I Ο Ο Ο o \ I ο Ο ο Ο ί 1 〇 o ο ο ! ί Ο Ο ο 0 ί 1 Ο o Ο ! i Ο Ο ο o I 1 ο ο & ο ί 1 〇〇 © ο I I Ο ο & 耐熱性 ο 1 * e ❹ 0 Ο \ I Ο Ο ο ❹ I 1 ο ο ❹ ο ί 1 〇 o ο ❹ { ί Ο ο ο 經乾燥之接著劑層黏著性 _ < 1 1 0 0 〇 <1 1 I <ί < ο <I I 1 < <Ι ο < I 1 < < ο < I I < < ο 光學特性 ο 1 1 ο o 〇 ο 1 1 Ο Ο ο o 1 1 ο ο ο ο I 1 〇 o ο ο ι I Ο ο ο 折射率 1.5255 1 1 ! 1.5278 1.5234 1.491 Β ί.5277 1 1 1.5254 1.0223 1.48Β7 1.6Z36 1 I t.5202 1.5211 1.4902 Ι.5258 ί 一 1 I 1.5198 | 1-5241 | 1.4879 | 1.5281 I ! | 1.5249 | 1.5242 | 1.4921 接著劑溶液塗佈加工性 Ο \ 1 Ο 〇〇 Ο 1 1 Ο Ο Ο 〇 1 1 Ο 0 0 Ο I 1 〇 < < ο I ! Ο Ο Ο 適用期 ο X X 0 0 〇 ο X X Ο Ο Ο 〇 X X Ο ο Ο ο X X 〇 o Ο ο X X Ο Ο Ο 接著劑組成物交聯劑（E) ΗΒΑΡ _ TQMXDA V-06 ΗΜΟχ 塞 I Ί ill ESSE3 SSBSnESESQ G9S3 居ΙΒ3Β3Β3 Β3Β3 圉团 SIS Β3Ι3 函国鬭固 ESR^3 S3|B^Hk2i3^3 !59^3»3|313^^3 KtiiSC·· SiBiE^yuMfcQ·· ESii3^3u*tS6· Hc&Bci^dkdE· μ··3^μ·ηΕη&3 聚酯樹脂（D1)溶液 I CJ卜 io in e»>Resj g&Ocd BQilXI 卜 ι6 to 00 CM CD 78.5 86.4 e%i ΙΟ CO GO CM β> 78.5 86.4 CM %6 id CO ce> <6 7Mj 86.4 C\l ιο r> co »!* 騸酾园 Ο 丁 ιο 了〇 o 7 IO 丁甲 Ο 丁 sr> Τ 1 甲 ΙΟ ? o 丁 ιη Τ S 1 甲 ΙΟ 丁 s I ο Τ ΙΟ τ Mw _ s i i s 100,000 1 l 1 8 1 £ no,οοο j 90,000 I s 95,000 130,000 1 S 100,000 160,000 230,000 95,000 130,000 1 S 1 δ ϊ ί ϊ Μ 95,000 130,000 90τ000 X 〇 τ— r- CNj »τ— • · τ— 擎_. τ- cvf 尸 1:1.4 οι Τ 1:1.4 C>l Τ 1:1,4 CSI Τ Ar 含有率 (wt%) CD 卜 CO ΙΑ o 哧 (Ο 卜 CO Η Ο CD 卜 r> ΙΩ Ο ί 寸卜 CO ΙΩ Ο CO 卜 CO ο 侧鏈含有率 (wt%) 00 esj τ-· 寸 τ— CO Ο τ— 00 CD CM τ 寸 00 ο GO 00 CM 'Γ α> Ο τ— 00 βο CM τ— rr ▼— CO 〇 0D 00 (Μ ν 0D ο 00 合成例 03 〇> CO ο g o ο s 〇> Ο» α) σ> g Ο ο S a> a> ΟΟ a> ο Ο S α» α> S 〇! o 5 3 α> 05 __ αό σ> g ο S 1實施例100 1 1比較例27 j 00 M 零 £ I賁施例icn | CM Ο τ- 苳 P) o 1實施例104 1 1比較例29 1 1比較例30 1 1實施例105 1 |實施例ιοβ i |貧施例107 |實施例ioe| |比較例31 | 1比較例32 i I實施例109 ! I賁施例110 I實施例111 I實施例112 1比較例33 1比較例34 |實施例Ii3 |實施例114 I實施例11 (9 I實施例118 |比較例35 I比較例36 |實施例119 I實施例120 |實施例121 璩(1吃嬸0)硃：VV1V (^f,lz)^4A 朗夂-hz: ΝΧ0Μ (鉍 &<<^^®^#s)SIA$nipoqg3:sIA 绪4^_奪1£-4«^费®- ^τ·ηΝ2Γ:ναχ3Ι 【溜毽祀(硪^苽*1-0^】砵敏卜砩&-硪1!制~.^2:$31 195 319793 200838965 《第2封閉型態：加成型聚酯樹脂（D2)》在下述合成例107至113中，針對經由三階段之步〃依序進行主鏈⑴之形成、羥基之封閉反應、以環狀酯^ = 側鏈的加成型聚酯樹脂（D2)的製造方法加以說明。" [以二階段型製造方法製造加成型聚酯樹脂（D2)] (合成例107) 〈步驟（9):聚酯主鏈⑴之形成> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴 _下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入作為二元酸（a-1)之二羧酸 (a-1-l)、於分子内具有2個環狀醚基之化合物（a_2)、觸媒、以及有機溶劑。 [聚合槽] 己^一酸（a-1-l)， 438份異敝酸（a-1-l) 332份 .乙酸乙酯 192份甲苯 384份四氫硼酸四丁基銨（觸媒） 1份 [滴下裝置] 雙酚A二環氧丙基醚（a-2) 1919 份四氫硼酸四丁基銨（觸媒） 1份乙酸乙醋 192份曱苯 384份 196 319793 200838965 將聚合槽内之空氣以氮氣置換後，一邊授掉内容物一邊升溫至iocrc。其次’於其中，藉由滴下裝置而將二環狀_化合物(a-2)之混合物耗費i小時以等速滴下。滴下完畢後’再-邊攪拌-邊每隔8小時加入觸媒〇 5份，丘：入2次後’使其進行合計24小時之反應、熟成，然後添加 1537份乙酸乙酯並冷卻至室溫’結束反應，而獲得主鏈用聚酯樹脂（B)之溶液。此溶液係淡黃色透明、其不揮發成分為5〇1重量〇/〇、黏度為18,000mPa· s，而樹脂⑴之酸價為12mgK〇H/g、經基價為175.2mgKOH/g、玻璃轉移溫度為。㈣ <步驟（10):封閉化合物（c)之加成反應> 、準備於聚合槽上附有授拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裳置中分別以下述比率加入步驟⑼所得之主鍵用聚醋樹鲁脂（B)溶液、封閉化合物（c)、觸媒、以及有機溶劑。 [聚合槽] 500份 90份〇·1份 10份主鏈用聚酯樹月旨（B)溶液 [滴下裝置] 異氰酸苯酯（c3) 四氫硼酸四丁基銨（觸媒）乙酸乙酯將聚合槽内之空氣以氮氣置換後，-邊攪拌溶液一邊升溫至100°c。其次，於溶液中，藉由滴下裝置而將封閉 319793 197 200838965 化合物（C)之混合物耗費丨小時以等速滴下。再一邊攪拌一达使其進仃12小時之反應、熟成’然後添加8〇份乙酸乙酉曰亚冷部至室溫，結束反應，而製得經封閉化合物⑷加成的I S旨樹脂（C2)之溶液。。此溶液係淡黃色透明、且其不揮發成分為5〇.丨重量 %、黏度為20,000mPa. s，該樹脂之酸價為〇5mgK〇H/g、羥基價為37.2mgKOH/g、玻璃轉移溫度為4(rc、重量平均分子量為160,000。 _ <步驟（11):環狀酯（b)之開環加成反應> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟（10)所得之聚酯樹脂（C2)溶液、作為環狀酯（b)之内酯（b-i)、觸媒、以及有機溶劑。 [聚合槽]· / 500份 32份 0.5份 10份步驟（10)所得之聚酯樹脂（C2)溶液 [滴下裝置] ε -己内酯（b-1) 四氫硼酸四丁基銨（觸媒）乙酸乙酯將聚合槽内之空氣以氮氣置換後，一邊攪拌溶液一邊升溫至100 C。其次，於溶液中，藉由滴下裝置而將環狀酯（b_l)混合物耗費1小時以等速滴下。滴下完畢後，再一邊攪拌一邊使其進行8小時之反應、熟成，然後添加22 份乙酸乙酯並冷卻至室溫，而獲得加成型聚酯樹脂（D2)之 319793 198 200838965 溶液。此溶液係淡黃色透明、且其不揮發成分為5 0.0重量 %、黏度為18,500mPa · s，該樹脂（D2)之酸價為0.2mg KOH/g、羥基價為15mgK0H/g、玻璃轉移溫度為一 1CTC、重量平均分子量為165,000。 (合成例108)\ 烬\ Bt® \\ Η W Ο 〇〇< 0 0 Ο Ο 0 0 < 〇〇1 J t O ο 戚mt eg Ο 〇〇Ο < 〇ο Ο 〇° 0 0 〇Ο 1 1 ! 0 Ο r* Φ 0 ο o & ◎ ◎ 0 o 0 ◎ ί 1 i ◎ 0 戚 @ © 〇© © 〇© ◎ 0 ◎ 0 0 ◎ ◎ 1 II © © 蘅雄璇 P Ο 〇0 0 0 〇 ο 0 < 〇0 0 〇0 1 1 1 0 Ο m ο 〇< 0 o 〇ο Ο 0 ο o < 〇0 ! 1 1 0 Ο δδ δ m S 1C 5 « i » &τ> £ 3 !q 卜 S ¥ u> IP 5 & jade 1 1 1 u> η S 1Γ> 焕3E Η Μ ο 0 << o 〇< 0 ο ο << 〇0 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 SX 娀/^\ P—<S 避1 i > X ο 〇> CO CO 5 m ιη ο CSI 00 Ιί> CSI ΙΧ> S 卜 ID eg % § I i Ξ 鼸S 1〇C0 CM ΙΟ ο CM ΙΟ CM S CM s GO Csi eg ΙΓ> ΙΑ d CD CSI « V> 1ft ο 1ί> ο in » CO eo ID d CM Ο d CM CD CSJ tn 5 eg OS ί ΙΟ ΙΟ ΙΟ & cp ir S S S S S S S S S S S S S S S S S S S S S 1 S S S S S S S S S S S S S S S 1 1 1 S S 1 1 1 1 1 1 1 1 1 1 1 S 1 S 1 S 1 1 1 1 Igis Ο 8 S ϊ 1 Ϊ | ϊ s Ϊ § 1 o I Ο *r- r- inch · calving r r- ΙΟ ο t-inch, r- CM· τ- inch · r- ^rQ umbrella, ✓ CO 00 CO Bu Bu CO CO ο CD Ο σ> Bu Bu CO to CO Jin Zhai 8 〇eg CM σ> 1—inch CM CM GO Bu τ—inch inch 00 CO os CM 〇> o 〇>苤ir> σ&gt ς〇CD Si 00 Oi ss τ—ST—· gy^· σ>σ> o T— o Ύ— ί ® ® 茗丨婼 1茗丨婼1舡ID 00 Φ GD 卜 CO φ m 荃ο α> 〇} shame τ- Ο a> w GE) inch 0) to 0> army φ σ> army ao s 窠ID N 玄Φ N •a 00 0>σ>σ>#3r4su purple W avoid tif«i:*r ^te-^4c:《ΗΗ/Ια· 哒哒4螇钇砩6-蝌蝌潜*W畹神%: il/IS 审哒矣绂肊硪轳川川丨避澍n砵q^fe- %: ds/lal 194 319793 200838965 [Table 13] An adhesive composition using the addition type polyester resin (D1) of the first type: using a low molecular weight Reaction product of a carboxylic acid (a-1-l) with various polyols (a-1-α) [high molecular weight dicarboxylic acid (a-1-2)] as a dibasic acid (a-1) Situation t ¥" \\ Reworkability 0 wmm 1 0 〇wmam Ο 0 1 i Ο < ΜΜ Ο MM o II <1 <J < 0 I 1 <<J Ο Ο I << ο Heat and humidity resistance ο 1 1 Ο 0 〇. II Ο \ o \ I ο Ο ο Ο ί 1 〇o ο ο ! ί Ο ο ο 0 ί 1 Ο o Ο ! i Ο Ο ο o I 1 ο ο & ο ί 1 〇〇© ο II Ο ο &Heat resistance ο 1 * e ❹ 0 Ο \ I Ο Ο ο ❹ I 1 ο ο ❹ ο ί 1 〇o ο ❹ { ί Ο ο ο Dry adhesive layer adhesion _ < 1 1 0 0 〇 <1 1 I < ί < ο <II 1 << Ι ο < I 1 << ο < II << ο Optical characteristics ο 1 1 ο o 〇ο 1 1 Ο ο ο o 1 1 ο ο ο ο I 1 〇o ο ο ι I Ο ο ο Refractive index 1.5255 1 1 ! 1.5278 1.5234 1.491 Β ί.5277 1 1 1.5254 1.0223 1.48Β7 1.6Z36 1 I t.5202 1.5211 1.4902 Ι. 5258 ί 1 I 1.5198 | 1-5241 | 1.4879 | 1.5281 I ! | 1.5249 | 1.5242 | 1.4921 Adhesive solution coating processability 1 1 1 Ο 〇〇Ο 1 1 Ο Ο 〇 11 1 Ο 0 0 Ο I 1 〇<< ο I ! Ο Ο Ο Applicable period ο XX 0 0 〇ο XX Ο Ο Ο 〇 XX Ο ο Ο ο XX 〇o Ο ο XX Ο Ο Ο Adhesive composition crosslinker (E) ΗΒΑΡ _ TQMXDA V-06 ΗΜΟχ 塞 I Ί i Ll ESSE3 SSBSnESESQ G9S3 ΙΒ3Β3Β3 Β3Β3 圉团SISSIS3Ι3 鬭国鬭固 ESR^3 S3|B^Hk2i3^3 !59^3»3|313^^3 KtiiSC·· SiBiE^yuMfcQ·· ESii3^3u*tS6· Hc&Bci^dkdE·μ··3^μ·ηΕη&3 Polyester Resin (D1) Solution I CJ io in e»>Resj g&Ocd BQilXI ι6 to 00 CM CD 78.5 86.4 e%i ΙΟ CO GO CM β> 78.5 86.4 CM %6 id CO ce><6 7Mj 86.4 C\l ιο r> co »!* 骟酾园Ο丁ιο了〇o 7 IO Ο甲Ο丁sr> Τ 1 甲ΙΟ? o 丁ιη Τ S 1 ΙΟ s s I ο Τ ΙΟ τ Mw _ siis 100,000 1 l 1 8 1 £ no, οοο j 90,000 I s 95,000 130,000 1 S 100,000 160,000 230,000 95,000 130,000 1 S 1 δ ϊ ί ϊ Μ 95,000 130,000 90τ000 X 〇τ— r- CNj »τ— • · τ— 擎_. τ- cvf corpse 1:1.4 οι Τ 1:1.4 C>l Τ 1:1,4 CSI Τ Ar Content (wt%) CD卜 ΙΑ 哧哧 Ο CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO τ inch00 ο GO 00 CM ' Γ α> Ο τ— 00 βο CM τ— rr ▼—CO 〇0D 00 (Μ ν 0D ο 00 Synthesis Example 03 〇> CO ο go ο s 〇> Ο» α) σ> g Ο ο S a>a> ΟΟ a> ο Ο S α» α> S 〇! o 5 3 α> 05 __ α ό σ > g ο S 1 embodiment 100 1 1 Comparative Example 27 j 00 M Zero £ I 贲 Example icn | CM Ο Τ- 苳P) o 1 Example 104 1 1 Comparative Example 29 1 1 Comparative Example 30 1 1 Example 105 1 | Example ιοβ i | Example 107 | Example ioe | | Comparative Example 31 | 1 Comparative Example 32 i I Example 109 ! I 实施 110 110 I Example 111 I Example 112 1 Comparative Example 33 1 Comparative Example 34 | Example Ii3 | Example 114 I Example 11 (9 I Example 118 | Comparative Example 35 I Comparative Example 36 | Example 119 I Example 120 | Example 121 璩(1 eat 婶0) Zhu: VV1V (^f, lz)^4A Recitation-hz: ΝΧ0Μ (铋&<<^^® ^#s)SIA$nipoqg3:sIA 绪4^_夺1£-4«^费®- ^τ·ηΝ2Γ:ναχ3Ι [slippery (硪^苽*1-0^]砵敏卜砩&-硪1!制~.^2:$31 195 319793 200838965 "2nd closed type: addition-formed polyester resin (D2)" In the following Synthesis Examples 107 to 113, The step for forming the main chain are sequentially 〃 ⑴, the blocking reaction of hydroxyl group to a method for producing a cyclic ester side chain = ^ addition type polyester resin (D2) will be described. " [Production of Additive Polyester Resin (D2) by Two-Phase Manufacturing Method] (Synthesis Example 107) <Step (9): Formation of Polyester Main Chain (1)> Prepared in a polymerization tank with a stirrer, thermometer, and reflux a polymerization device of a cooler, a drip-down device, and a nitrogen introduction tube, and a dicarboxylic acid (a-1-l) as a dibasic acid (a-1), in a polymerization tank and a dropping device, respectively, at a ratio of A compound (a_2) having two cyclic ether groups in a molecule, a catalyst, and an organic solvent. [Polymerization tank] hexamic acid (a-1-l), 438 parts of isophthalic acid (a-1-l) 332 parts. ethyl acetate 192 parts toluene 384 parts tetrabutylammonium tetrahydroborate (catalyst) 1 part [Dropping device] Bisphenol A diglycidyl ether (a-2) 1919 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 192 parts Benzene 384 parts 196 319793 200838965 Polymerization tank After the inside air was replaced with nitrogen, the temperature was raised to iocrc while the contents were discarded. Next, the mixture of the bicyclic compound (a-2) was dropped at a constant rate by dropping the apparatus for one hour. After the completion of the dropwise addition, 're-with stirring - 5 parts of catalyst was added every 8 hours, mound: after 2 times, 'to make a total of 24 hours of reaction, ripening, then add 1537 parts of ethyl acetate and cooled to room The reaction was terminated at a temperature to obtain a solution of the polyester resin (B) for the main chain. This solution is light yellow transparent, its nonvolatile content is 〇1 weight 〇 / 〇, viscosity is 18,000 mPa · s, and the acid value of resin (1) is 12 mg K 〇 H / g, base price is 175.2 mg KOH / g, glass The transfer temperature is . (4) <Step (10): Addition reaction for blocking compound (c)>, a polymerization reaction device equipped with a mixer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, which are prepared in a polymerization tank, and The polycarboxylate resin (B) solution, the blocking compound (c), the catalyst, and the organic solvent of the primary bond obtained in the step (9) are added to the polymerization tank and the dropping skirt, respectively, in the following ratios. [Polymerization tank] 500 parts 90 parts 〇·1 part 10 parts polyester resin for the main chain (B) solution [Dropping device] phenyl isocyanate (c3) tetrabutylammonium tetrahydroborate (catalyst) acetic acid The ethyl ester was replaced with nitrogen in the polymerization tank, and the temperature was raised to 100 ° C while stirring the solution. Next, in a solution, the mixture of the compound (C) of 319793 197 200838965 was closed by a dropping device at a constant rate of time to drip at a constant rate. After stirring, the reaction was carried out for 12 hours, and the mixture was aged, and then 8 parts of ethyl acetate subcooling portion was added to room temperature to complete the reaction, thereby obtaining an IS-based resin (C2) which was added with the blocking compound (4). Solution. . The solution is light yellow transparent, and its non-volatile content is 5 〇. 丨% by weight, viscosity is 20,000 mPa·s, the acid value of the resin is 〇5 mgK〇H/g, the hydroxyl value is 37.2 mgKOH/g, glass transfer The temperature is 4 (rc, weight average molecular weight is 160,000. _ < Step (11): ring-opening addition reaction of cyclic ester (b)> Prepared in a polymerization tank with a stirrer, thermometer, reflux cooler, drip device And a polymerization reaction device for the nitrogen introduction tube, and the polyester resin (C2) solution obtained in the step (10) and the lactone (bi) as the cyclic ester (b) are respectively added to the polymerization tank and the dropping device at the following ratios; Catalyst, and organic solvent [Polymerization tank]· / 500 parts 32 parts 0.5 parts 10 parts of the polyester resin (C2) solution obtained in the step (10) [Dropping device] ε-caprolactone (b-1) Tetrahydrogen Tetrabutylammonium borate (catalyst) Ethyl acetate was used to replace the air in the polymerization tank with nitrogen, and the temperature was raised to 100 C while stirring the solution. Next, the cyclic ester (b_l) was dropped in the solution by a dropping device. The mixture took 1 hour to drip at a constant rate. After the dropping was completed, it was stirred while stirring. After 8 hours of reaction, aging, and then adding 22 parts of ethyl acetate and cooling to room temperature, a solution of 319793 198 200838965 of the addition polyester resin (D2) was obtained. This solution was light yellow transparent and its non-volatile content was 5 0.0% by weight, viscosity 18,500 mPa·s, the acid value of the resin (D2) was 0.2 mg KOH/g, the hydroxyl value was 15 mgKOH/g, the glass transition temperature was 1 CTC, and the weight average molecular weight was 165,000. (Synthesis Example 108) )

在合成例107中省略步驟（10)，並在步驟（11)中使用步驟（9)所得之主鏈用聚酯樹脂（B)溶液（不揮發成分50.1重量 %)500份替代加成型聚酯樹脂（C2)溶液，且將ε -己内酯（b) 之量變更成44份，除此以外與合成例107同樣地操作進行調製，添加乙酸乙S旨3 4份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50.2重量％、黏度為17,000mPa · s 之聚酯樹脂之溶液。該溶液中所含有之樹脂的酸價為 0.5mgKOH/g、經基價為77:〇^1：011^、玻璃轉移溢度為40 °C、重量平均分子量為155,000。 (合成例109) 使用為二羧酸（a-1-l)之癸二酸1000份及為高分子量聚酯二羧酸（a-1-2)之Vylon GK110(數平均分子量： 16,000，酸價：6，東洋紡績公司製）800份替代合成例107 中所用之二元酸（a-Ι)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯265份及甲苯530份，除此以外與合成例107之步驟（9)同樣地進行反應，添加乙酸乙酯 2129份，而獲得主鏈用聚酯樹脂（B)溶液。其次，使用所得之樹脂（B)溶液（不揮發成分為50.2重 199 319793 200838965 里％)500份、且將為封閉化合物（c3)之異氛酸苯醋之量變更成65份，除此以外與合成例1〇7之步驟（1〇)同樣地進^ 反應，添加乙酸乙_55份並冷卻至室溫，而獲得經封閉化合物（C)加成的聚酯樹脂（C2)溶液。更進一步，使用所得之樹脂（C2)溶液（不揮發成分為 50.0重量％)500份、且將為環狀醋⑻之卜己内醋之量變更成23份，除此以外與合成例1〇7之步驟⑴）同樣地進行反應，添加乙酸乙酯13份並冷卻至室溫，而獲得淡黃色透 •明且其不揮發成分為5〇1重量％、黏度為，⑽. s 之加成型聚S旨樹脂（D2)之溶液。該樹脂（D2)的酸價為 1.2mgKOH/g、羥基價為19.5mgK〇H/g、玻璃轉移溫度為 —10°C、重量平均分子量為U5,000。 (合成例110) /使用為二羧酸（a-M)之癸二酸310份及為高分子量聚醯胺二羧酸（a_l-2b)之TXM80B(數平均分子量：L600，酸 _ ^貝· 20，虽士化成工業公司製）8〇〇份替代合成例中所用之二元酸（a-Ι)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯260份及甲苯52〇份，除此以外與合成例107之步驟（9)同樣地進行反應，添加乙酸乙酯2〇69 份，而獲得主鏈用聚酯樹脂溶液。其次，使用所得之樹脂（B)溶液（不揮發成分為5〇·2重量％)500份、且將為封閉化合物（c3)之異氰酸苯酯之量變更成67份，除此以外與合成例1〇7之步驟（1〇)同樣地進行反應，添加乙酸乙酯57份並冷卻至室溫，而獲得經封閉化 319793 200 200838965 合物（C)加成的聚酯樹脂（C2)溶液。更進一步，使用所得之樹脂（C2)溶液（不揮發成分 5〇·〇重量％)500份、且將為環狀醋⑻之卜己内酉旨之量變更成24份，除此以外與合成例1〇7之步驟（ιι)同樣地進ς 反應，添加乙酸乙酯14份並冷卻至室溫，而獲得淡黃色透明且其不揮發成分為50·1重量％、黏度為15,〇〇〇mpa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 1.5mgKOH/g、羥基價為18 3mgK〇H/g、玻璃轉移溫度為 _ —10C、重量平均分子量為130,00〇。 (合成例111) 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入替代合成例107所用之低分子量二羧酸（a-1-l)的低分子量二默酸（add)、聚酯多元醇類 (a-1-α )、具有2個環狀醚基之化合物（a_2)、觸媒、以及有 [聚合槽] KURARAY 多元醇 P4〇l〇(a-i-a ) 2078 份丁二酸酐（a-M) 50份乙酸乙酯 165份曱苯 330份四氳硼酸四丁基銨（觸媒） 1份 [滴下裝置] 雙_ A二環氧丙基醚（a-2) 192份 201 319793 200838965 四氫酸四丁基銨（觸媒）乙酸乙酯甲苯將聚合槽内之空氣以氮氣置換後 1份 165份 330份邊攪拌内容物 ^ 4 i t ^ 丨_丨____· 邊升溫至HKTC，進行8小時反應，而獲得作為二元之高分子量二《(a小3)。其次，藉由滴下裝置而將二产狀醚化合物（a-2)之混合物耗費】小時以等速滴下。，完畢後，一邊攪拌-邊每隔8小時加入觸媒〇.5份，妓入2次後’，行合計24小時之反應、熟成，然後：力: 1330伤乙酸乙_亚冷卻至室溫，結束反應，而製成主鍵用聚酉旨樹J!旨（B)。其次，使用所得之樹脂（B)溶液（不揮發成分為5〇 ι重量％)500份、且將為封閉化合物（c3)之異氣酸苯酉旨之量變更成12份’除此以外與合.成例1〇7之步驟⑽同樣地進行反應，添加乙酸乙酉旨2份並冷卻至室溫，而獲得經封閉化秦合物（C)加成的聚酯樹脂扣2)溶液。使用所得之樹脂（C2)溶液（不揮發成分為5〇〇重量 %)500份、且將為環狀酉旨⑻之卜己内酉旨之量變更成5份，除此以外與合成例107之步驟（η)同樣地進行反應，不添加乙酸乙酯並冷卻至室溫，而獲得淡黃色透明、且其不揮發成刀為49.7重1〇/〇、黏度為l5,5〇〇mpa. s之加成型聚醋 =脂（D2)之溶液巧樹脂(D2)的酸價為丨2叫丽仏、經基偏為7.5mgK〇H/g、玻璃轉移溫度為—2〇c>c、重量平均分子量為135,〇〇〇。 319793 202 200838965 (合成例112) 使用為矽烷化劑（cl)之二乙基甲基矽烷：77份替代合成例107之步驟（10)所用之封閉化合物（c3)，除此以外與合成例107同樣地進行反應，添加乙酸乙酯67份並冷卻至室溫，而獲彳于經封閉化合物⑷加成的聚酯樹脂（C2)溶液。在步驟（11)中，使用所得之樹脂（C2)溶液（不揮發成分為50.0重量％)500份、且將為環狀酯化）之£_己内酯之量變更成33份，除此以外與合成例1〇7同樣地進行反應，添鲁加乙酸乙酯23份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50·0重量％、黏度為13,〇〇〇mPa· s之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為〇.〇5mg KOH/g、羥基價為i8.5nigKOH/g、玻璃轉移溫度為—1〇。〇、重量平均分子量為120,000。 (合成例113) 使用酞酸酐（c2)112份替代合成例1〇7之步驟（1〇)所用癱之封閉化合物（c3)，除此以外與合成例1〇7同樣地進行反應’添加乙酸乙酯102份並冷卻至室溫，而獲得經封閉化合物（c)加成的聚酯樹脂（C2)溶液。在步驟（11)中，使用所得之樹脂（C2)溶液（不揮發成分為50.2重量％)500份、且將為環狀酯（1))之£_己内酯之量變更成31份，除此以外與合成例107同樣地進行反應，添加乙酸乙醋21份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50.3重量。/❶、黏度為i7,500mPa· s之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為85.lmg 319793 203 200838965 KOH/g、羥基價為12 8mgK〇H/g、玻璃轉移溫度為_ 1〇。。、重量平均分子量為175,000。 [以擬似二階段型製造方法製造加成型聚酯樹脂（D2)] 在下述合成例114至115中，針對經由擬似二階段型之步驟而獲得加成型聚酯樹脂（D2)的方法加以說明，該方法係生成酸價為5(mgKOH/g)以下之主鏈（Γ)，其次，同時進行主鏈(I)之完成與封閉反應，然後，進行侧鏈之加成。 (合成例114) _〈步驟（12)、（13):經封閉化合物（c)加成之聚酯樹脂（C2)的合成> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中为別以下述比率加入作為二元酸（a-l)之二缓酸 (a-M)、於分子内具有2個環狀醚基之化合物（a_2)、化合物（c3)、觸媒、以及有機溶劑。 ▲[聚合槽] 己二酸（a-M) 438份異酞酸（a-1-1) 332份雙紛A二環氧丙基醚（a_2) 1919 份乙酸乙酯 260份曱苯 520份四氳硼酸四丁基銨（觸媒） 1份 [滴下裝置] 異氰酸苯酯（c3) 952份 204 319793 200838965 四氳硼酸四丁基銨（觸媒） 1份乙酸乙酯 260份曱苯 520份將聚合槽内之空氣以氮氣置換後，一邊攪拌内容物一邊升溫至100°C，再使其反應8小時，而獲得酸價為 5(mgKOH/g)以下之主鏈（Γ)用聚酯。其次，藉由滴下裝置而將異氰酸酯混合物耗費1小時以等速滴下。滴下完畢後，一邊攪拌一邊於8小時後添加四氫硼酸四丁基銨1份，並再使其進行8小時之反應、熟成，然後添加2081份乙酸乙酯並冷卻至室溫，結束反應，而獲得經化合物（c3)加成的聚酯樹脂（C2)。此反應液係淡黃色透明、且其不揮發成分5 0.1重量 %、黏度 20,000mPa· s，該樹脂（C2)係酸價 0:5mgKOH/g、羥基價37.2mgKOH/g、玻璃轉移溫度40°C、重量平均分子量 160,000。 <步驟（14):環狀酯（b)之加成反應> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝置中分別以下述比率加入步驟（13)所調製之聚酯樹脂（C2) 溶液（不揮發成分50.2重量％)、環狀酯（b)、觸媒、以及有機溶劑。 [聚合槽] 步驟（13)所得之 205 319793 200838965 聚酯樹脂（C2)溶液 [滴下裝置] £ -己内醋（b-1) 四氫硼酸四丁基銨（觸媒）乙酸乙酯將聚合槽内之空氣以氮氣置換後 500份 16份〇·5份 10份，一邊攪拌溶液一邊升溫至loot。其次，於此溶液中，藉由滴下裝置而將上述環狀酯混合物耗費i小時以等速滴下。滴下完畢後，一邊授拌-邊使其進行6小時之反應、熟成1後添加6份乙酸乙_並冷卻至室溫，而獲得加成型聚g旨樹脂㈣。此溶液係淡黃色透明、且其不揮發成分5〇3重量％、黏度19,〇〇〇mPa· S，該樹脂（D2)係酸價〇,2mgK〇H/g、羥基“ 16.8mgKOH/g、玻璃轉移溫度—1〇〇c、重量平均分子量 170，Θ0Θ 〇 (合成例115) 使用為二羧酸（a_M)之癸二酸1〇〇〇份及為高分子量聚酉曰一叛酸(a-l-2a)之Vylon GKn〇 8〇〇份替代合成例114 中斤用之一元酉欠（a-丨）、且將分別加入反應槽及滴下裝置中的/合別之里變更成乙酸乙酯333份及甲苯666份，除此以卜口成例114之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯2673份，而從〜_ 、而I传經化合物（c3)加成之聚酯樹脂（C2) 溶液。其一人’使用所得之樹脂（C2)溶液（不揮發成分為50.0 重量％)500份、曰脸&四且將為裱狀酯（b)之ε -己内酯之量變更成 206 319793 200838965 12份，除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯2份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50.2重量％、黏度為2〇，遍mpa.s之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 O’lmgKOH/g、羥基價為22.6mgKOH/g、玻璃轉移溫度為 —10°C、重量平均分子量為i85,〇〇〇。 [加成型聚酯樹脂（D2)之二階段合成] 在下述合成例116中，針對加成型聚酯樹脂（D2)之製 •造方法加以說日月，該方法係使主鍵部⑴之形成反應與封閉化合物（c)之加成同時進行，然後藉由環狀酯之開環加成而形成側鏈。 (合成例116) <步驟（15) ·調製經封閉化合物（c)加成之聚酯樹脂(C2)> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽及滴下裝 _置中分別以下述比率加入低分子量二羧酸類（a」」）、多元醇類（a-1-α )、於分子内具有2個環狀醚基之化合物、封閉化合物（c)、觸媒、以及有機溶劑。 [聚合槽] KURARAY 多元醇 p4〇i〇(a_i_ j ) 2078 份丁二酸酐（a-1-1) 50份乙酸乙酯 173份甲苯 345份四氳硼酸四丁基銨（觸媒） 1份 207 319793 200838965 [滴下裝置] 192份 95份 1份 173份 345份雙紛A二環氧丙基_(a-2) 異氰酸苯酯（c3) 四氫硼酸四丁基銨（觸媒）乙酸乙酯甲苯將聚合槽内之空氣以氮氣置換後，—邊攪拌内容物一邊升温至loot：，使其反應8小時，而獲得為主鍵部⑴形 _成用之二元酸（a-ι)的高分子量二綾酸（心丨_3)。其次，藉由滴下裝置而將上述二環狀醚化合物（心2)及封閉化合物（c)之混合物耗費丨小時以等速滴下。滴下完畢後，一邊攪拌一邊每隔8小時添加四氫硼酸四丁基銨〇.5 份共添加2次，使其進行24小時之反應、熟成後，添加乙酉欠乙f曰1379份並冷卻至室溫，/結束反應，而獲得經加成封閉化合物⑷之聚酯樹脂（C2)溶液。 _ <步驟（16):環狀酯（b)之開環加成反應> 於聚合槽中添加上述聚酯樹脂（€：2)溶液（不揮發成分為50.2重里％)5〇〇份。以與合成例114之第2階段同樣之條件，將為（b-Ι)之ε _己内酯：24份、四氫硼酸四丁基銨（觸媒）· 〇·5份、及乙酸乙酯1〇份之混合物從滴下槽滴下至前述聚合槽中，使其反應，添加乙酸乙酯14份並冷卻至室 /里，而獲得淡黃色透明、且其不揮發成分為49.7重量％、黏度為l5,〇〇〇mPa· s之加成型聚§|樹脂（D2)之溶液。該樹月曰（D2)之酸價為〇 5mgK〇H/g、羥基價為7.5mgK〇Ii/g、玻 319793 208 200838965 璃轉移溫度為一 1(TC、重量平均分子量為130,000。 [加成型聚酯樹脂（D2)之擬似二階段合成] 在下述合成例117至13 7中，針對經由擬似二階段型之步驟而獲得加成型聚酯樹脂（D2)的方法加以說明，該方法係獲得酸價為5(mgKOH/g)以下之主鏈（I，）用聚酯，其次’同時進行主鏈⑴之形成與封閉反應，然後，進行侧鏈之加成。 (合成例117) 籲使用雙苯氧基乙醇第二環氧丙基醚2778份替代合成例114中所用之二環狀醚化合物（a_2)、且將分別加入反應槽及濟下裝置中的溶劑之量變更成乙酸乙酯321份及曱苯 642份，除此以外與合成例114之步驟（12)、（13)同樣地進打反應，添加乙酸乙醋2575份，而獲得經封閉化合物卜3) 加成之聚酯樹脂（C2)溶液a θ其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇1 籲重里/。)500份、且將為環狀酯（…之己内酯之量變更成 13份，除此以外與合成例114之步驟⑽同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為5〇·2重量％、黏度為21，_秦S之加成型聚轉脂_之溶液。該樹脂(D2)的酸價為〇.lmgK〇H/g、經基價為&㈣随玻璃轉移溫度為-HTC、重量平均分子量為19〇，綱。 (合成例118) 丁基）甲氧基]甲基}苯份替代合成例Π4中使用1，4-雙{[(3_乙基_3_氧雜環 685份及間苯二酚二環氧丙基醚7〇2 319793 209 200838965 所用之二環狀醚化合物（a_2)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯222份及甲苯444份，除此以外與合成例114之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯1777份，而獲得經封閉化合物（c3)加成之聚酉旨樹脂（C2)溶液。其次，使用所得之樹脂（C2)溶液（不揮發成分為498 重量％)500份、且將為環狀酯化合物卜）之ε _己内酯之量變更成19伤，除此以外與合成例114之步驟（14)同樣地進行春反應，添加乙酸乙酯9份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為49.7重量％、黏度為njoompa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 0.5mgKOH/g、羥基價為9.3mgKOH/g、玻璃轉移溫度為— 20°C、重量平均分子量為100,000。 (合成例119) - 使用雙龄A系高分子量環氧丙基樹脂「jER1〇〇2」（曰 _本環氧樹脂公司製）6060份替代合成例114中所用之二環狀醚化合物（a-2)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯556份及甲苯1112份，除此以外與合成例114之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯4446份，而獲得經封閉化合物03)加成之聚酯樹脂（C2) 溶液。其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇·2 重里/。）500伤、且將為環狀酯化合物（七)之己内酯之量變更成40伤，除此以外與合成例i 14之第二階段之反應步驟 319793 210 200838965 (14)同樣地進行反應，添加乙酸乙酯3〇份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為5〇·2重量％、黏度為25,000mPa· s之加成型聚酯樹脂（D2)之溶液。該樹脂（D2) 的酸價為〇.5mgKOH/g、羥基價為121mgK〇H/g、玻璃轉移溫度為一5C、重量平均分子量為195,〇〇〇。 (合成例120) 使用新戊一醇一環氧丙基轉526份替代合成例114中所用的於分子内具有2個環狀醚基之化合物（a_2)、且將分 _別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯 106份及甲苯212份，除此以外與合成例114之步驟（12)、 (13)同樣地進行反應，添加乙酸乙酯1〇42份，而獲得經封閉化合物（c3)加成之聚酯樹脂（C2)溶液。其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇·2 里置％)500份、’且將為環狀酯卬）之ε •己内酯之量變更成 39份，除此以外與合成例114之步驟（14)同樣地進行反 _應，添加乙酸乙酯29份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為5〇·2重量％、黏度為12,5⑼mPa · s 之加成型聚酯樹脂（D2)孓溶液。該樹脂（D2)的酸價為〇.2mgKOH/g、羥基價為10 4mgK〇H/g、玻璃轉移溫度為 —25°C、重量平均分子量為12〇,〇〇〇。 (合成例121) 使用雙-(3,4-環氧基環己基）己二酸酯96〇份替代合成例114中所用之二環狀醚化合物（a-2)、且將分別加入^應槽及滴下裝置中的溶劑之量變更成乙酸乙酯192份及τ苯 319793 211 200838965 384份，除此以外與合成例114之步驟（12)、同樣地進行反應，添加乙酸乙醋1530份，而獲得經化合物（c3)加成之聚酯樹脂（C2)溶液。其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇.2 重量％)500份、且將為環狀酯化合物（1})之£ •己内酯之量變更成22份，除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯12份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為5〇5重量％、黏度為19，刪『pa. s _之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 O.SmgKOH/g、羥基價為9.5mgK〇H/g、玻璃轉移溫度為— 10°c、重量平均分子量為175,000。 (合成例122) 使用聯苯-4,4，·二環氧丙基鱗1:5〇5份替代合成例114 中所用之二環狀鱗化合物（a_2)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯23〇份及曱苯46〇籲份，除此以外與合成例114之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯1847份，而獲得經封閉化合物（c3)加成之聚酯樹脂（C2)溶液。其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇1 重量％)500份、且將為環狀醋化合物（b)之卜己内酯之量變更成18份’除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯8份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為5〇〇重量％、黏度為⑻mPa. s 之加成型聚醋樹脂（D2)之溶液。該樹脂（D2)的酸價為 319793 212 200838965 破璃轉移溫度為〇.lmgKOH/g、羥基價為 u 2mgK〇H/g、 —i〇c、重量平均分子量為145,000。 (合成例123) 使用對-曱苯石基異氰酸§旨1578份替代合成例⑴ 中所用之封閉化合物（c)、且將分別加入反應槽及滴下裝置申的溶劑之量變更成乙酸乙酯3〇5份及甲苯61〇份，除此以外與合成例114之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯2435份，而獲得經封閉化合物卜3)加成之聚酯樹 _脂（€2)溶液。其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇〇重里％) 5 00份、且將為環狀酯化合物⑻之ε -己内酯之量變更成14份，除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯4份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50·2重量％、黏度為21，〇〇〇mpa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為馨80.5mgKOH/g、羥基價為i3.9mgKOH/g、玻璃轉移溫度為一 10°C、重量平均分子量為195,000。 (合成例124) 使用作為矽烷化劑（cl)之三曱基氯矽烷864份替代合成例114中所用之化合物（〇3)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯254份及曱苯508 份，除此以外與合成例Π4之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯2029份，而獲得經化合物（cl)加成之聚酉旨樹脂（C2)溶液。 213 319793 200838965 其次，使用所得之樹脂（C2)溶液（不揮發成分為49·: 重量％)500份、且將為環狀醋化合物⑻之^己内醋之量變更成17份，除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯7份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為49.8重量％、黏度為i 8，議mb . s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 1.5mgKOH/g、經基價$ 1G.2mgK〇H/g、玻璃轉移溫度為一 10°C、重量平均分子量為165,000。 _(合成例125) 使用作為矽烷化劑（cl)之三乙基矽烷醇1〇56份替代合成例114中所用之化合物⑽、且將分別加人反㈣及滴下裝置中的溶劑之量變更成乙酸乙酯268份及甲苯535 份，除此以外與合成例114之步驟（12)、（13)同樣地進行反應..，添加乙酸乙酯2029份，而獲得，經封閉化合物（cl)加成之t酯樹脂（C 2)溶液。 •曰其次，使用所得之樹脂（C2)溶液（不揮發成分為49.8 重量°/°)500份，除此以外與合成例114之步驟（14)同樣地進仃反應，而獲得淡黃色透明、且其不揮發成分為49 7重夏％、黏度為14,0〇〇mpa· s之加成型聚酯樹脂（D2)之溶液。 4树腊（D2)的酸價為〇.8mgK〇H/g、羥基價為n6mg K〇H/g、玻璃轉移溫度為一 1()、重量平均分子量為 13〇,0〇〇〇 (合成例126) 使用作為矽烷化劑（cl)之六甲基二矽氮烷725份替代 214 319793 200838965 合成例n4中所用之化合物（c3)、且將分別加入反應槽及滴下衣置中的溶劑之量變更成乙酸乙酯244份及甲苯份’除此以外與合成例114之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯1950份’而獲得經化合物（cl)加成之聚酯樹脂（C2)溶液。田其次，使用所得之樹脂（C2)溶液（不揮發成分為496 重里4)500伤、且將為環狀醋化合物0)之£ _己内醋之量變更成15份，除此以外與合成例114之步驟（1句同樣地進行 ♦反應’添加乙酸乙酷5份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為49 9重量％、黏度為i2,〇〇〇mPa. s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 l’ln^gKOH/g、羥基價為1〇 3mgK〇H/g、玻璃轉移溫度為 —10°C、重量平均分子量為11〇,〇〇〇。 ·(合成例127) •使用作為矽烷化劑（cl)之曱氧基三甲基矽烷862份替Step (10) is omitted in Synthesis Example 107, and 500 parts of the polyester resin (B) solution (nonvolatile content: 50.1% by weight) of the main chain obtained in the step (9) is used in place of the addition molding polyester in the step (11). A resin (C2) solution was prepared in the same manner as in Synthesis Example 107 except that the amount of ε-caprolactone (b) was changed to 44 parts, and 34 parts of acetic acid was added thereto, and the mixture was cooled to room temperature. Further, a solution of a polyester resin which was light yellow transparent and had a nonvolatile content of 50.2% by weight and a viscosity of 17,000 mPa·s was obtained. The resin contained in the solution had an acid value of 0.5 mgKOH/g, a base price of 77: 〇1: 011, a glass transfer scent of 40 ° C, and a weight average molecular weight of 155,000. (Synthesis Example 109) 1000 parts of sebacic acid which is a dicarboxylic acid (a-1-l) and Vylon GK110 which is a high molecular weight polyester dicarboxylic acid (a-1-2) (number average molecular weight: 16,000, acid) Price: 6, manufactured by Toyobo Co., Ltd.) 800 parts of the dibasic acid (a-Ι) used in the synthesis of Example 107, and the amount of the solvent added to the reaction tank and the dropping device was changed to 265 parts of ethyl acetate and toluene. A reaction was carried out in the same manner as in the step (9) of Synthesis Example 107, except that 530 parts were obtained, and 2129 parts of ethyl acetate was added to obtain a solution of the polyester resin (B) for the main chain. Next, 500 parts of the obtained resin (B) solution (nonvolatile content: 50.2 weight: 199 319793 200838965 %) was used, and the amount of the benzoic acid benzene vinegar which is the blocking compound (c3) was changed to 65 parts, and The reaction was carried out in the same manner as in the step (1) of Synthesis Example 1-7, and ethyl acetate (5) was added and cooled to room temperature to obtain a solution of the polyester resin (C2) which was added with the blocking compound (C). Furthermore, 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.0% by weight) was used, and the amount of the vinegar of the cyclic vinegar (8) was changed to 23 parts, and the synthesis example 1 was used. Step 7 (1)) The reaction was carried out in the same manner, and 13 parts of ethyl acetate was added and cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 5% by weight, a viscosity of (10). Poly S is a solution of the resin (D2). The resin (D2) had an acid value of 1.2 mgKOH/g, a hydroxyl value of 19.5 mgK〇H/g, a glass transition temperature of -10 °C, and a weight average molecular weight of U5,000. (Synthesis Example 110) / 310 parts of azelaic acid which is a dicarboxylic acid (aM) and TXM80B which is a high molecular weight polyamine dicarboxylic acid (a-1-2b) (number average molecular weight: L600, acid_^贝·20) 8 parts of the dibasic acid (a-Ι) used in the synthesis example, and the amount of the solvent added to the reaction tank and the dropping device was changed to 260 parts of ethyl acetate and toluene. The reaction was carried out in the same manner as in the step (9) of Synthesis Example 107, except for the above-mentioned step (9), and ethyl acetate (2 parts) of 69 parts was added to obtain a polyester resin solution for a main chain. Next, 500 parts of the obtained resin (B) solution (nonvolatile content: 5% by weight) was used, and the amount of the phenyl isocyanate which is the blocking compound (c3) was changed to 67 parts, and The procedure of Synthesis Example 1〇7 (1〇) was carried out in the same manner, and 57 parts of ethyl acetate was added and cooled to room temperature to obtain a polyester resin (C2) which was subjected to addition of 319793 200 200838965 compound (C). Solution. Further, 500 parts of the obtained resin (C2) solution (nonvolatile content: 5% by weight) was used, and the amount of the vinegar (8) was changed to 24 parts, and the synthesis was carried out. The procedure of Example 1〇7 (Im) was carried out in the same manner, and 14 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 50·1% by weight and a viscosity of 15, 〇〇. 〇mpa · s Addition of a solution of polyester resin (D2). The resin (D2) had an acid value of 1.5 mgKOH/g, a hydroxyl group value of 18 3 mg K〇H/g, a glass transition temperature of _10 C, and a weight average molecular weight of 130,00 Å. (Synthesis Example 111) A polymerization reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube was prepared in a polymerization tank, and was added to the polymerization tank and the dropping device at a ratio lower than that used in the alternative synthesis example 107, respectively. a low molecular weight dimer acid (add) of a molecular weight dicarboxylic acid (a-1-l), a polyester polyol (a-1-α), a compound having two cyclic ether groups (a_2), a catalyst, And [polymerization tank] KURARAY polyol P4〇l〇(aia) 2078 parts succinic anhydride (aM) 50 parts ethyl acetate 165 parts benzene benzene 330 parts tetrabutylammonium tetraborate (catalyst) 1 part [drop Device] bis-A diglycidyl ether (a-2) 192 parts 201 319793 200838965 tetrabutylammonium tetrahydrogenate (catalyst) ethyl acetate toluene 1 part of 165 parts of air in the polymerization tank after replacement with nitrogen After stirring the contents of the mixture, the mixture was heated to HKTC for 330 hours, and the reaction was carried out for 8 hours to obtain a high molecular weight two (a small 3) as a binary. Next, the mixture of the di-formed ether compound (a-2) was consumed by dropping the apparatus for an hour to drip at a constant rate. After completion, while stirring - add 5 parts of catalyst 每隔 every 8 hours, after 2 times into ', after a total of 24 hours of reaction, ripening, then: force: 1330 injury acetic acid B_ subcooled to room temperature The reaction was terminated, and the primary key was used to make a J (B). Next, 500 parts of the obtained resin (B) solution (non-volatile content: 5% by weight) was used, and the amount of the isophthalic acid benzoquinone which is the blocking compound (c3) was changed to 12 parts'. In the same manner as in the step (10) of Example 1 to 7, the reaction was carried out in the same manner, and 2 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a solution of the polyester resin clasp 2) obtained by adding the blocked homo compound (C). 500 parts of the obtained resin (C2) solution (nonvolatile content: 5% by weight) was used, and the amount of the cyclic (8) was changed to 5 parts, and the synthesis example 107 was used. Step (η) was carried out in the same manner, without adding ethyl acetate and cooling to room temperature, to obtain a pale yellow transparent, and its non-volatile to a knife of 49.7 weights 1 〇 / 〇, viscosity of l5, 5 〇〇 mpa. The acid value of the addition of styrene = fat (D2) solution resin (D2) is 丨2 called 仏仏, the base bias is 7.5mgK 〇 H / g, the glass transition temperature is -2 〇 c > c, The weight average molecular weight was 135, 〇〇〇. 319793 202 200838965 (Synthesis Example 112) diethyl ether decane which is a decylating agent (cl): 77 parts of the blocking compound (c3) used in the step (10) of Synthesis Example 107, and Synthesis Example 107 The reaction was carried out in the same manner, and 67 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of the polyester resin (C2) which was added to the blocked compound (4). In the step (11), the amount of the obtained resin (C2) solution (500 parts of a nonvolatile component: 50.0% by weight) and the cyclic esterification of the amount of £_caprolactone is changed to 33 parts. The reaction was carried out in the same manner as in Synthesis Example 1-7, and 23 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material, and its nonvolatile content was 50.0% by weight, and the viscosity was 13, 〇〇. A solution of 〇mPa·s added modified polyester resin (D2). The acid value of the resin (D2) was 〇.〇5 mg KOH/g, the hydroxyl value was i8.5 nigKOH/g, and the glass transition temperature was -1 Torr. 〇, weight average molecular weight is 120,000. (Synthesis Example 113) The reaction was carried out in the same manner as in Synthesis Example 1〇7 except that 112 parts of phthalic anhydride (c2) was used instead of the blocking compound (c3) used in the step (1) of Synthesis Example 1-7. The ethyl ester was 102 parts and cooled to room temperature to obtain a solution of the polyester resin (C2) added with the blocking compound (c). In the step (11), 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.2% by weight) and the amount of the ?-caprolactone which is the cyclic ester (1)) were changed to 31 parts. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 107, and 21 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material and a nonvolatile content of 50.3 parts by weight. /❶, viscosity is i7,500mPa·s addition of a solution of polyester resin (D2). The acid value of the resin (D2) was 85.lmg 319793 203 200838965 KOH/g, the hydroxyl value was 12 8 mg K〇H/g, and the glass transition temperature was _1〇. . The weight average molecular weight is 175,000. [Production of Additive Polyester Resin (D2) by a Quasi-Two-Phase Manufacturing Method] In the following Synthesis Examples 114 to 115, a method of obtaining an addition-molded polyester resin (D2) via a pseudo-two-stage type step will be described. This method produces a main chain (Γ) having an acid value of 5 (mgKOH/g) or less, and secondly, a completion and a blocking reaction of the main chain (I), and then addition of a side chain. (Synthesis Example 114) _ <Steps (12), (13): Synthesis of polyester resin (C2) added by blocking compound (c) > Prepared in a polymerization tank with a stirrer, a thermometer, a reflux cooler, and a drip a polymerization apparatus for a device and a nitrogen introduction tube, and a dibasic acid (aM) as a dibasic acid (al) and two cyclic ether groups in a molecule in the polymerization tank and the dropping device. Compound (a_2), compound (c3), catalyst, and organic solvent. ▲[Polymerization tank] Adipic acid (aM) 438 parts of isodecanoic acid (a-1-1) 332 parts of bis-diethylene epoxide (a_2) 1919 parts of ethyl acetate 260 parts benzene benzene 520 parts Tetrabutylammonium borate (catalyst) 1 part [Dropping device] Phenyl isocyanate (c3) 952 parts 204 319793 200838965 Tetrabutylammonium tetraborate (catalyst) 1 part ethyl acetate 260 parts benzene benzene After the air in the polymerization tank was replaced with nitrogen, the mixture was heated to 100 ° C while stirring the contents, and further reacted for 8 hours to obtain a polyester for a main chain having an acid value of 5 (mgKOH/g) or less. . Next, the isocyanate mixture was consumed by dropping the apparatus for 1 hour to drip at a constant rate. After the completion of the dropwise addition, 1 part of tetrabutylammonium tetrahydroborate was added thereto after stirring for 8 hours, and the reaction was further carried out for 8 hours, followed by aging, and then 2081 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to complete the reaction. Further, a polyester resin (C2) obtained by addition of the compound (c3) was obtained. The reaction liquid is light yellow transparent, and has a nonvolatile content of 5 0.1% by weight and a viscosity of 20,000 mPa·s. The resin (C2) is an acid value of 0:5 mgKOH/g, a hydroxyl group value of 37.2 mgKOH/g, and a glass transition temperature of 40°. C, weight average molecular weight of 160,000. <Step (14): Addition reaction of cyclic ester (b)> A polymerization reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube in a polymerization tank, and in a polymerization tank and dripping A polyester resin (C2) solution (nonvolatile content: 50.2% by weight), a cyclic ester (b), a catalyst, and an organic solvent prepared in the step (13) were added to the apparatus at the following ratios. [Polymerization tank] 205 319793 200838965 Polyester resin (C2) solution [Dropping device] £ - Caprolactam (b-1) Tetrabutylammonium tetrahydroborate (catalyst) Ethyl acetate will be polymerized The air in the tank was replaced with nitrogen, and 500 parts of 16 parts of 〇·5 parts of 10 parts were added, and the solution was heated to a loot while stirring the solution. Next, in this solution, the above cyclic ester mixture was dropped at a constant rate by dropping the apparatus for one hour. After the completion of the dropwise addition, the mixture was subjected to a reaction for 6 hours, and after the ripening was carried out, 6 parts of acetic acid was added thereto, and the mixture was cooled to room temperature to obtain a resin (4). This solution is light yellow transparent, and its nonvolatile content is 5〇3 wt%, viscosity 19, 〇〇〇mPa· S, the resin (D2) is acid value 〇, 2 mg K〇H/g, and hydroxyl group “16. 8 mg KOH/g. , glass transition temperature - 1 〇〇 c, weight average molecular weight 170, Θ 0 Θ 〇 (Synthesis Example 115) using a dicarboxylic acid (a_M) azelaic acid 1 〇〇〇 part and a high molecular weight poly 酉曰叛叛 ( Al-2a) Vylon GKn 〇 8 〇〇替代合成 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 333 parts and 666 parts of toluene, except that the reaction was carried out in the same manner as in steps (12) and (13) of Example 114, and 2673 parts of ethyl acetate was added, and the compound (c3) was transferred from ~_ and I. A polyester resin (C2) solution. One person's use of the obtained resin (C2) solution (non-volatile content of 50.0% by weight) 500 parts, 曰 face & four and will be the oxime ester (b) ε - The reaction was carried out in the same manner as in the step (14) of Synthesis Example 114 except that the amount of caprolactone was changed to 12 parts of 206 319793 200838965, and 2 parts of ethyl acetate was added and cooled. To the room temperature, a solution of a modified polyester resin (D2) which is light yellow transparent and has a nonvolatile content of 50.2% by weight and a viscosity of 2 Å and a mass of mpa.s is obtained. The acid value of the resin (D2) is O'lmgKOH/g, hydroxyl value of 22.6 mgKOH/g, glass transition temperature of -10 ° C, weight average molecular weight of i85, 〇〇〇. [Two-stage synthesis of addition-formed polyester resin (D2)] In Example 116, the method for producing the addition-molded polyester resin (D2) was carried out by simultaneously performing the formation reaction of the main bond portion (1) and the addition of the blocking compound (c), and then by ring-shaped. The ring-opening addition of the ester forms a side chain. (Synthesis Example 116) <Step (15) - Preparation of a polyester resin (C2) which is added by the blocking compound (c) > Prepared in a polymerization tank with a stirrer and a thermometer a polymerization reactor of a reflux condenser, a dropping device, and a nitrogen introduction tube, and a low molecular weight dicarboxylic acid (a"") and a polyol (a-1-) are added to the polymerization tank and the dropping device at the following ratios; α), a compound having two cyclic ether groups in the molecule, a blocking compound (c), a touch , And an organic solvent. [Polymerization tank] KURARAY polyol p4〇i〇(a_i_ j ) 2078 parts succinic anhydride (a-1-1) 50 parts ethyl acetate 173 parts toluene 345 parts tetrabutylammonium tetraborate (catalyst) 1 part 207 319793 200838965 [Dripping device] 192 parts 95 parts 1 part 173 parts 345 parts bis-diethylene oxide _ (a-2) phenyl isocyanate (c3) tetrabutylammonium tetrahydroborate (catalyst) Ethyl acetate toluene was used to replace the air in the polymerization tank with nitrogen, and the mixture was heated to a loot while stirring the contents, and allowed to react for 8 hours to obtain a dibasic acid (a-type) which was a main bond portion (1). Ig) high molecular weight dicaprylic acid (heart 丨 3). Next, the mixture of the above dicyclic ether compound (heart 2) and the blocking compound (c) was dropped by a dropping device at a constant rate for dropping at a constant rate. After the completion of the dropwise addition, tetrabutylammonium tetrahydroborate was added every 8 hours while stirring, and 5 parts were added twice, and after reacting for 24 hours, after ripening, 1379 parts of ethyl hydrazine was added and cooled. The reaction was terminated at room temperature, and a solution of the polyester resin (C2) which was subjected to addition blocking compound (4) was obtained. _ <Step (16): Ring-opening addition reaction of cyclic ester (b)> Adding the above polyester resin (€:2) solution to the polymerization tank (non-volatile content is 50.2% by weight) 5 parts . Under the same conditions as in the second stage of Synthesis Example 114, ε_caprolactone of (b-Ι): 24 parts, tetrabutylammonium tetrahydroborate (catalyst), 〇·5 parts, and acetic acid B A mixture of 1 part of the ester was dropped from the dropping tank into the polymerization tank, and reacted. 14 parts of ethyl acetate was added and cooled to the chamber to obtain a pale yellow transparent, and its nonvolatile content was 49.7% by weight. For l5, 〇〇〇mPa·s is added to form a solution of poly[|resin (D2). The acid value of the tree sorghum (D2) is 〇5mgK〇H/g, the hydroxyl value is 7.5mgK〇Ii/g, and the glass 319793 208 200838965 glass transition temperature is one (TC, weight average molecular weight is 130,000. [Additional molding Quasi-like two-stage synthesis of polyester resin (D2) In the following Synthesis Examples 117 to 13 7 , a method for obtaining an addition-molded polyester resin (D2) by a pseudo-like two-stage type step is described, which is an acid obtained. The main chain (I,) having a valence of 5 (mgKOH/g) or less has a polyester, and secondly, the main chain (1) is formed and blocked, and then the side chain is added. (Synthesis Example 117) 2778 parts of phenoxyethanol second epoxy propyl ether was used instead of the dicyclic ether compound (a_2) used in Synthesis Example 114, and the amount of solvent added to the reaction tank and the subsparent apparatus was changed to ethyl acetate 321 In the same manner as in the steps (12) and (13) of Synthesis Example 114, the reaction was carried out in the same manner as in the step (12) and (13) of Synthesis Example 114, and 2,575 parts of ethyl acetate was added to obtain a polyester resin which was added to the blocked compound 3). (C2) solution a θ secondly, using the obtained resin (C2) solution (nonvolatile content is 5 1) The reaction was carried out in the same manner as in the step (10) of Synthesis Example 114 except that 500 parts of the cyclic ester (the amount of the caprolactone was changed to 13 parts), and a pale yellow transparency was obtained. The non-volatile component is 5〇·2% by weight, and the viscosity is 21, and the solution of the modified polycondensed grease is _ Qin S. The acid value of the resin (D2) is 〇.lmgK〇H/g, and the base price is <(4) The transfer temperature with glass is -HTC, and the weight average molecular weight is 19 Å. (Synthesis Example 118) Butyl) methoxy]methyl} benzene is used in place of the synthesis example Π4 using 1,4-double {[ (3_ethyl_3_oxocyclic 685 parts and resorcinol diepoxypropyl ether 7〇2 319793 209 200838965 used dicyclic ether compound (a_2), and will be separately added to the reaction tank and drip device The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114 except that the amount of the solvent was changed to 222 parts of ethyl acetate and 444 parts of toluene, and 1777 parts of ethyl acetate was added to obtain a blocked compound. (c3) a solution of the added resin (C2) to be added. Next, 500 parts of the obtained resin (C2) solution (498% by weight of a nonvolatile component) was used, and The spring reaction was carried out in the same manner as in the step (14) of Synthesis Example 114 except that the amount of ε-caprolactone in the cyclic ester compound was changed to 19, and 9 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature. Further, a solution of a modified polyester resin (D2) having a pale yellow transparency and having a nonvolatile content of 49.7% by weight and a viscosity of njoompa·s was obtained. The resin (D2) had an acid value of 0.5 mgKOH/g, a hydroxyl value of 9.3 mgKOH/g, a glass transition temperature of - 20 ° C, and a weight average molecular weight of 100,000. (Synthesis Example 119) - 6060 parts of a double-aged A-based high molecular weight epoxy propyl resin "jER1〇〇2" (manufactured by Nippon Epoxy Co., Ltd.) was used instead of the dicyclic ether compound used in Synthesis Example 114 (a) And the reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114 except that the amount of the solvent added to the reaction vessel and the dropping device was changed to 556 parts of ethyl acetate and 1112 parts of toluene. 4,446 parts of ethyl acetate was added to obtain a solution of the polyester resin (C2) added with the blocked compound 03). Next, the obtained resin (C2) solution (non-volatile content is 5 〇·2 重量 /.) 500 wounds, and the amount of the caprolactone of the cyclic ester compound (VII) was changed to 40 wounds, and The reaction was carried out in the same manner as in the second step of Synthesis Example i 14 319793 210 200838965 (14), and 3 parts of ethyl acetate was added thereto and cooled to room temperature to obtain a pale yellow transparent material and a nonvolatile content of 5 〇. 2% by weight of a solution of the addition-molded polyester resin (D2) having a viscosity of 25,000 mPa·s. The resin (D2) had an acid value of mg. 5 mgKOH/g, a hydroxyl group value of 121 mgK 〇H/g, a glass transition temperature of 5C, and a weight average molecular weight of 195 Å. (Synthesis Example 120) The compound (a_2) having two cyclic ether groups in the molecule used in Synthesis Example 114 was replaced by using neopentyl alcohol monoepoxypropyl group to 526 parts, and the fraction was added to the reaction vessel and The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114 except that the amount of the solvent in the dropping apparatus was changed to 106 parts of ethyl acetate and 212 parts of toluene, and ethyl acetate was added in an amount of 42 parts. A solution of the polyester resin (C2) added with the blocked compound (c3) was obtained. Next, using the obtained resin (C2) solution (nonvolatile content is 5〇·2%), 500 parts, and the amount of ε·caprolactone, which is a cyclic ester oxime, is changed to 39 parts. In the same manner as in the step (14) of Synthesis Example 114, 29 parts of ethyl acetate was added and cooled to room temperature to obtain a pale yellow transparent material, and the nonvolatile content was 5 〇 2 wt%, and the viscosity was 12,5 (9) mPa · s plus shaped polyester resin (D2) bismuth solution. The resin (D2) had an acid value of mg. 2 mgKOH/g, a hydroxyl group value of 10 4 mg K 〇 H/g, a glass transition temperature of -25 ° C, and a weight average molecular weight of 12 Å. (Synthesis Example 121) The dicyclic ether compound (a-2) used in Synthesis Example 114 was replaced with 96 parts of bis-(3,4-epoxycyclohexyl) adipate, and was added separately. In the same manner as in the step (12) of Synthesis Example 114, 1530 parts of ethyl acetate was added, and the amount of the solvent in the tank and the dropping device was changed to 192 parts of ethyl acetate and 384 parts of τ benzene 319793 211 200838965. A solution of the polyester resin (C2) added with the compound (c3) was obtained. Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 5% by weight) was used, and the amount of the caprolactone which is the cyclic ester compound (1}) was changed to 22 parts, except The reaction was carried out in the same manner as in the step (14) of Synthesis Example 114, and 12 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 5% by weight and a viscosity of 19, Delete the solution of the molded polyester resin (D2) of "pa. s _". The resin (D2) had an acid value of O.SmgKOH/g, a hydroxyl group value of 9.5 mgK〇H/g, a glass transition temperature of -10 ° C, and a weight average molecular weight of 175,000. (Synthesis Example 122) The bicyclic quaternary compound (a_2) used in Synthesis Example 114 was replaced with 5 parts of biphenyl-4,4,diethylene propyl sulphate 1:5 Å, and they were separately added to a reaction vessel and dropped. The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114 except that the amount of the solvent in the apparatus was changed to 23 parts of ethyl acetate and toluene, and 1847 parts of ethyl acetate was added. A solution of the polyester resin (C2) added with the blocked compound (c3) was obtained. Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 5% by weight) was used, and the amount of the caprolactone of the cyclic vinegar compound (b) was changed to 18 parts'. Step (14) of Synthesis Example 114 was carried out in the same manner, and 8 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 5% by weight and a viscosity of (8) mPa·s. A solution of the shaped polyester resin (D2). The acid value of the resin (D2) was 319793 212 200838965. The glass transition temperature was 〇.1 mgKOH/g, the hydroxyl value was u 2 mgK〇H/g, -i〇c, and the weight average molecular weight was 145,000. (Synthesis Example 123) The blocking compound (c) used in the synthesis example (1) was replaced with p-pyridyl isocyanate, and the amount of the solvent added to the reaction vessel and the dropping device was changed to acetic acid B. The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114 except that the ester was obtained in the form of a mixture of the residue and the mixture. Polyester tree _ lipid (€2) solution. Next, the obtained resin (C2) solution (nonvolatile content is 5% by weight) of 500 parts, and the amount of ε-caprolactone which is a cyclic ester compound (8) is changed to 14 parts, and Step (14) of Synthesis Example 114 was carried out in the same manner, and 4 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 50·2% by weight and a viscosity of 21, 〇〇〇. A solution of mpa · s plus shaped polyester resin (D2). The resin (D2) had an acid value of 80.5 mgKOH/g, a hydroxyl value of i3.9 mgKOH/g, a glass transition temperature of 10 ° C, and a weight average molecular weight of 195,000. (Synthesis Example 124) The compound (〇3) used in Synthesis Example 114 was replaced with 864 parts of tridecylchloromethane as a decylating agent (cl), and the amount of the solvent added to the reaction tank and the dropping device was changed to The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 4 except for 254 parts of ethyl acetate and 508 parts of toluene, and 2029 parts of ethyl acetate was added to obtain a compound obtained by addition of compound (cl). A resin (C2) solution. 213 319793 200838965 Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 49%:% by weight) was used, and the amount of the vinegar of the cyclic vinegar compound (8) was changed to 17 parts, and The reaction was carried out in the same manner as in the step (14) of Synthesis Example 114, and 7 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 49.8% by weight and a viscosity of i8. A solution of the modified polyester resin (D2). The resin (D2) had an acid value of 1.5 mgKOH/g, a base price of $1G.2 mgK〇H/g, a glass transition temperature of 10 ° C, and a weight average molecular weight of 165,000. _ (Synthesis Example 125) The compound (10) used in Synthesis Example 114 was replaced with 1 part of triethyl decyl alcohol as a decylating agent (cl), and the amount of solvent added to the counter (IV) and the dropping device was changed. The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114 except that 268 parts of ethyl acetate and 535 parts of toluene were obtained, and ethyl acetate (2029 parts) was added to obtain a blocked compound (cl). Addition of t ester resin (C 2 ) solution. In the same manner as in the step (14) of Synthesis Example 114, except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 49.8 wt%/°) was used, a pale yellow transparency was obtained. The non-volatile component is a solution of 49% by weight of summer, and a viscosity of 14,0 mpa·s of the addition-molded polyester resin (D2). The acid value of 4 tree wax (D2) is 〇.8mgK〇H/g, the hydroxyl value is n6mg K〇H/g, the glass transition temperature is 1 (), the weight average molecular weight is 13〇, 0〇〇〇 (synthesis Example 126) The compound (c3) used in Synthesis Example n4 was replaced by 725 parts of hexamethyldioxane as a decylating agent (cl), and the solvent was separately added to the reaction vessel and the dropping agent. The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114 except that the amount was changed to 244 parts of ethyl acetate and toluene fraction, and 1950 parts of ethyl acetate was added to obtain a compound (cl) addition. Polyester resin (C2) solution. Tian Qiji, using the obtained resin (C2) solution (non-volatile content is 496 zhongli 4) 500 wounds, and the amount of vinegar of the cyclic vinegar compound 0) is changed to 15 parts, and other than the synthesis The procedure of Example 114 (1 sentence was carried out in the same manner as in the '1 reaction', adding 5 parts of ethyl acetate and cooling to room temperature, to obtain a pale yellow transparent, and its nonvolatile content was 499% by weight, the viscosity was i2, 〇〇〇mPa a solution of the modified polyester resin (D2). The acid value of the resin (D2) is l'ln^gKOH/g, the hydroxyl value is 1〇3mgK〇H/g, and the glass transition temperature is -10°C. The weight average molecular weight is 11 〇, 〇〇〇. (Synthesis Example 127) • 862 parts of decyloxytrimethyl decane as a decylating agent (cl)

其次，使用所得之樹脂（C2)溶液（不揮發成分為498 重量％)500份、且將為環狀s旨化合物（b)之卜署之ε -己内酯之量變之步驟（14)同樣地進行套溫’而獲得淡黃色透更成14份，除此以外與合成例丨14之步為反應，添加乙酸乙酯4份並冷卻至室溫， 319793 215 200838965 明、且其不揮發成分為49·7重量％、黏度為12,500mPa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為〇.5mgKOH/g、羥基價為8.5mgK〇H/g、玻璃轉移溫度為〜 10°C、重量平均分子量為120,〇〇〇。 (合成例128) 使用作為酸酐（C2)之酞酸酐1184份替代合成例114中所用之封閉化合物（c3)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯276份及曱苯554份，除此 •以外與合成例114之步驟（12)、（13)同樣地進行反應，添加乙酸乙酯2213份’而獲得經化合物（C2)加成之聚酯樹脂（C2) 溶液。其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇.2 重量％)500份、且將為環狀酯化合物〇3)之£-己内酯之量變更成15份，除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯5份並冷卻至室溫，而獲得淡黃色透 _明、且其不揮發成分為49·7重量❽/c、黏度為l6,〇〇〇mPa· s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 85.5mgKOH/g、羥基價為7.3mgK〇H/g、玻璃轉移溫度為 ~5°C、重量平均分子量為145，⑽〇。 ' (合成例129) 使用作為酸酐（C2)之酞酸酐148份替代合成例114中所用之封閉化合物（c3)、且將分別加入反應槽及滴下装置中的溶劑之量變更成乙酸乙酯202份及甲苯404份，除此以外與合成例114之步驟（12)、（13)同樣地進行反應，添加 319793 216 200838965 乙酸乙醋1625份，而獲得經封閉化合物（c2)加成之聚脂（C2)溶液。、其次’使用所得之樹脂（C2)溶液（不揮發成分為50.2 重1 /〇)500伤、且將為環狀酯化合物0)之£ _己内酯之量變更成50份，除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯4〇份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50.1重量％、黏度為13,〇〇〇mpa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為鲁12.5mgKOH/g、經基價為62 3mgK〇H/g、玻璃轉移溫度為一 i〇c、重量平均分子量為140，⑽〇。 (合成例130) 使用作為酸酐（C2)之丁二酸酐1〇〇份替代合成例114 中所用之封閉化合物（c3)、且將分別加入反應槽及滴下裝置中的溶劑之量變更減乙酸乙酯139份及曱苯278份.，除此以外與合成例Π4之步驟（12)、（13)同樣地進行反應，添瘳加乙酸乙酯2233份，而獲得經封閉化合物（c2)加成之聚酯樹脂（C2)溶液。曰其次，使用所得之樹脂（C2)溶液（不揮發成分為5〇Q 重里/ί>)500知、且將為壞狀醋化合物（b)之£ -己内醋之量變更成49份，除此以外與合成例114之步驟（14)同樣地進行反應，添加乙酸乙酯3 9份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為5〇·ΐ重量❹/。、黏度為12,5〇〇mPa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 13.8mgKOH/g、羥基價為68e7mgK〇H/g、玻璃轉移溫度為 319793 217 200838965 一 20°C、重量平均分子量為130,000。 (合成例131) 使用作為酸酐（c2)之海米克酸酐（Himic anhyddde) j料份替代合成例Π4中所用之封閉化合物（c3)、且將分別加入反應槽及滴下裝置中的溶劑之量變更成乙酸乙酯2〇4份及甲苯408份，除此以外與合成例114之步驟（1幻、（13) 同樣地進行反應，添加乙酸乙酯1635份，而獲得經封閉化合物（c2)加成之聚酯樹脂（(：2)溶液。審其次，使用所得之樹脂（C2)溶液（不揮發成分為49.7 重量％)500份^且將急援业略几人此/^、^， _ _Next, using the obtained resin (C2) solution (498% by weight of a nonvolatile component), 500 parts, and the amount of the ε-caprolactone of the compound (b) of the cyclic s group is changed to the same step (14). The mixture was subjected to a jacket temperature to obtain a pale yellow translucent portion, and was further reacted with the step of Synthesis Example 14 to add 4 parts of ethyl acetate and cooled to room temperature, 319793 215 200838965, and its nonvolatile content. A solution of the addition-molded polyester resin (D2) having a viscosity of 49.7% by weight and a viscosity of 12,500 mPa·s. The resin (D2) had an acid value of mg. 5 mgKOH/g, a hydroxyl group value of 8.5 mg K 〇 H/g, a glass transition temperature of ～10 ° C, and a weight average molecular weight of 120 Å. (Synthesis Example 128) The blocking compound (c3) used in Synthesis Example 114 was replaced with 1,184 parts of phthalic anhydride as the acid anhydride (C2), and the amount of the solvent added to the reaction tank and the dropping device was changed to 276 parts of ethyl acetate. In the same manner as in the steps (12) and (13) of Synthesis Example 114, the reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114, and the ethyl ester (22) was added to obtain a polyester resin (C2) which was added with the compound (C2). ) solution. Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 5% by weight) was used, and the amount of the cyclic ester compound 〇3) was changed to 15 parts, and the amount was changed. The reaction was carried out in the same manner as in the step (14) of Synthesis Example 114, and 5 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material, and its nonvolatile content was 49·7 weight ❽/c, viscosity. A solution of the molded polyester resin (D2) of l6, 〇〇〇mPa·s. The resin (D2) had an acid value of 85.5 mgKOH/g, a hydroxyl group value of 7.3 mg K〇H/g, a glass transition temperature of ～5 ° C, and a weight average molecular weight of 145, (10) 〇. (Synthesis Example 129) The blocking compound (c3) used in Synthesis Example 114 was replaced with 148 parts of the anhydride (C2), and the amount of the solvent added to the reaction tank and the dropping apparatus was changed to ethyl acetate 202. The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 114, except that 404 parts of toluene and 504 parts of toluene were added, and 165793 216 200838965 ethyl acetate vinegar (1625 parts) was added to obtain a polyester obtained by adding the blocking compound (c2). (C2) solution. Then, using the obtained resin (C2) solution (nonvolatile content: 50.2 weight 1 / 〇) 500, and changing the amount of the _caprolactone of the cyclic ester compound 0) to 50 parts, The reaction was carried out in the same manner as in the step (14) of Synthesis Example 114, and 4 parts of ethyl acetate was added thereto, and the mixture was cooled to room temperature to obtain a pale yellow transparent material having a nonvolatile content of 50.1% by weight and a viscosity of 13, 〇〇〇. A solution of mpa · s plus shaped polyester resin (D2). The resin (D2) had an acid value of 12.5 mgKOH/g, a base price of 62 3 mg K〇H/g, a glass transition temperature of one i〇c, a weight average molecular weight of 140, and (10) hydrazine. (Synthesis Example 130) The blocking compound (c3) used in Synthesis Example 114 was replaced with 1 part by weight of succinic anhydride as the acid anhydride (C2), and the amount of the solvent added to the reaction tank and the dropping device was changed to minus acetic acid. The reaction was carried out in the same manner as in the steps (12) and (13) of Synthesis Example 4 except for 139 parts of an ester and 278 parts of toluene, and 2233 parts of ethyl acetate was added thereto to obtain a blocked compound (c2). Polyester resin (C2) solution. Next, using the obtained resin (C2) solution (non-volatile content is 5 〇 Q zhongli / ί gt) 500, and the amount of vinegar of the bad vinegar compound (b) is changed to 49 parts. Other than the above, the reaction was carried out in the same manner as in the step (14) of Synthesis Example 114, and then ethyl acetate (3) was added and cooled to room temperature to obtain a pale yellow transparent material and a nonvolatile content of 5 〇·ΐ weight ❹/. A solution of a modified polyester resin (D2) having a viscosity of 12,5 〇〇 mPa · s. The resin (D2) had an acid value of 13.8 mgKOH/g, a hydroxyl group value of 68e7 mgK〇H/g, a glass transition temperature of 319793 217 200838965 to 20 ° C, and a weight average molecular weight of 130,000. (Synthesis Example 131) The amount of the solvent (c3) used in the synthesis example Π4 was replaced with hemiic acid anhydride (c2), and the amount of the solvent to be added to the reaction tank and the dropping device, respectively. The reaction was carried out in the same manner as in the procedure of Synthesis Example 114 (1, and (13), and 1635 parts of ethyl acetate was added to obtain a blocked compound (c2). Addition of polyester resin ((:2) solution. Secondly, use the obtained resin (C2) solution (non-volatile content of 49.7 wt%) 500 parts ^ and will be a few people in the emergency aid industry / ^, ^, _ _

明、且其不揮發成分為50.0重量％、 .k，而獲得淡黃色透黏度為 14,0〇〇mPa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為 10.8mgK〇H/g、羥基價為58 5mgK〇H/g、玻璃轉移溫度為省一20C、重量平均分子量為13〇,〇〇〇。 (合成例132) 使用5 -戊内酯14份替代合成例π 4之步驟（14)中所用之環狀酯（b)，除此以外與合成例114同樣地進行調製，添加乙酸乙酯4份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50·0重量％、黏度為2〇,〇〇〇1111^ 3之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為〇 img K〇f/g、經基價為18.5mgKOH/g、玻璃轉移溫度為一 1〇〇c、重1平均分子量為190,000。 319793 218 200838965 (合成例133) 使用丁内酯12份替代合成例114之步驟（14)中所用之環狀酯（b)，除此以外與合成例114同樣地進行反應，添加乙酸乙酯2份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50·2重量％、黏度為21，000mPa· s之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為〇.3mg KOH/g、羥基價為19e2mgKOH/g、玻璃轉移溫度為一 1(rc、重量平均分子量為205,000 〇肇（合成例134) 將合成例114所用之觸媒變更成氫硫酸四丁基銨，除此以外與合成例114同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為49·7重量％、黏度為17,〇〇〇mPa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為〇.2mgKOH/g、羥基價為15.5mgK〇H/g、玻璃轉移溫度為一 10°c、重量平均分子量為155,00〇。It was found that the non-volatile content was 50.0% by weight, .k, and a solution of the addition-molded polyester resin (D2) having a pale yellow viscosities of 14,0 〇〇 mPa · s was obtained. The resin (D2) had an acid value of 10.8 mg K 〇 H / g, a hydroxyl value of 58 5 mg K 〇 H / g, a glass transition temperature of 20 C, and a weight average molecular weight of 13 Å. (Synthesis Example 132) Ethyl acetate 4 was added in the same manner as in Synthesis Example 114 except that the cyclic ester (b) used in the step (14) of the synthesis example π 4 was replaced by 14 parts of 5- valerolactone. The mixture was cooled to room temperature to obtain a solution of the addition-molded polyester resin (D2) which was light yellow transparent and had a nonvolatile content of 50% by weight, a viscosity of 2 Å, and 〇〇〇1111^3. The resin (D2) had an acid value of 〇 img K〇f/g, a base price of 18.5 mgKOH/g, a glass transition temperature of 1 〇〇c, and a weight 1 average molecular weight of 190,000. 319793 218 200838965 (Synthesis Example 133) The reaction was carried out in the same manner as in Synthesis Example 114 except that 12 parts of butyrolactone was used instead of the cyclic ester (b) used in the step (14) of Synthesis Example 114, and ethyl acetate was added. The mixture was cooled to room temperature to obtain a solution of the addition-molded polyester resin (D2) which was light yellow transparent and had a nonvolatile content of 50.2% by weight and a viscosity of 21,000 mPa·s. The acid value of the resin (D2) was 〇.3 mg KOH/g, the hydroxyl value was 19e2 mgKOH/g, and the glass transition temperature was 1:1 (rc, weight average molecular weight was 205,000 Å (Synthetic Example 134). The reaction was carried out in the same manner as in Synthesis Example 114 except that the catalyst was changed to tetrabutylammonium hydrogensulfate, and a pale yellow transparent material was obtained, and the nonvolatile content was 49.7% by weight, and the viscosity was 17, 〇〇〇mPa. Adding a solution of the polyester resin (D2) to the resin. The acid value of the resin (D2) is mg.2 mgKOH/g, the hydroxyl value is 15.5 mgK〇H/g, the glass transition temperature is 10 ° C, and the weight average molecular weight is It is 155,00 baht.

(合成例135) 將合成例114所用之觸媒變更成對-甲苯磺酸四丁基銨，除此以外與合成例114同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為50.0重量％、黏度為18,〇⑽ mPa · s之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為0.2mgKOH/g、羥基價為15.8mgK〇H/g、玻璃轉移溫度為一io°c、重量平均分子量為16〇,〇〇〇。 (合成例136) 將合成例114所用之觸媒變更成過釕酸四丁基銨，除 219 319793 200838965 此以外與合成例114同樣地進行反應，而獲得淡黃色透明且其不揮發成分為50.1重量❹/〇、黏度為15,000mPa · s 之加成型聚酯樹脂（D2)之溶液。該樹脂（D2)的酸價為〇.2mfKOH/g、羥基價為14 3111§〖〇11/§、玻璃轉移溫度為 —1〇°C、重量平均分子量為150,000。 (合成例137) 不使用觸媒’除此以外與合成例丨14同樣地進行反應，而獲得淡黃色透明、且其不揮發成分為49.7重量％、黏度為14,500mPa· s之加成型聚酯樹脂（D2)之溶液。該樹月曰（D2)的酸價為〇 lmgKOH/g、羥基價為玻璃轉移溫度為-IGt：、重量平均分子量為125,〇〇〇。 [第3封閉型態：加成型聚酯樹脂①3)之合成] 在下述合成例138至140中，針對獲得加成型聚酯樹脂（D3)的方法加以說明，該方法係使合成例ιι4所得之加反應而成型聚酯樹脂（D2)中之羥基與封閉化合物（c)進行(Synthesis Example 135) The reaction was carried out in the same manner as in Synthesis Example 114 except that the catalyst used in Synthesis Example 114 was changed to tetrabutylammonium p-toluenesulfonate to obtain a pale yellow transparent material and a nonvolatile content of 50.0. A solution of the addition-molded polyester resin (D2) having a weight %, a viscosity of 18, and 〇(10) mPa · s. The resin (D2) had an acid value of 0.2 mgKOH/g, a hydroxyl group value of 15.8 mg K〇H/g, a glass transition temperature of io ° C, and a weight average molecular weight of 16 Å. (Synthesis Example 136) The catalyst used in Synthesis Example 114 was changed to tetrabutylammonium perruthenate, and reacted in the same manner as in Synthesis Example 114 except for 219 319793 200838965 to obtain a pale yellow transparent material and a nonvolatile content of 50.1. A solution of the formed polyester resin (D2) having a weight ❹/〇 and a viscosity of 15,000 mPa·s. The resin (D2) had an acid value of 〇.2mfKOH/g, a hydroxyl group value of 14 3111 § 〇 11/§, a glass transition temperature of -1 〇 ° C, and a weight average molecular weight of 150,000. (Synthesis Example 137) The reaction was carried out in the same manner as in Synthesis Example 14 except that the catalyst was not used, and an addition polyester having a pale yellow transparency and a nonvolatile content of 49.7% by weight and a viscosity of 14,500 mPa·s was obtained. A solution of the resin (D2). The acid value of the tree sorghum (D2) is 〇 lmgKOH/g, the hydroxyl value is - glass transition temperature is -IGt:, and the weight average molecular weight is 125, 〇〇〇. [Synthesis of the third closed form: addition-formed polyester resin 13] In the following Synthesis Examples 138 to 140, a method for obtaining the addition-molded polyester resin (D3) which is obtained by the synthesis example ι 4 is described. Adding a reaction to form a hydroxyl group in the polyester resin (D2) and blocking the compound (c)

獲得加成型聚酯樹脂（D3)。 (合成例138) 準備於聚合槽附有授拌機、溫度計、回流冷卻器及氣導入管的聚合反應裳置，並在聚合槽中分別以下述比率加入合成例114所製得之羥基16.8mgK〇H/g之加成型聚酯樹脂（D2)溶液、封閉化合物（C2)、以及觸媒。 [聚合槽] 合成例1H所得之加成型聚酯樹脂（D2)溶液 5〇〇铪 319793 220 200838965 3份 0·1份酉太酸肝（c2) 四氫爛酸四丁基銨（觸媒）將聚合槽内之空氣以氣#； $ u 見乳置換後，一邊攪拌溶液一邊升溫至赃。再-邊授拌—邊進行6小時之反應、熟成，然後添加乙酸乙酯2份並冷卻至室溫，結束反應，而獲得淡黃色透明、且其不揮發成分為5〇 ι重量％、黏度為 19’500mPa . s之加成型聚g旨樹脂（叫之溶液。該樹脂⑴ 之酸價為4.5mgKOH/g、羥基價為i2 imgK〇H/g、玻璃轉 ♦移溫度為-抓、重量平均分子量為議，〇〇〇。 (合成例139) 138㈣之封閉化合物㈣變更成異氰酸硬脂酉旨（c3)4份，除此以外與合成例138同樣地進行反應，添加乙酸乙醋4份並冷卻至室溫，而獲得淡黃色透明、且其不揮發成分為50.0重量％、黏度為-17,5〇〇mpa. s之加成型聚酯樹脂（D3)之溶液。該樹脂（D3)的酸價為〇.〗mgK〇H/g、鲁羥基價為8.5mgKOH/g、玻璃轉移溫度為—15<3c、重量平均分子量為160,000。 (合成例140) 將合成例138所用之封閉化合物（c2)變更成二曱基辛基氯矽烷（cl)3份，除此以外與合成例138同樣地進行反應，添加乙酸乙酯3份並冷卻至室溫，而獲得淡黃色透明、，且其不揮發成分為49.8重量％、黏度為17,〇〇〇mPa. s之加成型聚醋樹脂（D3)之溶液。該樹脂（D3)的酸價為〇.lmgKOH/g、羥基價為iSmgKOH/g、玻璃轉移溫度為— 221 319793 200838965 15°C、重量平均分子量為165,000。針對合成例107至140所得之各樹脂溶液，將該等溶液之外觀、不揮發成分、樹脂之重量平均分子量（Mw)、玻璃轉移溫度（Tg)、酸價（AV)以及羥基價（OHV)以與合成例1 至20同樣之方式評估，彙總顯示於表14、表15。 222 319793 200838965 [表14]加成型聚酯樹脂（D2)、（D3)之合成例 % f > X ο (meKOH^c) l__________ 卜 C\l K S s &〇 P5 CO ee GO cw ί； S CD s UD 2 畴〇 0» > < CM — IA M 〇 lfl o . to esi g CO u> tsi 5 &n d s in d cw u> d ^ e 5 § O ? Ο 丁 o T O 1 o T o 丁 s ο O T 〇 T 5 0 1 t ID N 〇 T o Έ 150,000 I 160.000 I 1 ID I to 135,000 1 ! 130,000 I I 135,000 I 1 <20,000 I 1 in 1 ιβο,οοο I 1 170,000 1 1 185,000 1 i g I 190.000 | 1100,0001 | ΐθδ,οοο | 120,000 1 | 175,000 | 145,000 t Vi· (mP*»e) I 18,000] I 20.0001 ! 18,5001 | 17.0001 1 15,5001 | 15,0001 I 15,5001 丨 13,0001 | t7,50〇| 1 20,0001 1 19,0001 | 20,5001 | 15,0001 I CM [11,0001 ! 25,0001 | )2,5001 ! 19.000 I 15,000 i i o S i i A o s w s i Λ S CM S c%t δ **r CSl s s in s p S 溶液外觀 m Ifi « m 1演黄色进明1 |班黄色透HJ 1»黄色透明1 1»黄色进明1 1 »黄色透明1 | *黄色透JiJ 1淡黄色透明1 丨濟黄色进明1 1嫌It色透明1 1淡黄色透明1 1庚黄色透明1 丨演黄色进明I 1淡黄色透明1 I淡黄色透明1 1溱黄色透明1 1濟黄色进明1 I班黄色透明I m « m « m 聚酯；^脂(沾)、（D3) 觸媒 TBATB TBATB ItbatbI ΙΤΘΑΤΒ | TBATB I 〇 1 1 « CO d d 2 2 ο 1 eg d CM d CO οι 2 CD d CM d t— r- r- T— t— r- t— t— 产 t— 1— τ— T*- 1— Ar 含有率 (wtX) 窝 5 σ> &2 Ϊ CO C4 $ s to ΙΟ C9 α> r> C4 卜 $ 侧鏈含有率 (wt%) I CD CNi in r> 5 co CM CD 04 r> ο r> δ s CM in eg Ο CO CM csi 1 1 i 1 i I 1 I 1 Γ ί 1 I 1 1 i I I 1 ! 1 j o to ci U> ί -1 Q to O U} ύ u> d M} 經封閉化合物（C)加成之聚酯樹脂（C2) 封閉化合物 (c) 1 PhNCO ! | PhNCO 1 1 PhNCO | | PHNCO | | DEMSi | 1 AnhPh 1 PhNCO | PhNCO ] I PhNOO | PhNOO 聚酯主鏈部（I) N I 雙 AHEp 雙 A-Ep 雙 Α-Ερ iS* ψ\ ω mJ ψ\ 丄 |Re*_Ep/B0XT| | JER1002 | | NPQ-Ep | | OHAi-Ep | CL 〒 t m I (a-1-2) (·Η-3) (a-1-4) I i 1 ί OK110 ] TXM80B | i AnhSu/P4010 | 1 ί 1 1 1 GKH0 ! | AnhSu/P4010 ] 1 1 1 1 \ \ AdA/!PA |AdA/!PA| t < » 1 AdA/IPA AdA/IPA < 1 AdA/lFA 合成例步驟 1(9X10) 1 K9X10X11) 1 |(9X1f) 1 1(9)00X11) I s i [(W10X11) 1 1(9X10X11) | 1(9X10X11) 1 1(12)(13) 1 1(12X13X14) | 1(12)(13)(14) | 1(12)(13)(14) | [(12)(13)(14) 1 1(12)(13)(14) | 1(12)(13)(14) | 1(12)(13)(14) | 1 X w g r— Ο o O 2 t^· 1" u> T— CO 卜 GO 〇> t— s CM CM CM T— l^#_®^fi# 屮令砸 f v^f^: S023i 盔给碱^命^: !sosa ^n^H^l^c: ZSQWH - —Hs .. 1H - ^USH 盔给硪.40M : isiAsa - ooi lx 二 lic^_5 餵 CTO丨Co lets ΊΛ5 dco 錄_h3^if^: npsvPQl 錄硪hs 齧资i4l4#: sivaH 錄W 卜 3 S5 : SHvai 壤_卜3齧琴碱s : gHvgl (apJJPXll§03H)fe^^呆瘐：q^lluv B^fnh .· 右盔銮：Mdmfcvss ^ .¾ - 施8械毽碱畹：ooiAn addition molded polyester resin (D3) was obtained. (Synthesis Example 138) The polymerization reaction was carried out in a polymerization tank equipped with a mixer, a thermometer, a reflux condenser and a gas introduction tube, and the hydroxyl group obtained in Synthesis Example 114 was added to the polymerization tank at a ratio of 16.8 mg K in the following ratio. 〇H/g addition of a polyester resin (D2) solution, a blocking compound (C2), and a catalyst. [Polymerization tank] Addition molding polyester resin (D2) solution obtained in Synthesis Example 1H 5〇〇铪319793 220 200838965 3 parts 0·1 part of 酉 too acid liver (c2) tetrahydroammonium tetrahydroammonium (catalyst) The air in the polymerization tank is heated to the enthalpy after the emulsion is replaced by the gas. Further, while mixing, the reaction was carried out for 6 hours, and aging was carried out. Then, 2 parts of ethyl acetate was added and cooled to room temperature, and the reaction was terminated to obtain a pale yellow transparent material having a nonvolatile content of 5 〇 by weight and a viscosity. It is a resin of 19'500mPa.s, which is called a solution. The acid value of the resin (1) is 4.5mgKOH/g, the hydroxyl value is i2 imgK〇H/g, and the temperature of the glass is - grab, weight. In the same manner as in Synthesis Example 138, the ethyl acetate was added. 4 parts and cooled to room temperature to obtain a solution of a modified polyester resin (D3) which is light yellow transparent and has a nonvolatile content of 50.0% by weight and a viscosity of -17,5 〇〇 mPa.s. The acid value of D3) is mg.mgK〇H/g, the ruthenium valence is 8.5 mgKOH/g, the glass transition temperature is -15<3>, and the weight average molecular weight is 160,000. (Synthetic Example 140) The synthesis example 138 is used. The blocking compound (c2) was changed to 3 parts of dimercaptooctylchlorodecane (cl), and otherwise the same as Synthesis Example 138. The reaction was carried out, and ethyl acetate (3 parts) was added and cooled to room temperature to obtain a pale-transparent transparent resin having a non-volatile content of 49.8% by weight and a viscosity of 17, 〇〇〇mPa.s ( A solution of D3). The resin (D3) has an acid value of 〇.1 mgKOH/g, a hydroxyl group value of iSmgKOH/g, a glass transition temperature of -221 319793 200838965 15 ° C, and a weight average molecular weight of 165,000. The resin solution obtained in 140, the appearance of the solution, the nonvolatile content, the weight average molecular weight (Mw) of the resin, the glass transition temperature (Tg), the acid value (AV), and the hydroxyl value (OHV) were compared with Synthesis Example 1. The evaluation was carried out in the same manner as in 20, and is shown in Table 14 and Table 15. 222 319793 200838965 [Table 14] Synthesis example of addition-molded polyester resin (D2), (D3) % f > X ο (meKOH^c) l__________卜C\l KS s &〇P5 CO ee GO cw ί; S CD s UD 2 domain 〇0» >< CM — IA M 〇lfl o . to esi g CO u> tsi 5 &nds in d Cw u> d ^ e 5 § O Ο o o TO 1 o T o s ο OT 〇T 5 0 1 t ID N 〇T o Έ 150,000 I 160 .000 I 1 ID I to 135,000 1 ! 130,000 II 135,000 I 1 <20,000 I 1 in 1 ιβο, οοο I 1 170,000 1 1 185,000 1 ig I 190.000 | 1100,0001 | ΐθδ, οοο | 120,000 1 | 175,000 | 145,000 t Vi· (mP*»e) I 18,000] I 20.0001 ! 18,5001 | 17.0001 1 15,5001 | 15,0001 I 15,5001 丨13,0001 | t7,50〇 | 1 20,0001 1 19,0001 20,5001 | 15,0001 I CM [11,0001 ! 25,0001 | )2,5001 ! 19.000 I 15,000 iio S ii A oswsi Λ S CM S c%t δ **r CSl ss in sp S Solution appearance m Ifi « m 1演黄进明1 |班黄透HJ 1»Yellow transparent 1 1»Yellow into the bright 1 1 »Yellow transparent 1 | *Yellow through JiJ 1 light yellow transparent 1 Relief yellow into the Ming 1 1 suspect It Color transparent 1 1 light yellow transparent 1 1 Geng yellow transparent 1 丨黄色进进 I I 1 light yellow transparent 1 I light yellow transparent 1 1 溱 yellow transparent 1 1 黄色 yellow into the Ming 1 I class yellow transparent I m « m « m Teflon (T3) Catalyst TBATB TBATB ItbatbI ΙΤΘΑΤΒ | TBATB I 〇1 1 « CO dd 2 2 ο 1 eg d CM d CO οι 2 CD d CM dt- r- r- T- t — r- t— t — 产 t— 1— τ— T*- 1 Ar content rate (wtX) pit 5 σ >& 2 Ϊ CO C4 $ s to ΙΟ C9 α>r> C4 卜 $ side chain content rate (wt%) I CD CNi in r> 5 co CM CD 04 r>r> δ s CM in eg Ο CO CM csi 1 1 i 1 i I 1 I 1 Γ ί 1 I 1 1 i II 1 ! 1 jo to ci U> ί -1 Q to OU} ύ u> d M} Blocking Compound (C) Addition Polyester Resin (C2) Blocking Compound (c) 1 PhNCO ! | PhNCO 1 1 PhNCO | | PHNCO | | DEMSi | 1 AnhPh 1 PhNCO | PhNCO ] I PhNOO | PhNOO Polyester Main Chain (I) NI Double AHEp Double A-Ep Double Α-Ερ iS* ψ\ ω mJ ψ\ 丄|Re*_Ep/B0XT| | JER1002 | | NPQ-Ep | | OHAi-Ep | CL 〒 tm I (a- 1-2) (·Η-3) (a-1-4) I i 1 ί OK110 ] TXM80B | i AnhSu/P4010 | 1 ί 1 1 1 GKH0 ! | AnhSu/P4010 ] 1 1 1 1 \ \ AdA/ !PA |AdA/!PA| t < » 1 AdA/IPA AdA/IPA < 1 AdA/lFA Synthesis Example Step 1 (9X10) 1 K9X10X11) 1 |(9X1f) 1 1(9)00X11) I si [ (W10X11) 1 1(9X10X11) | 1(9X10X11) 1 1(12)(13) 1 1(12X13X14) | 1(12)(13)(14) | 1(12)(13)(14) | [ (12)(13)(14) 1 1(12)(13)(14) | 1(12)(13)(14) | 1(12)(13)(14) | 1 X wgr— Ο o O 2 t^· 1"u> T—CO 卜 GO 〇> t— s CM CM CM T— l^#_®^fi# 屮令砸fv^f^: S023i Helmet Alkali ^ life ^: !sosa ^n^H^l^c: ZSQWH - —Hs .. 1H - ^USH Helmet to 硪.40M : isiAsa - ooi lx Two lic^_5 Feed CTO丨Co lets ΊΛ5 dco Record _h3 ^if^: npsvPQl 硪 hs 啮 i i4l4#: sivaH 录 W 卜 3 S5 : SHvai _ _ 3 啮碱碱 s : gHvgl (apJJPXll§ 03H) fe ^ ^ 瘐瘐: q^lluv B^fnh . Right Helmet: Mdmfcvss ^ .3⁄4 - 88 毽畹畹:ooi

S4®^fiu4vi4w:CL3AM8t 廊@^Mro(^TOlrf^fi4d:-制：.^-ζνΉυ s^c^fiM 翕：da-s-a «^«^fiulsMV 案：dw0dN- £2 i4{^As^lcfhfi 瀵^rA4od】}^-气 i :Hxoa i®w«^fiu <翕制：dpq-v 制 GIGM n AVWWTa : 01 齧澈4壤饍鉍：gospel 0ISO§>,A:0iso 毽 ¥5 : Vdl 你：vqs 盔-rrto: VPV 223 319793 200838965[表15 ]加成型聚 2 (D 匕曰月樹旨酉S4®^fiu4vi4w:CL3AM8t Gallery@^Mro(^TOlrf^fi4d:-System:.^-ζνΉυ s^c^fiM 翕:da-sa «^«^fiulsMV Case: dw0dN- £2 i4{^As^lcfhfi瀵^rA4od】}^-gas i: Hxoa i®w«^fiu < tanning: dpq-v GIGM n AVWWTa : 01 啮4 soil 铋: gospel 0ISO§>, A:0iso 毽¥5 : Vdl You: vqs Helmet-rrto: VPV 223 319793 200838965 [Table 15] Plus Forming Poly 2 (D 匕曰月树酉

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ZH 餵齧 qUD(硪Tofiw^fi-又 e)-t<:Oua-ZVHO f^c^frr 龕-ΤΪ4ΪΕ: d3,29pi »砩《^fiulgQ^審：da-oaK irte^fiu 維 tgo 蝴碱械粼：dafeva 械’cwhfi 難 ¥^_0-£)〕}粼-气 i : 1XOCQ 富硪《^V 畲剩：dtq-v 制 G i P音 d Awvmia : 0 i 齧嫌“壤 IS 鉍：ccl081ADa OISJhA : 0ΙΞΟ 毽銮衅：Vdl ，你：vqs ^qto:<pv 224 319793 200838965 (比較例37) 在合成例107之步液⑽重量份中添加甲笨25\所得之主鍵用聚酉旨樹脂⑻溶 (伸甲苯：異㈣i旨之更進―步’添加麗請 ^ / —反甲基丙烷加成物）2·5重量份作為交聯劑（Ε)，仔細攪拌， Μ ^ 而獲传接著劑組成物。雖欲將J: 塗佈於剝離薄膜上以獲得接、/、叁、+ 从卜接者溥片，但因接著劑組成物之 β度心速上升，故無法進行塗佈。 (比較例38) 合成例107之步驟(10)所得之加成型聚酯樹脂(C2) 溶液，除此之外與比較例19進行同樣操作，而獲得接著劑組成物。將其塗佈於剝離薄膜上，並經乾燥。乾燥後，欲將TAC/PVA/TAC」之構成之多層結構的偏光薄膜的單面貼合於接著劑層上。然而，由於接著劑層未顯現黏著性 (初期接著性），故無法貼合。 (實施例122) 在合成例107之步驟（11)所得之加成型聚酯樹脂（D2) 溶液100重量份中添加曱苯25份，更進一步，添加 ΙΌΙ/ΤΜΡ(伸甲苯二異氰酸醋之三羥甲基丙烷加成物）2.5 重1份作為交聯劑（E)，仔細攪拌，而獲得本發明之接著劑組成物。將該接著劑組成物以使乾燥後之厚度成為25“m 之方式塗佈於剝離薄膜上，以l〇(rc乾燥2分鐘，而形成接著劑層。更進一步’以與實施例1至19同樣之方式操作，而獲得「剝離薄膜/接著劑層/TAC薄膜/ PVA/ TAC薄膜」之構 319793 225 200838965 成之積層體，使接著劑層之反應進行，而獲得經接著加工之偏光板（積層體）。 (比較例39) 使用合成例108所得之樹脂溶液替代合成例1〇7之步驟（11)所得之加成型聚酯樹脂（D2)溶液，除此之外與實1 例122進行同樣操作’而欲製作經接著加工之偏光板。然而’因接著劑組成物之黏度急速上升v故無法塗佈於剝離薄膜上。 (實施例123至127) 分別使用合成例H)9 i 113所得之加成型聚酉旨樹脂 (D2)溶液替代合成例1G7之步驟⑴)所得之加成型聚醋樹脂（D2)溶液’除此之外與實施例122進行同樣操作，而製成經接著加工之偏光板。 " (比較例40). 、、使用合成例m之步驟（13)所得之加成型聚醋樹脂溶液，除此之外與實施例121進行同樣操作，而欲變作姐接著加工之偏光板，但因接著劑組成物之黏度急速了故不僅無法進行歸，並且於塗佈面上產㈣絲或繞曲，接著劑層又未顯現黏著性（勒期接著性），而無著加工之偏光板。卜、、二接 (實施例128) 在合成例m之步驟（14)所得之加成溶液100重量份中添加甲苯25份，更逸_: ( )EN Feeding qUD (硪Tofiw^fi-又e)-t<:Oua-ZVHO f^c^frr 龛-ΤΪ4ΪΕ: d3,29pi »砩"^fiulgQ^审:da-oaK irte^fiu 维 tgo粼 d:dafeva 械 'cwhfi 难¥^_0-£)]}粼-qi i: 1XOCQ rich 硪 "^V 畲 remaining: dtq-v system G i P sound d Awvmia: 0 i bite "s ccl081ADa OISJhA : 0ΙΞΟ 毽銮衅: Vdl , you: vqs ^qto: <pv 224 319793 200838965 (Comparative Example 37) In the step (10) parts by weight of Synthesis Example 107, the primary key obtained by adding a blunt 25\ Resin (8) dissolved (toluene: different (four) i is more advanced - step 'added ^ ^ / - anti-methyl propane adduct) 2 · 5 parts by weight as a crosslinking agent (Ε), carefully stirred, Μ ^ Adhesive composition. Although J: is applied to the release film to obtain the splicing, /, 叁, + 从溥 , , , , , , , , , , , , , , , , , , , , , , 接着接着接着接着接着接着接着接着接着接着接着(Comparative Example 38) The same procedure as in Comparative Example 19 was carried out except that the addition-molded polyester resin (C2) solution obtained in the step (10) of Synthesis Example 107 was used to obtain an adhesive composition. On the release film, After drying, the surface of the polarizing film having a multilayer structure of TAC/PVA/TAC" is applied to the adhesive layer. However, since the adhesive layer did not show adhesiveness (initial adhesion), it could not be bonded. (Example 122) To 100 parts by weight of the addition-molded polyester resin (D2) solution obtained in the step (11) of Synthesis Example 107, 25 parts of toluene was added, and further, yttrium/niobium (toluene diisocyanate vinegar was added). The trimethylolpropane adduct) 2.5 parts by weight as the crosslinking agent (E) was carefully stirred to obtain the adhesive composition of the present invention. The adhesive composition was applied onto the release film so that the thickness after drying became 25 μm, and dried at rc for 2 minutes to form an adhesive layer. Further, with Examples 1 to 19 In the same manner, a laminate of "release film/adhesive layer/TAC film/PVA/TAC film" 319793 225 200838965 was obtained, and the reaction of the adhesive layer was carried out to obtain a polarized plate which was subsequently processed ( (Comparative Example 39) The resin solution obtained in Synthesis Example 108 was used instead of the addition-molded polyester resin (D2) solution obtained in the step (11) of Synthesis Example 1 to 7 except for the actual example 122. In the same operation, it was intended to produce a polarizing plate which was subsequently processed. However, since the viscosity of the adhesive composition rapidly increased, v could not be applied to the release film. (Examples 123 to 127) Synthesis Example H) 9 i 113 was used, respectively. The addition molding polyether resin (D2) solution was used in the same manner as in Example 122 except that the addition molding resin (D2) solution obtained in the step (1) of the synthesis example 1G7 was subjected to the subsequent processing. Polarized plate. < (Comparative Example 40). The same operation as in Example 121 was carried out except that the addition-formed polyacetal resin solution obtained in the step (13) of Synthesis Example m was used, and the polarizing plate to be processed by the sister was changed. However, due to the rapid viscosity of the composition of the adhesive, it is not only impossible to return, but also produces (4) silk or winding on the coated surface, and then the adhesive layer does not show adhesion (extension), without processing Polarizer. Bu, and two (Example 128) To 100 parts by weight of the addition solution obtained in the step (14) of Synthesis Example m, 25 parts of toluene was added, and more _: ( )

Tm/TMi>(伸甲苯二異氰酸酯 /，添加 —I甲基丙烷加成物）2.5 319793 226 200838965 重量份作為交聯劑（E)，仔細攪拌，而獲得本發明之接著劑組成物。使用該接著劑組成物，以與實施例丨22同樣之方式操作，而製成經接著加工之偏光板。 (實施例129) 分別使用合成例115所得之加成型聚酯樹脂（D2)溶液替代合成例114之步驟（14)所得之加成型聚酯樹脂（D2)溶液，除此之外與實施例128進行同樣操作，而製成經接著加工之偏光板。 ·(實施例130) 分別使用合成例116所得之加成型聚酯樹脂（D2)溶液替代合成例114之步驟（14)所得之加成型聚酯樹脂①幻溶液，除此之外與實施例128進行同樣操作，而製成經接著加工之偏光板。 (實施例131至148) 为別使用合成例117至128及合成例132至137所得鲁之加成型聚酯樹脂（D3)溶液替代合成例114之步驟〇4)所得之加成型聚i旨樹脂（D2)溶液，除此之外與實施例128進行同樣操作，而製成經接著加工之偏光板。 (比較例41至43) 分別使用合成例U9 1 131所得之加成型聚酉旨樹脂 (D2)溶液替代合❹"14之步驟(14)所得之加成型聚醋樹脂㈣溶液，除此之外與實施例127進行同樣操作，而欲衣作經接著加玉之偏光板。然而，因接著劑組成物之黏产急速上升，故無法塗佈於剝離薄膜上。 #又 319793 227 200838965 (實施例149、150) 分別於實施例149使用XDI/TMP(伸茬基二異氰酸酯之三羥甲基丙烷加成物）2.5重量份、於實施例15〇使用 HMDI/縮二脲（六亞甲基二異氰酸酯之縮二脲加成物）2.$ 重量份，替代實施例U4中作為交聯劑（E)所用之 TDI/TMP ’除此之外與實施例128進行同樣操作，而獲得接著劑組成物。使用該接著劑組成物並與實施例128進行同樣操作，而製成經接著加工之偏光板。 ·(實施例151至153) 分別使用合成例138至140所得之加成型聚酯樹脂 (D3)溶液替代合成例114之步驟〇4)所得之加成型聚酯樹月曰（D2)溶液，除此之外與實施例15〇進行同樣操作，而製成經接者加工之偏光板。 (比較例44、45)(實施例154至156) 分別在合成例Γ23 428至131所得之加成型聚醋樹脂鲁（D2)溶液1〇〇重量份中添加甲苯25份，更進一步，添加 map(2,2，_雙羥基曱基丁醇參[3-(1_氮丙啶基）丙酸酯])0.25重量份作為交聯劑(E)，仔細授拌，而獲得本發明，接著劑組成物。然而，在比較例44、45之情形，因接著劑^成物之黏度急速上升，故無法塗佈於剝離薄膜上。關於貫施例154至156’則以與實施例128同樣之方式操作，製成經接著加工之偏光板。 (比較例46、47)(實施例157至159) 分別在合成例心⑵至131所得之加成型聚酉旨樹脂 319793 228 200838965 (D2)溶液100重量份中添加曱苯25份，步 ’力口Tm/TMi> (toluene diisocyanate /, -1 methylpropane adduct) 2.5 319793 226 200838965 parts by weight as a crosslinking agent (E), carefully stirred to obtain the adhesive composition of the present invention. Using this adhesive composition, it was operated in the same manner as in Example 22 to prepare a polarizing plate which was subsequently processed. (Example 129) The addition-molding polyester resin (D2) solution obtained in the synthesis example 115 was used in place of the addition-molded polyester resin (D2) solution obtained in the step (14) of Synthesis Example 114, respectively, except for Example 128. The same operation was carried out to prepare a polarizing plate which was subsequently processed. (Example 130) The addition-molding polyester resin (D2) solution obtained in Synthesis Example 116 was used in place of the addition-molding polyester resin 1 phantom solution obtained in the step (14) of Synthesis Example 114, respectively, except for Example 128. The same operation was carried out to prepare a polarizing plate which was subsequently processed. (Examples 131 to 148) The addition molding resin obtained by using the addition of the synthetic polyester resin (D3) solution obtained in Synthesis Examples 117 to 128 and Synthesis Examples 132 to 137 instead of the synthesis example 114 was carried out. A (D2) solution was used in the same manner as in Example 128 to prepare a polarizing plate which was subjected to subsequent processing. (Comparative Examples 41 to 43) The addition molding resin (D2) solution obtained in the synthesis example U9 1 131 was used in place of the addition-molded polyester resin (IV) solution obtained in the step (14) of the combination of "14", respectively. The same operation as in Example 127 was carried out, and the coating was applied as a polarizing plate with a jade. However, since the adhesive composition of the adhesive composition rapidly rises, it cannot be applied to the release film. #又319793 227 200838965 (Examples 149, 150) In Example 149, 2.5 parts by weight of XDI/TMP (trimethylolpropane adduct of decyl diisocyanate) was used, and HMDI/condensation was used in Example 15 Diurea (biuret adduct of hexamethylene diisocyanate) 2. Part by weight, in place of TDI/TMP used as crosslinking agent (E) in Example U4, except for Example 128 The same operation was carried out to obtain an adhesive composition. This adhesive composition was used and subjected to the same operation as in Example 128 to prepare a polarizing plate which was subjected to subsequent processing. (Examples 151 to 153) The addition-molded polyester resin (D2) solution obtained in the steps 〇4) of Synthesis Example 114 was used in place of the addition-molded polyester resin (D3) solution obtained in Synthesis Examples 138 to 140, respectively. Further, in the same manner as in Example 15A, a polarizing plate processed by a receiver was produced. (Comparative Examples 44 and 45) (Examples 154 to 156) Toluene 25 parts were added to 1 part by weight of the addition-molded polyester resin (D2) solution obtained in Synthesis Example 23 428 to 131, and further, a map was added. (2,2,_bishydroxymethylbutanol gin[3-(1-aziridine)propionate]) 0.25 parts by weight as a crosslinking agent (E), carefully mixed to obtain the present invention, followed by Agent composition. However, in the case of Comparative Examples 44 and 45, since the viscosity of the adhesive agent rapidly increased, it could not be applied to the release film. The respective examples 154 to 156' were operated in the same manner as in Example 128 to prepare a polarizing plate which was subsequently processed. (Comparative Examples 46 and 47) (Examples 157 to 159) 25 parts of toluene were added to 100 parts by weight of the solution of the addition molding resin 319793 228 200838965 (D2) obtained by synthesizing the cores (2) to 131, respectively. mouth

tGMXDA(n，n，n’，n，_四環氧丙基_間伸茗基二胺）〇25重旦份作為交聯劑⑻，仔細授拌，而獲得本發明之接著劑組二物。然而’在比較例46、47之情形，因接著劑组成物之與度急速上升’故無法塗佈於剝離薄臈上。關於實施例W 至159，則以與實施例122同樣之方式操作，製成經接著加工之偏光板。 (比較例48、49)(實施例160至162) 分別在合成例123、128至131所得之加成型聚醋樹脂 (D2)溶液1〇〇重量份中添加曱苯25 ，山一尺通—芡，添加為石厌二亞胺化合物之「Carbodilite V_〇5」（日清纺積股份公司製）〇.=重量份作為交聯劑⑻，仔細攪拌，而獲得本發明之接著劑組成物。然而，在比較例48、49之情形，因接著劑組成物之黏度急速上升，故無法塗佈於㈣薄膜上。ζ 於實施例160至162,則以與實施例122同樣之方式操Ρ，製成經接著加工之偏光板。 (比較例50、51)(實施例163至165) /分別在合成脚、128至131所得之加成型聚醋樹月旨 _液100重量份中添加異丙醇25份’更進一步，添加 Α1ΑΑ(麥（乙醯丙酮）鋁）0·25重量份作為交聯劑邙），仔细攪拌，而獲得本發明之接著劑組成物。然而，在比較例、、二 51之情形，因接著劑組成物之黏度急速上升，故無法塗佈於剝離薄膜上。關於實施例163至165，則以與實施例m 同樣之方式操作，製成經接著加工之偏光板。 319793 229 200838965 關於實施例及比較例所得之接著劑組成物的適用期及塗佈加工性，係依據與實施例1至19同樣之方法進行呷估。將結果示於表16、17。另外，針對實施例及比較例所得之經接著加板（積層體），係依據與實施例！至19同其塗膜之折射率、耐熱性、耐濕熱性、=進仃评估性。將結果示於表17。予寸〖及再剝離tGMXDA (n, n, n', n, _ tetraepoxypropyl _ hydrazinyl diamine) 〇 25 parts by weight as a crosslinking agent (8), carefully mixed to obtain the second agent of the present invention . However, in the case of Comparative Examples 46 and 47, the adhesion of the adhesive composition rapidly increased, so that it could not be applied to the peeling sheet. With respect to Examples W to 159, a polarizing plate which was processed subsequently was produced in the same manner as in Example 122. (Comparative Examples 48 and 49) (Examples 160 to 162) Toluene benzene 25 was added to 1 part by weight of the addition-formed polyester resin (D2) solution obtained in Synthesis Examples 123 and 128 to 131, respectively.芡, "Carbodilite V_〇5" (manufactured by Nisshinbo Co., Ltd.) added as a anadiamine compound, as a crosslinking agent (8), and carefully stirred to obtain the adhesive composition of the present invention . However, in the case of Comparative Examples 48 and 49, since the viscosity of the adhesive composition rapidly increased, it could not be applied to the film. In the same manner as in Example 122, in the same manner as in Example 122, a polarizing plate which was subsequently processed was produced. (Comparative Examples 50 and 51) (Examples 163 to 165) / 25 parts of isopropanol were added to 100 parts by weight of the addition-formed vinegar obtained from the synthetic legs and 128 to 131, respectively. Further, Α1ΑΑ was added. (Wheat (acetonitrile) aluminum) 0. 25 parts by weight as a crosslinking agent 邙), and the mixture was carefully stirred to obtain the adhesive composition of the present invention. However, in the case of the comparative example and the second 51, since the viscosity of the adhesive composition rapidly increased, it could not be applied to the release film. With respect to Examples 163 to 165, a polarizing plate which was subsequently processed was produced in the same manner as in Example m. 319793 229 200838965 The pot life and coating processability of the adhesive compositions obtained in the examples and the comparative examples were evaluated in the same manner as in Examples 1 to 19. The results are shown in Tables 16 and 17. Further, the subsequent addition of the sheets (layered bodies) obtained in the examples and the comparative examples is based on the examples! To 19, the refractive index, heat resistance, heat and humidity resistance, and evaluation of the film were evaluated. The results are shown in Table 17. 〗〖 and re-stripping

319793 230 200838965 [表16]使用第2或第3型態之加成型聚酯樹脂（D2)、（D3) 的接著劑組成物 \凑 \蘅咖瘦\ 重工性 I 1 〇 1 〇 < < Ο < I ο < o O 0 o o 〇 o < Ο ο 〇 Ο <J o ο Ο 〇〇 o ί I 1 耐濕熱性 N I I o [ o Ο ο Ο < I ο 〇〇 o 0 o 0 o o < Ο Ο o Ο < o ο ο o 0 o ! I 1 r- I \ o I o Ο ο Ο < 1 ο 0 o o o o o <J o < ο Ο o Ο <1 o ο ο o o o I I 1 耐熱性 1 1 o f o 0 ο < Ο 1 0 〇 o 0 o o o o < Ο 0 0 o Ο 〇 o ο ο o o 0 1 I 1 經乾燥之接著劑層 Ilf 1 X 〇 1 < < Ο ο < X ο < o < o < o o < < ο ο 0 0 <3 o ο ο o o D 1 i 1 光學特性 1 < 〇 i o ο Ο ο Ο X Ο 0 0 o o o o o o Ο ο ο 0 Ο 〇 o ο ο o o 0 ϊ ί 1 折射率 1 I 1.5389 | 1 1.5339 | t I 1,5312 | 1 1.5319 1 | U346 I | 1.53tz I | 1.S331 1 I 1.53981 1 1.5307 1 | 1.5321 | I 1-5223 | I 1J358I | t.$Z2Z | I I.$542 | I 1.5477 | I I 1.5l0f I 1 1.5298 | 1 1.5284 1 | 1.5342 1 I \MBA I « ΙΊ.4528 ] I 1.5165 | 1 1.5298 1 11.刪 ι | 1.5234 I I 1.5213 1 I f.5227 | 1 ( \ 接著劑溶液 l < o 1 < Ο Ο ο Ο X Ο < o o o o o o o Ο Ο ο o Ο 〇〇 ο <J < o 〇 ί I \ B? X 0 o X o ο ο < Ο 〇 ο 〇 o o 0 o o o o 0 ο ο o ο 〇〇 ο ο o o 〇 X X X 1 接著劑組成物 1 交聯劑（E) Μ %x> to S ID ΙΟ «D ICI S to to ΙΟ in m· in ip ID tf> ΙΟ iq ur> ID lf> ιη s ir> U> t£> iq TDI/TMP TDI/TMP I TD1AMP | TDI/TMP 聚酯樹脂（D2)、（D3)溶液 ⑻無 1 (〇)無 1 1(b)無 1 OHV 1 175.2 I 1 17.2 | in I t 9.5 | 丨皿1 1ί> i 1MJ 1 ιοί 1 37.2 1 1 16Β 1 CD CVJ l£> M e〇 eo 0» I 12.1 I I▲19A1 u> 〇> 1 11-2 1 I 13,9-1 1 10.2 1 ImJ I10,3,.1 u> CD o in cd 1 19-2 1 ΙΟ in cs u> 1 14.3 1 1 17.2 1 1 62.3 1 I mjJ I 58.5 I $ esi T··' u> o Cn| ID 〇 Cvl CSI V 0.05 [Μη ΙΑ Ο Csl ο IA d 5 IA 〇 it> d CSI IC> 5 80.5 ΙΟ CO ΙΟ Ο 85,5 5 Λ CNI CSI esi 〇 13.8 CO o o o § o ο τ S 1 ο τ Ο ο Τ ο τ o T O T 0 1 ? t 〇 T ο Τ ο τ ο τ 〇 T ο 1 ir> o T ο Τ o T 〇 T 圈 PS -10 s s 1 Mw ! 150,000 I 1160,000 | 「180,000 1 | 155,000 | | 135,000 | 1 130,000 1 1 136,000 1 1 120,000 | 1 175,000 | 1 160,000 1 ! 170,000 1 | 185,000 | | 130,000 1 I 100.000 | I 100,0001 | 105,000 1 I 120,000 | | 175,000 ] | 145,000 | 1 105,000 1 1 165,000 1 1 130,000 1 1 1 120,000 1 | 145,000 | I 190,000 1 1 205,000 1 I 155,000 I | 160,000 ] | 150,000 | I 125,000 | 丨 140,000 I I 130,000 | i 8 Ο 1 1 C9 CO CO ο 3 <· 1 esj CVI CO Ol CM 〇 o 0> a> JNJ CSI CSf eg CSJ esi 2 2 5 cu esi 04 ca <S1 €>} t— r- r- r- τ— τ— τ— r- t— r- r— r- r- — τ— τ— 尸尸 T— r- 产 τ— t— r- τ- Ar含有率（wt%) 8 5 〇> LP 寸兮 τ* TO CM CM CO <D 穿 u> CO 〇> r> 卜 5 CO csj INI S «Ο CM to CO σ> CM CD ca Jo in tn § § ? o 側鏈含有率（wt%) I CD CM iO CO r— 5 CO οα CD U ο CD CNi CM in CM CD CO S a ο σ> CM CO CO CD CM CO CM u> r> Οϊ es g CM o 合成例 5 g a> 〇 ο τ— τ—1 Cs| CO τ— ΙΟ o 卜 T— CO O CM τ-· esi CM CM ΙΜ 令 CM in esi τ» CO K eo o r> Γ> 才 2 o CD <*> •p-· 〇> CM I比較例37 | |比較例3 8 | M N I |比較例39 1 w ey i I實施例124 I I實施例126 I I實施例12β | 卜 Μ r- 苳 1比較例40 1 CO eg 5 l實施例129 | ¥ f貧施例131 | |實施例132 | I實施例133 | 實施例134 I |實施例135 | m n t— 荃 TO t- 苳告EC I實施例138 I |實施例139 | O T—' r- I實施例142 | 3 1 I實施例144 | |實施例145 | |實施例146 | |實施例I47 I |實施例14日ι 丨比較例41 I 丨比較例42 | |比較例43 ι 客嗜4®^·紫 WI8嬸 ί 碑“螬B-商^:^qsl/Ia 圉袭噠名袈苽砩i^螬神幸：dwl/sx #噶4埏苽蝴i«蚪δ-拿：dwi/iai 231 319793 200838965 [表17]使用第2或第3型態之加成型聚酯樹脂（D2)、（D3) 的接著劑組成物319793 230 200838965 [Table 16] The adhesive composition of the addition type polyester resin (D2), (D3) of the 2nd or 3rd type is used, and it is made up of the adhesive composition of the adhesive resin (D2) and the heavy duty I 1 〇1 〇 <<; Ο < I ο < o O 0 oo 〇o < Ο ο 〇Ο <J o ο Ο 〇〇o ί I 1 Heat and humidity resistance NII o [ o Ο ο Ο < I ο 〇〇o 0 o 0 oo < Ο Ο o Ο < o ο ο o 0 o ! I 1 r- I \ o I o Ο ο Ο < 1 ο 0 ooooo <J o < ο Ο o Ο <1 o ο ο ooo II 1 heat resistance 1 1 ofo 0 ο < Ο 1 0 〇o 0 oooo < Ο 0 0 o Ο 〇o ο ο oo 0 1 I 1 dried adhesive layer Ilf 1 X 〇1 << Ο ο < X ο < o < o < oo << ο ο 0 0 <3 o ο ο oo D 1 i 1 Optical characteristics 1 < 〇io ο Ο ο Ο X Ο 0 0 oooooo Ο ο ο 0 Ο 〇o ο ο oo 0 ϊ ί 1 Refractive index 1 I 1.5389 | 1 1.5339 | t I 1,5312 | 1 1.5319 1 | U346 I | 1.53tz I | 1.S331 1 I 1.53981 1 1.5307 1 | 1.5321 | I 1-5223 | I 1J358I | t.$Z2Z | I I.$542 | I 1.5477 | II 1.5l0f I 1 1.5298 | 1 1.5284 1 | 1 I \MBA I « ΙΊ.4528 ] I 1.5165 | 1 1.5298 1 11. Delete 1 | 1.5234 II 1.5213 1 I f.5227 | 1 ( \ Subsequent solution l < o 1 < Ο Ο ο Ο X Ο &lt ; ooooooo Ο Ο ο o Ο 〇〇ο <J < o 〇ί I \ B? X 0 o X o ο ο < Ο 〇ο 〇oo 0 oooo 0 ο ο o ο 〇〇ο ο oo 〇 XXX 1 Substance composition 1 Crosslinker (E) Μ %x> to S ID ΙΟ «D ICI S to to ΙΟ in m· in ip ID tf> ΙΟ iq ur> ID lf> ιη s ir>U>> iq TDI/TMP TDI/TMP I TD1AMP | TDI/TMP Polyester Resin (D2), (D3) Solution (8) None 1 (〇) None 1 1(b) None 1 OHV 1 175.2 I 1 17.2 | in I t 9.5 | Dish 1 1ί> i 1MJ 1 ιοί 1 37.2 1 1 16Β 1 CD CVJ l£> M e〇eo 0» I 12.1 II▲19A1 u>〇> 1 11-2 1 I 13,9-1 1 10.2 1 ImJ I10,3,.1 u> CD o in cd 1 19-2 1 ΙΟ in cs u> 1 14.3 1 1 17.2 1 1 62.3 1 I mjJ I 58.5 I $ esi T··' u> o Cn ID 〇Cvl CSI V 0.05 [Μη ΙΑ Ο Csl ο IA d 5 IA 〇it> d CSI IC> 5 80.5 Ι CO ΙΟ Ο 85,5 5 Λ CNI CSI esi 〇13.8 CO ooo § o ο τ S 1 ο τ Ο ο Τ ο τ o TOT 0 1 ? t 〇T ο Τ ο τ ο τ 〇T ο 1 ir> o T ο Τ o T 〇T circle PS -10 ss 1 Mw ! 150,000 I 1160,000 | "180,000 1 | 155,000 | | 135,000 | 1 130,000 1 1 136,000 1 1 120,000 | 1 175,000 | 1 160,000 1 ! 170,000 1 | 185,000 | 130,000 1 I 100.000 | I 100,0001 | 105,000 1 I 120,000 | | 175,000 ] | 145,000 | 1 105,000 1 1 165,000 1 1 130,000 1 1 1 120,000 1 | 145,000 | I 190,000 1 1 205,000 1 I 155,000 I | 160,000 ] 150,000 | I 125,000 | 丨140,000 II 130,000 | i 8 Ο 1 1 C9 CO CO ο 3 <· 1 esj CVI CO Ol CM 〇o 0>a> JNJ CSI CSf eg CSJ esi 2 2 5 cu esi 04 ca &lt ;S1 €>} t- r- r- r- τ— τ— τ— r- t— r- r— r- r- — τ— τ— 尸尸T— r- τ— t— r- τ-Ar content rate (wt%) 8 5 〇> LP inch 兮τ* TO CM CM CO <D 穿u> CO 〇>r> 卜5 CO csj INI S «Ο CM to CO σ> CM CD Ca Jo in tn § § ? o side Content ratio (wt%) I CD CM iO CO r - 5 CO οα CD U ο CD CNi CM in CM CD CO S a ο σ > CM CO CO CD CM CO CM u>r> Οϊ es g CM o Synthesis Example 5 g a> 〇ο τ— τ—1 Cs| CO τ— ΙΟ o Bu T—CO O CM τ-· esi CM CM 令 Let CM in esi τ» CO K eo o r> Γ> 2 2 CD <*>•p-·〇> CM I Comparative Example 37 | |Comparative Example 3 8 | MNI | Comparative Example 39 1 w ey i I Example 124 II Example 126 II Example 12β | Μ r- 苳1 Comparative Example 40 1 CO eg 5 l Example 129 | ¥ f lean example 131 | | Example 132 | I Example 133 | Example 134 I | Example 135 | mnt - 荃TO t- EC EC I Example 138 I | Example 139 | OT - ' r - I Example 142 | 3 1 I Example 144 | | Example 145 | | Example 146 | | Example I47 I | Example 14 ι 丨 Comparative Example 41 I丨Comparative Example 42 | |Comparative Example 43 ι 客客4®^·紫 WI8婶ί The monument "螬B-商^:^qsl/Ia 圉袭哒名袈苽砩i^螬神幸:dwl/sx #噶4埏苽 butterfly i«蚪δ- take: dwi/iai 231 319793 200838965 [Table 17] using the second or third type of addition polymerization Adhesive resin composition (D2), (D3) of

St \瑞璁噢 \茶牮\ 重工性〇 Ο Ο ο Ο I 1 o o o i i o o o I ί 〇 o o I I 〇〇 o 耐濕熱性 Ν 〇 Ο Ο ο Ο i I o 0 0 i 1 o o o I 1 o o o I t 〇 o o Τ- 〇 Ο Ο ο ο i 1 0 < o I i 0 < o ! I o <1 o i i 〇 < o 耐熱性〇 ο Ο ο ο I i o 0 o I 1 o o o I 1 o o o I I o 0 o 經乾燥之接著劑層黏性著〇 ο Ο ο ο I 1 o o o I ! o o o I 1 o o o j I o o o 光學特性〇 ο Ο ο ο I 1 o 0 o I I o 0 o I 1 o o o I 1 〇 o o 折射率 1.5288 | 1.5228 1 | t.5213 1 1 1.5203 1 I 1.5278 1 i 1 | 1.5288 ] | 1.5253 1 I 1.524« | I 1 1 1.5272 | [1.5277 | I 1.5301 1 I 1 I t.5256l | 1.5281 1 I 1.5239 | I i I 1.5232 | I 1.524! ! I 1.5238 1 接著劑溶液塗佈加工性〇 Ο Ο Ο Ο I [ o 0 o I ! o 〇 o I 1 o 〇〇 I i 〇 o o e B- 〇 Ο Ο ο Ο X X o 0 o X X o 〇 o X X o 〇 o X X 〇 o o I 接著剤組成物 | 交聯劑（E) 份數 u> ιη ΙΟ » u> s d 2 s w s d 2 1 i S u> s w d d IA S s o i i 種類 I XDIAMP | ο S X TDI/TMP HBAP TQMXDA v-os ΑΙΑΛ 聚酯樹脂（D2)、（D3)溶液， OHV LA6,8_J 00 CO ΙΟ αά CO 〇> r> I 62.3 I 1 68.7,1 to cd »〇 a> ci 1 62.3 I L68JJ IO cd m σ> CO CO 1 62.3 1 IMJJ io s Li 3.9,1 eo 1 62.3 1 I 68.7 ] 1 58.5 1 % CNI οι ΙΟ ο 5 80.5 85.5 imJ L13JJ CO 〇· s | 85.5 I ΓΪΖ5Ί LI3JJ 00 o in CO 85.5 MMJ 13.8 I 80.5 j 85.5 M2.5J [TO UMJ ο 7 ο τ tf> Τ HU blflj IT3 H〇J S 1 » ir> o 8 o CSi 〇 in o T s 1 o T 8 S I Σ 170,000 I s' 1 S· I CD | 195,000 1 | 145,000 | I 140,000 | | 130,000 | I « 1 涅 | 145,000 | | 140,000 1 | 130,000 | 1 130.000 1 I 195,000 | | 145,000 I [140,000 I | 130,000 1 1 130,000 1 195.000 145.000 | 140,000 1 | 130.000 i i g X 0 csi d Ο 卜 eM d CM d 寸· 寸· CM d Ol CNI 2 eg C\1 o τ- f r- r- r- r- r- r- r- τ- r- 产 t- r- r- r· r· r- r- T- T- r- iAr含有率 (wt%) 1_ 穿 ο ? ο S CO CO Λ 〇> CO 〇| S CO C7 s σ> CM CO OJ O 00 o σ> CM 00 CM S 00 CO 〇> CM S 讅>5 萃齋 ο η CM W O «r> e> a» βΜ CM ? in r> a> CM C\l o in CO a> CM CM O IO w a> a 合成例却 τ-f αο CO τ- σ> CO ο 工 CO CM CO CM a> CM g CO 3 CO 〇> CM T-· o CO CO to CM 〇〇 CM a> CM O r> »r— ΓΟ CO 52 CD CM a> CM g O TP- φ τ- te I實施例150 I 产 10 τ- 苳 fe I實施例162 I I實施例153 I |比較例44 | |比較例45 1 |實施例154 I |貧施例165 ] I貧施例156 I |比較例46 1 |比較例47 | |實施例1S7 | |實施例1 58 | l實施例169 I |比較例4β 1 I比較例49 | |實施例160 | |贫施例161 | |賁施例162 | s I比較例51 I |實施例163 | |實施例164 ] |實施例165 | 坻(區苽键0)咯：VVIV (鹖砥<<#^链发供B)s-A<D±:Iipo-ec3: S—A 银^t 神^JrhN-Khvaxwal 【I痛獾苽(硪^苽竑—1)-^-#锆卜硪&-^磔彰-.^2二| 232 319793 200838965 (合成例141) <聚酯多元醇之合成> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器及氣導入管的聚合反應裝置，並在聚合槽中分別以下述比率加入二羧酸、二元醇、以及觸媒？ [聚合槽] 對酞酸 392.8 份異酞酸 392.8 份乙二醇 210份新戊二醇 236.6 份氧化二丁基錫 0.5份將聚合槽内之空氣以氮氣置換後，一邊攪拌混合物一邊升溫至180°c，一邊脫水一邊耗費4小時緩緩降溫至260 •C並進行酯化反應，更進一步”·為了促進脫水，而一邊滴下30份之茬一邊進行回流，於23〇t：持讀進行反應6小時。其次，冷卻至5(TC以下並結束反應，添加乙酸乙酯使不揮發成分成為50%，而獲得聚酯多元醇之溶液。此聚酯多元醇係淡黃色透明，且為酸價為22mg K〇H/g、羥基價為2.5mgKOH/g、玻璃轉移溫度為4〇χ、數平均分子量（Μη)為5,000之樹脂。 <步驟（1):聚酯主鏈之形成> 準備於聚合槽附有攪拌機、溫度計、回流冷卻器、滴下裝置及氮導入管的聚合反應裝置，並在聚合槽中分別以下述比率加入上述聚酯多元醇（心i_a)、具有2個環狀醚基 319793 233 200838965 之化合物（a-2)、以及觸媒。 [聚合槽] 上述聚酯多元醇（a_l_a ) 200份雙酚A二環氧丙基醚型環氧樹脂（a_2) 「JER828(環氧當量 184 至 I94g/eq，曰本環氧樹脂公司製）」 3 7份雙盼A二環氧丙基謎系高分子量環氧兩基樹脂㈣）「JER1001(環氧當量 450 至 5〇〇g/eq，參日本環氧樹脂公司製）」 9.4份 2'甲基咪唑(觸媒） 0.06: 將聚合槽内之空氣以氮氣置換後，一邊攪摔内容物一邊升温至135t。再使其反應15小時。其:欠，添加乙酸乙酯將不揮發成分調整至40%，冷卻至室溫並結束反應，而獲得主鏈用聚酯樹脂（B)之溶液。此溶液係淡黃色透明、且其不揮發成分4〇1重量％、黏度3,000mPa · s。該溶液所含有之樹脂係酸價 3.8mgKOH/g、羥基價 5(K5mgK〇H/g、玻璃轉移溫度 6〇。〔、重量平均分子量30,〇〇〇。 <經環狀酯（b)加成之加成型聚酯前驅物（c丨）的合成〉將上述所付之主鏈用聚酯樹脂（B)溶液（不揮發成分 40.1重量％)100份加入聚合槽中，再添加作為環狀酯之 ε -己内醋ΐ·9份、作為觸媒之乙醯丙酮鋅〇〇2份，於 °匚進行反應1小時.，再於13(rc進行反應8小時，使用甲苯/乙酸乙酯=85/15(重量比）之混合溶劑將濃度調整至使不 319793 234 200838965 揮發成分成為40%，而獲得加成型聚酯前驅物（C1)溶液。此溶液係黏度$ 3,5GGmPa. s，且該溶液所含有之樹脂係酸價3.5mgKOH/g、經基價48.2mgK〇H/g、玻璃轉移溫度 5〇°C、重量平均分子量35,000。又 (合成例142) 在合成例72之步驟（7)中將所用之環狀醋化合物（b)之量變更成5份、且將加人滴下裝置中之乙酸乙醋之量變更成90份，除此之外與合成例72之步驟⑺同樣地操作進行調製，並添加6酸乙醋260份，而獲得經環狀醋化合物加成之聚酯樹脂（C1)溶液。又，在上述配方中，相對於源自二環㈣化合物(a-2)之二級錄！莫耳’環狀醋⑻成為約 0.2莫耳之比率。㈢其次，使用所得之樹脂（C1)溶液（不揮發成分為重篁％)500份、且將為.封閉化合物（c)之異氛酸苯醋之量變更成、6份’除此之外與合成合"2之步驛（8)同樣地進行反應，並添加乙酸乙酯i份，而獲得淡黃色透明、且其不揮發成分為49.8重量％、黏度為15，_mpa s之加成型聚醋 =脂(D1)之溶液。該樹脂（D丨）之酸價為i.5mgK〇H/g、羥^ 價為48.5mgKOH/g、玻璃轉移溫度為—5ΐ：、重量平均^ 子量為130,000。一刀 (比較例52、53) 分別在合成例141、142所得之加成型聚酯樹脂之溶液 1〇〇重量份中添加甲苯25份，更進一步，添加roi/TMp(伸曱苯二異氰酸醋之三經甲基丙垸加成物）25重量份作為交 319793 235 200838965 將其以使乾燥上，於100。〇耳即劑（E) ’仔細授摔，而葬现讦阳筏侍接者劑組成物。後，厚度成為25”之方式塗佈於剝離薄膜乾餘2分鐘，而形成接著劑層。再者，以與實施例1至19同樣之方p & 万式知作，獲得「離薄膜/接著劑層/TAC薄膜/pVA/TAc键赠 ’ a “ 士 Λ膜」之構成之積層體，並進行接著劑層之反應，而得到细 I、二接者加工之偏光板（積層體），同樣地進行評估。將結果砉；衣不於表18、19。修 319793 236 200838965 [表18]加成型聚酯樹脂之合成例St \瑞璁噢\茶牮\重工性〇Ο ο ο Ο I 1 oooiiooo I ί 〇oo II 〇〇o Heat and humidity resistance 〇Ο Ο ο Ο i I o 0 0 i 1 ooo I 1 ooo I t 〇 Oo Τ- 〇Ο Ο ο ο i 1 0 < o I i 0 < o ! I o <1 oii 〇< o heat resistance 〇ο Ο ο ο I io 0 o I 1 ooo I 1 ooo II o 0 o Dry adhesive layer sticky 〇ο Ο ο ο I 1 ooo I ! ooo I 1 oooj I ooo Optical characteristics 〇ο Ο ο ο I 1 o 0 o II o 0 o I 1 ooo I 1 〇oo Refractive index 1.5288 | 1.5228 1 | t.5213 1 1 1.5203 1 I 1.5278 1 i 1 | 1.5288 ] | 1.5253 1 I 1.524« | I 1 1 1.5272 | [1.5277 | I 1.5301 1 I 1 I t.5256l | 1.5281 1 I 1.5239 | I i I 1.5232 | I 1.524! ! I 1.5238 1 Adhesive solution coating processability Ο Ο Ο I [ o 0 o I ! o 〇o I 1 o 〇〇I i 〇ooe B- 〇Ο Ο ο Ο XX o 0 o XX o 〇o XX o 〇o XX 〇oo I Next 剤 composition | Crosslinker (E) Parts u> ιη ΙΟ » u> sd 2 swsd 2 1 i S u> swdd IA S Soii type I XDIAMP | ο SX TDI/TMP HBAP TQMXDA v-os 聚酯 Polyester resin (D2), (D3) solution, OHV LA6, 8_J 00 CO ΙΟ αά CO 〇>r> I 62.3 I 1 68.7,1 to cd »〇a> ci 1 62.3 I L68JJ IO cd m σ> CO CO 1 62.3 1 IMJJ io s Li 3.9,1 eo 1 62.3 1 I 68.7 ] 1 58.5 1 % CNI οι ΙΟ ο 5 80.5 85.5 imJ L13JJ CO 〇· s | 85.5 I ΓΪΖ5Ί LI3JJ 00 o in CO 85.5 MMJ 13.8 I 80.5 j 85.5 M2.5J [TO UMJ ο 7 ο τ tf> Τ HU blflj IT3 H〇JS 1 » ir> o 8 o CSi 〇in o T s 1 o T 8 SI Σ 170,000 I s' 1 S· I CD | 195,000 1 | 145,000 | I 140,000 | | 130,000 | I « 1 Nie | 145,000 | | 140,000 1 | 130,000 | 1 130.000 1 I 195,000 | | 145,000 I [140,000 I | 130,000 1 1 130,000 1 195.000 145.000 | 140,000 1 | 130.000 iig X 0 csi d Ο eM d CM d inch · inch · CM d Ol CNI 2 eg C\1 o τ- f r- r- r- r- r- r- r- Τ- r- production t- r- r- r· r· r- r- T- T- r- iAr content rate (wt%) 1_ wear ο ? ο S CO CO Λ 〇> CO 〇| S CO C7 s σ> CM CO OJ O 00 o σ> CM 00 CM S 00 CO 〇> CM S 讅>5 斋 ο CM WO «r>e> a» βΜ CM ? in r>a> CM C\lo in CO a> CM CM O IO w a> a synthesis example is τ-f αο CO τ- σ> CO ο CO CM CO CM a> CM g CO 3 CO 〇> CM T-· o CO CO to CM 〇〇CM a> CM O r> »r —ΓΟ CO 52 CD CM a> CM g O TP- φ τ- te I Example 150 I Production 10 τ- 苳fe I Example 162 II Example 153 I | Comparative Example 44 | | Comparative Example 45 1 | Example 154 I | poor example 165 ] I lean example 156 I | comparative example 46 1 | comparative example 47 | | example 1S7 | | example 1 58 | l example 169 I | comparative example 4β 1 I comparative example 49 | Example 160 | | Poor Example 161 | | Example 162 | s I Comparative Example 51 I | Example 163 | | Example 164] | Example 165 | 坻 (Zone 苽 Key 0): VVIV (鹖砥<<#^链发供 B)s-A<D±:Iipo-ec3: S-A Silver^t God^JrhN-Khvaxwal [I 獾苽獾苽(硪^苽竑-1)-^- #锆卜硪&-^磔彰-.^2二| 232 319793 200838965 (Synthesis Example 141) <Synthesis of Polyester Polyol> Prepared in a polymerization tank with a mixer, thermometer, and reflux It is introduced into the polymerization reactor and the gas pipes, respectively, and the following ratio of added acid, diol, and catalyst in the polymerization vessel? [Polymerization tank] 392.8 parts of citric acid 392.8 parts of ethylene glycol 210 parts of neopentyl glycol 236.6 parts of dibutyltin oxide 0.5 parts The air in the polymerization tank was replaced with nitrogen, and the mixture was heated to 180 ° C while stirring the mixture. While dehydrating, it takes 4 hours to slowly cool down to 260 ° C and carry out the esterification reaction. Further, in order to promote dehydration, 30 parts of the mixture is dripped while refluxing, and at 23 〇t: the reaction is carried out for 6 hours. Next, the mixture was cooled to 5 (TC or less and the reaction was terminated, and ethyl acetate was added to make the nonvolatile content 50%, and a solution of the polyester polyol was obtained. This polyester polyol was light yellow transparent and had an acid value of 22 mg. K〇H/g, a resin having a hydroxyl group value of 2.5 mgKOH/g, a glass transition temperature of 4 Å, and a number average molecular weight (?η) of 5,000. <Step (1): Formation of polyester main chain> The polymerization tank is provided with a polymerization apparatus of a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, and the above polyester polyol (heart i_a) is added in the polymerization tank at the following ratio, and has two cyclic ether groups. 319793 233 20 0838965 Compound (a-2), and catalyst. [Polymerization tank] The above polyester polyol (a_l_a) 200 parts bisphenol A diglycidyl ether type epoxy resin (a_2) "JER828 (epoxy equivalent 184 To I94g/eq, manufactured by Epoxy Epoxy Co., Ltd.)" 3 7 parts of bis, A, diepoxypropyl, high molecular weight epoxy two-base resin (4)) "JER1001 (epoxy equivalent 450 to 5 〇〇g/eq)参 9.4 parts of 2' methylimidazole (catalyst) 0.06: After replacing the air in the polymerization tank with nitrogen, the temperature was raised to 135 tons while stirring the contents. It was allowed to react for another 15 hours. It is: owed, ethyl acetate is added to adjust the nonvolatile content to 40%, cooled to room temperature, and the reaction is terminated to obtain a solution of the polyester resin (B) for the main chain. This solution was light yellow and transparent, and had a nonvolatile content of 4 〇 1% by weight and a viscosity of 3,000 mPa·s. The resin contained in the solution has an acid value of 3.8 mgKOH/g, a hydroxyl value of 5 (K5 mgK〇H/g, and a glass transition temperature of 6 〇. [, a weight average molecular weight of 30, 〇〇〇. < cyclic ester (b) Synthesis of Addition-Formed Polyester Precursor (c丨)> 100 parts of the polyester resin (B) solution (non-volatile content: 40.1% by weight) of the above-mentioned main chain was added to a polymerization tank, and then added as a ring. The ester of ε-hexyl vinegar 9·9 parts, 2 parts of acetonitrile zinc hydrazine as a catalyst, reacted at ° 1 for 1 hour, and then reacted at 13 (rc for 8 hours, using toluene / acetic acid The solvent of the ester=85/15 (weight ratio) was adjusted so that the volatile component of 319793 234 200838965 became 40%, and the solution of the addition polyester precursor (C1) was obtained. The viscosity of the solution was $3,5GGmPa.s. The resin contained in the solution has an acid value of 3.5 mgKOH/g, a base price of 48.2 mg K〇H/g, a glass transition temperature of 5 ° C, and a weight average molecular weight of 35,000. Further (Synthesis Example 142) In Synthesis Example 72 In step (7), the amount of the cyclic vinegar compound (b) used is changed to 5 parts, and the amount of ethyl acetate in the dropping device is added. In the same manner as in the step (7) of Synthesis Example 72, the preparation was carried out in the same manner as in the step (7) of Synthesis Example 72, and 260 parts of ethyl acetate was added to obtain a solution of a polyester resin (C1) added with a cyclic vinegar compound. In the above formulation, the ratio of the second-order Moor's ring vinegar (8) derived from the bicyclo (tetra) compound (a-2) is about 0.2 mol. (3) Next, the obtained resin (C1) solution is used. 500 parts of the non-volatile content (% by weight), and the amount of the benzoic acid benzene vinegar of the blocking compound (c) is changed to 6 parts, and the step of combining with the synthesis (2) The reaction was carried out in the same manner, and i part of ethyl acetate was added to obtain a solution of the addition-formed polyacetate = fat (D1) which was pale yellow transparent and had a nonvolatile content of 49.8% by weight and a viscosity of 15, mppas. The acid value of (D丨) was i.5 mg K〇H/g, the hydroxy group price was 48.5 mgKOH/g, the glass transition temperature was -5 ΐ:, and the weight average amount was 130,000. One knife (Comparative Examples 52, 53) 25 parts of toluene was added to 1 part by weight of the solution of the addition-molded polyester resin obtained in Synthesis Examples 141 and 142, and further, roi/TMp was added ( 25 parts by weight of phenyl diisocyanate vinegar by methyl propyl hydrazine adduct) as 319793 235 200838965 to make it dry, at 100. 〇 ear immediate agent (E) ' carefully The composition of the sputum sputum agent was buried, and then applied to the release film for 2 minutes in a thickness of 25" to form an adhesive layer. Further, in the same manner as in Examples 1 to 19, p & versatile, obtain a laminate of the composition of the film from the film/adhesive layer/TAC film/pVA/TAc key and a layer of the girth film, and react with the adhesive layer to obtain a fine I. The polarizer (layered body) processed by the second receiver was evaluated in the same manner. The results are 砉; the clothes are not shown in Tables 18 and 19.修 319793 236 200838965 [Table 18] Synthesis example of addition molding polyester resin

性狀 1 OHV CmgKOH/e) 48.2 48.5 1 AV in ci IA 1? s to Mw 35,000 130,000 Vis (rr»P«*e) 3.500 15,000 m Η ? 圓i 溶液外觀聚酯樹脂（D2)、（D3) 觸媒 MIMD ] TBAB 2* I 〇 1:1.4 CSI ψ^· 含有率 (wt%) CO 00 ir> 4 鸾 (SI) l£> u> CO 封閉化合物 (c) l PhNCO 加成型聚酯環狀酯 (b) eGL eCL 聚酯主鏈部（I) Ϊ3 I ja JER828/JER1001 CL IU < («—1〉 (e-1-2) (e-t^3) (a-1-4) TPA/IPA/ED/NPQ P4010 (a-1-1) ! 1 合成例 ·!—1 隸硪hea 盤 fwea :DQVQQI ^^: awiw 遛蝌潜缄碟：03| fro— 3 : 103 sgt^^rffi¥+^^fv^^:IOos3f - 1 I^^^fiMV 畲制：a3-vt< 0102ffirwf AVHVHio:GS2 ^f^^Iiuftu^^: d〒3cuM 敏-r-o: 93 潜銮畹：Vdl 镏溶欺：¥& 237 319793 200838965 [表 19]Traits 1 OHV CmgKOH/e) 48.2 48.5 1 AV in ci IA 1? s to Mw 35,000 130,000 Vis (rr»P«*e) 3.500 15,000 m Η ? Round i solution appearance polyester resin (D2), (D3) Medium MIMD ] TBAB 2* I 〇1:1.4 CSI ψ^· Content (wt%) CO 00 ir> 4 鸾(SI) l£>u> CO blocking compound (c) l PhNCO addition forming polyester ring Ester (b) eGL eCL polyester main chain (I) Ϊ3 I ja JER828/JER1001 CL IU < («—1> (e-1-2) (et^3) (a-1-4) TPA/ IPA/ED/NPQ P4010 (a-1-1) ! 1 Synthesis example·!—1 硪hea disk fwea :DQVQQI ^^: awiw 遛蝌缄 ::03| fro— 3 : 103 sgt^^rffi¥ +^^fv^^:IOos3f - 1 I^^^fiMV 畲 system: a3-vt< 0102ffirwf AVHVHio:GS2 ^f^^Iiuftu^^: d〒3cuM Min-ro: 93 銮畹銮畹: Vdl 镏镏欺:¥& 237 319793 200838965 [Table 19]

1 It « : \璩I 噢采1 蘅擊! 柳\ I 球聲: : 咖牮\ 重工性 X X 耐濕熱性 Ν X Ο < < 耐熱性〇 < .經乾燥之接著劑層黏著性 <1 < 光學特性 < < 折射率 \ 1.5322 1.5131 接著劑溶液塗佈加工性 < <3 適用期 <3 < 接著劑組成物交聯劑（E) TDI/TMP | TDI/TMP 加成型聚酯樹脂溶液、 OHV 48,2 „ to co % ΙΟ ΙΟ ΙΟ 35,000 1 eo X 〇气 r- CM Ο r- Λγ含有率 (wt%) CO 00 ιο 苳齋 iq te> CO 合成例 5· τ— 審嗜4埏甿蝴妒緦川》避柃1拿：dsl/lal 238 319793 200838965 W組成物在使用作為感工性、耐熱性、耐濕熱 ’而可發揮作為感壓接如上所述，可知本發明之接著壓接著劑使用時，易於調節塗佈加性、光學特性、再剝離性及折射率著劑之優異特性。相對於此’於各比較例中，作為錢接著劑之適為短，無法塗佈於剝離薄膜上，或切使可法進行接著加工。 …、忐 (產業上之可利用性）本發明之感麗式接著劑組成物，係由脂1 寺有之凝集力，同時亦可形成由將芳香環或脂1 = 而成的聚合物’故能顯現丙稀酸系樹脂所無法獲件之接者物性。就其例而言，可列舉如上述之光學積^ 之耐熱性、耐濕熱性、光學特性、再_性等。尤盆: ，學積層體之料中，就光學特㈣.言，係視= :會而料著近年來顯示器之大型化，對於折射率之 ^工％之抗靜電等所要求之性能係變得越來越嚴格 =因為本發明之接著劑組成物可發揮以往所難特性，故為非常有展望性。另外本發明之接著劑組成物除了可適於作為井風 =以外:亦非常適用於作為一般標藏、薄片、或塗;構卞壁材、塗膜防水材、地板材、增黏劑（tackifier)、接 J、積層結構體用接著劑、密封劑、成型材料、表面改所 =佈劑、黏結劑（bin㈣(磁性紀錄媒體、油墨黏結劑貝 &黏結劑、燒成磚黏結劑、接枝材（Graft 、微 319793 239 200838965 ' 膠囊、玻璃纖維上漿（fiberglass sizing)用等）、胺醋發泡體 (硬質、半硬質、軟質）、胺酯RIM、UV · EB硬化樹脂、南固形塗料、熱固型彈性體、微孔（micr〇cellular)、纖維加工劑、可塑劑、吸音材料、阻尼材料（damping material)、界面活性劑、膠塗劑、人工大理石用樹脂、人工大理石用 =衝擊性賦予#1、油墨用㈣、薄膜（積層接著齊卜保護膜等）、層合玻璃用樹脂、反應性稀釋劑、各種成型材料、彈赢=纖維、人工皮革、合成皮革等之原料’或是作為各種樹 •脂添加劑及其原料等。1 It « : \璩I 噢 1 sniper! Willow \ I Ball sound: : Curry \ Heavy work XX Heat and humidity resistance X Ο << Heat resistance 〇 < . Dry adhesive layer adhesion <1 <1<<><<>> Refractive index\1.5322 1.5131 Substituent solution coating processability <<3 expiration date<3<<3> Reagent composition crosslinker (E) TDI/TMP | TDI /TMP Addition of Polyester Resin Solution, OHV 48,2 „ to co % ΙΟ ΙΟ ΙΟ 35,000 1 eo X Xenon r- CM Ο r- Λγ Content (wt%) CO 00 ιο 苳斋iq te> CO Synthesis Example 5· τ— Appreciation of 4 埏氓妒缌》》》拿拿拿 : :: dsl/lal 238 319793 200838965 W composition can be used as a pressure sensitive connection As described above, it is understood that the adhesiveness, optical properties, re-peelability, and excellent properties of the refractive index agent can be easily adjusted when the adhesive agent of the present invention is used. In contrast, in each comparative example, it is used as a money adhesive. It is suitable for short coating, and it cannot be applied to the release film, or it can be cut and processed. (Industrial Applicability) The sensible adhesive composition of the present invention is formed by the cohesive force of the fat 1 temple, and can also be formed by the polymer obtained by the aromatic ring or the fat 1 = The acrylic resin is not able to obtain the physical properties of the article. Examples thereof include heat resistance, heat and humidity resistance, optical properties, re-saturation, etc. of the optical product described above. In the material of the body, the optical special (four). 言, 视视 = : will be expected to increase the size of the display in recent years, the performance required for the anti-static properties of the refractive index of the work is becoming more and more strict = Since the adhesive composition of the present invention exhibits the conventionally difficult characteristics, it is very promising. In addition, the adhesive composition of the present invention can be suitably used as a well wind = also suitable for use as a general label or sheet. Or coating; structural wall material, coating waterproof material, flooring, tackifier, J, adhesive for laminated structure, sealant, molding material, surface modification = cloth, bonding agent (bin (4) ( Magnetic recording media, ink bonding agent shell & adhesive, firing Adhesives, grafts (Graft, micro 319793 239 200838965 'capsules, fiberglass sizing, etc.), amine vinegar foam (hard, semi-rigid, soft), amine ester RIM, UV · EB hardening Resin, south solid coating, thermosetting elastomer, micr〇cellular, fiber processing agent, plasticizer, sound absorbing material, damping material, surfactant, glue coating, resin for artificial marble, For artificial marble = impact imparting #1, ink (4), film (layering followed by protective film, etc.), laminated glass resin, reactive diluent, various molding materials, elastic win = fiber, artificial leather, synthetic leather The raw materials are used as 'all kinds of tree and fat additives and their raw materials.

319793 240319793 240

Claims

200838965 Patent Application Included - A composition of a binder comprising a polyester resin (D) having a polyester backbone (1) and a plurality of side chains branched from the polyester backbone (1), and the plural The side chain system includes an i-side chain having a functional group selected from a group consisting of a hydroxyl group and a carboxyl group, and a second side chain having a hydroxyl group with T, and the plurality of side chains in the polyester resin (D) The ratio occupied by the molecule is 5 to 80% by weight of the average; and the crosslinking agent (E) which crosslinks the aforementioned polyester resin (D); wherein, when the crosslinking agent is used (E) when the hydroxyl group is reactive, the hydroxyl value of the polyester resin (D) is 5 〇 mg K 〇 H / g or less; when the crosslinking agent (8) is reactive with the yarn, the above-mentioned poly-resin (9) The base price is 100 mgKOH/g or less, and the acid value is 5 〇mgK〇H/g or less. 2. If you apply for a patent scope! The adhesive composition according to the above aspect, wherein the complex side chain contains a ring-opening structural unit of the cyclic vinegar (b), and the second side chain has a structure in which (4) is blocked by blocking the compound (4). 3. t Apply for the second grade of the first grade and then the remainder, where 'the open-loop structural unit of the first side chain and the second side 。. Both sides of the chain contain cyclic vinegar (8) 4. If the side chain of item i or 荽1 of the patent application contains a cyclic structural unit, the above-mentioned ang 2 side chain does not contain a ring (4) (8) open-loop structure single & 1 patent application scope In the terminator of the third or fourth aspect, the crosslinking agent (E) is reactive with respect to the hydroxyl group. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 4 wire cross-linking agent 7 · As claimed in the scope of the patent item i, to make the composition of the adhesive, :: the lyophilized vinegar _ constitutes the vinegar ring carbon number of 6 to 18 compounds. Adhesive composition

• As in any one of the scopes of claims 7 to 7, the cyclic ester (b) is a lactone. • For example, in the scope of the patent range, items 1 to 8 of the cup 5, straight, and the 8th of the brothers are the ingredients of the block. The block compound (4) contains the compound The anhydride (c2) and the isocyanate compound (4) are selected from the group consisting of + 1 drooping. 1〇ΐΙ=The adhesive composition of the ninth aspect of the patent range, wherein the aforementioned bismuth 1) is selected from the group consisting of hydrogen residue, oxime I, chlorite sulphide, shifanzhi and decylamine. At least one of them. U.=The adhesive composition of claim 9 of the patent scope, wherein the above interest: (: 2) is a small dicarboxylic acid having a molecular weight of 9 〇 to 5 ( (4). A composition of the above-mentioned iso 13 compound (° 3) is a monofunctional isocyanate compound. •成: 请ί利范_! The adhesive group of any of items 1 to 12, wherein the polyester backbone (I) is a dibasic acid (a-1) and has a 2% form Each structural unit of the ether group-containing compound (a_2) is bonded to each other via an ester bond at 319793 242 200838965. 14. For the follow-up product of the 13th article of the patent application (4), the molecular weight of the mono-acid (a-Ι) is 9〇, ^ ^ 17 , ^ . , one of the DUU carboxylic acids (&-1-1) or Dehydrated condensate under 3 parts. 〃夕凡一心) In the acid excess of the article I claim Fan ^ 13 or 14 followed by (four) adult, its Guangxi 70 alcohol (5) _α) contains polyester diol, polycarbonate monol and polyamide - 醢 &&# + ee makeup - at least one diol selected from the group of individuals and having an average molecular weight of IA 500 to 50,000. In the = the scope of the patent application! The adhesive group of any one of items 15 to 11, wherein the glass transition temperature of the '11 4 4 polyester resin (9) is ―(10) to 10 °G. Π·························································································· The adhesive composition of the fifth aspect, wherein the crosslinking agent (E) comprises a polyisocyanate compound. 19. The adhesive composition of claim 6, wherein the crosslinking agent (8) comprises an epoxy compound, an aziridine compound, a slave imine compound, an oxazoline compound, and a metal chelate. At least one selected from the group consisting of compounds. A layered body having: an optical member; and a layer of an adhesive composition laminated to any one of the above-mentioned optical members, in the above-mentioned optical component, from the first to the 243, 319, 793, 2008, 389, s. 2L-type liquid crystal cell components, which are patented by the scope! The layer of the tantalum yarn of the item to the item of item 19 and the glass member for the liquid crystal cell are laminated. 22. The manufacturing process of the composition of the adhesive composition has the following preparation steps: a preparation step of preparing a resin (9), wherein the poly-resin resin (D) has a polycondensation purpose Chain (1), the branch from the aforementioned chain of the main chain (ι)! Side chain (II) and second side chain m,), life, +, μ t +

Moreover, the side chain (π) of the brother 1 has a Guantai armor selected from the group consisting of a hydroxyl soil and a sulfhydryl group, and the second side chain (ΙΓ) has a closed compound (4). a structure in which (4) is blocked; wherein 'the modulation step is carried out by the following reaction: = addition polymerization of a dibasic acid (a-1) and a compound (4) having two cyclic (10) groups) to form a complex hydroxyl group a polyester backbone ester backbone forming reaction; a person forms a side chain formation reaction of a side chain by a ring-opening addition of a quinone ester compound (b) to a hydroxyl group of the aforementioned polyester backbone; The hydroxyl group blocking reaction of the blocking compound (c). The method for producing an adhesive composition according to the 22nd aspect of the invention, wherein the front side chain forming reaction system is carried out before the blocking reaction. The method for producing an adhesive composition according to claim 23, wherein the side chain formation reaction system starts in the middle of the formation reaction of the polyester main chain. - The manufacturing method of the adhesive composition of claim 23, / wherein the side chain formation reaction system forms a reaction with the polyester main chain 319793 244 200838965. A method for producing an adhesive composition of 22 cases, 27: the application reaction is carried out before the side chain formation reaction. The method for producing the composition of the adhesive of the 26th item, the second step, the closed reaction system starts from the manufacturing method of the adhesive composition of the above-mentioned polyurethane main chain formation reaction of 28.11\ patent scope item 26, 癍2 gt closed The reaction system forms a reaction with the aforementioned polyester backbone. The manufacturing method of the adhesive agent group according to any one of the items 26 to 28, wherein the aforementioned blocking reaction is carried out after the side bond forming reaction. The manufacturing method of the adhesive agent group according to any one of claims 22 to 29, wherein in the aforementioned preparation step, a salt, a quaternary ammonium salt, a quaternary ammonium salt, and a quaternary salt are used. The reaction catalyst selected from the group consisting of metal hydroxides, soil-based metal hydroxides, Lewis acids, organometallic compounds and metal sulphides. 3. The method for producing an adhesive composition according to any one of claims 22 to 3, wherein the crosslinking agent is formulated in the above-mentioned addition-molded polyester resin (D) The method for producing an adhesive composition according to any one of claims 22 to 31, wherein the first side chain (II) is formed by the side chain formation reaction. And forming the aforementioned second side chain (π,) from the hydroxyl group or from the aforementioned first side chain (II) by the aforementioned blocking reaction. 319793 245 200838965 33 · As in any one of the 22nd to 31st claims In the method for producing an adhesive composition, the first side chain (II) and the second side chain (ΙΓ) are formed by the blocking reaction.

246 319793 200838965 VII. Designated representative map: There is no schema in this case (1) The representative representative figure of this case is: (). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: This case does not represent the chemical formula 319793